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Book of Abstracts

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Table of Contents Poster Session (23rd August, Sunday evening) Abs. 1-30

Opening Ceremony and Moissan Session (24th August, Monday morning) Abs. 31-34

Alternative Energy/Energy Storage - I (24th August, Monday afternoon) Abs. 35-38

Inorganic/Organometallic (24th August, Monday afternoon) Abs. 39-42

Organic/Organometallic-I (24th August, Monday afternoon) Abs. 43-46

Alternative Energy/Energy Storage - II (24th August, Monday afternoon) Abs. 47-51

Bio/Medical (24th August, Monday afternoon) Abs. 52-56

Organic/Organometallic - II (24th August, Monday afternoon) Abs. 57-61

Poster Session (24th August, Monday evening) Abs. 62-92

ISoFT'09: Award Session (Monday, 24th August) Abs. 93-95

Inorganic/Organometallic: Bartlett Memorial Session- I (25th August, Tuesday) Abs.

96-100

Organic/Organometallic: Tatlow Memorial Session - I (Tuesday, 25th August) Abs.

101-105

ISoFT'09-I,II (Tuesday, 25th August) Abs. 106-114

Inorganic/Organometallic: Bartlett Memorial Session- II (25th August, Tuesday) Abs.

115-118

Organic/Organometallic: Tatlow Memorial Session - II (Tuesday, 25th August) Abs.

119-122

ISoFT'09-III (Tuesday, 25th August) Abs. 123-126

Inorganic/Organometallic: Bartlett Memorial Session- III (25th August, Tuesday)

Abs.127-130

Organic/Organometallic: Tatlow Memorial Session - III (Tuesday, 25th August)

Abs.131-134

ISoFT'09-I (Tuesday, 25th August) Abs. 135-139

Organic/Organometallic (Tuesday, 25th August) Abs. 140-144

Inorganic/Organometallic (Tuesday, 25th August) Abs. 145-150

Poster Session Including ISoFT'09: (Wednesday, 26th August) Abs. 78,150-185

Bio/Medical -I (27th August, Thursday morning) Abs. 186-190

Inorganic/Organometallic - I (27th August, Thursday morning) Abs. 191-195

Organic/Organometallic-I (27th August, Thursday) Abs. 196-200

Bio/Medical -II (27th August, Thursday morning) Abs. 201-204

Inorganic/Organometallic - II (27th August, Thursday morning) Abs. 205-208

Organic/Organometallic-II (27th August, Thursday) Abs. 209-212

Fluoropolymers/Materials - I (27th August, Thursday afternoon) Abs. 213-216

Organic/Organometallic-III (27th August, Thursday) Abs. 217-220

Physical (27th August, Thursday) Abs. 221-224

Environmental (27th August, Thursday) Abs. 225-228

Fluoropolymers/Materials - II (27th August, Thursday afternoon) Abs. 229-232

Organic/Organometallic-IV (27th August, Thursday) Abs. 233-236

Poster Session (27th August, Thursday evening) Abs. 237-260,286,287

Organic/Organometallic - I (28th August, Friday) Abs. 261-266

Fluoropolymers/Materials - I (28th August, Friday morning) Abs. 267-271

Inorganic/Organometallic - I (28th August, Friday morning) Abs. 272-276

Fluoropolymers/Materials - II (28th August, Friday morning) Abs. 277-279

Inorganic/Organometallic - II (28th August, Friday morning) Abs. 280-283

Organic/Organometallic - II (28th August, Friday morning) Abs. 283-285

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Poster Session (23rd August, Sunday evening) Presider: Steven H. Strauss, Colorado State University, Fort Collins, CO

1. Electrochemical Properties of Organo-Fluorine Compound-Containing Electrolytes for Lithium Ion Batteries

T. Achiha1, T. Nakajima1, Y. Ohzawa1, M. Koh2, A. Yamauchi2, M. Kagawa2 and H. Aoyama2,

(1)Department of Applied Chemistry, Aichi Institute of Technology, Toyota, Japan, (2)Daikin Industries,

Ltd., Settsu, Japan

Introduction: Organo-fluorine compounds are very stable against oxidation reaction, being possible to

increase the thermal and oxidation stability of lithium ion batteries. In present study, we have

investigated electrochemical behavior of organo-fluorine compounds to use them as solvents for lithium

ion batteries.

Experimental: Four organo-fluorine compounds have been used (A:4-(2,2,3,3-Tetrafluoro-

propoxymethyl)-[1,3]dioxolan-2-one, B:4-(2,2,3,3-Tetrafluoro-2-trifluoromethyl-propyl)-[1,3]dioxolan-2-

one, C:Bis-(2,2,3,3-tetrafluoro-propyl)carbonate, D:Bis-(2,2,3,3,3-pentafluoro-propyl)carbonate). A

three-electrode cell with lithium counter and reference electrodes was used for electrochemical

measurements. The 0.67 mol/l LiClO4–EC/DEC(1:1 vol.%), EC/DEC/PC(1:1:1 vol.%), EC/DEC/(A, B or

C)(1:1:1 vol.%) and EC/DEC/PC/(A, B or C)(1:1:1:1.5 vol.%) for were used for linear sweep voltammetry

and galvastatic charge/discharge cycling. For cyclic voltammetry, the 0.5 mol/l LiClO4–EC/DEC/(A, B or

C)(1:1:2 vol.%) was used.

Results and discussion: Organo-fluorine compounds A, B and C are mixed with EC/DEC and EC/DEC/PC in

whole range of composition at room temperature while the solubility of D is ca. 10 vol.% in both solvent

mixtures. Linear sweep voltammograms obtained in organo-fluorine compound-containing electrolytes are

shown in Fig. 1. The electrochemical oxidation of solvent mixtures was suppressed by A, B, and C.

Galvanostatic charge/discharge experiments have shown that charge/discharge capacities and first

coulombic efficiencies were nearly the same as each other in 0.67 mol/l LiClO4–EC/DEC and EC/DEC/(A, B

or C). The mixing of organo-fluorine compound A, B or C with EC/DEC/PC diminished the electrochemical

reduction of PC at 1st cycle. These results show that organo-fluorine compounds A, B and C not only give

anti-oxidation ability to electrolyte solutions but also contribute to the SEI formation on natural graphite

electrodes.

4

2. Synthesis and Polymerization of Novel Fluoroalkyl 2-Trifluoromethylacrylates

Akihiro Hosoya, Department of Materials Science, Graduate School of Engineering, Saitama Institute of

Technology, Fukaya, Japan

Radical addition of 2-benzoxypentafluoropropene [CF2=C(CF3)OCOC6H5] (BPFP) with cyclic ethers such as

tetrahydrofuran, tetrahydropyran and 1,3-dioxolane was achieved to afford addition products followed by

hydrolysis to yield fluorinated alcohols, which gave fluoroalkyl 2-trifluoromethylacrylates by the reaction

with 2-trifluoromethylacryloyl chloride (TFMAC). Radical addition of BPFP with ethanol and 2-propanol took

place to afford fluorinated alcohols which gave fluoroalkyl 2-trifluoromethylacrylates by the reaction with

TFMAC. Synthesis of 2-trifluoromethylacryloyl chloride (TFMAC) was carried out by the reaction of 2-

trifluoromethylacrylic acid (Tosoh F-Tech Inc) with phthaloyl dichloride (Iharanikkei Co). Radical and

anionic polymerizations of fluoroalkyl 2-trifluoromethylacrylates obtained were investigated. Radical

polymerization of fluoroalkyl 2-trifluoromethylacrylates was carried out by adding monomer, BPO or AIBN

as an initiator. Anionic polymerization were carried out by adding monomer, anionic initiators such as t-

BuOK, Et2Al(NCCHCOOC2H5), and ate-complex such as LiZn(C4H9)(C2H5)2 and LiAl(C4H9)(C2H5)3 in

benzene. The highest molecular weight polymer obtained was about 1.1x104 yielded under the radical

condition initiated with BPO. The anionic polymerization reactivity was also investigated to give low-

molecular weight polymers.

3. 2-Amino-2-Fluoro-1,3-Diaza-2,4-Disila-Cyclopentane - Synthesis and Reactions

Fatme Kanaan, Katharina Strueber, Uwe Klingebiel and Carola Schulzke, Department of Inorganic

Chemistry, University of Goettingen, Goettingen, Germany

Lithium salts of 2-amino-2-fluoro-1,3-diaza-2,4-disila-cyclopentanes were crystallized as four-membered

(SiFNLi) rings. The elimination of LiF leads to dimeric iminosilenes, eq. (1).

The result of the partial hydrolysis of the four-membered (SiFNLi) ring is a tetramer containing a central

Li6O-octahedron.

The chemistry of these compounds and crystal structures are presented.

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4. Size-Selective Passage of Hydrogen through a Single Crystal Keisuke Kataoka, Toshimasa Katagiri, Yasuhiro Tanaka, Teppei Asanuma and Kenji Uneyama,

Department of Applied Chemistry, Faculty of Engineering, Okayama University, Okayama, 700-8530,

Japan

Purification of hydrogen from carbon oxides at room temperature is an essential technology for the

realization of vehicles with methanol-reforming fuel cells. Filtration by a gas permeation membrane would

simplify the structure of the devices as well as reduce its size and weight. Size-exclusive filtration by

uniform-size micropores would allow the purification of molecular hydrogen at room temperature. In spite

of this possibility, in reality, some gaps between the particles of these porous materials allow bulk

diffusion of the gas, which depress the selectivity performance.

Here, we show a size-selective passage (f = 0.28 nm and length = 1 mm) that allows transport of

hydrogen molecules through a single crystal of double-headed trifluorolactate ((2S,2'S)-octane-1,8-diyl

bis(3,3,3-trifluoro-2-hydroxypropanoate): TFLA-d8). The gas passage was observed by the equipment

shown in Figure 1.

Figure 1. Equipment for gas passage measurement: (a) crystal set, (b) fixed crystal of TFLA-d8 through

a plastic sheet.

Hydrogen (vdW short axis f = 0.20 nm, kinetic diameter f = 0.29 nm) passed through the crystal, while

argon (vdW short axis f = 0.36 nm, kinetic diameter f = 0.34 nm) did not (Figure 2). Quantity of passed

hydrogen gas @ 300K was 4x10-3 mol/m2 sec atm estimated from the pressure change. Use of a large,

organic single crystal avoided bulk diffusion. Moreover, the fluorinated walls of the tunnel depressed

dispersion attraction (van der Waals interactions) between the filter material and the molecules in the

tunnel. This decrease in attractive interactions prevented capping of the tunnels.

Figure 2. Result of gas passage measurement test.

6

5. Polymorphism of K2AgF4 and Remarks On Reactivity of AgF2

Dominik Kurzydlowski, Faculty of Chemistry, University of Warsaw, Warsaw, Poland, Mariana Derzsi,

Interdisciplinary Centre for Mathematical and Computational Modelling (ICM), University of Warsaw,

Warsaw, Poland, Zoran Mazej, Department of Inorganic Chemistry and Technology, Jozef Stefan Institute,

Ljubljana, Slovenia and Wojciech Grochala, Faculty of Chemistry & ICM, The University of Warsaw,

Warsaw, Poland

Fluoroargentates (II) have recently raised considerable interest (1,2) as they exhibit many similarities to

oxocuprates (II), which are precursors of high-Tc superconductors (3). In all known layered fluorides of

silver (II) the unpaired d electrons of silver order ferromagnetically (3). This is in contrast to

antiferromagnetic ordering observed for undoped layered oxocuprates (believed to be a prerequisite for

the appearance of superconductivity). In order to obtain a layered antiferromagnetic fluoroargentate (II)

subtle modifications of the crystal structure of the known compounds are required.

In this work we examined polymorphism of K2AgF4. The room temperature crystal structure of its layered

polymorph, K2Ag(II)F4, has been determined only recently (4). We have lately succeeded in preparation

and structural characterization of novel high-temperature Na2CuF4–type phase. Both polymorphs have

been studied by 19F MAS NMR as well as by ab initio modelling (DFT). Evolution of the crystal structure,

phonon spectra, thermodynamic stability at various temperatures and phase transformations of K2AgF4 at

high pressures (up to 15 GPa) have been predicted.

In our search for novel fluoroargentates (II), we have performed reactions of AgF2 with KHF2 or AlF3 and

observed formation of new phases, which are now being analyzed.

(1) S. E. McLain et al., Nature Mater., 2006, 5, 561

(2) W. Grochala et al., Nature Mater., 2006, 5, 513

(3) W. Grochala, J. Mater. Chem. in press 2009

(4) Z. Mazej et al., CrystEngComm in press 2009

6. Preparation of the Trihydroxysulfonium Cation: Protonated Sulfurous Acid

Mathias Hopfinger and Andreas J. Kornath, Department of Chemistry and Biochemistry, Ludwig-

Maximilians-University, Munich, Germany

Sulfurous acid has not been prepared in the condensed phase as pure compound, yet. Similarly to

carbonic acid, aqueous solutions contain dissolved SO2 molecules and a very small amount of H2SO3

molecules. Nevertheless, gas phase experiments and theoretical considerations do not exclude the

existence of pure H2SO3. In this work we present the synthesis of protonated sulfurous acid (H3SO3+MF6

-).

The preparation was achieved by the reaction of Na2SO3 with the superacidic systems HF/MF5 (M = As,

Sb). For the H3SO3+ cation, as well as the isoelectronic phosphonic acid, two isomers are possible.

The discussed vibrational and NMR spectra together with quantum chemical calculations shows that the

formed H3SO3+ salts consist exclusively as trihydroxysulfonium salts.

7

7. Transition Metal Complexes of Phosphinous Acids and Their Catalytic Activity in Cross-Coupling-Reactions

Boris Kurscheid and Berthold Hoge, Institute of Inorganic Chemistry, University of Cologne, Cologne,

Germany

Diorganylphosphinous acids, R2POH, are in general not stable with respect to their phosphane oxide

tautomers, R2P(O)H.[[1]] Nevertheless, phosphinous acids can be trapped by coordination to transition-

metal complexes as it was shown already in 1968 by Chatt and Heaton.[[2]] These complexes are of

general interest according to their high activity in homogeneous catalysis [[3]] and they are already

commercially available.[[4]]

(1)

The introduction of electron withdrawing groups R at the coordinated phosphorus atom renders to increase

the Lewis acidity of the transition metal atom M[[5]] which influences the catalytic activity of the

corresponding transition metal complexes.[[6]] As for example the Suzuki type reaction:

(2)

[1] E. Corbridge, Phosphorus – An Outline of its Chemistry, 3rd edition 1995, p. 212.

[2] J. Chatt, B. T. Heaton, J. Chem. Soc. A 1968, 2745 – 2757.

[3] For example: L. Ackermann, Synthesis 2006, 10, 1557 - 1571; N. V. Dubrovina, A. Börner, Angew.

Chem. 2004, 116, 6007 – 6010; Angew. Chem. Int. Ed. 2004, 43, 5883 – 5886.

[4] CombiPhos Catalysts, Inc.

[5] Comp.: B. Hoge, P. Panne, Chem. Eur. J. 2006, 12, 9025 - 9035.

[6] For example: S. Jeulin, S. Duprat de Paule, V. Ratovelomananna-Vidal, J.-P. Genêt, N. Champion, P.

Dellis, Angew. Chem. 2004, 116, 324 – 329; Angew. Chem. Int. Ed. 2004, 43, 320 – 325; V. Alezra, G.

Bernardinelli C. Corminboeuf, U. Frey, E. P. Kündig, A. E. Merbach, C. M. Saudan, F. Viton, J. Weber, J.

Am. Chem. Soc. 2004, 126, 4843 – 4853, and references therein.

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8. Isocyanic Acid in Superacidic Media: Protonation, HF-Addition or Both?

Nadine R. Goetz and Andreas J. Kornath, Department of Chemistry and Biochemistry, Ludwig-

Maximilians-University, Munich, Germany

The basicity of the pseudohalogen acids have not been studied systematically yet. Only H2N3+ salts have

been isolated and characterized by Christe et al. The isocyanic acid (HNCO) is the more stable tautomer of

the cyanic acid (HOCN). It is found in the solid state with small amounts of HOCN in the gas-phase and it

has been detected in interstellar clouds. To our knowledge the protonated isocyanic acid is unknown.

In this work we present our studies on the reactions of isocyanic acid with the superacids HF/MF5 (M = As,

Sb) which yield colorless salts, stable at low temperatures. Isocyanic acid can react in the superacidic

media under formation of at least four different species. The vibrational data of the obtained salts together

with quantum chemical calculations show that only one species is formed exclusively.

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9. Protonation of Dithiocarbamic Acid: At Nitrogen or Sulfur?

Joachim Axhausen and Andreas J. Kornath, Department of Chemistry and Biochemistry, Ludwig-

Maximilians-University, Munich, Germany

Usually amino groups possess base properties, except when the environment of nitrogen is planar due to

steric ligands or a conjugation with a neighboured double bond. The latter case is given in dithiocarbamic

acid. The molecule contains a double bonded sulfur atom, which has typically a much lower basicity than

regular amino groups.

In this work we present our studies on the reactions of dithiocarbamic acid with the superacids HF/MF5 (M

= As, Sb), which yield colorless salts, stable at low temperatures. The vibrational data of the salts

together with quantum chemical calculations show that only one species is formed exclusively. This result

demonstrates that the amino group possesses a much lower basicity than one would expect at the first

sight.

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10. Protonated Organohalogen Compounds

Can-Carlos Doertbudak and Andreas J. Kornath, Department of Chemistry and Biochemistry, Ludwig-

Maximilians-University, Munich, Germany

Until now the protonation of the hydrogen halides HX (X = F, Cl, Br, I) lead only in case of HF/SbF5 to

isolable acidic halonium salts H2F+Sb2F11

- and H3F2+Sb2F11

- which are characterized by NMR, infrared

spectra, and single crystal structures. The salts represent the strongest, yet known super acidic system.

For the heavier protonated hydrogen halides, only hints were found by 1H-NMR spectroscopy, but the NMR

studies can also be interpreted in a different manner not involving protonated halides.

Earlier investigations of organohalogen compounds in superacidic solutions have shown that the iodine

compounds R-I (R = CH3, Ph) possesses the highest basicity among the organohalogen compounds, but

the protonated species are only stable at low temperatures and have not been isolated yet. In this work

we present our studies on the reactions of organoiodine compounds with the superacids HF/MF5 (M = As,

Sb) which yield colorless salts, stable at low temperatures. The vibrational data of the salts together with

quantum chemical calculations are discussed.

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11. Novel Perfluorinated Terpolymer Containing Sulfonimide and Phosphonic Acid Functionality

Li-Mei Jin, Stephen E. Creager and Darryl D. DesMarteau, Department of Chemistry, Clemson University,

Anderson, SC

The correlation between high conductivity and an ionomer's low equivalent weight (EW) is widely

accepted. However, the challenge for preparing low EW polymers is to prevent the disadvantageous

properties of extensive membrane swelling and even water solubility. A small amount of crosslinking

could possibly stabilize a very low EW ionomer and minimize swelling and perhaps prevent dissolution in

water. Fluoroalkyl sulfonic acid ionomers cannot be crosslinked to withstand very acidic as well as hot and

dry conditions. Fluoroalkyl phosphonic acid (FPA) groups bind strongly and irreversibly to the Zr4+ cation

and could offer a means of crosslinking in membranes that could stabilize the low EW ionomers. Herein,

we will present some preliminary results about the fluoropolymer illustrated – a terpolymer of TFE, a

fluoroalkyl phosphonic acid monomer, and a fluorosulfonic acid monomer. The FPA pendant would not act

as the primary proton donor but rather as a crosslinking site using Zr4+ or zirconia particles. The physical

and electrochemical properties of the zirconia composite films will be presented.

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12. Reactivity of Me4PF in Acetonitrile Solutions

Christian Hohenstein and Andreas J. Kornath, Department of Chemistry and Biochemistry, Ludwig-

Maximilians-University, Munich, Germany

In the course of our studies on methlyfluorophosphoranes we have reported on the structural properties of

Me4PF. It has an ionic structure in the solid state with weak interactions between cations and anions and

therefore it should be a promising source for "naked" fluoride. Moreover the compound possesses unique

properties compared to other sources of "naked" fluoride. The salt is volatile in vacuum. Me4PF possesses

in the gas-phase and in nonpolar solvents a phosphorane structure with an exceptionally weak P-Fax bond.

Besides the structural properties, the chemistry of Me4PF is unexplored. Me4PF could serve as a better

―naked‖ fluoride then Me4NF, but the nakedness of the fluoride could also be decreased by the bonding

isomerism which is impossible for Me4NF. We present our first studies on the reactivity of Me4PF in

acetonitrile solutions.

13. Copolymerization of Vinylidene Fluoride with Hexafluoropropylene

Sang Goo Lee1, Won Wook So1, Jong Wook Ha1, In Jun Park1, Soo Bok Lee1 and Jong Dae Lee2, (1)Korea

Research Institute of Chemical Technology, Daejeon, South Korea, (2)Department of Chemical

Engineering, ChungBuk University

The kinetics of copolymerization of vinylidene fluoride (VDF) with hexafluoropropylene (HFP) have been

studied by many researcher under emulsion polymerization. However, kinetics was relatively rare carried

out in solution radical process. In this study, we report the kinetics of the radical copolymerization of VDF

with HFP in solution. P(VDF-co-HFP)s with the range of 49 to 5 HFP mol% were successfully synthesized

using diisopropylperoxy dicarbonate (DIPPDC) as an initiator in 1,1,2-trichlorotrifluoroethane (R-113)

solvent. We obtained monomer reactivity ratios (rVDF=1.71, rHFP=0) and monomer-polymer composition

diagram of VDF-HFP using the fineman and ross method. In addition, the microstructure and the thermal

properties of copolymers have been investigated.

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14. Preparation of HFPO by Two-Phase System of An Aqueous and An Organic Phase

EunKyoung Kim, Jong Wook Ha, In Jun Park and Soo Bok Lee, Korea Research Institute of Chemical

Technology, Daejeon, South Korea

Hexafluoropropylene oxide (HFPO) plays an important role in industrial chemistry, where it is used in the

manufacture of high-quality fluorinated products. Products derived from HFPO, such as perfluorinated

vinyl ethers or perfluorinated polyethers are used in many industrial applications. The overwhelming

majority of the known reaction of HFPO was synthesized by oxidation methods using oxygen, hydrogen

peroxide, and sodium hypochlorite solution. In this study, HFPO is synthesized by the epoxidation of

hexafluoropropylene (HFP) in a two-phase system of an aqueous and an organic phase. Especially, HFPO

was obtained by the reaction of aqueous hypochlorite solution (NaOCl) as oxidizing agent, HFP, organic

solvent (1,1,2-trichloro-1,2,2-trifluoroethane, F-113), and trioctylmethylammonium chloride (TOMAC) as

phase transfer catalyst. After the reaction is completed, the organic phase containing HFPO/HFP and the

aqueous phase are separated. The conversion of HFP and the selectivity of HFPO were confirmed by gas

chromatography.

15. Synthesis and Structure of [Cd(XeF2)(HF)2](TaF6)2 – the First Example of Metal Center Simultaneously Coordinated with XeF2 and HF Ligands, and the First Example of Hydrogen Bonding by XeF2

Matic Lozinsek, Evgeny Goreshnik and Boris Zemva, Department of Inorganic Chemistry and

Technology, Jozef Stefan Institute, Ljubljana, Slovenia

Although a lot of compounds with XeF2 or HF coordinated to the metal center are known, up to now there

was no example of the compound in which metal center is simultaneously coordinated with XeF2 and HF

ligands. This is the case in a compound [Cd(XeF2)(HF)2](TaF6)2, which crystallizes in a triclinic, P –1 space

group (a = 5.6164(5) Å, b = 10.0377(8) Å, c = 12.6145(8), α = 96.672(2), β = 90.354(4), γ =

104.090(4), V = 684.65(9) Å3, Z = 2, R = 0.0433) from a solution of XeF2 and Cd(TaF6)2 in anhydrous HF.

Another very interesting feature is the hydrogen bonding between XeF2 coordinated on one metal center

and HF coordinated on the other one. Normally terminal XeF2 ligands are distorted with terminal Xe–F

bond shorter than the bridging one. In this case both Xe–F bonds are of the same length due to the strong

Xe–F∙∙∙H–F interaction with F–F distance of 2,544(13) Å. To our knowledge this is the first observed

hydrogen bonding of XeF2.

16. The Preparation of Precursor for Synthesis of Multi-Functional Perfluoropolyether Using HFPO Dimer

Eun Young Park, Jong Cheol Lee, Kwang Won Lee, In Jun Park, Jong-Wook Ha and Soo-Bok Lee, Korea

Research Institute of Chemical Technology, Daejeon, South Korea

The fluorinated polymers with perfluoroether moiety have industrial possible application in antifouling

agent, anti-fingerprint coating agent of displays, anti-reflection film, and fuel cell membrane because of

their excellent physical properties such as very low refractive index, anti-smudge property, superior heat

and chemical resistancy, and transparency, etc. In this study, we will discuss synthesis of

hexafluoropropylene oxide (HFPO) dimer and precursor for the synthesis of multi-functional

perfluoropolyether. HFPO dimer was synthesized in continuous process using bubble column reactor. The

precursor was prepared by the reaction of HFPO dimer and various diols, and the structure of precursor

was investigated by 19F-NMR and 1H-NMR.

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17. Synthesis of New Compounds Based On HFC-1225ye

Anthony Thomas, Department of Chemistry, University of Manchester, Manchester, United Kingdom and

Alan K. Brisdon, School of Chemistry, University of Manchester, Manchester, United Kingdom

The synthesis of perfluoropropenyl-containing compounds using Z-HFC-1225ye as a starting material was

undertaken based on existing methods1. Reactions of Z-HFC-1225ye with n-butyl lithium at low

temperature ( < -78°C) followed by the addition of a variety of organo group 14 halides resulted in the

corresponding perfluoropropenyl compounds in good yields. Organo germanium, tin and lead halides were

studied, with the x-ray crystal structure of Ph3Sn-CF=CF(CF3) being determined (Figure 1).

Figure 1. X-Ray crystal structure of Ph3Sn-CF=CF(CF3)

Using the same synthetic method, reactions with phenyl mercuric chloride and mercury dichloride resulted

in the synthesis of PhHg-CF=CF(CF3) and Hg-(CF=CF(CF3))2 respectively in good yields. Both underwent 19F NMR analysis to determine synthesis with the latter also undergoing 199Hg NMR analysis.

In addition, reactions were undertaken to determine the difference in reactivity between Z and E isomers

of HFC-1225ye with the organo group 14 halides. Results showed that the E isomer is the more reactive

isomer in these systems.

[1] Brisdon et al., Inorg. Chem., 2002, 41 (18), 4748-4755

18. Attempts to Use Fluorides of Ag(II) as Precursors towards Elusive Ag(II)SO4

Przemyslaw Malinowski, Faculty of Chemistry, University of Warsaw, Warsaw, Poland, Wojciech

Grochala, Faculty of Chemistry & ICM, The University of Warsaw, Warsaw, Poland and Zoran Mazej,

Department of Inorganic Chemistry and Technology, Jozef Stefan Institute, Ljubljana, Slovenia

Chemistry of Ag(II) is limited mainly to fluorides mostly because of the large positive redox potential of

this strong oxidizer (+2,27 V in aHF [1]). Only two pseudobinary Ag(II) oxo−compounds, silver (II)

fluorosulfate [2] (Ag(SO3F)2) and silver (II) triflate [3] (Ag(SO3CF3)2), have been characterized to date but

their crystal structures have not been solved. Extension of chemistry of divalent silver is clearly an

important goal because it has been proposed that some Ag(II) compounds may exhibit high-temperature

superconductivity [4]. Novel compounds of Ag(II) might also be used as oxidants in water treatment

applications, organic chemistry etc.

15

In this work we describe attempts of synthesis of a genuine silver (II) sulfate. The syntheses utilize AgF2

or Ag(SbF6)2 as the substrates:

Ag(SbF6)2 + K2SO4 (in aHF) → 2 KSbF6 + ‗AgSO4‘ (Eq.1)

AgF2 + H2SO4 → 2 HF + ‗AgSO4‘ (Eq.2)

The obtained black residue (insoluble in aHF or in excess H2SO4, respectively) has been characterized by

powder X-ray diffraction, Raman and IR vibrational spectroscopy, magnetic susceptibility and ESR

measurements. We have also examined its thermal decomposition with TGA/DSC/EGA analyses. Black

compound decomposes at ca. 110°C with evolution of O2 yielding silver (I) pyrosulfate, Ag2S2O7, which in

turn converts to Ag(I)2SO4 upon subsequent heating to 450 oC (with release of SO3). The combined

observations indicate that synthesis of Ag(II)SO4 has indeed been achieved.

[1] „Comprehensive Inorganic Chemistry‖, Pergamon, Oxford (1973).

[2] P.C. Leung, F. Aubke Inorg. Chem. (1978) 17, 1765.

[3] P.C. Leung, K.C. Lee, F. Aubke, Can. J. Chem. (1979) 57, 326.

[4] W. Grochala, R. Hoffmann, Angew. Chem. Int. Ed. Engl. (2001) 40, 2742.

19. Protonation of Mono-, Di,- and Trifluoroacetic Acid

Theresa Soltner and Andreas J. Kornath, Department of Chemistry and Biochemistry, Ludwig-

Maximilians-University, Munich, Germany

Hydroxycarbenium cations are well known as intermediates in various organic reactions. The cations have

a highly electron deficient carbocationic center, which is stabilized by n-π electron donating effects, i.e. by

the conjugation of the non-bonded electron pairs into the vacant p-orbital, and mesomeric effects.

Fluorine or fluorinated methyl groups are not able to stabilize the cations by n-π back-donation, and the

electron withdrawing effect causes further destabilization. The existence of the trifluoromethyl-substituted

hydroxycarbenium cations has been proofed by NMR spectroscopy in superacids, but the compounds have

never been isolated.

In this work we present our studies on the reactions of fluoro-substituted acetic acids with the superacids

HF/MF5 (M = As, Sb), which yield the corresponding dihydroxycarbenium salts, stable at low

temperatures. The vibrational data, single crystal X-ray structures and quantum chemical calculations are

discussed.

16

20. Defect Structure and Conductivity of Fluorite-Like and Tysonite-Like Solid Solutions in BiF3-Bi2O3-MX2 Systems (MX2=TeO2 or BaF2)

Evgeniya V. Khomyakova1, Vladimir A. Prituzhalov2, Ardashnikova Elena I,1 and Dolgikh Valeriy A.1,

(1)Department of Chemistry, Moscow State University, Moscow, Russia, (2)Rusnanotech, Moscow, Russia

Aim of this work is determination of relation between composition, defective structure-and anionic

conductivity of fluorite-like and tysonite-like phases in BiF3-Bi2O3-TeO2 and BiF3-Bi2O3-BaF2 systems.

Conditions of solid-state synthesis were 873 K (3-50 hours) with ampoules quenching in icy water.

Starting materials were BiF3, Bi2O3, BaF2, TeO2. BiF3-Bi2O3-TeO2: Au-test-tubes, vacuum-processed quartz

ampoules; BiF3-Bi2O3-BaF2: Cu-ampoules, filled with dry argon. Conductivity measurements: complex

impedance method (the two-contact method on tablets, Ag-electrodes,1-106 Hz, 293-673K, Ar+O2).

Conductivity does not depend on the oxygen maintenance in a gas phase for all phases except III-Bi1-

xTex(O,F)2. It decreases in the 0,06-0,21atm pO2 interval and become constant up to

1atm. Conductivity of II-, III- and IV-Bi1-xTex(O,F)2+δ fluorite-like phases rises with increasing of subcell

parameter and fluorine content.

Ionic conductivity of the investigated phases (Bi1-xBaxO0.07F2.86-x, II-, III- and IV-Bi1-xTex(O,F)2+δ),

containing high amount of doped defects, is well described by defective areas model [1] (for anion-

conductive phases) and by model of clusters formation and nanoinclusions [2](developed for fluorites).

Probably phase III (fluorite stoichiometry – MX2) has own anionic sublattice disordering without clusters

formation. Therefore presence of the mixed conductivity is possible: prevalence of p-type at low pressure

of oxygen and ionic conductivity at high pressures. Good conductivity (up to 537K), low values of Ea

(0,12-0,63eV) and revealed dependence of conductivity on the fluorides-ions content allow to assume

fluorine-ionic conductivity.

The work was done under financial support of the RFBR (project # 07-03-00985-a)

1. A.K. Ivanov-Shits et al., Solid State Ionics 37 (1990) 125.

2. B.P. Sobolev et al., Crystallography Reports 48 (2003) 141.

21. A New Series of Silylium Cations: Preparation Using the (7-12)-HCB11(CF3)6F5(-) Anion

B. Randall King, Matthew G. Fete and Josef Michl, Department of Chemistry and Biochemistry, University

of Colorado, Boulder, Boulder, CO

Preparation of several silylium cations is reported, taking advantage of the inertness and very low

nucleophilicity of the (7-12)-HCB11(CF3)6F5(-) anion, accessible by direct fluorination of the (7-12)-

HCB11(CH3)6H5(-) anion. Results include NMR characterization of salts of the known (CH3)3Si(+) cation and

the new (CH3)2SiH(+) and CH3SiH2(+) cations formed by hydride abstraction from an appropriate silane in

liquid SO2 or hexafluoropropane CF3CF2CH2F solvent. The hydride abstracting reagents are alkyl cations

such as (CH3)3C(+) and (CH3)2CH(+), readily accessible by metathesis from the Ag(+) salt of (7-12)-

HCB11(CF3)6F5(-) and alkyl halides. The parent silylium cation SiH3(+) appears much harder to access than

its various methylated analogs and we have not yet found an alkyl cation capable of abstracting a hydride

from SiH4.

17

22. Dendrimer Encapsulated Platinum Nanoparticles (Pt DENs): Preparation, Characterization, and Potential Applications in Fuel Cells Huizhen Zhu1, Litao Bai1, Wei Li2, Shane C. Street1, Alan M. Lane2, Richard E. Fernandez1 and Joseph S.

Thrasher1, (1)Department of Chemistry, The University of Alabama, Tuscaloosa, AL, (2)Department of

Chemical and Biological Engineering, The University of Alabama, Tuscaloosa, AL

Pt nanoparticles (Pt DENs) were prepared by the photoreduction of H2PtCl6 in the presence of

polyamidoamine generation 4 (PAMAM G4) dendrimer. These nanoparticles are highly monodisperse with

an average of 2.6 nm in diameter, exhibit high specific activity for the oxygen reduction reaction, and are

inert to methanol oxidation, showing great potential for application in Polymer Electrolyte Membrane Fuel

Cells (PEMFCs) and Direct Methanol Fuel Cells (DMFCs). A simplified membrane electrode assembly has

been fabricated by the electrostatic self-assembly between Nafion® and Pt DENs. Two methods were

proposed to increase Pt loading: layer-by-layer self assembly and immobilization of Pt DENs and carbon

powder onto carbon fiber. Approximately 80 layers were proposed to reach the required loading using a

dipping machine. Immobilization of Pt DENs and carbon powder simultaneously on the carbon fiber can

easily be achieved by electrochemical coupling, which is promising for replacing the conventional method

of electrode fabrication.

23. Advances in the Selective Fluorination of Fullerenes

Natalia B. Shustova1, Zoran Mazej2, Steven H. Strauss1 and Olga V. Boltalina1, (1)Department of

Chemistry, CSU, Fort Collins, CO, (2)Department of Inorganic Chemistry and Technology, Jozef Stefan

Institute, Ljubljana, Slovenia

In this presentation we will discuss our most recent studies on the fluorination of fullerenes. This type of

exohedral derivatization was one of the first ever reported for fullerenes and is also one of the most

successful with respect to the selective preparation of a number of highly fluorinated compounds with

unprecedented structures and properties. This success is largely due to the use of transition metal

fluorides in higher oxidation state as fluorinating agents. For example, syntheses of specific isomers of

C60F36 and C60F18 were developed with the use of this approach. At the same time, some aspects of

fluorination have not yet been fully understood, and some problems in the synthesis have not been

solved. For example, no suitable method has been developed for the preparation of fluorofullerenes with

low F content. Furthermore, molecular structures of many previously isolated compounds have yet to be

determined (only four C60Fx compounds, with x ≥ 18, have been structurally characterized to date by

single-crystal X-ray diffraction). In this work, we have introduced new fluorinating agents developed

specifically for this project, and these have allowed us to prepare previously unknown fluorofullerenes and

to improve the yield of known fluorofullerenes. New single-crystal X-ray structures will also be presented.

18

24. Thermal Stability and Structures of Transition Metal Salts of Superweak B12F122–

Anion Dmitry Peryshkov and Steven H. Strauss, Department of Chemistry, Colorado State University, Fort

Collins, CO

The remarkable thermal and chemical stability of the weakly coordinating B12F122- anion has allowed us to

thermally generate reactive transition metal cations in the solid state by thermal desolvation of

M(solv)xB12F12 salts. Their reactivity, and therefore the weakly coordinating nature of this anion, were

tested by CO binding to the desolvated salts MxB12F12 to form nonclassical cationic carbonyls. The thermal

stabilities of various salts of B12F122- (up to 500+ °C) will be discussed and compared with that

homologous salts of other weakly coordinated anions, which decompose at much lower temperatures.

X-ray structures of a wide range of metal salts of B12F122-, including K2(H2O)2B12F12, K2(H2O)4B12F12,

K2(CH3CN)2B12F12, Cs2(CH3CN)B12F12, Cs2(H2O)B12F12, Ni(H2O)6B12F12, Co(CH3CN)6B12F12,

Ag2(CH3CN)8B12F12, Ag2(CH3CN)5B12F12, and others will be presented. Details of (i) the packing of B12F122-

anions in the lattice and (ii) hydrogen bonding between F atoms of B12F122- and coordinated solvent

molecules will be discussed in light of the possible use of the partially or completely-desolvated reactive

salts of B12F122- for small-molecule catalysis.

25. Ionic Liquids with the Bis[Bis(pentafluoroethyl)Phosphinyl]Imido – Anion [(C2F5)2 P(O)]2N

- Synthesis and Characterization

Dana Bejan1, Jane Hübner1, Helge Willner1 and Nikolai Ignatiev2, (1)Anorganische Chemie, Bergische

Universität Wuppertal, Wuppertal, Germany, (2)PLS R&D LSS, Merck KGaA, Darmstadt, Darmstadt,

Germany

In the last decade room temperature ionic liquids (RTILs) received much attention. [1,2] Recently we

reported the synthesis and characterization of Na, K, Cs, Ag salts with the new weekly coordinating anion

bis[bis(pentafluoroethyl)phosphinyl]imide (shortly named FPI).[3] Here we would like to report about

ionic liquids containing the FPI anion, and their characterization (melting point, thermal stability, viscosity, density, conductivity). Their properties are presented and compared with IL‘s of others anions, [4] e.g.

Table 1. Dynamic viscosity and density of the ionic liquids containing different anions at T=20 ºC

(FAP = tris(pentafluoroethyl)trifluorophosphate; TCB = tetracyanoborate)

Ionic Liquids dynamic viscosity

η /mPa·s

density

ρ /g·cm-1

EMIM FAP 75.3 1.715

EMIM TCB 22.2 1.040

EMIM BF4 61.5 1.304

EMIM FPI 171.9 1.683

[1] N. Ignatiev, U. Weltz-Biermann, M. Heckmeier, G. Bissky, H. Willner, WO 2006/128563, Merck

Patent GmbH, Germany.

[2] P. Wasserscheid, Ionic Liquids in Synthesis, Wiley-VCH, Weinheim, 2003.

[3] D. Bejan, H. Willner, N. Ignatiev, C. W. Lehmann, Inorg. Chem., 2008, 47, 9085-9089.

[4] www.ionicliquids-merck.de

19

26. Preparation and Handling of Tetrafluoroethylene (TFE) in An Academic Laboratory

Todd S. Sayler, Alfred Waterfeld, Christian Schiel, Richard E. Fernandez and Joseph S. Thrasher,

Department of Chemistry, The University of Alabama, Tuscaloosa, AL

Accelerating rate calorimeter (ARC) studies have been carried out on the thermal decomposition of several

metal salts of pentafluoropropionic acid, producing tetrafluoroethylene (TFE) and carbon dioxide (CO2).

ARC studies were also carried out on the reaction of TFE and CO2 mixtures with CO2 absorbers, such as

ascarite® and soda lime. These methods of producing TFE have been employed in order to safely create

both co- and ter-polymers through emulsion and solution polymerizations in an academic laboratory. The

polymerization system allows solution polymerizations of TFE to be safely carried out in the presence of

CO2 with the capacity to create 100-gram quantities of co-polymers per run. If desired, a CO2 scrubber

can be inserted into the system, allowing emulsion and solution polymerizations to be carried out without

the interference of CO2 pressure. The system allows polymers to be engineered to give desired properties

by altering the concentration and addition rate of TFE and/or co-monomer as well as addition rate and

concentration of free-radical initiator.

The authors make no warranties, expressed or implied, and assume no liability in connection with any use

of the information presented on this poster. No one but persons having technical skill in this area of

fluorine chemistry should attempt or repeat anything presented herein, and then at their own discretion

and risk.

27. Isolation, Structure, and Physical-Chemical Properties of Long-Chain Perfluoroalkyl Fullerenes

James B. Whitaker1, Igor V. Kuvychko2, Alexey A. Popov3, Olga V. Boltalina2 and Steven H. Strauss2,

(1)Department of Chemistry, Colorado State University, Fort Collins, CO, (2)Department of Chemistry,

CSU, Fort Collins, CO, (3)Department of Chemistry, Moscow State University, Moscow, Russia

Perfluoroalkyl fullerenes (PFAFs) constitute an intriguing class of compounds due to their high thermal

stability combined with unique electrochemical behavior (stability of the corresponding anions). PFAFs

have shown promise for development of the advanced photovoltaic cells and other applications. Much of

the recent research has centered on trifluoromethylated fullerene derivatives due to relative ease of their

synthesis. It is known that the properties of PFAFs depend on the nature of substituents and especially on

their addition patterns. Therefore, perfluoroalkyl (PFA) groups with different steric requirements provide

an exciting opportunity to create PFAFs with unprecedented addition patterns and, concomitantly,

unprecedented optoelectronic properties. In this work, we have prepared multiple PFAFs carrying normal,

iso, and tertiary PFA groups using a novel low-temperature preparative method. This method has allowed

us to circumvent PFA degradation that is generally observed when these reactions are carried out at high

temperature. This is the first time that PFAFs with tertiary PFA groups have been prepared and

characterized. The relatively selective preparation of PFAFs with two substituents was successfully

realized. PFAFs with higher number of substituents were also prepared and isolated. These PFAFs were

purified using HPLC procedure and studied by a variety of analytical methods. The addition patterns and

structures of these products were studied; combined with electrochemical studies we were able to

correlate the addition patterns of PFAFs with their corresponding reduction potentials. Stabilities of PFAFs

featuring various perfluoroalkyl groups were also evaluated.

20

28. Exploration of SF5-Containing Derivatives of Fullerenes Bryon W. Larson1, Igor V. Kuvychko2, Olga V Boltalina1, Steven H. Strauss1, Gary L. Gard3 and Rolf W.

Winter3, (1)Chemistry Department, Colorado State University, Fort Collins, CO, (2)Department of

Chemistry, Colorado State University, Fort Collins, CO, (3)Department of Chemistry, Portland State

University, Portland, OR

It is known that fluorine containing fullerene derivatives possess useful electron-accepting properties.

Perfluoroalkylated fullerenes are particularly interesting because they generally have high thermal

stabilities and tunable electrochemical properties, lending themselves to possible applications in

optoelectronic devices such as photovoltaics. A large variety of these fullerene derivatives have been

reported, with different perfluoroalkyl substituents and addition patterns giving rise to significant

differences in electrochemical properties. We hypothesize that a stronger electron withdrawing group

would yield even more beneficial electrochemical properties. The pentafluorosulfanyl (SF5) functional

group is the obvious candidate; compared with the CF3 substituent, it is more electron withdrawing,

bulkier, and comparably as stable. SF5 has been incorporated into numerous organic molecules (e.g., SF5X

addition to organic double bonds is well studied), but there have been no reports of SF5-containing

fullerene derivatives.

This work presents an account of the synthetic routes explored to realize the first known fullerene

derivatives containing SF5 groups. We have investigated a number of reactions and reaction conditions for

various SF5-carrying reagents and have found strong evidence that SF5 can be bound directly to the

fullerene cage or through a linker under the right conditions. Characterization of the new compounds by

APCI-MS, HPLC, 19F NMR, UV-Vis, and FTIR spectroscopy and their structures and chemical and physical

properties will be presented and compared to those of trifluoromethylated fullerenes.

29. New Method of High-Temperature Perfluoroalkylation of Fullerenes

Igor V. Kuvychko, James B. Whitaker, Bryon L. Larson, Natalia B. Shustova, Olga V. Boltalina and

Steven H. Strauss, Department of Chemistry, Colorado State University, Fort Collins, CO

Perfluoroalkylation presents an attractive and rapidly evolving area of fullerene chemistry, since these

compounds combine high thermal stability with promising electrochemical properties (tunable reduction

properties and generally reversible electrochemical transitions). The preparation of

poly(perfluoroalkyl)fullerenes (PFAFs) has been generally carried out at high temperature (e.g., 300–600

°C), with an exception of our novel low-temperature synthetic method that we describe during this

conference. Earlier literature methods generally yield mixtures of highly substituted PFFs; products with

only two or four substituents are only available in trace quantities. A novel synthetic procedure that is

capable of selective preparation of C60(CF3)2 with 80+% molar purity without HPLC purification from crude

fullerene extract in large scale will be presented. This process employs high-temperature

perfluoroalkylation in the reactor of special geometry (reactor design and operation are described in

detail). Other PFAFs can also be economically produced using this system. The effects of different reaction

parameters (reaction time, reaction temperature, geometry of the reaction zone, gas pressure and

composition, and the presence or absence of a promoter) on the selectivity of the perfluoroalkylation

process and the PFAFs distribution are carefully studied. The scaling up of the process is investigated,

providing highly valuable findings. Moreover, the limitations of the high-temperature perfluoroalkylation

process are also studied.

21

30. Langmuir-Blodgett and Spin-Coated Films Formed by Non-Polar Fluorophilic/Lipophilic Gemini Amphiphiles Caroline de Gracia Lux, Institute Charles Sadron, University of Strasbourg, Strasbourg, France and

Marie Pierre Krafft, Systèmes Organisés Fluorés à Finalités Thérapeutiques (SOFFT), Université de

Strasbourg, Institut Charles Sadron (CNRS), Strasbourg Cedex, France

The two-dimensional behavior of fluorinated/hydrogenated tetrablocks (di(FnHm)) is investigated. These

compounds, which are the first examples of non-polar gemini amphiphiles, have recently been synthesized

in our group.

Langmuir monolayers of di(FnHm) tetrablocks were spread and compressed at the air/water interface. The

influence of compression speed on surface pressure/molecular area isotherms is discussed, as well as the

influence of water subphase temperature. By contrast with standard semi-fluorinated alkanes

CnF2n+1CmF2m+1 (FnHm diblocks), which have monotonous isotherms,1-3 di(FnHm) monolayers exhibit a well

defined transition. The Langmuir monolayers are then transferred onto solid substrates (silicon wafers or

mica plates) at various surface pressures and imaged using atomic force microscopy (AFM). While

retaining the propensity of FnHm diblocks to self-assemble in surface hemimicelles,1-3 the new gemini

tetrablocks display a significantly different 2D behavior. Finally, AFM images of di(FnHm) spin-coated

monolayers reveal that, depending on molecular structure and nature of the substrate, a second layer of

tetrablocks co-exist with the hemimicelles in contact with the solid surface.

(1) Krafft, M. P.; Riess, J. G. Chem. Rev. 2009, 109, 1714.

(2) Maaloum, M.; Muller, P.; Krafft, M. P. Angew. Chem. Int. Ed. Eng. 2002, 41, 4331.

(3) Zhang, G.; Marie, P.; Maaloum, M.; Muller, P.; Benoit, N.; Krafft, M. P. J. Am. Chem. Soc. 2005,

127, 10412.

Opening Ceremony and Moissan Session (24th August, Monday morning)

Presiders: Joseph S. Thrasher, Richard Fernandez, University of Alabama, Olga V. Boltalina, Steven

Strauss, Colorado State University, John Gladysz, Texas A&M University

31. Never Say No to a Challenge

Karl O. Christe, Department of Chemistry, University of Southern California, Los Angeles, CA

Highlights are given of a lifelong pursuit of problems which most chemists would consider impossible.

Subjects of my presentation include the syntheses of the tetrafluoroammonium and

hexafluorochlorine(VII) cations, and of chlorine tri-fluoridedioxide, the chemical synthesis of elemental

fluorine, the synthesis of pentagonal-planar AX5 species, polynitrogen and polyazide chemistry, oxygen

balanced ionic-liquid liquid monopropellants, green replacements for ammonium perchlorate, and

quantitative scales for oxidizer strength and Lewis acidity.

22

32. Footsteps of a Fluorine Chemist Richard D. Chambers, Department of Chemistry, University of Durham, Durham, United Kingdom

It is clear that the chemistry of organo-fluorine chemistry is now an integral part of Organic Chemistry, to

the credit of generations of workers in the field, but it has taken some time to reach this stage because

the chemistry of highly fluorinated systems is quite unique. Over the years we have found it helpful to

pursue various simple concepts and models on which our synthetic work is based, much of which is

mechanism-led. Also, various motivating factors have had an influence on our output, which will be

described. These points will be illustrated by reference to some of the achievements of the group in the

presentation of an overview. It is impossible to acknowledge the great number of excellent co-workers

from the group but many are referenced in my book.1

1. Fluorine in Organic Chemistry, R.D. Chambers, Blackwell, 2004.

33. You Win Some and You Lose Some: The Winners Are Mostly a Matter of Public Record but You Probably Do Not Know about the Losers

Darryl DesMarteau, Department of Chemistry, Clemson University, Anderson, SC

Over a period of 46 years carrying out research in fluorine chemistry, one looks back with pleasure on all

that was accomplished and all the good times had. You think about all the good ideas that had positive

outcomes and you have a certain degree of frustration about ―good ideas‖ that did not work. I thought it

might be both interesting and entertaining to share some of my selected frustrations with you as I near

retirement.

34. Preparation of Compounds with Low Valent Elements of Group 14

Herbert W. Roesky, Rajendra S. Ghadwal, Anukul Jana and Sakya S. Sen, Institute of Inorganic

Chemistry, University of Goettingen, Goettingen, Germany

The chemistry of silicon is quite different compared to the chemistry of carbon. SiO2 is a solid material

with a high melting point, while CO2 is a gas at room temperature. We were interested in stabilizing low

valent monomeric silicon precursor. To reach this goal, we applied N-heterocyclic carbenes (NHC) as Lewis

bases and developed two methods for low valent silicon halides. The single crystal X-ray structural

analysis of this compound will be reported. The reactions of NHC•SiCl2 with alkenes will be discussed. SiF4

forms a 1:1 and a 1:2 crystalline adduct with NHC.

The selective reduction of LSiCl3 (L = amidinate) results in the formation of a substituted silylene of

composition LSi(II)Cl. In LSi(II)Cl the chloride can be replaced by a number of other substituents. Further

reduction of LSi(II)Cl leads to LSi(I)Si(I)L, a room temperature stable compound with a lone pair of

electrons on each of the silicon atoms. An analogue of carbon is not known.

The fluorine containing compounds of germanium and tin of composition LGeF (L = HC(CMeNAr)2), LSnF,

LGe(S)F, and LSnOCAr‘H(CF3), (Ar‘ = C6H5, C4H3S) have been prepared.

23

Alternative Energy/Energy Storage - I (24th August, Monday afternoon) Presider: Rika Hagiwara, Kyoto University, Kyoto, Japan

35. Advanced Fluorinated Materials for Use in High Energy, Long Life and Safe Lithium Batteries for Automotive Applications

Khalil Amine, Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL

In its goal of developing more fuel efficient vehicles, the US Department of Energy in collaboration with

the US auto industries are focusing on high-power and high energy lithium-ion batteries to meet the

energy storage requirements for hybrid electric vehicle (HEV) and Plug in hybrid vehicle (PHEV)

applications. Under these auspices, Argonne National Laboratory is investigating several different lithium

ion chemistries in order to address the calendar life, cost and safety of high power and high energy lithium

ion batteries for transportation applications. Several fluorinated metal oxide cathode materials that offer

twice the capacity of conventional cathodes will be reported. In addition, fluorine based functional

electrolyte additives to stabilize the electrode/electrolyte interface and improve significantly the cycle and

calendar life of lithium battery will be discussed. Furthermore, fluorinated aromatic compounds were also

investigated as effective redox shuttle to prevent battery overcharge and improve the overall safety of

lithium battery.

36. Synthesis of Functional Fluoropolymers by Borane/Oxygen Control Radical

Initiators and Their Applications in Energy Storage

T. C. Mike Chung, Materials Science and Engineering, Penn State University, University Park, PA

This presentation will discuss a new synthetic route to prepare functional fluoropolymers that contain

reactive functional (polar) groups. The chemistry is centered on a combination of control radical

polymerization mechanism and a specifically designed borane initiator bearing a functional (polar) group.

The mechanistic study indicates that the borane/oxygen control radical initiator is very effective for

initiating fluoromonomers at ambient temperature. The in situ formed alkyl radical (C*) is responsible for

the initiation, and the borinate radical (B-O*) forms a reversible bond with the propagating radical to

prolong the polymerization. The control polymerization is characterized by predictable molecular weight,

narrow molecular weight and composition distributions. The other aspect of this paper is to apply this

control polymerization to prepare a whole family of PVDF copolymers. By systematically tuning the

polymer chain conformation and crystal structure, we have identified the most suitable fluoropolymer for

thin film capacitor that exhibits high energy density and low energy loss, important for electric energy

storage.

37. Inorganic Fluorides: Opportunities and Challenges in Energy Sector

Dayal T. Meshri, Sanjay Meshri, Robert Adams, Ritesh Jain, N.C. Mathur and Dr. Devender

Pinnapareddy, Advance Research Chemicals, Inc., Catoosa, OK

In the next twenty years energy consumption will increase by about fifty percent. Efforts are being done

to explore new fossil resources, develop alternative forms of energy and improve energy efficiency. New

materials that can bring positive changes or result in the development of energy production devices are

being investigated in laboratories.

Inorganic fluorides play important role in energy sector from UF6 processing to fuel cells to batteries. In

this presentation, role of inorganic fluorides in energy sector shall be briefly discussed. Special attention

shall be paid to Lithium /CFx battery and battery electrolytes. Some of the opportunities and challenges in

this area shall also be highlighted.

24

38. New Generation of Carbon-Fluorocarbon Nanocomposition Porous Materials for Energy Conversion and Storage

Valentin N. Mitkin, Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of

Sciences, Novosibirsk, Russia

The directed synthesis of nanocomposites ―CF1+x + C + FM‖ (FM – functional material) with the targeted

hydrophobic or/and hydrophilic properties is an inter-nano-phase crosslinkings among the border surface

atoms of sp2- and sp3-carbons (including O-donor groups – sp2-C-OH, sp2-C=O, sp2-COOH, etc.) from

carbon nanoblocks, nanoblocks of fluorocarbons CF1+x (SFCM), and surface heteroatoms from nanoblocks

of FM. Physico-chemical and electrophysical characteristics of these chemical carbon nanocontacts were

studied by means of NMR 13C, 19F and vibrational spectroscopy, XPS C1s, F1s, O1s and methods of

electroconductivity. The main feature of obtained new porous carbon-fluorocarbon nanocomposition

materials is the presence of a chemical electroconductive carbon contact in their surface structures.

Chemical combining of SFCM, thermally expanded graphite (TEG), soot and Teflon binder has allowed to

create a new high porous nanocomposition cathode material FUCM and FUCM-M for Li-cells. Principles of

hydrochemical and mechanical activation were used at the creation of new hybrid nanocomposition ―TEG-

Si‖ anodes for Li-ion cells (specific capacity ~400-560 mAh/g at 5 cycle). The same methods were used

for creation of new hybrid catalysts.

There were developed and tested new nanocomposition porous electrode and resistive materials with

superficial chemical carbon contact (current-collector) on a base of various carbon-fluorocarbon

structures, having a tailored resistivities in range 0.01-1012 Ohm*cm, new ionometric gauges ―FUCM-O-

Sb‖ and nanocomposition materials for thermocouple sensors.

There were developed and studied new types of the nanocomposition ―carbon-carbon‖, ―carbon-

fluorocarbon‖ and fluorocarbon sorbents (FUCM-OH and FS-OH) for effective sorption of creatinine, uric

acid, bilirubine, urea and toxic metals from Human Serum.

Inorganic/Organometallic (24th August, Monday afternoon)

Presider: Konrad Seppelt, Freie Universität Berlin, 14195 Berlin, Germany

39. On a Generalized Brønsted Acidity Scale

Ingo Krossing1, Daniel Himmel1, Sascha Goll1 and Ivo Leito2, (1)Institut für Anorganische und

Analytische Chemie, Albert-Ludwigs-Universität Freiburg, Freiburg, Germany, (2)Institute of Chemistry,

University of Tartu, Tartu, Estonia

The talk will present first results on a generalized Brønsted acidity scale that in principle may be used all

phases (gas, liquid/solution and solid).

The reference state for defining Brønsted acidity is the absolute chemical potential of the proton in the gas

phase in its standard state. Upon interaction with any kind of a medium, the chemical potential of the

proton in this (gaseous, liquid or solid) medium is lowered. The lowering of the chemical potential of the

proton in any medium with respect to the gas phase is taken as the basis of the new acidity scale.

First results on establishing such a scale are reported and the absolute chemical potential of the proton in

various media will be presented. Implications of such a definition are given as well as a sound

thermodynamic definition of Gillespie‘s Brønsted superacidity criterion (―A Brønsted acid stronger than

100% H2SO4.‖).

40. The Gas-Phase Superacidity of Derivatives of Monocarba-Closo-Borates: a Computational

Study

25

Lauri Lipping, Ivo Leito, Ivar Koppel and Ilmar A. Koppel, Institute of Chemistry, University of Tartu,

Tartu, Estonia

The electronic structures and acidities (GA) of a large number of monocarba-closo-dodecaborate acid

derivatives with different degrees of substitution were investigated with DFT B3LYP method at 6-311+G**

level. Several derivatives were also calculated with the correlated ab initio G3(MP2) method with the

results, which within the limits of error validate the use of the more economic DFT B3LYP method for the

present purposes.

The protonation sites and thus the GAs were found to be highly dependent on the properties of the

substituents. The most acidic systems were the ones that had vertexes filled with CF3- and F-substituents.

The most stable protonated form of CB11(CF3)11H1H is predicted to have unprecedented GA of 173

kcal×mol-1, or 95 powers of ten stronger than the classical reference, H2SO4, whereas the predicted GA

value for CB11F12H is 212.8 kcal/mol. Nevertheless, the overall stability of the (CF3)12-derivative remains

questionable, because of the likely elimination of HF.

To obtain better understanding how the substituents affect the basicity of the carborane anion three

hypothetical reaction series were investigated, in which the protonation center was fixed on the boron

atom (B12), antipodal to the carbon (C1) and a single substituent replaced the hydrogens at the vertexes

of the three remaining positions (C1, B2 and B7). The intrinsic GAs in these series of neutral carborane-

based acids CB11H12X are found to clearly depend on the field-inductive and resonance effects of the

substituent X. Some polarizability effect of X on the reaction center (B12) could be detected only in the

alpha-position (B7).

41. Free Acid and Salts of the Weakly Nucleophilic (7-12)-HCB11(CF3)6F5(-) Anion

B. Randall King, Matthew G. Fete and Josef Michl, Department of Chemistry and Biochemistry, University

of Colorado, Boulder, Boulder, CO

Substitution of the hydrogens of the weakly nucleophilic anion CB11H12(-) with trifluoromethyl groups

makes it even less nucleophilic and harder to oxidize, but salts of the dodecasubstituted anion

CB11(CF3)12(-) as well as the undecasubstituted anion HCB11(CF3)11(-) unfortunately are treacherously

explosive. In contrast, we have found it impossible to bring about a detonation of the salts of the

analogous partially fluorinated and partially trifluoromethylated monocarborate anion (7-12)-

HCB11(CF3)6F5(-), which we have prepared by direct fluorination of the previously reported (7-12)-

HCB11(CH3)6H5(-) anion. Although undoubtedly not as weakly nucleophilic and hard to oxidize as its more

highly trifluoromethylated analogs, it still represents an advance over other anions currently available. We

shall describe the preparation of the solid free acid [H(7-12)-HCB11(CF3)6F5] and the preparation, NMR

spectroscopy, and some reactions of solutions of the acid and several of its salts in liquid SO2 and in

CF3CF2CFH2. We shall further describe the initial results of our attempts to oxidize the (7-12)-

HCB11(CF3)6F5(-) anion with AgF2(+) in liquid HF and extraction of the product into perfluorohexane. It

appears likely that the resulting EPR active blue-green solution, which is indefinitely stable in a Teflon

vessel at -60 ̊C, contains the neutral radical (7-12)-HCB11(CF3)6F5(•). Warming to room temperature

causes the disappearance of the color and EPR signal and regeneration of (7-12)-HCB11(CF3)6F5(-). It thus

seems that (7-12)-HCB11(CF3)6F5(•) is capable of extracting an electron either from n-C6F14 or from Teflon,

and is one of the strongest neutral one-electron oxidants known in the condensed phase.

26

42. Surface Modification of Materials through Rf-Plasma Fluorination

Alain Tressaud1, Christine Labrugere1, Etienne Durand1, Helene Serier1, Larisa Demyanova2 and

Alexandre Kharitonov3, (1)ICMCB-CNRS, Pessac, France, (2)Institute of Geology and Nature Management,

FEB-RAS,, Blagoveshchensk, Russia, (3)Institute of Energy Problems, RAS, Chernogolovka, Russia

Treatments involving fluorinated gases and radio-frequency (rf) plasma-enhanced fluorination constitute

exceptional tools for modifying the surface properties of materials. The topics will be illustrated by several

examples on silica, silicate minerals, oxide ceramics and polymers. Coating of silicate minerals by c-C4F8

plasma fluorination – Phyllosilicates are of particular interest because the network offers numerous

possibilities of substitutions and/or intercalations. Depending of the used fluorination route, either a

reactive etching process involving M-F bonding occurs (direct F2-gas; O2-CF4 rf-plasma), or a carbon

fluoride deposition, ~50nm thick (c-C4F8 rf-plasma) takes place.

“Switchable” hydrophobic-hydrophilic surface of porous alumina -A ―dry‖ process involving PEF fluorination

has been proposed to obtain ―switchable‖ hydrophobic-hydrophilic layer on porous alumina for offset

applications. Once highly hydrophobic layers are obtained for c-C4F8 PEF treatments, the pristine

hydrophilic properties of the surface can be recovered by a heat pulse.

Fluorination of polymer vessels and membranes - Fluorination of polymer film packaging results in a

substantial decrease of the gases permeability, for instance for automotive fuel tanks. Fluorinated polymer

membranes can be successfully used in many industrial domains, for enhancing for instance the

purification of natural gas from CO2. Changes of surface properties of F-treated polymers will be presented

through XPS, AFM and contact angle measurements.

Organic/Organometallic-I (24th August, Monday afternoon)

Presider: Pierangelo Metrangolo, Politecnico di Milano, Milano, Italy

43. What Lies Beyond Traditional Fluorine Substitution? New Vistas From a Synthetic Standpoint

Gerald B. Hammond, Bo Xu, Weibo Wang and Han Yang, Department of Chemistry, University of

Louisville, Louisville, KY

During the last decade there have been transformational changes in the development of reagent-

controlled fluorinations and the use of fluorine-containing building blocks for the synthesis of an ever more

complex catalogue of organofluorine compounds. Our group entered the field of fluorination by

investigating the influence of traditional fluorination reagents on alkyne substrates. This was followed by

the development of fluorine-containing alkynes capable of propargyl-allene interconversion, and their use

in the synthesis of a diverse array of selectively fluorinated cyclic systems or as potential therapeutic

agents. In recent times, we became intrigued by the question of whether fluorine-containing reagents can

be coaxed to play multiple roles depending on the reaction conditions. The first outcome of this

investigation was the use of TBAF in alkynylogation and allenylogation reactions modeled after the well-

known principle of vinylogy. This presentation will unveil examples from our laboratory where we

demonstrate that well-known reagents such as TBAF or Selectfluor can behave as a highly selective base,

a cyclization partner, or, in some cases, participate simultaneously as fluorinating agent or co-catalyst in

transition metal-mediated transformations.

27

44. Preparation of Novel 2,2-Difluoro-1-Phenylethenylstannane, and Its Arylation, Alkenylation and Alkynylation Reactions In Howa Jeong, Ji Hoon Choi and Seung Yeon Han, Department of Chemistry, Yonsei University, Wonju,

South Korea

Novel 2,2-difluoro-1-phenylethenylstannane 4 was prepared in 60% yield from the reaction of 2,2-

difluoro-1-phenylethenylsulfone 3 with tributyltin hydride (4 equiv) in benzene for 5 hours at reflux

temperature. The concentration of 3 in the reaction mixture is very important to maximize the yield of 4,

in which the best result was obtained in 0.045 M solution. 2,2-Difluoro-1-phenylethenylsulfone 3 can be

easily prepared in 2 steps from the trifluoromethylated dithioketal 1.

Reactions of 4 with aryl iodides in the presence of 10 mol% Pd(PPh3)4/10 mol% CuI in DMF at 80 oC for 5-

9 hours afforded the 1,1-difluoro-2,2-diarylethene 5 in 22-82% yields. When 4 was reacted with alkenyl

iodides in the presence of catalytic amount of Pd(PPh3)4 and CuI in DMF at 80oC for 1-2 hours, the

corresponding 1,1-difluoro-1,3-butadienes 6 were obtained in 43-82% yields. Treatment of 4 with alkynyl

iodides in the presence of the same catalysts at 50-80 oC for 1-2 hours resulted in the formation of 1,1-

difluoroenynes 7 in good yields. The scope of these reactions will be presented.

45. A General Route to Both Cis- and Trans-Symmetrical and Unsymmetrical 1,2-Difluoro Stilbenes

Donald J. Burton1, Chongsoo Lim1 and Yi Wang2, (1)Department of Chemistry, University of Iowa, Iowa

City, IA, (2)AMRI, Albany, NY

Although routes to trans-symmetrical and unsymmetrical stilbenes have been reported, the routes to

these compounds are multi-step and the overall yields are modest at best. The corresponding cis-stilbenes

are essentially unknown. We have recently prepared new bi-functional cis- and trans-1,2-difluoroethenyl

synthons capable of sequential functionalization to provide either symmetrical or unsymmetrical cis- or

trans-1,2-difluorostilbenes in excellent yields. The details of these new bi-functional synthons will be

presented and their application for the preparation of the titled stilbenes will be discussed.

28

46. New Difluorinated Isocyanide and Its Application in Ugi Reaction

Song Cao, Nianjin Liu, Li Shen, Jingjing Wu, Lina Li and Xuhong Qian, Shanghai Key Lab of Chemical

Biology, School of Pharmacy, East China University of Science and Technology, Shanghai, China

Nowadays, multicomponent reactions have attracted great interest due to the fact that the products are

formed in a single step and the diversity can be simply achieved by varying the reacting components.

When searching in the literature, we found that there were only a few reports on the use of fluoro-

containing building blocks as one of component in the multicomponent reactions. Therefore, we have

proposed a new strategy, multicomponent reactions including fluoro-containing building blocks

(MCRs-FBB), for the construction of fluoro-containing compounds [1]. The fascinating scope of this

strategy lies in the straightforward assembly of complex fluorinated compounds from simple and available

fluoro-containing building blocks as well as the high level of diversity that can be obtained by varying the

fluoro-containing components taking part in the MCRs [2].

Isocyanide is an extremely versatile component in multicomponent reactions due to their exceptional

reactivity. Isocyanide-based multicomponent reactions have attracted much attention as useful strategy

for the discovery and development of novel MCRs. In this presentation, firstly we synthesized a novel

fluoro-containing building block, α,α-difluoro-β-amino amide bearing the isocyanide functionality and then

utilized the MCRs-FBB strategy for the synthesis of fluorinated pseudopeptides via Ugi reaction under

solvent-free conditions [3].

Reference

1. Synlett. 2008, No.19, 3058 2. Org. Biomol. Chem., 2008, 6 (7), 1293

3. Tetrahedron Lett., 2009, 5, 1982

29

Alternative Energy/Energy Storage - II (24th August, Monday afternoon)

Presider: Alain Tressaud, Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB-CNRS),

University Bordeaux, Bordeaux, France

47. The Use of Fluorinated Compounds in Li-Ion Battery Electrolytes

Marshall C. Smart1, Kiah A. Smith2, Frederick C. Krause2, Pooja Bhalla 2, Jinbo Hu 2, G. K. Surya Prakash 2 and Ratnakumar V. Bugga 1, (1)Jet Propulsion Laboratory, California Institute of Technology, Pasadena,

CA, (2)Department of Chemistry, Loker Hydrocarbon Research Institute, University of Southern California,

Los Angeles, CA

Lithium-ion batteries have been identified as the battery chemistry of choice for a number of NASA‘s

future applications, including planetary orbiters and rovers. In addition, Li-ion batteries are actively being

developed for use in hybrid electric vehicles (i.e., HEV and PHEV applications). Although the current

state-of-art lithium-ion technology meets many of the performance requirements of these applications,

there is still a desire to improve the safety characteristics and the ability to operate over a wide

temperature range while still providing the requisite life characteristics. Thus, our research is currently

devoted to improving a number of Li-ion attributes, including the specific energy, the temperature range

of operation, the power characteristics, and the inherent safety. The present work involves our efforts at

developing improved lithium-ion battery electrolytes, by using fluorinated co-solvents and fluorinated

additives, with the intent of widening the operating temperature and improving the safety by reducing the

flammability of the system. Electrolytes have been developed which include fluorinated carbonates, such

as ethyl 2,2,2-trifluoroethyl carbonate and bis(2,2,2-trifluoroethyl) carbonate, and fluorinated esters, such

as trifluoroethyl butyrate and ethyl trifluoroacetate. These electrolytes were studied in experimental Li-

ion three electrode cells (equipped with reference electrodes) and characterized with respect to their

influence upon the lithium intercalation/de-intercalation kinetics. These cells were subjected to electrical

characterization (charge and discharge at different temperatures and rates), as well as, electrochemical

characterization (EIS, linear polarization and Tafel polarization measurements). Promising electrolytes

were also evaluated in large capacity prototype cells (i.e., > 7Ah).

48. Proton Exchange Membrane for Fuel Cell

Iqbal Sharif, Darryl D. DesMarteau, Wan Chao Jiang, Bing Liu and Stephen Creager, Department of

Chemistry, Clemson University, Anderson, SC

The research goal is to make a proton exchange membrane with a new functional group for use as PEMs in

fuel cells. The emphasis of the work is to produce a PEM which operates at higher temperatures(>120˚C)

and that has better proton conducting properties then the current Sulfonic acid polymers (Nafion®,

XUS®). The polymers which are developed are known as perfluorosufonimide ionomers or PFSI (Fig. 1).

Numerous Polymers having equivalent weights (1000-1500) are made which incorporated

perfluoroalkylsulonyl monomers onto a Teflon backbone.

It was found that the polymers with higher equivalent weight have lower conductivity but better

mechanical properties, whereas polymers with lower equivalent weight have higher conductivity but poor

30

mechanical properties. We blended two polymers one with lower equivalent weight and the other with

higher equivalent weight to give a polymer with higher conductivity and better mechanical properties. The

polymer so obtained can be used at higher temperature and at higher humidity in a fuel cell also the

conductivities of blended polymer were comparable to Nafion®.

Cross-linked polymers were prepared by ter-polymerization of functionalized divinyl ethers with TFE, and

PFVESI (Fig. 2). Various crosslinked polymers having equivalent weights (1000-1500) were prepared with

1-5% of cross-linker divinyl ethers. These cross-linked polymers show higher conductivity both at 80°C,

and 120°C as compare to non-crosslinked polymers (PFVESI:TFE) and Nafion (PFVSA:TFE). Also the

membranes are tested on fuel cell and show better performance than Nafion®.

49. Build up Supersurfaces From Fluorine-Containing Conductive Polymers

Frederic Guittard, Laboratoire Chimie des Matériaux Organiques et Métalliques, Université de Nice

Sophia Antipolis, Nice, France

The surface wettability, very important property of advanced materials, is depending on both the

chemistry and the roughness or morphology of the surface. Thus, superhydrophobic surfaces can be

obtained by combining a hydrophobic material and a surface roughness [1] (equations of Wenzel and

Cassie-Baxter). The electrochemical deposition of substituted conductive polymers is fast and inexpensive

to obtain superhydrophobic materials with various surface morphologies [2-4].

This work relates to the development of micro or nanoporous functionalized films obtained by

electrochemical polymerization of perfluoroalkyl monomers. These films, which exhibit both

superhydrophobic and superoleophobic properties are prepared in few minutes and in one step. The

introduction of fluorine in these polymers leads to fascinating properties.

[1] T. DARMANIN; F. GUITTARD; Journal of the American Chemical Society, 2009, in press

[2] T. DARMANIN; F. GUITTARD; Langmuir, 2009, in press (DOI: 10.1021/la901193g)

[3] E. TAFFIN de GIVENCHY, S. AMIGONI, C. MARTIN, G. ANDRADA, L. CAILLIER, S. GERIBALDI, F.

GUITTARD, Langmuir, 2009, in press (DOI:10.1021/la900064m)).

[4] T. DARMANIN; F. GUITTARD; Chemical Communications, 2009, accepted, online

DOI:10.1039/B822791H.

[5] T. DARMANIN, M. NICOLAS, F. GUITTARD; Langmuir, 2008, 24(17), 9739-9746.

[6] M. NICOLAS, F. GUITTARD, S. GERIBALDI, Angew. Chem. Int. Ed., 2006, 24(14), 2251-2254.

50. Fluorination of Nanocarbons

Fujio Okino, Faculty of Textile Science and Technology, Shinshu University, Ueda, Japan

Fluorination is one of the most effective chemical methods to modify and control physicochemical

properties of carbon materials. Before the advent of fullerenes, carbon nanotubes and other forms of

nano-sized carbon materials, the idea of fluorination of carbon materials was limited mainly to the

formation of C–F covalent bonds on the network of sp3-hybridized carbon atoms from a bulk sp2-

hybridized graphene layers or the substitutional covalent C-F formation on sp3-hybridized carbon, e.g.

31

diamond. With a series of emerging nanocarbons that contain carbon atoms arranged with various

degrees of s-p hybridizations, fluorination could play a more important role to modify and control the

physicochemical properties of nanocarbons, and lead to a better understanding of the interaction between

carbon and fluorine. Our recent work on the fluorination of nanocarbons such as fullerenes, single-walled

carbon nanotubes (SWNTs), double-walled carbon nanotubes (DWNTs), cup-stacked carbon nanotubes

and carbon nanohorns will be presented. Formation and properties of the graphenes prepared by the

defluorination of graphite fluoride (CF)n will also be addressed.

51. Synthesis and Properties of Fluorinated Silicon-Containing Compounds and Their

Composites

Joseph Mabry, Lead, Polymer Working Group, Air Force Research Laboratory, Propulsion Directorate,

Edwards AFB, CA

The Polymer Working Group at Edwards Air Force Base is developing on a number of novel fluorinated

compounds, fluorinated nanoparticles, and fluorinated polymer nanocomposites. Numerous types of

fluorinated particles and compounds have been produced, including polyhedral oligomeric silsesquioxanes

(POSS), cyclo-silicates, and cyclo-siloxanes. Several of these materials have been shown to improve

various properties of the polymers into which they are incorporated. These polymer nanocomposites may

have general applicability, in addition to their usefulness in defense-related applications. Selected

applications include: seals for liquid rocket engines, space-survivable satellite insulation materials,

corrosion-resistant coatings, and anti-icing surfaces for aircraft. The synthesis and characterization of

these compounds and their polymer nanocomposites will be discussed.

Bio/Medical (24th August, Monday afternoon)

Presider: Beate Koksch, Freie Universität Berlin, Berlin, Germany

52. Fluorine in Pharmaceuticals: Enhancing Binding Efficacy and Selectivity

François Diederich, Department of Chemistry and Applied Biosciences, ETH Zürich, Zürich, Switzerland

The introduction of organofluorine is well established in drug discovery research as a tool to improve

physico-chemical and ADME properties of lead compounds. On the other hand, the participation of

organofluorine in molecular recognition processes and its potential to enhance binding efficacy and

selectivity had not been investigated in a systematic way. Therefore, in 2002, we started a fluorine scan of

a class of highly preorganized inhibitors of thrombin, a key serine protease from the blood coagulation

cascade, to map the fluorophilicity/fluorophobicity of an enzyme active site. We found that orthogonal

dipolar C–F...C=O interactions contribute substantially to binding efficacy, and this led to a comprehensive

database mining showing the abundance of orthogonal dipolar interactions in chemistry and structural

biology. Orthogonal geometries are clearly favored at short intermolecular distances over other dipolar

interaction geometries, mainly for steric reasons. The first quantification of a dipolar interaction (C–

F...C=O) was achieved using synthetic unimolecular systems, molecular torsional balances, under

application of chemical double-mutant cycles. In the fluorine scan, we elucidated the large σ-transmission

effects of remote organofluorine, which strongly affect aliphatic amine basicities that can be tuned over a

range of 10 pKa units. The F-scan was extended to small-molecule inhibitors of Neprilysin, a Zn(II)-

dependent metalloprotease, and new fluorinated building blocks, such as SF5.

32

53. 1,3,5-Trifluorobenzene - A Molecule with High Technical Challenges

Michael Rack, Sebastian P. Smidt and Manual Budich, Global Research Crop Protection, BASF SE,

Ludwigshafen, Germany

1,3,5-Trifluorobenzene (TFB) is an intermediate for the synthesis of novel active ingredients in

pharmaceutical and agrochemical industry. We have developed a catalyst-free one-step process of TFB

starting from inexpensive and commercially available 1,3,5-trichlorobenzene by a technically feasible

route.

Our report comprises route scouting, up scaling, corrosion issues and production design for this industrial

development process of the key intermediate TFB.

54. Biomedical Applications of Semifluorinated Block Copolymers

Sandro Mecozzi, School of Pharmacy and Department of Chemistry, University of Wisconsin-Madison,

Madison, WI

Amphiphilic polymers that assemble in micelles in aqueous solutions have found several applications in

biomedical research, specifically for the delivery of sparingly soluble, hydrophobic drugs. Nevertheless,

micelles and related nanoaggregates can be used for pharmaceutical purposes only if they are stable in

presence of blood proteins. Furthermore, micelles must be resistent to blood dilution, that is, they must be

characterized by a very low critical micelle concentration. All these properties can rarely be found in

micelles composed of traditional hydrophilic-hydrophobic block copolymers. We have devised a novel

series of di- and triblock semifluorinated copolymers that add the peculiar properties of a fluorous phase

to those of classical amphiphilic polymers. We have used these polymers for forming hyperstable micelles

and also as polymeric stabilizers of nanoemulsions. Specifically, we have devised a new series of diblock

copolymers that can be used to form very stable nanoemulsions of fluorinated volatile anesthetics in

water. In general, emulsions are not kinetically stable, and the original formulation of these

nanoemulsions was characterized by rapid Ostwald ripening of the nanoparticles. By taking into account

the physical and chemical phenomena behind the ripening, we have been able to devise a new generation

of semifluorinated polymers that completely stabilize the emulsions in terms of particle size. These newly

formulated fluorinated nanoemulsions have been successfully tested for inducing and maintaining

anesthesia. Finally, we have used semifluorinated triblock copolymers for the delivery of anticancer drugs.

55. Medicinal Chemistry of Fluorinated Heterocycles: Prostate Cancer Chemotherapy

Andrei A. Gakh, Oak Ridge National Laboratory, Oak Ridge, TN

Prostate cancer is the most common malignancy affecting men in the United States, with more than

150,000 new cases registered annually. About 1 man in 5 will be diagnosed with prostate cancer during

his lifetime, and 1 man in 33 will die of this disease. Up until recently, the late androgen-independent

stage of prostate cancer was considered to be a very difficult-to-treat, if not terminal, condition. Emerging

chemotherapy protocols provide new hope for prostate cancer patients (e.g., the use of pyridine derivative

Abiraterone). There is a growing body of evidence that fluorinated heterocycles could play a significant

role as antiproliferative compounds for prostate cancer chemotherapy. Here we report our recent results in

the synthesis and biological testing of novel fluoroheterocyclic compounds for prostate cancer

chemotherapy. Significant progress in both efficacy and safety of prospective drug candidates was

achieved using fine-tuning of heterocyclic systems via proper alignment of fluorinated and non-fluorinated

pharmacophoric fragments. Further improvements were achieved through the application of Acceleration

Factor (AF) and Modular Chemical Descriptor Language (MCDL) methodologies leading to rational design

33

of potent inhibitors of key regulatory proteins responsible for cancer cell proliferation. The synthetic effort

entails the use of novel fluorination procedures and methods such as tandem iodination-fluorination,

microwave-assisted nucleophilic fluorination in non-anhydrous conditions, fluorodesulfidation, hypervalent

chemistry, and others (see also: Fluorinated Heterocycles; A. A. Gakh, K.L. Kirk, Eds.; ACS Symposium

Series 1003, American Chemical Society - Oxford University Press, Washington, DC; 2009). The Discovery

Chemistry Project is sponsored by the IPP program, US Department of Energy.

56. New Perfluorinated Surfactants for Applications in Digital Microfluidics

Estelle Mayot1, Felix Kleinschmidt1, Jean-Christophe Baret1, Abdeslam El Harrak2 and Andrew Griffiths1,

(1)Institut de Science et d'Ingenierie Supramoleculaires (ISIS), Université de Strasbourg (UdS), CNRS

UMR 7006, Strasbourg, France, (2)Raindance Technologies France, Strasbourg, France

Microfluidic droplet based systems are a powerful tool to study and optimize a wide range of biological and

chemical reactions. These systems consist in the formation of water droplets in a continuous oil phase. To

make these droplets independent microreactors, they must be stable with no possibility of exchange

between each other. In this case, the usefulness of a perfluorinated oil as continuous phase is undeniable,

and suitable surfactants are also required. In this context, our laboratory is interested in novel surfactants

soluble in perfluorinated oil.

The challenges were multiple: the molecules had to be designed both to be efficient for microfluidic

manipulations and to present no interaction with the biological or chemical assays contained in the

droplets. A commercially available perfluorinated polyether with an acid end function was used as a

starting material; different chain lengths exist and were used to modulate the fluorophilicity of the

surfactant. For the polar head, various types of hydrophilic patterns as polyethylene glycol, phosphate and

sugar derivatives were grafted on the fluorinated tail, by using coupling functions as ketone, amide or

phosphoryl.

We will present the synthesis of these new surfactants and the evaluation of their properties on chip,

concerning the stability of the emulsion, the build up of the interface and the transport effect

phenomenon.

Organic/Organometallic - II (24th August, Monday afternoon) Presider: Henryk Koroniak II, Adam Mickiewicz University, Poznan, Poland

57. Improved Arene Fluorination with Iodonium Salts

Stephen G. DiMagno, Department of Chemistry, University of Nebraska, Lincoln, Lincoln, NE

Nucleophilic fluorination of electron rich arenes remains difficult. This presentation will summarize

transition metal catalysis approaches to arene fluorination, and compare and contrast metal-mediated

34

chemistries with the reductive elimination of fluoroarenes from iodonium salts. Recent developments from

our laboratory in rapid nucleophilic arene fluorination will be discussed.

58. Zn-Mediated Formation of Trifluoromethyl Ethers From Alcohols Using Hypervalent Iodine Trifluoromethylation Reagents

Raffael Koller, Kyrill Stanek, Daniel Stolz, Raphael Aardoom, Katrin Niedermann and Antonio Togni,

Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology, ETH Zurich,

Zurich, Switzerland

The incorporation of fluorine atoms into biologically active organic molecules has become an increasingly

important tool in the life science industry. Properties such as metabolic stability, lipophilicity and

bioavailability of drug candidates and crop protection agents may be drastically improved even by just one

fluorine atom, or by a trifluoromethyl group. The trifluoromethoxy moiety is less often encountered.

However, the drug Riluzole and the pesticide Triflumuron are prominent examples of compounds

containing the OCF3 group at an aromatic position, whereas aliphatic trifluoromethyl ethers have been

incorporated, e.g. into liquid crystalline materials. None of the trifluorohalomethanes reacts with alcohols

or their deprotonated form directly affording the corresponding trifluoromethyl ethers. The syntheses of

these compounds typically require harsh reaction conditions and special equipment. We have overcome

this problem by a direct transfer of an intact trifluoromethyl group from the hypervalent iodine reagent to

alcohols, which occurs smoothly at room temperature upon activation by zinc bis(triflimide). The

corresponding trifluoromethyl alkyl ethers may be isolated in up to 81% yield. This constitutes a

straightforward method for the preparation of trifluoromethoxy alkyl derivatives, compounds otherwise

difficult to access. ESI-MS- and PGSE-diffusion studies in solution, as well as the X-ray crystal structure of

an intermediate suggest that the activation of the hypervalent iodine reagent by Zn(II) occurs via the

formation of a 1 to 2 adduct with the metal.

59. 4-Tert-Butyl-2,6-Dimethylphenylsulfur Trifluoride (FLUOLEADTM): A Novel New Fluorinating Agent with High Stability and Ease of Handling

Teruo Umemoto1, Rajendra P. Singh1 and Norimichi Saito2, (1)IM&T Research, Inc., Denver, CO, (2)UBE

America, Inc., Denver, CO

Fluorine is having an increasingly important role in medicinal chemistry and drug design, as it often

imparts enhanced biological activity or desirable changes in physical properties to drug molecules. In the

past there have been extensive studies of fluorination reactions, and a number of useful fluorinating

agents have been developed. Diethylaminosulfur trifluoride (DAST) has long been a useful reagent with

wide application. However, its relatively unstable and potentially explosive nature precludes significant

application in large scale industrial processes. An analog of DAST, bis(methoxyethyl)aminosulfur trifluoride

(Deoxo-Fluor) with enhanced thermal stability has been developed in recent years. We wish to report the

development of a new and versatile reagent, 4-tert-butyl-2,6-dimethylphenylsulfur trifluoride

(FLUOLEAD), which possesses high stability and ease of handling, as an alternative to DAST and its

analogs. In this presentation we will elaborate on the synthesis, properties, and reactivity of FLUOLEAD.

35

60. The Chemistry of N(CF3)2 and OCF3 Compounds: New Developments

Nikolai V. Ignat'ev1, Martin Seidel1, Wolfgang Hierse1, Norbert Fichtner1, Thorsten Meier2, Christoph

Breitenstein2, Karsten Koppe2, Peter Barthen2, Walter Frank2 and Helge Willner3, (1)Merck KGaA,

Darmstadt, Germany, (2)Institut für Anorganische Chemie und Strukturchemie II, Heinrich Heine

Universität Düsseldorf, Düsseldorf, Germany, (3)Anorganische Chemie, Bergische Universität Wuppertal,

Wuppertal, Germany

(CF3)2N- and CF3O- groups are known substituents in organo-fluorine chemistry. Many aromatic

compounds bearing these substituents have been synthesized in the past [1] but only a limited number of

aliphatic compounds having (CF3)2N- and CF3O- end-groups are described in the literature. Recently, we

have developed a convenient procedure for the preparation of aliphatic (CF3)2N- and CF3O- compounds.

The method is based on the application of (CF3)2N- and CF3O- salts with metal cations (K+ or Rb+) or with

tetraalkylammonium cations [2-3] in the nucleophilic substitutions reactions. The syntheses of aliphatic

(CF3)2N- and CF3O- compounds with different functional groups will be presented. The physico-chemical

properties of these compounds and their possible application as new generation of fluorosurfactants [4-6]

will be discussed. The data related to the biodegradation of (CF3)2N- and CF3O- compounds will be

presented.[7]

References

1. L.M. Yagupolskii, Aromatic and Heterocyclic compounds with Fluor-Containing Substituents, Naukova

Dumka, Kiev, 1988.

2. Patent Application, WO 2000/046180, Merck Patent GmbH, Germany.

3. Patent Application, EP 1 081 129 A2, Merck Patent GmbH, Germany.

4. Patent Application DE 10200603 2391, Merck Patent GmbH, Germany.

5. Patent Application DE 10200603 1151, Merck Patent GmbH, Germany.

6. Patent Application DE 10200603 1149, Merck Patent GmbH, Germany.

7. T. Frömel, M. Peschka, N. Fichtner, W. Hierse, N.V. Ignatiev, K.-H. Bauer and T.P. Knepper, Rapid

Communications in Mass Spectrometry, 22 (2008), p. 3957-3967.

61. Improved Preparation of Uneyama's Imidoyl Halides. A General Synthesis of Both Fluorinated and Non-Fluorinated Heterocyclic 1,3-Diazoles and Indoles

Jian Hao, Wen Wan and Haizhen Jiang, Department of Chemistry, Shanghai University, Shanghai, China

Since Uneyama's preparation of fluorinated imidoyl halides was first reported in 1993,[1] numerous

synthetic applications of this important and multifunctionalized building block have been achieved

especially in the areas of fluorinated heterocycles, amino acid derivatives, and other pharmaceutical

intermediates.[2] The preparation of fluorinated imidoyl halides is simple and scalable, however, the

substantial use of CCl4 has raised environmental concerns.

In our recent investigation, we found that reduction of the quantity of CCl4 or CBr4 from large excess to 3

equivalent in modified condition could also carry out the reaction and yield the fluorinated imidoyl halides

in relatively higher yields and shorter reaction times. Moreover, this improved condition is applicable to

those non-fluorinated acids, for instance, non-fluorinated aliphatic acids, heterocyclic acids, and aromatic

acids.

The applications of this improved preparation has been successfully subjected to the synthesis of both

fluorinated and non-fluorinated heterocyclic 1,3-diazoles and indoles via a one-pot process.

36

This work was financially supported by National Natural Science Foundation of China (20772079), Science

and Technology Commission of Shanghai Municipality (07JC14020, 07ZR14040, 08JC1409900) and

Shanghai Municipal Education Commission.

References

(1) Tamura, K.; Mizukami, H.; Maeda, K.; Watanabe, H.; Uneyama, K. J. Org. Chem. 1993, 58, 32.

(2) (a) Uneyama, K.; Amii, H.; Katagiri, T.; Kobayashi, T.; Hosokawa, T. J. Fluorine Chem. 2005, 126,

165. (b) Uneyama, K.; Katagiri, T.; Amii, H. Acc. Chem. Res., 2008, 41, 817. (c) Amii, H.; Uneyama, K.

Chem. Rev. 2009, ASAP.

Poster Session (24th August, Monday evening)

Presider: Richard E. Fernandez, Rf Consulting, LLC, Tuscaloosa, AL

62. A Geminally Perfluoro-Tert-Butylated Amino Acid as a Potential Pharmacokinetic Modulator and Reporter

ZhongXing Jiang and Y. Bruce Yu, Fischell Department of Bioengineering, University of Maryland, College

Park, MD

To modulate and report the pharmacokinetics of peptide-based pharmaceuticals, a novel geminally

perfluoro-tert-butylated β-amino acid (βFa) and its Fmoc- and Boc- protected forms were designed and

synthesized. βFa was incorporated into a model tripeptide via standard solid-phase chemistry. Both the

amino acid (free and protected) and the tripeptide show a sharp singlet 19F NMR signal. Reversed phase

chromatography and 1-octanol/water partition measurements demonstrate that βFa is extremely

hydrophobic.

37

63. The Design and Synthesis of Highly Branched and Spherically Symmetric Fluorinated Oils and Amphiles as Potential 19F MRI Agents

ZhongXing Jiang and Y. Bruce Yu, Fischell Department of Bioengineering, University of Maryland, College

Park, MD

A new 19F MRI agents design principle, based on spherically symmetric, is proposed. Using this principle, a

class of highly branched and spherically symmetric fluorinated oils, amphiles and macrocyclic chelators

has been designed and synthesized, for potential applications in the construction of fluorocarbon

nanoparticles as 19F MRI agents. The Mitsunobu reaction was employed as the key step for introducing

three perfluoro-tert-butoxyl groups into pentaerythritol derivatives with excellent yields and extremely

simple isolation procedures. Due to the symmetric arrangement of the fluorine atoms, all 27 fluorine

atoms in each fluorinated oil or amphile molecule give one sharp singlet 19F NMR signal.

64. The Influence of Gamma - Irradiation On Morphology Structure of Polytetrafluoroethylene

Sadulla Reimovich Allayarov1, Yurii Andreevich Olkhov1, Lowell D. Kispert2, Joseph S. Thrasher2, Richard

E. Fernandez2, David Nikles3 and David Adams Dixon2, (1)Institute of Problems of Chemical Physics of

the Russian Academy of Sciences, Chernogolovka, Russia, (2)Department of Chemistry, The University of

Alabama, Tuscaloosa, AL, (3)Department of Chemistry, University of Alabama, Tuscaloosa, AL

Four morphological structures of polytetrafluoroethylene (PTFE, trade mark ―F-4‖ (Russia) the amorphous

(Tg=17 oC) and three crystalline forms (high- (Tm1=345 oC), intermediate (Tm2=374 oC) and low-melting

modifications (Tm3=411 oC)), were identified by thermomechanical analysis. The temperature of the

molecular flow of PTFE began at TF=481±2oC. The weight shares of topological blocks fa/fcr1/fcr2

/fcr3=0.78/0.13/0.04/0.05 testify that the crystallized fragments PTFE macromolecules, which functions as

interchain branching are approximately the fifth part of all macromolecules. Heating was stopped at 500 oC because at this temperature there are initial indications of thermodestruction of PTFE as gas is evolved

and the polymer weight decreases. In the crystal phase, gamma-irradiation reduces the molecular weight

of the crystallized chains of the low-melting modification and results in the disappearance of the

intermediate and high-melting crystal phases as a result of their transformation into the amorphous form.

Thus, the molecular flow of the polymer arises after fusion of the low-melting crystal modification is

completed with a significant decrease of its flow temperature (TF=332 oC). At a dose of 140 kGy, the

macromolecules completely lose the ability to form the intermediate and high-melting crystalline

modifications. Such reorganization can promote loss of PTFE mechanical stability.

65. Crystal Structure and Electrochemical Properties of Nd2Eu2O3F6

Jae-ho Kim, Ryusin Shiun, Takuya Kita, Susumu Yonezawa and Masayuki Takashima, Department of

material science & engineering, University of Fukui, Fukui, Japan

Binary rare earth metal oxide fluorides, Ln2Ln‗2O3F6 exhibit oxide ion conductivity in spite of coexisting of

fluoride ion [1]. Among them, Nd2Eu2O3F6 exhibits the highest oxide ion conductivity of 5.5 Sm-1 at 600 oC

and the crystal structure is monoclinic (a0=0.3961 nm, b0=1.1325 nm, c0=0.5632 nm, β=134.84°).

Nd2Eu2O3F6 is expected to be used in oxgen sensors and/or fuel cells. A new preparation method (TFA

method) in which the precursor prepared from the rare earth acetates containing trifluoroacetic acid (TFA)

alcohol solution has been investigated. To obtain a new solid electrolyte thin film having high electric

conductivity, Nd2Eu2O3F6 thin film has been prepared on some ceramics substrate and been

characterized. The result of SEM observation shows that the film surface is rough, while there is no crack

or no cavity. It is thought that the dense Nd2Eu2O3F6 film can be prepared. In addition, the cross section

image shows that the film of Nd2Eu2O3F6 was made on a platinum electrode. Total film thickness of the

electrodes was 100-120 μm, and Nd2Eu2O3F6 film was 20-30 μm. The film performed the interchange

impedance measurement.

38

66. Electrochemical Properties of Surface Fluorinated Lithium Containing Transition Metal Composite Oxides

Jae-ho Kim1, Ippei Tokihara1, Susumu Yonezawa1, Masayuki Takashima1, Junichi Imaizumi2 and Yoshiaki

Nitta2, (1)Department of material science & engineering, University of Fukui, Fukui, Japan, (2)Tanaka

Chemical Corporation, Fukui, Japan

The modification of the surface of the cathode active material must have effects on the battery

performance strongly because the electrochemical reaction takes place at the interface among the active

material, carbon as the electrical conduction aid material and the electrolyte. In this paper, surface

fluorination of various Li containing transition metal oxides by using F2 gas and its effect on the

electrochemical properties and thermal properties were discussed. LiNi1/3Co1/3Mn1/3O2 has been reacted

with fluorine gas at room temperature in 0.67, 1.33 and 2.66 kPa F2. XPS, SEM and XRD measurements

were carried out to characterize the products. Active material (untreated or fluorinated sample), acetylene

black and polyvinylidene fluoride were mixed in a proper ratio and the slurry of the mixture was prepared

with NMP. This slurry was painted onto the aluminium foil and was dried to form the cathode. Lithium

metal was used as an anode. 1.0mol/L LiPF6 / EC+DEC (1:1 vol) or EC+DMC (3:7 vol) was used as the

electrolyte. Charge/discharge test was basically performed between 4.5 and 3.0 V at the rate of 0.2 C

using TOMcell (two electrode cell). The thermal properties were measured by using DSC with a sealed

sample pan. The construction and destruction of the cell and the pan was done in argon.

67. Synthesis and Polymerization of Novel Bis(2-trifluoromethylacrylate)

Tadashi Narita, Department of Applied Chemistry, Graduate School of Engineering, Saitama Institute of

Technology, Fukaya 369 0293, Japan

2-Benzoxypentafluoropropene [CF2=C(CF3)OCOC6H5] is a high radical acceptor and the reaction is

applicable to preparation of polymers from bis(a-trifluoromethyl-b,b-difluorovinyl) terephthalate

[CF2=C(CF3)OCOC6H4COOC(CF3)=CF2] with 1,4-dioxane [1]. Methyl 2-trifluoromethylacrylate derivatives

hardly produces polymers under radical condition and polymers are obtained by anionic polymerization

[2]. The paper concerns about the synthesis and polymerization of novel fluorinated monomers such as

CH2=C(CF3)COO-R-OCOC(CF3)=CH2 and radical polymerization, where R = -CH2CH2- (EBTFA), -C6H4-

(PBTFA), and -CH2CF2CF2CH2- (OFTA). Monomers were synthesized by the reactions of 2-

trifluoromethylacryloyl chloride with corresponding glycols in the presence of triethylamine. 2-

Trifluoromethylacryloyl chloride was synthesized by the reaction of 2-trifluoromethylacrylic acid (Tosoh F-

Tech Inc) with phthaloyl dichloride (Iharanikkei Co.). Radical homopolymerization of these monomers

produced corresponding oligomers possessing trifluoromethylvinyl groups in side chains by addition

polymerization mechanism. The radical reaction of these monomers in tetrahydrofuran yielded mainly 1:2

addition products with small amounts of oligomers bearing THF moieties added to vinyl groups in side

chains. The reactivity was decreased by the order of PBTFA > EBTFA > OFTA. EBTFA produced a polymer

in the presence of 12 eq of 1,4-dioxane under radical condition, and gel formation was observed in the

case of PBTFA and OFTA. It might be concluded that the addition polymerization took place in the

presence of cyclic ethers though low radical polymerization reactivity has been previously reported.

[1] T. Narita, Prog. Polym. Sci., 1999, 24, 1095. [2] T. Narita, J. Polym. Sci., A, Polym. Chem., 2004, 42,

4101.

39

68. New Fluorinated Polymers with Cyclic Structure for Immersion Lithography

Koichi Murata, Naoko Shirota, Yoko Takebe, Osamu Yokokoji and Yoshitomi Morizawa, Research Center,

Asahi Glass Co., Ltd., Yokohama, Japan

The pattern on computer chips has become finer and finer. Currently, 193-nm immersion process is

utilized for features at the 32-45 nm node. Moreover, double patterning is focused as the primary

lithography technique introduced for the next 22 nm node generation. Thus, the development of the

materials for the process, including organic polymers used as photoresists, is desired very much.

Thus far, transparency at the wavelength, high resolution, resistance to etching and heat, and the affinity

with alkaline developers after the exposure are pointed out as the desired properties for photoresists.

Additionally, appropriate water repellency on the surface is required for the ones used in the immersion

process, because the space between exposure lens and wafer is filled with water.

Here we wish to present new fluorinated polymers with cyclic structure for immersion lithography. The

monomers are derivatives of 1,1,2,3,3-pentafluoro-1,6-heptadiene, which were polymerized in

cyclopolymerization manner. The key step of the monomer preparation was malonate ester synthesis with

perfluoroallyl fluorosulfonate. The obtained monomers were polymerized using general radical initiator

such as IPP, and the afforded polymers were clear, soluble in various kinds of solvent.

The polymers are considered as a hydrophobic additive in photoresist material for 193-nm immersion

photolithography. The investigation to develop the synthetic path of the monomers and the properties of

the polymers will be described.

69. Luminescent Solutions of Modified Silicon Nanocrystals Via a Wet Chemical Process

Uwe Klingebiel and Christian Klingbeil, Department of Inorganic Chemistry, University of Goettingen,

Goettingen, Germany

In the last decades there have been numerous publications on nanocrystalline silicon structures, e.g.

Porous Silicon, and their surface chemistry, mainly because of their luminescent properties. However, the

research so far has mainly concentrated on wafers. Only recently, surface modifications of nanocrystalline

silicon powders have been published.

For our work, we use the wafer‘s industrial predecessor, powdery silicon from a hot wall or microwave

reactor. Similar to wafers, these powders are naturally capped by a SiO2-layer. In a two-step wet chemical

process, we obtain brightly luminescent colloidal solutions of silicon nanocrystals: hydrogenation in

anhydrous HF followed by hydrosilylation leads to surface-modified nanocrystals soluble in different

solvents. Here, we present TEM-images of these colloids as well as luminescence and IR-spectra proving

the presence of fluorine atoms on the nanocrystals' surface.

[1] Canham, L. T., Nature, 408, 411 (2000)

[2] Buriak, J., Chem. Rev., 102, 2171 (2002)

[3] Nelles, J.; Sendor, D.; Bertmer, M.; Ebbers, A.; Petrat, F.M.; Simon, U., J. Nanosci. Nanotechnol., 7,

2818 (2007)

70. Synthesis of Selected Highly Fluorinated Vinyl Ethers

C. Grand Huang1, Leonid Rozov2, Linas Kudzma2, Kamalesh Johri3 and Carol Liu3, (1)Chemical

Development, Baxter Healthcare Corp, New Providence, NJ, (2)Chemical Development, Baxter Healthcare

Corp., New Providence, NJ, (3)Chemical Analysis, Baxter Healthcare Corp, New Providence, NJ

We report a novel method using CH3Li in diethoxymethane to prepare the fluorinated vinyl ethers,

CF3C(=CF2)OCH2F, CF3C(=CF2)OCH3, CF2=CHOCHF2 and CF2=CClOCHF2, which are related to the

inhalation anesthetics sevoflurane, desflurane and isoflurane. Good isolated yields of these compounds

were obtained and the methodology was extended to synthesize other fluorinated vinyl ethers,

CF2=CFOCHF2, CF3C(=CF2)OCH2Cl, CF2=CFOCHFCF3, and CF2=CFOCF=CF2, the last of which polymerizes

40

shortly after isolation. Details of an unexpected competing reaction leading to defluoromethylation

products will also be presented.

71. Selective Etching of Fused Silica Samples with Low Pressure Gaseous Hydrofluoridric ACID

Francesco Venturini1, Walter Navarrini1, Giuseppe Resnati1, Giulio Cerullo2, Roberto Osellame2 and

Pierangelo Metrangolo1, (1)Dipartimento di Chimica, Materiali e Ingegneria Chimica ―Giulio Natta‖,

Politecnico di Milano, Milano, Italy, (2)Istituto di Fotonica e Nanotecnologie-CNR, ULTRAS-INFM-CNR, Dipartimento di Fisica, Politecnico di Milano, Milano, Italy

We report on the fabrication of microfluidic devices using a novel technique based on high-energy

femtosecond laser irradiation followed by selective removal of the irradiated region by gaseous chemical

etching.

The microfluidic channels in commercial biochips are currently fabricated using intrinsically two-

dimensional techniques borrowed from semiconductor processing thus creating surface channels that need

to be covered by a glass slab so multilayer processing is required to produce three-dimensional structures.

Recently, femtosecond laser assisted micro machining has emerged as a revolutionary technique for

three-dimensional microchannel fabrication in glass. The procedure attested in literature [1] consists of

laser irradiation of the silica sample followed by chemical etching using an aqueous solution of hydrofluoridric acid.

The constraint that currently affects the aqueous hydrofluoridric etching procedure is the low aspect ratio

of the obtainable micro channels, this is due to internal diffusion problems of the etching reactants and products respectively in and out of the growing channel.

To overcome the diffusion limits and consequently realize longer microchannels with high aspect ratio we

have investigated the use of low-pressure gaseous hydrofluoridric acid as etching agent. The influence of dilution, pressure, temperature, humidity and sampling-gas on laser ablated silica will be presented.

In particular the optimization of this technique allows the fabrication of high aspect ratio (L/D > 25)

microchannels with an almost constant etching rate of 4-10 um/min and a theoretical depth limit of about 3-5 mm.

[1] Maselli et al. Appl. Phys. Letters 88, 2006.

41

72. Ionic Liquids: Cost-Efficient Preparation and Application in Homogeneous Catalysis

Karsten Koppe1, Peter Barthen1, Walter Frank1, Hermann-Josef Frohn2 and Nikolai V. Ignat'ev3,

(1)Institut für Anorganische Chemie und Strukturchemie II, Heinrich Heine Universität, Düsseldorf,

Germany, (2)Inorganic chemistry, University of Duisburg-Essen, Duisburg, Germany, (3)PLS R&D LSS,

Merck KGaA, Darmstadt, Germany

In recent years Ionic Liquids (IL) became very useful for an almost endless spectrum of different

applications ranging from chemical, bio-chemical, biological to technical areas. The combination of a great

number of anions with as many cations gives the possibility to design process-dedicated ILs with unique

properties for a certain application. Here we want to demonstrate a new convenient one-pot synthesis of

high purity triflate-ILs in quantitative yields including an optimized synthesis of alkyltriflates [1,2].

Non-volatile ILs of low viscosity are not only attractive as alternatives to organic solvents in chemical

processes but are further more promising as active reaction media in homogenous and biphasic catalysis.

Recently, we have developed new catalytic systems consisting of ILs with Brønsted acids [3]. Volatile

Brønsted acids, dissolved in IL with the corresponding counter anion, are found to stay in the system well

above the boiling point of the pure acid. These new catalytic systems were successfully applied in

deprotection of ketals [4], ring-closure reactions (preparation of chromane derivatives) [5] or dehydration

of alcohols yielding the corresponding alkenes [3].

References

1. Patent Application WO 2002/098844; US 7,084,290 Merck Patent GmbH, Darmstadt, Germany.

2. Patent Application WO 2003/053918, EP 1472217 B1, US 7,247,740; Merck Patent GmbH, Darmstadt,

Germany.

3. Patent Application WO 2007/014613, Merck Patent GmbH, Darmstadt, Germany.

4. Patent Application WO 2007/104380, Merck Patent GmbH, Darmstadt, Germany.

5. Patent Application WO 2008/086847, Merck Patent GmbH, Darmstadt, Germany.

73. CF3-Pseudoprolines : a Tool for Conformationally Constrained Dipeptides Synthesis

Thierry Brigaud, Grégory Chaume, Olivier Barbeau and Caroline Caupène, Department of Chemistry,

University of Cergy-Pontoise, Cergy-Pontoise, France

We are interested in the development of efficient synthetic routes for the preparation of enantiopure α-

and β- trifluoromethylated amino acids (Tfm AAs). Because of their ability to control the conformation of

peptides, we recently particularly focused on the preparation of pyrrolidine-type α-trifluoromethylated

amino acids. Incorporation of proline derivatives is known to restrict the amino acyl-proline cis/trans

isomerization, to control the peptides folding and consequently to modulate their biological activity. Based

on these observations, Mutter's group introduced pseudoproline building blocks (ψPro) into peptide

sequences as reversible protecting groups for Ser, Thr and Cys. The corresponding ψPro residues turned

out to be inducers of β–turns containing predominantly cis-amide bond and to be useful tools in peptide

cyclization. Thus, as a complementary strategy, we are developing the preparation of trifluoromethylated

pseudoprolines (CF3–ψPro) since conformational restrictions as well as unique physical and biological

properties imparted by the fluorinated group are expected from the incorporation of such kind of amino

acids into a peptide chain. Because the chemical stability of ψPro systems strongly depends on the

electronic effects of the C2 substituents, pseudoprolines containing a CF3 group at the C2 show a high

degree of stability towards acidic media. This property could also make them convenient building blocks

for the purification of peptides issue from SPPS. We will report the preparation of various CF3–ψPro as well

as the methodological studies of the synthesis of various C-terminal and N-terminal CF3-ψPro containing

dipeptides.

42

74. Original Fluorinated Surfactants Potentially Non-Bioaccumulable

Frederic Boschet, Georgi Kostov and Bruno Ameduri, Chemistry, Institute Charles Gerhardt, Montpellier,

France

Fluorinated surfactants1 are interesting products involved in cosmetics, detergents, extinguishers, and in

emulsion or suspension polymerizations. They show better performances than H-surfactants. Among

them, PFOA or PFOS are the best references in these applications. However, they are bioaccumulable,

toxic, persistent since the high stability of the C7F15 perfluorinated chain which cannot be degradated by

enzymatic or metabolic processes. Companies involved in their productions are struggling for finding

alternatives and are gathered under the PFOA Stewardship programme2.

The challenge to synthesize non-bioaccumulable surfactants in which the hydrophobic counterpart

contains methylene weak points motivates the objective of this presentation.

Instead of using tetrafluoroethylene telomers, our strategy lies on the telomerization of vinylidene fluoride

(VDF)3 or 3,3,3-trifluoropropene (TFP)4,5 with various telogens: short length perfluorinated alkyliodides3-5

or other hydrogenodiethylphosphonate6.

First, radical telomerization of VDF with 1-iodoperfluoroethane followed by ethylenation, hydrolysis, and

oxidation led to PFOA alternatives of similar chain length3, as above with good surface property (19.8

mN.m-1 at 5 g.L-1).

Second, TFP (co)telomers were functionalized to obtain original surfactants. Telomerization of TFP with

perfluoroiodides4,5 or non-fluorinated telogens4-6 led to compounds with low surface tensions, thermal and

chemical stability.

1. E. Kissa Fluorinated Surfactants: Synthesis, Properties and Applications, Marcel Dekker, New-York,

2001.

2. PFOA Stewardship Program; US EPA, 2006.

3. G. Boutevin et al. Langmuir (submitted).

4. G. Kostov et al. US Patent 2007/027349 (assigned to Great Lakes) and Coll. Czech. Chem. Comm.,

2008, 1747-1763.

5. G. Kostov et al. J. Amer. Chem. Soc., (submitted).

6. G. Kostov et al. J. Fluorine Chem., 2007, 910-918.

43

75. The Fluorine-Containing Curable Coating Materials with Antifouling Property for Hardcoat Eun Young Park, Jong Cheol Lee, Jong Wook Ha, In Jun Park and Soo Bok Lee, Korea Research Institute

of Chemical Technology, Daejeon, South Korea

In this study, perfluorinated acrylate polymers were prepared by ring opening reaction of

hexafluoropropylene oxide and successive condensation reaction with hydroxy hydrocarbon acrylated. The

polymers were obtained by radical polymerization, and possibility of the polymer as the antifouling agent

for hardcoat materials was investigated. The synthesis method, characterization and surface physical

properties such as durability to scraches and abrasions, and resistance to inks and stains will be

described.

76. Revision of the Gas-Phase Acidity Scale of Strong Acids

Ivo Leito1, Elin Raamat1, Agnes Kütt1, Jaan Saame1, Karin Kipper1, Ilmar A. Koppel1, Ivar Koppel1, Min

Zhang2 and Masaaki Mishima2, (1)Institute of Chemistry, University of Tartu, Tartu, Estonia, (2)Institute

for Materials Chemistry and Engineering, Kyushu University, Fukuoka, Japan

The strong acids part of the gas-phase acidity scale (J. Am. Chem. Soc. 1994, 116, 3047-3057) – ca 24

kcal/mol range of gas-phase acidities (GA) from (CF3CO)2NH to (C2F5SO2)2NH – was reexamined using the

FT-ICR equilibrium measurement approach. Gas-phase acidities of 18 compounds were determined for the

first time. Most of the new compounds were substituted sulfonimides, which were particularly useful for

compiling the gas-phase acidity scale. pKa values of most of the sulfonimides were also determined in

acetonitrile.

The results of GA measurements reveal a contraction of the previously published values in this part of the

GA scale. The GA values of (CF3SO2)2NH and (C2F5SO2)2NH (important components of lithium ion battery

electrolytes and ionic liquids) were revised downwards towards stronger acidities from 291.8 kcal/mol to

286.5 kcal/mol and from 289.4 kcal/mol to 283.7 kcal/mol, 5.3 and 5.7 kcal/mol respectively.

Experimental and high-level computational evidence is presented in support of the current results.

77. Generation of Negative Ions Fluxes From Vapors of Fluorides Systems Under [F-]-Ionic Conductivity of Solid Phase

Norbert S. Chilingarov1, Sergey V. Abramov1, Alexandra L. Serebrennikova1, Igor M. Shlyapnikov1, Zoran

Mazej2 and Matjaž Kristl3, (1)Department of Chemistry, M.V. Lomonosov Moscow State University,

Moscow, Russia, (2)Department of Inorganic Chemistry and Technology, Jozef Stefan Institute, Ljubljana,

Slovenia, (3)Laboratory of Inorganic Chemistry, Faculty of Chemistry and Chemical Engineering, Maribor,

Slovenia

It was ascertained recently, that formation of negative ion fluxes (AlF4-, Al2F7

-, NaAl2F8-) from vapour of

NaF-AlF3 system is controlled by [F-] conductivity of solid phase formed on the internal surface of effusion

cell.[1]

In this work the way of the formation of practically continuous layer of CeF3(s) – superionic [F-] anions

conductor – is proposed. The CeF3 layer formation is based on cerium tetrafluoride thermolysis. CeF4(s)

sublimation in temperature interval 700–900 K is accompanied by its decomposition and formation of solid

CeF3(s) on the surface. The composition and morphology of the surface layer was investigated by X-ray

analysis and SEM/EDXS methods.

44

Modified cells were used for evaporation of some fluoride systems to generate the anion fluxes.

Composition and intensity of ionic fluxes were determined by mass spectrometry method.

Intensive fluxes of AlF4- ions were obtained in Na5Al3F14-AlF3 system. Note, without CeF3(s) layer,

detection of negative ions in this system is impossible.

Special attention was made to the stability of ionic conductor layer. Layer of ionic conductor NaF(s)

formed during NaF-Na3AlF6 system evaporation was transformed into NaCeF4(s) phase after addition of

CeF3(s). Evaporation of NaF-CeF3 (molar ratio = 2 : 3 ) system using cell with internal surface layer of

CeF3(s), caused the destruction of the layer and the formation of NaCeF4(s). After these transformations

negative ions were not detected anymore in mass spectra.

[1] S.V. Abramov, A.Ya. Borshchevsky, N.S. Chilingarov, L.N. Sidorov, Inter. J. Mass Spectrometry,

267(2007) 215-219

79. Systematic Thermolysis of Aluminium, Gallium and Indium Tris(trifluoroacetates)

Christos Nikolaou, Walter Frank, Karsten Koppe and Georgi Genchev, Institut für Anorganische Chemie

und Strukturchemie II, Heinrich Heine Universität, Düsseldorf, Germany

Inorganic trifluoroacetates are known since many years, beginning with studies of Swarts et al. in 1922.1

Syntheses of the tris(trifluoroacetates) of Al, Ga, and In under strictly anhydrous conditions were first

reported in 1971.2 In the course of our investigations the Lewis-acidic compounds, M(O2CCF3)3 (M = Al,

Ga, and In), were obtained in quantitative yield by reaction of CF3COOH with Al2Cl6, Ga2Cl6, or Indium,

respectively.

The reaction of Ga2Cl6 with CF3COOH at RT gave the formerly unknown compound GaCl2(O2CCF3). The X-

ray crystal structure has shown that GaCl2(O2CCF3) is a chain coordinated polymer having μ-trifluoracetato

ligands.

The three tris(trifluoroacetates) mentioned above are thermally stable up to 280°C in inert gas

atmosphere. However, attempts to prepare crystals by sublimation gave decomposition products. A series

of solid state structures of these compounds has been determined by single-crystal X-ray diffraction:

The thermolysis of Al(O2CCF3)3 at 290°C yielded [AlF(O2CCF3)2]8, a molecular wheel having μ-bridging

trifluoracetato and fluoro ligands.

The decomposition of In(O2CCF3)3 in vacuum at 200°C yielded the mixed valent chain compound

[InIII3O(O2CCF3)7 · In

I(O2CCF3)]∞, which contains a planar oxo-centered InIII3O fragment and a InI(O2CCF3)

fragment. This compound is the first carboxylate of a group 13 element in the +1 oxidation state.

Beyond that, the thermolysis of In(O2CCF3)3 in vacuum at 260°C yielded the reduced carboxylate

[In2(O2CCF3)4]∞. In the solid state, metal-metal bonded In2 fragments are bridged by means of

trifluoroacetate ligands, resulting in a chain arrangement.

1. F. Swarts, Bull. Cl. Sci., Acad. Roy. Belg. 1922, 8, 343.

2. P. Sartori, J. Fazekas, J. Schnackers, J. Fluorine Chem. 1971, 1, 463.

45

80. Synthesis and Structure of Trifluoroacetic Acid Adducts of Antimony(III) Oxotrifluoroacetates

Nina van Gellecom, Walter Frank, Karsten Koppe and Bruno Kugel, Institut für Anorganische Chemie und

Strukturchemie II, Heinrich Heine Universität, Düsseldorf, Germany

Two trifluoroacetic acid adducts of antimony(III) oxotrifluoroacetates - [Sb3O2(O2CCF3)5•CF3COOH] (1)

and [Sb5O3(O2CCF3)9•CF3COOH] (2) - have been prepared by mild thermolysis of antimony(III)

trifluoracetate[1,2] in trifluoroacetic acid solution. For this purpose, monoclinic Sb(O2CCF3)3[3] was dissolved

in strictly anhydrous trifluoroacetic acid and refluxed for three (1) and four (2) days, respectively (T =

72,4 °C). Slow evaporation of the solvent under reduced pressure yielded colourless crystals.

1 crystallizes in the triclinic space group P-1 with lattice parameters a = 9.5422(19) Å, b = 12.5478(3) Å,

c = 12.7616(3) Å, α = 101.94(3) °, β = 104.89(3) °, γ = 109.38(3) °, Z = 2.

The crystal shows fragments, which consist of six antimony atoms, four µ3-oxygen atoms, ten

trifluoroacetate groups and two trifluoroacetic acid molecules. These fragments are linked by means of

bridging trifluoroacetate groups to form chains along [100] (Fig. 1, some tfa and Htfa omitted for clarity).

2 crystallizes in the triclinic space group P-1 with lattice parameters a = 11.7198(10) Å, b = 12.7328(10)

Å, c = 17.3960(12) Å, α = 70.31(1) °, β = 84.38(1) °, γ = 66.76(1) °, Z = 2.

The crystal is composed of Sb5O3-fragments, coordinated by nine trifluoroacetate groups and one

trifluoroacetic acid molecule, which is only bonded by a hydrogen bond. These fragments are linked by

bridging trifluoroacetate groups to form chains along [001].

References:

[1] G.S. Fujioka et al., J. Am. Chem. Soc. 1956, 79, 2451.

[2] D.C. Bullivant et al., J. Chem. Soc. Dalton. Trans. 1980, 105.

[3] B. Kugel, W. Frank, Z. Krist. Suppl. 2000, 17, 62.

46

81. Kinetical Aspect and Molecular Weight Evolution of Anionic Oligomerization of Hexafluoropropylene Oxide Sang Goo Lee, Jong-Wook Ha, In Jun Park and Soo-Bok Lee, Korea Research Institute of Chemical

Technology, Daejeon, South Korea

Perfluoropolyethers (PFPEs) show unique properties such as flexibility, amorphous and optical

transparency while preserving most of advantageous characteristics of common fluoropolymers, for

example, thermal and chemical stabilities, low surface energy and friction coefficient. Furthermore, PFPEs

are known to be non-toxic and biocompatible. Commercialized PFPEs are usually synthesized from the

direct photooxidation of tetrafluoroethylene, hexafluoropropylene, and perfluoro vinyl ether or ring-

opening polymerization of hexafluoropropylene oxide or 2,2,3,3-tetrafluorooxetane. Although the anionic

ring-opening oligomerization of hexafluoropropylene oxide (HFPO) in the presence of alkali metal fluoride

is the well-known industrial process to produce perfluoropolyether (PTFE), there are few studies on the

kinetical aspect of HFPO oligomerization systemically. The present study aims at giving simple

experimental conditions to prepare moderate molar mass PFPE (Mn 1000~2000) without using harmless

reactants such as cesium fluoride and 1,1,2-trifluorotrichloroethane. An extensive investigation of the

oligomerization of HFPO using the potassium fluoride/tetraethylene glycol dimethyl ether system with the

continuous addition of gaseous monomer is carried out, looking specifically into the influence of the

temperature, nature of alkali metal fluorides, and solvents on the polymerization mechanism and the

molecular mass of final PFPE products. The number-average molecular weight of synthesized oligomers is

calculated from 19F-NMR spectroscopy and gas chromatography.

82. Convenient Synthesis of N-Terminal Tfm-Dipeptides From Unprotected Enantiopure Alpha-Tfm-Proline and Alpha-Tfm-Alanine

Thierry Brigaud, Grégory Chaume, Caroline Caupène and Nathalie Lensen, Department of Chemistry,

University of Cergy-Pontoise, Cergy-Pontoise, France

The major disadvantages of peptides as therapeutic agents are their rapid degradation by peptidase and

their low lipophilicity. In this context, α-trifluoromethyl α-amino acids (α-Tfm-AAs) are very attractive

compounds for the design of biologically active molecules. Indeed, the incorporation of trifluoromethyl

group containing amino acids into peptides increases chemical and thermal stability, resistance to

protease degradation and enhances hydrophobicity giving a better affinity for lipid membranes. Moreover,

their incorporation into peptides induces particular conformational stabilisations and better auto-assembly.

In addition, labelled 19F peptides should be of a big interest for structure elucidation and for the

investigations of biochemical processes. Despite these promising properties, two major drawbacks have to

be overcome for their use in medicinal chemistry: 1) the synthesis of α-Tfm AAs in enantiopure form in

large scale remains a challenge, 2) their incorporation into peptide sequences is very limited due to both

the low nucleophilicity of the amino group and the steric hindrance imparts by the trifluoromethyl group.

We are already interested in the development of efficient synthetic routes for the preparation of

enantiopure α-Tfm AAs starting from chiral CF3-oxazolidines (Fox) or imines. We are now particularly

focused on the development of efficient peptide coupling reactions of our α-Tfm-AAs in order to

incorporate them into peptide chains. Here, we report the convenient synthesis of N-terminal dipeptides

from unprotected enantiopure α-Tfm-Alanine and α-Tfm-Proline.

47

83. Polymerizable Semi-Fluorinated Surfactants Designed for Antimicrobial Materials Elisabeth Taffin de Givenchy, Laurent Caillier, Sonia Amigoni and Frederic Guittard, Laboratoire Chimie

des Matériaux Organiques et Métalliques, Université de Nice Sophia Antipolis, Nice, France

Introduction of biocide monomers during the process of polymerization is one of promising approaches in

the development of new permanent non leaching biocide materials. However, these kinds of surfactant

monomers (surfmers) have been extensively studied in the literature for their surface active properties

and their ability to enhance the properties of film-forming polymers but to our knowledge, the

antibacterial activity of such fundamental precursors has not been investigated. In this perspective, new

polymerizable semi-fluorinated surfactants, with quaternary ammonium groups as polar heads and an

acrylic function as the polymerizable moiety have been synthesized and tested to evaluate their surface

active properties alongside with their antibacterial and antifungal properties. Critical micellar concentration

(cmc), equilibrium surface tension (gs) and Gibbs micellization free enthalpy (ΔG0M) were studied as a

function of the molecular parameters. The biocide efficacy measured by bacterial and fungal growth

inhibition expressed as MIC (minimal inhibitory concentration) and MLC (minimal lethal concentration)

values were evaluated against Gram-positive, Gram-negative bacteria and fungi. The purpose of the

present study was the elucidation of how the structural modifications can influence the surface active

properties and the antibacterial properties. We will discuss the chemical-biological relationships, mainly

the bond between molecular structure and biological activity of these new highly fluorinated surfmers as

precursor of bioactive materials.

84. Covalent LbL Approach for the Construction of Water Repellent Perfluorinated Surfaces

Sonia Amigoni, Elisabeth Taffin de Givenchy, Mikael Dufay and Frederic Guittard, Laboratoire Chimie des

Matériaux Organiques et Métalliques, Université de Nice Sophia Antipolis, Nice, France

The appropriate texturing/roughening of surfaces in the nano- and microscale is known to impart unusual

optical, wetting and mechanical characteristics and in particular, can amplify hydrophobicity that plays an

increasing role in numerous industrial applications. Two factors have to be controlled in order to produce

highly hydrophobic surfaces: their topography and their chemical composition. Among all the procedures

known in the literature, the layer-by-layer thin film technique (LbL) is one of the most elegant and simple

method to realise nano- or microparticulate assembled structures on solid substrate. LbL structures are

therefore an emerging technique that provides structured and functional surfaces like, for example,

superhydrophobic or therapeutic and functional biomaterial surfaces. They can contain various structural

entities: inorganic or organic micro and nanoparticles. The sticking function is generally electrostatic and

devoted to polyelectrolytic linear or hyperbranched polymers. The innovative point afforded by our work is

the covalent grafting of the film to the surface and the use of silica nanoparticles of two different sizes (14

and 205 nm diameter) for the construction of a covalent building. Then a self assembled monolayer of

semifluorinated molecules, combined to this induced roughness affords highly hydrophobic materials.

48

85. Nucleophilic Substitution On 2,3,4,5,6-Pentafluorobiphenyl: SN2 or SN Ar?

Jaroslav Kvicala, Oldrich Paleta and Michal Benes, Department of Organic Chemistry, Institute of

Chemical Technology, Prague, Prague 6, Czech Republic

We recently became aimed in supramolecular systems containing polyfluoroalkylated polyfluorobiphenyl

moduls. As a part of this project we studied nucleophilic substitution of 2,3,4,5,6-pentafluorobiphenyl with

a series of O-, S- and N-nucleophiles and found that the reaction proceeds exclusively at the C4 of

pentafluorophenyl moiety. This stemmed our interest in the regioselectivity and mechanism of this

reaction and we decided to study it by the methods of computational chemistry at the DFT level of theory.

We chose ammonia, fluoride and hydroxide anions as the respective nucleophiles. Moreover, as the two

latter naked nucleophiles displayed unnaturally high reactivity, we added them lithium cation

microsolvated with two dimethyl ether molecules. For all three calculated systems we found that the

transition state of the attack at the C4 atom is preferred over that at the corresponding C3 atom of the

pentafluorophenyl ring by ca. 10 kJ/mol, which corresponds to ca. 98:2 ratio of C4/C3 attack and high

regioselectivity. Moreover, we found surprisingly that in contrast to the previously published calculations

the reaction does not proceed by an SNAr mechanism through the corresponding Meisenheimer complex,

but by an SN2 mechanism through the sole transition state, e.g. that of the reaction of 2 DME-LiOH

complex with 2,3,4,5,6-pentafluorobiphenyl (see fig. below).

86. Synthesis and Studies of Hydrophilized Carbon–Fluorocarbon Polyfunctional Nanocomposition Matrices and Sorbents

Ljudmila M. Levchenko, Valentin Mitkin, A.Yu. Predein and P. S. Galkin, Russian Academy of Sciences,

Nikolaev Institute of Inorganic Chemistry Siberian Branch, Novosibirsk, Russia

Methodology for preparation of new nanocomposition fluorocarbon sorbents, based on fluorocarbon FS and

carbon-fluorocarbon matrices FUCM, having the tailored properties to recovery of alkali and alkali-earth

metals, is included three main stages – hydrophilization of the contact surface of matrices‘ pores,

impregnation the hydrated antimony pentoxide Sb2O5*xH2O onto the surface of prepared matrix and final

chemical fixation of the hydrated Sb(V) oxides onto the contact surface of matrix. Immobilization of Sb(V)

oxides proceeds with the chemical crosslinking of superficial sp3-C-OH-groups with Sb-O and Sb-OH-

bonds.

The new matrices and sorbents FS-OH, FUCM-OH, FC-O-Sb, FUCM-O-Sb were tested for the extraction of

alkaline and alkaline-earth ions from aqueous solutions. It has been shown, that sorption of Na, Ca, Cs, Rb

and Sr from water solutions by hydrophilic surface of FS-OH and FUCM-OH matrices, impregnated with

Sb(V) is provided by the chemisorption mechanism. The best sorption properties to Cs, Ca, Rb and Sr are

shown for FUCM-O-Sb-Li nanocomposite (49 mg Ca per 1 g of sorbent).

Novel heteronanocomposition carbon-fluorocarbon materials FS-O-Sb and FUCM-O-Sb, having excellent

electroconductivity, were also studied as a sensor materials for alkali and alkali-earth ions determination.

49

It was shown that new materials are stable in strong oxidizing media, e.g. in H2O2 solutions and in [ClO–]

media and have a good working characteristics.

An important applications for a studied matrices and sorbents should concerned the effective recovery of 90Sr and 137Cs from the liquid wastes of nuclear industrial plants.

R&D were supported by the ―Rosnauka‖ State Contracts in 2005-2006 and 2009.

87. XPS and Diffraction Study of Carbon-Fluorocarbon Nanocomposition Electroconductive Porous Materials Valentin N. Mitkin, I. P. Asanov, Yu. V. Shubin and A.Yu. Predein, Nikolaev Institute of Inorganic

Chemistry, Siberian Branch of Russian Academy of Sciences, Novosibirsk, Russia

The carbon-fluorocarbon nanocomposition electroconductive porous materials of the FUCM type have been

prepared with the mechanochemical activation (MA) methods in the heterogeneous mixed systems ―nano-

C (TEG) – nano-CF1+x (FS)‖, where nano-C (TEG) is thermally expanded graphite (porosity up to 92%) and

nano-FS – superstoichiometrical mesoporous fluorocarbon material CF1.20. Atomic ratio C:F in initial

powder mixtures was made in a range 1.14-1.70. Duration of MA syntheses (a=40-100 g) was made 0.5–

60 min.

From XRD data is followed that relationship among intensities of 002 and 004 peaks relatively to 001 and

003 reflections of fluorocarbon FS is decreased ca. at order against the initial state versus MA processing

time and it does means that graphitic phase is converted into another C-CF-contained product – carbon-

fluorocarbon ―TEG-FS‖ nanocomposite.

The differential charging effect in XPS is appreciable depending on MA time. The C1s spectra in samples

consist of the components at 284.7 eV and 290.2 eV showing the presence of the graphitic phase and the

sp3-C-F bonds in nanocomposites. Contribution of the graphitic surface concentration is maximal at 10 min

MA, whereas the surface fluorine concentration is minimal at the same MA time. Content of O on the

surface of the samples was 0.7-1.2 %.

The presented new data are additionally confirmed earlier published concept (Mitkin, 2002) about

formation of electroconductive chemical carbon nanocontact on the surface of dielectric particles of the

fluorocarbon materials.

This R&D was supported by Russian State Contracts among ―Rosnauka‖ and our Institute in 2005-2006,

2007-2008 and 2009.

88. Catalytic Synthesis of High Purity Xenon Difluoride with Usage of Chlorine Trifluoride

Valentin N. Mitkin, Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of

Sciences, Novosibirsk, Russia

Regular studies in the chemistry of noble metal coordination fluorides in Novosibirsk have been started in

1970 by professor S.V. Zemskov after remarkable works of Neil Bartlett in the field of chemistry of higher

fluorides of noble metals and xenon fluorides. The first our task was a creation of simple, inexpensive and

effective method of pure XeF2 production and at first stage we have developed the catalytic fluorination of

Xe with ClF3. The guaranteed 99.9% purity XeF2 was achieved via fluorination process with use MnF2+x as

catalyst. However this method had two drawbacks - low yield of XeF2 and low degree of Xe linkage (~ 30-

35%). Increased yield (up to 100%) was provided in fluorination of Xe by ClF3 with catalyst NiF2+x, and

process rate was 6-7 times faster, than with MnF2+x, however the synthesis products were always

contaminated by 25-28% XeF4 and 4-5% XeF6.

For prevention of XeF4 and XeF6 formation in system ―Xe –- NiF2+x‖ it was found the modified process of

XeF2 synthesis in gas mixes ―Xe + ClF3 + Cl2‖ and ―Xe + F2 + Cl2‖, operating in the reactor of ideal

replacement with a porous nickel nozzle, filled by NiF2 or mixed catalyst on the base of Mn, Tb and other

transition fluorides. New scheme of catalytic process has just provided a possibility of development of a

simple, fast and convenient lab method of XeF2 preparation, having 99.92% purity and Xe linkage degree

~ 96%.

50

89. New Synthetic Approaches to a Bifunctional Aromatic Sulfur Tetrafluoride Derivative Joseph S. Thrasher and Alfred Waterfeld, Department of Chemistry, The University of Alabama,

Tuscaloosa, AL

T. Umemoto et al. reported in 2009 the synthesis and commercialization of 4-t-butyl-2,6-

dimethylphenylsulfur trifluoride as a versatile and easy to handle substitute for sulfur tetrafluoride [1]. To

further improve on this very useful reagent, we will report on new synthetic routes to a bifunctional

aromatic sulfur tetrafluoride derivative starting from 1,2,4,5-tetramethylbenzene (durene).

1. T. Umemoto, R. P. Singh, N. Saito, 19th Winter Fluorine Conference, 2009, Abstr. 96

90. Features of Fluoroxidants Application for Decomposition and Noble Metals Analyses in the Geochemical Carbonaceous Samples (Short Review)

Valentin N. Mitkin1, A. A. Galizky1 and S. B. Zhmodik2, (1)Nikolaev Institute of Inorganic Chemistry,

Siberian Branch of Russian Academy of Sciences, Novosibirsk, Russia, (2)Institute of Geology and

Mineralogy SB RAS, Novosibirsk, Russia

There were studied more than 100 geochemical samples of graphitized ores in Hankai terrain (Primorie),

gold-sulphide black shales and carbonaceous Ag-polymetal ores from Sayano-Baikal region (Zun-Kholba,

etc.), North-East of Russia (Natalka) and dictionemic shales of Leningrad region, contained 1.5-35 wt.% of

carbonaceous substance (CS) at various metamorphism stages - bitumoids from dictionemic shales, humic

and fulvic acids and cerogene in black shales (BS) and in the graphitized ores. Traditional methods of

platinum group metal (PGM) determination in such objects ―do not work‖, giving 0.1 mg/t - 50 g/t range

in PGM contents.

Main features for development of convenient analytical techniques were connected with the specifics of

each type CS interaction with KBrF4 and selections of appropriate processings for extraction of noble

metals from fluorinated CSs and samples. Analyses of these problematic objects were executed with

oxidizing fluorination decomposition of 3-10 g samples in a molten KBrF4 with the subsequent specific pre-

sampling and final determination of the noble metals by AAS (liquid samples) and direct atomic emission

spectral in powders. It was shown that contents of platinum, palladium and rhodium in the thoroughly

averaged samples of initial Zun-Kholba ores makes in range 0.05-1.5 g/t, but grows in floatation

concentrates up to 0.3-10 g/t, and in tailings contains ~0.1-0.8 g/t of the Pt+Pd+Rh sum, that speaks

about loses of PGM from sulfide or CS matrices of ores in the conventional hydrometallurgical

technologies.

The research was supported by Integration Projects of Siberian Branch RAS ¹ IP-119 (2006-2008) and ¹

IP-29 (2008-2010).

51

91. Fluoro-Raman Spectroscopy: A Potent Technology to Detect Ex-Vivo Proteins

Farid Menaa1, Ahmed Boucharaba2, Bouzid Menaa1, Carla Aiolfi Guimarães3, Leo Avakyants1 and Olga

Sharts1, (1)Fluorotronics Inc., San Diego, CA, (2)Department of Neurobiology, Ecole Polytechnique

Federale de Lausanne, Lausanne, Switzerland, (3)Department of Pharmacy, University of Sao Paulo, Sao

Paulo, Brazil

The specific detection of markers of disease from biological samples is possible by our patented Carbon-

Fluorine Spectroscopy technology (www.fluorotronics.com). A single type of fluoro-modified amino-acid

(e.g., 4-Fluoro-L-phenyalanine) was added to the medium-containing cells at the final concentration of 10

mM. The corresponding non-modified amino-acid (L-phenylalanine) was used as control. The cells (e.g.,

cancer ones) incorporated naturally the amino-acid during the natural occurring protein synthesis process

without interfering with the activity or the conformation of the proteins of interest. After C-F labelling, the

biomarker (e.g., p21) was isolated and enriched by immunoprecipitation using a specific antibody.

Eventually, the enriched fluoro-labelled protein and the corresponding non-fluoro-labelled protein were

comparatively analysed by FRS. A 532 nm DPSS Q-switched laser (Sierra, General Atomics, USA) with 20

kHz repetition rate and 10 ns pulse duration was used to deliver 10 mW of average power to a small

amount of the sample. The Raman spectra of the F-labelled protein were specifically and more sensitively

detected than the corresponding non-labelled protein. The vibrational assignments of the main spectral

regions were identified. Because the C-F signal is directly proportional to the concentration of the analyte,

it was also possible to quantify the protein amount. Thus, we show that our non-destructive technology

can be routinely used to selectively, sensitively and rapidly detect F-labeled biological molecules in vitro,

ex-vivo or in vivo.

Eventually, our emerging fluoro-imaging Raman spectrometry device, using stable and non-fluorescent or

radioactive labelling, will definitively offer advantages in terms of health safety (prevention, diagnostics,

therapeutics) and cost-effectiveness.

92. Protein Folding Enhancement Via Fluorine Surface Modification of Organosilica Nanoporous Sol-Gel Glasses Host Matrices

Bouzid Menaa1, Farid Menaa1, Carla Aiolfi Guimarães2, Leo Avakyants1 and Olga Sharts1, (1)Fluorotronics

Inc., San Diego, CA, (2)Department of Pharmacy, University of Sao Paulo, Sao Paulo, Brazil

Organic-inorganic nanoporous silica sol-gel glasses constitute the ideal support for protein

bioencapsulation and for studying the different factors influencing the protein folding process in a crowded

environment. The enhancement of the protein folding in such host matrices is important to develop

efficient bionanodevices (e.g., biocatalysts, sensors) and find novel therapies against diseases that are

due to protein misfolding (e.g. Alzheimer). Modified ―wet-aged‖ silica-based glasses, obtained via sol-gel

process, can be used to mimic the protein local micro-environment and tune the properties (e.g., surface

hydration, crowding, hydrophobicity etc.) influencing the protein folding. The incorporation of fluorine into

amino-acids became a prominent strategy to enhance the structural stability of peptides and proteins.

Numerous studies showed that silica-based nanoporous glasses can stabilize bioactive proteins due to the

hydrophobic effect. For instance, the increase of ellipticity and folding of apomyoglobin encapsulated or

adsorbed in fluorinated sol-gel glasses (e.g., fluorinated silica matrix trifluoropropyltrimethoxysilane) has

been enlightened using CD Spectroscopy with signals observable at 222 nm characterizing the secondary

structure at the far UV. The results demonstrated the critical effect of fluorine on the protein folding near

to its native state. Following our statements on the role of fluorine, its incorporation to new sol-gel glass

systems might bring both steric and hydrophobic effects to enhance the protein folding.

52

Eventually, the precise role of fluorine on the protein folding enhancement is further investigated by our

group at Fluorotronics, Inc. (www.fluorotronics.com) using a patented technology known as Carbon-

Fluorine Raman Spectroscopy.

ISoFT'09: Award Session (Monday, 24th August)

Presider: John Gladysz, Texas A&M University, College Station, TX

93. Perfluorinated Ethers as Novel Reaction Media for Greener Chemical Synthesis and Processes

Ilhyong Ryu, Department of Chemistry, Osaka Prefecture University, Sakai, Osaka, Japan

The vapor pressure of traditional organic solvents generally makes them hazardous, since the solvents

evaporate easily into atmosphere. However, less volatile high boiling organic solvents are far from ideal

because separation of the solvent and product by distillation requires high temperatures which can cause

damage to products. In recent years, ionic liquids have emerged as possible green solvents. However,

the fact that they have no measurable vapor pressure has posed a problem in purification of ionic liquids

by vacuum distillation. In this regard, we believe that fluorous ether solvents having high boiling points

have a good potential as green solvents because they are easy to separate from organic compounds and

purification by distillation is also easy. In this talk, I would like to discuss the use of perfluorinated ether

solvents, such as F-626, in non-fluorous organic synthesis.

94. Combining Perfluoroalkyl Tags with Triazole Moieties: A Match Made for Catalysis!

Tamilselvi Chinnusamy, Ramesh Rasappan, Alexandru Gheorghe and Oliver Reiser, Institut für

Organische Chemie, Universität Regensburg, Regensburg, Germany

The copper(I)-catalyzed azide-alkyne cycloaddition offers a convenient method to tag organic molecules

with perfluoroalkyl chains. We have used such strategy to create metal- and organocatalysts containing

multiple triazole and perfluoroalkyl moieties, which display interesting properties that are beneficial in

catalytic processes. Depending on the number of moieties incorporated, facile recovery either by

precipitation of homogeneous catalysts from an appropriate solvent or by direct filtration of heterogeneous

ones becomes possible. Moreover, problems that can arise by competitive complexation of metals by the

triazole moieties seem to be alleviated by the close proximity of the unpolar perfluoroalkyl chains.

53

95. Automated Fluorous-Based Synthesis and Array Formation

Nicola Pohl, Department of Chemistry, Iowa State University, Ames, IA

The covalent attachment of molecules to solid-phases has allowed the automated syntheses of a range of

bioactive molecules. Unfortunately, solid-phase approaches usually expend large excesses of building

blocks to achieve the high yields required when intermediates cannot be purified and therefore are

practically limited to building blocks that are made in a few steps. This talk will discuss an alternative

solution-phase automation strategy to iterative synthesis based on noncovalent fluorocarbon interactions.

The challenges in implementing such as automated approach based on noncovalent interactions will be

presented in the context of the synthesis of a range of oligosaccharides. Further discussions on the

strength of fluorocarbon interactions will be presented in the context of fluorous-based microarrays of

compounds for biological screening.

Inorganic/Organometallic: Bartlett Memorial Session- I (25th August, Tuesday)

Presider: Karl O. Christe, University of Southern California, Los Angeles, CA

96. A Retrospective On the Life and Scientific Achievements of Professor Neil Bartlett

Alain Tressaud, Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB-CNRS), University

Bordeaux, Bordeaux, France

No abstract

97. Recent Synthetic and Structural Developments in Krypton and Xenon Chemistry; From Linear NgF2 (Ng = Kr, Xe) to Non-Octahedral XeF6

Gary J. Schrobilgen, David S. Brock, Jonathan Casalis de Pury, Hélène P.A. Mercier, Kazuhiko

Matsumoto and Gregory L. Smith, Department of Chemistry, McMaster University, Hamilton, ON, Canada

Thiazyltrifluoride reacts with XeF+AsF6– to form F3S≡NXeF+AsF6

–, which rearranges in the solid state and

N≡SF3 solvent to form F4S=NXe+AsF6– and F4S=NXe---N≡SF3

+AsF6–, respectively. The F3S≡NXeF+ cation

also rearranges in HF to give F4S=NXe+, which either undergoes HF addition or XeF2 displacement to form

F5SN(H)Xe+ or F4S=NH2+. The cations have been characterized as their AsF6

– salts in HF by multi-NMR

spectroscopy and in the solid state by Raman spectroscopy and single crystal XRD.

Although XeF2 forms fluorine-bridged adducts with a large number of metal cations, e.g., [Cd(XeF2)][BF4]2

and [Ca2(XeF2)9][AsF6]. Both KrF2 and XeF2 have now been shown to interact with BrOF2+AsF6

- in HF to

form BrOF2+AsF6

-·2NgF2 and in BrF5 to form BrOF2+AsF6

-·XeF2.

The reaction of TMA+F– (TMA+ = N(CH3)4+) and Cs+F– with XeOF2 in CH3CN has led to the synthesis and

solid-state characterizations of TMA+XeOF3– and Cs+XeOF3

–. The TMA+XeOF3− salt provides an example of

an AX3YE2 VSEPR geometry. The oxygen of XeOF2 is protonated in the superacid media, PnF5/HF (Pn = As,

Sb), forming HOXeF2+PnF6

–, the first hydroxyl derivative of xenon(IV).

The fluoride ion acceptor properties of XeO2F2 have been investigated in its reactions with M+F–, resulting

in M+XeO2F3– (M = Cs, TMA, NO) and NO+Xe2O4F5

–. Hydrolysis of Cs+XeO2F3– in CH3CN yields

(Cs+)2(Xe2O6F–)(FHF–), which contains the fluorine-bridged O3Xe---F---XeO3

– anion. Highly endothermic,

shock-sensitive XeO3 forms a stable adduct with CH3CN that is shock insensitive. Xenon hexafluoride

forms adducts with CH3CN, XeF6·CH3CN, and XeF6·2CH3CN that exhibit geometries in their low-

temperature crystal structures that are derived from the monocapped octahedral structure of XeF6

predicted by VSEPR.

54

98. Towards a Layered Antiferromagnetic Fluoroargentate (II) and the Dream of High–Tc Superconductivity in Fluorides

Wojciech Grochala, Faculty of Chemistry & ICM, The University of Warsaw, Warsaw, Poland

Fluorine is the most electronegative among all chemical bond–forming elements. Because of this, the vast

majority of binary and higher inorganic fluorides are high–melting large–band gap electronic insulators,

which are transparent in the visible region of the electromagnetic spectrum. Rare examples of metallic

fluorides are known, but valence orbitals of F marginally participate in the electronic transport in these

compounds. In this account we describe recent theory–driven attempts to turn a family of TM fluorides

into a novel class of high–temperature superconductors (1,2).

Substantial mixing of F‘s 2p orbitals and metal valence functions (‗covalence‘) as well as partial band

occupation are needed to generate band crossing judged responsible for unusually strong vibronic

coupling and for the appearance of superconductivity (3). This precondition is satisfied for unusual

fluorides of divalent silver – fluoroargentates (II) (4). Unfortunately, in all known layered fluorides of

silver (II) the unpaired d electrons of silver order ferromagnetically (5). This is in contrast to

antiferromagnetic ordering observed for undoped oxocuprates. In this account attempts will be described

of crystal-engineering of fluoroargentates (II) which target a layered antiferromagnetic precursor of a

superconductor (6,7).

(1) W. Grochala & R. Hoffmann Angew. Chem. Int. Ed. Engl., 2001, 40, 2743.

(2) W. Grochala, J. Mater. Chem., in press.

(3) K. Fijałkowski & W. Grochala, Dalton Trans., 2008, 5, 447.

(4) W. Grochala et al. ChemPhysChem., 2003, 4, 997.

(5) W. Grochala, Nature Mater., 2006, 5, 513.

(6) T. Jaroń & W. Grochala, Phys. Stat. Sol. RRL, 2008, 2, 71.

(7) Z. Mazej et al. Cryst. Eng. Commun., in press.

99. Fluorophenyl Xe(II) and I(III) Chemistry

Vural Bilir, Hermann-Josef Frohn and Markus Hirschberg, Inorganic Chemistry, University of Duisburg-

Essen, Duisburg, Germany

The substitution of fluorine under electrophilic assistance in the IIII-F moiety of ArFIF2 and in the XeII-F

moiety of XeF2 and ArFXeF by carbon-nucleophiles will be reported and compared. Even the coordinatively

saturated adduct 4-FC6H4IF2∙1,10-phenanthroline undergoes fluorine substitution with cyanide. The

reactivity of the molecule C6F5I(CN)2 towards Lewis acids is shown. C6F5I(CN)2 splits off one cyanide ion

when treated with BF3 yielding [C6F5(NC)I][BF3CN×BF3]. The [BF4]– anions in aryliodonium and -xenonium

tetrafluoroborates react with Me3SiCN and form the corresponding [NCBF3]– salts. [C6F5Xe][NCBF3] is less

stable than [(C6F5)2I][NCBF3] and decomposes to C6F5H and [C6F5Xe][BF3CN×BF3]. Finally, the preparation

of the first zwitterion, p-–F3B-C6F4-Xe+, with a xenon-carbon bond will be presented.

55

100. Syntheses and Crystal Structures of XeF2.MF4 and XeF2.2MF4. What Do We Know about the Crystal Structure of the First Noble Gas Compound "XePtF6"?

Boris Zemva, Matic Lozinsek and Evgeny Goreshnik, Department of Inorganic Chemistry and Technology,

Jozef Stefan Institute, Ljubljana, Slovenia

The historical reaction of PtF6 vapor with comparable molar quantity of xenon gas, performed by Prof. Neil

Bartlett on March 23, 1962, yielded the first noble gas compound ―XePtF6‖. This was the beginning of the

noble gas chemistry which is still flourishing forty-seven years after this event. Unfortunately the

compound ―XePtF6‖ was amorphous and no structural data were available. Although many experimental

efforts were performed, especially in the last decade, no reliable structural data on this compound were

obtained. In this paper an overview of very interesting chemistry in the system PtFx – XeF2, with x = 4, 5

and its comparison with the chemistry in the system PdFx – XeF2, with x = 3, 4 will be given. Besides,

similar systems like XeF2.MF4 and XeF2.2MF4 with M = Mn, Cr, Sn, Ti, will be analyzed in order to get an

idea what the structure of ―XePtF6‖ could be. The compound XeF2.MnF4 could be written as (XeF)4.(MnF5)4.

It consists of four membered rings of MnF6 octahedra and Xe – F groups strongly interacting with (MnF5)4

rings. It should be noted that a single crystal structural analysis of XeF2.CrF4 has shown that it is

polymeric F-bridged chain (CrF5)n, with six coordinated Cr(IV) and with pendent Xe – F groups, linearly

aligned via strong F bridges, to F ligands of the (CrF5)n. The compound ―XePtF6‖ could be structurally

related to XeF2.CrF4.

Organic/Organometallic: Tatlow Memorial Session - I (Tuesday, 25th August)

Presider: Richard D. Chambers, University of Durham, Durham, United Kingdom

101. Enzymatic C-F Bond Formation. Biotechnology, Biotransformations and Applications of the Fluorinase

David O'Hagan, Centre for Biomolecular Sciences and School of Chemistry, University of St Andrews, St

Andrews, United Kingdom

Although organofluorine natural products are extremely rare, the bacterium Streptomyces cattleya has the

unusual capacity to biosynthesise the organo-fluorine metabolites, fluoroacetate and 4-fluorothronine. The

fluorination enzyme (fluorinase) has been identified and isolated from the organism.1-4 It has been shown

to mediate a reaction between S-adenosyl-L-methionine (SAM) and fluoride ion to generate 5‘-fluoro-5‘-

deoxyadenosine (5‘-FDA) and the full pathway to fluoroacetate and 4-fluorothreonine has been uncovered,

and reconstituted in vitro.5 The prospects of developing the fluorinase in coupled bio-transformations is

emerging. The enzyme has been used as a catalyst for C-F synthesis for PET6,7 whereby it is used to

incorporate the 18F isotope from 18F-fluoride ion.

[1] C. Schaffrath, H. Deng, D. O‘Hagan FEBS Letts., 2003, 547, 111-114.

[2] C. Dong, F. L. Huang, H. Deng, C. Schaffrath, J. B. Spencer, D. O‘Hagan and J. H

Naismith, Nature, 2004, 427, 561.

[3] H. M. Senn, D. O‘Hagan, W. Thiel, J. Am. Chem. Soc., 2005, 127, 13643 – 13655.

[4] X. Zhu, D. A. Robinson, A. R. McEwan, D. O‘Hagan, J. H Naismith, J. Am. Chem. Soc.,

2007, 129 , 14597 -14604.

[5] H. Deng, S. M. Cross, R. P. McGlinchey, J, T.G. Hamilton and D. O‘Hagan, Chem & Biol., 2008,

2008, 15, 1268 -1276.

[6] H. Deng, S. L. Cobb, A. D. Gee, A. Lockhart, L. Martarello, R. P. McGlinchey, D. O‘Hagan, and M.

Onega Chem. Commun, 2006, 652 – 654.

[7] M. Winkler, J. Domarkas, L. F. Schweiger, D. O‘Hagan, Angewandte Chemie., Int., Ed., 2008,

47, 10141 - 10143.

56

102. The Construction of the CF3 Group

Shlomo Rozen, Youlia Hagooly and Or Cohen, School of Chemistry, Tel Aviv University, Tel Aviv, Israel

There are two major strategies for constructing organic compounds possessing the CF3 group.

The first is to transfer this group from one molecule to the other (e.g. CF3I ¨ organic molecule-CF3) and

the second to build this group directly on the molecule of interest. As we will concentrate on the second

route, we will discuss the creation of the R2NCF3 family and the rare transformation of the carboxylic

moiety into the CF3 one (RCOOH ¨ RCF3). The source of the fluorine atoms in all reactions is the

commercial reagent bromine trifluoride – BrF3.

103. Recent Advances in Pentafluoroethylation

Gerd-Volker Roeschenthaler, Department of Chemistry, University of Bremen, Bremen, Germany

Reagents for nucleophilic and ―electrophilic‖ pentafluoroethylation will be described and compared with the

respective trifluoromethylation derivatives. Especially C2F5Li will be discussed in detail and compared with

(EtO)2P(O)CF2Li. The first examples of preparative 1,4- and 1,6-perfluoroalkylation using

(perfluoroalkyl)trimethylsilanes and regioselective 1,4-trifluoromethylation of α,β-enones using a ―protect-

in-situ” methodology are discussed.

104. Selective and Efficient Low-Temperature Method for the Perfluoroalkylation of Fullerenes

Igor V. Kuvychko, James B. Whitaker, Bryon W. Larson, Natalia B. Shustova, Olga V. Boltalina and

Steven H. Strauss, Department of Chemistry, CSU, Fort Collins, CO

Poly(perfluoroalkyl)fullerenes (PPFs) are attractive candidates for electron-acceptor building blocks due to

a unique combination of physicochemical properties, including high thermal stability, a range of first

reduction potentials that spans 0.8 V depending on the addition pattern, and the formation of

exceptionally stable radical anions. The preparation of PPFs is usually accomplished at high temperatures

(e.g., 300–600 °C), leading to the formation of mixtures of PPFs with different number of substituents and

different addition patterns. However, these methods are most effective for the preparation of PPFs with

CF3 and (to a lesser extent) C2F5 substituents; heavier perfluoroalkyl groups appear to undergo

fragmentation at these temperatures leading to the formation of complex mixtures of PPFs with different

types of Rf chains attached. We now report a new synthetic approach that allows one to prepare PPFs in

high yield at relatively low temperatures, thus eliminating the problems of Rf chain

fragmentation/rearrangement. Our method is suitable for the preparation of PPFs with Rf substituents of

57

different sizes and branching structures. The number of Rf groups in the resulting PPFs can be easily

controlled over a wide range, including the selective preparation of a number of fullerene (Rf)2

derivatives. The performance of this method versus the conventional approach will be evaluated, and the

effects of the Rf structure on yields, reaction times, properties, etc. will also be presented. Our new

synthetic methodology can be scaled up without the use of specialized apparatus, making the large-scale

preparation of various PPFs considerably more economical than previously believed.

105. Nucleophilic Fluoroalkylations with Phosphonates

Petr Beier, Academy of Sciences of the Czech Republic, Institute of Organic Chemistry and Biochemistry,

Prague, Czech Republic

Selectively fluorinated compounds play increasingly important role in the preparation of novel biologically

active molecules and materials. We have investigated the reactivity of fluorinated phosphonates for

nucleophilic introduction of various fluorine-containing functional groups.

We have developed a new methodology for nucleophilic introduction of –CHF2 and –CF2– groups into

aldehydes and ketones starting from diethyl difluoromethylphosphonate.1 Reaction sequence outlined in

Scheme 1 shows conditions for the formation of hydroxy phosphonates 1, difluoromethyl containing

phosphates 2 and alcohols 3, difluoromethylene containing phosphates 4 and diols 5. Additionally,

phosphonates 1 (R1 = aryl, R2 = H) in the presence of excess of t-BuOK in DMF undergo phosphonate-

phosphate rearrangement followed by HF elimination to afford fluoroenol phosphates 6 in high yields and

Z/E ratio.2

Scheme 1

A milder reagent – diethyl difluoro(trimethylsilyl)methylphosphonate was used for base free fluoride ion induced difluoromethylenations (Scheme 2).3

Scheme 2

58

Diethyl trifluoromethylphosphonate and tetraethyl fluoromethylene bisphosphonate are under investigation for the introduction of the trifluoromethyl and fluoromethyl groups respectively.

References:

1 Beier, P.; Alexandrova, A. V.; Zibinsky, M.; Prakash, G. K. S. Tetrahedron 2008, 64, 10977–10985.

2 Beier, P.; Pohl, R.; Alexandrova, A. V. Synlett 2009, 957–962.

3 Alexandrova, A. V.; Beier, P. J. Fluorine Chem. 2009, 130, in press.

ISoFT'09-I (Tuesday, 25th August)

Presider: Alison M. Stuart, University of Leicester, Leicester, United Kingdom

106. Host-Guest Chemistry in Receptor-Doped Fluorous Membranes

Philippe Buhlmann, Chun-Ze Lai and Li Chen, Department of Chemistry, University of Minnesota,

Minneapolis, MN

The use of chemical sensors as inexpensive, highly sensitive and selective analytical tools offers a variety

of advantages, such as simplicity of measurement, high analysis throughput, rapid detection, and low cost

of analysis. For this purpose, we previously developed fluorous polymeric membranes doped with

fluorophilic cation and anion exchanger sites and receptors, and showed that ion-selective potentiometric

sensors with fluorous sensing membranes have exceptional selectivities and robustness. Taking advantage

of the recently developed physicochemical models for these sensors, it is possible not only to develop

highly selective sensors but also to quantitatively characterize host-guest interactions in fluorous phases

with relatively small amounts of sample. This permitted, for example, a quantitative assessment of the

basicity of perfluorotrialkylamines and the cation properties of a perfluorotetraether and the polymer

Teflon AF 2400. This contribution will discuss new results that extend the study of cation binding by

perfluoroethers to perfluoro crown ethers. Moreover, the surprising anion selectivities of novel fluorophilic

tetraalkylammonium and phosphonium-based anion exchangers will be presented.

107. Peptide Microarrays Using Fluorous Immobilization

Marvin S. Yu1, Tadamichi Nagashima1, Bruhaspathy Miriyala1, Nicola Pohl2 and Beatrice Y.M. Collet2,

(1)Fluorous Technologies, Inc, Pittsburgh, PA, (2)Department of Chemistry, Iowa State University, Ames,

IA

Peptides were immobilized on a fluorous modified glass slide to provide microarrays which could then be

interrogated with various enzymes as a demonstration of activity assays. The synthesis of these fluorous

tagged peptides, factors which are important for immobilization, and examples of enzyme activity

detected using these microarrays will be presented. The work described represents the first examples of

peptides being immobilized on a fluorous glass surface.

108. Synthesis and Applications of a Fluorous Photoaffinity Labeling Reagent

Qisheng Zhang, Zhiquan Song and Weigang Huang, School of Pharmacy, University of North Carolina at

Chapel Hill, Chapel Hill, NC

Identifying cellular targets of bioactive small molecules from endogenous and synthetic chemical libraries

is essential for their further applications as drug candidates and research tools. Various techniques,

including biochemical pulldown and cDNA complementation, have been developed for that purpose.

However, it remains challenging when the target is low-abundant protein, the small molecule-protein

interaction is weak, or the target protein is one member of a family of proteins with similar functions. To

address this challenge, we designed and synthesized a fluorous photoaffinity labeling reagent to capture

59

transient, weak, or low abundant small molecule-interacting proteins in vivo. Preliminary results on

applying the reagent to two biological systems are described. In one application, the reagent reacts with a

small molecule Wnt synergist, QS11, which binds to GTPase-activating protein of ADP-ribosylation factor

(ARFGAP). The resulting product is then used to probe QS11‘s binding sites with ARFGAP. In the other

application, the reagent is conjugated to phosphatidylinositol 4,5-bisphosphate (PIP2) to identifyPIP2-

interacting proteins.

109. Combinatorial Fluorous Technologies for Green Chemistry Applications

Wei Zhang, Department of Chemistry, University of Massachusetts - Boston, Boston, MA

Described in this presentation is a personal overview of the green chemistry aspects of fluorous

technologies for small-scale organic synthesis. The unique phase separation and broad combinatorial

capability of fluorous technologies have led to the development of fluorous chromatography-free

separations, chemical recycling techniques, atom economic reactions, energy-focused microwave

reactions, metal-free organocatalysis, aqueous media reactions, and modified reagents. The utilities of

these green chemistry tools have been demonstrated in the discovery chemistry, medicinal chemistry, and

academic labs.

110. Fluorous Chemistry and Materials to Enable Droplet Microfluidics

Roger A. Nassar, Randall Scanga, Ben Miller, Xinyu Li, Hu Gang and J. Brian Hutchison, Department of

Chemistry, Raindance Technologies Inc., Lexington, MA

Accelerating discoveries in human health and disease research by performing 10 million biological tests or

chemical reactions per hour is enabled by droplet microfluidics technology. The power of such a

technology incites researchers to re-think their experiments and to approach discovery in a revolutionary

way while minimizing experimental error in a high speed and simple workflow. Fluorous chemistry and

materials are critical for chemical and biological compatibility and stability of droplets against undesired

coalescence. These properties enable each individual droplet to be equivalent to a test tube or a micro-

titer plate well. In particular, fluorous oils provide the immiscible continuous phase separating droplets;

fluorinated amphiphilic polymers act as droplet stabilizers; and, microfluidic channels and storage vials are

treated with fluorinated materials to promote preferential wetting by oil rather than droplets.

This contribution describes fluorous fluids that have been selected for the continuous phase of this

technology due to their immiscibility with water, chemical inertness, and low solubility for encapsulated

chemical and biological molecules. The synthesis and characterization of perfluoropolyether-

polyethyleneglycol block copolymer surfactants are discussed. In addition, the performance of these

surfactants as biocompatible droplet stabilizers is evaluated. Finally, the generation, processing, and

sorting of pico-liter droplets is performed on a thermoplastic chip, and emulsions are stored for many

months in glass vials. In order to decrease the interaction of aqueous droplets with surfaces of chips and

vials, these surfaces are rendered hydrophobic/fluorophilic following tuned coating with fluorinating

agents. The implications of the coating process on device performance will be discussed.

60

ISoFT'09-II (Tuesday, 25th August) Presider: Roman Dembinski, Oakland University, Rochester, MI

111. Crystalline Solids From Haloperfluoroalkanes: An Opportunity for Structural Study of Perfluoroakyl Chains

Giuseppe Resnati, Pierangelo Metrangolo, Serena Biella and Giancarlo Terraneo, Dipartimento di

Chimica, Materiali ed Ingegneria Chimica "Giulio Natta", Politecnico di Milano, Milano, Italy

Single crystal X-ray analysis of perfluoroalkane derivatives is typically a challenge. In most structures

available in the Cambridge Structure Database the perfluoroalkyl chain is covalently bound to quite

complex moieties (for instance phosphine or organometallic residues) which probably play a major role in

driving the crystal formation. Very few crystallographic structures are available for simple perfluoroalkane

derivatives, for instance trifluoromethyliodide is the only haloperfluoroalkane reported to the best of our

knowledge.

Recently we have shown that the heavy halogen in iodo- and bromoperfluoralkanes works as an electron

acceptor site when interacting with neutral lone pair possessing atoms (e.g. the nitrogen atom of a

pyridine or amine residue) or anions (e.g. halide anions). The resulting interactions, named halogen

bondings, are strong enough to drive effectively the self-assembly of mono- and diiodoperfluoroalkanes

with a variety of hydrocarbon derivatives. The formed hybrid perfluorocarbon/hydrocarbon materials are

frequently crystalline materials amenable for single crystal X-ray analyses.

The crystallographic structure of several iodoperfluoroalkanes was thus determined for the first time and it

will be described in the details in this presentation. Among others, we will discuss the structure of

perfluorododecyliodide, the longest perfluoroalkyl chain reported to now. The conformational aspects of

perfluoroalkyl residues and their possible helical arrangement will be considered. A particular attention will

be paid to some cases where spontaneous resolution has been observed and the perfluoroalkyl chains of

the crystal all adopt one of the two enatiomorphic conformations.

61

112. Fluorous Copper(II)-Carboxylate Complexes Applied to the Magnetic Detection of Humidity and to the Preparation of Super-Hydrophilic Surfaces Exhibiting Coordinating Properties

Artur Motreff1, Jean-Marc Vincent1, Mounir El bakkari2 and Rosenildo Correa da Costa1, (1)CNRS, Institut

des Sciences Moléculaires, Talence, France, (2)Department of chemistry, University of Alberta, Canada

Dicopper(II)-carboxylates complexes are a very important class of coordination compounds which have

been extensively studied for their spectroscopic/magnetic properties and have found many applications

such as in catalysis or as building block for the preparation of coordination polymers. In 2002, we have

reported that the highly fluorophilic dicopper(II)-carboxylate complex 1 could be used to reversibly

transfer non-fluorophilic pyridyl-tagged compounds from an organic phase to a perfluorocarbon. This

highly efficient phase-switching process has been applied successfully for multi-step organic synthesis,

catalysis, or to develop an original colorimetric assay for ethanol. Contrasting with the reactivity of 1, we

discovered recently that the dicopper(II) complexes 2 or 3, in which the perfluorinated chain is directly

appended to the carboxylate group, exhibit an extremely high affinity for water. Of particular interest is

that 1 behaves as a ―magnetic sponge‖. In the solid state (powdered crystals), exposition of the complex

[Cu2(C8F17CO2)4(acetone)2] (2) to humidity leads to a fast and dramatic decrease of the exchange

magnetic coupling between the copper(II) ions (from 2J = –480 cm–1 to 2J = –7 cm–1) and to a drastic

change of its powder EPR spectrum. Interestingly, adsorption of complexes 2 or 3 onto materials such as

Teflon, glass or polypropylene, strongly affect their surface properties as it leads to surfaces exhibiting

both super-hydrophilic and coordinating properties. In the communication, the preparation of the

modified surfaces, their characterization (AFM, SEM, fluorescence microscopy, contact angles…), wetability

and binding properties will be described.

62

113. Coordination Chemistry of Perfluoroalkylated Ligands

Eric G. Hope and Alison M. Stuart, Department of Chemistry, University of Leicester, Leicester, United

Kingdom

Although catalytic and tagging/separation applications of fluorous technologies receive the highest

accolades, much of this chemistry depends upon the synthesis of perfluoroalkylated ligands and their

subsequent coordination chemistry with transition metals. In the 15 years since Horváth and Rábai‘s

seminal paper, the number and complexity of perfluoroalkylated ligands and their coordination compounds

have grown to such an extent that surely it is now possible (and timely) to provide reliable insight into the

impact and influence of long chain perfluoroalkyl groups on the physical and chemical properties of metal

complexes. Here, we will compare and contrast fluorous and non-fluorous ligands taking selective

examples from late transition metal complexes of phosphine, xanthate, dithiophosphate, β-diketonate and

phosphonite ligands. This will illustrate: (i) the diversity of fluorous coordination chemistry; (ii) the

structural impact of fluorous ponytails; (iii) the close synergies between fluorous and non-fluorous

coordination chemistry, and some unusual exceptions; and (iv) the significant variance in the apparent

effects of perfluoroalkyl substituents on the spectroscopic properties of the metal complexes. In order to

clearly delineate these effects, for the aryl phosphine systems at least, definitive data on the electronic

influence of the perfluoroalkyl substituents will be presented from an alternative spectroscopic probe.

114. Supramolecular Associations with Fluoro-Alcohols

Daniele Bonnet-Delpon, Faculty of Pharmacy, BIOCIS, CNRS-University Paris-South, Chatenay-Malabry,

France

Hexafluoroisopropanol (HFIP) and its derivatives, by their specific properties, with a combination of

hydrogen bonding donor ability, low nucleophilicity, high ionizing power, have been intensively

investigated as solvents or additives to promote chemical reactions1,2.

We have recently focused our interest on the remarkable ability of HFIP to form H-bond complexes with

Lewis bases and we could isolate and characterize a crystalline HFIP-piperidine complex.3 The stability of

the cluster is the result of multi-centered H-bonds where both HFIP and piperidine are H-bond donors and

acceptors.

This ability to form supramolecular networks has been exploited for the design of hybrid materials with

tuned physico-chemical properties4.

1. J.P. Bégué, D. Bonnet-Delpon, B. Crousse, Synlett 2004, 18-29.

2. I. A. Shuklov, N. V. Dubrovina, A. Borner, Synthesis 2007, 2925.

3. J.F. Berrien, M. Ourévitch, G. Morgant, N.E. Ghermani, B. Crousse, D. Bonnet-Delpon, J. Fluorine

Chem. 2007, 128, 839-843

4. D. Vuluga, J. Legros, B. Crousse, D. Bonnet-Delpon, Chem. Commun., 2008, 4954–4955

63

Inorganic/Organometallic: Bartlett Memorial Session- IIIi(25th August, Tuesday)

Presider: Darryl D. DesMarteau, Clemson University, Anderson, SC

115. Oxidation of Benzenes and Di-Chalcogenides by High Potent Oxidisers

Konrad Seppelt, Hashem Shorafa, Birgit Mueller, Beate Paulus and Helmut Poleschner, Institut für

Chemie und Biochemie, Freie Universität Berlin, Berlin, Germany

The transition metal hexafluorides WF6, ReF6, OsF6, IrF6, and PtF6 are strong to extremely strong one

electron oxidators. Fluorinated benzenes are oxidised to radical cations, and the corresponding structures

are elucidated. The Jahn-Teller distortions are discussed. Disulfides, diselenides, and ditellurides are

oxidised also to radical cations. These appear monomeric in case of sulphur, but are loose dimers in case

of selenium and tellurium. Fluorination of sterically protected selenium precursors result in organo

selenium monofluorides, which are here obtained for the first time.

116. How Far Can We Go? New Insides Into the Highest Oxidation States of Transition Metals

Sebastian Riedel, Institut für Anorganische und Analytische Chemie, Albert-Ludwigs Universität Freiburg,

Freiburg i. Br., Germany

The discovery of novel inorganic species in high oxidation states helps to enhance and expand chemical

understanding of the behavior of the elements and their compounds.[1, 2] Furthermore, high oxidation

states of transition-metals and main-group elements serve in many fields of chemistry as potent catalysts,

oxidants and fluorinating agents.[3]

The maximum oxidation states for the early transition metals of the 5d row follow the group number up to

group 8 as for example in OsO4. The trends of the later metals tend to be less clear-cut.[4] Our recent

investigations on these last missing secrets of high oxidized transition metal species by high level

quantum-chemical calculations in combination with matrix-isolation techniques have lead into the

discovery of new oxidation states.

64

References:

[1] X. Wang, L. Andrews, S. Riedel, M. Kaupp, Angew. Chem. Int. Ed. 2007, 46, 8371.

[2] P. Hrobarik, M. Kaupp, S. Riedel, Angew Chem Int. Ed. 2008, 47, 8631.

[3] S. Riedel, M. Kaupp, Coord. Chem. Rev. 2009, 253, 606.

[4] S. Riedel, M. Kaupp, Angew. Chem. Int. Ed. 2006, 45, 3708.

117. Neil Bartlett's Influence on Sulfur-Nitrogen-Fluorine Chemistry

Ruediger J. Mews, Department of Chemistry, University of Bremen, D-28359 Bremen, Germany

This contribution reviews the influence of Neil Bartlett‘s work on the development of N-S-F-chemistry, a

field of some importance for synthetic and also for theoretical inorganic chemistry. Following his early

scientific work, the preparation [1] and X-ray structural characterization [2] of the SF3+ cation, a large

number of nitrogen containing cations SFnR3-n+ has been prepared, structurally characterized, used for the

elucidation of reaction mechanisms and for the development of new synthetic pathways. Extension to

S(+6) led to extremely interesting cations: to [RNSF3]+ with the shortest sulfur-element bond (besides

OSF3+) [3], to [(R2N)2SF2]

++, the first S(+6) dication, to the penta- and hexa-coordinated cations

[R2NSF4]+ and [RnNH3-nSF5]

+, cations with an even broader chemistry than that of S(+4).

A special type of sulfur cations are the organometallic complexes (e.g. [CpFe(CO)2NSF2R]+,

[M(CO)5NSF2R]+, M=Mn,Re)), the coordination compounds [M(NSF3)4][FAsF5]2 [M= e.g, Fe, Co, Ni) and

[M=[M(NSF3)6(FAsF5)2 ][AsF6] (M= e.g., Sm, Er).

Early connections to Neil Bartlett‘s noble gas chemistry are selective oxidative fluorinations of sulfur-

nitrogen derivatives with XeF2. An exciting new field was recently developed by the Schrobilgen group[4]:

the use of xenon-fluorine cations as electrophiles towards NSF3, followed by unusual additions and

transformations.

[1] N. Bartlett P. L. Robinson, Chem. Ind. 1956, 1361; JCS (London) 1961, 3417.

[2] N. Bartlett et al. Inorg. Chem.1972, 11, 2325

[3] J. Passmore et al. JCS Dalton Trans. 1973, 2535.

[4] G. Schrobilgen et al. Inorg. Chem. 2007, 46, 1369.

118. XeF2 as Ligand to Metal Ions; Review and Recent Achievements

Melita Tramsek, Evgeny Goreshnik, Gasper Tavcar and Boris Zemva, Department of Inorganic Chemistry

and Technology, Jozef Stefan Institute, Ljubljana, Slovenia

In 1991 Prof. Neil Bartlett with the co-workers, in the course of systematic attempts to oxidize Xe with

Ag(II), prepared Ag(XeF2)2(AsF6), the first compound with XeF2 acting as a ligand to the metal centre.

Nearly decade later we started with systematic investigations of the reactions of various metal salts of the

type M(AF6)x with XeF2. So far we synthesized and characterized numerous compounds with metals in

oxidation states I, II, III and various AF6- anions (A = P, As, Sb, Bi, Ru, Ta…) and BF4

- anion. The metal

centers in these compounds usually exhibit the highest coordination number of fluorine ligands. The

coordination sphere of the metal consists of fluorine atoms from XeF2 and the anions. In several examples

the metals homolepticaly coordinated only with XeF2 molecules were found. XeF2 in the coordination

compounds can be either bridging, connecting two metal centers or non-bridging. Metal centers are beside

XeF2 usually connected also via anions. Structural diversity of these compounds is one of the most

interesting features. Different structures from a molecular structure (e.g. [Mg(XeF2)4](AsF6)2) over a

dimeric structure (e.g. [Cd2(XeF2)10](SbF6)4,) to different polymeric structures such as chain (e.g.

[Ca(XeF2)5](PF6)2), layer (e.g. [Ca(XeF2)4](AsF6)2) and 3D structure (e.g. [Ca(XeF2)2.5](AsF6)2) were found.

Recently besides XeF2 and MF6- anions also XeF4, as a ligand to metal center, was found.

65

Organic/Organometallic: Tatlow Memorial Session - II (Tuesday, 25th August)

Presider: Graham Sandford, Durham University, Durham, United Kingdom

119. Organocatalytic Asymmetric Direct Aldol Reactions of Trifluoroacetaldehyde Ethyl Hemiacetal

Kazumasa Funabiki, Department of Materials Science and Technology, Gifu University, Gifu, Japan

In this presentation, we will disclose the commercially available L-proline derivatives-catalyzed

asymmetric direct aldol reactions of trifluoroacetaldehyde ethyl hemiacetal with unmodified ketones or

aldehydes.

120. Continuous Flow Microreactor Oxidations of Alkenes and Amines with HOF.MeCN Produced in-Situ Christopher B. Murray1, Christopher B. McPake2 and Graham Sandford2, (1)AWE, Aldermaston, Reading,

United Kingdom, (2)Department of Chemistry, Durham University, Durham, United Kingdom

HOF.MeCN, perhaps the most powerful oxidant for organic chemistry, has been studied extensively by

Rozen et al. Various oxidation processes have been described and, in general, these give higher yields and

occur under milder conditions than those with traditional oxidants. The reagent has been shown to

effectively oxidize certain nitrogen centers to N-oxides and nitro compounds, groups of interest to the energetic materials community.

Whilst there have been many publications detailing the chemistry of HOF.MeCN in batch reactions, reports

of its use in flow chemistry have been very limited. The use of flow systems can be advantageous when

working with reactive or otherwise hazardous materials, enabling minimization of inventory, precise

control of contact time and excellent heat transfer, potentially leading to improved safety, selectivity and yields.

The instability of HOF.MeCN means that it must be prepared as required, making it particularly amenable

to flow techniques, where a known concentration can be generated and used in-situ. This is in contrast to

the published batch reactions where the solution must be titrated in order to establish the concentration of HOF.MeCN.

The Durham group have developed a scalable gas-liquid microreactor design which has been used for

direct fluorination processes. Here we report the use of this microreactor for the continuous flow synthesis

of HOF.MeCN and subsequent oxidation processes. Initial work on alkene epoxidation will be described, as

well as more recent results on the oxidation of amines to the corresponding nitro compounds.

© British Crown Owned Copyright 2009/MOD

66

121. Trifluoroacetaldehyde N,O-Acetals: Highly Effective Building Block for α,α-Difluoroketone Derivatives

Hikaru Yanai, Tatsunori Ichikawa and Takeo Taguchi, School of Pharmacy, Tokyo University of Pharmacy

and Life Sciences, Tokyo, Japan

Since difluoromethyl and difluoromethylene groups perform as bioisosteric structures for

hydroxymethylene group or ethereal oxygen, these functionalities are widely found in the structure of

biologically active molecules. α,α-Difluoroketone structure also performs as a transition state mimic

against several peptidases. For these reasons, the development of effective synthetic strategies for

difluoromethylene compounds has been one of the top concerns in organofluorine chemistry for a long

time.

Recently, we found that the reaction of trifluoroacetaldehyde N,O-acetal derivatives with 2 molar

equivalents of alkyllithium reagents proceeded via β-elimination of fluoride followed by alkyl transfer from

excess alkyllithium onto the β-carbon of fluorine groups in the generated ketene N,O-acetal intermediate

(Chem. Commun. 2009, 1034). This procedure is a new entry toward functionalization of trifluoromethyl

compounds through mono-defluorination. In addition, the reaction of the N,O-acetal with alkyl lithium

reagents followed by the treatment by aldehydes resulted in a clean formation of β-hydroxy-α,α-

difluoroketone N,O-acetals. Furthermore, with several electrophiles such as ketones, iminiums and N-

halosuccinimides instead of aldehyde component, the corresponding functionalized α,α-difluoroketone

N,O-acetals were obtained in excellent yields.

This one-pot procedure provides a convenient and convergent construction method for functionalized α,α-

difluoroketone derivatives. Full detail on this work will be presented.

122. The Synthesis of Alpha-Trifluoromethylated Carboxylic Acid Derivatives

Magdalena Tomas-Szwaczyk1, Justyna Walkowiak2, Günter Haufe3 and Henryk Koroniak2, (1)Chemistry,

Adam Mickiewicz University, Poznañ, Poland, (2)Faculty of Chemistry, Adam Mickiewicz University,

Poznañ, Poland, (3)Organisch-Chemisches Institut, Universität Münster, Münster, Germany

The synthesis of alpha-trifluoromethylated carboxylic acid derivatives is an important goal in

organofluorine chemistry, particularly if the absolute configuration of the perfluoroalkylated centre can be

controlled. Recently, adducts of secondary amines with 1,1,3,3,3-pentafluoropropene (PFPSA) has been

developed in our laboratory and applied as new reagents for the direct transformation of alcohols to

corresponding alkylfluorides.1 Moreover, treatment of fluorinated allylic alcohols with PFPSAs in the basic

conditions leads to the formation of alpha-trifluoromethylated alpha-fluorinated alpha,alpha-unsaturated

amide derivatives via [3,3]-sigmatropic Eschenmoser-Claisen-type rearrangement.2,3 We wish to present

the results of some non-fluorinated allylic alcohols reactions with PFPDSA in the presence of tertiary amine

as a useful route to ?-trifluoromethylated amides.

67

1. H. Koroniak, J. Walkowiak, K. Grys, A. Rajchel, A. Alty, R. Du Boisson, J. Fluorine Chem., 2006, 127,

1245.

2. A. E Wick, D. Felix, K. Stehen, A. Eschenmoser, Helv. Chim. Acta, 1964, 47, 2425.

3. S. N. Gradl, J. J. Kennedy-Smith, J. Kim, D. Trauner, Synlett., 2002, 1.

ISoFT'09-III (Tuesday, 25th August)

Presider: Veronique Gouverneur, University of Oxford, Oxford, United Kingdom

123. Ionic Solutes in Fluorous Media; From Curiosities to Recoverable Catalysts

John A. Gladysz, Department of Chemistry, Texas A&M University, College Station, TX

Although fluorous liquid phases are justifiably regarded as the least polar known, there is a growing

recognition that some fluorous salts - i.e., ionic compounds - dissolve, either at room temperature or upon

mild heating. Most chemists would be hard pressed to name an ionic species that is hexane soluble. This

leads to obvious questions, such as (1) how is the solvation of such salts best described, and (2) do any

self assemble into microstructures?

This presentation will begin with a review of soluble fluorous salts. A series of fluorous phosphonium and

ammonium salts have been found to be effective phase transfer catalysts for ionic displacements in

fluorous media, per the Figure below.1,2 The salts can easily be recovered by several protocols. More

recently, fluorous [R3P…N…PR3]+ salts and iron sulfur clusters have been synthesized.2 The latter

constitute phase- and redox-shifted analogs of metalloenzyme active sites. Ionic fluorous species also play

important roles as reaction intermediates, and in fluorous ionophore-based sensing membranes.3

Figure. Phase transfer catalysis by fluorous phosphonium and ammonium salts.

(1) Mandal, D.; Jurisch, M.; Consorti, C. S.; Gladysz, J. A. Chem. Asian Journal 2008, 3, 1772.

(2) Mandal, D.; Gladysz, J. A. manuscripts in preparation.

(3) Boswell, P. G.; Szíjjáró, C.; Jurisch, M.; Gladysz, J. A.; Rábai, J.; Bühlmann, P. Anal. Chem. 2008, 80,

2084.

68

124. Convenient Synthesis of Fluorous Siloxanes and Halosilanes and Their Application for Heck- and Hiyama-Coupling Reactions József Rábai1, Ágnes Csapó1, Csongor Szíjjártó1 and Valentin N. Mitkin2, (1)Department of Organic

Chemistry, Eötvös Loránd University, Budapest, Hungary, (2)Nikolaev Institute of Inorganic Chemistry,

Siberian Branch of Russian Academy of Sciences, Novosibirsk, Russia

Fluorous disiloxanes {(RfnCH:CHSiMe2)2O, 1} and vinylfluorosilanes (RfnCH:CHSiMe2F, 2) can be prepared

by the AIBN catalyzed radical addition reactions of n-perfluoroalkyliodides (RfnI, n=4,6,8) to

tetramethyldivinyldisiloxane, followed by treatment of the formed iodosiloxanes {(RfnCH2CH(I)SiMe2)2O,

3} with Et2NH, and 1 with BF3*OEt2, respectively. Compound 3 can also be prepared in a one-pot reaction

using chlorodimethylvinylsilane, aq-K2S2O5, AIBN and RfnI. The reaction of 3 with Bu4NF*3H2O/THF affords

the appropriate perfluoroalkyl-ethenes (RfnCH:CH2, 4) in good yields. The Heck-coupling of 4 and

RfnCH2CH:CH2 (5) with aryliodides have been effected using either homogeneous (Pd(PPh3)4, Pd(OAc)2) or

heterogeneous (Pd/C, Pd/montmorillonite K10, Pd/CFCM) palladium precatalysts. The effect of solvents

(DMF, CH3CN, and BTF), and that of the bases have been studied. Our favorite catalyst was a palladium

nanocluster, supported onto nanocomposition carbon-fluorocarbon matrix, CFCM, which can be easily

recovered and reused several times without significant loss of activity. The latter porous CFCM (system

CF1.2-C) consists of the chemically bonded nanosized subphases of the graphite fluoride-like

superstoichiometric carbonfluoride (CF1.2) with the nanoblocks of thermally expanded graphite. The CF1+x

component of the latter nanocomposite material is considered as a novel solid fluorous phase, and its

potential uses for fluorous applications are being evaluated. Iodosiloxanes 3 can also be used in a one-pot

procedure for Heck-reactions, if Bu4NF*3H2O is substituted for the Et3N base. The potential of using

disiloxanes 1 and fluorosilanes 2 as novel perfluoroalkylvinyl-transfer reagents for Pd-catalyzed Hiyama-

coupling reaction of aryliodides is under evaluation. The support from the Hungarian Scientific Research

Foundation (OTKA K-62191) is acknowledged.

125. The Effect of Fluorous Solvent on the Stereoselectivity of Halogenation of Alkenes in “Phase-Vanishing” Method

Jernej Iskra, Department of Physical and Organic Chemistry, "Jožef Stefan" Institute, Ljubljana, Slovenia

The fluorous ―phase-vanishing‖ method (PVM) is used for diffusion controlled addition of a reagent to a

reaction phase through the fluorous liquid bulk membrane.1 Therefore, reagent is transferred from its bulk

through the fluorous solvent to the reaction phase through the fluorous/organic interface in a slow and

diffusion controlled way. PVM is an alternative to classical drop-by-drop addition of reagent, where a high

local concentration of reagent around the drop is formed. The difference in both types of addition is

important with very reactive reagents and exothermic reactions where high local concentration leads to

local overheating and consequently selectivity of reaction is difficult to obtain. It is not surprising that

―phase-vanishing‖ method was introduced with bromination of alkenes by Br2.2 Furthermore, ―phase

vanishing‖ reactions were applied for electrophilic halogenation with Br2 and Cl2, as well as radical

bromination.3

The role of the fluorous-organic phase border in the PV reactions and the reason for its necessity is still

not well understood. A study on the solubility of halogens (Br2, Cl2, F2) in fluorous solvents revealed

interesting differences in interactions between molecular halogens and fluorous solvents.4 Present study

shows the research on the interaction of reaction components on the fluorous-organic interface through

the stereoselectivity of addition of halogens to alkenes. Different modes of addition of bromine to the

solution of alkene (in polar, non-polar solvent and neat) was studied in order to elucidate if the fluorous

phase has a specific effect on the course of reaction at the fluorous-organic phase border.

69

126. PTFE as a Phase Screen in Chemiluminescent Phase-Vanishing Reactions

Veljko Dragojlovic, Wilkes Honors College, Florida Atlantic University, Jupiter, FL

Phase-vanishing reactions are triphasic reactions, which involve a reagent, a liquid perfluoroalkane as a

phase screen and a substrate. The reagent in the lower layer diffuses through the perfluoroalkane layer,

reaches the top layer and reacts with it. Since the rate of diffusion is relatively low, the reaction proceeds

at a moderate rate, as opposed to a vigorous reaction that would occur if the two reactants were mixed

directly. In a phase-vanishing reaction with PTFE tape as the phase screen there is no limitation related to

the density of a phase, and the denser phase can be in the top layer. The method can be used to both

prepare chemiluminescent compounds as well as run chemiluminescent reactions, which in turn provide

information about permeability of PTFE and suitability of the method for other synthetic transformations.

70

Inorganic/Organometallic: Bartlett Memorial Session- III (25th August, Tuesday)

Presider: Boris Zemva, Jozef Stefan Institute, Ljubljana, Slovenia

127. Understanding Some Electrophilic Group 16 and 17 Main Group Cations with Geometries That Do Not Obey VSEPR Theory Rules

Jack Passmore, Department of Chemistry, University of New Brunswick, Fredericton, NB, Canada

VSEPR theory and its successors have been very successful at predicting and accounting for a wide range

of molecular structures, especially those of the main groups. Some exceptions include AsF6- salts S4

2+,

I42+, I5

+, S2I42+, the diradical +.SSSNC-CNSSS.+, the weakly π*-π* bonded dimers (RCNSSS+.)2 (e.g. R =

Cl, Br, I). We will show that the existence of these salts and structures of the cations can be largely be

understood on the basis of electrostatics and thus conform to the underlying spirit of VSEPR theory

despite being exceptions at first sight. We will also show the dependence on the state, gas, solution, or

solid.

128. Elimination of Arsenic From Hydrogen Fluoride Prepared From Low Quality Fluorite

Rika Hagiwara and Kazuhiko Matsumoto, Graduate School of Energy Science, Kyoto University, Kyoto,

Japan

The production of HF at the industrial level in Japan is now declining due to the difficulty in importing high

quality fluorite (CaF2) of which the market price has been doubled in the last five years. Although low

quality fluorite is cheap and attractive source of fluorine, impurities are not suitable for some applications

including semiconductor industry. Arsenic (+3) is one of the difficult species to be eliminated from HF by

distillation due to the similarity of physical properties of HF and AsF3, the latter being formed in the

process of HF production. On the other hand, once AsF3 is oxidized to AsF5, it is easy to remove it from

HF. The preliminary experiments using HF containing ~500 ppm of AsF3 has demonstrated that some

fluorides containing transition metals at high oxidation states such as K2NiF6 and AgFAsF6 work effectively

to convert it to pentavalent species that is easily eliminated from HF. In particular, the use of AgFAsF6 is

more attractive from the viewpoint of industrial process because AgFAsF6 is easily regenerated from

AgAsF6 in HF by fluorination at room temperature even with diluted elemental fluorine. When the fluorides

soluble into HF like AgFAsF6 are used in this process, the oxidation of AsF3 is much faster than that by

elemental fluorine. The lab-scale test was performed using HF prepared from fluorite containing 61 ppm

As. The use of AgFAsF6 as an oxidizer and NaF as an AsF5 scavenger resulted in the As content in the

treated HF below 3 ppm.

71

129. Effect of Surface Fluorination and Conductive Additives on the Electrochemical Behavior of Lithium Titanate (Li4/3Ti5/3O4) for Lithium Ion Battery

Tsuyoshi Nakajima1, Akimi Ueno1, Takashi Achiha1, Yoshimi Ohzawa1 and Morinobu Endo2,

(1)Department of Applied Chemistry, Aichi Institute of Technology, Toyota, Japan, (2)Department of

Electrical and Electronic Engineering, Shinshu University, Nagano, Japan

Effect of surface fluorination and conductive additives on the charge/discharge behavior of lithium titanate

(Li4/3Ti5/3O4) has been investigated using F2 gas and vapor grown carbon fiber (VGCF). Light fluorination of

Li4/3Ti5/3O4 at 70°C-150°C slightly decreased the peak intensity of X-ray diffraction lines, which suggests

slight increase in the disorder of Li4/3Ti5/3O4 lattice in surface region. BET surface areas and meso-pore

volumes were reduced with increasing fluorination temperature from 70°C to 150°C, which suggests slight

decrease in the surface roughness. XPS analysis indicated that concentrations of Li and F increased with

increasing fluorination temperature while those for Ti and O were reduced probably because trace

amounts of products such as O2, OF2 and TiF4 were lost. The Li4/3Ti5/3O4 samples fluorinated at 70°C and

100°C provided the higher charge capacities than non-fluorinated sample at high current densities of 300

and 600 mA/g while those fluorinated at 25°C and 150°C gave the lower capacities than original sample,

particularly Li4/3Ti5/3O4 fluorinated at 150°C showed very low capacities at 600 mA/g. The results indicated

that the optimum fluorination temperatures were 70°C and 100°C. Since Li4/3Ti5/3O4 is an electric

insulator, a conductive additive plays an important role for utilization of available capacity of Li4/3Ti5/3O4.

The result showed that VGCF with fibrous structure gave the higher capacities than normally used

acetylene black (AB).

130. Azoles as Reactive Nucleophiles with Cyclic Perfluoroalkenes

Sonali Garg, Brendan Twamley, Zhuo Zeng and Jean‘ne M. Shreeve, Department of Chemistry, University

of Idaho, Moscow, ID

Fluorinated olefinic compounds have been of considerable interest for many years because of the presence

of the reactive vinylic fluorine atoms. Nucleophillic substitution of these vinylic fluorine atoms with

nitrogen-containing heterocyclic compounds can be used to carefully design compounds with desired

physical and chemical properties. Herein, we report the synthesis and characterization of a new family of

compounds in which mono-, di-, and multi-azole substituted fluorocyclic products were obtained in good to

high yields. This work involves nucleophilic substitution reactions of perfluorocycloalkenes with azoles

(i.e., imidazole, triazole) using simple reaction procedures. Interestingly, these azoles were later found to

be reactive not only with the vinylic but also with the allylic fluorine atoms. This resulted in the

substitution of up to six azoles on the fluorinated rings. Stoichiometry plays a key role in determining the

degree of substitution. For comparison, the analogous reactions of N- substituted, 1-(trimethylsilyl)-

imidazole and 1-(trimethylsilyl)-1,2,4-triazole, were also investigated.

72

Organic/Organometallic: Tatlow Memorial Session - III (Tuesday, 25th August)

Presider: David O'Hagan, University of St Andrews, St Andrews, United Kingdom

131. Efficient Preparation of (Phenylsulfonyl)Difluoromethyl Ketones and Imines, and Their Application in Organic Synthesis

Jinbo Hu, Chuanfa Ni and Laijun Zhang, Key Laboratory of Organofluorine Chemistry, Shanghai Institute

of Organic Chemistry, Shanghai, China

An efficient preparation of (phenylsulfonyl)difluoromethyl ketones was achieved by using nucleophilic

(phenylsulfonyl)difluoromethylation of esters with difluoromethyl phenyl sulfone under basic reaction

conditions. The chemical yields of the (phenylsulfonyl)difluoromethyl ketone products are generally high

(>80%). Upon acid-catalyzed condensation reactions with Ellman's N-tert-butylsulfinamide,

(phenylsulfonyl)difluoromethyl ketones can be converted to corresponding PhSO2CF2-containing N-tert-

butylsulfinimines (1). Unlike previously known CF3- and CF2H-containing N-tert-butylsulfinimines that are

moisture-sensitive, compounds 1 can be easily purified and stored at ambient temperature. We found that

sulfinimines 1 can undergo stereospecific [3 + 2] cycloaddition reactions with arynes to give

corresponding cyclic sulfoximines.

132. Preparation, NMR and X-Ray Structural Characterization and Computational Study of a Persistent α-Fluorocarbanion (FCA) and Its Analogues

G. K. Surya Prakash1, Fang Wang1, Nan Shao2, Thomas Mathew1, Golam Rasul2, Ralf Haiges3 and George

A. Olah1, (1)Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern

California, Los Angeles, CA, (2)Loker Hydrocarbon Research Institute, University of Southern California,

Los Angeles, CA, (3)Department of Chemistry, University of Southern California, Los Angeles, CA

The first preparation and X-ray structural characterization of a persistent α-

fluorobis(phenylsulfonyl)methide anion with different counter cations have been accomplished. X-ray

crystal structure of FCA with tetrabutylammonium counter cation adopts pyramidal configuration, which

agrees with theoretical studies on FCAs. High level theoretical calculations coupled with X-ray

crystallographic and NMR studies have shown that electron-withdrawing substituents play crucial role in

modulating the properties of bis(phenylsulfonyl)methide anions.

133. A New Method for the Oxidative Desulfurization/Fluorination of Aryl Thioethers

Günter Haufe, Verena Hugenberg and Anil K. Podichetty, Organisch-Chemisches Institut, Universität

Münster, Münster, Germany

The difluoromethyl group in organic molecules gains considerable interest for biochemical and medicinal

purposes. This group is anticipated to be bioisosteric with a carbonyl group. Indeed several compounds

bearing this moiety are potent enzyme inhibitors.1 Recently, we communicated a new synthetic pathway

towards terminal geminal difluorides.2

We will now report on the extension of this fast and selective method for the introduction of one, two, or

three fluorine atoms by an oxidative desulfurization/fluorination technique starting from alkyl aryl

thioethers. Thus, treatment of thioethers 1 with DBH and Olah's reagent, depending on the equivalents of

the electrophile, the fluorinating reagent and the reaction conditions leads preferably to either the terminal

difluorides 2 or the geminal bromofluoro compounds 3 bearing different substituents in ω-position.

Similarly, polyfluoro substituted compounds of biological interest can be prepared.

73

The reaction mechanism as well as the scope and limitations of this new method will be discussed in detail.

1. J. T. Welch, Tetrahedron 1987, 43, 3123-3197.

2. V. Hugenberg, G. Haufe, Synlett 2009, 106-108.

134. Palladium-Catalyzed C-F Activation in Suzuki-Miyaura Cross-Coupling Reactions of Polyfluoronitrobenzene Derivatives

Matthew R. Cargill1, Graham Sandford1, Andrzej J. Tadeusiak1 and Pinar Kilickiran2, (1)Chemistry,

Durham University, Durham, United Kingdom, (2)Materials Science laboratories, SONY Deutschland,

Stuttgart, Germany

Palladium-catalyzed cross-coupling reactions have been the subject of intense research over the past

decade because of the variety of synthetically useful carbon-carbon bond forming reactions that may be

achieved in high yield, regioselectivity and under mild conditions. In general, the electrophilic species in

many palladium-catalyzed processes are aryl iodides and bromides because of the low carbon-halogen

bond strength that facilitates the oxidative addition step, whereas aryl chlorides are used less frequently.

Analogous reactions involving aryl fluorides as substrates that requires C-F bond activation are even more

difficult due to the high carbon-fluorine bond strength and the lack of suitable metal catalysts, but

recently, several groups have reported stoichiometric C-F bond activation involving partially and

completely fluorinated arene systems using a number of transition metal complexes. In this presentation,

we report successful Suzuki-Miyaura coupling of perfluoro- and polyfluoro-arene substrates, such as

pentafluoronitrobenzene, with a number of arylboronic acids and esters using conventional palladium

catalyst systems and reaction conditions.

74

ISoFT'09-IV (Tuesday, 25th August) Presider: Eric G. Hope, University of Leicester, Leicester, United Kingdom

135. Out of the Frying Pan and into the Frog: Fluorous Proteins Meet Bio-Active Peptides

E. Neil G. Marsh, Lindsey M. Gottler, Hwang-Yeol Lee, Benjamin C. Buer, Roberto de la Salud-Bea and A.

Ramamoorthy, Department of Chemistry, University of Michigan, Ann Arbor, MI

Fluorocarbons are a quintessentially man-made class of molecules – fluorine being nearly absent from

biology – that possess novel and useful physicochemical properties, typified by the non-stick nature of

polytetrafluoroethylene (better known as Teflon). Can biology benefit from embracing fluorine more

widely? By replacing hydrophobic amino acid residues with extensively fluorinated analogs we have been

able to modify the properties of de novo-designed model proteins in a predictable manner. This has led to

the design of proteins with enhanced thermal and chemical stabilities. We have extended this strategy by

introducing fluorous amino acids into bio-active peptides, thereby modulating their biological activity.

Fluorinated bio-active peptides are also promising as sensitive probes of chemical environment to monitor

the interactions of peptides with their target biological macromolecules by 19F NMR.

136. Fluorous Racemic Mixture Synthesis of Non-Proteinogenic Chiral Fluorinated Amino Acids

Tomoko Yajima1, Takayuki Tonoi1, Yuichi Tomita2, Hajime Nagano1 and Koichi Mikami2, (1)Department

of Chemistry, Ochanomizu University, Tokyo, Japan, (2)Department of Applied Chemistry, Tokyo Institute

of Technology, Tokyo, Japan

Fluorine-containing amino acid derivatives have recently received much attention in materials science and

medicinal chemistries. Here we report efficient methods for the synthesis of fluorinated a-amino acids and

peptides by perfluoroalkyl radical addition using fluorous technology.

We have already uncovered that photoinduced iodoperfluoroalkylation of acrylic ester derivatives can be

applied to an efficient synthesis of perfluoroalkylated a-amino acid derivatives. A variety of racemic

iodoperfluoroalkylated products, which are precursors of fluorine-containing amino acids and dipeptides,

bearing different length of perfluoroalkyl chains were separated respectively into their enantiomers and

diastereomers by virtue of the orthogonal use of fluorous and chiral HPLC columns. We also tried a direct

synthesis of fluorinated chiral amino acids by perfluoroalkyl radical additions to dehydroamino acid

derivatives.

137. Stereocontrolled Synthesis of Oligodeoxyribonucleoside Phosphorothioates Using Light Fluorous Chemistry

Takeshi Wada, Ryosuke Murakami, Tomoaki Kondo and Natsuhisa Oka, Department of Medical Genome

Sciences, The University of Tokyo, Kashiwa, Japan

In recent years, a great deal of attention has been focused on nucleic acids as therapeutic agents for

selective inhibition of gene expression. Oligonucleotide therapeutic agents such as antisense DNAs,

ribozymes, and siRNAs act on the target mRNAs and arrest the protein synthesis. In order to meet the

glowing demands for these relatively short oligonucleotides, a completely new method for the large-scale

synthesis of DNA and RNA should be developed. Under these circumstances, we have focused on the light

fluorous chemistry and its application to the solution-phase synthesis of nucleic acids. In this paper, we

wish to describe a novel oxazaphosphoridine method for the synthesis of stereodefined

oligodeoxyribonucleoside phosphorothioates (PS-ODNs) using a light fluorous chemistry.

75

138. Oligosaccharide Synthesis with Fluorous Tags

Mamoru Mizuno, Kohtaro Goto, Hiroko Kawakami, Mami Tojino and Kenji Osumi, Laboratory of Glyco-

organic Chemistry, The Noguchi Institute, Tokyo, Japan

Oligosaccharides on cell surfaces play important roles in biological processes, such as cell recognition, cell

adhesion, immunogenic recognition, and so on. To study these roles, efficient synthesis of oligosaccharide

is required.

Herein we will describe the rapid syntheses of oligosaccharides and monosaccharide units, which are

building blocks of oligosaccharide through the use of various heavy fluorous tags and fluorous liquid-liquid

extraction (F-LLE) method. This fluorous carbohydrate synthesis was demonstrated in microreactor

including F-LLE microfluidic extraction system.

Additionally, the synthesis of an oligosaccharide library by a fluorous mixture synthesis (FMS) will be

presented.

139. Incorporation of Fluorous Glycoside in Cell and Oligosaccharide Production

Kenichi Hatanaka1, Maria Carmelita Z. Kasuya1, Shinya Nakano1, Mami Tojino2 and Mamoru Mizuno2,

(1)Institute of Industrial Science, The University of Tokyo, Tokyo, Japan, (2)Laboratory of Glyco-organic

Chemistry, The Noguchi Institute, Tokyo, Japan

Largely fluorinated ―fluorous‖ compounds are usable for synthetic reaction, purification, and

immobilization. In this study, we investigated biochemistry of fluorous compounds. Oligosaccharide with

(fluoroalkyl)alkyl chain such as (perfluorooctyl)propyl lactoside was added to the cell culture medium.

Fluorous oligosaccharide was taken into the cell, transported to golgi apparatus, and glycosylated by

endogenous sugar nucleotide (glycosyl donor) with glycosyl transferase (enzyme). The saccharide-

elongated compounds were produced from the cell to the culture medium. However, the yield of products

depended on the content of fluorine atoms. We had first of all to investigate the incorporation process into

the cell membrane. Since the cell membrane is very complex, the incorporation of the fluorous lactoside

into liposome of which the size is similar to the cell. The hydrophobicity of fluoroalkyl chain was estimated

from the values of CMC (critical micelle concentration). The increase of hydrophobicity of fluoroalkyl

lactoside resulted in the increase of incorporation into the liposome. Saccharide elongation of fluorous

lactosides which contain polyethylene glycol spacers were also examined.

Organic/Organometallic (25th August, Tuesday afternoon)

Presider: G. K. Surya Prakash Loker Hydrocarbon Research Institute, University of Southern California,

Los Angeles, CA

140. Fluorocyclizations: Problems and Solutions

Veronique Gouverneur, Department of Chemistry; Chemistry Research Laboratory, University of Oxford,

Oxford, United Kingdom

The ability of fluorine to alter the physical and chemical properties of organic molecules has been used in

the design of fluorine-containing bioactive compounds. Rapid and efficient protocols for the preparation of

fluorinated compounds are therefore in high demand. As part of our continuing investigations into novel

fluorination methodology, we have developed novel approaches for the stereoselective construction of C-F

bonds using organosilanes as our starting materials. To date, vinylsilanes, allylsilanes and allenylsilanes

were fluorinated to deliver fluoroalkenes, allylic fluorides and propargylic fluorides respectively. We will

present the state of play of this chemistry and how it has progressed towards the development of novel

cascade fluorination-cyclization processes.

76

141. Thiophilic Reactions of Fluorinated Sulfur Containing Heterocycles

Viacheslav A. Petrov, DuPont CR&D, Wilmington, DE

This presentation will cover an interesting type of the reactions of polyfluorinated sulfur containing

heterocyclic materials, involving attack of soft nucleophiles on the sulfur of heterocycle. Although this

type of reaction is quite common for thiocarbonyls compounds, examples of this reaction involving cyclic

sulfides are very rare. We have found that 2,2-bis(trifluoromethyl)-alkoxythietanes can be converted into

either 1,2- or 1,3- dithiolanes, depending on reaction conditions. Also, treatment of thietanes with certain

phosphines leads to the formation of the corresponding 1,1-bis(trifluoromethyl)2-alkoxycyclopropanes.

The mechanism, scope, and limitations of these new reactions will be discussed in the presentation.

142. New Azido-Tetrazoles: Transformation of CF3N=N- Into the 5-Azido-Tetrazolyl-

Imino Group

Takashi Abe, Guo-Hong Tao, Young-Hyuk Joo, Brendan Twamley and Jean‘ne M. Shreeve, Department of

Chemistry, University of Idaho, Moscow, ID

The synthesis of energetic heterocyclic compounds has attracted considerable interest in recent years,

especially for the syntheses and applications of new members of heterocyclic-based energetic

materials.[1] High-nitrogen compounds constitute a unique class of energetic materials. The high heats of

formation are directly related to the large number of energetic N-N, N-C, and N-O bonds.[2] Therefore,

new methodologies for the ready introduction of high-nitrogen groups into molecules are important for the

development of high energetic compounds. We have found that the trifluoromethylazo group (CF3-N=N-R)

reacts with sodium azide via a hydrazono intermediate giving rise to the (5-azido-1H-tetrazol-1-yl)-imino

group when the substituent alkyl group contains a hydrogen atom at the α carbon. Based on this new

method, high nitrogen compounds consisting of mono- and diazido-tetrazoles were prepared from

compounds which contained one or more CF3-N=N- group(s). For example, new 5-azido-tetrazoles, 2a–g,

were obtained in good yields from the corresponding trifluoromethyl-azo-alkanes (1a–g), respectively.

Reaction mechanisms involving the activation of the C-F bond and properties of new type of high energetic compounds are discussed.

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143. 5-Endo-dig Cycloisomerization of 2-Fluoro-Alk-3-Yn-1-Ones: Synthesis of 3-Fluorofurans

Yan Li and Roman Dembinski, Chemistry, Oakland University, Rochester, MI

Numerous cycloisomerizations reactions are known, but protocols leading to fluoroaromatic compounds

are scarce. 5-Endo-dig electrophilic cyclization of 1,4-substituted 2-fluoro-but-3-yn-1-ones provides 3-

fluoro-2,5-diarylfurans in high yields. The key for this methodology is secured in the synthesis of 2-

monofluoro-butynone, since regular fluorination of non-fluorinated butynone leads to its 2,2-

difluoroderivative. The results of this work provide new cycloisomerization preparative options.

144. Synthesis and Reactions of Difluoro(methylene)Cyclopropanes

Ji-Chang Xiao Sr., Xiao-Chun Hang and Qing-Yun Chen, Key Laboratory of Organofluorine Chemistry,

Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China

Methylenecyclopropane derivatives (MCPs), which are relatively stable but highly strained molecules, have

attracted chemists‘ attention for their remarkable chemical reactivities over the past decades. However,

difluoro(methylene)cyclopropanes (F2MCPs), the fluorinated analogues of MCPs, have been less studied

due to the difficulties in synthesis. Using FSO2CF2CO2Si(CH3)3 (TFDA) as the difluorocarbene source, we

found that difluoro(methylene)cyclopropanes (F2MCPs) could be readily prepared by the reaction of

difluorocarbene with 1,2-allenes. The corresponding F2MCPs could undergo a variety of reactions including

ring-opening, rearrangement, cycloaddition reactions, etc.

Inorganic/Organometallic: (25th August, Tuesday afternoon)

Presider: Wojciech Grochala The University of Warsaw, Warsaw, Poland

145. Sol Gel Synthesis of HS-MgF2: Synthesis, Properties and Applications

Erhard Kemnitz, Department of Chemistry, Humboldt-University Berlin, Berlin, Germany

The fluorolytic sol gel synthesis of nanoscopic metal fluorides has been developed by our group over the

past 6 years. The principle consists in the reaction of a metal alkoxide with anhydrous HF in alcoholic

solution resulting in an OR against F exchange (fluorolysis)

M(OR)n + n HF ® MFn + n ROH

that results in metal fluoride sols which – under appropriate conditions – can be converted into nanoscopic

pure Lewis acidic metal fluorides with a very high surface area [1-3].

This talk will focus on synthesis, properties and applications of HS-MgF2. Whereas crystalline MgF2 is

neutral, nanoscopic HS-MgF2 exhibits medium strong Lewis acidic surface sites. Surface areas range from

200 up to 500 m2 g-1. By modifying the synthesis approach (usage of either understochiometric amounts

of HF or aqueous HF), nanoscopic metal (hydroxide fluorides are accessible which might either act as

Brønsted acids or bases. Thus, new solid fluoride based catalysts are accessible with tuneable surface

properties and exciting new catalytic properties.

An alternative field of application becoming accessible based on transparent MgF2-sols is the manufacture

of transparent, low refractive index coatings being of high interest, e.g. for optical lenses and solar panels.

78

Along with phyisico-chemical property data, examples for catalytic applications and comprehensively

characterized optical layers will be presented.

[1] E. Kemnitz, U. Groß, St. Rüdiger, S.C. Shekar, Angew. Chem. Int. Ed. 42 (2003) 4251;

[2] S. Rüdiger, U. Groß, E. Kemnitz, J. Fluorine Chem. 128 (2007) 353.

[3] S. Rüdiger, E. Kemnitz, Dalton Trans. (2008) 1117.

146. Platinum Complexes in Super-Acetic Solutions

Roland Friedemann and Konrad Seppelt, Institut für Chemie und Biochemie, Anorganische Chemie, Freie

Universität Berlin, 14195 Berlin, Germany

C2H4[(CF3)2P]2 Pt (CH3)2 (1) reacts in super-acetic solution of HF/SbF5 at 210 K forming C2H4[(CF3)2P]2 Pt

(SbxF5x+1)2 (x = 1 or 2).

1 reacts with an excess AsF5 in a HF-solution to give C2H4[(CF3)2P]2 Pt (AsF6)2 quantitatively. If AsF5 is

used in stoichiometric deficiency a binuclear platinum complex bridged by two fluorine atoms is formed,

which is crystallographic characterized (see plot).

147. Poly[Perfluorotitanate(IV)] Salts of Single Charged Cations

Zoran Mazej and Evgeny Goreshnik, Department of Inorganic Chemistry and Technology, Jozef Stefan

Institute, Ljubljana, Slovenia

Previous attempts to prepare Ti(IV) compounds with isolated [Ti2F9]- anions failed.[1] Crystal structure

determination of Me4N+ and Ph4P

+ salts showed that both compounds are not [Ti2F9]- but [Ti4F18]

2- salts

(i.e. [Me4N]2[Ti4F18] and [Ph4P]2[Ti4F18]).[1] Smaller cations as [H3O]+ and Cs+ formally gave [Ti2F9]- salts,

however instead of isolated [Ti2F9]- anions, infinite [Ti2F9]n

n- chains are present.[1]

In 1976 it was reported that reactions between TiF4 and an excess of XeF6 at 60 oC yielded products with

compositions 4XeF6·TiF4, XeF6·TiF4, and XeF6·2TiF4.[2] Investigations of reactions between XeF6 and TiF4 in

anhydrous hydrogen fluoride (aHF) showed that two [XeF5]+ salts and one or two [Xe2F11]

+ salts could be

isolated. The former are [XeF5]3[Ti4F19] (3XeF6·4TiF4) and [XeF5][Ti3F13] (XeF6·3TiF4), meanwhile the

compositions of the [Xe2F11]+ salts remain unknown. The crystal structure of [XeF5]3[Ti4F19] consists from

79

[XeF5]+ cations and, previously unknown, isolated [Ti4F19]

3- anions. The crystal structure of [XeF5][Ti3F13]

is built from [Ti3F13]nn- layers and [XeF5]

+ cations placed between them.

Additionally, the products in the systems XeF6/MF4/aHF (M = Sn, Pb) were investigated. The crystal

structure determination of 4XeF6·PbF4 showed that its crystal structure consists from [Xe2F11]+ cations and

[PbF6]2- anions (i.e. [Xe2F11]2[PbF6]).

1. Z. Mazej, E. Goreshnik, 19th Winter Fluorine Conference, St. Pete Beach, Florida, 2009, Abstract Book.

p. 31.

2. B. Žemva, J. Slivnik, M. Bohinc, J. Inorg. Nucl. Chem. 38 (1976) 73-74.

148. Uranium and Beryllium Fluorides In Liquid Ammonia

Florian Kraus, AG Fluorchemie, Technische Universität München, Garching, Germany

Green Salt UF4 is a key compound in the synthesis of uranium hexafluoride UF6. Uranium nitride UN is

expected to be superior to the conventional UO2, and is seen as a promising nuclear fuel for the fourth

generation nuclear reactors. It is currently synthesized at temperatures above 1100 °C from UO2, and the

product often contains carbidic or oxidic impurities, which include problematic nuclei.

Obviously, a more direct pathway towards uranium nitrides could use reactions between UF6 and NH3.

Studies of the reaction of UF6 with NH3 were reported 51 years ago for the first time. The products were

assumed to be UF5 and NH4UF5 based on observation of their colors and elemental analyses data.

In our own studies of the reactions of UF6 and UF4 with liquid ammonia we obtained signal-green

tris(ammonium) monammine heptafluorouranate(IV) ammonia, (NH4)3[UF7(NH3)] · NH3 and emerald-

green tetraammine tetrafluorouranium(IV) ammonia, [UF4(NH3)4] · NH3 as the products in almost

quantitative yields and were thus able to finally clarify the course of the reactions of these uranium

fluorides with liquid ammonia. To the best of our knowledge the compounds represent the first

characterized ammonia complexes of uranium fluorides.

Beryllium difluoride BeF2 reacts with liquid ammonia forming diammine difluoro beryllium(II) [BeF2(NH3)2]

molecules. The colorless compound crystallizes in the monoclinic space group P21/c with a = 4.8815(2),

b = 6.8528(3), c = 10.3690(5) Å, β = 92.008(5)°, V = 346.65(3) Å3 at 123 K with Z = 4. [BeF2(NH3)2] is

the first structurally characterized example of a beryllium−ammonia complex. The compound has been

characterized further by Raman, IR, and DTA-TG measurements and by quantum chemical ELF, AIM and NBO calculations.

149. Nanostructured Metal Fluorides with High Surface Areas

Tomaž Skapin, Gašper Tavcar, Andreja Bencan and Zoran Mazej, Jožef Stefan Institute, Ljubljana,

Slovenia

In the last ten years, high surface (HS) area and/or nano-structured metal fluorides received considerable

attention. Impressive progress achieved specially in the last five years is the result of the development of

new preparation procedures to HS metal fluorides: (i) plasma fluorination, (ii) non-aqueous sol-gel route

and (iii) oxidative decomposition of inorganic precursors. Among these three, sol-gel procedure was most

extensively investigated due to its versatility. On the other side, plasma fluorination and oxidative

decomposition represent an inorganic alternative to the sol-gel process and enable the preparation of

complementary HS fluorides that, for example, are not contaminated with carbon residues.

A short overview of the oxidative decomposition route, developed in our laboratory, will be given.

Oxidative decomposition allows the preparation of AlF3 or CrF3 with very high surface areas up to 300 m2g-

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1. Recent investigations of the nano structure showed some distinctive differences between these two HS

fluorides. CrF3 is completely amorphous while AlF3 consists of an amorphous phase and of nanocrystalline

α-AlF3 and β-AlF3 phases. The later phase forms nano-rods 5-10 nm wide (Figure 1).

Figure 1: TEM micrograph of β-AlF3 nano-rods in AlF3 with high surface area

Poster Session Including ISoFT'09: (Wednesday, 26th August)

Presider: Olga V. Boltalina, Colorado State University, Fort Collins, CO

Presider: John Gladysz, Texas A&M University, College Station, TX

78. Synthesis and Complexes of Heptafluoroisopropyldiphenylphosphine

Lesley Lewis-Alleyne1, Makeba B. Murphy-Jolly2, Andrew J. M. Caffyn1 and Xavier F. Legoff3,

(1)Department of Chemistry, The University of the West Indies, St Augustine, Trinidad and Tobago,

(2)Department of Chemistry, University of Alabama-Birmingham, Birmingham, AL, (3)Laboratoire

Hétéroéléments et Coordination, Ecole Polytechnique, CNRS, F-91128 Palaiseau Cedex, France

Perfluoroalkylphosphines, of interest as tunable alternatives to the carbon monoxide ligand, have been

synthesized, including the new phosphine heptafluoroisopropyldiphenylphosphine, which contains a

branched-chain perfluoroalkyl group. Crystal structures of this novel ligand, as well as metal complexes of

the phosphine have been obtained.

150. Regioselective Synthesis of Trifluoromethyl Group Substituted Allylic Amines Via Palladium-Catalyzed Allylic Amination

Motoi Kawatsura, Takuya Hirakawa, Daiji Ikeda, Hiroshi Ogasa, Tomoko Tanaka and Toshiyuki Itoh,

Department of Chemistry and Biotechnology, Tottori University, Graduate School of Engineering, Tottori,

Japan

We have demonstrated the regioselective formation of both the α- and γ-trifluoromethyl group-substituted

allyl amines via the palladium catalyzed allylic amination of α-trifluoromethylated allyl acetate. The

conventional γ-product was obtained using the Pd(OAc)2/DPPE catalyst, and the unusual α-product was

obtained using the [Pd(π-allyl)(cod)]BF4/DPPF catalyst. We also revealed that the γ-product was easily

81

isomerized to the α-product under the [Pd(π-allyl)(cod)]BF4/DPPF catalyzed reaction conditions, then

concluded that the α-product was formed by isomerization of the γ-product.

151. A New Method for the Synthesis of Novel 2-Fluoro-3-Phenylthio-1,3-Butadiene and Its Diels-Alder Reactions In Howa Jeong, Yeon Hui Jung and Kamaldeep Paul, Department of Chemistry, Yonsei University, Wonju,

South Korea

Novel 2-fluoro-3-phenylthio-1,3-butadiene 5 was prepared in 77% yield from the reaction of 1-bromo-3-

fluoro-2-phenylthio-2-butene 3 with t-BuO-K+ in THF at room temperature. Alternatively, 5 can be

prepared in 90% yield from the reaction of 1,4-dibromo-2-fluoro-3-phenylthio-2-butene 4 with Zn dust(2

equiv)/NH4Cl(6 equiv) in CH3OH at room temperature. The precursors 3 and 4 were synthesized from the

reaction of 2-fluoro-3-phenylthio-2-butene 2 with NBS/AIBN in benzene at reflux temperature for 6 hours

in 60% and 72% yields, respectively, in which 1.5 equiv of NBS for 3 and 3 equiv of NBS for 4 were used.

The compound 2 was prepared from the treatment of 1 with 6 equiv of MeLi in ether at -78 oC, followed

by stirring at 0 oC for 1 hour.

Diels-Alder reactions of 5 with tetracyanoethylene, 3-buten-2-one, acrolein, p-benzoquinone and N-

phenylmaleimide in the presence of BF3.Et2O at room temperature for 1-3 days provided the

corresponding cyclized products 6 in 51-77% yields, whereas dienophiles such as maleic anhydride, 2-

chloroacrylonitrile, methyl acrylate, acrylonitrile, 2,3-dichloro-5,6-dicyano-p-benzoquinone and dimethyl

acetylenedicarboxylate were not reacted with 5 under the same reaction condition. The scope and

limitation of the synthesis of 5 and its Diels-Alder reactions will be presented.

152. Preparation of Novel 1,1-Difluoro-2-Phenylsulfonyl-1,4-Enynes and Their Reactions

In Howa Jeong and Ji Hye Hwang, Department of Chemistry, Yonsei University, Wonju, South Korea

Novel 1,1-difluoro-2-phenylsulfonyl-1,4-enynes 6 were prepared in 4 steps from trifluoromethylated

dithioketal 1. The reaction of 1 with a mixture of TiCl4(2 equiv) and LiAlH4(3 equiv) in THF at reflux for 3

hours afforded 1,1-difluoro-2-phenylthiopropene 2 in 78% yield. Bromination reaction of 2 with NBS(1.2

equiv)/AIBN in CH3CN at reflux for 3 hours provided the regioisomers 3 and 4 in 58% and 24% yields,

respectively. Treatment of 3 with alkynyllithium reagents in THF at -35 oC for 3 hours resulted in the

formation of 1,1-difluoro-2-phenylthio-1,4-enynes 5 in 45-85% yields via SN2' type allylic substitution.

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Oxidation of 5 with MCPBA(2.5 equiv) in CH2Cl2 at reflux for 1 hour yielded the enynes 6 in 80-87%

yields. In contrast to the reaction of 3 with alkynyllithium reagents, the treatment of 4 with

alkynyllithium reagents resulted in the formation of the messy reaction mixture.

Reaction of 6a with NBS(4 equiv)/AIBN in CH3CN at reflux for 6 hours gave the brominated product 7 in

78% yield. When 6a was treated with sodium thiophenoxide in THF at room temperature for 2 hours, the

phenylthio substituted product 8 was obtained in 82% yield as an E and Z isomeric mixture. The scope

and limitation of the reactions of 6a with nucleophiles and electrophiles will be presented

153. Biophysical Aspects of Single Fluoroamino Acid Substitutions within the Natural Environment of a Coiled Coil Peptide

Mario Salwiczek, Toni Vagt and Beate Koksch, Department of Biology, Chemistry and Pharmacy -

Institute of Chemistry and Biochemistry, Freie Universität Berlin, Berlin, Germany

Systematic investigations of the molecular interactions of fluorinated amino acids within model protein

environments substantially improve our understanding of the unique properties of these building blocks

and may help pave the way to diverse applications in peptide and protein engineering. Because of its

predictable secondary and quaternary structure, the α-helical coiled coil serves as an appropriate model to

investigate the interactions of a wide variety of fluorinated amino acids within environments that are

either hydrophobic or hydrophilic, depending upon their position within the heptad repeat. We have

characterized four such amino acids, having different numbers of fluorine atoms, with respect to their

hydrophobicity and their effects on the hydrophobic core formation of a heterodimeric coiled coil model by

applying numerous biophysical methods (RP-HPLC, CD spectroscopy, FRET, analytical ultracentrifugation,

SPR, molecular dynamics). We demonstrate that the coiled coil imposes position-dependent conformations

onto the fluorinated side chains that in turn affect their packing and relative orientation with respect to

their native interaction partners. Furthermore, our results indicate that such packing effects, rather than

the bulk properties of the fluorinated side chains like polarity, are primarily responsible for the observed

differential thermodynamic stabilities of the peptide models. These data explain in part why fluorine‘s role

in the context of proteins remains difficult to generalize and predict.

83

154. Prevention of Defluorination in Grignard Reagent Preparation of 4-Bromobenztrifluoride Shinya Utsumi1, Toshimasa Katagiri2 and Kenji Uneyama2, (1)Department of Applied Chemistry,

Okayama University, Okayama, Japan, (2)Department of Applied Chemistry, Faculty of Engineering,

Okayama University, Okayama, 700-8530, Japan

Grignard reagent preparation of halogenated benzotrifluorides (especially 3- or 4-halogenated

benzotrifluoride) has a potential danger of a run-away reaction and resulted in low yield1c. This has been

attributed to highly exothermic defluorinative side reaction. Thus, a method to avoid defluorination has

been demanded for the safe and efficient preparation of the Grignard reagents.

Previously, we have presented selective in-situ Grignard reagent formation type silylation2 with

suppression of defluorosilylation3. The reaction in Mg/TMSCl reduction system of 4-chloro-1-

(pentafluoroethyl)benzene (1) gave Grignard reagent formation-type silylated product (2) in good yield

(85% of isolated yield). We have found that the use of less polar solvent is the key to prevent the

defluorination.

Then, we applied this optimized condition to the preparation of 4-(trifluoromethyl)phenylmagnesium

bromide and used for Grignard reaction of carbonyl compounds. A mechanism will be proposed and

discussed.

References

1. (a) R. Waymouth, E. J. Moore Chem.& Eng. News, 1997, 75, 6. (b) E. C. Ashby, D. M. Al-Feski J.

Organomet.Chem.,1990, 390, 275-292. (c) H. E. Ramsden, A. E. Balint, W. R. Whiteford, J. J. Walburn, R.

Cserr J. Org. Chem., 1957, 22(10), 1202-1206.

2. a) Effenberger, F.; Häbich, D.; Liebigs Ann. Chem., 1979, 842-857.

3. a)Y., Nakamura; K. Uneyama, J. Org. Chem. 2007, 72, 5894-5897.

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155. The Study about Surface Characterization of Perfluoropolyether(PFPE) Thin Film

YunMi NamKuong, Jong Wook Ha, Sang Goo Lee, In Jun Park and Soo Bok Lee, Korea Research Institute

of Chemical Technology, Daejeon, South Korea

Perfluoropolyether(PFPE) is widely used because of its low surface energy, high thermal oxidative stability

and low coefficient of friction. Recently, study will be demanded for the thin film because the PFPE have

industrial demand as good fouling resistance materials. In this work, Thin film of PFPE of average

molecular weight 500~2000 was deposited. And the surface properties according to molecular weight of

PFPE were studied by analysis of thin film properties using AFM, XPS and contact angle.

156. New Application of Chiral Auxiliary Fox : Highly Diastereoselective Hydroxylation Using O2

Hodney Lubin, Julien Pytkowicz, Gregory Chaume and Thierry Brigaud, Departement de Chimie,

Laboratoire SOSCO, Université de Cergy-Pontoise, Cergy-Pontoise, France

The trifluoromethylated oxazolidine Fox 1 is a very stable and readily made chiral auxiliary derived from

(R)-Phenylglycinol which has already proven itself to be very efficient for the alkylation of amide enolates.

This oxazolidine has also been used with great success for the α-hydroxylation of amides. The amide

enolates 2 derived from the oxazolidine are easily oxidized in the presence of O2 to give the α-

hydroxylamides 3 with an excellent diastereoselectivity. In comparison with the other methods of α-

hydroxylation commonly used, the advantages of our synthetic approach lie in the easiness of its

implementation, in the use of a very smooth oxidizing agent and most of all in its high diastereoselectivity.

After removal of the chiral auxiliary, 3 gives access to enantiomerically pure α-hydroxylated aldehydes,

acids and alcohols which are often hard to obtain.

85

157. Highly Diastereoselective Electrophilic Fluorination Using Fluorinated Oxazolidine (Fox) as Chiral Auxiliary

Hodney Lubin, Christophe Dupuis, Julien Pytkowicz, Gregory Chaume and Thierry Brigaud, Departement

de Chimie, Laboratoire SOSCO, Université de Cergy-Pontoise, Cergy-Pontoise, France

Over the past few decades, the preparation of chiral nonracemic fluorinated carbonyls has attracted a

great deal of attention. Among the developed methodologies, the electrophilic fluorination of a chiral

auxiliary based imide enolate remains the most efficient and selective. Our group recently developed a

novel fluorinated oxazolidine (Fox) based chiral auxiliary. Alkylation or hydroxylation of different amides

derived from 2-trifluoromethyl-4-phenyl-oxazolidine 1 occurred with almost complete diastereoselectivity.

Moreover, Fox chiral auxiliary allows the use of hindered amides or electrophiles.

In this poster we report the extension of the Fox methodology to the synthesis of enantiomerically pure a-

fluoro acids and aldehydes or b-fluoro alcohols by diastereoselective fluorination. Treatment of enolates

derived from various amides 2 with N-Fluorobenzenesulfonimide (NFSI) as electrophilic fluorinating agent

affords the a-fluoro amides 3 with an excellent diastereoselectivity. After removal of the chiral auxiliary

and consecutive oxydation or reduction of the intermediate a-fluoro aldehydes, corresponding

enantiomerically pure acids 4 or alcohols 5 are obtained. In each case the trans - Fox chiral auxiliary 1

was recovered in good yields.

158. Efficient Method for the Synthesis of Purine FPMP Derivatives

Ondrej Baszczynski, Antonin Holy, Martin Dracinsky and Blanka Klepetarova, Institute of Organic

Chemistry and Biochemistry AS CR, v.v.i., Prague, Czech Republic

N9-(3-fluoro-2-phosphonomethoxypropyl) (FPMP) derivatives1 of purine and pyrimidine bases were

described as potent and selective anti-retroviral agents2 [including human immunodeficiency virus type 1

(HIV-1) and type 2 (HIV-2)] but without any significant effect on RNA or DNA viruses. We finished our

recent structure-activity relationships study of N6-substituted FPMP derivatives of adenine and

86

2,6-diaminopurine3 and we have continued with the synthesis of additional derivatives with different

substituted purine moiety.

Methodology for preparation of fluorinated alcohol 3 was successfully simplified into three steps. Ring-

opening reaction of chiral glycidol 1 gives corresponding fluorohydrine 2 which was alkylated with

phosphonate synthon4 and detritylated. Obtained compound 3 was used for reaction with an appropriate

base to give 4. Intermediates 4 were further modified on purine moiety and phosphonate diesters to give

deprotected 5.

Study was performed as a part of research project of the Institute OZ40550506 of Organic Chemistry and

Biochemistry. It was supported by the Programme of Targeted Projects of Academy of Sciences of the

Czech Republic #1QS400550501, by the Centre of New Antivirals and Antineoplastics 1M0508 by the

Ministry of Education, Youth and Sports of the Czech Republic, by the NIH grant 1UC1AI062540-01 and by

Gilead Sciences and IOCB Research Centre.

1. Jindrich J., Holy A., Dvorakova H.: Collect. Czech. Chem. Commun. 1993, 58, 1645.

2. Balzarini J., Holy A., Jindrich J., et al.: Proc. Natl. Acad. Sci. USA. 1991, 88, 4961.

3. Baszczynski O., Holy A., Dracinsky M., Klepetarova B.: Collect. Czech. Sym. 2008, 10, 315.

4. Holy A.: Collect. Czech. Chem. Commun. 1993, 58, 649.

159. High Purity Separation of Hexafluoropropylene From Perfluorocarbons Gas Using Adsorption Process

EunKyoung Kim, Hyung Dal Lee, Jong Kuk Jung, Jong-Wook Ha, In Jun Park and Soo-Bok Lee, Korea

Research Institute of Chemical Technology, Daejeon, South Korea

In this study, we report the process for high purity separation of hexafluoropropylene (HFP) from

perfluorocarbons gas with HFP. An adsorbent composed of metal molecular sieve (average micropore

diameter of 5-11 Å) is used in this process. The change of purity of perfluorocarbons and separated HFP

were observed by gas chromatography (GC) analysis. Content of perfluoro-2-butyne and

hexafluoropropylene oxide in perfluorocarbons were effectively decreased by liquid phase adsorption, and

purity of separated HFP was increased up to 99.9 %. The comparison of separation performance according

to adsorbents and the characteristics will be described.

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160. The Preparation of Aliphatic α-Difluoro-β-Amino Esters Via Reformatsky Reaction

Taryn L. March1, Martin R. Johnston1 and Peter J. Duggan2, (1)School of Chemistry, Physics and Earth

Sciences, Flinders University, Adelaide, Australia, (2)Molecular and Health Technologies, CSIRO,

Melbourne, Australia

As part of our work on fluorinated β-amino acids, we sought to probe the effect mono and difluorination

has on the binding of substrates to the serine protease trypsin. As trypsin's active site is specific for

arginine, and to a lesser extent lysine, this required the synthesis of compounds of the type shown in

Figure 1.

Of the various ways to synthesise enantiomerically pure α-difluoro-β-amino compounds, the Reformatsky

reaction of bromodifluoroacetates with chiral imines is amongst the most common. Most examples in the

literature deal primarily with aromatic imines; the few examples using aliphatic imines are generally less

impressive due to their greater instability.

The use of sonication in the Reformatsky reaction can overcome the troublesome problem of zinc

activation, while the bromozinc reagent, which decomposes quickly at the high temperatures usually

required for these reactions, is also stable under sonicating conditions. When used in conjunction with

imines derived from the ethyl ester of 2-phenylglycine, a cheaper alternative to the commonly used 2-

phenylglycinol, a range of fluorinated β-amino esters were synthesised in good yield and

diastereoselectivity. Our efforts to optimise this Reformatsky methodology for aliphatic substrates will be

discussed.

161. Gold Catalysis in the Presence of Electrophilic Fluorinating Reagents

Matthew N. Hopkinson1, Andrew Salisbury1, Arnaud Tessier1, Antony D. Gee2 and Veronique

Gouverneur1, (1)Department of Chemistry; Chemistry Research Laboratory, University of Oxford, Oxford,

United Kingdom, (2)GSK Clinical Imaging Centre, Imperial College London, London, United Kingdom

The homogeneous catalysis of organic reactions by gold salts has received significant attention in recent

years. Soft and carbophilic in nature, gold has been shown to selectively activate unsaturated

functionalities such as alkynes, allenes and alkenes, leading to the development of a wide variety of

transformations under mild conditions.

Gold-catalysis has been successfully applied to the formation of carbon-halogen bonds. Fluoroalkenes

have been prepared via the nucleophilic fluorination of alkynes activated by gold(I) complexes. Carbon-

halogen bonds have also been prepared from gold-catalysed reactions carried out in the presence of

electrophilic sources of iodine, bromine and chlorine. In these processes, halogenation is thought to occur

via electrophilic attack on the halogen source by electron-rich organo-gold intermediates. Recently, by

performing a gold-catalyzed cyclization in the presence of Selectfluor®, our group has reported the first

example of an analogous electrophilic fluorination process, leading to trifluorinated pyranones.

88

More recent data on other gold-catalyzed transformations performed under similar conditions will be

reported. This study, aimed at evaluating the scope and limitations of ‗fluorodeauration' as a method of C-

F bond formation, led to the discovery of a novel reactivity profile not leading to fluorinated products.

162. Towards a New Class of Cationic Hypervalent Iodine Reagents for Electrophilic Trifluoromethylation

Katrin Niedermann, Jan M. Welch, Ján Cvengroš, Nico Santschi and Antonio Togni, Department of

Chemistry and Applied Biosciences, ETH Zurich, Zurich, Switzerland

Recently we developed a new class of electrophilic hypervalent iodine trifluoromethylation reagents 1,

which exhibit good to excellent reactivity towards a variety of nucleophiles. These reagents are

synthesized via oxidation, followed by a ligand exchange and the introduction of the CF3 group from

TMSCF3.

To improve the reactivity of the CF3 moiety towards nucleophiles, we outlined the synthesis to a new class

of hypervalent iodine reagents. According to the established procedure, new cationic iodane (III)

compounds 3 were synthesized, in which the oxygen of the former reagent is now replaced by a nitrogen-

donor.

If Y=Cl in compound 3, X-ray structures show, that the I-N-bond is elongated as compared to the I-O

bond in the analogous compounds. These results suggest an enhanced reactivity for the corresponding

hypervalent iodine CF3 reagent.

163. Asymmetric Reformatsky Reaction of Ethyl Iododifluoroacetate with Aromatic Ketones

Michal Fornalczyk and Alison M. Stuart, Department of Chemistry, University of Leicester, Leicester,

United Kingdom

One of the most challenging topics in organofluorine chemistry is the asymmetric introduction of fluorine

atoms, difluoromethyl and trifluoromethyl groups. Outstanding progress has been made in recent

years,[1] but further developments are necessary for chiral fluorinated molecules to be increasingly used

in medicinal, agricultural and material chemistry. Although the asymmetric Reformatsky reaction of ethyl

bromodifluoroacetate with aromatic aldehydes in the presence of chiral amino alcohols to give a,a-

difluoro-b-hydroxy esters in good enantiomeric excess is well established,[2-4] to the best of our

knowledge, the asymmetric Reformatsky reaction has not been reported with ketones.

Here, we will compare a convenient one-pot asymmetric Reformatsky reaction of ethyl iododifluoroacetate

using diethyl zinc to generate the Reformatsky reagent homogeneously with the classical two step

Reformatsky procedure using zinc dust with a series of aromatic ketones.

1. J.-A. Ma, D. Cahard, Chem. Rev., 2004, 104, 6119.

2. M. Braun, A. Vonderhagen, D. Waldmuller, Liebigs Ann., 1995, 1447.

3. J. M. Andrés, M. A. Martínez, R. Pedrosa, A. Pérez-Encabo, Synthesis, 1996, 1070.

4. R. J. Kloetzing, T. Thaler, P. Knochel, Org. Lett., 2006, 1125.

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164. New Approaches to Α,Α-Difluorinated Alkenes and Alkynes From a Common Difluoro Ester Building Block

Matthew L. Barchok, Paul Sampson and Alexander J. Seed, Department of Chemistry, Kent State

University, Kent, OH

Three new approaches for the synthesis of α,α-difluorinated alkenes and alkynes from readily available

difluoroester 1 are reported. A Wittig approach affords easy access to α,α-difluorinated alkenes 2 in good

yield, albeit with modest Z/E selectivity. A cross metathesis approach has proven successful at creating

simple (E)-alkenes 3 but has limited utility for substrates containing non-halo heteroatoms. A Corey-

Fuchs approach yields the dibromoalkene 4, bromoalkyne 5, and/or terminal alkyne 6 in varying amounts

depending on the reaction conditions. Each of these difluoromethylated compounds has promise as a

synthetic building block.

165. Regio- and Stereoisomeric Methyl 2,3-Fluorohydroxyalkanoates – Selective

Synthesis and Conformation Analysis

Wibke S. Husstedt, Susanne Wiehle, Christian Stillig, Klaus Bergander, Stefan Grimme and Günter

Haufe*, Organisch-Chemisches Institut, Universität Münster, Münster, Germany

The substitution of a C-H group by a C-F group causes dramatic changes of the physico-chemical

properties, of the chemical reactivity, and of the biological behavior. Besides the well-known similarities

between C-F and C-O-bonds, fluorine is able to form hydrogen bonds, which lead in case of fluoroethanol

in liquid phase to a preference of a gauche conformation. The same results have been observed both by

NMR spectroscopy and quantum chemical calculations for 2-fluoropropanol and trans-2-

fluorocyclohexanol. Conformations of fluorohydrins derived from long chain α,β-unsaturated fatty acid

esters are not known yet.

We report on selective syntheses of enantiopure regio- and diastereomeric methyl 2,3-fluorohydroxy-

alkanoates via four different routes employing two types of fluorination reagents. The anti- and syn-3-

fluoro-2-hydroxyalkanoates (1 and 3) were prepared by treating the corresponding epoxides with Olah‘s

reagent (Py·9HF). Cyclic sulfates prepared from the enantiomeric diols were opened with TBAF to give the

90

anti- and syn-2-fluoro-3-hydroxyalkanoates (2 and 4). The stereochemical analysis was performed mainly

by temperature dependent NMR spectroscopy. Applying DFT/B3LYP and SCS-MP2 quantum chemical

methods, the coupling constants and relative energies of conformers were calculated in order to confirm

the conformations. Solvent effects were considered using the COSMO continuum model.

166. Trifluoromethylated Metallic Nitride Endometallofullerenes

Natalia B. Shustova1, Yu-Sheng Chen2, Alexey A. Popov3, Mary A. Mackey4, Curtis E. Coumbe4, J. Paige

Phillips4, Steven A. Stevenson4, Steven H. Strauss1 and Olga V. Boltalina1, (1)Department of Chemistry,

CSU, Fort Collins, CO, (2)ChemMatCARS Beam Line, University of Chicago, Advanced Photon Source,

Argonne, IL, (3)Department of Chemistry, Moscow State University, Moscow, Russia, (4)Department of

Chemistry & Biochemistry, University of Southern Mississippi, Hattiesburg, MS

Preparative synthesis of fullerenes with encapsulated metal cluster opens the opportunities to use them

for the fundamental studies and potential practical applications (e.g., as MRI or X-ray contrast agents).1

Nearly all derivatizations of endohedral metallic-nitride fullerenes (MNFs) reported to date are

cycloadditions.2 Radical perfluoroalkylation reactions were chosen by us as an alternative approach to the

derivatizations of MNFs. The results of the high-temperature trifluoromethylation of Sc3N@C80 with CF3I,

demonstrates that Sc3N@C80(CF3)n compounds are very soluble as well as stable, and, in favorable cases,

are separable as single isomers by HPLC (this is in contrast to unmodified Sc3N@C80).3 We will also discuss

an improved method for the preparation of trifluoromethylated MNFs in a closed high-temperature reactor.

We have isolated and characterized a variety of polytrifluoromethylated MNFs in good yields, including

MNF derivatives with up to 16 CF3 groups per cage. All of the new compounds were studied by mass

spectrometry, 19F NMR and UV-Vis spectroscopy, and quantum-chemical calculations at the DFT level of

theory. In addition, we will present the first X-ray crystal structures of perfluoroalkylated MNFs, in which

there is either negligible or no endohedral atom disorder. For the first time, a correlation between the

number and locations of the perfluoroalkyl groups and specific orientations of the encapsulated metal

cluster can be experimentally demonstrated. 1 Iezzi, E. B. et al. Nano Lett. 2002, 2, 1187. 2 Cai, T. et al. J. Am. Chem. Soc. 2006, 128, 6486. 3 Shustova, N. B. et al. J. Am. Chem. Soc. 2007, 129, 11676.

167. Screening for Preferred Interaction Partners of Fluorinated Amino Acids Applying

Phage Display

Elisabeth Nyakatura, Toni Vagt and Beate Koksch, Department of Biology, Chemistry and Pharmacy -

Institute of Chemistry and Biochemistry, Freie Universität Berlin, Berlin, Germany

Structural modifications of peptides and proteins using non-natural amino acids provide the opportunity to

improve their biophysical and pharmaceutical properties as well as to modulate their biological activity.

The successful application of fluorine in the development of small molecule pharmaceuticals also motivates

the interest in using fluorine as a heteroatom in amino acid side chains. Since fluorine is absent in native

amino acids, it is especially desirable to discover fluorophilic environments within native protein

surroundings.

To this end, we applied the phage display technology in search for preferred interaction partners of four

different fluorinated amino acids using a heterodimeric α-helical coiled coil model system. The predefined

secondary and tertiary structure of the model allows to randomize the direct interaction partners of the

respective amino acid and therefore to select specific binders for fluorinated amino acids out of the pool of

the canonical amino acids.

91

We find that despite the polarity that is induced by partial fluorination of aliphatic amino acids these

building bocks preferably interact with hydrophobic side chains within the hydrophobic core of the coiled

coil.

168. Palladium-Catalyzed Carbonylation of Trifluoromethylated Arenes and Heteroarenes Using a Water-Soluble, Air-Stable Phosphine Ligand System

Matthew D. Hennek, William S. Brown, Joseph S. Thrasher and Kevin H. Shaughnessy, Department of

Chemistry, The University of Alabama, Tuscaloosa, AL

Palladium-catalyzed alkoxycarbonylation of aryl and heterocylic bromides, iodides, and triflates is a

mature field of chemistry. Most of these systems use low catalyst loading, moderate temperatures, and

low carbon monoxide pressures. The main drawbacks are these systems typically either do not perform

well or at all with aryl chlorides, use air sensitive phosphines, and the palladium-ligand system is difficult

to purify away from the product. The resulting difficulty in purifying the product away from the catalyst

creates limited use toward industrial commercialization due to elevated ppm levels of potentially toxic

palladium in the product. Reported here is a water-soluble, air-stable phosphine ligand system that is

capable of reacting with aryl bromides and even the less reactive chlorides. Additionally, due to its' water

solubility, the present system offers the benefit of simple recovery and potential for recyclability of the

catalyst after completion of the reaction. Using this chemistry, we have been able to prepare a variety of

trifluoromethyl picolinic acids as well as esters in good to excellent yield using trifluoromethyl-bromo

pyridines as well as the less expensive trifluoromethyl-chloro pyridines. We have also demonstrated that a

number of other trifluoromethyl-halo aromatics demonstrate good reactivity and give good to excellent

yields of the desired products. Moreover, the current route to many of these products uses less harsh

conditions than traditional syntheses would have offered.

169. Fluorous Technology in the Context of Fluorine-18 Radiochemistry

Sophie Boldon1, Veronique Gouverneur1 and Jane E. Moore2, (1)Department of Chemistry; Chemistry

Research Laboratory, University of Oxford, Oxford, United Kingdom, (2)AstraZeneca, Macclesfield, United

Kingdom

Fluorous technology exploits the unique separation properties of highly fluorinated molecules to aid the

rapid purification of target compounds. Conventional detagging strategies of fluorous-tagged species are

most often traceless reactions. A more challenging approach is to take advantage of the detagging process

to functionalize the end-product. To investigate this approach, a range of light fluorous-tagged

organosilanes has been prepared and a novel detagging process validated. Cross-metathesis of a light

fluorous-tagged allylsilane afforded more elaborate organosilanes and their subsequent electrophilic

fluorodesilylation resulted in the cleavage of the fluorous tag with concomitant formation of an allylic

fluoride. This detagging process features an unprecedented C-F bond forming reaction. The results of this

study will be presented in detail. Radiochemistry applications, particularly in the area of positron emission

tomography (PET), could be envisaged where fast purification strategies are highly desirable for the

production of short half-life fluorinated 18F-radiotracers. The combination of a fluorous-tagged precursor

and a detagging event featuring a C-F bond forming reaction could permit the rapid synthesis and

purification of 18F-labelled building blocks. It is envisioned that both nucleophilic and electrophilic routes to 18F-labelled tracers are feasible. Our results validating the fluorodetagging approach will be disclosed as

well as a novel strategy employing 18F-labelled prosthetic groups and a suitable coupling partner tagged

with a fluorous linker to build 18F-labelled radiotracers.

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170. Palladium-Catalyzed Heck Reaction in Supercritical Carbon Dioxide Using Novel Fluoro-Ponytailed Bipyridine

Yi-Chuan Chen, Wen Han Tu and Jhong Wei Wu, Department of Molecular Science and Engineering,

National Taipei University of Technology, Taipei, Taiwan

Palladium-catalyzed Heck reactions have previously been studied under fluorous biphasic system (FBS)

conditions and thermomorphic mode. These results showed that Heck reactions carried out under

thermomorphic mode were better than those under FBS conditions in terms of efficiency and solvent

usage. Under thermomorphic mode, excellent catalytic efficiency and recycling 8 times could be easily

achieved, although a high reaction temperature (ca 140ºC) was required. Thus, the Heck reaction of

iodobenzene and methyl acrylate was also investigated with the same Pd catalysts under supercritical CO2

(ScCO2) at 80ºC. During the condition of ScCO2 media, we find that the catalysts are insoluble in the

organic phase in the absence of CO2, and the reaction occurs in a solid-liquid biphasic system. When the

organic liquid mixture is pressurized by CO2, CO2 is dissolved into the organic phase and this promotes the

dissolution of Pd catalysts. As a result, the Heck reaction occurs homogeneously in the organic phase,

which enhances the rate of reaction. This positive effect of CO2 pressurization competes with the negative

effect of reactant dilution by an increasing amount of dissolved CO2. After the reaction, it is possible to

recover and reuse catalyst without loss of activity. Therefore, by using ScCO2 conditions we not only carry

out solvent-free Heck reactions, but also are able to overcome the shortcomings of the high reaction

temperature (140ºC) needed for Pd-23F-catalyzed Heck reactions under thermomorphic mode.

171. Synthesis, Structure and Electrochemical Properties of Novel Metal (M= Pt, Pd) Dichloride-2,2′-Bipyridine with 4,4′-Bis(fluorous-ponytail)

Chien-Ting Lin, Jia-Sheng Shing and Chieh-Keng Li, Department of Molecular Science and Engineering,

National Taipei University of Technology, Taipei, Taiwan

Two novel fluorous-ponytailed bpy ligands, 4,4′-bis(RfCH2OCH2)-2,2′-bpy [Rf= n-C3F7 (1a), HCF2(CF2)3

(1b)], were prepared and treated with MCl2 (M = Pt or Pd) to result in the corresponding metal complexes,

[MCl2(4,4′-bis(RfCH2OCH2)-2,2′-bpy)], (2a-b M = Pt; 3a-b M = Pd). Both ligands and metal complexes

were fully characterized by multi-nuclei NMR (1H, 19F and 13C), FTIR, and mass (GC/MS or HR-FAB)

methods. The X-ray structures of 2a-b and 3a-b were studied. These four complexes (2a-b, 3a-b)

represent an unusual class of complexes with fluorous O-alkylated bipyridyl ponytails. The structures of 2a

and 3a exhibit disordered fluorous regions in solid state. With terminal HCF2, the structures of 2b and 3b

show a π-π stacking of the bpy planes and an unusual intramolecular blue-shifting C-H…F-C hydrogen

bond system, whereas without terminal HCF2, the structures of 2a and 3a show the similar π-π stacking

and orientation of fluorous ponytails, but not the C-H…F-C hydrogen bond system. The

spectroelectrochemical studies (including cyclic voltammetry and UV-Vis) were also carried out.

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172. Oligosaccharide Production From Fluorous Compound by Using Cells

Mami Tojino1, Maria C. Z. Kasuya2, Kenichi Hatanaka3 and Mamoru Mizuno1, (1)The Noguchi Institute,

Tokyo, Japan, (2)Institute of Industrial Science, The University of Tokyo, Tokyo, (3)Institute of Industrial

Science, The University of Tokyo, Tokyo, Japan

The glycosylation using alkyl glycoside (lactose primer) and cells is simple and convenient method for the

regio- and stereo- selective synthesis to produce biologically important oligosaccharides. Using this

method, it was found that the lactose primer with a fluorous tag was afforded the oligosaccharide. In this

study, we describe that glycosylation using novel lactose primer with the PEG-fluorous tag by B16 cells

gave a GM3-type oligosaccharide as well as lactose primer with a simple fluorous tag. Additionally, we will

present the GM3-type oligosaccharide with the PEG-fluorous tag was immobilized on fluorous filter by

using the noncovalent fluorous-fluorous interaction.

173. Fluorous Tagged Saccharides: Scaffolds for the Biocombinatorial Synthesis of Glycolipids

Maria Carmelita Z. Kasuya1, Mami Tojino2, Shinya Nakano1, Mamoru Mizuno2 and Kenichi Hatanaka1,

(1)Institute of Industrial Science, The University of Tokyo, Tokyo, Japan, (2)Laboratory of Glyco-organic

Chemistry, The Noguchi Institute, Tokyo, Japan

Biocombinatorial synthesis, combining chemical synthetic methods with cellular biosynthetic processes, is

becoming an important tool to generate a library of glycolipid-specific saccharides that play important

roles in biological systems. In this research, animal cells were treated with 2 sets of chemically

synthesized saccharide primers (lactose and GlcNAc derivatives) with various fluorous tags. These partially

fluorinated glycosides served as scaffolds for the rapid and convenient synthesis of oligosaccharides. The

primers were non-cytotoxic. The numerous fluorine atoms did not pose a steric barrier to primer

assimilation into cells and did not inhibit glycosylation by cellular enzymes. The lactoside primers were

sialylated to give GM3-type oligosaccharide. On the other hand, the GlcNAc primers were galactosylated to

generate a lactosamine derivative that was further sialylated to afford a sialylated lactosamine.

M.C. Z. Kasuya, et al., Chem. Lett. 2005, 34(6), 856-857.

M.C. Z. Kasuya, et al., J. of Fluorine Chem, 2007 (128) 562-565.

174. Fluorinated Silylcyclopentadienes and Their Titanium(IV) Complexes

Lucie Cervenkova Stastna and Jan Cermak, Institute of Chemical Process Fundamentals ASCR, v.v.i.,

Prague, Czech Republic

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Our research is targeted towards fluorinated cyclopentadienyltitanium(IV) complexes, which will be used

as catalyst precursors in fluorous biphase catalysis. The fluorous biphase system combines the advantages

of both homogeneous and heterogeneous catalysis. On the one hand, it allows maintaining the

homogeneous reaction conditions due to the miscibility of perfluorinated solvent with organic solvents at

higher temperature and, on the other hand, the simple separation of the mostly expensive catalyst is

possible allows its reuse for further reaction runs. There was reported a large number of articles

concerning complexes suitable as catalysts in fluorous biphase systems. Surprisingly, only a few of them

contain perfluoroalkyl-substituted cyclopentadienyls.

We have recently published the synthesis of fluorinated dichlorotitanocenes and their fluorophilic

properties. In the past, we have been able to prepare cyclopentadienes modified with up to two ponytails

and now we are reporting the synthesis of silylcyclopentadienes substituted at least by three ponytails. We

used them for synthesis of titanium(IV) complexes which are supposed to be suitable for use in model

catalytic reactions in fluorous biphase systems.

luorinated dimethyltitanocene was also prepared from dichlorotitanocene by the reaction with MeLi and its

catalytic activity was tested in the intramolecular hydroamination reaction. The activity was compared

with that of non-fluorinated complexes.

Acknowledgements: The authors thank Ministry of Education, Youth and Sports (LC06070) for financial

support.

175. Environmental Aspect in Fluorous Biphasic System (Our approach)

Nobuto Hoshi and Akihiro Yoshida, The Noguchi Institute, Tokyo, Japan

We report herein our approach to environmental impact (PFOS/PFOA problem and global warming) in the

case of the fluorous Lewis acid-catalyzed reactions that we have previously developed as an example of

the fluorous biphasic system (FBS) that consists of fluorous catalyst/perfluorinated solvent.

For the fluorous catalyst, we developed the novel fluorous catalysts bearing the ponytail of perfluoro-

polyether instead of C8F17 group as an action on the PFOS/PFOA problem. The new catalysts were able to

be used as well as the previous C8F17 catalyst.

On the other hand, the perfluorinated solvent was compared at first with other greenhouse gases, which

was previously reported on the amount of the release, in order to consider the influence on global

warming. Thus, it was thought that the higher boiling point solvent could be used in the closed system,

and then we tested some kinds of such solvents. Our conclusion is that the fluorous solvent of about 200

°C or more in boiling point was possible to use enough in FBS with the great merit of lower leaching.

Particularly, perfluoro-polyether solvents were preferable because of lower viscosity.

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176. Synthetic Study of Urukthapelstatin A by Fluorous Tag Method

Yutaka Nakamura, Saki Ito, Masaru Kojima and Seiji Takeuchi, Niigata University of Pharmacy and

Applied Life Sciences, Niigata, Japan

Urukthapelstatin A, a novel cyclic peptide, is a potent cytotoxic substance from marine-derived

Mechercharmyces asporophorigenes YM11-542. This structurally interesting peptide contains three

oxazoles and two thiazoles in its cyclic structure and is structurally related to telomestatin. The synthetic

study of urukthapelstatin A using a fluorous protecting groups is described. The key elements of our

approach include the synthesis of penta-azole skeleton of uruktapelstatin A via Hantzsch reaction between

bis-oxazole thioamide 1 and 2‘-bromoacetylthiazoyl-oxazole ester 2. Thioamide 1 and 2‘-bromoacetyl

derivative 2 were prepared from N-fluorous Boc (FBoc) protected serine and O-fluorous TIPS (FTIPS)

protected lactamide, respectively, via a biomimetic pathway based on cyclization–oxidation of serine

containing peptides combined with the Hantzsch synthesis. The Hantzsch reaction of FBoc-protected

thioamide 1 and 2‘-bromoacetyl bis-azole 2 proceeded smoothly, and the corresponding penta-azole ester

3 was obtained in 87% yield. The linear precursor 4 was prepared in high yield by hydrolysis of ester 3

with LiOH, followed by condensation with H-D-allo-Ile-Ala-OtBu using BOP as Condensing agent. In this

synthetic route, the fluorous intermediates were separated from by-products by a fluorous solid phase

extraction. Further studies toward the total synthesis of urukthapelstatin A are currently underway.

177. Synthetic Study of Acylated Phenolic Glycosides Cucurbitosides by Fluorous Mixture Synthesis Masaru Kojima, Yutaka Nakamura, Takayuki Sekigawa and Seiji Takeuchi, Niigata University of

Pharmacy and Applied Life Sciences, Niigata, Japan

Thirteen new acylated phenolic glycosides, cucurbitosides A-M, were isolated from the seeds of Cucurbita

moschata and Cucurbita pepo in 2005. The cucurbitosides have a β-D-apiofuranosyl-(1→2)-β-D-

glucopyranose sugar chain and an ester linkage of various acyl moiety at C-5‘ of apiofuranose.

Apiofuranose-containing glycosides, such as saponins, flavinoids or phenolic glycosides play a crucial role

in the biochemistry of plants. Therefore, the chemical synthesis of cucurbitosides is an important step in

elucidating the relationship between the partially acylated structures and the promising biological activities

of the natural products. On the other hand, Curran and co-workers have recently proposed a fluorous

mixture synthesis as a new combinatorial technique for simple and fast synthesis of natural products.

Fluorous mixture synthesis has shown power in preparing small molecule libraries and studying

structure/activity relationships and structure assignments of natural products. We thought that fluorous

mixture synthesis is suited for the expeditious synthesis of cucurbitosides, because these natural products

are structurally similar and comparatively small molecule. In addition, acyl groups at C-5‘ of apiofuranose

is considered to be chromatographically sorting tag, because the structure of these acyl groups are

different. We report here the simultaneous synthesis of four kinds of cucurbitosides via glycosylation of

two fluorous acceptors with two acylated donors by fluorous mixture synthetic method and the separation

of four components of the mixture by fluorous and normal silica gel column chromatography depending

upon their fluorine contents and difference of acyl groups.

178. Fluorous Mixture Synthesis of Sch725674 and 15 Stereoisomers

Jared Moretti and Dennis P. Curran, Department of Chemistry, University of Pittsburgh, Pittsburgh, PA

The technique of fluorous mixture synthesis (FMS) was used to build a stereoisomer library of the

macrolactone natural product Sch725674. Four "quasistereoisomers," each bearing different combinations

of only two fluorous tags were mixed in equimolar fashion, taken through a brief synthesis containing only

one split, and subjected to late-stage demixing and detagging to afford eight individually pure natural

product stereoisomers. A survey of each member of the synthetic library suggests that cross-talk

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between two remote stereocenters on a macrocycle can have distinct effects on the observed

spectroscopic and optical properties of that particular macrocycle. The eight stereoisomers generate four

distinct sets of NMR spectra, but none of the synthetic samples reported herein matched the spectroscopic

data reported for the natural product, thereby demonstrating the power of FMS in natural product

stereostructure determination.

179. Synthesis and Application of Second-Generation Fluorous TIPS Tag: Fluorous Mixture Synthesis and Structure Assignment of Petrocortyne A

Bin Sui and Dennis P. Curran, Department of Chemistry, University of Pittsburgh, Pittsburgh, PA

Synthesis and Application of Second-generation Fluorous TIPS Tag: Fluorous Mixture Synthesis and

Structure Assignment of Petrocortyne A

A series of new fluorous TIPS tags with propylene spacer have been synthesized. The new tags show the

similar solubility, reactivity, etc. as the first-generation fluorous TIPS tags bearing ethylene group, but the

new tags exhibit greater stability under the basic condition and greater tolerance in the present of

nucleophiles. The new reagents serving as protecting groups and separation tags have been used in the

fluorous mixture synthesis of natural product prtrocortyne A. All four stereoisomers of petrocortyne A have

been obtained in good yields. These isomers and their Mosher ester derivatives are used to assign the

(3S, 14S) configuration to petrocortyne A.

180. Functional Molecular Glass Materials Patternable in Hydrofluoroethers

Eisuke Murotani, Jin Kyun Lee, Margarita Chatzichristidi, Alexander Zakhidov, Priscilla Taylor and

Christopher Ober, Materials Science and Engineering, Cornell University, Ithaca, NY

Organic electronics has been emerging as a promising technology to enable the fabrication of mechanically

flexible devices via solution processing of organic functional materials. The challenge in the current

processing methods lies in the difficulties of patterning organic materials without damaging their

performance; processing solvents can contaminate an underlying layer while depositing materials or

photolithographic imaging processes. Fluorous solvents are highly fluorinated liquids, typically immiscible

with general organic and aqueous solvents. Using fluorous solvents can therefore be expected not to

damage organic layers, consequently solving complicated problems in the organic device fabrication. We

identified hydrofluoroethers (HFEs) as suitable solvents because they are chemically benign to general

organic materials and also environmentally friendly. Functional materials processable in HFEs are thus

required, which can be achieved by the incorporation of fluorine moieties into the organic materials. In

particular, small molecular glasses are promising because of their favorable properties, such as good

solubility, higher purity and reproducible synthesis compared to other polymeric materials. According to

this strategy, we synthesized fluorinated molecular glasses with cross-linkable or acid-labile end-groups.

97

In this presentation, we demonstrate their performance as positive/negative tone photoresists and

patternable low dielectric constant materials. Their chemical properties and lithographic patterning

characteristics will also be discussed.

181. Synthesis and Evaluation of Perfluoropolyether-Polyethyleneglycol Surfactants to

Enable Water-in-Fluorocarbon Droplet Microfluidics

Roger A. Nassar, Randall Scanga, Ben Miller, Xinyu Li, Hu Gang and J. Brian Hutchison, Department of

Chemistry, Raindance Technologies Inc., Lexington, MA

Multi-phase microfluidics technology enables generation and processing of pico-liter size droplets, which

are invaluable for high-throughput chemical and biological applications. The stability of droplets under

conditions required by such processes, in addition to the inertness and biocompatibility of droplet

interfaces, are critical features for droplet microfluidics. Ref

Herein, we describe the synthesis, characterization, and evaluation of perfluoropolyether-

polyethyleneglycol block co-polymers (PFPE-PEG). These surfactants are designed to stabilize an emulsion

of aqueous droplets inside a continuous fluorous phase. The synthesis of the surfactant is described in

Figure 1. The determination of purity and average molecular weight of the PFPE-PEG surfactants is mainly

achieved using NMR spectroscopy (Figure 2), while the molecular weight distribution is determined by

HPL-Chromatography. Finally, the performance of the surfactant is further quantified using interfacial

tension measurements and analysis of emulsions stabilized by this material. In particular, emulsions are

analyzed for stability during generation and microfluidic manipulation, during storage, and during process

conditions, such as thermocycling.

In cases where the PFPE-PEG synthesis was not complete, a PFPE-ammonium salt was detected. The

characterization and stability of this salt will be discussed. Additionally, the size of the PFPE-PEG molecules

as well as the relative size ratio of PFPE:PEG fragments are examined in relation to the final performance

of the surfactants for chemistry and biology experiments within droplets.

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182. Focused Chemical Libraries Produced Using Fluorous Techniques Marvin S. Yu1, Yimin Lu1, Tadamichi Nagashima1 and Wei Zhang2, (1)Fluorous Technologies, Inc,

Pittsburgh, PA, (2)Department of Chemistry, University of Massachusetts - Boston, Boston, MA

As part of the NIH Roadmap Initiative for Medical Research, Fluorous Technologies, Inc (FTI) is a

participant in the Molecular Libraries Roadmap, the goal of which is to provide a collection of diverse

chemical entities which will be available for high-throughput screening. FTI has leveraged fluorous

techniques to efficiently produce a series of chemical libraries of unique structure for inclusion into this

collection. This poster will highlight the libraries produced and the methods used in their production.

183. Development of a Fluorous Tag as An Anomeric Protecting Group, a Purification Aid and a Protein Linker

J. James Bailey and D. R. Bundle, Department of Chemistry, University of Alberta, Edmonton, AB,

Canada

As our synthetic techniques and understanding of the role of carbohydrates in biological systems expand,

it is of no surprise that carbohydrate-protein conjugates are finding more and more uses in therapeutics

and vaccines. Carbohydrates are coupled to their carrier protein via a linker that is either installed late

into the carbohydrate synthesis or heavily modified before coupling. A more convenient linker design

would already incorporate the spacer and require few modifications before conjugation.

Herein we describe the synthesis and utilization of a novel fluorous tag for use in carbohydrate synthesis.

The tag can be installed at the reducing end early in the synthesis allowing simplified purification through

fluorous solid-phase extraction. When the carbohydrate is ready for conjugation, the fluorous portion of

the tag can be cleaved through an internal safety-catch feature, exposing a unique functional group for

conjugation.

184. The Disorder of Perfluoroalkyl Chains in Crystals: Interpretation and Refinement

Pierangelo Metrangolo1, Tullio Pilati2, Giuseppe Resnati1 and Giancarlo Terraneo1, (1)Department of

Chemistry, Materials, and Chemical Engineering "Giulio Natta", Politecnico di Milano, Milan, Italy,

(2)I.S.T.M.-C.N.R., University of Milan, Milano, Italy

Fluorine atoms are typically located at the periphery of organic molecules and, when bonded to neutral

groups, are characterized by very weak intermolecular interactions with any kind of atom. Consequently,

perfluorocarbon derivatives (PFCs) have lower boiling point compared with hydrocarbons having

comparable molecular weight and very low friction coefficient; they are also hydrophobic and lipophobic

and are poorly miscible with many organic solvents. Partially fluorinated molecules show similar trends as

a function of the number of fluorine atoms. Weak intermolecular interactions mean crystallization

problems, too. Plastic phases, liquid crystals, amorphous glasses and structural disorder are common in

fluorinated compounds. Long PFCs show steric hindrance between fluorine atoms bonded in position 1,3

on the carbon chains; their stable conformation is then helical, distorted all-trans, with a pitch of 27-30 C-

C bonds; near always the two enantiomeric helixes are found in the same crystallographic site as

disordered groups. The present work will show how common this disorder is and how frequently it is

ignored, also in molecules with small fluorinated residues such as -CF3. Asking for X-CF3 (X any atom)

under the conditions No error, Not polymer, No ions, No powder structures, we found 8752 hits from

CCDC (version November, 2008); they became 6117 with No disorder and 3204 also with R≤0.05. In spite

of these restraints, the following scattergram shows that the dispersion of F-C distances and F-C-F angles

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is very broad, indicating that, in a large number of cases, disorder was possibly present but ignored by the

authors.

185. Diels-Alder Reaction Catalyzed by Hexameric Capsule of Teflon-Footed Resorcinarene in Fluorous Biphase System

Shoichi Shimizu, Asuka Usui, Masae Sugai, Seiji Shirakawa and Hayato Ichikawa, Department of Applied

Molecular Chemistry, College of Industrial Technology, Nihon University, Narashino, Chiba, Japan

Reactions within artificial receptor molecules have attracted considerable attention in recent years.

Although remarkable acceleration of the reactions was observed in most cases, catalytic turnover was

inhibited except only a limited number of receptor systems. To realize efficient catalytic reaction with

synthetic receptor, we have applied Teflon-footed resorcinarene 1 to Diels-Alder reaction in fluorous

biphase system.

Treatment of 3-buten-2-one with 2,3-dimethyl-1,3-butadiene in wet perfluorohexanes (FC-72) for 4 h at

50 ˚C afforded the cyclic adduct in 6% yield. However, when we carried out the same reaction in the

presence of 1 (10 mol%), the yield increased 62% (Scheme 1). Efficient catalytic turnover was observed

in FC-72 and the turnover number was decreased with increase in C6F6 content in the fluorous solvent. No

acceleration effect was observed in C6F6, where the resorcinarene 1 existed as hexameric capsule 16.

From these results, it is considered that the reaction catalyzed by 1 takes place predominantly within the

capsule 16.

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Bio/Medical -I (27th August, Thursday morning)

Presider: Samuel A. Wickline, Washington University School of Medicine, Saint Louis, MO

186. The Role of the Trifluoromethyl Group in Protease Inhibitors

Matteo Zanda, Institute of Medical Sciences, College of Life Sciences and Medicine, University of

Aberdeen, Aberdeen, United Kingdom

The trifluoromethyl group is recognized in medicinal chemistry as a substituent of distinctive qualities. It is

in fact at the same time highly hydrophobic, electron-rich, sterically demanding, moreover it can provide

high in vivo stability, and can display a good mimicry with several naturally occurring residues such as

methyl, isopropyl, phenyl, etc. This presentation will provide an overview of the role and effect of a

trifluoromethyl group when incorporated as a backbone substitutent in potent inhibitors of different

proteinases, such as plasmepsins, matrix metalloproteinases and cathepsins.

187. Chemo-Enzymatic Synthesis of Chiral Gem-Difluorocyclopropane as Core Molecule Candidate for Material and Medicinal Sciences

Toshiyuki Itoh1, Shino Nakajima1, Manabu Kanbara1, Shuichi Hayase1, Motoi Kawatsura1, Takashi Kato2,

Kazutoshi Miyazawa2 and Hidemitsu Uno3, (1)Department of Chemistry and Biotechnology, Tottori

University, Graduate School of Engineering, Tottori, Japan, (2)Goi Research Center, Research Laboratory

I, Chisso Petrochemical Corporation, Ichihara, Japan, (3)Integrated Center for Sciences, Ehime University,

Matsuyama, Japan

The synthesis of two types of bis-gem-difluorocyclopropane building blocks has been accomplished in

optically pure form using chemo-enzymatic reaction protocol. We prepared various types of diesters or

dialkyl ethers from the diol 1 or 2 and investigated their physical properties such as helical twisting power

(HTP) to a non-chiral nematic liquid crystal host. We also report the results of biological activities of

molecules that involve gem-difluorocyclopropane moiety.

Figure 1. Core molecules for synthesizing various gem-difluorocyclopropane derivatives

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188. 5-Fluoropyrazinoic Acid Derivatives: Inhibition of Mycobacterium Tuberculosis Fatty Acid Synthase I

John T. Welch, Halimah Sayahi, Swamy Puttamadappa, Kaitlin M. Peck and Alex Shekhtman, Department

of Chemistry, University at Albany, SUNY, Albany, NY

5-Fluoropyrazinoates are very efficient inhibitors of Mycobacterium tuberculosis Fatty Acid Synthase I. In

comparison with the clinical agent for the treatment of tuberculosis, pyrazinamide, the 5-

fluoropyrazinoates are 5,000 fold more efficient inhibitors. The relative efficacy of the 5-

fluoropyrazinoates on inhibition of mycobacterial cell growth will also be described.

189. Methylsulfonylpyrazolyl Thiadiazoles as Potent, Orally Bioavailable Cannabinoid-1 Receptor Antagonists for the Treatment of Obesity

Jinhwa Lee, Green Cross Corp., Gyeonggi-do, South Korea

Since rimonabant, a CB1 cannabinoid receptor antagonist, was reported to modulate food intake, CB1

antagonism has been considered as a new therapeutic target for the treatment of obesity. In the present

study, biarylpyrazole analogues based on a sulfur-containing pyrazole core coupled with 1,3,4-oxadiazole

and 1,3,4-thiadiazole were synthesized and assayed for rat CB1 receptor binding affinity. The SAR studies

to optimize pyrazole substituents as well as 1,3,4-thiadiazole ring led to four novel CB1 antagonists with

IC50 ~1 nM for the rat CB1 receptor binding. Among these derivatives, we identified a

trifluoromethylcyclobutyl analogue as promising pre-candidates for the development as an anti-obesity

agent.

190. Stereoselective Synthesis of Beta-Trifluoromethyl Amino Acids

Vittorio Montanari, Equinox Chemicals, Albany, GA and Krishna Kumar, Chemistry, Tufts University,

Medford, MA

Stereoselective synthesis of beta-trifluoromethyl amino acids

Introduction of fluorinated nonnatural amino acids into peptides and proteins has become in the past few

years a potent method of biochemical investigation. Current studies are showing that properties of de

novo designed peptides, such as self assembly into supramolecular structures, subtly depend on

fluorocarbon group positioning and stereochemistry of the nonnatural units. Prompted by these exciting

new developments, we report a versatile, scalable diastereoselective synthesis of the title amino acids 3

from trifluoromethyl ketones 1. The intermediate azides 2 can be useful per se as peptide building blocks.

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103

Inorganic/Organometallic - I (27th August, Thursday morning)

Presider: Andreas J. Kornath, Ludwig-Maximilians-University, Munich, Germany

191. Carbon-Fluorine Bond Activation with Main Group Catalysts

Oleg V. Ozerov, Department of Chemistry, Texas A&M University, College Station, TX

Carbon-fluorine bond activation attracts interest chiefly from two fronts. Carbon-fluorine bond is one of

the most robust functionalities in chemistry and its activation is a serious fundamental challenge. At the

same time, a number of polyfluorinated molecules are recognized atmospheric pollutants and their

remediation must involve cleavage of carbon-fluorine bonds. This presentation will describe our efforts in

carbon-fluorine bond activation that is catalyzed by extremely electrophilic Si, Al, and other main-group

cations. We will show how aliphatic carbon-fluorine bonds can be efficiently converted to carbon-hydrogen

and carbon-carbon bonds at room temperature and discuss the accompanying synthetic and mechanistic

issues.

192. C-F Activation and Derivatization of Fluorinated Alkenes In the Coordination Sphere of Rhodium

Thomas Braun1, Kai Altenhöner2, Daniel Noveski2, Michael Teltewskoi1 and Falk Wehmeier2, (1)Institut

für Chemie, Humboldt-Universität Berlin, Berlin, Germany, (2)Fakultät für Chemie, Universität Bielefeld,

Bielefeld, Germany

One interesting tool for the derivatization of fluorinated molecules is based on the C-F activation of a

carbon-fluorine bond at a transition metal center. The strategy often involves the selective removal of a

fluorine atom from highly fluorinated precursors, followed by functionalization reactions in the coordination

sphere of the metal.1

We will report on the C-F-activation and the stoichiometric or catalytic derivatization of fluorinated

pyridines and alkenes at rhodium.2 Hexafluoropropene can be activated, and be selectively converted into

1,1,1-trifluoropropane in the presence of H2.3 Investigations on the reactivity of the fluoro complex

[RhF(PEt3)3], which is also produced, led to the development of a cyclic process for the formation of 1,1,1-

trifluoropropane from perfluoropropene, HSiPh3 and H2.4 We also describe studies on the catalytic

derivatization of hexafluoropropene to give silyl derivatives by transition metal mediated cleavage

reactions of carbon-fluorine bonds.5 Finally, borylation reactions which are based on C-F activation steps

will be discussed.6

(1) T. Braun, R. N. Perutz, Chem. Commun. 2002, 2749; W. D. Jones, Dalton Trans., 2003, 399. (2) T.

Braun, D. Noveski, M. Ahijado, F. Wehmeier, Dalton Trans. 2007, 3820-3825. (3) T. Braun, D. Noveski,

B. Neumann, H.-G. Stammler, Angew. Chem. Int. Ed. 2002, 41, 2745. (4) D. Noveski, T. Braun, M.

Schulte, B. Neumann, H.-G. Stammler, Dalton Trans. 2003, 4075; (5) T. Braun, K. Altenhöner, F.

Wehmeier, Angew. Chem. Int. Ed. 2007, 46, 5321. (6) T. Braun, M. Ahijado-Salomon, K. Altenhöner, M.

Teltewskoi, S. Hinze, Angew. Chem. Int. Ed. 2009, 47, 1818.

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193. Cycloaddition Reactions of Main-Group Trifluoropropenyl Building Blocks

Alan K. Brisdon and Gavin R Potter, School of Chemistry, University of Manchester, Manchester, United

Kingdom

Thermal and metal-catalysed cycloaddition reactions1 of alkenes and alkynes provide a useful synthetic

route for the generation of substituted ring systems. Main-group trifluoropropynyl systems offer versatile

building blocks, which may be incorporated using this strategy.

Using HFC-245fa (CF3CH2CH2F) compounds of the type R3E-CCCF3 (E = C, Si, Ge, Sn).2 may be readily

prepared.

An alternative phosphorus-ylid route was also utilised, and the charge-separated intermediate was fully

characterised by X-ray crystallography.

These building blocks were converted into cyclic compounds via a series of cycloaddition reactions, such as

the metal-catalysed symmetry-allowed [2+2+2] cyclotrimerisation to generate trifluoromethyl-substituted

benzenes. In a series of reactions using dicobalt octacarbonyl as catalyst the stepwise cyclotrimerisation

could be followed spectroscopically and via X-ray crystallography. The structures of the first step of the

reaction, the metal-bound ―fly-over‖ complex and the final product were all determined. Further

derivatisation of the resulting cyclic systems was attempted by modifying the main-group "handle".

References:

1. See for example, S. Saito and Y. Yamamoto, Chem. Rev., 2000, 100, 2901.

2. A. K. Brisdon and I. R. Crossley, Chem. Commun. 2002, 2420.

194. The Diversity of Difluoroacetylene Coordination Modes Obtained by Coupling Fluorocarbyne Ligands On Binuclear Metal Carbonyl Sites

R. Bruce King1, Henry F. Schaefer2, Qian-shu Li3, Yaoming Xie2 and Xian-Mei Liu4, (1)Department of

Chemistry and Center for Computational Chemistry, Department of Chemistry, University of Georgia,

Athens, GA, (2)Center for Computational Chemistry, Department of Chemistry, University of Georgia,

Athens, GA, (3)Center for Computational Quantum Chemistry, Guangzhou, China, (4)Center for

Computational Quantum Chemistry, South China Normal University, Guangzhou, China

Recent work has shown that the fluorocarbyne ligand, CF, isoelectronic with the NO ligand, can be

generated by the defluorination of CF3 metal complexes, as illustrated by the 2006 synthesis by Hughes et

al. of C5H5Mo(CO)2(CF) in good yield by the defluorination of C5H5Mo(CO)3CF3. The fluorocarbyne ligand

has now been investigated as a ligand in the manganese carbonyl complexes Mn(CF)(CO)n (n = 4, 3) and

Mn2(CF)2(CO)n (n = 7, 6, 5, 4) using density functional theory. In mononuclear complexes, such as

Mn(CF)(CO)4, the CF ligand behaves very much like the NO ligand in terms of ¹-acceptor strength.

However, in the binuclear complexes the two CF ligands couple in many of the low energy structures to

form a bridging C2F2 ligand derived, at least formally, from difluoroacetylene, FC¼CF. The geometries of

such Mn2(C2F2)(CO)n complexes suggest several different bonding modes of the bridging C2F2 unit. These

include bonding through the orthogonal ¹-bonds of FC¼CF, similar to the well-known R2C2Co2(CO)6

complexes or bonding of the C2F2 unit as a symmetrical or unsymmetrical biscarbene. This research

suggests that fluorocarbyne metal chemistry can serve as a means for obtaining a variety of

difluoroacetylene metal complexes, thereby avoiding the need for synthesizing and handling the very unstable difluoroacetylene.

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195. Ammonium Acid Fluoride as Fluorinating Agent in the South-African Minerals Processing Industry

Philip L. Crouse1, Wilna du Plessis2 and Johann T. Nel2, (1)Department of Chemical Engineering,

University of Pretoria, Pretoria, South Africa, (2)Applied Chemistry, Nuclear Energy Corporation of South

Africa (NECSA), Pretoria, South Africa

The use of ammonium acid fluoride (NH4F.xHF, with x = 1-5) for treatment of mineral ores is fairly well

known in the literature, yet evidently underexploited in the processing industry. Recent results in this

regard pertaining to the beneficiation of South-African ores, with special reference to zircon and plasma-

dissociated zircon, are presented. The ammonium acid fluoride system provides an effective dry

hydrofluorinating medium, and is easier to handle than anhydrous hydrogen fluoride. Metal oxides react

readily to form ammonium fluoro-metallates, which in turn are easily thermally decomposed to yield pure

metal fluorides along with ammonia and hydrogen fluoride. In the case of zircon and/or plasma-

dissociated zircon, the reaction yields (NH4)3ZrF7(s) and (NH4)2SiF6(s), the latter decomposing to form

volatile products at relatively low temperatures, affording easy separation of silicon from the zirconium

compound. One useful aspect of the process is that the ammonia and hydrogen fluoride in the waste

stream are easily recombined in a cold trap, making them available for re-use. Details of the

thermodynamics and kinetics are described, along with the use of these data in the development of the

full process. The work forms part of a larger program supporting local value addition to various mineral

streams normally exported from South Africa.

Organic/Organometallic-I (27th August, Thursday)

Presider: Stephen G. DiMagno, University of Nebraska, Lincoln, Lincoln, NE

196. Synthesis of Fluorinated α-Hydroxy-β-Amino Acids by Means of β-Lactam Synthon Method and Their Applications to Medicinal Chemistry

Iwao Ojima, Institute of Chemical Biology & Drug Discovery and Department of Chemistry, State

University of New York at Stony Brook, Stony Brook, NY

Enantiopure 1-acyl-3-hydroxyl-4-Rf-azetidin-2-ones serve as versatile intermediates for the syntheses of

fluorine-containing alpha-hydroxy-beta-amino acids, dipeptides, and taxoid anticancer agents. 3-Hydroxy-

4-CF2H-beta-lactams with >99% ee can be obtained in high yields through the DAST reaction of the

corresponding enantiopure 4-formyl-beta-lactam obtained through ketene-imine [2+2] cycloaddition,

followed by enzymatic optical resolution. An efficient method has been developed for the synthesis of 3-

hydroxy-4-CF3-beta-lactams (>99% ee) through [2+2] cycloaddition of a CF3-imine with acetoxyketene

and subsequent enzymatic optical resolution. (3R,4S)-1-t-Boc- 3-TIPSO-4-difluorovinyl-beta-lactam was

prepared in three steps from enantiopure 4-formyl-beta-lactam using the Wittig-like reaction of the formyl

moiety with difluoromethylphosphorus ylide generated in situ from (Me2N)3P/CF2Br2/Zn. Practical

processes for the preparations of these enantiopure 3-hydroxy-4-Rf-beta-lactams (Rf = CF2H, CF3,

CH=CF2) as well as their applications to organic synthesis and medicinal chemistry will be presented.

197. Crystal Engineering with Using Symmetries of Molecular Components

Toshimasa Katagiri, Keisuke Kataoka, Tetsuaki Yasumoto, Satoshi Takahashi, Yousuke Manabe and

Kenji Uneyama, Department of Applied Chemistry, Faculty of Engineering, Okayama University, Okayama,

700-8530, Japan

An anisotropic bundle of sub-nano diameter tunnels with linear ratchet gear walls were constructed as a

single needle crystal. The single crystal X-ray diffraction analysis of double headed trifluorolactate

connected by o-xylylene spacer showed existences of the bundled tunnels. The facing two walls of every

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tunnel were lined by inclined benzene rings. These lines of aromatic rings constructed parallel linear

ratchet gears, which made the tunnel anisotropic. Moreover, these anisotropic tunnels in a needle run

parallel in the crystal. That is, the needle crystal itself is anisotropic, based on the huge number of a few

millimeter length tunnels with sub-nano meter sized linear ratchet gears. Construction of this type of

molecular architecture with using symmetry of the molecular components will be discussed.

198. “Non-Polar”- Fluorophilic/Lipophilic Gemini Amphiphiles: Synthesis, Solid State Structures and Behavior at Interfaces

Caroline de Gracia Lux and Marie-Pierre Krafft, Institute Charles Sadron, University of Strasbourg,

Strasbourg, France

The pronounced lipophobic character of fluorinated chains causes semi-fluorinated alkanes, CnF2n+1CmH2m+1

(FnHm diblocks) to have an amphiphilic character in spite of the absence of a hydrophilic moiety. This

endows them with distinctive properties in solid state (liquid crystal properties) and liquid state (micelle

formation in hydrocarbons and fluorocarbons, co-surfactant effect in emulsion films, component of

phospholipids bilayers). We have recently shown that FnHm diblocks form circular, monodispersed

hemimicelles at the air/water interface and onto solid substrates. Arrays of such nanostructures have

potential for biosensors fabrication. One of our general objectives is to synthesize amphiphiles with a

modular architecture comprising multiple fluorinated and hydrogenated chains in order to control their

amphiphilic and amphisteric character. Such control is expected to help direct formation of

compartmented self-assemblies.

In this talk, we will report the synthesis of a series of the first ―non-polar‖ gemini amphiphiles (coded

di(FnHm)). The two-step route includes the radical addition of a perfluoroalkyl iodide, F(CF2)nI to a linear

1-alkene and subsequent coupling of the resulting two iodo-adducts by treatment with zinc.

We will discuss the structures of the di(FnHm) gemini diblocks in the solid state, as assessed by

transmission electron microscopy (TEM) using selected area diffraction (SAED) observation mode, and X-

ray scattering (WAXS and SAXS). Cryogenic TEM images of the lamellar phases formed by the gemini

diblocks will be presented. We will also describe the original monolayer behavior of the gemini amphiphiles

at the water and solid (silicon, mica) surfaces.

199. Dynamically Porous Organic Solids for the Selective Encapsulation of Diiodoperfluoroalkanes

Pierangelo Metrangolo1, Giuseppe Resnati1, Tullio Pilati2, Kari Rissanen3, Manu Lahtinen4, Yvan

Carcenac5 and Ashwani Vij6, (1)Dipartimento di Chimica, Materiali ed Ingegneria Chimica "Giulio Natta",

Politecnico di Milano, Milano, Italy, (2)I.S.T.M.-C.N.R., University of Milan, Milano, Italy, (3)Nanoscience

Center, Department of Chemistry, University of Jyväskylä, Jyväskylä, Finland, (4)Department of

Chemistry, University of Jyväskylä, Jyväskylä, Finland, (5)Department of Chemistry, University François-

Rabelais, Tours, France, (6)Air Force Research Laboratory, 10 East Saturn Blvd, Edwards AFB, CA

107

Halogen bonding has increasingly facilitated assembly of diverse host-guest solids. Here we show that a

well-known class of organic salts, bis(trimethylammonium) alkane diiodides, can reversibly encapsulate

alpha,omega-diiodoperfluoroalkanes (DIPFAs) through intermolecular interactions between the host‘s I-

anions and guest‘s terminal iodine substituents. The process is highly selective for the fluorocarbon that

forms an I-∙∙∙I(CF2)mI∙∙∙I- superanion matched in length to the chosen dication. DIPFAs two to twelve

carbons in length – common industrial intermediates – can thereby be isolated from mixtures by

crystallization from solution on addition of the dissolved size-matched ionic salt. Remarkably, the solid

state salts can also selectively capture the DIPFAs from the vapor phase, yielding the same product

formed from solution despite a lack of porosity of the starting lattice structure. Heating liberates the

DIPFAs and regenerates the original salt lattice, highlighting practical potential for the system in

separation applications.

200. Transition Metal Complexes Based On Polyfluoroalkylated NHC Ligands

Jaroslav Kvicala, Martin Skalicky, Marketa Rybackova, Martin Schindler, Jana Paterova, Vendula

Kelbichova, Ondrej Kysilka and Laudine Ducrocq, Department of Organic Chemistry, Institute of Chemical

Technology, Prague, Prague 6, Czech Republic

Transition metal complexes based on polyfluoroalkylated NHC ligands

In continuing study of polyfluoroalkylated imidazolylidene carbenes we synthesized a series of Ag(I) or

Cu(I) complexes 1 bearing fluorous NHC ligands based on imidazolium salts containing two

polyfluoroalkylated chains with perfluorohexyl or perfluorooctyl ponytail and methylene or ethylene

spacer. Starting from 1-mesitylimidazoles, we also obtained analogous complexes with one mesityl and

one polyfluoroalkyl group. Alternatively, we employed Heck reaction of (perfluorohexyl)ethene with

diimine prepared from glyoxal and 4-iodo-2,6-dimethylaniline, which after further transformations led to

polyfluoroalkylated dimesitylcarbene Ag(I) complex 2.

In a parallel study of polyfluoroalkylated analogues of Grubbs metathesis catalyst, we employed

Mitsunobu reaction for the preparation of polyfluoroalkyl styryl ethers, which on reaction with Grubbs

catalyst yielded polyfluoroalkylated complex 3. In the model reaction of N,N-diallyltosylamide catalyzed

with 3 the RCM product was obtained in excellent yield.

Finally, we synthesized a series of imidazolium salts 4 with one or two perfluoropolyether-based

substituents, which can be employed as fluorous ionic liquids. In contrast to bis(polyfluoroalkylated)

imidazolium salts used as precursors of complexes 1, polyfluoropolyalkoxyimidazolium salts 4 displayed

surprisingly high fluorophilicity with perfluoro(methylcyclohexane)-based fluorous partition coefficients as

high as 90 for toluene or 35 for water and on the other hand as low as 0.05 for acetonitrile.

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Bio/Medical -II (27th August, Thursday morning)

Presider: François Diederich, ETH Zürich, Zürich, Switzerland

201. Targeted Fluorocarbon Nanoemulsions for Molecular Imaging and Therapy

Samuel A. Wickline, Internal Medicine, Division of Cardiology, Washington University School of Medicine,

Saint Louis, MO

Molecular imaging and therapy with targeted nanoparticles is a promising approach for early diagnosis and

drug delivery to various pathologies. Liquid perfluorocarbon nanoemulsions combine flexible and

multi/polyvalent targeting ligands with therapeutic agents against a host of pathological targets. Drugs

such as doxorubicin, rapamycin, and fumagillin, and other agents such as siRNA and cytolytic peptides can

be incorporated in a self assembling particle that is approximately 200 nm diameter and contains a

perfluorocarbon (PFC) core. The unique spectral (19F) signature of the PFC core renders it useful for

unique-signature, no-background, multicolor magnetic resonance imaging and quantitative spectroscopy.

The pharmacokinetics of these agents allows excellent cellular targeting, and drug delivery is achieved by

a unique mechanism that promotes fusion of the particles with the targeted cell membrane followed by

active drug transport directly to the cytoplasm thereby avoiding endosomal sequestration. Examples of

diagnostic and therapeutic uses in experimental cancer and cardiovascular disease will be presented.

202. A Stable and Rapidly Excreted Fluorinated Dendrimer as Imaging Agent for 19F MRI

ZhongXing Jiang and Y. Bruce Yu, Fischell Department of Bioengineering, University of Maryland, College

Park, MD

1H and 19F are the most sensitive nuclei for nuclear magnetic resonance imaging (MRI), with 1H MRI suited

for collecting information of the body and 19F suited for collecting information of drugs in the body.

Although 19F MRI is only four years younger than 1H MRI, it is not in clinical use. The progress of 19F MRI

has been stalled by lack of suitable imaging agents. Current 19F imaging agents are perfluorocarbon (PFC)

emulsions and suffer severe shortcomings, including heterogeneity, instability, split 19F signal, complex

formulation procedure and, most importantly, excessive organ retention for months or longer. We

developed a bi-spherical fluorocarbon dendrimer, denoted as 19FIT, which overcame all the major

deficiencies of PFC-based imaging agents. With suitable imaging agents like 19FIT, 19F MRI has the

potential to play an important role in drug therapy, analogous to the role played by 1H MRI in disease

diagnosis.

203. Catalytic Fluorination of Chlorinated Molecules: Preparation of the Bis-1,3-Trichloromethylbenzene IN the PRESENCE of HF and A Lewis ACID

Sylvette Brunet, Umr 6503 Cnrs, University of Poitiers, Poitiers, France

Catalytic system HF/Lewis acid or HF alone was commonly used for the fluorination of chlorinated

molecules by Cl/F exchanges in order to obtain the corresponding fluorinated compounds. Some halide

compounds need vigorous conditions to be fluorinated and most of the time, HF is required. Moreover,

new routes were developed by using a catalyst and HF by Cl/F exchanges from the chlorinated starting

material in order to obtain selectively the desired fluorinated products without by product. An example is

the preparation of substituted trichloromethyltrifluoromethylbenzenes from the bis-1,3-

trichloromethylbenzene.

The transformation of the bis-1,3-trichloromethylbenzene depends on the experimental conditions

(temperature, amount of HF and the presence of a Lewis acid). In the presence of HF in excess, the

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hexafluorinated product was selectively observed whatever the conditions. The best conditions to produce

the 1-trichloromethyl-3-trifluoromethylbenzene were with HF in default. After the consumption of HF, the

various fluorinated intermediates compounds were observed to lead to the most thermodynamically stable

compounds, i.e., mainly the bis-1,3-trichloromethylbenzene and 1-trichloromethyl-3-

trifluoromethylbenzene. These results were explained by theoretical calculations. An important

consequence is, provided that some conditions are satisfied (presence of catalyst or elevated

temperature), that the composition of the reactive medium tends toward the thermodynamic equilibrium.

Indeed the presence of a Lewis acid increases the formation of the most stable products depending on

their Lewis acidity. SbCl5 which is the most acid is the most efficient catalyst corresponding to a decrease

of 150°C to obtain similar results compared with HF alone.

204. Molecular Interactions of Fluorinated Amino Acids within Native Protein-Like Environments

Beate Koksch, Mario Salwiczek, Toni Vagt and Elisabeth Nyakatura, Department of Biology, Chemistry

and Pharmacy - Institute of Chemistry and Biochemistry, Freie Universität Berlin, Berlin, Germany

Fluorinated amino acids are prominent building blocks for modulating the structure and interactions of

peptides and proteins. As fluoroalkyl groups uniquely combine two contrary properties - polarity and

hydrophobicity - their effects as substituents in native proteins are not easily predicted. A model system

has been designed on the basis of a heterodimeric a-helical coiled coil peptide. The native monomer was

used to screen complementary peptides that carry various fluorinated amino acids at either of two

positions within the hydrophobic interface of the coiled coil dimer. The heteromers were

thermodynamically characterized by temperature induced unfolding monitored by CD-spectroscopy.

Applying SPR we are currently investigating the impact of fluorine substitutions on the kinetics of coiled

coil formation. Furthermore, we apply phage display technology to search for preferred interaction

partners for fluorinated amino acids within the pool of the genetically encoded amino acids. These studies

will help to gain a better understanding of the way fluorinated amino acids direct peptide/protein

interactions and pave the way towards the application of fluorinated peptides in medicinal chemistry.

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Inorganic/Organometallic - II (27th August, Thursday morning)

Presider: Erhard Kemnitz, Humboldt-University Berlin, Berlin, Germany

205. Molecules to Function - the Influence of Electron Withdrawing Groups On Main Group Chemistry

Berthold Hoge1, Boris Kurscheid1, Julia Bader1 and Nikolai Ignatiev2, (1)Institute of Inorganic Chemistry,

University of Cologne, Cologne, Germany, (2)PLS R&D LSS, Merck KGaA, Darmstadt, Darmstadt, Germany

Diorganylphosphinous acids, R2P-O-H, and their anhydrides, R2P-O-PR2, are in general not stable toward a

tautomerization into the corresponding phosphane oxide isomers R2P(O)H and R2P(O)-PR2, respectively.

However, the trivalent derivatives R2P-O-H and R2P-O-PR2 can by stabilized by the influence of electron

withdrawing groups such as R = CF3,[1] C2F5

[2] and 2,4-(CF3)2C6H3[3] or by the coordination to suitable

transition metal complexes.

Within this contribution we will present the synthesis of novel phosphinous acid transition metal complexes

such as I and their application as catalysts in Suzuki-type cross-coupling reactions.[4] The influence of the

electron withdrawing groups R on the catalytic cycle will be discussed.

1) J. E. Griffiths, A. B. Burg, J. Am. Chem. Soc. 82 (1960) 1507; B. Hoge, P. Garcia, H. Willner, H.

Oberhammer, Chem. Eur. J., 12 (2006) 3567.

2) B. Hoge, J. Bader, H. Beckers, Y. S. Kim, R. Eujen, H. Willner, N. Ignatiev, Chem. Eur. J., 15 (2009)

3567.

3) B. Hoge, B. Kurscheid, Angew. Chem. Int. Ed., 47 (2008) 6814.

4) B. Hoge, J. Bader, B. Kurscheid, N. Ignatiev, E. Aust, patent application filed, Merck Patent GmbH,

Darmstadt.

111

206. Fluoroalkyl-Phosphines and Their Chemistry

Christopher J. Herbert and Alan K. Brisdon, School of Chemistry, University of Manchester, Manchester,

United Kingdom

Phosphorus (III) ligand systems are among the most widely studied and utilised in transition metal

chemistry, and they, or their metal complexes find applications in organocatalysis and pharmaceutics. 1

When one (or more) of these substituents are perfluorinated, unusual steric and electronic properties

result. 2 Many fluoroaryl-containing phosphanes are known,3 only fluoroalkylphosphanes containing the -

CF34 and –CF2CF3

5 groups have been studied in detail-this is largely due to the lack of simple synthetic

methodologies. The synthesis of Ph2PCF2Br was reported in 2003 by Clarke et al., from CF2Br2 and

Ph2PSiMe3 at -20°C6. We have extended this method to generate new phosphanes.

The synthesis of Ph2PCF(CF3)2 is accomplished by reacting (CF3)2CFI with Ph2PSiMe3 in hexane at -30°C.

Work-up affords the compound in 75 % yield as white needles suitable for X-ray crystallography (see

Figure 1). We have extended this route to produce the –CF3, -CF2CF3, s-C4F9, cyc-C6F11, and t-C4F9

containing phosphanes.

The oxidative properties and coordination compounds of these compounds have been investigated.

Figure 1: ORTEP representation of the molecular structure of Ph2PCF(CF3)2.

[1] D. W. Allen, Organophosphorus Chem. 2006, 35, 1. [2] K. D. Cooney, et al. J. Amer. Chem. Soc.

2003, 125, 4318. [3] C. L. Pollock, et al. J. Fluorine Chem. 2008, 129, 142. [4] H. J. Emeleus, J. D.

Smith, J. Chem. Soc., 1958, 527; A. B. Burg, W. Mahler J. Am. Chem. Soc., 1958, 80, 2334. [5] a) R. G.

Peters et al., Inorg. Chem. 1997, 36, 5962; b) J. D. Palcic, et al. Dalton Trans., 2004, 1644.

112

207. Fluorinated Ligands for Hydrogen Transfer Catalysis

Graham C. Saunders, Department of Chemistry, The University of Waikato, Hamilton, New Zealand and

Andrew C. Marr, School of Chemistry and Chemical Engineering, Queen's University Belfast, Belfast,

United Kingdom

Rhodium, iridium and ruthenium complexes of polyfluorinated arylphosphine and N-heterocycle-stabilized

carbene (NHC) ligands have been found to be active catalysts for transfer hydrogenation. Although simple

piano stool complexes of polyfluoroarylphosphines do show catalytic activity, they are not as active as the

commercially available catalyst systems. However greater activity and greater stability is achieved by

tethering the phosphine ligand to the carbocyclic polyene ligand. The tethering is achieved by

intramolecular dehydrofluorinative carbon-carbon coupling, which gives complexes of ligands coordinated

by two functionalities from methylene-bridged diphosphines and three functionalities from ethylene-

bridged diphosphines. Since these complexes lack proton-accepting or -donating groups and possess

electron-withdrawing polyfluorinated substituents, they might be expected to have low catalytic activity.

However, rhodium complexes of these ligands are at least as active as the commercial systems, and for

one complex the activity is significantly greater. Hydrogen transfer can be coupled with enzymatic

reactions to provide dynamic kinetic resolution of chiral secondary alcohols. Our studies show that not

only are simple piano stool complexes of fluoroaryl NHCs compatible with the enzyme (lipase B from

Candida antarctica), but also that the reactivity is remarkable - the transformation can be performed in

the absence of added base!

208. Synthesis and Structural Peculiarities of Ba(BF4)(AF6) (A= P, As, Sb, Bi, V, Nb, Ta, Ru) and Ba2(BF4)2(AF6)(H3F4) (A=As, V) Compounds

Evgeny Goreshnik, Matic Lozinšek, Melita Tramšek and Boris Žemva, Department of Inorganic Chemistry

and Technology, Jozef Stefan Institute, Ljubljana, Slovenia

In the system BaF2/BF3/PF5/anhydrous hydrogen fluoride (aHF) a compound Ba(BF4)(PF6) was isolated and

characterized by Raman spectroscopy and X-ray diffraction on the single crystal. Ba(BF4)(PF6) crystallizes

in a hexagonal P 6b 2 m space group. Both crystallographically independent Ba atoms possess

coordination polyhedra in the shape of tri-capped trigonal prisms, which include F atoms from BF4- and

PF6- anions. Related compounds of Ba(BF4)(AF6) (A= As, Sb, Bi, V, Nb, Ta, Ru) composition crystallize in

an orthorhombic Pnma space group. In all these compounds the coordination around Ba atom is in the

shape of tri-capped trigonal prism which includes five F atoms from AF6- and four F atoms from BF4

-

anions. When the system BaF2/BF3/AsF5/aHF is made basic with an extra addition of BaF2, compounds

Ba2(BF4)2(AsF6)(H3F4) and Ba2(BF4)2(VF6)(H3F4) were obtained, both crystallize in a hexagonal P63/mmc

space group. The barium environment in the shape of tetra-capped trigonal prism involves 10 F atoms

from 4 BF4-, 3 AF6

- (A=As, V) and 3 H3F4- anions. All F atoms, except the central atom in H3F4

moiety, act

as m2-bridges yielding a complex 3-D structural network. An influence of the AF6- size on the stability of

Ba2(BF4)2(AF6)(H3F4) compounds, explanation and prediction of some crystallographic peculiarities in the

raw of Ba(BF4)(AF6) compounds have been performed.

113

Organic/Organometallic-II (27th August, Thursday)

Presider: Takeo Taguchi, Professor Tokyo University of Pharmacy and Life Sciences, Tokyo, Japan

209. Catalytic Asymmetric Synthesis of Fluoro-Organic Compounds

Norio Shibata, Department of Frontier Materials, Nagoya Institute of Technology, Graduate School of

Engineering, Nagoya, Japan

Optically active organo-fluorine compounds are attractive in both modern pharmaceutical chemistry and

material science; especially the simple chiral esters and their derivatives with fluorine at a chiral centre

are one of the most versatile and important monofluorinated chiral synthons utilized in the synthesis of

liquid crystals, antitumor agents, and enzyme inhibitors. A variety of enantioselective syntheses of

fluorinated compounds have been developed for this notable approach to the elaboration of the optically

active mono-fluorinated compounds. Enantioselective electrophilic fluorination promoted by metal

complexes and organocatalysts is expanding into one of the most effective strategies for C-F bond

construction on chiral centres. It provides in fact a straightforward approach to the asymmetric synthesis

of fluorinated β-keto esters, β-keto phosphates, cyanoacetates, oxindoles, aldehydes and malonates.

However, the enantioselective fluorination of aryl acetate derivatives is still a matter of challenge, albeit

importance in drug synthesis. We disclose here the enantioselective fluorination of 3-(2-arylacetyl)-2-

thiazolidinones by DBFOX based combinatorial catalyst, and the enantioselectivities with ee values up to

99% were achieved. This combinatorial catalytic system can be applicable for the first catalytic

asymmetric fluorination of aryl-3-butenoyl derivatives. The catalyst system is also applicable to

enantioselective α-chlorination as well as α-hydroxylation of aryl acetyl thiazolidinones. Recent progress of

enantioselective trifluoromethylation reactions from our group will also be discussed.

210. Synthesis and 19F and 1H NMR Features of 4-Me-FICA

Jyunichi Koyanagi, Tomoyo Kamei, Kazuya Hirano, Miyuki Ishizaki, Hiroshi Nakamura and Tamiko

Takahashi, Faculty of Pharmaceutical Sciences, Josai International University,

Togane, Japan

One of the most popular and reliable procedures to establish the absolute

configuration of chiral compounds is the 1H NMR spectroscopic analysis of its MTPA

ester (the modified Mosher's method). Recently, we developed 1-fluoroindan-1-

carboxylic acid (FICA) and revealed that it can be a reliable CDA for the

determination of absolute stereochemistry of secondary alcohols by both 19F and 1H

NMR. In order to get more efficient CDAs than FICA, we set out to investigate the synthesis of FICA

derivatives having a substituent on benzene moiety and the examination of their ability as CDAs. 4-Me-

and 5-Me-FICA methyl esters were prepared from the corresponding 1-indanone derivatives. As a

preliminary experiment, 4-Me-FICA esters of secondary alcohols were obtained by ester exchange reaction

of 4-Me-FICA methyl ester to estimate the chemical shifts differences in both 19F and 1H NMR. The

features of 4-Me-FICA compared with FICA were as follows; (1) introduction of 4-Me group had little effect

on chemical shift differences in both 19F and 1H NMR of the esters obtained from linear secondary alcohols;

(2) much larger chemical shift differences in 19F NMR were observed in the cases of esters prepared from

cyclic secondary alcohols. Further details of 19F and 1H NMR features of 4-Me-FICA will be discussed in the

presentation.

114

211. A One-Pot Asymmetric Reformatsky Reaction of Ethyl Iododifluoroacetate with Aromatic Ketones Alison M. Stuart and Michal Fornalczyk, Department of Chemistry, University of Leicester, Leicester,

United Kingdom

One of the most useful methods for the synthesis of medicinally important compounds containing a

difluoromethylene group is the Reformatsky reaction of ethyl bromodifluoroacetate with aldehydes.[1]

The enantioselective addition of the fluorinated Reformatsky reagent to aromatic aldehydes in the

presence of chiral amino alcohols to give a,a-difluoro-b-hydroxy esters in good enantiomeric excess is well

established.[2-4] However, the inconvenient zinc activation, as well as the relatively high temperatures

required for the generation of the fluorinated Reformatsky reagent and its' thermal instability limit the

applications of this methodology and, to the best of our knowledge, the asymmetric Reformatsky reaction

has not been reported with ketones.

Here, we will report a convenient one-pot asymmetric Reformatsky reaction of ethyl iododifluoroacetate

with aromatic ketones using diethyl zinc to generate the Reformatsky reagent homogeneously and

(1R,2S)-1-phenyl-2-(1-pyrrolidinyl)-1-propanol as the chiral auxiliary. We will also compare the new one-

pot method using diethyl zinc with the classical two step Reformatsky procedure using zinc dust with a

series of aromatic ketones.

1. T. S. Chou, P. C. Heath, L. E. Paterson, L. M. Poteet, R. E. Lakin, A. H. Hunt, Synthesis, 1992, 565.

2. M. Braun, A. Vonderhagen, D. Waldmuller, Liebigs Ann., 1995, 1447.

3. J. M. Andrés, M. A. Martínez, R. Pedrosa, A. Pérez-Encabo, Synthesis, 1996, 1070.

4. R. J. Kloetzing, T. Thaler, P. Knochel, Org. Lett., 2006, 1125.

212. Facile Stereoselective Synthesis of Fluorinated Flavanone Derivatives Via a One-Pot Three-Component Reaction

Gang Zhao, Shanghai Institute of Organic Chemistry, Shanghai, China

Flavanones represent an important structural motif occurring in many natural products with a variety of

biological activities such as anti-tumor and anti-inflammatory properties. Therefore, a great deal of

methods have been developed for the synthesis of flavanones and their derivatives. In our studies, a

series of fluorinated flavanones were synthesized under mild conditions via a one-pot three-component

tandem procedure involving a proline-catalyzed Knoevenagel condensation, a Michael addition and an

electrophilic fluorination process in moderate to good yields with high diastereoselectivities.

115

Fluoropolymers/Materials - I (27th August, Thursday afternoon)

Presider: Paul A. Deck, Virginia Tech, Blacksburg, VA

213. Probing [C–H···F–C] Contacts as Models of Weak Attractive Ligand–Polymer Interactions

Michael C.W. Chan, Department of Biology and Chemistry, City University of Hong Kong, Kowloon, Hong

Kong

What are ‗weak attractive ligand–polymer interactions'? In metal-catalyzed olefin polymerization

reactions, the study of non-covalent interactions between a non-innocent ancillary ligand and the growing

polymer chain is a new concept. Moreover, the existence, importance, and applicability of extremely weak

hydrogen bonds such as C-H···F-C remain controversial.

We have described a family of Group 4 post-metallocene catalysts, supported by F-functionalized

tridentate ligands with fluorine group(s) adjacent to the active site, as models of weak attractive ligand–

polymer interactions. For the first time, the elusive C-H···F-C interaction was manifested as NMR-

discernible 1H-19F coupling in solution and characterized by a neutron diffraction study.1 These

observations carry important implications with regards to polyolefin catalyst design, since they corroborate

the practical feasibility of the ortho-F···H(b) ligand–polymer contacts proposed for the living Group 4

fluorinated phenoxyimine catalysts.2 In recent developments, new types of intramolecular non-covalent

interactions have been realized, and unexpected design features for improving their olefin polymerization

activities have been established.

1. (a) Kui, S. C. F.; Zhu, N.; Chan, M. C. W. Angew. Chem. Int. Ed. 2003, 42, 1628. (b) Chan, M. C. W.;

Kui, S. C. F.; Cole, J. M.; McIntyre, G. J.; Matsui, S.; Zhu, N.; Tam, K. H. Chem. Eur. J. 2006, 12, 2607.

(c) Chan, M. C. W. Chem. Asian J. 2008, 3, 18.

2. Mitani, M.; Mohri, J.; Yoshida, Y.; Saito, J.; Ishii, S.; Tsuru, K.; Matsui, S.; Furuyama, R.; Nakano, T.;

Tanaka, H.; Kojoh, S.; Matsugi, T.; Kashiwa, N.; Fujita, T. J. Am. Chem. Soc. 2002, 124, 3327.

214. Transparent Polymers Containing Partially Fluorinated Spiro-Structure in Their Main Chains

Toshio Kubota1, Ayako Takaki1, Ko-ichi Yanai1, Takehiro Nagasawa2 and Akira Hirooka2, (1)Department

of Materials Science, Ibaraki University, Hitachi, Japan, (2)Chemical Research Laboratories, Nissan

Chemical Industries, LTD, Funabashi, Japan

1-(3-Butenyloxy)heptafluorocyclopentenes (1) were prepared by the addition-defluoride reaction between

octafluorocyclopentene (OFCP) and 4-hydroxy-1-alkenes in the presence of potassium hydroxide without

solvent. The radical polymerization without solvent of 1,6-diene-type ether (1a) prepared from 3-buten-1-

ol was carried out using benzoyl peroxide (BPO) or azobisisobutyronitrile (AIBN) as a radical initiator at 80

°C for 24 h proceeded to produce the new fluoropolymer 2a (the weight-average molecular weight: 1.1—

1.7Χ104). The resulting polymer 2a exhibited unique properties as follows:

•Polymers 2a dissolved in acetone, ethyl acetate and THF.

116

•Tg was about 190 °C. [CYTOP (Tg 108 °C), Teflon AF (Tg 165 °C)]

•The weight-loss temperatures(10%), TWL(10%) > 290 °C.

•The large transmittance value (> 90%) in wide range from 250 to 900 nm (100 mm film). The refractive

index measured by ellipsometer was 1.38 (633 nm) in spite of the H/F rate of the polymer 2a was 1.0.

As there is a CH2 moiety as an adjacent group of CF moiety in the 1-oxaspiro[4.4]nonane structure (2aa),

and CH moiety in the 2-oxabicyclo[4.3.0]nonane structures (2ab), it was speculated that the difference

between 2aa and 2ab was reflected as the different sets of correlations. The obtained 2D-nmr spectra

(19F-13C HMQC, 1H-13C HMQC, 1H-19F COSY) clearly showed that the main chain of 2a is the mixed

structure of spiro-2aa and bicyclo-2ab (ca. 4:1). In this presentation, the fluoropolymers 2 prepared from

1-(1-alkyl-3-butenyloxy)heptafluoro-cyclopentenes and the copolymerization of 2a with a series of

monomers will be introduced.

215. Radical Copolymerization of Fluorinated Acrylates with Fluoromonomers

Frederic Boschet, Georgi Kostov and Bruno Ameduri, Chemistry, Institute Charles Gerhardt, Montpellier,

France

The radical co- and ter-polymerization in both solution and emulsion of various fluorinated olefins

FCX=CYZ (M), where X, Y and Z represent F, H, or any other atom or group, such as vinylidene fluoride

(VDF), hexafluoropropene (HFP), etc., and fluorinated methacrylic compounds such 2-

(trifluoromethyl)acrylic acid (MAF), tert-butyl 2-(trifluoromethyl)acrylate (MAFTBE), leading to poly(M-co-

MAF(TBE)) were investigated. Polymers with molecular weights up to 100,000 g.mol-1 were obtained in

good yields.

The kinetics of the radical copolymerization of (2,2,2-trifluoroethyl)methacrylate (TFEMA) and tert-butyl 2-

(trifluoromethyl)acrylate (MAFTBE) in solution was also and led to the assessment of the reactivity ratios

(rTFEMA=4.12 ± 0.03 and rMAFTBE=0.09 ± 0.01 at 74 °C).1

The thermal stability of the resulting polymers has been evaluated.

1. F. Boschet, G. K. Kostov, B. Ameduri, T. Yoshida, K. Kawada. Submitted to J. Polym. Sci. Part A: Polym.

Chem.

117

216. Kinetic Study of the Reaction Between Perfluoro-Methyl-Hypofluorite and Fluoro-Olefins

Walter Navarrini1, Francesco Venturini1, Maurizio Sansotera1, Pierangelo Metrangolo1, Giuseppe

Resnati1, Marco Galimberti2 and Vito Tortelli2, (1)Dipartimento di Chimica, Materiali ed Ingegneria Chimica

"Giulio Natta", Politecnico di Milano, Milano, Italy, (2)R &D Centre, Solvay-Solexis, Bollate(MI), Italy

In the known reaction between perfluoroolefins and perfluoroalkylhypofluorites we have recently observed

the existence of two different free radical reaction mechanisms; this observation is demonstrated by the

presence of different and characteristic by-products [1].

In our previous studies we have noticed that the concentration of hypofluorite in the reaction media is an

important variable to control the course of the main reaction, in particular in the reaction with bis-

fluoroxydifluoromethane BDM and tetrafluoroethylene TFE conducted in high excess of BDM [2]. This

observation prompted us to study the addition of highly reactive fluoroolefins to perfluoromethyl

hypofluorite taking into account the concentration of the hypofluorite in the reaction media. This

experimental approach allowed the identification of a simple and economical methodology for the

preparation of highly pure perfluoroethers with low boiling point and low Ostwald coefficient [3].

In the reaction between trifluoromethyl hypofluorite and highly reactive perfluoroolefins like CF2=CFOCF3

and CF2=CF2, the free radical oligomerization and dimerization products can be suppressed by utilizing the

opportune experimental conditions.

[1] W. Navarrini, F. Venturini, M. Sansotera, M. Ursini, P. Metrangolo, G. Resnati, M. Galimberti, E.

Barchiesi. J. Fluorine Chemistry 129 (2008) 680-685.

[2] W. Navarrini, S. Corti, J. Fluorine Chem. 125 (2004) 189-197.

[3] W. Navarrini, G. Resnati, P. Metrangolo, M. Cantini, F. Venturini, IT Patent ITMI20071481A1( 2007)

Organic/Organometallic-III (27th August, Thursday)

Presider: Giuseppe Resnati, Politecnico di Milano, Milano, Italy

217. Propargylic Fluorides as Highly Versatile Intermediates for the Synthesis of Challenging Fluorinated Molecules

René Grée, CNRS UMR 6510 Chimie et Photonique Moléculaires, University of Rennes1, 35042 Rennes

Cedex, France

Propargylic fluorides have become easily accessible molecules. For instance the monofluorinated

derivatives can be obtained in high ee's through different methods, including our DAST-mediated reaction

of propargylic alcohols. On the other hand, we have also shown that the reaction of DAST with propargylic

ketones was very fruitful for the preparation of propargylic compounds with difluoromethyl, as well as

difluoroalkyl side chains. Therefore these new propargylic fluorides now appear as versatile intermediates

for the preparation of various types of challenging molecules. This will be illustrated by recent examples

from our group including: i) preparation of linear compounds with the total synthesis of fluorinated

analogues of polyunsaturated fatty acid metabolites, ii) new synthesis of benzylic fluorides, iii) preparation

of various fluorinated heteroaromatic, as well as heterocyclic derivatives.

218. The Use of Perfluorobutyl Methyl Ethers as Methylating Agents for Amines

Chadron Mark Friesen1, Christopher Greever2, Jon L. Howell3 and Justin M. Hoerter2, (1)Department of

Chemistry, Trinity Western University, Langley, BC, Canada, (2)Jackson Laboratory, E. I. du Pont de

Nemours, Deepwater, NJ, (3)Experimental Station, E. I. du Pont de Nemours, Wilmington, DE

118

Perfluorobutylmethyl ether (PFBME) has been commonly used as detergents, heat-transfer media, as well

as fluorochemical solvents where replacement of chlorofluoro-carbons is required. The popularity of this

fluorochemical solvent has been due to its moderate boiling point (61 oC) and its inertness. Little work as

been done to explore the use of these particular hydrofluoro ethers as reactants in organic synthesis. A

historical review of such work will be discussed as well as our current research findings. The points of

discussions will be as follows: 1) The use of perfluorobutylmethyl ethers as methylating agents for

various amines with different R groups 2) Ability to form ammonium fluorides

219. Fluorinated Benzoenediynes: Preparation, Structures and Reactivities

Markus Etzkorn, Christopher M. Kane, Tiffany B. Meyers and Reece M. Arlin, Department of Chemistry,

UNC Charlotte, Charlotte, NC

In our effort to obtain highly fluorinated naphthalene derivatives for our fluorinated molecular tweezer

project we have explored a Bergman cyclization approach, starting with fluorinated benzoenediynes. We

describe the syntheses of several fluorinated benzoenediyne derivatives, discuss their structures and will

present our results on the cyclization toward selected target compounds. We will compare the Bergman

cyclization approach with alternative routes and show examples for their use in molecular tweezer

chemistry.

220. CuBr-Catalyzed Oxidative C-H Bond Difluoromethylation of Tertiary Amines

Feng-Ling Qing and Lingling Chu, Shanghai Institute of Organic Chemistry, Chinese Academy of

Sciences, Shanghai 200032, China

The α,α-difluoro-β- amino acids have attracted much interest due to their importance in chemical biology.

The most commonly used methods for the synthesis of β-amino-α,α-difluoro ketone or acid derivatives

thus far are Reformatsky addition of α-halodifluoro ketones or bromodifluoroacetate to imines and the

reaction of difluoroenol ethers with N-acyliminiums or imines under Lewis acid activation. Although these

are effective methods, they require the use of imines or N-acyliminiums prepared from aldehydes and

amines. Recently, transition-metal-catalyzed C-H bond functionalization of tertiary amine has attracted

great attention in both academia and industry because of its atom- and step-economy, high efficiency, low

cost and minimal environmental impact. Inspired by these works, an effective copper(I)-catalyzed

oxidative difluoromethylation of tertiary amine with difluoroenol silyl ethers under mild conditions was

developed in our group. This new method provides a simple way to synthesize β-amine-α,α-difluoro

ketones from readily available amines. The scope of the present reaction, as well as the application of the

resulting difluoromethyleneated building blocks will be presented at this symposium.

119

Physical (27th August, Thursday )

Presider: Berthold Hoge, University of Cologne, Cologne, Germany

221. Spectroelectrochemistry of Perfluoroalkylfullerenes: Redox Potentials, ESR Spectra, and DFT Calculations

Alexey A. Popov1, Ivan E. Kareev2, Natalia B. Shustova3, Sergei F. Lebedkin4, Steven H. Strauss3, Olga

V. Boltalina3 and Lothar Dunsch5, (1)Department of Chemistry, Moscow State University, Moscow, Russia,

(2)Institute of Problems of Chemical Physics, Chernogolovka, Russia, (3)Department of Chemistry,

Colorado State University, Fort Collins, CO, (4)Institute for Nanotechnology, Forschungszentrum

Karlsruhe, Karlsruhe, Germany, (5)Leibniz Institute for Solid State and Materials Research, Dresden,

Germany

Recent developments in fullerene perfluoroalkylation methodologies have resulted in the isolation and

structural characterization of more than 100 perfluoroalkyl derivatives of C60, C70, higher fullerenes, and

endohedral metallofullerenes. Electrochemical studies have shown that most of these compounds exhibit

two or three reversible reductions at low voltammetric scan rates. This fact indicates that the radical

anions of these derivatives are stable enough at 25 °C to be studied by spectroscopic methods. In this

work we review the results of an in-depth ESR spectroelectrochemical studies of perfluoroalkylated

fullerenes C60(CF3)n and C70(CF3)n (n = 2–12). Experimental studies are accompanied by DFT calculations

of the spin density distributions and ESR hyperfine spitting constants in the respective anion-radicals.

222. Design and Synthesis of Electron Conducting Materials

Sonja Hettel and Berthold Hoge, Institute of Inorganic Chemistry, University of Cologne, Cologne,

Germany

Beside a few exceptions organic semiconductors exhibit either preferred electron or hole conducting

behavior. Accordingly they are classified into n- or p-type semiconducting materials.

Quantum chemical calculations offer the possibility to develop promising frameworks, which exhibit on the

one hand an electron affinity from 3 to 4 eV[1] and on the other hand possess a low reorganization energy.

120

The perfluorinated diarylazo derivatives C6F5N=NC6F5 and C5NF4N=NC5NF4 show comparatively high

adiabatic electron affinities of 2.32 and 3.04 eV respectively. After the synthesis of C5NF4N=NC5NF4[2]

the

calculated electron affinity could be proven by cyclovoltammographic measurements. Beside the high

electron affinities of diarylazo compounds, the corresponding radical anions exhibit strongly delocalized

SOMOs, as it could be demonstrated by EPR measurements. Based on the obtained data, diarylazo units

represent a promising key structure for the development of high performance semiconducting materials.

[1]. Newman, C. R. ; Frisbie, C. D.; da Silva Filho, D. A.;. Brédas, J. L; Ewbank, P. C.; Mann, K. R., Chem.

Mater., 16, 2004, 4436 - 4451.

[2]. Dolenko, G. N.; Zibarev, A. V.; Krupoder, S. A.; Mazalov, L. N.; Poleshchuk, O. Ch.; Furin, G. G.;

Khudorozhko, G. F.; Yakobson G. G., J. Fluorine Chem., 17, 1981, 1 - 14.

223. The Intramolecular, Blue-Shifting C-H•••F-C Hydrogen Bond in Solid State: Excellent Agreement Between Experimental and Calculated Data for Vibrational

Spectra

Norman Lu1, Hsi-Chun Hou1, Chien-Ting Lin1, Ling-Kang Liu2 and J.-C. Jiang3, (1)Department of

Molecular Science and Engineering, National Taipei University of Technology, Taipei, Taiwan, (2)Institute

of Chemistry, Academica Sinica, Taipei 115, Taiwan, (3)Department of Chemical Engineering, National

Taiwan University of Science and Technology, Taipei, Taiwan

In solid state, the two fluorous-ponytails in [4,4′-bis(HCF2CF2CF2CF2CH2OCH2)-2,2′-bpy]MCl2 (M = Pt 2; Pd

3) reveal one with a transoidal HCF2CF2CF2CF2CH2- chain on carbon backbone, similar to that with a

normal fluorous alkyl group, and the other with a cisoidal HCF2CF2CF2CF2CH2- chain on carbon backbone,

exhibiting a six-membered, intramolecular C-H…F-C hydrogen-bond. The distance between F and H

is 2.34(7) Å in 2 and 2.34(4) Å in 3, significantly shorter than the sum (2.54 Å) of van der Wals radii of H

and F atoms. To our knowledge, the crystallographically characterized six-membered, intramolecular C-

H…F-C hydrogen-bonds in 2 and 3 are the first ones determined and analyzed to date. The structure of 2

(or 3) provides a good opportunity to demonstrate the intramolecular H-bonding which is not easy to be

characterized since the unperturbed characteristics are usually missing, unlike in the case of

intermolecular H-bonding, for comparison. These two examples are among the blue-shifting hydrogen

bonds as defined by Hobza et al. because of the observations of the C-H bond contraction, of the increase

in C-H stretching frequency, and of the C-F bond elongation. Furthermore, the calculated C-H stretches

with periodic density functional theory (VASP: Vienna a,b-initio similation package) are in good agreement

with IR observations. The results reported here are likely to help in better understanding the nature of

blue-shifting H-bonding and to create a new area in the weak hydrogen bond research.

224. Perfluoroalkylated Arenes for Stable and Efficient Organic Light-Emitting Diodes

Haoran Sun and Anjaneyulu Putta, Department of Chemistry, University of South Dakota, Vermillion, SD

Fluorinated materials offer many advantages over nonfluorinated ones including high stability, tolerance to

extreme environmental conditions, and profound effects upon tuning the electronic and optical properties

of organic compounds. They are found in many state-of-the-art materials including active matrix liquid

crystal displays, polymers for 193 nm and 157 nm photolithography, and proton exchange membranes for

fuel cells. The ability to modulate the HOMO and LUMO energy, HOMO-LUMO energy gap, redox potential,

and heterogeneous and homogeneous electron transfer (ET) rate of organic semiconducting compounds is

essential to electronic and optoelectronic applications, for example, organic solar cells, organic light-

emitting diodes (OLEDs), and organic thin film transistors (OTFTs). Strong C-F and corresponding strong

C-C bonds in fluorocarbons make them less polarizable than typical hydrocarbons. The highly polar,

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weakly polarizable, non-hydrogen bonding, non-coordinating properties of fluorinated materials,

particularly perfluoroalkylated materials, underlie the motto ―Nothing sticks to Teflon® and Teflon®-

coated products‖. Here we report the synthesis and characterization of perfluoroalkylated arenes for stable

and efficient OLEDs, particularly, deep blue OLEDs. Developing deep blue light emitters remains a

challenge because of the difficulties inherent in preparing organic compounds with high energy emission

(2.7 eV to 3.2 eV range), having, at the same time, high emission quantum efficiency and stability. 9,10-

bis(perfluorooctal)anthracene, synthesized in good yield from a low cost precursor, exhibits a dramatically

enhanced deep blue light emission when compared to anthracene in both solution and solid state under

ambient conditions. The origin of this luminescence enhancement will also be discussed.

Environmental (27th August, Thursday afternoon)

Presider: Philippe Buhlmann, University of Minnesota, Minneapolis, MN

225. Polyfluorinated Chemicals: Why Are They Viewed as Environmental Pollutants?

Scott A. Mabury, Department of Chemistry, University of Toronto, Toronto, ON, Canada

Perfluorinated acids (PFCAs and PFOS) are widely disseminated in the global environment and appear at

high concentrations in humans and in Arctic mammals; a new PFA, the perfluorophosphonic acid or PFPAs,

was recently discovered in our lab. We have developed the ‗precursor alcohol atmospheric reaction and

transport‘ or PAART theory to potentially explain these observations. Residual fluoro-alcohols are

significant in fluorinated polymers and surfactants (food contact paper coatings) and may contribute

significantly to the global burden, though we know little about the stability of the linkage chemistry within

the fluorinated materials. Recent experiments have shown the ester and phosphate esters in monomers

and surfactants are readily hydrolyzed through microbial and mammalian metabolism. We have

discovered relatively high concentrations of diPAPs, a phosphate based polyfluorinated surfactant, in

human blood. The building block fluoro-alcohols and the surfactants themselves are readily metabolized,

via reactive intermediates, to the resulting PFCAs. Some of these intermediates have been shown to be

highly toxic to D. Magna (ie 10:2 FTCA) or readily react with GSH (the acrylic aldehydes). These

fluoroalcohols are also readily found in the atmosphere and have been shown to undergo atmospheric

transport and OH driven transformation reactions to yield the observed perfluorinated acids. Model

studies suggest significant production of these acids in remote Arctic regions have been confirmed by flux

measurements into the ice cap. Temporal studies of biota contamination yield body burdens that appear

to closely match production changes by industry.

226. Efficient Decomposition of Environmentally Persistent Fluorochemical Surfactants Using Persulfate in Hot Water

Hisao Hori, Yumiko Nagaoka, Misako Murayama and Shuzo Kutsuna, National Institute of Advanced

Industrial Science and Technology (AIST), Tsukuba, Japan

Perfluorocarboxylic acids (PFCAs) such as perfluorooctanoic acid (PFOA) have recently received much

attention because they are ubiquitous environmental contaminants. After PFCAs were shown to be

persistent and bioaccumulate in the environment, efforts to eliminate them from facility emissions began.

The development of techniques for decomposing waste PFCAs (especially in wastewater) to harmless

species under mild conditions is important. The method should produce F– ions, because F– ions have well

established treatment processes: addition of Ca2+ results in the formation of environmentally harmless

CaF2.

We previously reported that persulfate (S2O82–) efficiently decomposes aqueous PFCAs to F– ions and CO2

photochemically; the photolysis of S2O82– produces sulfate radical anions (SO4·

–), which act as strong

oxidants [1]. Although the photochemical technique effectively decomposes PFCAs, a simpler and more

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convenient reaction system in terms of equipment is desirable for large-scale treatment.

Because SO4·– may be obtained from S2O8

2– not only photochemically but thermally, we investigated the

decomposition of PFCAs by hot water in a simple sealed reactor. Here we show that PFCAs can be

effectively decomposed in hot water to F– and CO2 at a relatively low temperature (80 ºC) in the presence

of S2O82– [2]. We also applied this method to the decomposition of perfluoroether carboxylic acids,

representative alternatives to PFCA-based surfactants.

[1] H. Hori, A. Yamamoto, E. Hayakawa, S. Taniyasu, N. Yamashita, S. Kutsuna, H. Kitagawa, R. Arakawa,

Environ. Sci. Technol, 2005, 39, 2383–2388.

[2] H. Hori, Y. Nagaoka, M. Murayama, S. Kutsuna, Environ. Sci. Technol, 2008, 42, 7438–7443.

227. The Acute Inhalation Toxicity Ratio: A First Step in Toxicological Evaluation of Volatile Chemicals

Paul H. Lieder, Medical Department, 3M Company, St. Paul, MN

Many industrial chemicals induce acute inhalation toxicity due to chemical narcosis. This class includes

most CFCs, CFC alternatives and volatile hydrocarbons. Understanding this endpoint and the ability to

predict the levels at which lethal narcosis occur (baseline toxicity) are important first steps for toxicity risk

assessment. Narcosis biological activities are closely predicted using thermodynamic parameters (Kow,

Kaw) which are estimated using chromatographic techniques. The Toxicity Ratio, or T.R., (Predicted LC50

(narcosis endpoint)/Observed LC50) can be employed to quantitate deviations from narcosis-based

toxicity.

Though useful for predicting lethal levels for narcosis-inducing chemicals, this understanding is more

valuable in identifying chemicals and their structures (or substructures), which result in non-narcosis

endpoints. Toxicities can be attributed to the following:

Class 1: Toxicity is predicted by this thermodynamic approach. It includes inert chemicals which are not

otherwise biologically reactive (CFCs, other baseline toxicants). Toxicity is technically independent of

chemical structure. (T.R.) = 1

Class 2: Toxicity is due to chemical reaction with biological processes or bioactivation processes (CH3I,

1,2-difluoroethane, T.R.= 2 to 1000+).

Class 3: Toxicity is due to specific interaction with certain receptors (certain neurologically active

chemicals, T.R.=2 to 100+).

A QSAR and analytical technique will be described for estimating baseline toxicity values (LC50s).

Examples for using T.R. and comparative symptomologies to understand modes of action and bioactivation

pathways will be discussed. Selected applications of this technique in evaluation of industrial chemicals

will be presented including the importance of using pharmacokinetics and other highly focused short-term

studies in early evaluation of chemicals.

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228. Recent Developments in Fluoro-Raman Spectroscopy

Farid Menaa1, Bouzid Menaa1, Carla Aiolfi-Guimarães2, Leo Avakyants1 and Olga Sharts1, (1)Fluorotronics

Inc., San Diego, CA, (2)University of Sao Paulo, University of Sao Paulo, San Paolu, Brazil

Carbon-Fluorine Spectroscopy is a patented platform technology using various methods and a family of

devices called PLIRFATM (―Pulsed Laser Isochronic Raman and Fluorescence Apparatus‖) developed by

Fluorotronics, Inc. (www.fluorotronics.com). The key feature of this technology is based on the discovery

of a characteristic optical signature of carbon-fluorine bond(s) in the fingerprint spectral area of 550 cm-1

and 950 cm-1 allowing detection, characterization, imaging, and measurement of fluoroorganics. The FRS

method is ultra-specific, ultra-sensitive, non-destructive, rapid, require no sample preparation, easy to

use and therefore cost effective. Furthermore, the C-F bond signal is directly proportional to the

concentration of the analyte, allowing a quantitative determination of F-labelled compounds. Since the C-F

bond is unique in its character, it can be used as an external or internal chemical tag/molecular marker.

Furthermore, the C-F label is efficient, soluble, cheaper, smaller, more stable and less toxic than

fluorescent dyes, nanoparticles or quantum dot materials. Consequently, FRS can be used for numerous

applications. For instance, C-F bonds are often incorporated into pharmaceutical, agrochemical and

biological molecules as well as in polymers and nano-materials to achieve special properties (e.g.

molecular stability, tracing a compound during the production or the synthesis cycle). FRS is applicable for

multiplexing, high throughput analysis of any type of fluoroorganics in various media, in any physical state

as well as in cells.

Eventually, Fluoro-Raman spectroscopy represents a powerful and flexible technology. We will present

some of our promising data and review the most important applications of our patented technology.

Fluoropolymers/Materials - II (27th August, Thursday afternoon)

Presider: Bruno Ameduri, Institute Charles Gerhardt, Montpellier, France

229. Self-Assembly of Fluorinated Block Polymers: a Flexible Route to Novel Nanostructures

Timothy P. Lodge, Department of Chemistry, University of Minnesota, Minneapolis, MN

Block polymers consist of two or more distinct polymers covalently linked together. As most polymer pairs

are immiscible at reasonable molecular weights, the components attempt to form separate domains. The

covalent linkages prevent macrophase separation, and as a result the molecules self-assemble into a

variety of nanostructures. This occurs both in bulk polymer and in solution, when the solvent favors one

block over the other. For simple ―AB‖ diblocks such as poly(styrene-b-isoprene), the bulk phases that form

(lamellae, cylinders, gyroid, body-centered spheres) are well understood. Similarly, in solution the factors

that dictate whether the resulting micelles are spheres, worms, or vesicles are known. However, when the

strength of the interaction between blocks is greatly increased, for example by fluorination, then new

regimes of self-assembly can be accessed. Examples of the novel morphologies that result from the

strategic incorporation of fluorine, both in bulk and in solution, will be presented. Furthermore, when the

polymer contains three distinct blocks, the resulting ABC terpolymer can form higher-order structures

such as multicompartment micelles and gels. In this case the fluorine-containing block is both extremely

hydrophobic and lipophobic, allowing the formation of separate nanoscopic domains within a given micelle.

124

230. Functionalization of Carbonaceous Materials with High Fluorine Content Organic Peroxides

Maurizio Sansotera1, Walter Navarrini1, Pierangelo Metrangolo1, Giuseppe Resnati1, Claudia L. Bianchi2

and Pier Antonio Guarda3, (1)Dipartimento di Chimica, Materiali ed Ingegneria Chimica "Giulio Natta",

Politecnico di Milano, Milano, Italy, (2)Dipartimento di Chimica Fisica ed Elettrochimica, Università degli

Studi di Milano, Milan, Italy, (3)Research and Technology, Solvay Solexis, Bollate, Italy

Perfluorodiacyl peroxides and perfluoropolyether peroxides (FOMBLIN® peroxides) are suitable organic

peroxides for direct linkage of perfluoroalkyl and perfluoropolyether chains on unsaturated substrates

through a radical pathway. Highly graphitic carbon black and aC:H diamond-like carbon are carbonaceous

materials characterized by sp2 hybridized carbon atoms in the structure. Consequently a chemical

treatment with high fluorine content organic peroxides allows the introduction of fluorinated groups onto

carbonaceous substrates with carbon-carbon bond formation [1]. Depending on the peroxide involved

during the treatment, several fluorinated chains, i.e. perfluoroethyl, CF3CF2-, perfluoro-n-propyl,

CF3CF2CF2-, perfluoro-iso-propyl, (CF3)2CF-, and perfluoropolyether residual, has been covalently linked on

the surface of the carbonaceous materials. Functionalization of carbon black transfers the typical

hydrophobic properties of perfluorinated chains to the carbon black surface even preserving its conductive

properties. This chemical treatment on diamond-like carbon films produces a covalently bonded protective

layer with the typical lubricant properties of perfluorinated compounds.

[1] Navarrini W., Sansotera M., Metrangolo P., Cavallotti P., Resnati G. WO 2009/019243 A1.

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232. γ-Radiation Induced Graft Polymerisation On Fluorinated Microfiltration Membrane

Nicolas Fortin1, Sophie Rouif2, Jean-Yves Sanchez3, Daniel Portinha1 and Etienne Fleury1, (1)IMP/LMM,

Laboratoire des Matériaux Macromoléculaires, Université de Lyon; INSA de Lyon, Villeurbanne, France,

(2)R&D, IONISOS, Dagneux, France, (3)Laboratoire d'Electrochimie et de Physicochimie des Matériaux et

des Interfaces, Institut National Polytechnique Grenoble, Saint Martin d‘Hères, France

Fluoropolymers, especially poly(vinylidene fluoride) (PVDF), are well known for their excellent properties

in terms of chemical stabilities and high resistance to ageing and oxidation. However, its high

hydrophobicity could limit its application for membrane production when the mobile phases to be treated

are dispersed in an aqueous media.

The use of radiation-processing for modification of polymeric materials has been explored for the last 50

years. In our case, we have developed a clean and robust process to graft hydrophilic monomers in mild

conditions initiated by γ-radiation onto a PVDF-based microfiltration membrane (Figure 1).

Pre-irradiation technique allows generating alkyl radicals, which are able to react with vinylic monomers

without chemical treatments of the surface. The polymerization of hydrophilic monomers was performed in

aqueous medium at 35°C, in order to minimize environmental impact. The monomer conversion obtained

can be treated by typical kinetics law of a free radical polymerisation which confirms that alkyl radicals at

surface of the membrane are able to initiate the polymerization. The grafting of hydrophilic polymers onto

PVDF membrane was confirmed by XPS and contact angle analysis.

Additionally, the radical concentration into irradiated membrane was determined as a function of the dose

by ESR spectroscopy. Figure 2 shows that the concentration of radicals in the membrane increases with

dose, up to a maximum value reached from 50 kGy. The quantity of radicals able to initiate polymerization

was determined precisely in function of dose, in order to adjust the grafting rate and to control the

contribution of hydrophilicity on the membrane.

126

Organic/Organometallic-IV (27th August, Thursday)

Presider: Viacheslav A. Petrov, DuPont CR&D, Wilmington, DE

233. Fluorinated Oxazolidines (FOX) Chiral Auxiliaries: Recent Advances In Asymmetric Synthesis

Thierry Brigaud, Department of Chemistry, University of Cergy-Pontoise, Cergy-Pontoise, France

The fluorinated oxazolidines derived from fluoral hemiacetal and (R)-phenylglycinol (Fox) proved to be

very stable to hydrolysis because of the electron-withdrawing effect of fluorine. Therefore these

oxazolidine can be used as highly efficient chiral auxiliaries for several stereoselective amide enolates

reactions. A screening of these reactions will be presented (aldol reactions, alkylations, …). As a major

result, the a-alkylation of various amide enolates occurred in good yield and with an extremely high

diastereoselectivity (>99% de).1 The chiral auxiliary was recovered in good yield after cleavage and the

target aldehyde, alcohol and carboxylic acid were obtained in good yield in enantiopure form. The origin of

this excellent diastereocontrol was investigated by a theoretical (DFT) study.2 The results of this study

indicate that both Na•••F and Na•••Ph interactions can rigidify the transition state demonstrating why the

pseudo C2 symmetry of the cis Fox chiral auxiliary is necessary to reach such a high level of

diastereoselectivity. We will also report the extension of the Fox methodology towards the synthesis of b2-

amino acids,3 the O2 oxidation and the electrophilic fluorination of the enolates.

References

(1) Tessier, A.; Pytkowicz, J.; Brigaud, T. Angew. Chem. Int. Ed. 2006, 45, 3677.

(2) Sini, G.; Tessier, A.; Pytkowicz, J.; Brigaud, T. Chem. Eur. J. 2008, 14, 3363.

(3) Tessier, A.; Lahmar, N.; Pytkowicz, J.; Brigaud, T. J. Org. Chem. 2008, 73, 3970.

234. Synthesis of Pentafluorosulfanyl (SF5) Heterocycles. Pyrroles and Thiophenes William R. Dolbier Jr. and Zhaoyun Zheng, Department of Chemistry, University of Florida, Gainesville,

FL

Few heterocycles bearing an SF5 substituent have thus far been reported in the literature: furans,

pyrazoles and triazoles. In this talk, work directed towards the synthesis of 4-SF5-substituted pyrrole-2-

carboxylic acid esters and 3-SF5-substituted thiophenes will be presented. Classic approaches to these

heterocycles using condensation chemistry, proved fruitless, with the SF5 group being destroyed in all

such processes thus far. However, a synthetic approach involving 1,3-dipolar cycloadditions to SF5-

alkynes allowed retention of the SF5 group in the product. For the pyrroles, an azomethine ylide was

utilized, whereas for the thiophenes, a thiocarbonyl ylid proved useful.

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35. Unusual Behavior of Anionic Species From (E)-1-Chloro-3,3,3-Trifluoropropene (HCFC-1233t)

Takashi Yamazaki, Akiko Miyagawa and Tomoko Kawasaki-Takasuka, Department of Applied Chemistry,

Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Japan

Non-ozone depleting (E)-1-chloro-3,3,3-trifluoropropene, abbreviated as HCFC-1233t, is manufactured as

the convenient intermediate for the preparation of 1,1,1,3,3-pentafluoropropane as the potent

chlorofluorocarbon substitute. In addition to the usage for this purpose, this material also recognized as

the useful CF3-containing building unit by installation of structurally-defined (E)-olefin and a chlorine atom

as the useful synthetic handles. For synthetic application, anion formation from HCFC-1233t was carried

out by base-mediated reactions which unexpectedly furnished either allylic or propargylic alcohols with a

product selectivity highly dependent on the amount of a base used. In this talk, possible mechanism of

this quite intriguing reaction will be discussed.

236. Tetrakis(trifluoromethanesulfonyl)Propane: Highly Effective Brønsted Acid

Catalyst for Vinylogous Mukaiyama-Michael and Aldol Reactions Using 2-Silyloxyfurans

Takeo Taguchi, Arata Takahashi, Hikaru Yanai and Yasuhiro Yoshino, School of Pharmacy, Tokyo

University of Pharmacy and Life Sciences, Tokyo, Japan

Today development of highly active Brønsted acid catalysts is an important subject in the field of organic

synthesis and fluorine chemistry has been playing a mojor role for this purpose. Among these examples,

bis(trifluoromethanesulfonyl)methyl structure (Tf2CH-) attracts much attention due to its good proton

donor ability caused by gem-substitution of two electron-withdrawing triflyl groups, its steric bulkiness as

well as its chemical stability. Recently, we have demonstrated that a sterically bulky aluminum methide

Tf2CHAlMe2 generated by the reaction of bis(trifluoromethane-sufonyl)methane (Tf2CH2, pKa = -1 in

AcOH) with Me3Al acts as an effective catalyst in the Diels-Alder reaction of alpha,beta-unsaturated

lactones (Tetrahedron Lett., 2007, 38, 2993) and a sequential Mukaiyama-Michael reaction of alpha,beta-

enones with 2-silyloxyfurans followed by the Diels-Alder reaction of the resultant alpha,beta-unsaturated

lactone with cyclopentadiene. In these reactions relatively high catalyst loading (20-30 mol%) required for

the high yield within an appropriate reaction period was one of the issues to be solved. Further efforts

have been made to examine the catalyst activity of carbon acids having a Tf2CH-moiety in the molecule.

In this presentation, we report on the vinylogous Mukaiyama-Michael and aldol reactions using 2-

silyloxyfurans, which are effectively catalyzed by 1,1,3,3-tetrakis(trifluoromethanesulfonyl)propane

(Tf2CHCH2CHTf2) having two acidic protons attached on the 1,3-positions (Chem. Commun. 2008, 2385).

128

Poster Session (27th August, Thursday evening)

Presider: Joseph S. Thrasher, The University of Alabama, Tuscaloosa, AL

237. Sc[N(SO2C8F17)2]3 Catalyzed Condensation of â-Naphthol and Aldehydes In Fluorous Solvent: An Efficient Procedure for the Synthesis of 14-Substituted-14H-

Dibenzo[a,j]Xanthenes

Chun Cai, Chemical Engineering College, Nanjing University of Science and Technology, Nanjing , China,

Nanjing, China and Mei Hong, Chemical Engineering College, Nanjing University of Science and

Technology, Nanjing, China

Sn[N(SO2C8F17)2]4 and Hf[N(SO2C8F17)2]4 have been reported as efficient FBS Lewis acid catalysts for

several useful synthetic reactions such as Bayer-Villiger oxidation [1], esterification [2], Friedel-Crafts

acylation [3] and Prins reaction [4]. Here we have prepared fluorous Lewis acid catalysts M[N(SO2C8F17)2]n

M=Ln, Sn, Hf). Sc[N(SO2C8F17)2]3 in perfluorodecalin was found to be an efficient catalyst for the

condensation of β-naphthol with aldehydes to provide 14-substituted-14H-dibenzo[a,j]xanthenes in good

yield. Mild reaction conditions, facile experimental procedure, catalyst reusability and good yield of

products render this new method attractive for synthesis of xanthenes.

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238. Research of KBrF4 Production by Fluorination Methods of Potassium Bromide

Roman Ostvald, Vladimir Shagalov and Ivan Gerin, Chemical Engineering Department, Tomsk

Polytechnic University, Tomsk, Russia

Oxidative fluorination becomes an important process in modern engineering and laboratory practice. For

example, strong oxidizing reagents are necessary for successful oxidation of stable, refractory materials.

Halogen fluorides are unique class of compounds with strong oxidation ability that could be well suited for

such processes.

Nevertheless, application of bromine trifluoride in the laboratory and industrial practice is complicated. As

a safe alternative to BrF3 we propose to use KBrF4, a bromine trifluoride complex compound with

potassium fluoride. The processes with its participation are very safe and can be carried out in any

analytical laboratory.

In this paper, we present results of preparation of KBrF4 by direct fluorination of KBr with gaseous

fluorine. The reaction was carried out in the vertical reactor, with continuous recording of the sample

weight change as a function of time. Final product was characterized by weight uptake and chemical

analysis. Optimal conditions for the synthesis of KBrF4 were found.

Based on the obtained results, the three-stage reaction mechanism was proposed: displacement of bromine by fluorine in KBr: 2KBr + F2 → 2KF + Br2;

formation of bromine trifluoride molecule in the gaseous state: Br2 + 3F2 → 2BrF3;

sorption of bromine trifluoride on potassium fluoride with the formation of complex KBrF4: KF + BrF3 →

KBrF4

These data provide the foundation for the development of the technology of the KBrF4 production by gas-

phase method.

239. Effect of the Alternation Order of CH2 and CF2 Groups On the Mechanism of Direct Fluorination of Fluorine - Containing Polymers

Sadulla Reimovich Allayarov1, Tatayna Andreevna Konovalova2, Alfred Waterfield2, Virgil E. Jackson2,

Joseph S. Thrasher2, Lowell D. Kispert2 and David Adams Dixon2, (1)Institute of Problems of Chemical

Physics of the Russian Academy of Sciences, Chernogolovka, Russia, (2)Department of Chemistry, The

University of Alabama, Tuscaloosa, AL

Direct fluorination of polyvinylidenefluoride (PVDF) and the copolymer of tetrafluoroethylene with ethylene

(CTE) by molecular fluorine were studied at 35-300 K. The fluorinated polymers were studied by energy

dispersion microscopy (EDAX). The EDAX data shows that PVDF has the same content of fluorine before

and after fluorination. In contrast, the content of fluorine in CTE increases by ~2% after fluorination. This

indicates that only CTE reacts with fluorine under experimental conditions. The dependence of the radical

formation on temperature and reaction time were obtained by EPR spectroscopy. Primary alkyl radicals

formed as a result of the fluorine reaction with a polymer were detected at 35 K. They rapidly react with

molecular oxygen producing peroxide radicals. The peroxide radicals when subjected to UV-irradiation

(<280 nm) decompose into other radicals which are not stable at T > 77 K. The concentration of the

radicals produced during fluorination of PVDF at 77-200 K is one order of magnitude less than that of the

CTE radicals formed under similar conditions. The concentration of radicals formed at 77 K during the

reaction of CTE with F2 depends on fluorine pressure and the reaction time. If the fluorine pressure

increases from 30 torr to 700 torr (F2 : CTE = 0.15 : 1.0), the radical concentration increases by a factor

of 3. An increase of the reaction time from 3 to 10 min leads to a doubling of the concentration of

radicals. The mechanism of PVDF and CTE fluorination depends on the location of –CH2– group.

130

240. Simple Preparation of Optically Pure Alcohol Using Ionic Liquid through Lipase Catalyzed Reaction

Yumiko Takagi1, Hiroaki Ishihara1 and Toshiyuki Itoh2, (1)Department of Chemistry, Kagawa University,

Faculty of Education, Takamatsu City, Kagawa, Japan, (2)Department of Chemistry and Biotechnology,

Tottori University, Graduate School of Engineering, Tottori, Japan

Antiferroelectric liquid crystal compounds(AFCLs), which possess a chiral 1,1,1-trifluoromethyl-2-alkanol

moiety, are known to be important high-speed switching devices[1]. We previously reported that Candida

antarctica lipase catalyzed trans-esterification of racemic 1,1,1-trifluoro-2-alkanols with perfect

enantioselectivity. We also achieved the hydrolysis of acetate more effectively [2-4].

Ionic liquids(ILs) were primarily explored for their applications in electrochemical technologies and as

solvents in electronic. ILs are salts which are liquid at room temperature and capable of solubilizing a

great number of compounds. ILs are regarded as environmental-benign alternatives to volatile organic

solvents in chemical and biocatalytic processes, due to their negligible vapor pressure and nonflammable

nature.

This characteristic is very interesting to perform enzymatic reactions with lipases which are well known to

be active on interfaces. Investigated enantioselectivity in the enzymatic kinetic resolution of

trifluoromethylalkanol employing immobilized lipase from Candida antarctica results from the use of the

ionic liquids [bmim][PF6], [bmim][TFSI] and [bmim][NTf2] as reaction medium. Hydrolysis reaction of

1,1,1-trifluoromethyl-2-acetate proceeded smoothly to provide corresponding to alcohol with efficient

enantioselectivity. The influence of ionic liquid on the catalytic efficiency and selectivity has been studied.

The results will be discussed.

References

1) T. Kusumoto et al., Chem. Lett. 1995, 719. 2) T. Itoh et al., J. Org. Chem. 1996, 61, 2332. 3) T. Itoh

et al., Tetrahedron Lett. 1996, 37, 5001 4) Y. Takagi et.al, Tetrahedron Asym. 2004, 15, 2591.

241. Metal Cation Induced Multifluorescence of Azacrown-Substituted

(Tetrafluorophenyl)Imidazo[1,2-a]Pyridine

Kiyoshi Tanaka, Takashi Takeyama, Ryousuke Yukawa, Satoru Iwata and Tohru Kurushima, Faculty of

Science and Technology, Seikei University, Musashino-shi, Tokyo, Japan

Selective recognition of chemical species by a fluorophore modified with a recognition site has been

designed for a molecular device such as a logic gate, where a couple of chemical species play a role as

input signals and the difference in the fluorescent intensity as an output signal. In most cases, a sole

wavelength-fluorescence is utilized as output signal. However, the single-molecular multifluorescence is

of interest from the viewpoints of optoelectronic device such as a photoconverter. para-Azacrown-

substituted (tetrafluorophenyl) imidazo[1,2-a]pyridine (1) was simply prepared by the substitution of 2-

(pentafluorophenyl)imidazo[1,2-a]pyridine with 1,4,7-trioxa-10-azacyclododecane. Multifluorescence of 1

was found to be enhanced by several kinds of cations in an acetonitrile solution. Thus, 1 emits three

different fluorescent lights responding to Li+, Zn2+ or H+ cation, respectively; 388 nm light to Li+, 433 nm

light to Zn2+ or 469 nm light to H+.

131

242. Preparation of 4-Perfluoroisopropylbenzene Derivatives by Use of Trifluoromethanesulfonyl Fluoride (TfF)

Shintaro Sasaki, Tsutomu Nanmyo and Takashi Kume, Department of Chemistry, CHEMICAL RESEARCH

CENTER, CENTRAL GLASS CO., LTD., Yamaguchi Prefecture, Japan

4-Perfluoroisopropylbenzene derivatives are very versatile intermediates for medicines and agrochemicals

[1]. These compounds have been prepared from hexafluorocumyl alcohols with deoxyfluorinating reagents

such as SF4 [2]. However, in the case of aniline derivatives, these reagents provide the corresponding

fluorinated products only in poor yields. Recently, we have found that 4-perfluoroisopropylaniline

derivatives 2 are obtained from hexafluorocumyl alcohols 1 in good yield using trifluoromethanesulfonyl

fluoride (TfF) in the presence of triethylamine and HF. The results are summarized in table below.

When the fluorination of 1a was carried out at 70°C, the corresponding product 2a was obtained in a

moderate yield (Entry 1 in table). On the other hand, the reaction of 1b and 1c gave 2b and 2c,

respectively in good yield, as the results of steric hindrance of 2-methyl or 2,6-dimethyl groups (Entries

2, 3). The details of the reaction will be discussed.

[1] M. Ohnishi, et. al., Jpn. Kokai Tokkyo Koho, 2001, JP2001-288129.

[2] W. A. Sheppard, J. Am. Chem. Soc., 1965, 87, 2410.

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243. Effect of Fluorine Atom(s) in Propargylic Position On Reactivity in Click Chemistry

Danielle Grée and René Grée, CNRS UMR 6510 Chimie et Photonique Moléculaires, University of Rennes,

35042 Rennes Cedex, France

It is widely recognized that introduction of fluorine in organic molecules modifies their physical, chemical

and biological properties. It has also effect on chemical reactivity, as demonstrated for instance recently in

the increase of the rate for click chemistry by going from cyclooctyne to gemdifluorocyclooctyne.1 As part

of our programme dealing with the use of propargylic fluorides in synthesis,2 it appeared of interest to

study in a systematic manner the effect of fluorine atom(s) in propargylic position on the reactivity of the

triple bond, in linear systems, and compare fluorine to other atoms such as oxygen and hydrogen for

instance. Towards this goal, we have designed and prepared new model alkynes and studied their

reactivity in click chemistry.

This allowed us to obtain a reactivity scale for various atoms and substituents in propargylic position and

corresponding results will be reported in this communication.

244. Mono- and Trifluorination of the Heterocyclic Ring of 2,5-Diarylthiazoles Using An N-F Reagent

Julie M. Hatfield and Chad E. Stephens, Department of Chemistry and Physics, Augusta State University,

Augusta, GA

Considering the potentially beneficial effects of fluorine substitution on the physical and biological

properties of aromatic compounds, we are interested in the synthesis of fluorinated thiazoles. We have

previously described the direct fluorination of 2,4-diarylthiazoles at the 5-position in good yield using an

N-F reagent. We have now undertaken a study of the direct fluorination of the isomeric 2,5-diarylthizoles

at the 4-position. N-F reagents used in this study include N-fluorobenzenesulfonimide (NFSI),

Selectfluor®, and Accufluor®. Initial experiments showed that, unlike the 2,4-diarylthiazole isomers, the

2,5-disubstituted isomers often give a mixture of the desired monofluoro thiazole, along with a unique,

non-aromatic 4,4,5-trifluorothiazole product. As efficient separation of these products was difficult, we set

out to develop chemoselective reaction conditions for each. Using the parent 2,5-diphenylthiazole as

substrate, our most optimal method for monofluorination involves heating with NFSI in bromobenzene,

while our most optimal method for trifluorination involves heating with NFSI without solvent. Similar

results were obtained when using 2,5-bis(4-chlorophenyl)thiazole as substrate. However, when using

substrates containing a strongly electron withdrawing CF3 group on one or both of the phenyl rings, only

monofluorination was observed. Spectral data for the compounds prepared in this study include IR, 1H-

NMR, 13C-NMR, 19F-NMR, GC-MS, and HRMS. In addition, an x-ray crystal structure has been obtained for

one of the novel 4,4,5-trifluorothiazole products.

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245. Synthesis of SF5 Substituted Acetylenes and Diene for Novel Liquid Crystals

Maxim Ponomarenko1, Nataliya Kalinovich2, Yurii Serguchev1, Matthias Bremer3 and Gerd-Volker

Roeschenthaler2, (1)Institute of Organic Chemistry,, National Academy of Sciences of Ukraine, Kiev,

Ukraine, (2)Department of Chemistry, University of Bremen, Bremen, Germany, (3)Liquid Crystals

Division, Merck KGaA, Darmstadt, Germany

Liquid crystals with SF5 groups are of interest as new materials because of their combination of high

polarity with very low birefringence, which is of particular importance for LCDs. For the synthesis of diene

SF5CH=CHC(R)=CH(R1) (1) synthetic key steps were UV-irradiation initiated addition of SF5Cl to an olefin

precursor (2), followed by dehydrochlorination, bromination and successive dehydrobromination. For the

synthesis of SF5C≡C-cyclohexyl-R2 derivatives, an acetylene precursor (3) was obtained from the

corresponding olefin 2, then SF5Cl was added to 3 under Et3B catalysis, followed by dehydrochlorination.

The same two approaches were used for the preparation of SF5C≡C-(p-alkylsubstituted-aromatics)

246. Novel Perfluoroalkenylphosphonates and a Fluorinated Bisphosphonate

Jolanta Ignatowska1, Gerd-Volker Roeschenthaler2, Katja Vlasov2 and Krzysztof Cichowicz2, (1)Institute

of Inorganic & Physical Chemistry, University of Bremen, Bremen, Germany, (2)Department of Chemistry,

University of Bremen, Bremen, Germany

Perfluoroalkenylphosphonates are precursors for compounds with potential biological activity. The

corresponding acids are possible electrolytes for fuel cells. When perfluorovinylethers were allowed to

react with tris(trimethylsilyl) phosphite, fluorinated Z-isomers of phosphonates were obtained as sole

products. The reaction of 2,2,3,3-tetrafluoro-3-(trifluoromethoxy)propanoyl chloride and

tris(trimethylsilyl) phosphite furnished a fluorinated bisphosphonate as the main product.

247. Methyl 2-Methoxytetrafluoropropionate as a Synthetic Equivalent of Methyl Trifluoropyruvate in the Claisen Condensation. First Synthesis of 2-

(Trifluoroacetyl)Chromones and 5-Aryl-2-Hydroxy-2-(trifluoromethyl)Furan-3(2H)-Ones

Olesya Kazakova1, Vyacheslav Sosnovskikh2, Roman Irgashev2, Nataliya Kalinovich1 and Gerd-Volker

Roeschenthaler1, (1)Department of Chemistry, University of Bremen, Bremen, Germany, (2)Department

of Chemistry, Ural State University, Ekaterinburg

2-(Trifluoroacetyl)chromones and 5-aryl-2-hydroxy-2-(trifluoromethyl)furan-3(2H)-ones were obtained in

good yields via the Claisen condensation of acetophenones with methyl 2-methoxytetrafluoropropionate,

followed by sulfuric acid induced deprotection of the reaction products.

248. One-Pot Synthesis of Fluorinated Nitrogen-Containing Bicyclic Heterocycles

Hongwei Zhuang, Minghua Hou, Wen Wan, Haizhen Jiang and Jian Hao, Department of Chemistry,

Shanghai university, Shanghai, China

The importance of the pyrrolo[ 1,2-a ] imidazol-1-one , pyrrolo [2,1-b] oxazol-1(2H)-one and

pyrrolo[2,1-b]thiazol-1 (2H)-one skeletons are well recognized due to its significant as a subunit of a wide

panel of synthetic pharmaceutical compounds.[1] Some of these structures have been patented and

reported to have a wide variety of biological activities, for instance, anti-inflammatory, analgesic, blood

134

pressure lowering, spasmolytic, tranquilizing, tranquilizer and antitusive properties, and use in the

treatment of rheumatism.[2-5]

Herein, we'd like to report our preliminary results of one-pot synthesis of fluorinated analogues of theses

bicyclic heterocycles from a tandem reaction of fluorinated keto esters and diamines catalysized by p-

toluene sulfonic acid.

This work was financially supported by National Natural Science Foundation of China (20772079), Science

and Technology Commission of Shanghai Municipality (07JC14020, 07ZR14040, 08JC1409900) and

Shanghai Municipal Education Commission.

References:

[1] Viresh, H. R.; Cava, M. P. Tetrahedron Letters, 1985, 26, 6141-6142.

[2] Alba, C.; Angelina, D. S. J. Med. Chem. 1989, 32, 93-95.

[3] Genin, M. J.; Mishra, R. K.; Johnson, R. L. J. Med. Chem. 1993, 36, 3481-3483.

[4] Armelle, C.; Adam, D.; Bernard, D.; G¨¦rard, S.; Lllluc, V. H. Tetrahedron, 2004, 60, 11029-11039.

[5] Alan, R. K.; He, H-Y.; Akhilesh, K. V. Tetrahedron: Asymmetry, 2002, 13, 933-938.

249. One-Pot Synthesis of 1,3-Diazole Compounds and Application

Haizhen Jiang, Shijie Yuan, Wen Wan, Lan Sun and Jian Hao, Shanghai University, Shanghai, China

1,3-diazoles and their derivatives are important heterocycles and are wildly employed as key

intermediates in pharmaceutical production.[1] They are also valuable as synthetic intermediates or

protecting groups in organic synthesis or as chiral ligands in asymmetric synthesis.[2]

Herein, we'd like to report a new method for the synthesis of 1,3-diazoles and their derivatives via a rapid

and mild one-pot intramolecular cyclization process (Scheme1). Some known compounds, such as 2-

trifluoromethyl and 2-difluoromethyl substituted benzo-1,3-diazole derivatives were reported having the

potential anti-HIV-1 bioactivities.[3] 1,3-Diazoles and their derivative products were subjected to

135

synthesize the fluorinated analogous, such as 2-difluoromethylene-linked 1,3-diazole compounds.(Scheme

2)

This work has been financially supported by National Natural Science Foundation of China(20772079),

Science and Technology Commission of Shanghai Municipality (07JC14020, 07ZR14040, 08JC1409900)

and Shanghai Municipal Education Commission.

Reference:

[1]. Lombardino, J. G.; Wiseman, E. H. J. Med. Chem. 1974. 17. 1182.

[2]. Castellano,S.; Kuck,D.; Sala,M.; Novellino,E.; Lyko,F.; J. Med. Chem. 2008. 51(7). 2321-2325.

[3]. Conrad R. Burkholder, William R. Dolbier Jr., Maurice MeÂdebielle. J. Fluorine Chem. 2000. 102. 369-

376.

250. Synthesis of SF5-Substituted Carbocyclic Compounds by Transannular Cyclization of Non-Conjugated Dienes with SF5Cl

Maxim Ponomarenko1, Yurii Serguchev1 and Gerd-Volker Roeschenthaler2, (1)Institute of Organic

Chemistry, National Academy of Sciences of Ukraine, Kiev, Ukraine, (2)Department of Chemistry,

University of Bremen, Bremen, Germany

Introduction of an SF5 group into organic compounds has been known since half a century, but the

number of SF5-containing compounds is restricted by sources for SF5 or respective building blocks. Herein

we report the experimental results on the transannular cyclization of non-conjugated dienes with SF5Cl

reagent. In the case of 3,7-dimethylenebicyclo[3.3.1]nonane, norbornadiene and 1,5-cyclooctadiene the

reactions were carried out with SF5Cl using UV irradiation or Et3B catalysis. As the result new SF5-

substituted carbocyclic compounds have been obtained. To the best of our knowledge no cyclizations with

SF5Cl have been already reported.

251. A Novel Synthetic Route and Reactivity of Ortho-Fluorine-Containing Arylphosphosphonates

Sergey Tverdomed1, Jacek Kolanowski2, Nataliya Kalinovich1, Henryk Koroniak2 and Gerd-Volker

Roeschenthaler1, (1)Department of Chemistry, University of Bremen, Bremen, Germany, (2)Faculty of

Chemistry, Adam Mickiewicz University, Poznan, Poland

Fluorine-containing aryl and vinylphosphonic acids play an important role in the construction of biologically

active compounds, as flame retardants or polymer additives. However, the synthesis and reactivity of

ortho-CF2X-arylphosphonates (X = H, F, Cl, Br and CF3) has never been studied. For these reasons, we

136

report a new methodology for the synthesis of this type of compounds via Diels-Alder reaction of XCF2–≡–

P(O)(OEt)2 (1) with various 1,3-butadienes, followed by the aromatization of the corresponding cyclic

vinylphosphonates (2) using KMnO4/Al2O3 system. The reactivity of ortho-CF2X-arylphosphonates (3) was

then examined in some reactions of fluorine-containing and phosphonate functionality. These

transformations afforded ortho-CF2X-arylphosphonic chlorides (4) which hydrolize to appropriate

phosphonic acids (5) or give corresponding phosphine oxides (6). When o-CF2X-arylphosphonates (X = Cl,

Br) were treated with Zn/CuBr and electrophile, only dimer ArCF2CF2Ar was isolated and no coupling

reactions were observed. However, the lithiation of CF2H group permit to obtain products of reaction (7)

with various electrophiles.

252. The Quest for Bridging Trifluorophosphine Ligands in Binuclear Iron and Cobalt Complexes: A Density Functional Theory Study

R. Bruce King1, Henry F. Schaefer2, Qian-shu Li3, Yaoming Xie2, Rong Zou3 and Hua-qing Yang3,

(1)Department of Chemistry and Center for Computational Chemistry, Department of Chemistry,

University of Georgia, Athens, GA, (2)Center for Computational Chemistry, Department of Chemistry,

University of Georgia, Athens, GA, (3)Center for Computational Quantum Chemistry, Guangzhou, China

In mononuclear transition metal complexes the trifluorophosphine ligand behaves very much like the

carbonyl ligand in terms of its back-bonding characteristics. Thus homoleptic zerovalent metal

trifluorophosphine complexes such as Cr(PF3)6, Fe(PF3)5, and Ni(PF3)4 are very oxidatively stable volatile

solids or liquids very much like the corresponding metal carbonyls. However, analogues of binuclear

metal carbonyls such as Fe2(CO)9 and Co2(CO)8 with bridging trifluorophosphine ligands are unknown.

We have now studied the binuclear derivatives Fe2(PF3)n (n = 9, 8) and Co2(PF3)n (n = 9, 8, 7, 6) by

density functional theory in order to determine whether such derivatives with bridging trifluorophosphine

ligands are viable. In the lowest energy structure predicted for Fe2(PF3)9 one of the iron atoms has

inserted into a P–F bond of one of the PF3 ligands to give a structure with a bridging PF2 group and a direct

Fe–F bond. An intact bridging PF3 group without a direct iron-iron bond is found in a considerably higher

energy predicted Fe2(PF3)9 structure. The lowest energy structure for Fe2(PF3)8 has two Fe(PF3)4 units

linked only by an Fe=Fe double bond. For the cobalt derivatives the lowest energy Co2(PF3)n (n = 8, 7,

and 6) structures are unbridged structures. However, higher energy bridged structures are also found for

Co2(PF3)n (n = 7 and 6).

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253. Synthesis, Optical and Electrical Properties of Trifluoromethylated 1H-Pyrazolo[3,4-ß]-Quinolines as Novel Blue Light-Emitting Chromophores

Wen Wan, Yuansong Jiang, Haizhen Jiang and Jian Hao, Department of Chemistry, Shanghai University,

Shanghai, China

Among organic luminophores, 1H-pyrazolo[3,4-b]-quinolines (PQ) are strongly luminescent compounds

and presents a considerable interest as this organic compound recently has been found highly fluorescent

in the blue spectral range [1] and suitable for electroluminescent applications [2, 3]. In this work, the

trifluoromethylated group have been successfully introduced into the PQs, and the optical and electro-

luminescence are also characterized.

Table 1. Optical and Electrochemistry Properties of PQs

°° 6-H-PQ 6-CH3-PQ 6-PQ-CN 6-CF3-PQ

Absorption Peaks /nm 264 266 271 264

EM /nm 449 445 472 464

EX /nm 376 381 377 375

HOMO /eV 5.096 5.0939 5.137 5.1212

LUMO /eV 2.1607 2.1341 2.2694 2.2065

This work has been financially supported by National Natural Science Foundation of China (20772079),

Science and Technology Commission of Shanghai Municipality (07JC14020, 07ZR14040, 08JC1409900)

and Shanghai Municipal Education Commission.

References:

[1] Z. He, G.H.W. Milburn, K.J. Baldwin, D.A. Smith, A. Danel, P. Tomasik, J. Lumin. 2000, 36, 1.

[2] Z. He, G.H.W. Milburn, A. Danel, A. Puchala, P. Tomasik, D. Rasala, J. Mater. Chem. 1997,7, 2323.

[3] A. Danel, Z. He, G.H.W. Milburn, P. Tomasik, J. Mater. Chem. 1999, 9, 339.

138

254. Cr(II)-Mediated Fluoroalkenylation Reaction of Aldehyde: Synthesis of Fluoroalkene-Containing Bestatin Analogues

Midori Okada1, Azusa Sato1, Rieko Okatani1, Hikaru Yanai2 and Takeo Taguchi2, (1)School of Medicine,

Tokyo Women‗s Medical University, Tokyo, Japan, (2)School of Pharmacy, Tokyo University of Pharmacy

and Life Sciences, Tokyo, Japan

Fluoroalkenes are well recognized as useful functional moiety as isosteric and isoelectronic replacement of

amide bond, while the enhancement of lipophilicity and extreme stabilization against hydrolysis as

compared with amide compound may improve the value of fluoroalkene moiety as peptide mimics in the

area of medicinal chemistry. Development of synthetic methods for fluoroolefin derivatives directed to

peptide mimetics or enzyme inhibitors has been one of our research subjects. Recently, fluoroalkenylation

reactions of aldehydes using Cr(II), Ni(II) and (E)-1-bromo-1-fluoroalkene derivatives were reported by

us and the other research group independently. Further efforts to reveal the scope and limitation of the

Cr(II)-mediated fluoroalkenylation reaction have been made using a variety of both 1-bromo-1-

fluoroalkene derivatives and aldehydes. For example, the reaction of 2-alkylated (E)-4-bromo-4-fluoro-3-

butenol 1 with amino acid-derived amino aldehydes also proceeded to provide the corresponding 4-fluoro-

3-alkenols 2 having amino group at 6-position and hydroxy group at 5-position, which can be converted to

fluoroalkene-containing Bestatin analogues through several steps.

255. Synthesis of 2-Phenyl-5-Fluoroalkyl Thiazole-4-Carboxylates by Fluorine-Containing Building Blocks 2-Dibenzylamino-4-Fluoroalkyl-â-Ketoesters

Haizhen Jiang, Wen Wan and Jiao Hao, Department of Chemistry, Shanghai University, Shanghai, China

Fluorine-containing building blocks for the introduction of fluorine or a fluorinated moiety into organic

molecule have attracted a wide spread attention in pharmaceutical and agrochemical researches.[1]

Fluorine-containing building blocks 2-Dibenzylamino-4-fluorinated--ketoesters have been reported for

synthesis of 2-amino-4,4,4-trifluoro-3-hydroxybutanoic acid by Scolastico group[2] and the fluorine-

containing cyclopropyl ¦Á-amino esters and dihydrooxazole by our group.[3]

Herein, we'd like to report our new applications of this fluorine-containing building block for efficient

synthesis of biologically interesting 2-Phenyl-5-fluoroalkyl thiazole-4-carboxylates (1) and 5-

trifluoromethyl pyrazolidin-3-one (2). Furthermore, the synthesis of some fluorine-containing compounds,

such as, ¦Á, -diamino esters and -lactams, from 2-Dibenzylamino-4-fluoroalkyl--ketoester building

block may be also applicable by the intermediate of aziridinium ions.[4]

This work was financially supported by National Natural Science Foundation of China (20772079), Science

and Technology Commission of Shanghai Municipality (07JC14020, 07ZR14040, 08JC1409900) and

Shanghai Municipal Education Commission.

139

References

(1) a) Purser, S.; Moore, P. R.; Swallow, S.; Gouverneur, V. Chem. Soc. Rev. 2008, 37, 320. b)

Műller, K.; Faeh, C.; Diederich, F. Science 2007, 317, 1881. c) Kirsch, P. Modern Fluoroorganic

Chemistry: Synthesis, Reactivity, and Applications, WILEY-VCH Verlag GmbH & Co. KgaA: Weinheim,

2004.

(2) Scolastico, C.; Conca, E.; Prati, L. Synthesis 1985, 5, 850.

(3) Wan, W.; Gao, Y. H.; Jiang, H. Z.; Hao, J. J. Fluorine Chem. 2008, 129, 510.

(4) Chuang, T. H.; Sharpless, K. B. Org. Lett. 2000, 23(2), 3555.

256. Molecular and Supramolecular Chirality Induced by Perfluoroalkyl Chains

Alessandro Zaggia1, Lino Conte2, Giuseppe Resnati3, Pierangelo Metrangolo3, Francesco Lelj4, Mario

Amati4, Alfonso Venzo5 and Roberta Bertani2, (1)Dipartimento di Processi Chimici dell'Ingegneria,

Università degli studi di Padova, Padova, Italy, (2)Dipartimento di Processi Chimici dell'Ingegneria,

Università degli Studi di Padova, Padova, Italy, (3)Dipartimento di Chimica, Materiali ed Ingegneria

Chimica "Giulio Natta", Politecnico di Milano, Milano, Italy, (4)Dipartimento di Chimica, Università della

Basilicata, Potenza, Italy, (5)Istituto di Scienze e Tecnologie Molecolari, C.N.R., Padova, Italy

Perfluoralkylated chains are known to adopt a helical structure as a consequence of interaction between

fluorine atoms in the relative 1,3-positions as demonstrated by X-Ray determinations in the solid state. It

was proposed that perfluorinated alkyl chains preserve a helical structure in solution while linear

hydrocarbons exhibit as the most populated one a strictly all-trans conformation along the chain. Little

experimental evidence has been reported concerning the helical structure in solution. A possible strategy

can involve the design of molecules having a chiral headgroup bearing additional functional groups able to

stabilize conformations to different extent in order to observe them by spectroscopic methods in solution.

We prepared molecules of the type RF-CH2-C*H(OH)-CH2-OR and their solution behaviour has been

studied by multinuclear/dimension NMR techniques. The presence of two diasteroisomers was sometimes

observed in solution thus confirming the occurrence and stability of helical structures in solution.

To evaluate the parameters that determine the relative stability of different conformations DFT

computations using the Perdew–Burke–Erzenhorf hybrid exchange correlation functional and 6-31g(d,p)

basis set have been performed on model molecules where the R= Met and RF= C6F13.

Results confirm that the RF moiety shows as the most stable conformation an antiperiplanar one with

dihedral angles along the chain around 162. or -162. deg in helical structures with opposed chirality

showing different stability.

The influence of perfluoralkyl helical structure on supramolecular arrangements mediated by halogen

bonding is also discussed in terms of ability of long chain perfluoroalkyliodides to be involved in

spontaneous resolution processes.

140

257. Preparation of Fluorous Ponytail Primary Phosphines Via Phthaloylphosphide Ion

Brian A. O'Brien1, Jason W. Schultz1, Alexander D. Burum2 and Karrie-Ann Kubatko2, (1)Department of

Chemistry, Gustavus Adolphus College, Saint Peter, MN, (2)Soil Sciences, Department of Natural

Resources, Ohio State University, Columbus, OH

Potassium phthaloylphosphide [K+][o-C6H4(CO)2P-] has proven to be a versatile reagent for preparation of

P-substituted derivatives either by direct reaction (alkyl halides, pentafluorophenyl halides) or by

irradiation with 420 nm blue light (CF3CH2I). Here we describe the preparation of fluorous ponytail

phthaloylphosphines and their further transformation into primary phosphines (RfCH2CH2-PH2). Primary

phosphines can, in turn, be converted to difluorophosphines and tetrafluorophophoranes by Selectfluor®.

Characterization of the phthaloylphosphines and primary phosphines, along with details of preparation and

further transformations, will be discussed.

258. Organocatalyzed Asymmetric Domino Michael-Aldol Reaction of Ketones and Fluorine-Containing α,β-Unsaturated Ketones

Jin-Tao Liu and Yan Zhao, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,

Shanghai, China

Using pyrrolidine as the catalyst, domino Michael-aldol reaction of ketones and fluorine-containing α,β-

unsaturated ketones such as trifluoromethyl α,β-unsaturated ketones and γ,d- unsaturated α,α-difluoro-β-

keto esters took place readily under mild conditions to give the corresponding cyclic tertiary alcohols in

good yields with high diastereoselectivities. Either diastereomer could be obtained from the reaction of

trifluoromethyl α,β-unsaturated ketones and cycloketones when appropriate chiral catalyst was used.

Acknowledgements: Financial support from the National Natural Science Foundation of China (No.

20872166) is gratefully acknowledged.

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259. Synthesis of Fluorous Tripyrazolylmethanes and Scorpionates

Jaroslav Kvicala, Martin Skalicky, Martin Holan, Veronika Frankova, Marketa Rybackova and Mario

Babunek, Department of Organic Chemistry, Institute of Chemical Technology, Prague, Prague 6, Czech

Republic

Highly fluorinated ligands are the key components of fluorous homogeneous catalysts. In the search for

fluorous analogues of cyclopentadiene ligands we turned our attention to the synthesis of

polyfluoroalkylated scorpionate and tripyrazolylmethane ligands. Our first attempts to employ tris(4-

iodopyrazol-1-yl)methane as the key component of the Heck reaction with (perfluorohexyl)ethene resulted

in very low yields of tris{4-[2-(perfluorohexyl)ethenyl]pyrazol-1-yl}methane. We hence employed for the

preparation of highly fluorinated tripyrazolylmethane 1 alternative strategy using Heck reaction of

protected 4-iodopyrazole with (perfluorohexyl)ethene followed by deprotection and catalytic

hydrogenation, which gave the key intermediate, 4-[2-(perfluorohexyl)ethyl]pyrazole. Its PTC reaction

with CHCl3 led to a good yield of the target product 1. Reaction of NaBH4 with the key polyfluoroalkylated

pyrazole in the melt gave moderate yield of analogous scorpionate 2. In an alternative approach, we

modified 2,2,2-tripyrazol-1-ylethan-1-ol by standard allylation - radical perfluoroalkylation - reduction

protocol and obtained a series of polyfluoroalkylated tripyrazolylmethanes 3. Fluorophilicities and

preliminary complexation results of the ligands prepared will be reported.

260. Progress Toward the Synthesis of Pentafluorosulfanyl- and Gem-Difluoro- Cyclic Compounds, Including Microwave Assistance

Douglas Armstrong and John Hanson, Department of Chemistry, Olivet Nazarene University,

Bourbonnais, IL

This poster will describe the level of success of very recent progress toward the synthesis of cyclic

compounds of the following two types:

1. Pentafluorosulfanyl-substituted six-membered rings via Diels-Alder reactions of a pentafluorosulfanyl-

substituted butadiene precursor (R.W. Winter and G.L. Gard, J. Fluorine Chem., 128 (2007), 896-901)

with selected dienophiles. (Acknowledgment and thanks are hereby expressed to Dr. Gard for supplying

the precursor.)

2. Three-membered rings containing the gem-difluoromethylene group, from reactions of compounds

containing double bonds, with trimethylsilyl 2-(fluorosulfonyl)difluoroacetate.

Included will be the role played by our Biotage microwave instrument (the ―Initiator‖ model).

286. β-Fluoroamides and Amines From Alkenes Via Electrophilic Fluorination

Melvin Druelinger and Kathleen McLallen, Department of Chemistry, Colorado State University - Pueblo,

Pueblo, CO

β-Fluoroamines are of interest as synthetic building blocks and for their biomedical potential. They have

been prepared by a number of routes but those currently available suffer from difficulties such as

requiring special conditions, extended reaction times, and the use of dangerous and/or costly reagents.

We report a simple two step synthesis for these compounds. F-TEDA (SelectfluorTM) reacts with alkenes in

the presence of dry acetonitrile to generate β-fluoroamides. The reaction proceeds via the electrophilic

addition of fluorine to the alkene. The intermediate β-fluorocarbocation is subsequently trapped by the

solvent to afford β-fluoroamides. These can be transformed into β-fluoroamines by hydrolysis. F-TEDA is

142

an excellent fluorinating agent for many reasons - it is reactive, stable, non-toxic, non-explosive,

inexpensive, and it is capable of site-selective fluorination in a wide range of organic molecules. We have

prepared a number of fluoroamides from a structurally diverse group of alkenes.

287. Fluorination of β-Ketsulfones in Ionic Liquids Using SelectfluorTM by Ultrasound

Mohammad Reza Poor Heravi Jr., Department of Chemistry, Abhar Payame Noor University (PNU),

Abhar, Iran

Selective fluorination of organic compounds under mild reaction conditions through an electrophilic

reaction process is one of the most important strategies for accomplishing this task of wide interest to the

basic and applied research community [1, 2].

The importance of fluorinated compounds in pharmaceuticals, agrochemicals and material sciences has

been thoroughly recognized [3]. The use of ultrasound in organic transformation is now well known to

enhanced reaction rates and yields/selectivity of reactions, and in several cases facilities organic

transformation at ambient conditions which otherwise require drastic conditions of temperature and

pressure [4].

References:

1. M. Shimizu, T. Hiyama, Angew. Chem. Int. Ed., 44, 2004, 214-231.

2. S. Rozen, Chem. Rev., 96, 1996, 1717-1736.

3. Y. S. Lee, J. Fluorine Chem., 128, 2007, 392-403.

4. T. Wetan, Chem. Rev., 99, 1999, 2071-2083.

Organic/Organometallic - I (28th August, Friday)

Presider: Günter Haufe, Universität Münster, Münster, Germany

261. Acidities of Superacids in 1,2-Dichloroethane

Agnes Kütt, Toomas Rodima, Ivo Leito and Ilmar A. Koppel, Institute of Chemistry, University of Tartu,

Tartu, Estonia

The acidities of superacids in a medium of constant composition – 1,2-dichloroethane (DCE) – have been

measured using a UV-vis spectrophotometric method.

DCE has very low basicity and it is appropriate solvent studying very strong acids. Well-known superacids

such as triflic acid, perchloric acid, Tf2NH, Tf2CH2, cyanoform, etc. have been studied in the present work.

In order to get reliable results, many new acids (among them numerous polyfluorinated molecules) have

been synthesized and used to compose self-consistent acidity scale.

Until now, the most popular non-aqueous solvents for acid-base measurements have been acetonitrile and

DMSO. The strongest measured acids in acetonitrile (pKa around 3.5 in acetonitrile) are among of the

weakest measured acids in DCE. In this work the DCE acidity scale is covering the acidity range more

than 10 pKa units from picric acid to Tf2CHCN.

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262. Effect of Basic Solvent on the Reaction of Fluorination of Chlorinated Aromatic Compounds with HF as Fluorinating Agent

Alexandre Piou, Stephane Celerier and Sylvette Brunet, Umr 6503 Cnrs, University of Poitiers, Poitiers,

France

The incorporation of fluorine into organic compounds results in changes in the physical, chemical and

biological properties. These changes make them suitable for diverse applications in the areas of

agrochemistry and pharmaceuticals. The reaction of Cl/F exchange allows the preparation of the

fluorinated aromatic compounds. The use of HF as fluorinating agent is well known but the acidity of the

medium may lead to the formation of by products like polymers. To avoid this issue, the reaction can be

carried out in a solvent which complex HF and decreases the acidity of the medium.

Basic solvents such as dioxane and tributylphosphate have been studied and are compared to HF-pyridine

complex. The fluorinating properties of these systems are tested in the fluorination of chlorinated aromatic

compounds such as the trichloromethyl toluene and the benzalchloride. For each HF/solvent complex, the

reaction has been optimized (quantity of solvent or HF, temperature of reaction…) to favor the fluorination

and to control the degree of fluorination corresponding to the formation of mono, di or trifluorinated

product with a maximum of selectivity. Moreover the presence of a catalyst with low Lewis acidity

increases the transformation of chlorinated compounds. For example at 50°C with tributylphosphate and 3

equivalents of HF, fluorodichloromethyl toluene is formed with a selectivity of 90%.

To explain these results and therefore the nucleophilicity of F-, all HF/solvent complexes have been

characterized by Raman spectroscopy and 19F NMR. These analyses show interaction between HF and

solvent with variable intensity depending on the solvent.

263. The Preparation and Reactions of Aliphatic Pentafluorosulfanyl Aldehydes and Ketones

John T. Welch, Silvana C. Ngo, Paul R. Savoie, Kaitlin M. Peck and Linbin Zhong, Department of

Chemistry, University at Albany, SUNY, Albany, NY

The synthesis of pentafluorosulfanyl aldehydes and ketones based on the addition of pentafluorosulfanyl

bromide to functionalized alkenes such as enol acetates will be described. The reactions of the product

ketones and aldehydes, as well as acetals derived from those carbonyl compounds, will be reported. A

comparison of the relative reactivity of these materials with corresponding trifluoromethylated compounds

will be emphasized.

264. BF3 in Fluorinated Alcohols – a Very Effective Lewis Acid for C-F Bond Activation

Jernej Iskra, Department of Physical and Organic Chemistry, "Jožef Stefan" Institute, Ljubljana, Slovenia

Special physico-chemical properties of fluorinated alcohols were first applied in biochemistry for their

influence on the tertiary structure of proteins. Afterwards, fluorinated alcohols have found diverse

application in organic chemistry as solvents, co-solvents and additives. Their interesting properties are

connected mainly to a great difference in strong interactions with nucleophiles and weak ones with

electrophiles, as exemplified by their strong hydrogen bond donor properties and weak hydrogen bond

144

acceptor properties. Therefore, fluorinated alcohols are very good solvents for reactions with electrophiles

and oxidations with hydrogen peroxide, where template catalysis was proposed as their mode of action.

As could be judged from the difference in the interaction of fluorinated alcohols with electrophiles and

nucleophiles, fluorinated alcohols should be an interesting media for acid-catalyzed reactions, where the

active part – acidic proton – is not strongly solvated, while its nucleophilic counterpart is strongly

solvated, leading to increased acidity of acids in fluorinated alcohols. The activating effect of fluorinated

alcohols on reactions of oxidation and acid-catalysis were clearly demonstrated in the peroxidative

cyclization of ketones into antimalarial 1,2,4,5-tetraoxanes with H2O2 and HBF4 that could only be achieved in these solvents.

We are presenting a study on the effect of fluorinated alcohols on the Lewis acid catalyzed reactions,

where we studied a catalytic system of ethereal solution of boron trifluoride (BF3.OEt2) in 1,1,1,3,3,3-

hexafluoropropanol (HFIP) and 2,2,2-trifluoroethanol (TFE). An example is activity of such a Lewis acid

system is defluorination of trifluoromethylbenzene (PhCF3) in HFIP by BF3.OEt2 leading to a formation of

hexafluoropropyl benzoate (PhCOOCH(CF3)2).

265. Synthesis and Application of Trifluoroacetaldehyde

Kosuke Kawada and Hideyuki Mimura, Research Laboratory, Tosoh F-Tech, Inc., Shunan Yamaguchi,

Japan

Trifluoroacetaldehyde 2, which possesses a simple chemical structure and a highly reactive aldehyde

group, is one of the widely applicable building blocks for fluorine containing organic molecules. From the

viewpoint of industrial production of 2, we have developed the vapor-phase oxidation process of 2,2,2-

trifluoroethanol 1[1].

In addition, to confirm the availability as the building block of this aldehyde, we examined the application

to the synthesis of fluorinated amino compounds.

As the result, we found that the trifluoroethylamino compounds 4, which have been widely used as the

raw materials for pharmaceutical purpose, can be synthesized with good yield by the reductive amination

reaction of 2 via the N,O-acetal 5.

On the other hand, we also found that trifluoroethylamino compounds which have a substituting group at

-position can be synthesized by the reaction of trifluoroaldimines with nucleophiles.

Especially, to apply this reaction to the synthesis of the optical active compounds, we examined the

reaction of 8 with some nucleophiles in detail.

The stability, reactivity and chiral inducing ability of 8 will be discussed.

145

Literature:

[1] H. Mimura, A. Watanabe, K. Kawada, J. Fluor. Chem., 127,519 (2006).

266. A Simple and Convenient Synthesis of 2-(Perfluoroalkyl)-4H-Chromenes From Salicyl N-Tosylimines or Salicylaldehydes with Methyl 2-Perfluoroalkynoates

Lei Lu, Jie Chen, Jiamei Wei, Jiaping Zhang, Hui Zhang and Weiguo Cao, Department of Chemistry,

Shanghai University, Shanghai, China

4H-Chromenes are an important class of compounds being the main components of many biologically

active compounds, and are widely employed as key intermediates in the synthesis of numerous natural

products and medicinal reagents. Thus, the development of new efficient processes for their construction

has been the subject of increasing attention over the last couple of years. Although it is well known that

the introduction of polyfluoroalkyl groups into organic molecules can bring about some remarkable

changes in the properties of the derived fluorinated compounds, and selective perfluoroalkylation has been

recognized as an important tool in developing new biologically important compounds, methods for

preparing polyfluoroalkyl-substituted 4H-chromenes remain very limited.

As part of our ongoing efforts, we built upon the recent reports by Shi's group on the synthesis of the

chromenes. It was found that although the amine-catalyzed reaction between ethyl 2-butynoate and

salicyl N-tosylimine did not give the substituted chromenes in satisfactory yield under various reaction

conditions, the reaction of diethyl acetylenedicarboxylate with salicyl N-tosylimines or salicylaldehydes

proceeded smoothly because of the substitution of the methyl group in ethyl 2-butynoate for the electron-

withdrawing ester group. We developed a new general and efficient methodology for the preparation of

perfluoroalkyl containing substituted 4H-chromenes from the Et3N-catalyzed reaction of salicyl N-

tosylimines or salicylaldehydes with methyl 2-perfluoroalkynoates. The structures of these compounds

were fully confirmed and characterized.

Scheme 1

Acknowledgement

Thanks are due to the NSFC (20872088), Leading Academic Discipline Project of Shanghai Municipal

Education Commission (08ZZ44 and J50102).

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Fluoropolymers/Materials - I (28th August, Friday morning) Presider: Timothy P. Lodge, University of Minnesota, Minneapolis, MN

267. Controlled Radical Copolymerization of Fluoromonomers: The Golden Tool to Achieve Well Architectured F-Polymers

Georgi Kostov, Cyrille Boyer and Bruno Ameduri, Chemistry, Institute Charles Gerhardt, Montpellier,

France

After summarizing various methods of controlled radical polymerization1 (NMP, ATRP, RAFT, MADIX, ITP),

this tutorial deals with the iodine transfer copolymerization of vinylidene fluoride (VDF) with various

comonomers such as a-trifluoromethacrylic acid2, 1,1,2-trifluoro-pentafluorothiosulfanyleethylene3 and

perfluoromethyl vinyl ether4, as follows:

Molecular weights (assessed by 19F NMR or by SEC) versus monomer conversion linear relationship

evidences the controlled behavior of these copolymerizations. Specific properties, especially thermal

properties-assessment of Tg and Tdec - have been provided.

Various applications from the produced poly(VDF-co-M) copolymers will also been reported5.

REFERENCES

1- B. AMEDURI, B. BOUTEVIN, ―Well Architectured Fluoropolymers‖ Elsevier, Amsterdam (2004).

2- C. BOYER, B. AMEDURI, Japanese Patent 2007/51201 (assigned to Tosoh F-Tech) 2007-03-01

3- C. BOYER, B. AMEDURI, W.R. DOLBIER, R. WINTER, G. GARD, Macromolecules, 2008, 41, 1254-1263

4- C. BOYER, B. AMEDURI, M.H. HUNG, US Patent (assigned to DuPont Performance Elastomers) 2008-09-

12.

268. Miscibility of Polyvinylidene Fluoride with Polymers Containing Imide Moieties

Shiow-Ching Lin, Solvay Solexis, West Deptford, NJ

As a versatile industrial polymer, polyvinylidene fluoride known as PVDF has been concluded to be

thermodynamically miscible or partially miscible with a few polymers. The miscibility has been attributed

to its high segment polarity which provides capability for the formation of H-bonding with polymers

containing -C=O groups. The frequently used polymers for blending with PVDF are acrylic resins in

industry specifically for highly weatherable architectural coatings. An imide ring contains two -C=O

linkages and is expected to provide strong interactions with vinylidene fluoride repeating units. Such

strong interaction would enforce the miscibility between PVDF and polymers containing imide moieties.

Imide groups in a polymer provide an increased heat resistance and hardness. In this study, miscibility of

PVDF with polymers containing imide groups was analyzed. The properties of such polymer blends were

also investigated.

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269. Computer Simulation On Distillation Process for Purification of HFP

Jungsikk Oh, Dongjae Jeong, Mihye Yun, Ina Yum and Yongtaek Lee, Department of Chemical

Engineering, Chungnam National University, Daejeon, South Korea

Hexafluoropropylene (C3F6, HFP) can be produced as much as 5 to 20 wt% as a byproduct together with

the rest of tetrafluoroethylene (C2F4, TFE) if poly(tetrafluoroethylene) is thermally decomposed. Both

compounds of TFE and HFP may be used as a feed material for the synthesis of various fluorocompounds.

In this study, the Aspen Plus software is used to design the distillation processes for separation and

purification of HFP from the HFP/TFE mixture gases. For a typical feed gas composed of 6.9 mol% HFP and

93.1 mol% TFE, the feed gas is supplied at 10 kg/hr to the first distillation tower equipped with a partial

condenser. The target with the first distillation is to obtain that the concentration of TFE in the top product

is higher than 99 mol%. It turns out that the optimum number of the trays is 15 and the reflux ratio is

0.6. At the second distillation process, the bottom product is used as a feed material which is composed of

mainly C3F6, and the rest of C4F8, C4F8O, C2F4, and C3F8, with a mole fraction of 0.8, 0.1, 0.05, 0.001, and

0.002, respectively. The goal of the second distillation process is to obtain the molar concentration of TFP

as high as 0.99. The number of trays is needed be more than 20 trays. As the operating pressure

increases from 4.5 atm to 7.5 atm, the temperature in the condenser increases from 12.75°C to 31.45°C

at the given number of the trays.

270. Electrospinning of Superhydrophobic PFCB - RTIL Hybrid Composites

Rajneesh Verma, Neetu Tomar and Dennis Smith, Department of Chemistry, Clemson University,

Clemson, SC

Superhydrophobic surfaces with high contact angle and low contact angle hysteresis also exhibit a self-

cleaning effect and low drag for fluid flow. The perfluorocyclobutyl polymers are the semifluorinated class

of polymer, which has the same advantages as of fluorinated polymers such as high chemical resistance,

high thermal resistance, low refractive index as well as they are solution processable which lowers their

cost. These polymers can be prepared by the radical mediated [2+2] thermal cyclo dimerization of

trifluorovinyl ethers.

We have successfully prepared the superhydrophobic surfaces of biphenyl perfluorocyclobutyl (BP-PFCB)

by using electrospinning. The electrospinning technique is well known to produce high surface area-to-

volume ratio, high porosity and one of the simplest methods to generate different surface morphologies

i.e. surface roughness. The superhydrophobic surfaces of PFCB were prepared by incorporating room

temperature ionic liquids (RTIL) like BMIM-PF6. The surfaces of different roughness were generated by

varying the processing parameters like flow rate, voltage and inter electrode distance. The surface

morphology of these composites was studied by SEM. These electrospun mats of superhydrophobic

composites may find potential applications in antistatic self-cleaning coating, polymer electrolyte,

electronics and biosensor etc.

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271. Heavily Fluorinated Electronic Polymers and Their Properties

Jeewoo Lim and Timothy M. Swager, Department of Chemistry, Massachusetts Institute of Technology,

Cambridge, MA

Fluorescent conjugated polymers (CPs) constitute an important class of materials for detecting chemical

and biological analytes. Most CPs reported thus far are electron-rich, p-type materials well-suited for

detecting electron-poor and/or positively charged substrates. To expand the range of sensory response,

there is a need for novel electron-poor (n-type) CPs. Incorporation of fluorine, the most electronegative

element, into the polymer backbone is an attractive way to synthesize n-type CPs. Organic compounds

with perfluoroalkyl chains are known to have interesting properties such as strong resistance to photo

oxidation and unique fluorous solubility. We have synthesized poly(phenylene ethynylene)s (PPEs)

decorated with long perfluoroalkyl chains. These polymers are n-type CPs and display preferential

solubility in perfluorinated solvents over typical organic solvents. Methods of synthesizing fluorous

polymers will be described, along with the properties and applications of perfluorinated polymers.

Inorganic/Organometallic - I (28th August, Friday morning) Presider: Ingo Krossing, Albert-Ludwigs-Universität Freiburg, Freiburg, Germany

272. New Aspects in Superacid Chemistry

Andreas J. Kornath and Nadine R. Goetz, Department of Chemistry and Biochemistry, Ludwig-

Maximilians-University, Munich, Germany

The acidity of some conjugate Brønsted-Lewis superacids is still not clarified without doubt. Especially the

acidity of HF/SbF5 in comparison with FSO3H/SbF5 and CF3SO3H/SbF5 was discussed controversially in the

past. In case of HSO3F and CF3SO3H the isolation of the protonated species H2SO3F+ SbF6

- and CF3SO3H2+

succeeded.

The salts were prepared, isolated and characterized by their vibrational spectra and in case of H2SO3F+

SbF6- by a single-crystal X-ray structure analysis. These are the first examples of isolated H2SO3F

+ and

CF3SO3H2+ salts. The conjugate Brønsted-Lewis superacid HF/SbF5 can be claimed as the strongest

superacid, but recent studies on carborane and borane acids describe these compounds as the strongest

isolable acids. This apparent contradiction leads to more general questions: Is the definition of acidity by

Brønsted sufficient to describe these systems? Is HF/SbF5 the strongest conjugate Brønsted-Lewis

superacid or have appropriate Lewis acids not been found yet? These questions will be discussed on

examples recently found in our studies of the HF/SbF5 system.

149

273. Reinvestigation of Os(VII) Compounds and Molybdenum Dioxide Difluoride

Hashem Shorafa and Konrad Seppelt, Institut für Chemie und Biochemie, Freie Universität Berlin, Berlin,

Germany

We have inspected the compounds OsO3F, OsO2F3 OsOF5 and OsF7 in order to find out, whether these are

true Os VII (d1-Metal) compound. The tetrahalides OsOF4, RuOF4 OsOCl4 and the trihalide RuOF3 are

mentioned in the literature, but no crystal X-ray studies have been published. Also the compounds MoO2F2

and WO2F2 analogue to CrO2F2 are known, but their characterization is not complete.

Model of MoO2F2

274. Bis(pentafluoroethyl)Phosphinous Acid

Julia Bader1, Bert Hoge1, Helge Willner2, Helmut Beckers2, Yong Seol Kim2, Reint Eujen2 and Nikolai V.

Ignat'ev3, (1)Institute of Inorganic Chemistry, University of Cologne, Cologne, Germany, (2)Anorganische

Chemie, Bergische Universität Wuppertal, Wuppertal, Germany, (3)PLS R&D LSS, Merck KGaA, Darmstadt,

Germany

The introduction of perfluoroalkyl groups to a phosphane derivative results in a significantly reduced

electron density at the phosphorus atom and therefore in a reduced Lewis basicity.1 The bonding of two

CF3 groups to a phosphorus atom effects a drastically decreased basicity, i.e. the phosphorus atom is the

least basic centre in the compound (CF3)2POH. Therefore, bis(trifluoromethyl)phos-phinous acid,

(CF3)2POH, represents to date the only literature-known example of a phosphinous acid which is stable

towards tautomerization.2 Non-fluorinated derivatives of diorganyl phosphinous acids, however, favor the

phosphane oxide structure.

150

Bis(trifluoromethyl)phosphinous acid is a highly volatile, colorless liquid that burns violently on contact

with air. Therefore, safety precautions are required for handling this compound.

For the homologue (C2F5)2POH with its somewhat sterically more demanding pentafluoroethyl groups, a

lower sensitivity towards air is expected. In this contribution we will present a safe synthesis of

(C2F5)2POH, the second known example of a stable phosphinous acid.

References:

1. for example: Apel, J.; Grobe, J., Z. Anorg. Allg. Chem., 1979, 453, 53.

2. Griffiths, J. E.; Burg, A. B., J. Am. Chem. Soc., 1960, 82, 1507; Griffiths, J. E.; Burg, A. B., J. Am.

Chem. Soc., 1962, 84, 3442; Dobbie, R. C.; Mason, P. R., J. Chem. Soc., Dalton Trans., 1974, 2439;

Dobbie, R. C.; Straughan, B. P., Spectrochim. Acta, 1971, 27, 255; Hoge, B.; Garcia, P.; Willner, H.;

Oberhammer, H., Chem. Eur. J., 2006, 12, 3567.

275. New Ionic Liquids Based On the Difluorophosphate Anion Kazuhiko Matsumoto and Rika Hagiwara, Graduate School of Energy Science, Kyoto University, Kyoto,

Japan

A series of new ionic liquids based on the difluorophosphate anion have been synthesized and

characterized by spectroscopic, physical, chemical, and electrochemical methods. The ionic liquids

obtained show low melting points, 9 ºC for EMImPO2F2 (EMIm: 1-ethyl-3-methylimidazolium), 19 ºC for

BMImPO2F2 (BMIm: 1-butyl-3-methylimidazolium), 27 ºC for BMPyrPO2F2 (BMPyr: 1-butyl-1-

methylpyrrolidinium), and 41 ºC for BMPipPO2F2 (BMPip: 1-butyl-1-methylpiperidinium). The melting point

of EMImPO2F2 is lower than the other simple EMIm fluorocomplex salts (BF4–, PF6

–, AsF6–, SbF6

–, NbF6–,

and TaF6–). The conductivity (12 mS cm–1) and electrochemical window (4.2 V) observed for EMImPO2F2

are comparable to those for EMImBF4 (13 mS cm–1 and 4.2 V). The stability of the ionic liquids towards

hydrolysis is improved by changing the anion from PF6– to PO2F2

–. The donor abilities of the EMImPO2F2

and BMImPO2F2 are stronger than those of the corresponding PF6–, BF4

– and N(SO2CF3) 2–-based ionic

liquids, which results from the negatively charged oxygen atoms in PO2F2–. Crystal structure of BMPipPO2F2

shows that the oxygen atoms in PO2F2– anion have shorter contacts to the cation than the fluorine atoms.

One of the two crystallographically independent BMPip+ cations is disordered in BMPipPO2F2 where the two

disordered piperidinium rings cross each other.

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276. Nature of the Band at 700-800 cm-1 in Vibrational Spectra of Inorganic Fluoride Compounds

Natalia M. Laptash and Anatoly A. Udovenko, Institute of Chemistry Far Eastern Branch of RAS,

Vladivostok, Russia

Inorganic fluoride compounds synthesized at ambient conditions quite often contain more or less intensive

band in the range of 700-800 cm-1 in their infrared spectra. Its interpretation available in the literature

should be criticized. In the case of fluorocomplexes with coordinated water, it was assigned to a libration

mode of H2O. We noted that F…O distance in similar systems is smaller than 2.6 Å, so we assign the

discussed band to transversal vibration of proton in the ternary system O–H…F with strong hydrogen

bond. The same concerns the fluorospecies with partial isomorphous substitution of fluoride ions for

hydroxide ones which can occur in nano-sized metal fluorides.

In the case of oxofluorospecies with M–O–M bridging bonds, the discussed band can be undoubtedly

assigned to the stretches of these bonds, which are both infrared and Raman active. In this regard, how

one can treat oxofluorocomplexes with isolated polyhedra (CN is five or higher)? In this case, the

discussed band is taken as the ―odd‖ line which is usually appears in the infrared spectra but is absent in

the Raman ones. We assume this band to be connected with strong dynamic O/F disorder when M–O and

M–F distances are physically equalized in polyhedron under its fast reorientational motion. Today we have

the unique Raman spectrum of oxofluoroelpasolite Rb2KTiOF5 under the laser beam of 1064 nm, which

confirms our assumption.

Fluoropolymers/Materials - II (28th August, Friday morning)

Presider: Paul Resnick, Fluoroscience LLC, Cary, NC

277. Perfluorocyclobutyl (PFCB) Aryl Ether Polymer Based Copolymers and Composites

Dennis W. Smith1, Scott T. Iacono2, Stephen M. Budy3, Andrew R. Neilson4, Rhett C. Smith2, John Ballato

Ballato3, Jiyoung Park3, Neetu Tomar5, Dakarai Brown3, Ken Tackett3 and Rajneesh Verma3,

(1)Department of Chemistry and Center for Optical Materials Science and Engineering Technologies

(COMSET), Clemson University, Clemson, SC, (2)Department of Chemistry and Center for Optical

Materials Science and Engineering Technologies (COMSET), Clemson University, Clemson, SC,

(3)Department of Chemistry and Center for Optical Materials Science and Engineering Technologies

(COMSET), Clemson University, Department of Chemistry and Center for Optical Materials Science and

Engineering Technologies (COMSET), Clemson, SC, (4)Department of Chemistry, Clemson University,

Clemson, SC, (5)Department of chemistry, Clemson University, Clemson, SC

Perfluorocyclobutyl (PFCB) aryl ether polymers are prepared via step-growth [2+2] thermal dimerization

of aryl trifluorovinyl ethers (TFVE)1 and have been demonstrated as processable fluoropolymers for high

performance passive optics, electro-optics, polymer light-emitting diodes (PLEDs), space survivability,

polymeric fuel cell membranes (PEMs), high use temperature fluorosilcones, POSS composites, and liquid

crystalline polymers. PFCB polymers are tailored for a wide variety of thermoplastic and thermoset

materials employing a versatile intermediate strategy using commercial TFVE monomers.2

During past decade, the hierarchically ordered block copolymers and systems based on these block

copolymers have been a subject of great interest for experimental as well as theoretical exploration due to

152

their possibility of creating structures by combining different periodicities. In addition to PFCB and FAVE

polymers for passive photonics applications, this presentation will detail our recent advances semi-

fluorinated block copolymers tuned for light emission, PEMs and superhydrophobic coatings. We have

successfully prepared new rod-coil block copolymers by incorporating polyethylene glycol (PEG) to various

trifluorovinyl monomers. Our sulfonated membranes of PFCB-BPVE block copolymers showed better

properties as compared to their corresponding homopolymers. These membranes will find their utility in

electrolyzers developed for use in hybrid sulfur process, to produce economically high temperature

hydrogen production. Solution processable fluorinated aryl vinyl ether (FAVE) polymers prepared from

functionalized bisphenols and TFVEs possess the ability to undergo thermal cross-linking without the use of

post-curatives. The wettability of our fluoropolymers was studied in the presence of room temperature

ionic liquid (RTIL).

278. Biphenyl-Containing Fluoropolycarbonates: Synthesis and Comparison with Non-

Fluorinated Counterparts

David A. Boyles and Tsvetanka Filipova, Department of Chemistry, South Dakota School of Mines and

Technology, Rapid City, SD

The remarkable properties enjoyed by commercial polycarbonate (BPA-PC) are nonetheless constrained by

the high melt viscosity of the material, and monomer modifications to date have led to more brittle

materials. Ductility appears to be a function of structural uniqueness attributable to the bisphenol A (BPA)

repeat unit—virtually all known monomeric analogues of BPA have led to polycarbonates having higher

glass transitions than BPA-PC at the expense of ductility. Keeping molecular cross sectional area low,

however, is one strategy which may lead to ductile materials, as we have sought to verify.1 In particular,

monomeric analogues of BPA containing rigid biphenyl units often show desired ductility properties,

although such units may lead to insoluble and unprocessable materials evidently owing to cohesive

energies promoting undesirable crystallinity. In this work we discuss four new monomeric biphenols

containing biphenyl units and their respective polycarbonates synthesized by interfacial polymerization.

Each synthesis of non-fluorinated biphenyl monomers has been complemented with a synthesis of the

corresponding fluorinated biphenyl unit analogue. Relying upon a single commercially available fluorinated

precursor in each case, monomer synthesis and resulting polycarbonate property comparisons of non-

fluorinated and fluorinated polycarbonates will be presented. In general the substitution of a single

fluorine atom for an aryl hydrogen imparted significant differences to the materials.

1Boyles, D.A.; Filipova, Ts.; Bendler, J.T.; Longbrake, G.; Reams, J., Macromolecules, 2005, 38, 3622.

279. Fluorinated Diels-Alder Polymers

Paul A. Deck, Charles S. Carfagna Jr., Jessica P. Evans, Brian S. Hickory and Sanghamitra Sen,

Department of Chemistry, Virginia Tech, Blacksburg, VA

Diels-Alder polyphenylenes (DAPPs) are chemically and thermally stable polymers with existing and

emerging applications in a variety of membrane and coating technologies. We are working on synthetic

approaches to highly fluorinated DAPPs that should exhibit exceptional stability (especially in acidic

environments) while hopefully maintaining the useful processibility of their non-fluorinated counterparts.

Meanwhile, we are also exploring fluorinated Diels-Alder ―self-mending‖ polymers where the propagation

reaction is reversible under certain conditions. Both chemistries are based on general methods involving

nucleophilic substitution reactions of cyclopentadienyl anions with perfluoroaromatic compounds. A

prototypical retrosynthesis is illustrated in the accompanying scheme. This strategy makes use of unique

153

expertise that our laboratory has built up over the past several years, in addition to new chemical

methods developed specifically to reach these new targets. This lecture will summarize our overall

objectives and highlight our synthetic accomplishments to date.

Inorganic/Organometallic - II (28th August, Friday morning)

Presider: Thomas Braun, Humboldt-Universität Berlin, Berlin, Germany

280. Inert Yet Reactive Molecules in Catalysis, Photophysics and Electronic and Magnetic Materials Via Fluorine Chemistry

Sergiu Gorun, Department of Chemistry and Environmental Science, New Jersey Institute of Technology,

Newark, NJ

Molecules the exhibit highly selective functionalities constitute the basis for many technological

applications. The replacing of all C-H bonds of phthalocyanine metal-organic complexes by fluorinated

groups results in active sites that are no longer thermally and chemically susceptible to reactive oxygen

species while exhibiting unusual oxidative and oxygenation external substrate chemistry, including

reactivity not exhibited by the parent, non-fluorinated molecules. Intermolecular interactions are also

affected allowing the formation of single-crystals and unprecedented atomic level characterizations of

halogen substituted phthalocyanines. A combination of computational and experimental chemistry reveals

severely depressed frontier orbitals, facile electron addition in solution and in easily formed solid-state

films. The fluorine-based steric tuning insures site isolation that imparts favorable photophysical and

photocatalytic properties, yet does not preclude the formation of lanthanide sandwich complexes

displaying intra- and intermolecular spin-spin coupling and "cogwheel" stereoisomerism.

281. Thermodynamic Stability of Fluorocomplexes of the Platinum Metals

Ljudmila M. Levchenko, Russian Academy of Sciences, Nikolaev Institute of Inorganic Chemistry

Siberian Branch, Novosibirsk, Russia

In our previous investigation using differential scanning calorimetry, we measured the heat effects of

reactions in hydrogen of the major part of known octahedral fluorocomplexes of platinum metals and

calculated standard enthalpies of formation DÍîf298ÊnMeF6, where Ìå = Pt, Pd, Ir, Rh, Ru, Os; and n = 3, 4,

5.

The goal of this communication is to compare the known calculated thermodynamic data for

fluorocomplexes of the platinum metals and to determine approaches to reveal the reasons of the change

in stability when passing from the gas phase to the condensed state and finally to aqueous solutions.

Comparison of the energies of complex formation with halide ions in the gas phase and in solution shows

that, in spite of the large bond energies in the metal-fluoride systems, compared to other halide ions,

fluorocomplexes of the platinum metals in the highest oxidation states possess smaller stability in aqueous

solutions than the fluorocomplexes in oxidation states (IV) and (III).

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282. Ionic Liquids Based On the Transition Metal Fluorocomplex Anions

Takatsugu Kanatani, Kazuhiko Matsumoto and Rika Hagiwara, Graduate School of Energy Science,

Kyoto University, Kyoto, Japan

Fluorohydrogenate ionic liquids based on the (FH)nF- anions are good starting reagents to synthesize

fluorocomplex salts including ionic liquids by simple acid-base reactions with binary fluorides (AFn). A

series of 1-ethyl-3-methylimidazolium (EMIm+) and N-butylpyridinium (BPy+) ionic liquids based on NbF6-,

TaF6-, and WF7

- were prepared with this method. Although ionic liquids based on VF6- and MoF7

- were not

prepared in the same way due to the strong oxidizing power of VF5 and MoF6 to decompose the organic

cation, VOF3 and MoOF4 are relatively mild oxidizers to give ionic liquids such as EMImVOF4, BPyVOF4,

EMImMoOF5, and BPyMoOF5 by neutralization with fluorohydrogenates. The melting points of EMImVOF4,

BPyVOF4, and BPyMoOF5 are 75, 73, and 73 ºC, respectively, whereas EMImMoOF5 is a liquid at room

temperature exhibiting only a glass transition at -81 ºC. Density, viscosity, and ionic conductivity of

EMImMoOF5 are 1.76 g cm-1, 86 cP, and 5.1 mS cm-1 at 25 ºC, respectively. The UF6- salts, EMImUF6,

BMImUF6 (1-butyl-3-methylimidazolium; BMIm+), BPyUF6, and BMPyrUF6 (N-butyl-N-methylpyrrolidinium;

BMPyr+) are also synthesized by the stoichiometric reaction of corresponding fluorohydrogenates and UF5.

The two imidazolium-based salts, EMImUF6 and BMImUF6, are room temperature ILs, whereas the

pyridinium-based salt, BPyUF6, melts at 62 ºC. Although the non-aromatic cation-based BMPyrUF6 does

not exhibit a melting point, it shows a crystal-plastic crystal phase transition at 67 ºC with a small

enthalpy change followed by decomposition at 340ºC without melting.

Organic/Organometallic - II (28th August, Friday)

Presider: Gerd-Volker Roeschenthaler, University of Bremen, Bremen, Germany

283. Aldol Reaction of (E)- and (Z)-Enolborinates of Alkyl and Aryl Trifluoropropionates

P.V. (Chandran) Ramachandran, Gowrisankar Parthasarathy and Pravin Gagare, Department of

Chemistry, Purdue University, West Lafayette, IN

Very few reports on boron-mediated aldol reaction of esters have appeared in the literature since the

description of (E)-enolborinates of thioesters by Masamune three decades ago. A decade ago Masamune

and Abiko reported the dialkylboron triflate-mediated enolization of esters, followed by aldolization of

aldehydes, which led to a substrate-controlled asymmetric aldol reaction of norephedrine-derived ester

enolates. They obtained either syn- or anti-hydroxy esters, depending on the alkyl group on boron. We

recently reported a convenient and general, reagent-controlled, diastereo- and enantioselective aldol

reaction of diisopinocampheylboron enolates of esters and its application for the double diastereoselective

synthesis of C11-C17 subunit of (-)-dictyostatin (Org. Lett. 2009, 11, 1467). We have now carried out a

systematic study of the enolization-aldolization of a series of alkyl and aryl trifluoropropionates using a

variety of dialkylboron halides and triflates in the presence of trialkylamines of different steric

requirements. Our successful preparation of both syn- and anti-α-trifluoromethyl-β-hydroxyl esters,

including optically active hydroxyl esters will be discussed.

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284. New Processes for Producing Arylsulfur Pentafluorides

Teruo Umemoto, IM&T Research, Inc., Denver, CO

The pentafluorosulfanyl (SF5) group on a benzene ring is stable, and more lipophilic and electronegative

than a trifluoromethyl (CF3) group. Thus, the chemistry and industrial applications of arylsulfur

pentafluorides (ArSF5) have been expected to be developed largely to the same or greater extent as the

corresponding benzotrifluorides (ArCF3), which have grown up into a huge chemistry and industry since

their discovery of the industrial production methods more than half a century ago. However, in particular,

the industrial applications of arylsulfur pentafluorides have not developed at all because of any practical

industrial production methods. Since a DuPont chemist first prepared arylsulfur pentafluorides in very low

yields from diaryl disulfides and expensive silver difluoride in the early 1960's, much effort has been

expended to develop a useful and industrially practical synthesis for these compounds. About a decade

ago, a process whereby nitro-substituted diphenyl disufides were reacted with elemental fluorine was

developed. A stepwise method starting from a reaction of pentafluorosulfur chloride or bromide with a

cyclo olefin was also reported. However, these methods are not practical for applications to large scale

industrial production and different arylsulfur pentafluorides. I wish to report a new method, suitable for

industrial scale-up, for the production of various arylsulfur pentafluorides. In this presentation I will

elaborate on the synthesis of arylsulfur pentafluorides employing our new processes (Eqs. 1 and 2).

1. ArSSAr + KF + Cl2 → ArSF4Cl

2. ArSF4Cl + Fluoride source (ZnF2 etc.) → ArSF5

285. Octakis(trifluoromethyl)Corroles

Abhik Ghosh, Department of Chemistry, University of Tromso, 9037 Tromso, Norway

Palladium-catalyzed coupling of copper b-octabromo-meso-triarylcorrole derivatives with methyl 2,2-

difluoro-2-(fluorosulfonyl)acetate yielded the corresponding octakis(trifluoromethyl)corrole complexes,

Cu[(CF3)8T(p-XP)C] (X = H, Me, OMe), in moderate yield. The new complexes embody a conglomeration

of most remarkable substituents effects, both steric and electronic. DFT (OLYP/TZP) geometry

optimization of Cu[(CF3)8TPC] (i.e. X = H) indicates a sterically hindered, strongly saddled geometry, with

numerous short FÉF nonbonded contacts of 2.5 – 2.9 • and certain b carbons displaced by over 1.5 •

relative to the mean corrole plane. For all three complexes, the CF3 groups appear as quartets in the 19F

NMR spectra, with unexpectedly large 5JFF coupling constants of about 14 Hz, apparently a manifestation

of the highly crowded structure. The eight CF3 groups together exert a powerful influence on the redox

potentials of the copper corrole core. Thus, the E1/2ox of Cu[(CF3)8TPC] (1.4 V vs. SCE) is a full half-volt

above that of Cu(TPC) (0.9 V) and a quarter of a volt above that of Cu(Br8TPC) (1.14 V). Intriguingly, the

b CF3 groups also greatly intensify the influence of the meso aryl substituents on the redox potentials,

relative to the other Cu[Y8T(p-XP)C] series, where Y = H, F, and Br. The Cu[(CF3)8T(p-XP)C] complexes

also exhibit the most red-shifted optical spectra of any series of metallocorroles synthesized to date. Thus,

from Cu(TPC) and Cu[(CF3)8T(p-MeO-P)C], the Soret maximum shifts by nearly 100 nm. The observed

red-shifts are attributed in part to charge-transfer transitions of the Soret region and in part to the

extreme nonplanar distortions.