| 摘要 |
#CMT# #/CMT# Substituted cyanobutyrate compounds (I) and their N-oxides or salts are new. #CMT# : #/CMT# Substituted cyanobutyrate compounds of formula (I) and their N-oxides or salts are new. R : halo, CN, nitro, 1-4C-(halo)alkyl, 2-6C-alkenyl, 2-6C-alkynyl, 1-4C-(halo)alkoxy, S(O) xRaa, Z-(tri-1-4C-alkyl)silyl; x : 0-2; Raa : 1-4C-(halo)alkyl, 2-6C-alkenyl or 2-6C-alkynyl; R 1>H, Z-CN, 1-8C-(halo)alkyl, Z-3-6C-cycloalkyl, 1-4C-alkoxy-1-4C-alkyl, 1-4C-alkylthio-1-4C-alkyl, 3-8C-alkenyl, Z-3-6C-cycloalkenyl, 3-8C-alkynyl, NR1aR2a, Z-(tri-1-4C-alkyl)silyl, Z-N=C(R3a) 2, Z-C(R3a)=NR3a, Z-C(=T)-R3a, Z-P(=T)(R3a) 2, Z-phenyl, over C or N bonded 3-7-membered monocyclic, or 9 or 10 membered bicyclic, optionally saturated or aryl heterocycle containing 1-4 heteroatoms of O, N or S, which optionally contains carbonyl or thiocarbonyl group; R 2>halo, CN, nitro, 1-4C-(halo)alkyl, 1-4C-(halo)alkoxy, S(O) xRbb or NR1aR2a, where the groups in R, R 1>and R 2>or its low substituted carbon chain and/or cyclic group are optionally substituted by R1a and/or R1b; T : O or S; R3a : OH, 1-8C-alkyl, 1-4C-haloalkyl, Z-3-6C-cycloalkyl, 2-8C-alkenyl, Z-5-6C-cycloalkenyl, 2-8C-alkynyl, Z-1-6C-alkoxy, Z-1-4C-haloalkoxy, Z-3-8C-alkenyloxy, Z-3-8C-alkynyloxy, NR1aR2a, 1-6C-alkylsulfonyl, Z-(tri-1-4C-alkyl)silyl, Z-phenyl, Z-phenoxy, Z-phenylamino or 5- or 6-membered monocyclic or 9- or 10-membered bicyclic heterocycle containing 1-4 heteroatoms of O, N or S, where the cyclic group is optionally substituted by 1-4 R1b; either R1a, R2a : H, 1-8C-alkyl, 1-4C-haloalkyl, 3-8C-alkenyl, 3-8C-alkynyl, Z-3-6C-cycloalkyl, Z-1-8C-alkoxy, Z-1-8C-haloalkoxy or Z-C(=O)-R1A; R1A : OH or 1-4C-alkoxy; or R1aR2aN : a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic heterocycle containing 1-4 heteroatoms of O, N or S; either R1b : Z-CN, Z-OH, Z-NO 2, Z-halo, 1-8C-alkyl, 1-4C-haloalkyl, 2-8C-alkenyl, 2-8C-alkynyl, Z-1-8C-alkoxy, Z-1-8C-haloalkoxy, Z-3-10C-cycloalkyl, O-Z-3-10C-cycloalkyl, Z-C(=O)-R3a, NR1aR2a, Z-(tri-1-4C-alkyl)silyl, Z-phenyl or S(O) xRbb; or R1b+C : 5 or 6 membered, optionally saturated ring containing 1-3 heteroatoms of O, N or S; Rbb : 1-8C-alkyl or 1-6C-haloalkyl; Z : a covalent bond or 1-8C-alkylene; m, n : 0-5; and X, Y 1>O or S, where at least one of X and Y 1>is S. #CMT#[Image]#/CMT# #CMT#ACTIVITY : #/CMT# Herbicide. #CMT#MECHANISM OF ACTION : #/CMT# None given. #CMT#USE : #/CMT# (I) are useful for combating weeds (claimed) in culture plants e.g. cotton, rice, maize or wheat. Tests details are described but no results given. #CMT#ADVANTAGE : #/CMT# (I): exhibit high herbicidal activity even in low application rates and good plant compatibility; and are nontoxic. #CMT#ORGANIC CHEMISTRY : #/CMT# Preparation (Disclosed): Preparation of (I) comprises Michael-addition of phenylacetonitrile derivative of formula (II) with cinnamate derivative (III) in a solvent e.g. pentane and in the presence of a base e.g. lithium amide and/or catalyst e.g. hydrochloric acid. #CMT#[Image]#/CMT# #CMT#DEFINITIONS : #/CMT# Preferred Definitions: R 1>H, CH 3, C 2H 5, CH 2-C 6H 5, CH 2-(2-F-C 6H 4), CH 2-(3-F-C 6H 4), CH 2-(4-F-C 6H 4), CH 2-(2,4-F 2-C 6H 3), C 6H 5, 2-F-C 6H 4, 3-F-C 6H 4, 4-F-C 6H 4, 2,4-F 2-C 6H 3or 2,4-Cl 2-C 6H 3; R : Cl, F, CN or nitro; and n : 1-3. #CMT#ADMINISTRATION : #/CMT# Application of (I): to combat weeds is 0.001-3, preferably 0.01-1 kg/hectare and for treating seeds is 0.001-10/100 kg of seeds. Application of (I) for seed treatment is via dressing, coating, dusting, soaking, film coating, multilayer coating, encrusting or dripping. #CMT#SPECIFIC COMPOUNDS : #/CMT# 10 Compounds (I) are disclosed e.g. 4-cyano-3-(2,3-difluoro-phenyl)-4-(4-fluoro-phenyl)-thiobutyric acid S-phenyl ester (Ia), 3-(5-chloro-2-fluoro-phenyl)-4-cyano-4-(4-fluoro-phenyl)-thiobutyric acid S-phenyl ester, 4-cyano-4-(4-fluoro-phenyl)-3-(2,3,5,6-tetrafluoro-phenyl)-thiobutyric acid S-phenyl ester, 4-cyano-3-(3,5-dichloro-phenyl)-4-phenyl-thiobutyric acid S-(4-fluoro-phenyl) ester and 4-cyano-3-(3,5-dichloro-phenyl)-4-phenyl-thiobutyric acid S-phenyl ester. #CMT#[Image]#/CMT# #CMT#EXAMPLE : #/CMT# 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (180 mg) and 4-(dimethylamino)-pyridine (1 mg) were added to a solution of 4-cyano-3-(2,3-difluorophenyl)-4-(4-fluorophenyl)butyric acid (200 mg) and thiophenol (72 mg) in dichloromethane (5 ml) and stirred at 20-25[deg] C for 15 hours. After washing with 10% hydrochloric acid, the obtained mixture was treated with diazabicyclo[5.4.0]undecane, the organic phase was dried, the solvent was removed and purified to obtain 4-cyano-3-(2,3-difluorophenyl)-4-(4-fluorophenyl)thiobutyric acid-phenylester (110 mg). |
