Chemistry and Application of H-Phosphonates (eBook)

Kolio D. Troev (Autor)

eBook Download: EPUB

2006 | 1. Auflage
336 Seiten
Elsevier Science (Verlag)
978-0-08-047649-0 (ISBN)

Infos

Chemistry and Application of H-Phosphonates is an excellent source for those planning the synthesis of new phosphorus-containing compounds and in particular derivatives containing a phosphonate, phosphoramide or phosphonic acid diester group. The rich chemistry, low cost and easy availability of diesters of H-phosphonic acid makes them an excellent choice as synthone in a number of practically important reactions.

Phosphonic acid esters are intermediates in the synthesis of important classes of compounds such as alpha-aminophosphonic acids, bisphosphonates, epoxyalkylphosphonates, alpha-hydroxyalkylphosphonates, phosphoramides, poly(alkylene H-phosphonate)s, poly(alkylene phosphate)s, nucleoside H-phosphonates. The synthesis of each of these compound classes is reviewed in detail.

Alpha-Aminophosphonic acids are an important class of biologically active compounds, which have received an increasing amount of attention because they are considered to be structural analogues of the corresponding Alpha-amino acids. The utilities of alpha-aminophosphonates as peptide mimics, haptens of catalytic antibodies, enzyme inhibitors, inhibitors of cancers, tumours, viruses, antibiotics and pharmacologic agents are well documented. Alpha-Hydroxyalkanephosphonates are compounds of significant biological and medicinal applications. Dialkyl epoxyalkylphosphonates are of interest because of their use as intermediates in the synthesis of bioactive substances, and as modifiers of natural and synthetic polymers. Bisphosphonates are drugs that have been widely used in different bone diseases, and have recently been used successfully against many parasites. Poly(alkylene H-phosphonate)s and poly(alkylene phosphate)s are promising, biodegradable, water soluble, new polymer-carriers of drugs. Nucleoside H-phosphonates seem to be the most attractive candidates as starting materials in the chemical synthesis of DNA and RNA fragments. The 5'-hydrogen phosphonate-3'-azido-2',3'-dideoxythimidine is one of the most significant anti-HIV prodrug, which is currently in clinical trials.

Chapters review the synthesis; physical and spectral properties (¹H, ¹³C, ³¹P and ¹⁷O NMR data); characteristic reactions; important classes of compounds based on these esters of H-phosphonic acid; their application as physiologically active substances, flame retardants, catalysts, heat and light stabilizers, lubricants, scale inhibitors, polymer-carriers of drugs; preparation of H-phosphonate diesters and general procedures for conducting the most important reactions.
* provides ideas for the synthesis of phosphonates, phosphoramides and diesters of phosphonic acid (new phosphorus-containing compounds)
* reviews structure, spectra and biological activity of H-phosphonates and their derivatives
* examines new areas of application of phosphorus-containing compounds

Inhalt

Cover 1
Chemistry and Application of H-Phosphonates 4
Preface 8
About the Author 10
Contents 12
1: Methods for Preparation and Physical Properties of H-Phosphonates 16
1.1 From Phosphorus Trichloride and Alcohols 16
1.2 From H-Phosphonic Acid 18
1.3 From White Phosphorus and Alcohols 19
1.4 Others 19
1.5 Physical Properties 19
1.6 Thermal Stability 20
Appendix 23
2 Structure and Spectral Characteristics of H-Phosphonates 26
2.1 Electronic Structure of the Phosphorus Atom 26
2.2 Nature of Chemical Bonds in the Phosphoryl Group 27
2.3 Molecular Structure of Dimethyl H-Phosphonate 28
2.4 Tautomerization of Dialkyl H-Phosphonates 30
2.5 Spectral Characteristics 33
2.5.1 Infrared spectra 33
2.5.2 1H NMR spectra 33
2.5.3 31P NMR spectra 34
2.5.4 13C NMR spectra 35
2.5.5 17O NMR spectra 35
Appendix 36
3 Reactivity of H-Phosphonates 38
3.1 Acidity of H-Phosphonate Diesters 38
3.2 Disproportionation 40
3.3 Reduction 40
3.4 Hydrolysis 40
3.5 Acidolysis 44
3.6 Substitution Reactions at the Phosphorus Atom 44
3.6.1 Transesterification reaction 44
3.6.2 Side reactions 47
3.6.3 Synthetic applications 48
3.7 Characteristic Reactions of P–H Group 54
3.7.1 Oxidation of P–H group 54
3.7.2 Addition Reactions 68
3.8 Reactions with the Participation of the -Carbon Atom 92
3.8.1 Reaction of dialkyl H-phosphonates with amines 92
3.8.2 Reaction of diaryl H-phosphonates with amines 97
3.8.3 Reaction with amides and urethanes 100
3.8.4 Reaction with hydrogen halides 102
3.8.5 Reaction with metal salts 103
3.8.6 Reaction with ammonium halides 106
3.8.7 Reaction with chlorosilanes 107
Appendix 117
4 Important Classes of Compounds 122
4.1 Aminophosphonates and Aminophosphonic Acids 122
4.1.1 Methods for the preparation of aminophosphonates 123
4.1.2 Hydrolytic cleavage of phosphorus–carbon bond 153
4.1.3 Synthetic application 156
4.2 Bisphosphonates 159
4.2.1 Methods for preparation of bisphosphonates 160
4.3 Nucleoside H-Phosphonates 174
4.3.1 Methods of preparation 175
4.3.2 Reactivity of nucleoside H-phosphonates 181
4.3.3 Synthetic application 189
4.4 Dialkyl Epoxyalkylphosphonates 195
4.4.1 1,2-Epoxyalkylphosphonates 195
4.4.2 2,3-Epoxyalkylphosphonates 200
4.4.3 Reactivity of 1,2-epoxyalkylphosphonates 200
4.5 Poly(Alkylene H-Phosphonate) 203
4.5.1 Methods of preparation 204
4.5.2 Reactivity of poly(alkylene H-phosphonate)s 210
4.5.3 Application of poly(alkylene H-phosphonate)s 216
4.6 Metal Salts of Dialkyl H-Phosphonates 225
4.6.1 Phosphite-type metal salts 226
4.6.2 Phosphonate-type metal salts 235
4.7 Complexes of Dialkyl H-Phosphonates 237
4.7.1 Molecular complexes with Lewis acids 238
4.7.2 Complexes with some main group and f-elements 239
4.7.3 Complexes with transition metals 241
4.7.4 Complexes containing P(III)-type ligands 242
Appendix 260
5 Application of H-Phosphonate Diesters and their Derivatives 268
5.1 Physiologically Active Substances 268
5.1.1 Fungicides and bactericides 269
5.1.2 Herbicides 271
5.1.3 Plant-growth regulators 273
5.1.4 Insecticides 275
5.1.5 Drugs suppressing the growth of cancer, tumor, virus, or parasites 275
5.1.6 Anti-HIV prodrugs 276
5.1.7 Antiresorption drugs, carriers of radioactive metals 278
5.2 Polymer Additives 279
5.2.1 Flame retardants and antioxidants 279
5.3 Degrading and Alkylating Agents of Polymers 286
5.4 Heat, Light, and UV Stabilizers 290
5.5 Catalysts 291
5.6 Corrosion Inhibitors 293
5.7 Scale Inhibitors 294
5.8 Lubricants 295
Subject Index 300

Produkt-Details

• Erscheint lt. Verlag: 25.9.2006
• Sprache: englisch
• Themenwelt: Sachbuch/Ratgeber
• Themenwelt: Naturwissenschaften ► Chemie ► Analytische Chemie
• Themenwelt: Naturwissenschaften ► Chemie ► Anorganische Chemie
• Themenwelt: Technik
• ISBN-10: 0-08-047649-X / 008047649X
• ISBN-13: 978-0-08-047649-0 / 9780080476490