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Contents

List of contributors xi

1. Organophosphorus chemistry 1

Patrick J. Murphy

1. Introduction 1

2. Nomenclature 1

3. Practical methods 2

References 12

2. The synthesis and applicationsof phosphines 15

Matthew L. Clarke and Jonathan M. J. Williams

1. Introduction 15

2. Preparation of tertiary phosphines 18

3. Preparation and reactivity of primary and secondary phosphines 26

4. Polydentate phosphines and macrocycles 32

5. Chiral phosphines 35

6. Synthesis and applications of phosphines in environmentallybenign catalysis 42

7. Applications of phosphines in catalysis 45

References 48

3. Applications of phosphorus (III) and (V)compounds as reagents in synthesis 51

R. Alan Aitken and Nazira Karodia

1. Introduction 51

2. Deoxygenation and desulfurization reactions 51

3. Halogenation reactions 63

4. Dehydrative coupling and cyclization reactions 74

5. Sulfurization reactions 81

6. Miscellaneous reactions 87

References 95

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Contents

4. The Wittig and related reactions 99

Andrew D. Abell and Michael K. Edmonds1. Introduction 99

2. Standard reagents and procedures 104

3. Modifications to the standard reagents and procedures 111

4. Role in synthesis 116

References 126

5. Applications of the Wittig reaction inthe synthesis of heterocyclic andcarbocyclic compounds 129

Rainer Schobert1. Introduction 129

2. Ring-closure variants utilizing highly reactiveω-carbonyl-ylides 131

3. Ring-closure variants employing less reactive ω-carbonyl ylides or‘non-classical’ Wittig olefinations of esters and amides 137

References 148

6. Preparation and reactions ofiminophosphoranes and their syntheticapplications in the aza-Wittig reaction 151

J. Mike Southern and Ian A. O’Neil1. Introduction 151

2. Preparation of iminophosphoranes 152

3. Removal of triphenylphosphine oxide 154

References 168

7. Phospho-transfer processes leading to[P−−C] bond formation 171

Matthew D. Fletcher1. Introduction 171

2. The Michaelis–Arbuzov reaction 172

3. The Michaelis–Becker reaction 185

4. The Perkow reaction 191

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5. The Abramov reaction 194

6. The Pudovik reaction 198

7. The Kabachnik–Fields reaction 204

8. Conjugate additions of phosphorus(III) reagents 208

References 210

8. Low-coordinated phosphorus compounds 215

Sven Asmus, Uwe Bergsträßer, Heinrich Heydt,Marion Schmitz and Manfred Regitz1. Introduction 215

2. Phosphorus compounds having coordination number 1 217

3. Phosphorus compounds having coordination number 2 223

References 233

9. Phosphorus methods innucleotide chemistry 237

David M. Williams and Vicki H. Harris1. Introduction 237

2. Outline of chemistry 237

3. Synthesis 241

4. Analysis and purification 264

Acknowledgements 271

References 271

Index 273

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1

Organophosphorus chemistryPAT R I C K J . M U R P H Y

1. IntroductionThe impact of organophosphorus chemistry on modern synthetic chemistry isdifficult to quantify, but one can safely assume that the study of this elementhas influenced all areas of chemical endeavour.1 Organophosphorus chemistry,as a discrete area of study, is the study of compounds containing a C−−P bondand this book is largely focused on this topic. However, other areas of interestincluding azaphosphorus, oxyphosphorus and metallophosphorus chemistry arediscussed either explicitly as topics or in an implicit manner within the chemistrydetailed in each chapter. The purpose of this introductory chapter is to covermany of the general aspects of organophosphorus chemistry and the chemicaltechniques required for their preparation, including practical methods commonlyencountered and some aspects of spectroscopy.

Many texts on organophosphorus chemistry have been published ranging fromin-depth studies of the subject as a whole1,2 to more general texts,3 which wouldserve as a general introduction to the field. Of the more comprehensive texts, thefour-volume2a–d series entitled The Chemistry of Organophosphorus Compoundsedited by Hartley provides core material published before 1990 and representsan excellent starting point for those new to the field. A considerable amountof organophosphorus chemistry is published in the core literature, which canbe difficult to access, however, the periodical Organophosphorus Chemistry4

published annually by the Royal Society of Chemistry offers a yearly review ofthe highlights and key developments in the field.4 Several other periodicals, whichare no longer published are worthy of note5 and the two journals Phosphorus,Sulfur and Silicon, and the Related Elements and Heteroatom Chemistry providea considerable quantity of useful information for the serious researcher.6

2. NomenclatureThe nomenclature of phosphorus-containing compounds is complicated to someextent by the overlap of inorganic and organic nomenclature, particularly withrespect to compounds containing the P−−O−−H functionality. From the point ofview of this volume, the basic nomenclature used for trisubstituted phosphorus

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P. J. Murphy

compounds is given in Scheme 1, and that for tetrasubstituted compounds isshown in Scheme 2.1

R

P

R

R

Phosphines; R = H, alkyl, aryl R = Hal

RO

P

OR

R

Phosphonites;R = H, alkyl, aryl

R

P

OR

R

Phosphinites;R = H, alkyl, aryl

ROP

OR

OR

Phosphites;R = H, alkyl, aryl

Scheme 1 Nomenclature for trisubstituted phosphorus compounds.

O

P

R

R

R

R

P

R

R

R Phosphonium salts;R = alkyl, aryl

Phosphine oxides; R = alkyl, arylPhosphoryl halides; R = Hal

+

R2C

P

R

R

R Alkyene phosphoranes (ylides);R = alkyl, aryl

RN

P

R

R

R Azaphosphenes;R = alkyl, aryl

OP

OR

R

R Phosphinates;R = alkyl, aryl

O

P

OR

R

OR Phosphonates;R = alkyl, aryl

O

P

OR

OR

OR Phosphates;R = alkyl, aryl

Scheme 2 Nomenclature for tetrasubstituted phosphorus compounds.

3. Practical methodsThe reader is referred to more general texts for further information on generalexperimental techniques.7 However, it is hoped that for those not experienced

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with organic chemistry, enough information has been provided here to perform theexperiments. This chapter is intended to familiarize the reader with the equipmentand techniques, which are used in the protocols throughout the book.

3.1 SolventsAs with most synthetic organic chemistry, the availability of pure, and in manycases, dry and oxygen-free solvents is essential for both effecting synthetic trans-formations and for purification purposes. A wide range of organic solvents areemployed in organophosphorus chemistry, and many are available from suppliersin an anhydrous form, packaged under nitrogen in SureSeal™ bottles, which areusually suitable for use in the reactions we will cover. However, an alternativemethod is to purchase technical-grade solvents, which are then treated with chem-ical drying agents to remove the moisture present and then distilled, either directlybefore use or onto a drying agent for storage, such as molecular sieves. A range ofmethods are available for drying solvents8–10 and the typical solvents employed inorganophosphorus chemistry and their method of distillation are detailed below.

3.1.1 Diethyl ether and tetrahydrofuran (THF)These solvents can be dried efficiently by first drying over sodium wire and thendistilling directly before use, from sodium metal under an inert atmosphere inthe presence of a small amount of benzophenone. This combination producesa deep-blue/purple solution of sodium benzophenone ketyl if the solvent is dry,and the ketyl colour acts as an indicator, which, when it fades, indicates thatadditional sodium is needed. This is also an advantageous method as the ketylis an extremely efficient oxygen scavenger.8 It is important that peroxide-freediethyl ether and tetrahydrofuran (THF) are employed in the still, and it is alsoimportant to ensure that peroxides do not accumulate in stored samples of thesesolvents. A simple test for this is to mix a sample of the solvent (approximately1 mL) with glacial acetic acid (1 mL) containing KI crystals (100 mg). A yellowcolouration indicates the presence of a small quantity of peroxides, whilst a deepbrown colouration indicates a higher concentration. Peroxides can be removedin a number of ways,8,9 the most convenient being to wash repeatedly with anacidified FeSO4 solution (FeSO4 (60 g), concentrated H2SO4 (6 mL), and water(110 mL)), until a negative peroxide test is obtained. The solvent should thenbe washed with KMnO4 solution (0.5%), NaOH solution (5%), water, and thendried over CaCl2 for 24 h.

3.1.2 Benzene and tolueneThese solvents are most conveniently dried by treatment with calcium hydridefollowed by distillation onto 4 Å molecular sieves.

3.1.3 Petroleum ether (petrol)Petroleum ether can be dried by distillation onto activated 4 Å molecular sieves.

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3.1.4 DichloromethaneDichloromethane can be dried by treatment with calcium hydride in a continuousstill or can be stored by distillation onto 4 Å molecular sieves. Caution! Nevertreat chlorinated solvents with sodium or strong bases—an explosion may occur.

3.1.5 Dimethylformamide (DMF)Stir over calcium hydride or phosphorus pentoxide for 24 h, filter under an inertatmosphere and distil (56◦C at 20 mmHg) onto 3 Å molecular sieves. An altern-ative method is to dry over three batches of 3 Å molecular sieves (5% w/v,3 × 12 h).

3.1.6 Molecular sievesThe immediate use of dried, deoxygenated solvents is recommended, althoughnon-ethereal solvents can be stored over activated molecular sieves in thoroughlydried containers under N2/Ar. It is recommended that new molecular sieves bedried before use by heating them in a well-ventilated oven at 320◦C for 3 hfollowed by cooling them in an evacuated desiccator, which is filled with dryN2/Ar. Sieves may be reused if they are free from residual solvents.

3.1.7 Distillation set-upIf regular amounts of solvent are required, it is convenient to set up a solventdistillation apparatus, commonly referred to as a solvent still. A solvent stillenables a continuous supply of dry solvent to be available, which can be conveni-ently collected under an inert atmosphere. Common stills are those for dryingdiethyl ether, THF, and dichloromethane. The still shown in Figure 1.1 has anadaptation for removing solvents from the still-head collection reservoir througha septum cap by syringe or, if larger quantities are required, a flask can be con-nected to the Quickfit adapter on the still-head. These two methods minimizethe exposure of the solvent to the atmosphere. When using a solvent still, thefollowing precautions should be observed:

1. The still should be situated in an efficient fume hood, and all tubing for inertgas and water supplies should be securely attached using copper wire or plasticcable ties.

2. The heating mantle should be of such a design that there is no risk of sparksigniting the solvent. This also applies to all electric cables and plugs. Themantle should also incorporate an electricity cut-out device to operate if thewater supply to the condenser fails.

3. It is imperative that the bottom flask containing the drying agent should notbe allowed to boil dry. This risk can be minimized if the flask is of greatercapacity than the collection reservoir and is regularly topped up with solvent.

4. During cooling, an adequate flow of inert gas should be maintained.

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Inert gas supply

Water

Water

Septum

Two-way tap

To receiving flask

Round-bottomed flask

Three-way tap

Overflow device

Stoppered side-armwith retaining clip(to refill still)

Condenser

Two-way tap

Fig. 1.1 General set-up for a solvent still (reproduced with permission from Ref. 13).

5. Caution! The use of a semi-permanent still for ethereal solvents can leadto a build-up of peroxides. The solvent should be checked for peroxides atfrequent intervals, and if these are detected, the still should be dismantled andthe drying agent and peroxides carefully destroyed. Also, when renewing thestill, fresh batches of the solvent and drying agent should be used.

3.2 Working under an inert atmosphereMany preparations require the use of an inert atmosphere and are thus carried outunder an atmosphere of anhydrous nitrogen or argon. Argon has the advantageof being heavier than air and, therefore, provides a more effective barrier againstthe outside atmosphere, but nitrogen is more commonly used owing to its lowercost. The best method for ensuring that reactions are purged free of oxygen is toemploy a purpose-built double manifold of the type shown in Figure 1.2. Thisapparatus provides the inert gas and a vacuum source via two-way stopcocksand allows several inert atmosphere experiments to be run simultaneously. It canalso be fitted with a Quickfit adapter fitted with a septum, which can be used for

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P. J. Murphy

Connector

Two-way stopcock

To apparatus

Inert gas supply

To vacuum

Paraffin oil

Fig. 1.2 Double manifold apparatus (reproduced with permission from Ref. 13).

purging syringes with inert gas. The supply of inert gas to the manifold should becontrolled in two stages using a cylinder regulator and then a needle valve, andthe apparatus should also be equipped with a bubbler to control the release of gas.

Further examples of apparatus designed for specific applications appear inthe recommended experimental texts for organic synthesis.7

3.3 Reaction apparatusA variety of experimental set-ups will be employed throughout this book. In caseswhere cooling of a process is required, an arrangement of glassware similar tothat shown in Figure 1.3 will be suitable. This consists of a three-necked flaskequipped with a magnetic stirring bar, a septum, a low temperature thermometer,and an inlet for inert gas and vacuum. Liquid reagents and solvents can be addedvia syringe through the septum and, provided that an adequate flow of inert gasis maintained, the septum can be removed to allow the addition of solids.

If heating of the reaction is required, the flask should be equipped with a refluxcondenser and an efficient heating apparatus. Two options are generally availablefor heating a reaction, first, an isomantle which offers direct heating to the flaskand can be equipped with a stirring mechanism. Alternatively, an oil-bath is morefrequently used as illustrated (Figure 1.4) as this option offers more controlledheating. It is recommended that only fresh paraffin or silicone oil is used in thebath and that a temperature regulating device is fitted to the bath in conjunctionwith a water cut-out mechanism.

3.4 Standardization of organolithium reagentsIn many of the preparations detailed in this book, the use of n-BuLi is required.It is recommended that for any purchased solution, this reagent is standardizedbefore use as there is generally a considerable difference between the expected

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Balloon

Tubing

To vacuumFasten with anelastic bandThermometer

Stirring bar

Graduated syringe

Needle

Septum

Nitrogen/argon entry

Three-waystopcock

Dry-ice Dewar orinsulated cold bath

Fig. 1.3 Apparatus for performing a reaction at low temperature (reproduced with permis-sion from Ref. 13).

Condenser

Water out

Clamp

Clamp

Magneticstirrer bars

Waterin

Thermometer

Heating bath(oil, etc.)

Magneticstirrer/ hotplate

Fig. 1.4 Apparatus for performing a reaction under reflux.

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concentration and the actual one, as the reagent may have deteriorated over time.Many methods are available for the standardization, but the most convenientare those which rely on the formation of coloured dianions.11–13 A procedure(Protocol 1) using 1-pyreneacetic acid is one of the most convenient in view ofthe distinctive red end-point obtained and the fact that the reagent can be recoveredeasily from titration mixtures and then reused.12,13 The procedure described canbe used for the standardization of butyl-lithium and allows an estimation of thereagent concentration within approximately 0.1 M; it is recommended that theprotocol be performed in duplicate.

Protocol 1.

Titration of n-butyl-lithium using 1-pyreneacetic acid12,13

Caution! Carry out all procedures in a well-ventilated hood, and wear disposablevinyl or latex gloves and chemical-resistant safety goggles.

Equipment (see Figure 1.5)• A pre-dried, two-necked, round-bottomed flask

(50 mL) incorporating side-arm tap adapter (forinert gas inlet), with magnetic stirring bar,septum and gas outlet

• Dry, gas-tight syringes [1 mL, with 0.01 mLgraduations (preferably fitted with a screwdriverplunger), and 10 mL]

• Inert gas supply

Materials• Butyllithium solution to be standardized pyrophoric

• 1-Pyreneacetic acid (FW 260.3), pre-dried to constant weight in vacuo, (100–200 mg)• Anhydrous THF 10 mL flammable, irritant

Graduated syringe

Two-way stopcock

Stirring bar

Septum

Vent needle to bubbler

To vacuuminert atmosphere

Fig. 1.5 Apparatus for standardization of n-BuLi (reproduced with permission fromRef. 13).

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Method

1. Flush the round-bottomed flask and accessories with dry, oxygen-free N2/Ar.Flame dry the flask and allow it to cool in a stream of inert gas. Maintain aninert atmosphere during the remaining steps.

2. Weigh out the 1-pyreneacetic acid accurately, using an analytical balance,and transfer to the round-bottomed flask. Add the THF and stir the mixtureuntil a homogeneous solution is obtained.

3. Charge the 1 mL syringe with the organolithium reagent, and then insertthe needle through the septum. Add the organometallic reagent slowly anddropwise (over a period of 3–4 min; slow addition is essential to minimizereaction between THF and BuLi). The end-point is when the red colour of thedianion just persists.

4. The molarity of the butyl-lithium can now be calculated from a considerationof the number of moles of 1-pyreneacetic acid utilized and the volume of BuLirequired to obtain a permanent end-point (molarity (M) = mols/vol).

3.5 Cooling bathsMany reactions are carried out in the temperature range 0 to −100◦C and a range ofcooling systems are available for achieving these temperatures. Table 1.1 is a listof common slush bath compositions, however, many others are available.9, 14, 15

The temperature of the reaction mixture should be monitored by means of aninternal thermometer (or a temperature probe), as shown in Figure 1.3, sincethe internal temperature may differ significantly from that of the cooling bath

Table 1.1 Common slush bath compositions

Solvent/additive Temperature (◦C)

Ice 0Ice/salt (3 : 1) −8Carbon tetrachloride/CO2 −23Ice/CaCl2 · 6H2O (4 : 5) −40Acetonitrile/CO2 −42Chloroform/CO2 −61Ethanol/CO2 −72Acetone/CO2 −78Hexane/liquid N2 −94Ethanol/liquid N2 −116Liquid N2 −196

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Motor

Vacuum

Heating controlTemperature gauge

OvenSample

Fig. 1.6 A Kugelrohr bulb-to-bulb distillation apparatus.

medium, particularly during the addition of reagents which produce an exothermicreaction.

3.6 Vacuum distillationStarting materials, reaction products and solvents often need to be distilled inorder to enhance purity. For small-scale distillations, a Kugelrohr bulb-to-bulbdistillation apparatus is convenient (Figure 1.6). The sample is placed in the endbulb, the system placed under vacuum if required and the oven temperature israised. The sample distils into the next bulb (which is outside of the heatingcompartment) and collected. The distillate can then be redistilled into the nextbulb, if required. If the sample has a relatively low boiling point under the pressureemployed, it is common practice to cool the receptor bulb with ice, dry ice, oreven liquid nitrogen (absorbed onto cotton wool).

A short-path distillation procedure may be used in situations where a simpledistillation is required, as purification from non-volatile components/fractionaldistillation with a Kugelrohr apparatus is difficult. A water-jacketed, semi-microdistillation apparatus is illustrated in Figure 1.7. Heating can either be achievedwith the aid of an oil-bath, an isomantle, or a flame (Caution! ensure that there areno flammable solvents nearby). For larger scale distillations, a round-bottomedflask should be attached to a distillation column, a still-head, and condenser. Thecolumn used in the distillation is variable, and may be either a Vigreux columnor a column packed with glass helices.

3.7 Spectroscopic techniquesA variety of spectroscopic techniques are available to the practising organicchemist, and many sources of information are available with excellent cover-age of the essential methods and analysis of spectroscopic data.16 It is widelyaccepted that nuclear magnetic resonance (NMR) spectroscopy has become themost essential tool for the organic chemist and the reader is assumed to have

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Quick fit thermometer

Short path destilation apparatus

To vaccum pump

Magnetic stirrer bar

Fig. 1.7 A semi-micro distillation apparatus.

a basic understanding of the principals of the technique and the analysis of thespectra obtained from them.

The stable isotope of phosphorus 31P has a spin of I = 1/2 and is, thus,NMR active. A considerable amount has been written17 on 31P NMR and thereader is referred to these texts for more specialized information. In the spe-cific examples presented in this volume, 31P chemical shifts will be referredto as and when they are required. In general, the magnitudes of the chemicalshifts observed are dependent on both the electronegativity of the substituientsdirectly attached to the phosphorus and the amount of back donation of elec-trons by π-bonding. Thus, increasing the electronegativity of the substituientgroups decreases the electron density at the phosphorus atom and leads to a shiftto higher frequency (deshielding). Phosphorus compounds resonate over a verywide range (circa +600 to −450 ppm relative to an 85% orthophosphoric acidstandard), however, direct correlation between chemical shift and structure arenot as predictable as those in 1H and 13C NMR spectroscopy. A small selectionof chemical shifts for organophosphorus compounds is given in Table 1.2 forcomparison and reference purposes.

Infrared spectroscopy can also be of diagnostic use for the identification oforganophosphorus compounds and comprehensive data is available from sev-eral sources.18 Diagnostic absorptions include the P−−H stretch, which typicallyoccurs in the region 2460–2450 cm−1, the P==O stretch at 1320–1200 cm−1 andthe P==N at 1440–1120 cm−1. Other useful absorptions include the P−−O−−(C)stretch at 870–730 cm−1 and the P−−O−−P stretch at 800–650 cm−1 found inphosphate esters.

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Table 1.2 Chemical shifts for someorganophosphorus compounds

Structure Chemical shift

PMe3 −62PPh3 −6PCl3 +219PCl5 −80PBr3 +227MePCl2 +191PhPCl2 +162Ph2PCl +81Ph2PH −41P(OEt)3 +137P(OPh)3 +127(EtO)2PCl +165Et3PO +48Ph3PO +29(MeO)3PO +2(Me2N)3PO +24(MeO)2POCl +8(MeO)2POH +10Ph3P=CH2 +20Ph3PCH+

3 Br− +23H3PO4 0H3PO2 +13Me2PO2H +49

References1. For a major review of the general chemistry of phosphorus and its impact on the

20th century see: Corbridge, D. E. C., Phosphorus 2000; Elsevier: Amsterdam;2000.

2. (a) Hartley, F. R. ed. The Chemistry of Organophosphorus Compounds. Primary,Secondary and Tertiary Phosphines, Polyphosphines and Heterocyclic Organo-phophorus(III) Compounds; John Wiley & Sons: Chichester; 1990, Vol. 1.(b) Hartley, F. R. ed. The Chemistry of Organophosphorus Compounds. PhosphineOxides, Sulphides, Selenides and Tellurides; John Wiley & Sons: Chichester; 1992,Vol. 2. (c) Hartley, F. R. ed. The Chemistry of Organophosphorus Compounds. Phos-phonium Salts, Ylides and Phosphoranes; John Wiley & Sons: Chichester; 1994,Vol. 3. (d) Hartley, F. R. ed. The Chemistry of Organophosphorus Compounds. Ter-and Quinque-Valent Phosphorus Acids and Their Derivatives; John Wiley & Sons:Chichester; 1996, Vol. 4.

3. (a) Quin, L. D. Guide to Organophosphorus Chemistry; Wiley-Interscience:NewYork; 2000. (b) Engel, R. Synthesis of Phosphorus–Carbon Bonds; CRCPress: Boca Raton, FL; 1988. (c) Goldwhite, H. Introduction to Phosphorus Chem-istry; Cambridge University Press: Cambridge, UK; 1981. (d) Cadogan, J. I. G.

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Organophosphorus Reagents in Organic Synthesis; Academic Press: NewYork; 1979.(e) Emsley, J.; Hall, D. The Chemistry of Phosphorus: Environmental, Organic,Inorganic, Biochemical and Spectroscopic Aspect; Harper and Row Publishers: NewYork; 1976. (f) Walker, B. J. Organophosphorus Chemistry; Penguin Books: England;1972.

4. Organophosphorus Chemistry; specialist periodical reports. The Chemical Society(London); 1970–2003, Vols. 1–33.

5. (a) Topics in Phosphorus Chemistry; Interscience Publishers: New York; 1964–1983,Vols. 1–11. (b) Organe Phosphorus Compounds; Kosolapott, G. M.; Maier, L., Wiley-Interscience; New York, 1972–1976, Vols. 1–7. (c) Edmundson, R. S. ed. Dictionaryof Organophosphorus Compounds; Chapman & Hall: New York; 1988.

6. (a) Phosphorus, Sulfur and Silicon, and the Related Elements; Gordon and BreachPublishers: New York. (b) Heteroatom Chemistry; Wiley Publishers: New York.

7. (a) Harwood, L. M.; Moody, C. J.; Percy, J. M. Experimental Organic Chemistry:Preparative and Microscale; Blackwell Science (UK); 1998. (b) Leonard, J.; Lygo,B.; Procter, G. Advanced Practical Organic Chemistry; Chapman & Hall: New York;1995, 2nd edn. (c) Palleros, D. R. Experimental Organic Chemistry; John Wiley &Sons: Chichester; 2000. (d) Zubrik, J. W. The Organic Chem Lab Survival Manual. AStudents Guide to Techniques; John Wiley & Sons: Chichester; 1997. (e) Pavia, D. L.;Lampman, G. M.; Engel, R. G. Introduction to Organic Laboratory Techniques: ASmall-scale Approach; Sanders College Publishing Philadelphia; 1998. (f) Wilcox,C. F.; Wilcox, M. F. Experimental Organic Chemistry: A Small Scale Approach;Prentice Hall: New York; 1994. (g) Furniss, B. S.; Hannaford, A. J.; Smith, P. W. G.;Tatchell, A. R., eds. Vogel’s Textbook of Practical Organic Chemistry; Longmans:London; 1989, 5th edn.

8. Armarego, W. L. F.; Chai, C. Purifaction of Laboratory Chemicals; Butterworth-Heinemann: Woburn, MA; 2003, 5th edn.

9. Gordon, A. J.; Ford, R. A. The Chemists Companion; John Wiley & Sons: New York;1972.

10. Gill, G. B.; Whiting, D. A. Aldrichimica Acta 1986, 19, 31–41.11. Crompton, T. R. Chemical Analysis of Organometalic Compounds; Academic Press:

London; 1973.12. Kiljunen, H.; Haas, T. A. J. Org. Chem. 1991, 56, 6950–6952.13. Taylor, R. J. K.; Casy, G. Organocopper Reagents; Taylor, R. J. K., ed.; Oxford

University Press: New York; 1994, pp. 52–56.14. Phillips, A. M.; Hulme, D. N. J. Chem. Ed. 1968, 54, 664.15. Rondeau, R. E. J. Chem. Eng. Data 1966, 11, 124.16. (a) Breitmaier, E. Structure Elucidation by NMR in Organic Chemistry—A Practical

Guide; John Wiley & Sons: New York; 2002. (b) Field, L. D. Organic Structuresfrom Spectra; John Wiley & Sons: New York; 2002. (c) Silverstein, R. M.; Web-ster, F. X. Spectrometic Identification of Organic Compounds; John Wiley & Sons:New York; 2000. (d) Harwood, L. M.; Claridge, T. D. W. Introduction to OrganicSpectroscopy (Oxford Chemistry Primers); Oxford University Press: New York;1996. (e) Williams, D. H.; Fleming, I. Spectroscopic Methods in Organic Chemistry;McGraw-Hill Education, Europe; 1995, 5th edn.

17. (a) Tebby, J. C. CRC Handbook of Phosphorus-31 Nuclear Magnetic Resonance Data;CRC Press: Boca Raton, FL; 1991. (b) Quin, L. D.; Verkade, J. G. Phosphorus-31

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NMR Spectral Properties in Compound Characterisation and Structural Analysis;VCH: New York; 1994. (c) Verkade, J. G.; Quin, L. D. Phosphorus-31 NMRSpectroscopy in Stereochemical Analysis; VCH Publishers: Deerfield Beach, FL;1987. (d) Gorenstein, D. G. Phosphorus-31 NMR: Principles and Applications; Aca-demic Press: Orlando, FL; 1984. (e) NMR Spectra of Phosphorus Compounds, Topicsin Phosphorus Chemistry; Interscience Publishers: New York; 1967, Vol. 5.

18. (a) Thomas, L. C. Interpretation of the Infrared Spectra of Organophosphorus Com-pounds; Heyden: London; 1974. (b) Corbridge, D. E. C. In Topics in PhosphorusChemistry; Grayson, M.; Griffith, J. eds; Interscience: New York; 1969, Vol. 6,pp. 235–365. (c) Corbridge, D. E. C. J. Appl. Chem. 1956, Vol. 6, 456–465.

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