doctoral thesis ppt-dr. parantap sarkar
TRANSCRIPT
THE CERAMIDONINE AND PERKIN APPROACHES TO AROMATIC
NANORIBBONSTHÈSE
UNIVERSITÉ BORDEAUX 1
(CENTRE DE RECHERCHE PAUL PASCAL / CNRS)
PARANTAP SARKAR
SPÉCIALITÉ : PHYSICO-CHIMIE DE LA MATIÈRE CONDENSÉE
DIRECTEUR DE RECHERCHE : DR. HARALD BOCK
1
Table of Contents:
A. Introduction to GNRs.
B. Ceramidonine Approach.
C. Perkin Approach: Cyclodehydrogenation Variant.
D. Perkin Approach: Cyclodebromodehydrogenation Variant.
E. Conclusions & Perspectives.
2
Table of Contents:
A. Introduction to GNRs.
B. Ceramidonine Approach.
C. Perkin Approach: Cyclodehydrogenation Variant.
D. Perkin Approach: Cyclodebromodehydrogenation Variant.
E. Conclusions & Perspectives.
3
4
A. Introduction: Conjugated Polymers
SS
SS
nH17C8 C8H17
H17C8C8H17
SS
SS
nH17C8 C8H17
C8H17H17C8
P5Eg = 2.0 eV
P6Eg = 1.9 eV
SS
SS
nH17C8 C8H17
H17C8C8H17
SS
SS
nH17C8 C8H17
C8H17H17C8
P5Eg = 2.0 eV
P6Eg = 1.9 eV
5
A. Introduction: CNTs
Stable Clar Structures of triphenylene and isomeric tetracene
OrangeUncolored
chiral, partially sextetted,
semiconducting
chiral , fully sextetted, metallic
armchair, fully sextetted, metallic
zig-zag , fully sextetted, metallic
zig-zag, partially sextetted,
semiconducting
6
A. Introduction: CNTs, Conjugated Polymers and GNRs
strong and stiff good conductors poor solubility difficult chemistry of functionalization
flexible easily functionalized and soluble less rigid/coplanar, less conductive often easily oxidised
fully coplanar even if fully sextetted, so well conjugated and potentially very stable towards oxidation
functionalisable at H positions, so soluble and electronically tunable
SS
SS
nH17C8 C8H17
H17C8C8H17
SS
SS
nH17C8 C8H17
C8H17H17C8
P5Eg = 2.0 eV
P6Eg = 1.9 eV
7
A. Introduction: different structural types of Nanoribbons
Phenacene-like Orientation (PO)
Slanted Orientation (SO)
Acene-like Orientation (AO)
OOO
O O OOOOOOO
O O O O O O
8
A. Introduction: Common approaches towards nanoribbons
• Robust Chemistry.
• Doesn't maintain theProperties and
smoothness of the edges
• Insoluble outcome; hard to purify
9
A. Introduction: “bottom-up” synthesis of ribbons on Au-Surface
Br Br
n n
200oC 400oC
Au Ausurface surface
Br Br
250oC
Ausurface
n
440oC
Ausurface
n
J. Cai et. al., Nature, vol. 466, no. 7305, pp. 470–473, 2010.
10
A. Introduction: “bottom-up” synthesis of functionalized “free-standing” ribbons
N
N
O O
OOAlk
AlkAlk
Alk
BrBrBr
Br
CuI,proline,K2CO3
N
N
O O
OOAlk
AlkAlk
Alk
N
N
O O
OOAlk
AlkAlk
Alk
N
N
O O
OOAlk
AlkAlk
Alk
N
N
O O
OOAlk
AlkAlk
Alk
N
N
O O
OOAlk
AlkAlk
Alk
N
N
O O
OOAlk
AlkAlk
Alk
+
O O.
.
Alk
Alk
+
Alk
Alk Alk
Alk
Alk
Alk Alk
AlkAlk
Alk n
- H2OAlk
Alk Alk
AlkAlk
Alk n
O O
I I
Alk
Alk
Alk
Alk
B BO
O O
O
Alk
Alk Alk
Alk
+
n n
Pd[0] FeCl3
Alk
Alk
Alk
AlkAlk
Alk Alk
Alk
B
B
OO
O OAlk Alk
Br Br
+
n n
Pd[0] FeCl3
Alk Alk
Alk Alk
Alk
Alk Alk
Alk
H. Qian et. al. Journal of the American Chemical Society, vol. 130, no. 52, pp. 17970–17976. 2008
X. Yang, et. al.; Journal of the American Chemical Society, vol. 130, no. 13, pp. 4216–4217, 2008
M. Löffler et. al., Angewandte Chemie International Edition in English, vol. 33, no. 21, pp. 2209–2212, 1994
11
A. Introduction: Heteroaromatic nanoribbons
N
N
N
N
N N
N N
N
N N
N
N N
N
N
N N
N
N N
N
N N
N N N
N N
NNNN
N N
N
N N
N
N N
N
N NN
N NN
N
N N
F F
NMe3Si SiMe3
– Me3SiF
N N
N N
N
N N
N
N N N
N
N N
N N
N
N
N
N N
N N
N
N
N
N N
NN
N N
N N
N
NH2
NH2H2N
N N
N
N
N
N N
NH2
H2N NH2
– NH2
– NH2
H2N
NH2HX
XH+
O
OCl
ClR
Ror
H2N
NH2Cl
Cl+
O
OHX
XHR
R
N
X
X
N
R
R n
U. Scherf, Journal of Materials Chemistry, vol. 9, no. 9, pp. 1853–1864, 1999.
B. Jürgens et. al. Journal of the American Chemical Society, vol. 125, no. 34, pp. 10288–10300, 2003.
12
A. Introduction: Heteroaromatic nanoribbons
N N
N N
N
N
N
N
N
N
N
N
N N
N NN
N
NN
NN
NN
Os Os
N
NN
N
N
N N
N N
N N
N
N
N
N
N
N
NN
N
eilatin, isoeilatin, dibenzoeilatin and a dinuclear complex of the latter,*
*J. Kouvetakis et. al., Chemistry of Materials, vol. 6, no. 6, pp. 811–814, 1994.
13
A. Introduction: Our Aim
1. efficient and controlled methodologies towards functionalized ribbon
fragments
2. homo and hetero aromatic polyarene systems
3. controlled solubility
4. tunable electronic properties; “donor” and “acceptor” type materials
5. removable solubilizing groups to get unsubstituted GNRs at the end
Study of synthetic “bottom-up” approaches towards Nanoribbons:-
Table of Contents:
A. Introduction.
B. Ceramidonine Approach.
C. Perkin Approach: Cyclodehydrogenation Variant.
D. Perkin Approach: Cyclodebromodehydrogenation Variant.
E. Conclusions & Perspectives.
14
15
B. Ceramidonine approach: Introduction
N ON OH
O-H2O
12
Bis-ceramidonine
Cera-diamidine
A.H. Cook and W. Waddington; Imperial college of science and Technology, London, S.W. 7, January 20th, 1945 *D.W.Rangnekar & S.V. Sunthankar ; Indian journal of Technology; vol. 12, December 1974, pp. 548-550
Ceramidonine
O
ONH
NH O
O
N
N
O
O
O
ONH
NH
N
N
O
ONH
HN
N
N
16
B. Ceramidonine approach: Plan
N
N
O
O
O
O
TfO
TfO
TfO
OTfN
N
N
N
O
O
O
O
OH
OH
OH
HON
NNO2
NH2
NH2 NH2 NH2
NO2 NO2 NO2
N
N
3 4 5 6
Di-aminophenazine Di-activated anthraquinone
N N
N N
N N
N N
n
N
N
NN
NN
N
N
n
N N
N N N
N
N
N
n
N
N
N N N
N
N
n
N
3 + 5
3 + 6
4 + 5
4 + 6
poly35
poly36
poly45
poly46
WE NEED TO INCORPORATE SOLUBILIZING CHAINS
17
B. Ceramidonine approach: Synsthesis of di-activated bricks
O
O
OH
OH
O
O
OH
OH
Tf2O, Pyridine,0o C to 23o C, 24 hr.
Tf2O, Pyridine,0o C to 23o C, 24 hr.
O
O
OTf
OTf
O
O
OTf
OTf
Anthrarufin
Qunizarin
6
5
89%
94%
OTf O SO
O
F
FF
N
N Fuming HNO3
Conc. H2SO4 + fuming H2SO4
N
N
N
N
NO2
NO2
NO2NO2
N
NNH2NH2
N
NNH2
NH23
4
100o C, 1 hr
Pd-C, N2H4. H2O, EtOH
Pd-C, N2H4. H2O, EtOH
30%
37%
48%
74%
B. Ceramidonine approach: Insertion of solubilizing chains
18
BuNH2
CoCl2
Tf2O
N N N
NO2NH2
O
O
O
O O
OOH OH
Bu Bu
TfO
HNO3
H2SO4
Bu4Sn
Pd(dppf)Cl2
7
8
DMFBr Br Bu
Can react 2 equivalent witha di-aminophenazine
Can react 2 equivalent witha di-activated anthraquinone
N
NNH2
NH23
N
NNH2NH2
4
O
O
OTf
OTf
O
O
OTf
OTf5 6
19
B. Ceramidonine approach: Test systems for amination reaction
Amination condition: Pd(dba)2 , dppf t BuONa, LiCl, toluene, over night, reflux, Ar. atm.
O
O
OTf
OTf6
O
O
OTf
OTf
5
++
NH2
Bu
NH2
Bu
O
OHN
Bu
NH
Bu
O
O
NH
Bu
NH
Bu
1113
63%60%
O
O
OTf
Bu
+N
NH2
O
OBu
NHN
9
7
57%
20
B. Ceramidonine approach: Test cyclisations
N N
N
N
N N
N N
OO
O
O
H H
H
H
Bu Bu
Bu
Bu
Bu
Bu
BuBu
N
OH
Bu
Bu
N
11 12
13 14
N OH
N O
O
9 10
N N
Bu Bu
70% H2SO4 170o C , 30 min
70% H2SO4 130o C , 8 min
21
B. Ceramidonine approach: Tetraazaarene
=
O
O
OTf
OTf
N
BuNH2
N
BuNH2
NH
HN
O
O
N
NBu
Bu
N
N
N
N
868
Bu
Bu
pre868 40% 64%
Pd(dba)2, dppf
NaO-tBu, LiCl90o C, Toluene
Over night, Ar. atm.
22
N
N
N
NBu
Bu
N
N
N
N
Bu
Bu
N
Bu
NH2
N
BuNH2
N
Br
N
N
NO2
Br
BrNO2
S. Doherty et. al., Tetrahedron:
Asymmetry, 2003, 14, 1517.
J. D. Crowley et. al., Chem.–Eur.
J., 2006, 12, 8935.
HNO3 + H2SO4
- 20oC - -0oC
M = Fe2+, Fe3+,
Ni2+, Co2+, Ru2+
M = Fe2+, Fe3+,
Ni2+, Co2+, Ru2+
?????
LOGICAL
B. Ceramidonine approach:
23
B. Ceramidonine approach: Tetraazaarene
N N
N NO
N
N N
N
3 + 7
4 + 7
5 + 8
6 + 8
O
Bu
Bu
N
N
NN OO
BuBu
N
N
N
N
747
858
737
868
NN
NN O
N
N N
N
O
Bu
Bu
NH
N
NHN
OO
BuBu
NN N
N
O
O
OO
OO
O
O
H
H
H H
H
H
pre737
pre747
pre858
pre868
Bu
Bu
Bu
Bu
Bu
Bu
Bu
Bu
70% H2SO4 at 1300 C for 8 min
70% H2SO4 at 1700 C for 30 min
53%
41%
68%
70% H2SO4 at 1300 C for 8 min
24
B. Ceramidonine approach: Tetraazaarenes
868 C60
1st Red(V)
-0.85 -0.92
2nd Red(V)
-1.25 -1.32
868
NN
N
N
O
O Bu
Bu
N N
N
N
Bu
BuO
O
868 737 747
N
N
N
NBu
Bu
25
B. Ceramidonine approach: Alkoxy chains in di-activated anthraquinone brick
CO2H
HO2C
OH
OH
HO
HO
O O
HO
OH
O
O
H
HO O
O
O
O
O
H
H
O O
O
O
O
O
S
S
F3COO
CF3OO
O O
O
O
N
N
H
H
O
O
N
N
17
1615
18 19
+
26
B. Ceramidonine approach: Conclusion
Achieved: Electron “acceptor-type”, Soluble, extended Tetraazaarenes
WHY NOT FURTHER ?? [Difficulties with Ceramidonine approach]
1. Tricky cyclisation
2. Difficulties in incorporation of solubilizing chains
Table of Contents:
A. Introduction.
B. Ceramidonine Approach.
C. Perkin Approach: Cyclodehydrogenation Variant.
D. Perkin Approach: Cyclodebromodehydrogenation Variant.
E. Conclusions & Perspectives.
27
28
C. Perkin Approach: Cyclodehydrogenation Variant: introduction
Perkin Reaction:- α-β-diaryl acrylic acids by condensation of aromatic aldehydes with arylacetic anhydrides in presence of weak base
28
HOOC O
+Ac2O
Et3N
HOOC
COOR
ROOC ROOC
COOR n
HOOC
COOH
O
O
+
Ac2O
Et3NCOOR
ROOC ROOC
COOR n
RBr
DBU
29
C. Perkin Approach: Cyclodehydrogenation Variant: Previous work on DDQ/MeSO3H oxidant
T.S. Navale et. al. , Org. Lett. 2011, 13, 7, 1634-1637
L.Zhai et. al.; Org. Lett. 2009, 11, 15, 3474-3477
OO
OH
+
OOH
OOR
OOR
Ac2O, NEt3 ROH, H+DDQ,
MeSO3H
* T.S.NAVALE, K.THAKUR, R.RATHORE, Org. Lett. 2011, 13, 7, 1634-1637
30
C. Perkin Approach: Cyclodehydrogenation Variant: DDQ/MeSO3H cyclizations on acrylates
O
S
OO
CO2H
CO2H
CO2HS
CO2H
O
31
C. Perkin Approach: Cyclodehydrogenation Variant: DDQ/MeSO3H cyclizations on acrylates
CO2Me
S
CO2Me CO2Me
CO2Me
S
CO2Bu CO2Me
CO2Me SCO2Me CO2MeS S
S
O
S
OO
CO2H
CO2H
CO2HS
CO2H
O
S
S
CO2Bu
CO2BuCO2Bu
CO2Me
CO2Me
CO2Me CO2Me
1 2 3 4
5 6 7 8
9 10 11 12
13 14 15 16
32
C. Perkin Approach: Cyclodehydrogenation Variant: DDQ/MeSO3H cyclizations on acrylates
CO2Me
S
CO2Me CO2Me
CO2Me
S
CO2Bu CO2Me
CO2Me SCO2Me CO2MeS S
S
O
S
OO
CO2H
CO2H
CO2HS
CO2H
O
S
S
CO2Bu
CO2BuCO2Bu
CO2Me
CO2Me
CO2Me CO2Me
1 2 3 4
5 6 7 8
9 10 11a, b 12
13 14 15 16
33
C. Perkin Approach: Cyclodehydrogenation Variant: DDQ/MeSO3H cyclizations on acrylates
CO2Me
S
CO2Me CO2Me
CO2Me
S
CO2Bu CO2Me
CO2Me SCO2Me CO2MeS S
S
O
S
OO
CO2H
CO2H
CO2HS
CO2H
O
S
S
CO2Bu
CO2BuCO2Bu
CO2Me
CO2Me
CO2Me CO2Me
1 2 3 4
5 6 7 8
9 10 11a, b 12
13 14 15 16
34
C. Perkin Approach: Cyclodehydrogenation Variant: DDQ/MeSO3H cyclizations on acrylates
CO2Me
S
CO2Me CO2Me
CO2Me
S
CO2Bu CO2Me
CO2Me SCO2Me CO2MeS S
S
O
S
OO
CO2H
CO2H
CO2HS
CO2H
O
S
S
CO2Bu
CO2BuCO2Bu
CO2Me
CO2Me
CO2Me CO2Me
60%
41%
70%53% 85% 63%
11%
0°C
20°C
20°C 20°C 20°C 20°C
20°C64h
64h
64h
64h
16h 16h 16h
*
1 2 3 4
5 6 7 8
9 10 11a, b 12
13 14 15 16
C. Perkin Approach: Cyclodehydrogenation Variant: Assumed Mechanism
35
HOOMe
OOMe
H+
HOOMe
Nucleophile (N) Electrophile (E)
HOOMe
HOOMe
Bad N Bad E
S
OHMeO
Very Good NS
HOOMe
Bad E
S
HO
OMe
S
OHMeO
Increasing Nucleophilicity
S
OHMeO
S
OMeHO
S S
OMeHO
Very Good N
OBuHO
OBuHO
Moderate N Better E Moderate N
Worse E
36
C. Perkin Approach: Cyclodehydrogenation Variant: crystal structures
CO2Bu
S
CO2Me
S
CO2Me
C. Perkin Approach: Cyclodehydrogenation Variant: Chryseneo-dithiophene
37
O
O
S
S
CO2H
HO2CHO2C S
CO2HS
+
+S
S
CO2Bu
BuO2C
S
S
CO2Bu
BuO2C
18 20
higher dilution Yield: 50%
SS
CO2Bu
BuO2C S
S
CO2Bu
CO2Bu
38
C. Perkin Approach: Cyclodehydrogenation Variant: di-acrylates with three naphthalene units
BuO2C BuO2C
BuO2C
CO2Bu
BuO2C
CO2Bu
BuO2C
CO2Bu
BuO2C
CO2Bu
BuO2C
CO2Bu
BuO2C
CO2Bu
39
C. Perkin Approach: Cyclodehydrogenation Variant: absorption spectra (UV-Vis)
325 345 365 385 405 425 4450
0.1
0.2
0.3
0.4
0.5
0.6Chryseno [1,2-b : 7,8-b’] dihiophene-3,9-(di-nbutylcarboxylate
Phenanthro [1,2-b] thiophene-9-methylcar-boxylate
Benzo [2,1-b : 3,4-b’] dithiophene-5-methylcarboxylate
Picene-13-(n-butyl)-carboxylate
Wave lenghth (nm)
INT
EN
SIT
Y
40
C. Perkin Approach: Cyclodehydrogenation Variant: Conclusions
efficiency of DDQ/MeSO3H promoted oxidative cyclisation on carboxy-functionalized systems
On homoaromatic substrates, the approach has limited efficiency
efficient for 3-thienylacetic acid and aromatic aldehyde combinations including multiple cyclisations that might lead to partially rigidified soluble polymers.
SSS S SS
S S
n
COOMe
COOMe
COOMe
COOMeCOOBu
BuOOC
S
S
COOBu
BuOOC
S
S
COOBu
BuOOC
S
S*
n
STILL NOT TRUE RIBBON
PERSPECTIVES
Table of Contents:
A. Introduction.
B. Ceramidonine Approach.
C. Perkin Approach: Cyclodehydrogenation Variant.
D. Perkin Approach: Cyclodebromodehydrogenation Variant.
E. Conclusions & Perspectives.
41
42
D. Perkin Approach: Cyclodebromodehydrogenation Variant: Introduction
CO2Me
Br
CO2Me
86%CO2Me
Br
CO2Me
77%
CO2Me
Br
CO2Me
70%CO2Me
Br
CO2Me
80%
NO2NO2 NO2 NO2
CN CN NO2 NO2
Cl Cl
F3C
CF3
CO2Me
Br
CO2Me
60%
MeMe
CO2Me
Br
CO2Me
70%
MeMe
Me Me
Pd(OAc)2 [5 mol %]K2CO3 Anhy. DMF
15 h, 1100 C, Ar-atm
L. Nassar-Hardy, C. Deraedt, E. Fouquet, and F.-X. Felpin; Eur. J. Org. Chem., vol. 2011, no. 24, pp. 4616–4622, 2011.
MeO2C MeO2C
DDQ
MeSO3H
MeO2C
Br
MeO2C
Pd(OAc)2
BuO2C BuO2C
43
D. Perkin Approach: Cyclodebromodehydrogenation Variant: Modification on Perkin reaction
O
RO2C RO2C
Ac2O, NEt3
HO2C CO2H
CO2R CO2R
OO O
Br+
Br
Br
Pd(OAc)2
ROH, RHal, DBU
RNH2
Br
Pd(OAc)2
N NO O O ORRGlyoxylic Perkin reactions for
- More solubilizing groups- Variable electronics (imides
more A, esters more D)
44
D. Perkin Approach: Cyclodebromodehydrogenation Variant: bricks for Ribbons
Monomeric units for Ribbons: Aromatic diglyoxylic acid & Aromatic di-bromo-di-acetic acid
HOOC
COOH
HOOC
COOH
HOOC
COOH
HOOC
COOH
HOOC
COOH
HOOC
COOH
Br Br
Br
Br
Br
Br
BrBr+ + + +
2 eqv. NBS
H2SO4 / H2O
9% 8% 53% 19% 8%
CO2Et
CO2EtBr
CO2Et
CO2Et
HO2C O
Br
CO2H i) Et3N, Ac2O THF, 2 hr, ref lux
ii) EtBr/ EtOH, reflux 4 h
Pd(OAc)2 [5 mol %]
K2CO3 Anhy. DMF
15 h, 1100 C, Ar-atm
92%
+
68%
14 20
EtO2CCOCl
AlCl3 / DCM5 day
COOEt
O O
COOEt
O
COOEt
+
COOEt
O
COOEt
O
O
EtOOC
O
EtOOC
+ +
28% 8% 7%Trace
45
D. Perkin Approach: Cyclodebromodehydrogenation Variant: Cyclizations
CO2Et
CO2Et
CO2Et
CO2Et
Br
15 (58%) 21 (90%)
EtO2C
EtO2C
CO2Et
CO2EtEtO2C
EtO2C
CO2Et
CO2Et
Br
Br
16 (49%)22 (89%)
EtO2C
EtO2C
CO2Et
CO2EtEtO2C
EtO2C
CO2Et
CO2Et
Br
Br
17 (62%) 23 (66%)
CO2Et
CO2Et
CO2Et
CO2Et
Br
CO2Et
CO2Et
CO2Et
CO2Et
Br19 (68%) 25 (91%)
EtO2C
EtO2C
CO2Et
CO2EtEtO2C
EtO2C
CO2Et
CO2Et
Br
Br
18 (60%) 24 (79%)
46
D. Perkin Approach: Cyclodebromodehydrogenation Variant: bricks for selective Perkin
CH2CO2H
CH2CO2H
Br
Br
MeOH,SOCl2
CH2CO2Me
CH2CO2Me
Br
Br
CH2CO2Me
CH2CO2H
Br
Br
1 eq.KOH
9 26
EtO2CCOCl
AlCl3Ac Ac
COCO2Et
SeO2
COCO2H
COCO2Et
10
Ac
COCO2H
27
Does NOT undergo Perkin
Condensation
Undergoes Perkin Condensation
Selective Perkin Reaction at that site only
Oxidation after Perkin
condensation
47
D. Perkin Approach: Cyclodebromodehydrogenation Variant. Imide bricks & Cyclizations
NCHEt2
O
O
NCHEt2
O
O
NCHEt2
Et2HCN
O
OO
O
O
OBr
NCHEt2
O
O
NCHEt2
28 (82%) 31 (93%)
O
OBr
NCHEt2
O
OBr
Et2CHN
29 (53%)
O
OBr
NCHEt2
O
OBr
NCHEt2
30 (70%)
O
OBr
NCHEt2Br
MeO2CCH2
32 (50%)
O
OBr
NCHEt2
Ac
33 (22%)
48
D. Perkin Approach: Cyclodebromodehydrogenation Variant.
49
C. Perkin Approach: Cyclodebromodehydrogenation Variant.
50
D. Perkin Approach: Cyclodebromodehydrogenation Variant: Conclusions
RN
NR
NR
RN
RN
NR
NR
RN
RN
NR
NR
RN
RN
NR
NR
RN
RN
RN
RN
NRO
O
O
O O
O
O
O
O
O O O
O
O
OO
O
O
O
O
O
O
O
OO
O
O
O
O
O
O
O
O
O O
O
O
OO
O
palladium diacetate catalysed cyclo-dehydrodebromination of orthobrominated Perkin condensation products is of satisfactory efficiency
towards nanoribbons
NCHEt2
Et2HCN
O
OO
O
CO2Et
CO2Et
EtO2C
EtO2C
CO2Et
CO2Et
EtO2C
EtO2C
CO2Et
CO2Et
EtO2C
EtO2C
NCHEt2
O
O
NCHEt2
O
O
Et2HCN
O
O
Et2HCN
O
O
tunable electronic properties
Soluble nanoribbons
PERSPECTIVES
Table of Contents:
A. Introduction to GNRs.
B. Ceramidonine Approach.
C. Perkin Approach: Cyclodehydrogenation Variant.
D. Perkin Approach: Cyclodebromodehydrogenation Variant.
E. Conclusions & Perspectives.
51
52
E. Conclusion & Perspectives
N NNO2 NH2
N
N
N
N
N
N N
N
O
O
H
H
O
O
Br Bu
Bu Bu
Bu
Bu
OTf
TfO
S
SRO2C
CO2R
SS
RO2C
CO2R
SS
RO2C
CO2R
n
Ceramidonine approach Perkin Approach: Cyclodehydrogenation
Variant
NN
N
N
O
O Bu
Bu
N N
N
N
Bu
BuO
O
868 737 747
N
N
N
NBu
Bu
SSS S SS
S S
n
COOMe
COOMe
COOMe
COOMe
53
E. Conclusion & Perspectives
NN
NN OO
OOOO
OOR R
R R n
n
NN
NN OO
OOOO
OOR R
R R n
CO2HHO2CCO2HHO2C
HO2C CO2HHO2C CO2H
n
Br
Br
Br
Br
O
OHN
HO
OOO
O
R
Br
BrO
OEtN
MeO
OOO
O
R
Br
Br
CO2RRO2CCO2RRO2C
RO2C CO2RRO2C CO2R
n
OO
OEtHO OOOH
MeO
O
OBr
Br
+
1. Ac2O, Et3N2. RNH2Perkin Approach:
Cyclodebromodehydro-genation Variant
54
E. Conclusion & Perspectives
NR
NR
NR
NR
O
O
O
O
O
O
O
ONR
NR
NR
NR
O
O
O
O
O
O
O
O
Br Br
Br Br
CO2H
CO2H
CO2H
CO2H
CO2H
CO2H
CO2H
CO2H
O
OHN
HO
OOO
O
R
Br
Br
Perkin Approach:Cyclodebromodehydro-
genation Variant
WHAT HAPPENS UNDER TORSION ?
55
MY SPECIAL THANKS TODr. Harald Bock
Dr. Fabien DurolaDr. Rodolphe Clerac
Dr. Julien KelberDr. Pierre Dechambenoit
Ie-Rang JeonAnirban Pradhan
To all my Jury members
To all CRPP members
56
Thank you very much for attention
57
OBuO
OBuO
DDQ, MeSO3H
0°C
20°C OO
6
17
58
SS
CO2MeMeO2C CO2HSS
O
SS
CO2MeMeO2C
SS
OO O
+
22
SS
CO2HHO2CO+
SS
SS
S S
MeO2C
MeO2C
CO2Me
CO2Me
CO2Me
MeO2C
SS
SS
SS
CO2Me
CO2MeMeO2C
MeO2C
CO2MeMeO2C
23 24
Perkin reaction with aromatic glyoxylic acid
to form maleate
B. Ceramidonine approach: Insertion of solubilizing chains
N
Br
N
BrNO2
N
BuNH2
Bu4Sn
PdCl2(dppf) DMF
HNO3
H2SO4
839%
N
Br
NO2
-20o C - 0o C
C-8 nitration, Minor product, 10%
C-5 nitration, Major product, 80%
59
60
C. Perkin Approach: Cyclodehydrogenation Variant: scheme towards chryseneo-dithiophene
60
S
COOHO
O
+Ac2O
Et3N
ROH
DBU
COOR
ROOCS
S
COOR
ROOCS
S
61
3,3
1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 10,0 11,0 12,0
1,1 2,1 3,1 4,1 5,1 6,1 7,1 8,1 9,1 10,1 11,1
2,2
4,4
5,5
6,6
7,7
8,8
3,2 4,2 5,2 6,2 7,2 8,2 9,3 10,2 11,2
4,3 5,3 6,3 7,3 8,3 9,3 10,3
5,4 6,4 7,4 8,4 9,4 10,4
6,5 7,5 8,5 9,5
7,6
8,7
8,6 9,6
0,0
Diagram for the construction of the roll-up indices n,m for any given CNT. If the graphene sheet is rolled up to make a given hexagon marked n,m coincide with the 0,0-hexagon, the n,m-CNT is formed. As examples, the
horizontal set of arrows describes a tour around a 8,0-zig-zag-CNT (8 hexagons in one direction, 0 in the other), and the descending set of arrows describes a tour around a 5,5-armchair-CNT (5 hexagons in one direction, 5 hexagons in the other). The indices of fully benzenoid = metallic nanotubes with n–m = 3p are marked in blue, the indices of semiconducting CNTs with n–m = 3p+1 are marked in green, and those of semiconducting CNTs
with n–m = 3p+2 are marked in red.
62
S S
OO
n S S S nP1 P2
Eg = 1.2 eV Eg = 1.1 eV
S n
P3Eg = 1.5 eV
O O
SS
n
H2N NH2
NO2O2N
SS
n
H2N+ N+H2
N+N+O-
O- O-O-
P4Eg = 1.1 eV
SS
SS
nH17C8 C8H17
H17C8C8H17
SS
SS
nH17C8 C8H17
C8H17H17C8
P5Eg = 2.0 eV
P6Eg = 1.9 eV
63