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E-raamat: Environmentally Friendly Alkylphosphonate Herbicides

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  • Ilmumisaeg: 04-Nov-2014
  • Kirjastus: Springer-Verlag Berlin and Heidelberg GmbH & Co. K
  • Keel: eng
  • ISBN-13: 9783662444313
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  • Formaat: PDF+DRM
  • Ilmumisaeg: 04-Nov-2014
  • Kirjastus: Springer-Verlag Berlin and Heidelberg GmbH & Co. K
  • Keel: eng
  • ISBN-13: 9783662444313

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This book presents essential research on a class of environmentally friendly alkylphosphonate herbicides. This class of herbicides acted as a competitive inhibitor of the pyruvate dehydrogenase complex (PDHc) to control weeds. The bioreasoning and systematic approach, from basic research to field tests of candidate compounds, are introduced. The basic research covers the molecular design, chemical synthesis, biological activities evaluation, structure-activity relationship analysis and structural optimization. Subsequently, the book reviews the biochemistry of PDHc inhibitors, the selectivity between mammals and plants, and the mechanism of herbicidal activity of novel alkylphosphonates as selective PDHc inhibitors. Field trials for selected alkylphosphonate candidates as herbicides are also included. This book provides a sound basis for the rational design and development of novel herbicides as effective PDHc inhibitors with good enzyme-selective inhibition of plant PDHc between mammals and plants. These studies take full advantages of the low toxicity and low residual impact of selective PHDc inhibitors to design an effective and environmentally friendly herbicide. This book is based on twenty years of research on alkylphosphonates and phosphorus-containing PDHc inhibitors, and demonstrates how to develop these PDHc inhibitors as an effective and “green” herbicide candidate.

Hong-Wu He, PhD, is a Professor at the Key Laboratory of Pesticide & Chemical Biology, Ministry of Education of China, and Director of the Institute of Pesticide Chemistry, College of Chemistry, Central China Normal University, China.
Hao Peng, PhD, and Xiao-Song Tan are both Associate Professors at the Key Laboratory of Pesticide & Chemical Biology, Ministry of Education of China, College of Chemistry, Central China Normal University, China.

1 Overview
1(44)
1.1 Introduction
1(9)
1.1.1 Mode of Action of Herbicide
5(1)
1.1.2 Herbicide Resistance
5(1)
1.1.3 New Opportunity for Novel Herbicides
6(3)
1.1.4 Basic Methodology for Discovery of Hit/Lead Compounds
9(1)
1.2 Pyruvate Dehydrogenase Complex (PDHc)
10(3)
1.2.1 Function of PDHc
10(1)
1.2.2 Distribution of PDHc
11(1)
1.2.3 Plant PDHc E1 as Site of Action of Herbicide
12(1)
1.3 Progress in the Research of PDHc Inhibitors
13(10)
1.3.1 OP Compounds as Inhibitors of E. coli PDHc
13(7)
1.3.2 OP Compounds as Inhibitors of Plant PDHc
20(2)
1.3.3 Enzyme-Selective Inhibition of OP Compounds
22(1)
1.4 Design of Novel PDHc E1 Inhibitors as Herbicides
23(13)
1.4.1 Selecting Plant PDHc E1 as Target of New Herbicide
23(1)
1.4.2 PDHc E1 Inhibitor Acylphosphonate as Hit Compound
24(1)
1.4.3 Finding Lead Structure IA
25(3)
1.4.4 Optimization Strategy
28(8)
1.5 Book
Chapter Organization
36(9)
References
39(6)
2 Alkylphosphonates
45(78)
2.1 (Alkyl or Substituted Phenyl) Methylphosphonates IA-IF
46(45)
2.1.1 Introduction
46(2)
2.1.2 Synthesis of O,O-Dialkyl 1-Hydroxyalkylphosphonates M2
48(1)
2.1.3 Synthesis of Substituted Phenoxyacetic Acids M4 and Substituted Phenoxyacetyl Chlorides M5
49(2)
2.1.4 Synthesis of IA--IF
51(5)
2.1.5 Spectroscopic Analysis of IA--IF
56(7)
2.1.6 Crystal Structure Analysis of IC-7
63(2)
2.1.7 Herbicidal Activity of IA--IF
65(22)
2.1.8 Structure-Herbicidal Activity Relationships
87(2)
2.1.9 Herbicidal Activity of IC-22
89(1)
2.1.10 Summary
90(1)
2.2 Heterocyclylmethylphosphonates IG--IJ
91(25)
2.2.1 Introduction
91(1)
2.2.2 Synthesis of IG--IJ
92(2)
2.2.3 Spectroscopic Analysis of IG--IJ
94(4)
2.2.4 Crystal Structure Analysis of IH-18 and IG-21
98(4)
2.2.5 Herbicidal Activity of IG--IJ
102(9)
2.2.6 Structure-Herbicidal Activity Relationships
111(1)
2.2.7 Herbicidal Activity of IG-21
112(4)
2.2.8 Summary
116(1)
2.3 (1-Phenyl-1,2,4-Triazol-3-yloxyacetoxy) Alkylphosphonates IK
116(7)
2.3.1 Introduction
116(1)
2.3.2 Synthesis of IK
116(2)
2.3.3 Spectroscopic Analysis of IK
118(1)
2.3.4 Herbicidal Activity of IK
119(1)
2.3.5 Summary
119(1)
References
119(4)
3 Salts of Alkylphosphonates
123(56)
3.1 Alkali Metal Salts of O-Alkyl Alkylphosphonic Acids IIA--IIE
125(29)
3.1.1 Introduction
125(1)
3.1.2 Synthesis of IIA--IIE
126(4)
3.1.3 Spectroscopic Analysis of IIA--IIE
130(3)
3.1.4 Crystal Structure Analysis of IIB-20
133(1)
3.1.5 Herbicidal Activity of IIA--IIE
133(16)
3.1.6 Summary
149(5)
3.2 Alkali Metal Salts of Alkylphosphonic Acids IIF, IIG and IIH
154(12)
3.2.1 Introduction
154(1)
3.2.2 Synthesis of IIF, IIG and IIH
155(2)
3.2.3 Spectroscopic Analysis of IIF, IIG and IIH
157(2)
3.2.4 Herbicidal Activity of IIF, IIG and IIH
159(7)
3.2.5 Summary
166(1)
3.3 t-Butylaminium Salts of Alkylphosphonates IIJ
166(13)
3.3.1 Introduction
166(1)
3.3.2 Synthesis of IIJ
167(2)
3.3.3 Spectroscopic Analysis of IIJ
169(1)
3.3.4 Crystal Structure Analysis of IIJ-24
169(3)
3.3.5 Herbicidal Activity of IIJ
172(5)
3.3.6 Summary
177(1)
References
177(2)
4 Alkylphosphinates
179(42)
4.1 Alkylphosphinates IIIA-IIIG
180(25)
4.1.1 Introduction
180(3)
4.1.2 Synthesis of Dichloro(Methyl)Phosphine M10
183(1)
4.1.3 Synthesis of O-Methyl (1-Hydroxyalkyl)-Methylphosphinates M12
183(1)
4.1.4 Synthesis of IIIA--IIIG
184(3)
4.1.5 Spectroscopic Analysis of IIIA-IIIG
187(3)
4.1.6 Crystal Structure Analysis of IIIE-9
190(1)
4.1.7 Herbicidal Activity of IIIA--IIIG
191(13)
4.1.8 Summary
204(1)
4.2 Sodium Salts of Alkylphosphinic Acids IIIH
205(8)
4.2.1 Introduction
205(1)
4.2.2 Synthesis of IIIH
206(1)
4.2.3 Spectroscopic Analysis of IIIH
207(2)
4.2.4 Herbicidal Activity of IIIH
209(4)
4.2.5 Summary
213(1)
4.3 [ (5-Methylisoxazol-3-yloxyacetoxy)Alkyl]-Methylphosphinates IIIJ
213(8)
4.3.1 Introduction
213(1)
4.3.2 Synthesis of IIIJ
214(1)
4.3.3 Spectroscopic Analysis of IIIJ
215(1)
4.3.4 Herbicidal Activity of IIIJ
216(2)
4.3.5 Summary
218(1)
References
218(3)
5 Cyclic Phosphorates and Caged Bicyclic Phosphates
221(58)
5.1 Cyclic 1-Hydroxyalkylphosphonates IVA and IVB
222(8)
5.1.1 Introduction
222(1)
5.1.2 Synthesis of IVA and IVB
222(2)
5.1.3 Spectroscopic Analysis of IVA and IVB
224(2)
5.1.4 Crystal Structure Analysis of IVA-3
226(2)
5.1.5 Herbicidal Activity of IVA and IVB
228(2)
5.1.6 Summary
230(1)
5.2 Cyclic Alkylphosphonates IVC--IVF
230(31)
5.2.1 Introduction
230(1)
5.2.2 Synthesis of IVC--IVF
231(3)
5.2.3 Spectroscopic Analysis of IVC--IVF
234(5)
5.2.4 Crystal Structure Analysis of IVC-19
239(2)
5.2.5 Herbicidal Activity of IVC--IVF
241(18)
5.2.6 Summary
259(2)
5.3 Caged Bicyclic Phosphates IVG and IVH
261(18)
5.3.1 Introduction
261(1)
5.3.2 Synthesis of IVG and IVH
261(3)
5.3.3 Spectroscopic Analysis of IVG and IVH
264(2)
5.3.4 Crystal Structure Analysis of IVG-10
266(2)
5.3.5 Herbicidal Activity of IVG and IVH
268(5)
5.3.6 Summary
273(2)
References
275(4)
6 Optically Active Alkylphosphonates
279(44)
6.1 Optically Active 1-Hydroxyalkylphosphonates IVB and M2
281(11)
6.1.1 Introduction
281(1)
6.1.2 Asymmetric Synthesis of 1-Hydroxyalkylphosphonates IVB and M2 via Hydrophosphonylation
282(7)
6.1.3 Asymmetric Synthesis of 1-Hydroxyalkylphosphonates M2 via Hydroxylation
289(2)
6.1.4 Summary
291(1)
6.2 Optically Active (Substituted Phenyl)methylphosphonates IA, IE and IF
292(18)
6.2.1 Introduction
292(1)
6.2.2 Synthesis of Optically Active IA, IE and IF
292(4)
6.2.3 Herbicidal Activity of Optically Active IA, IE and IF
296(12)
6.2.4 Summary
308(2)
6.3 Optically Active Substituted Ethylphosphonates IA and IC
310(13)
6.3.1 Introduction
310(1)
6.3.2 Synthesis of Optically Active IA and IC
310(4)
6.3.3 Herbicidal Activity of Optically Active IA and IC
314(2)
6.3.4 Aquatic Toxicity of Optically Active IA and IC
316(2)
6.3.5 Summary
318(1)
References
319(4)
7 Biochemical Mechanism of Alkylphosphonates
323(36)
7.1 Molecular Docking and 3D-QSAR Studies
324(11)
7.1.1 Introduction
324(1)
7.1.2 Binding Conformational Analysis
325(1)
7.1.3 CoMFA and CoMSIA Analysis
325(5)
7.1.4 Validation of the 3D-QSAR Models
330(1)
7.1.5 Molecular Docking
330(1)
7.1.6 Molecular Alignment and 3D-QSAR Modeling
331(1)
7.1.7 CoMFA Analysis and CoMSIA Analysis Modeling
331(3)
7.1.8 PLS Calculations and Validations
334(1)
7.1.9 Summary
334(1)
7.2 Enzyme Inhibition
335(24)
7.2.1 Introduction
335(1)
7.2.2 Inhibitory Potency Against Plant PDHc
336(2)
7.2.3 Kinetic Experiment of PDHc
338(1)
7.2.4 Selective Enzyme Inhibition
339(2)
7.2.5 Structure-Activity Relationships
341(9)
7.2.6 Assay of PDHc from Plant
350(2)
7.2.7 Assay of PDHc from E. coli and Pig Heart
352(2)
7.2.8 Assay of Other Enzymes
354(1)
7.2.9 Summary
354(1)
References
355(4)
8 Evaluation and Application of Clacyfos and HWS
359(32)
8.1 Evaluation of Clacyfos
359(22)
8.1.1 Introduction
359(1)
8.1.2 Physiochemical Properties
360(1)
8.1.3 Stability of Clacyfos
361(2)
8.1.4 Herbicidal Activity in Greenhouse
363(3)
8.1.5 Systemic Property of Clacyfos
366(1)
8.1.6 Rainfast Characteristics of Clacyfos
366(1)
8.1.7 Field Trials of Clacyfos
367(10)
8.1.8 Toxicity Evaluation
377(1)
8.1.9 Environmental Fate
378(1)
8.1.10 Residues
379(1)
8.1.11 Adsorption of Clacyfos on Soils
379(1)
8.1.12 Ecological Effects
380(1)
8.1.13 Summary
380(1)
8.2 Evaluation of HWS
381(10)
8.2.1 Introduction
381(1)
8.2.2 Physiochemical Properties
381(1)
8.2.3 Herbicidal Activity in Greenhouse
382(3)
8.2.4 Systemic Property of HWS
385(1)
8.2.5 Rainfast Characteristics of HWS
385(1)
8.2.6 Field Trials of HWS
386(2)
8.2.7 Toxicity Evaluation
388(1)
8.2.8 Ecological Effects
389(1)
8.2.9 Summary
389(1)
References
390(1)
9 General Methodology
391(58)
9.1 General Synthetic Procedure
391(51)
9.1.1 Chemicals, Reagents, and Solvents
391(1)
9.1.2 O,O-Dialkyl Phosphonates M1
391(1)
9.1.3 O,O-Dialkyl 1-Hydroxyalkylphosphonates M2
392(1)
9.1.4 O,O-Dialkyl 1-(Chloroacetoxy)-Alkylphosphonates M3
393(1)
9.1.5 Substituted Phenoxyacetic Acids M4
393(3)
9.1.6 Substituted Phenoxyacetyl Chlorides M5
396(2)
9.1.7 O,O-Dialkyl 1-(Substituted Phenoxyacetoxy)-Alkylphosphonates IA--IJ
398(7)
9.1.8 Phenylhydrazinecarboxamide M6 and Sodium Triazol-3-olate M7
405(1)
9.1.9 (1-Phenyl-1,2,4-Triazol-3-yloxyacetoxy)-Alkylphosphonates IK
406(1)
9.1.10 Alkali Metal Salts of O-Alkyl Alkylphosphonic Acids IIA--IIE
407(3)
9.1.11 O,O-Bis(Trimethylsilyl) Alkylphosphonates M8 and Alkylphosphonic Acids M9
410(1)
9.1.12 Alkali Metal Salts of Alkylphosphonic Acids IIF--IIH
411(2)
9.1.13 t-Butylaminium Salts of Alkylphosphonates IIJ
413(1)
9.1.14 Dichloro(Methyl)Phosphine M10
414(1)
9.1.15 O-Methyl Methylphosphinate M11
415(1)
9.1.16 O-Methyl (1-Hydroxyalkyl)Methylphosphinates M12
415(1)
9.1.17 Alkylphosphinates IIIA--IIIG
416(3)
9.1.18 Sodium Salts of Alkylphosphinic Acids IIIH
419(1)
9.1.19 3-Hydroxy-5-Methylisoxazole Derivatives M13--M16
420(1)
9.1.20 O-Methyl [ 1-(5-Methylisoxazol-3-yloxyacetoxy)-Alkyl]Methylphosphinates IIIJ
421(1)
9.1.21 1-Phenyl-2,2-Dimethyl-1,3-Propanediol M17
422(1)
9.1.22 Cyclic Phosphonates M18
423(1)
9.1.23 Cyclic 1-Hydroxyalkylphosphonates IVA and IVB
423(2)
9.1.24 Substituted Phenoxypropionic Acids M19
425(1)
9.1.25 Substituted Phenoxypropionyl Chlorides M20
425(1)
9.1.26 Cyclic Alkylphosphonates IVC--IVF
426(3)
9.1.27 4-(Hydroxymethyl)-2,6,7-Trioxa-1-Phosphabicyclo-[ 2.2.2]Octane-1-One/Thione M21/M22
429(1)
9.1.28 Caged Bicyclic Phosphates IVG and IVH
429(2)
9.1.29 Optically Active Cyclic 1-Hydroxyalkylphosphonates IVB
431(1)
9.1.30 O,O-Diethyl (Substituted Benzyl)Phosphonates M23
432(1)
9.1.31 Optically Active 1-Hydroxyalkylphosphonates M2
433(2)
9.1.32 Optically Active (Substituted Phenyl)-Methylphosphonates IA, IE, and IF
435(2)
9.1.33 1-Keto Phosphonates M24 and Vinylphosphonates M25
437(4)
9.1.34 Optically Active 1-Substituted Ethylphosphonates IA and IC
441(1)
9.2 General Information of Structural Characterization
442(1)
9.3 Herbicidal Activity Assay
443(6)
9.3.1 Test in Petri Dishes
444(1)
9.3.2 Test in Greenhouse
445(1)
References
446(3)
Index 449