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AMBIDENT PROPERTIES of PHOSPHORAMIDAT'es and SULPHONAMIDES a Thesis Submitted by JAMES NICHOLAS ILEY in Partial Fulfillment of T

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AMBIDENT PROPERTIES of PHOSPHORAMIDAT'es and SULPHONAMIDES a Thesis Submitted by JAMES NICHOLAS ILEY in Partial Fulfillment of T Fsci AMBIDENT PROPERTIES OF PHOSPHORAMIDAT'ES AND SULPHONAMIDES A Thesis submitted by JAMES NICHOLAS ILEY in partial fulfillment of the requirements for the Degree of Doctor of Philosophy of the University of London DEPARTMENT OF ORGANIC CHEMISTRY IMPERIAL COLLEGE LONDON, SW7 SEPTEMBER 1979 ACKNOWLEDGEMENTS I wish to thank Dr. Brian Challis for his supervision and advice throughout this project and also for his friendship. I also thank Dr. Henry Rzepa for the use of the MNDO molecular orbital programme and teaching me to use it. The award of a Scholarship by the Salters' Company has enabled me to carry out this work and I acknowledge their generous gift. I greatly appreciate the friendship of all my colleagues throughout the past three years. My wife, Ruth, especially deserves mention for her love and support. Finally, my thanks go to Mrs. Sue Carlile, for typing this manuscript. ABSTRACT The nucleophilic chemistry of amides, phosphoramidates and sulphon- amides is reviewed. Particular reference is paid to the site of substi- tution and its variation with reaction conditions. The phosphorimidate-phōsphoramidate rearrangement is examined. The nature of electrophilic catalysis, particularly by alkyl halides is stud- ied and the mechanism of the reaction is discussed. The relevance of this mechanism to the nucleophilic chemistry of phosphoramidates is outlined. The behaviour of phosphoramidates in aqueous H2SO4, oleum and tri- fluoroacetic acid is briefly examined and the site of protonation in these media discussed. The acylation of phosphoramidates by acyl halides and anhydrides is reported and the effect of base and electrophilic catalysis on the reac- tions is examined. The usual product of these reactions is the N-acylphos- phoramidate although tertiary phosphoramidates undergo P-N bond cleavage. Factors affecting the reaction rates are studied and possible mechanisms for the reactions are discussed. The sulphonimidate-sulphonamide rearrangement is described. Electro- philic catalysis is examined and the reaction mechanism is discussed in relation to its relevance to the nucleophilic properties of sulphonamides. The alkylation and acylation of sulphonamides is also described and the nature of the products discussed in terms of the reaction profile for the sulphonimidate-sulphonamide rearrangement. The alkylation of [1,3]-amidic systems is discussed. Perturbational and transition-state structure approaches are used to describe the alkyl- ation of carboxamides. Modified neglect of diatomic overlap (MNDO) SCF MO calculations are reported to test both theories. The relevance of these results to phosphoramidates and sulphonamides is discussed. Page CONTENTS CHAPTER 1. INTRODUCTION NUCLEOPHILIC REACTIVITY OF AMIDE COMPOUNDS 1 1.1. Ambident Nucleophilicity 2 1.2. Nucleophilic Properties of Amides 5 1.2.1. Protonation 5 1.2.2. Alkylation 6 1.2.3. Acylation 8 1.2.4. Summary 12 1.3. Nucleophilic Properties of Phosphoramidates 15 1.3.1. Protonation 15 1.3.2. Alkylation 18 1.3.3. Acylation 20 1.3.4. Other Reactions 23 1.3.5. Summary 24 1 4. Nucleophilic Chemistry of Sulphonamides 25 1.4.1. Protonation, Hydrogen-Bonding and Complexing Properties 25 1.4.2. Alkylation 26 1.4.3. Acylation 27 1.4.4. Other Reactions 28 1.4.5. Summary 28 CHAPTER 2. THE PHOSPHORIMIDATE-PHOSPHORAMIDATE REARRANGEMENT 30 2.1. Introduction 31 2.2. Thermal Rearrangement 32 2.3. Base Catalysed Rearrangement 37 2.4. Alkyl Halide Promoted Rearrangement 37 2.4.1. Order of Reaction 37 2.4.2. Dependence on Alkyl Halide 40 2.4.3. Effect of Other Electrophilic Reagents 45 2.4.4. Temperature Dependence 47 2.4.5. Solvent Effect 49 2.4.6. Substituent Effects 50 Page 2.5. Mechanism of the Rearrangement Reaction 51 2.6. Ambident Nucleophilic Properties of Phosphoramidates 53 CHAPTER 3. THE PROTONATION OF PHOSPHORAMIDA'1'FS 58 3.1. Introduction 59 3.2. Behaviour in Aqueous Sulphuric Acid 59 3.3. Behaviour in Oleum and Fluorosulphonic Acid 62 3.4. Behaviour in CF3CO2H 66 CHAPTER 4. THE ACYLATION OF PHOSPHORAMIDA'1'ES 68 4.1. Introduction 69 4.2. - Acylation by Acyl Halides 70 4.2.1. In the Absence of Bases 70 4.2.1.1. Kinetics 77 4.2.2. In the Presence of Bases 85 4.3. Acylation by Acid Anhydrides 89 4.3.1. Acetic Anhydride 89 4.3.1.1. Base Catalysed Acetylation 89 4.3.1.2. Electrophilic Catalysed Acylation 91 4.3.2. Other Acid Anhydrides 93 4.4. Acylation of Amines in the Presence of (Et0)2PONHMe and CH3CON(CH3)2 102 4.4.1. Acylation of N-Methyl-4-nitroaniline 102 4.4.2. Acylation of 2,4-Dinitroaniline 107 4.5. Reaction of Diethyl N-Methylphosphoramidite with AgOAc in C014 108 4.6. Discussion 109 CHAPTER 5. THE SULPHONIMIDATE-SULPHONAMIDE REARRANGEMENT AND THE ALKYLATION OF SULPHONAMIDES 114 5.1. The Sulphonimidate-Sulphonamide Rearrangement 115 5.1.1. Synthesis of Substrates 116 5.1.2. Thermal Reaction 117 5.1.2.1. 0-Ethyl-N-methyl-4-toluenesulphonimidate 117 5.1.2.2. 0-Phenyl-N-methyl-4-toluenesulphonimidate 122 5.1.3. Alkyl Halide Promoted Rearrangement 123 5.1.3.1. 0-Ethyl-N-methyl-4-toluenesulphonimidate 123 Page 5.1.3.1.1. Order of Reaction 123 5.1.3.1.2. Effect of Catalyst 127 5.1.3.1.3. Effect of Other Electrophilic Reagents 129 5.1.3.1.4. Effect of Temperature 131 5.1.3.1.5. Solvent Effects 131 5.1.3.2. 0-Phenyl-N-methyl-4-toluenesulphonamide 132 5.1.4. Mechanism of the Rearrangement Reaction 134 5.1.5. Nucleophilic Properties of Sulphonamides 136 5.2. The Alkylation and Arylation of Sulphonamides 138 5.2.1, Alkylation 138 5.2.2. Arylation 141 CHAPTER 6. MOLECULAR ORBITAL CALCULATIONS FOR AMIDE ALKYLATION 144 6.1. A General Mechanism for Amide Alkylation 145 6.2. The Perturbational Approach to the Chemistry of Amides 147 6.3. Product Control of the Transition State 151 6.4. Stabilisation of the Transition State 156 6.5. Amide Anion 165 6.6. Application to Phosphoramidates and Sulphonamides 166 CHAPTER 7. EXPERIMENTAL AND REbRENCES 168 7.1. The Phosphorimidate-Phosphoramidate Rearrangement 169 7.1.1. Preparation of Substrates and Products 169 Diethyl N-phenylphosphoramidate 169 Diethyl N-ethyl-N-phenylphosphoramidate 169 Triethyl N-phenylphosphorimidate 170 Benzoyl azide 170 Triethyl N-benzoylphosphorimidate 170 O-Methyl-N-methylbenzimidate 172 7.1.2. Purification of Solvents and Reagents 172 7.1.3. Measurement of Rearrangement Rates 173 Product analysis 173 7.2. The Protonation of Phosphoramidates 177 7.2.1. Preparation of Substrates 177 Diethyl N-methylphosphoramidate 177 Diethyl phosphoramidate 177 Diethyl N,N-dimethylphosphoramidate 177 Page 7.2.2. Preparation of Solvents 178 7.2.3. Procedure 178 7.3. The Acylation of Phosphoramidates 179 7.3.1. Preparation and Purification of Reagents and Solvents 179 7.3.2. Preparation of Substrates 180 Diethyl N-benzyloxyphosphoramidate 180 Diethyl N-methylphosphoramidite 181 7.3.3. Preparation of Products 181 Diethyl N-acetyl-N-methylphosphoramidate 181 Diethyl N-acetyl-N-phenylphosphoramidate 182 Diethyl N-acetyl-N-benzyloxyphosphoramidate 182 Diethyl N-methyl-N-trichloracetylphosphoramidate 182 Diethyl N-(4-chlorobenzoyl)-N-methyl-phosphoramidate 182 Diethyl N-benzoyl-N-methylphosphoramidate 182 Diethyl N-methyl-N-trifluoroacetylphosphoramidate 183 Diethyl N-phenyl-N-trifluoroacetylphosphoramidate 183 Diethyl N-benzyloxy-N-trifluoroacetylphosphoramidate 183 N,N-Dimethyltrifluoroacetamide 183 N-Methyl-1,1,1-trimethylacetamide 183 N-Methyl-4-chlorobenzamide 184 7.3.4. General Procedure 184 7.3.5. Reaction of diethyl N-methylphosphoramidite with AgOAc in CC14 190 7.3.6. Acylation of Amines in the Presence of Amides and Phosphoramidates 190 7.4. The Chemistry of Sulphonamides 194 7.4.1. The Sulphonimidate-Sulphonamide Rearrangement 194 7.4.1.1. Preparation of Substrates 194 0-Ethyl-N-methyl-4-toluenesulphonimidate 195 0-Phenyl-N-methyl-4-toluenesulphonimidate 195 7.4.1.2. Preparation of Products 196 N-Methyl-4-toluene sulphonamide 196 N,N-Dimethyl-4-toluenesulphonamide 196 N-Methyl-N-phenyl-4-toluene sulphonamide 196 N-Ethyl-N-methyl-4-toluene sulphonamide 198 7.4.1.3. Purification of Solvents and Reagents 198 7.4.1.4. Measurement of Rearrangement Rates 199 7.4.1.5. Product Analysis 203 7.4.2. The Alkylation of Sulphonamides 203 Page 7.4.2.1. Preparation of Substrates and Products 203 N-Methylbenzene sulphonamide 203 N-Methyl-N-phenylbenzene sulphonamide 203 N-Chloro-N-methyl-4-toluenesulphonamide '204 1-Methyl-1-(4-toluenesulphonyl)-3-phenyltriazene 204 7.4.2.2. Reagents and Solvents 204 7.4.2.3. Reaction of 4-toluenesulphonamides with Methyl Iodide 205 7.4.2.4. Reaction of Arenesulphonamides with Methyl Fluoro- sulphonate and Methyl Trifluoromethanesu]phonate 205 7.4.2.5. Reaction of Arenesulphonamides with Benzenediazonium tetrafluoroborate 206 7.4.2.6. Thermolysis of 1-Methyl-1-(4-toluenesulphonyl)- 3-phenyltriazene 207 7.4.2.7. Reaction of Sodium N-methyl-4-toluenesulphonamide with Benzenediazonium tetrafluoroborate 207 7.4.2.8. Reaction of N-Methyl-4-toluenesulphonamide with Benzoyl peroxide 207 7.4.2.9. Reaction of N-chloro-N-methyl-4-toluenesulphonamide with Benzoyl peroxide 208 7.5. Amide Alkylation: Molecular Orbital Calculations 209 References 214 1 CHAPTER 1 INTRODUCTION: NUCLEOPHILIC REACTIVITY OF AMIDIC COMPOUNDS 2 1.1. AMBIDENT NUCLEOPHILICITY A molecule which possesses two different sites which display nucleo- philic reactivity may be described as ambidentl. Of most interest are those in which the two nucleophilic sites interact with (or peri.urb) each other. The most common type of interaction involves tautomerism or resonance via one or more double-bonds. This class of nucleophile includes [1,3]- (1) and D,5]- (2) ambident systems. Any interaction between the X !I L Y (1) (2) nucleophilic sites, X and Y, of these systems will change their relative reactivity and, obviously, the site of reaction.
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