本专著系统总结了我国新农药创制性的成果——烷基膦酸酯类除草剂的研发总结。从化合物的合成、毒性研究、作用机制，从中试到生产整个程序，为今后我国农药新创制提供一条有效途径。
本书可供广大新农药研发、生产等人员阅读，也可供高等学校农药、植保等相关专业师生阅读。 环境友好型烃基膦酸酯类除草剂= Environmentally friendly alkylphosphonate herbicides_贺红武_化学工业出版社_

1 Overview 1
1 1 Introduction 1
1 1 1 Mode of Action of Herbicide 5
1 1 2 Herbicide Resistance 5
1 1 3 New Opportunity for Novel Herbicides 6
1 1 4 Basic Methodology for Discovery of Hit/Lead
Compounds 9
1 2 Pyruvate Dehydrogenase Complex (PDHc) 10
1 2 1 Function of PDHc 10
1 2 2 Distribution of PDHc11
1 2 3 Plant PDHc E1 as Site of Action of Herbicide 12
1 3 Progress in the Research of PDHc Inhibitors 13
1 3 1 OP Compounds as Inhibitors of E coli PDHc 13
1 3 2 OP Compounds as Inhibitors of Plant PDHc 20
1 3 3 Enzyme-Selective Inhibition of OP Compounds 22
1 4 Design of Novel PDHc E1 Inhibitors as Herbicides 23
1 4 1 Selecting Plant PDHc E1 as Target of New
Herbicide 23
1 4 2 PDHc E1 Inhibitor Acylphosphonate as Hit
Compound 24
1 4 3 Finding Lead Structure IA 25
1 4 4 Optimization Strategy28
1 5 Book Chapter Organization 36
References39
2 Alkylphosphonates 45
2 1 (Alkyl or Substituted Phenyl)Methylphosphonates IA–IF 46
2 1 1 Introduction 46
2 1 2 Synthesis of O,O-Dialkyl
1-Hydroxyalkylphosphonates M2 48
2 1 3 Synthesis of Substituted Phenoxyacetic Acids M4
and Substituted Phenoxyacetyl Chlorides M5 49
2 1 4 Synthesis of IA–IF 51
2 1 5 Spectroscopic Analysis of IA–IF 56
2 1 6 Crystal Structure Analysis of IC-7 63
2 1 7 Herbicidal Activity of IA–IF 65
2 1 8 Structure-Herbicidal Activity Relationships 87
2 1 9 Herbicidal Activity of IC-22 89
2 1 10 Summary 90
2 2 Heterocyclylmethylphosphonates IG–IJ 91
2 2 1 Introduction 91
2 2 2 Synthesis of IG–IJ 92
2 2 3 Spectroscopic Analysis of IG–IJ 94
2 2 4 Crystal Structure Analysis of IH-18 and IG-21 98
2 2 5 Herbicidal Activity of IG–IJ 102
2 2 6 Structure-Herbicidal Activity Relationships 111
2 2 7 Herbicidal Activity of IG-21 112
2 2 8 Summary 116
2 3 (1-Phenyl-1,2,4-Triazol-3-yloxyacetoxy)
Alkylphosphonates IK 116
2 3 1 Introduction 116
2 3 2 Synthesis of IK 116
2 3 3 Spectroscopic Analysis of IK 118
2 3 4 Herbicidal Activity of IK 119
2 3 5 Summary 119
References119
3 Salts of Alkylphosphonates 123
3 1 Alkali Metal Salts of O-Alkyl Alkylphosphonic
Acids IIA–IIE 125
3 1 1 Introduction 125
3 1 2 Synthesis of IIA–IIE 126
3 1 3 Spectroscopic Analysis of IIA–IIE 130
3 1 4 Crystal Structure Analysis of IIB-20 133
3 1 5 Herbicidal Activity of IIA–IIE 133
3 1 6 Summary 149
3 2 Alkali Metal Salts of Alkylphosphonic Acids IIF,
IIGandIIH 154
3 2 1 Introduction 154
3 2 2 Synthesis of IIF, IIG and IIH 155
3 2 3 Spectroscopic Analysis of IIF, IIG and IIH 157
3 2 4 Herbicidal Activity of IIF, IIG and IIH 159
3 2 5 Summary 166
3 3 t-Butylaminium Salts of Alkylphosphonates IIJ 166
3 3 1 Introduction 166
3 3 2 Synthesis of IIJ167
3 3 3 Spectroscopic Analysis of IIJ 169
3 3 4 Crystal Structure Analysis of IIJ-24169
3 3 5 Herbicidal Activity of IIJ 172
3 3 6 Summary 177
References177
4 Alkylphosphinates 179
4 1 Alkylphosphinates IIIA–IIIG 180
4 1 1 Introduction 180
4 1 2 Synthesis of Dichloro(Methyl)Phosphine M10 183
4 1 3 Synthesis of O-Methyl (1-Hydroxyalkyl)-
Methylphosphinates M12 183
4 1 4 Synthesis of IIIA–IIIG 184
4 1 5 Spectroscopic Analysis of IIIA–IIIG 187
4 1 6 Crystal Structure Analysis of IIIE-9190
4 1 7 Herbicidal Activity of IIIA–IIIG 191
4 1 8 Summary 204
4 2 Sodium Salts of Alkylphosphinic Acids IIIH 205
4 2 1 Introduction 205
4 2 2 Synthesis of IIIH206
4 2 3 Spectroscopic Analysis of IIIH 207
4 2 4 Herbicidal Activity of IIIH 209
4 2 5 Summary 213
4 3 [(5-Methylisoxazol-3-yloxyacetoxy)Alkyl]-
Methylphosphinates IIIJ 213
4 3 1 Introduction 213
4 3 2 Synthesis of IIIJ 214
4 3 3 Spectroscopic Analysis of IIIJ 215
4 3 4 Herbicidal Activity of IIIJ 216
4 3 5 Summary 218
References218
5 Cyclic Phosphonates and Caged Bicyclic Phosphates 221
5 1 Cyclic 1-Hydroxyalkylphosphonates IVA and IVB222
5 1 1 Introduction 222
5 1 2 Synthesis of IVA and IVB 222
5 1 3 Spectroscopic Analysis of IVA and IVB 224
5 1 4 Crystal Structure Analysis of IVA-3 226
5 1 5 Herbicidal Activity of IVA and IVB 228
5 1 6 Summary 230
5 2 Cyclic Alkylphosphonates IVC–IVF 230
5 2 1 Introduction 230
5 2 2 Synthesis of IVC–IVF 231
5 2 3 Spectroscopic Analysis of IVC–IVF 234
5 2 4 Crystal Structure Analysis of IVC-19239
5 2 5 Herbicidal Activity of IVC–IVF 241
5 2 6 Summary 259
5 3 Caged Bicyclic Phosphates IVG and IVH 261
5 3 1 Introduction 261
5 3 2 Synthesis of IVG and IVH 261
5 3 3 Spectroscopic Analysis of IVG and IVH 264
5 3 4 Crystal Structure Analysis of IVG-10266
5 3 5 Herbicidal Activity of IVG and IVH 268
5 3 6 Summary 273
References275
6 Optically Active Alkylphosphonates 279
6 1 Optically Active 1-Hydroxyalkylphosphonates IVB and M2 281
6 1 1 Introduction 281
6 1 2 Asymmetric Synthesis of 1-Hydroxyalkylphosphonates
IVB and M2 via Hydrophosphonylation 282
6 1 3 Asymmetric Synthesis of 1-Hydroxyalkylphosphonates
M2 via Hydroxylation289
6 1 4 Summary 291
6 2 Optically Active (Substituted Phenyl)methylphosphonates IA,
IEandIF 292
6 2 1 Introduction 292
6 2 2 Synthesis of Optically Active IA, IE and IF 292
6 2 3 Herbicidal Activity of Optically Active IA,
IEandIF 296
6 2 4 Summary 308
6 3 Optically Active Substituted Ethylphosphonates IA and IC 310
6 3 1 Introduction 310
6 3 2 Synthesis of Optically Active IA and IC 310
6 3 3 Herbicidal Activity of Optically Active IA and IC 314
6 3 4 Aquatic Toxicity of Optically Active IA and IC 316
6 3 5 Summary 318
References319
7 Biochemical Mechanism of Alkylphosphonates 323
7 1 Molecular Docking and 3D-QSAR Studies 324
7 1 1 Introduction 324
7 1 2 Binding Conformational Analysis 325
7 1 3 CoMFA and CoMSIA Analysis 325
7 1 4 Validation of the 3D-QSAR Models 330
7 1 5 Molecular Docking 330
7 1 6 Molecular Alignment and 3D-QSAR Modeling 331
7 1 7 CoMFA Analysis and CoMSIA Analysis Modeling 331
7 1 8 PLS Calculations and Validations 334
7 1 9 Summary 334
7 2 Enzyme Inhibition 335
7 2 1 Introduction 335
7 2 2 Inhibitory Potency Against Plant PDHc 336
7 2 3 Kinetic Experiment of PDHc 338
7 2 4 Selective Enzyme Inhibition 339
7 2 5 Structure-Activity Relationships 341
7 2 6 Assay of PDHc from Plant 350
7 2 7 Assay of PDHc from E coli and Pig Heart 352
7 2 8 Assay of Other Enzymes 354
7 2 9 Summary 354
References 355
8 Evaluation and Application of Clacyfos and HWS 359
8 1 Evaluation of Clacyfos 359
8 1 1 Introduction 359
8 1 2 Physiochemical Properties 360
8 1 3 Stability of Clacyfos 361
8 1 4 Herbicidal Activity in Greenhouse 363
8 1 5 Systemic Property of Clacyfos 366
8 1 6 Rainfast Characteristics of Clacyfos 366
8 1 7 Field Trials of Clacyfos 367
8 1 8 Toxicity Evaluation 377
8 1 9 Environmental Fate 378
8 1 10 Residues 379
8 1 11 Adsorption of Clacyfos on Soils 379
8 1 12 Ecological Effects 380
8 1 13 Summary 380
8 2 Evaluation of HWS 381
8 2 1 Introduction 381
8 2 2 Physiochemical Properties 381
8 2 3 Herbicidal Activity in Greenhouse 382
8 2 4 Systemic Property of HWS 385
8 2 5 Rainfast Characteristics of HWS 385
8 2 6 Field Trials of HWS 386
8 2 7 Toxicity Evaluation 388
8 2 8 Ecological Effects 389
8 2 9 Summary 389
References 390
9 General Methodology 391
9 1 General Synthetic Procedure 391
9 1 1 Chemicals, Reagents, and Solvents 391
9 1 2 O,O-Dialkyl Phosphonates M1 391
9 1 3 O,O-Dialkyl 1-Hydroxyalkylphosphonates M2 392
9 1 4 O,O-Dialkyl 1-(Chloroacetoxy)-
Alkylphosphonates M3 393
9 1 5 Substituted Phenoxyacetic Acids M4 393
9 1 6 Substituted Phenoxyacetyl Chlorides M5 396
9 1 7 O,O-Dialkyl 1-(Substituted Phenoxyacetoxy)-
Alkylphosphonates IA–IJ 398
9 1 8 Phenylhydrazinecarboxamide M6 and Sodium
Triazol-3-olate M7 405
9 1 9 (1-Phenyl-1,2,4-Triazol-3-yloxyacetoxy)-
Alkylphosphonates IK 406
9 1 10 Alkali Metal Salts of O-Alkyl Alkylphosphonic
Acids IIA–IIE 407
9 1 11 O,O-Bis(Trimethylsilyl) Alkylphosphonates
M8 and Alkylphosphonic Acids M9 410
9 1 12 Alkali Metal Salts of Alkylphosphonic
Acids IIF–IIH 411
9 1 13 t-Butylaminium Salts of Alkylphosphonates IIJ 413
9 1 14 Dichloro(Methyl)Phosphine M10 414
9 1 15 O-Methyl Methylphosphinate M11 415
9 1 16 O-Methyl (1-Hydroxyalkyl)Methylphosphinates
M12 415
9 1 17 Alkylphosphinates IIIA–IIIG 416
9 1 18 Sodium Salts of Alkylphosphinic Acids IIIH 419
9 1 19 3-Hydroxy-5-Methylisoxazole Derivatives
M13–M16 420
9 1 20 O-Methyl [1-(5-Methylisoxazol-3-yloxyacetoxy)-
Alkyl]Methylphosphinates IIIJ 421
9 1 21 1-Phenyl-2,2-Dimethyl-1,3-Propanediol M17 422
9 1 22 Cyclic Phosphonates M18 423
9 1 23 Cyclic 1-Hydroxyalkylphosphonates IVA and IVB 423
9 1 24 Substituted Phenoxypropionic Acids M19 425
9 1 25 Substituted Phenoxypropionyl Chlorides M20 425
9 1 26 Cyclic Alkylphosphonates IVC–IVF 426
9 1 27 4-(Hydroxymethyl)-2,6,7-Trioxa-1-Phosphabicyclo-
[2 2 2]Octane-1-One/Thione M21/M22 429
9 1 28 Caged Bicyclic Phosphates IVG and IVH 429
9 1 29 Optically Active Cyclic 1-Hydroxyalkylphosphonates
IVB 431
9 1 30 O,O-Diethyl (Substituted Benzyl)Phosphonates
M23 432
9 1 31 Optically Active 1-Hydroxyalkylphosphonates M2 433
9 1 32 Optically Active (Substituted Phenyl)-
Methylphosphonates IA, IE, and IF 435
9 1 33 1-Keto Phosphonates M24 and Vinylphosphonates
M25 437
9 1 34 Optically Active 1-Substituted Ethylphosphonates
IAandIC 441
9 2 General Information of Structural Characterization 442
9 3 Herbicidal Activity Assay 443
9 3 1 Test in Petri Dishes 444
9 3 2 Test in Greenhouse 445
References 446
Index 449

1.原创性专著，我国新农药创制的阶段性成果。