Reactivity of P-H Group of Phosphorus Based Compounds

Description

Reactivity of P-H Group of Phosphorus Based Compounds bridges the gap between inorganic and organic phosphorus compounds, providing a basis to explore the myriad possibilities for synthesis of novel low and high molecular phosphorus-containing compounds. It covers well-documented reactions in detail, including: tautomerization, oxidation, reduction, alkylation, oxidation coupling, addition reaction to: carbon-carbon multiple bonds, Schiff base, isocyanates, nitriles, epoxides; addition to carbonyl group, Kabachnik- Fields reaction, cross-coupling reaction and more. In an accessible style complete with synthetic routes and figures, the resource then covers the reactivity of multiple P-H group members: phosphines, phosphine oxides, hypophosphorus acid, H-phosphinic acids and polys(alkylene H-phosphonate).

This valuable coverage supports the advancement of research and applications in this area for scientists solving a scientific problem or starting a variety of new projects, such as a new reaction for the synthesis of biologically active compounds, new methods of polymer synthesis or a new methodology for polymer modification.

Describes the diverse reactivity of the phosphorus-hydrogen group, perhaps the most powerful in organic chemistry
Includes practical information for the synthesis of catalysts, biologically active substances, flame retardants, advance materials and polymer materials
Offers a visually-accessible guide to important reactions by an internationally recognized chemist

Front Cover 2
Reactivity of P–H Group of Phosphorus Based Compounds 5
Copyright Page 6
Contents 7
About the Author 11
Preface 13
1 Acidity and Tautomerization of P–H Group 15
- 1.1 Acidity 15
- 1.2 Tautomerization 18
  - 1.2.1 Tautomerization of Phosphine Oxides 19
  - 1.2.2 Tautomerization of Hypophosphorous Acid 23
  - 1.2.3 Tautomerization of H-Phosphinic Acid 24
  - 1.2.4 Tautomerization of H-Phosphonic Acid 25
- References 30
2 Reactivity of P–H Group of Phosphines 33

Front Cover 2
Reactivity of P–H Group of Phosphorus Based Compounds 5
Copyright Page 6
Contents 7
About the Author 11
Preface 13
1 Acidity and Tautomerization of P–H Group 15
- 1.1 Acidity 15
- 1.2 Tautomerization 18
  - 1.2.1 Tautomerization of Phosphine Oxides 19
  - 1.2.2 Tautomerization of Hypophosphorous Acid 23
  - 1.2.3 Tautomerization of H-Phosphinic Acid 24
  - 1.2.4 Tautomerization of H-Phosphonic Acid 25
- References 30
2 Reactivity of P–H Group of Phosphines 33
- 2.1 Phosphine 33
  - 2.1.1 Methods for Preparation 34
  - 2.1.2 Reactivity of P–H Group 35
    - 2.1.2.1 Reaction with Metals 35
    - 2.1.2.2 Addition Reactions 36
      - 2.1.2.2.1 Addition to Carbon–Carbon Multiple Bonds 36
        
        Radical Addition 37
        
        Nucleophilic Addition 40
        
        Catalyzed Hydrophosphination 43
      - 2.1.2.2.2 Addition to Carbonyl Group 44
    - 2.1.2.3 Nucleophilic Substitution Reactions 52
  - 2.2 Primary Phosphines (RPH2) 52
    - 2.2.1 Methods for Preparation 52
    - 2.2.2 Reactivity of P–H Group 56
      - 2.2.2.1 Addition Reactions 56
        
        2.2.2.1.1 Addition to Carbon–Carbon Multiple Bonds 56
        
        2.2.2.1.2 Addition to Carbonyl Group 59
      - 2.2.2.2 Cross-Coupling Reactions 64
      - 2.2.2.3 Cross-Dehydrogenative Coupling 65
    - 2.3 Primary Diphosphines 70
      - 2.3.1 Methods for Preparation 70
      - 2.3.2 Reactivity of P–H Group 72
        
        2.3.2.1 Metalation 72
        
        2.3.2.2 Cross-Dehydrogenative Coupling 72
        
        2.3.2.3 Addition Reactions 73
        
        2.3.2.3.1 Addition to Carbonyl Group 73
        
        2.3.2.3.2 Addition to Carbon–Carbon Multiple Bonds 75
        
        2.4 Secondary Phosphines R2PH 78
        
        2.4.1 Methods for Preparation 78
        
        2.4.2 Reactivity of P–H Group 79
        
        2.4.2.1 Oxidation 79
        
        2.4.2.2 Addition Reactions 79
        
        2.4.2.2.1 Addition to Carbon–Carbon Multiple Bonds 79
        
        Radical Activation 79
        
        Pincer Complexes 88
        
        2.4.2.2.2 Addition to Carbonyl Group 93
        
        2.4.2.3 Substitution Reactions 94
        
        2.4.2.4 Cross-Coupling Reactions 95
        
        2.4.2.5 Cross-Dehydrogenative Coupling 110
        
        2.5 Secondary Diphosphines—RPH-R′-PRH 111
        
        2.5.1 Methods for Preparation 111
        
        2.5.2 Reactivity of P–H Group 111
        
        2.5.2.2 Cross-Coupling Reactions 111
        
        2.5.2.2.1 Diphenyldiphosphine PhHP–PHPh 112
        
        2.5.2.2.2 Tetraphenyldiphosphane 113
        
        2.5.2.1 Condensation Reactions 111
        
        2.6 Phosphine–Borane Complexes 114
        
        2.6.1 Phosphine–Borane 115
        
        2.6.1.1 Methods for Preparation 115
        
        2.6.2 Primary Phosphine–Boranes 116
        
        2.6.2.2 Reactivity of P–H Group 116
        
        2.6.2.2.1 Hydrophosphination 116
        
        2.6.2.2.2 Oxidative Addition 117
        
        2.6.2.2.3 Cross-Dehydrogenative Coupling 117
        
        2.6.2.2.4 Alkylation 119
        
        2.6.2.1 Methods for Preparation 116
        
        2.6.3 Secondary Phosphine–Boranes 119
        
        2.6.3.1 Methods for Preparation 119
        
        2.6.3.2 Reactivity of P–H Group 120
        
        2.6.3.2.1 Alkylation 120
        
        2.6.3.2.2 Hydrophosphination 122
        
        2.6.3.2.3 Nucleophilic Substitutions 124
        
        2.6.3.2.4 Cross-Coupling Reactions 125
        
        2.6.3.2.5 Cross-Dehydrogenative Coupling 131
        
        Poly(phosphinoborane)s 137
        
        2.7 Conclusion 145
        
        References 146
        
        3 Reactivity of P–H Group of Phosphine Oxides 159
        
        3.1 Phosphine Oxide 159
        
        3.1.1 Methods for Preparation 159
        
        3.1.2 Reactivity of P–H Group 160
        
        3.2 Primary Phosphine Oxides 162
        
        3.2.1 Methods for Preparation 162
        
        3.2.2 Reactivity of P–H Group 163
        
        3.2.2.2 Addition Reactions 163
        
        3.2.2.2.1 Addition to Carbon–Carbon Multiple Bonds 163
        
        3.2.2.1 Dehydration 163
        
        3.3 Secondary Phosphine Oxides 164
        
        3.3.1 Methods for Preparation 165
        
        3.3.2 Reactivity of P–H Group 166
        
        3.3.2.1 Reduction 166
        
        3.3.2.2 Oxidation 166
        
        3.3.2.3 Addition Reactions 167
        
        3.3.2.3.1 Addition to Carbonyl Group 167
        
        3.3.2.3.2 Addition to Isocyanates 167
        
        3.3.2.3.3 Addition to Carbon–Carbon Multiple Bonds 168
        
        3.3.2.3.4 Addition to Schiff Bases 183
        
        3.3.2.4 Cross-Coupling Reactions 188
        
        3.3.2.5 Cross-Dehydrogenative Coupling 200
        
        3.3.2.6 Allylic Substitution 203
        
        3.4 Secondary Diphosphine Oxides 205
        
        3.4.1 Methods for Preparation 205
        
        3.4.2 Reactivity of P–H Group 205
        
        3.4.2.1 Oxidation 205
        
        3.4.2.2 Addition to Carbonyl Group and Schiff Bases 206
        
        References 207
        
        3.5 Conclusion 207
        
        4 Reactivity of P–H Group of Hypophosphorous Acid and Its Derivatives 213
        
        4.1 Hypophosphorous Acid Its Salts and Esters 213
        
        4.1.1 Methods for Preparation of Hypophosphorous Acid Its Salts and Esters 213
        
        4.1.1.1 Hypophosphorous Acid 213
        
        4.1.1.2 Salts 214
        
        4.1.1.3 Esters of Hypophosphorous Acid 215
        
        4.1.2 Reactivity of P–H Group of Hypophosphorous Acid and Its Salts 217
        
        4.1.2.1 Alkylation 217
        
        4.1.2.2 Addition Reactions 218
        
        4.1.2.2.1 Addition to Carbon–Carbon Multiple Bonds 218
        
        4.1.2.2.2 Addition to Schiff Bases 227
        
        4.1.2.2.3 Addition to Carbonyl Group 231
        
        4.1.2.3 Transfer Hydrogenation 240
        
        4.1.2.4 Cross-Coupling Reactions 242
        
        4.1.3 Reactivity of P–H Group of Esters of Hypophosphorous Acid 244
        
        4.1.3.1 Alkylation 245
        
        4.1.3.2 Addition Reactions 246
        
        4.1.3.2.1 Addition to Carbon–Carbon Multiple Bonds 246
        
        4.1.3.3 Cross-Coupling Reactions 249
        
        4.1.4 Hypophosphite Borane Complexes 253
        
        4.1.4.1 Methods for Preparation 253
        
        4.1.4.2 Reactivity of P–H Group 254
        
        4.1.4.2.1 Alkylation 254
        
        4.1.4.2.2 Addition to Carbon–Carbon Double Bond 255
        
        4.1.4.2.3 Addition to Carbonyl Group 255
        
        References 255
        
        4.2 Conclusion 255
        
        5 Reactivity of P–H Group of H-Phosphinic Acid and Its Derivatives 259
        
        5.1 H-Phosphinic Acid 259
        
        5.1.1 Methods for Preparation H-Phosphinic Acid 259
        
        5.1.2 Reactivity of P−H Group 262
        
        5.1.2.1 Alkylation 262
        
        5.1.2.2 Addition to Carbon–Carbon Double Bond 264
        
        5.2 Esters of H-Phosphinic Acid (H-Phosphinates) 264
        
        5.2.1 Methods for Preparation 264
        
        5.2.2 Reactivity of P–H Group 267
        
        5.2.2.1 Alkylation 267
        
        5.2.2.2 Addition Reactions 270
        
        5.2.2.2.1 Addition to Carbon–Carbon Multiple Bonds 270
        
        5.2.2.2.2 Addition to Carbonyl Group 279
        
        5.2.2.2.3 Addition to Schiff Bases 281
        
        5.2.2.2.4 Addition to Epoxides 281
        
        5.2.2.3 Cross-Coupling Reactions 282
        
        5.2.2.5 Reaction with Orthoacetates 289
        
        5.2.2.4 Cross-Dehydrogenative Coupling 289
        
        5.2.2.6 Transformation into Phosphine Boranes 290
        
        5.3 α-Amino H-Phosphinic Acids 291
        
        5.3.1 Methods for Preparation 291
        
        5.3.2 Reactivity of P–H Group 292
        
        5.3.2.1 Addition to Acrylates 292
        
        5.4 Conclusion 301
        
        References 301
        
        6 Reactivity of P–H Group of H-Phosphonic Acid and Its Derivatives 305
        
        6.1 H-Phosphonic Acid 305
        
        6.1.2 Reactivity of P–H Group 306
        
        6.1.2.1 Addition to Carbonyl Group and Schiff Bases 306
        
        6.1.2.2 Reduction 310
        
        6.1.1 Methods for Preparation 306
        
        6.2 Diesters of H-Phosphonic Acid (Dialkyl H-Phosphonates) 310
        
        6.2.2 Reactivity of P–H Group 311
        
        6.2.2.1 Oxidation 311
        
        6.2.2.2 Atherton-Todd Reaction 313
        
        6.2.2.2.1 Azidation, Cyanation, and Thiocyanation 316
        
        6.2.2.3 Addition Reactions 317
        
        6.2.2.3.1 Addition to Carbon–Carbon Multiple Bonds 317
        
        6.2.2.3.2 Homolytic Addition to Unsaturated Hydrocarbons 324
        
        6.2.2.3.3 Addition to Schiff Bases 330
        
        6.2.2.3.4 Addition to Nitriles 334
        
        6.2.2.3.5 Addition to Carbonyl Group (Abramov Reaction) 334
        
        6.2.2.3.6 Addition to Epoxides and Isocyanates 342
        
        6.2.2.3.7 Kabachnik–Fields Reaction 344
        
        6.2.2.3.8 Neat Conditions 348
        
        6.2.2.3.9 Catalyzed Reaction 351
        
        6.2.2.3.10 Reactions in Organic Solvents 354
        
        6.2.2.3.11 Reactions in Water 355
        
        6.2.2.3.12 Reactions in Ionic Liquids 357
        
        6.2.2.3.13 Microwave Irradiation 360
        
        6.2.2.3.14 Ultrasonic Irradiation 363
        
        6.2.2.3.15 Constant Magnetic Field 364
        
        6.2.2.4 Substitution Reactions 364
        
        6.2.2.4.1 Phosphitylation 368
        
        6.2.2.5 Reduction 368
        
        6.2.2.6 Cross-Coupling Reactions 369
        
        6.2.2.7 Reactions With Activated C–H Bond 386
        
        6.2.2.7.1 Cross-Dehydrogenative Coupling 387
        
        6.3 Conclusion 407
        
        References 408
        
        6.2.1 Methods for Preparation 311
        
        7 Reactivity of P–H Group of Poly(alkylene H-phosphonate)s 425
        
        7.1 Poly(alkylene H-Phosphonate)s 425
        
        7.1.1 Methods for Preparation 425
        
        7.1.2 Reactivity of P–H Group 427
        
        7.1.2.1 Oxidation 427
        
        7.1.2.2 Oxidation with N2O4 435
        
        7.1.2.4 Reduction 436
        
        7.1.2.3 Nonoxidative Chlorination 436
        
        7.1.2.5 Addition Reactions 437
        
        7.1.2.5.1 Addition to Carbon–Carbon Double Bond 437
        
        7.1.2.5.2 Addition to Carbonyl Group 439
        
        7.1.2.5.3 Addition to Schiff Bases 440
        
        7.2 Conclusions 441
        
        References 441
        
        Index 445
        
        Back Cover 466

Author's affiliation

Kolio D. Troev: Institute of Polymers, Bulgarian Academy of S

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