|
|
1 | (44) |
|
|
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) |
|
|
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) |
|
|
39 | (6) |
|
|
45 | (78) |
|
2.1 (Alkyl or Substituted Phenyl) Methylphosphonates IA-IF |
|
|
46 | (45) |
|
|
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) |
|
|
90 | (1) |
|
2.2 Heterocyclylmethylphosphonates IG--IJ |
|
|
91 | (25) |
|
|
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) |
|
|
116 | (1) |
|
2.3 (1-Phenyl-1,2,4-Triazol-3-yloxyacetoxy) Alkylphosphonates IK |
|
|
116 | (7) |
|
|
116 | (1) |
|
|
116 | (2) |
|
2.3.3 Spectroscopic Analysis of IK |
|
|
118 | (1) |
|
2.3.4 Herbicidal Activity of IK |
|
|
119 | (1) |
|
|
119 | (1) |
|
|
119 | (4) |
|
3 Salts of Alkylphosphonates |
|
|
123 | (56) |
|
3.1 Alkali Metal Salts of O-Alkyl Alkylphosphonic Acids IIA--IIE |
|
|
125 | (29) |
|
|
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) |
|
|
149 | (5) |
|
3.2 Alkali Metal Salts of Alkylphosphonic Acids IIF, IIG and IIH |
|
|
154 | (12) |
|
|
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) |
|
|
166 | (1) |
|
3.3 t-Butylaminium Salts of Alkylphosphonates IIJ |
|
|
166 | (13) |
|
|
166 | (1) |
|
|
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) |
|
|
177 | (1) |
|
|
177 | (2) |
|
|
179 | (42) |
|
4.1 Alkylphosphinates IIIA-IIIG |
|
|
180 | (25) |
|
|
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) |
|
|
204 | (1) |
|
4.2 Sodium Salts of Alkylphosphinic Acids IIIH |
|
|
205 | (8) |
|
|
205 | (1) |
|
|
206 | (1) |
|
4.2.3 Spectroscopic Analysis of IIIH |
|
|
207 | (2) |
|
4.2.4 Herbicidal Activity of IIIH |
|
|
209 | (4) |
|
|
213 | (1) |
|
4.3 [ (5-Methylisoxazol-3-yloxyacetoxy)Alkyl]-Methylphosphinates IIIJ |
|
|
213 | (8) |
|
|
213 | (1) |
|
|
214 | (1) |
|
4.3.3 Spectroscopic Analysis of IIIJ |
|
|
215 | (1) |
|
4.3.4 Herbicidal Activity of IIIJ |
|
|
216 | (2) |
|
|
218 | (1) |
|
|
218 | (3) |
|
5 Cyclic Phosphorates and Caged Bicyclic Phosphates |
|
|
221 | (58) |
|
5.1 Cyclic 1-Hydroxyalkylphosphonates IVA and IVB |
|
|
222 | (8) |
|
|
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) |
|
|
230 | (1) |
|
5.2 Cyclic Alkylphosphonates IVC--IVF |
|
|
230 | (31) |
|
|
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) |
|
|
259 | (2) |
|
5.3 Caged Bicyclic Phosphates IVG and IVH |
|
|
261 | (18) |
|
|
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) |
|
|
273 | (2) |
|
|
275 | (4) |
|
6 Optically Active Alkylphosphonates |
|
|
279 | (44) |
|
6.1 Optically Active 1-Hydroxyalkylphosphonates IVB and M2 |
|
|
281 | (11) |
|
|
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) |
|
|
291 | (1) |
|
6.2 Optically Active (Substituted Phenyl)methylphosphonates IA, IE and IF |
|
|
292 | (18) |
|
|
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) |
|
|
308 | (2) |
|
6.3 Optically Active Substituted Ethylphosphonates IA and IC |
|
|
310 | (13) |
|
|
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) |
|
|
318 | (1) |
|
|
319 | (4) |
|
7 Biochemical Mechanism of Alkylphosphonates |
|
|
323 | (36) |
|
7.1 Molecular Docking and 3D-QSAR Studies |
|
|
324 | (11) |
|
|
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) |
|
|
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) |
|
|
334 | (1) |
|
|
335 | (24) |
|
|
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) |
|
|
354 | (1) |
|
|
355 | (4) |
|
8 Evaluation and Application of Clacyfos and HWS |
|
|
359 | (32) |
|
8.1 Evaluation of Clacyfos |
|
|
359 | (22) |
|
|
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) |
|
|
378 | (1) |
|
|
379 | (1) |
|
8.1.11 Adsorption of Clacyfos on Soils |
|
|
379 | (1) |
|
8.1.12 Ecological Effects |
|
|
380 | (1) |
|
|
380 | (1) |
|
|
381 | (10) |
|
|
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) |
|
|
389 | (1) |
|
|
389 | (1) |
|
|
390 | (1) |
|
|
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) |
|
|
445 | (1) |
|
|
446 | (3) |
Index |
|
449 | |