CN1479718A

CN1479718A - Aryl and heteroarylcyclopropyl oximie ethers and their use as fungicides

Info

Publication number: CN1479718A
Application number: CNA018203086A
Authority: CN
Inventors: R・小罗斯; R·小罗斯; 源; D·V·源; 沙别尔; S·H·沙别尔
Original assignee: Dow AgroSciences LLC
Current assignee: Corteva Agriscience LLC
Priority date: 2000-12-08
Filing date: 2001-12-07
Publication date: 2004-03-03
Also published as: EP1347952A1; JP2004515486A; MXPA03005093A; EP1347952A4; BR0116471A; KR20030059315A; AU2002229049A1; WO2002046142A1

Abstract

The present invention relates to certain cyclopropyl oxime ether compounds having substituted aryl and heterocyclic substituents, compositions containing these compounds, and methods for controlling fungi by the use of a fungitoxic effective amount of these compounds. The compounds and possess broad spectrum fungicidal properties.

Description

Aryl and heteroaryl cyclopropyl oximidoether and as the purposes of mycocide

The present invention requires the right of priority of the U.S. Provisional Application 60/254,120 of application on December 8th, 2000.

The present invention relates to some aryl cyclopropyl oxime ether compound, comprise these compound compositions and use the method for these compound control fungies of fungitoxicity significant quantity.

At United States Patent (USP) 5,824, the compound with some oxime ether structure is disclosed in 705.We have found that one group has the aryl with replacement of wide spectrum fungicide performance and the cyclopropyl oximidoether of heterocyclic moiety.

Cyclopropyl oximidoether of the present invention has formula (I)

Wherein:

A is hydrogen, halogen, cyano group, (C ₁-C ₁₂) alkyl or (C ₁-C ₁₂) alkoxyl group;

R ₁Be (C ₁-C ₁₂) alkyl or halo (C ₁-C ₁₂) alkyl;

R ₂Be hydrogen, (C ₁-C ₁₂) alkyl, halo (C ₁-C ₁₂) alkyl, (C ₃-C ₇) cycloalkyl, halo (C ₃-C ₇) cycloalkyl, (C ₂-C ₈) alkenyl, halo (C ₂-C ₈) alkenyl, (C ₂-C ₈) alkynyl, halo (C ₂-C ₈) alkynyl or cyano group;

R ₃Be hydrogen;

R ₄And R ₅Be hydrogen, (C independently ₁-C ₁₂) alkyl, halo (C ₁-C ₁₂) alkyl, (C ₃-C ₇) cycloalkyl, halo (C ₃-C ₇) cycloalkyl, (C ₂-C ₈) alkenyl, halo (C ₂-C ₈) alkenyl, (C ₂-C ₈) alkynyl, halo (C ₂-C ₈) alkynyl, halogen, cyano group or (C ₁-C ₄) alkoxy carbonyl;

Wherein:

A) R ₇Be aryl, arylalkyl, heterocycle or heterocycle (C ₁-C ₄) alkyl, wherein aryl or heterocycle are replaced by 2-5 substituting group, and wherein all are substituted with cyclopropyl ring key position adjacent on aryl or the heterocycle; And R ₆Be hydrogen, (C ₁-C ₁₂) alkyl, halo (C ₁-C ₁₂) alkyl, (C ₃-C ₇) cycloalkyl, halo (C ₃-C ₇) cycloalkyl, (C ₂-C ₈) alkenyl, halo (C ₂-C ₈) alkenyl, (C ₂-C ₈) alkynyl, halo (C ₂-C ₈) alkynyl, halogen, cyano group or (C ₁-C ₄) alkoxy carbonyl; Perhaps

B) R ₇Be aryl, arylalkyl, heterocycle or heterocycle (C ₁-C ₄) alkyl, wherein aryl or heterocycle are not substituted or are replaced by 1-4 substituting group, and wherein at least one and cyclopropyl ring key position adjacent are hydrogen on aryl or the heterocycle; And R ₆Be hydrogen, (C ₁-C ₁₂) alkyl, halo (C ₁-C ₁₂) alkyl, (C ₃-C ₇) cycloalkyl, halo (C ₃-C ₇) cycloalkyl, (C ₂-C ₈) alkenyl, halo (C ₂-C ₈) alkenyl, (C ₂-C ₈) alkynyl, halo (C ₂-C ₈) alkynyl, halogen, cyano group or (C ₁-C ₄) alkoxy carbonyl;

With their salt, title complex, enantiomorph, steric isomer and composition thereof.

Above-mentioned (C ₁-C ₁₂) alkyl, (C ₂-C ₈) alkenyl, (C ₂-C ₈) alkynyl and (C ₃-C ₇) cycloalkyl can choose wantonly and independently by at the most 3 be selected from nitro, halogenated methyl, (C ₁-C ₄) substituting group of alkoxy carbonyl and cyano group replaces.

The term alkyl comprises the side chain and the straight chained alkyl of 1-12 carbon atom.Typical alkyl is methyl, ethyl, n-propyl, different-propyl group, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, iso-octyl, nonyl, decyl, undecyl, dodecyl etc.The term haloalkane refers to by the alkyl of 1-3 halogen replacement.

The term alkenyl refers to the alkene unsaturated alkyl, and described group is a straight or branched, has chain length and 1 or 2 ethylene linkage of 2-8 carbon atom.The term halogenated alkenyl refers to by the alkenyl of 1-3 halogen atom replacement.The term alkynyl refers to unsaturated alkyl, and described group is a straight or branched, has chain length and 1 or 2 acetylene bond of 2-8 carbon atom.

Term aryl comprises phenyl and naphthyl, described group can by at the most 5 be independently selected from following substituting group and replace: halogen, cyano group, nitro, trihalomethyl group, three halogenated methoxies, phenyl, phenoxy group, (C ₁-C ₄) alkyl, (C ₃-C ₇) cycloalkyl, (C ₂-C ₈) alkenyl, (C ₁-C ₄) alkoxyl group, (C ₁-C ₄) alkylthio, (C ₁-C ₄) alkyl sulfoxide, halo (C ₁-C ₄) alkyl, halo (C ₁-C ₄) alkoxyl group, halo (C ₃-C ₇) cycloalkyl, halo (C ₂-C ₈) alkenyl or (C ₁-C ₄) alkoxy carbonyl.At least one and cyclopropyl ring key position adjacent are included but not limited to 2-chlorine by the typical phenyl substituent that hydrogen replaces on the phenyl ring, 3-chlorine, 4-chlorine, the 2-fluorine, the 3-fluorine, the 4-fluorine, the 2-bromine, the 3-bromine, the 4-bromine, the 2-methyl, the 3-methyl, the 4-methyl, the 2-trifluoromethyl, 3 trifluoromethyls, the 4-trifluoromethyl, the 2-methoxyl group, the 3-methoxyl group, the 4-methoxyl group, 2 trifluoromethoxies, the 3-trifluoromethoxy, the 4-trifluoromethoxy, 2-cyano group, 3-cyano group, 4-cyano group, 2, the 3-dichloro, 2, the 3-difluoro, 2, the 3-dibromo, 2, the 3-dimethyl, 2, the 3-dimethoxy, 2,3-pair-(trifluoromethyl), 2,3-pair-(trifluoromethoxy), 2, the 4-difluoro, 2, the 4-dichloro, 2,4 dibromos, 2, the 4-dimethyl, 2, the 4-dimethoxy, 2,4-two (trifluoromethyl), 2,4-pair-(trifluoromethoxy), 2, the 5-difluoro, 2, the 5-dichloro, 2, the 5-dibromo, 2, the 5-dimethyl, 2,5 dimethoxys, 2,5-two (trifluoromethyl), 2,5-pair-(trifluoromethoxy), 3, the 4-difluoro, 3,4 dichloros, 3, the 4-dibromo, 3, the 4-dimethyl, 3, the 4-dimethoxy, 3,4-two (trifluoromethyl), 3,4-pair-(trifluoromethoxy), 3, the 5-difluoro, 3, the 5-dichloro, 3, the 5-dibromo, 3, the 5-dimethyl, 3,5-pair-(trifluoromethyl), 3,5-two (three fluoro-methoxyl groups), 2,3, the 4-trifluoro, 2,3, the 4-trichlorine, 2,3,4 tribromos, 2,3, the 4-trimethylammonium, 2,3, the 4-trimethoxy, 2,3,4-three (trifluoromethyl), 2,3,4 three (trifluoromethoxies), 2,3, the 5-trifluoro, 2,3, the 5-trichlorine, 2,3, the 5-tribromo, 2,3, the 5-trimethylammonium, 2,3,5-three (trifluoromethyl), 2,3,5-three (trifluoromethoxy), 2,4, the 5-trifluoro, 2,4, the 5-trichlorine, 2,4, the 5-tribromo, 2,4, the 5-trimethylammonium, 2,4, the 5-trimethoxy, 2,4,5-three (trifluoromethyl), 2,4,5 three (trifluoromethoxies), 3,4, the 5-trifluoro, 3,4, the 5-trichlorine, 3,4, the 5-tribromo, 3,4, the 5-trimethylammonium, 3,4, the 5-trimethoxy, 3,4,5-three (trifluoromethyl), 3,4,5-three (trifluoromethoxy), 2,3,4, the 5-tetrafluoro, 2,3,4, the 5-tetrachloro, 2,3,4, the 5-tetrabromo, 2,3,4, the 5-tetramethyl-, 2,3,4, the 5-tetramethoxy, 2,3,4,5-four (trifluoromethyl) and 2,3,4,5-four (tetrafluoro methoxyl group.

On the phenyl ring two with all substituted typical phenyl substituent of cyclopropyl ring key position adjacent include but not limited to 2,6 dichloros, 2,3, the 6-trichlorine, 2,4, the 6-trichlorine, 2, the 6-difluoro, 2,3, the 6-trifluoro, 2,4, the 6-trifluoro, 2, the 6-dibromo, 2,3, the 6-tribromo, 2,4,6-tribromo 2,3,4, the 6-tetrachloro, 2,3,5, the 6-tetrachloro, 2,3,4,5, the 6-pentachloro-, 2,3,4, the 6-tetrabromo, 2,3,5, the 6-tetrabromo, 2,3,4,5, the 6-pentabromo-, 2,3,4, the 6-tetrafluoro, 2,3,5, the 6-tetrafluoro, 2,3,4,5,6-five fluorine, 2, the 6-dimethyl, 2,3, the 6-trimethylammonium, 2,4, the 6-trimethylammonium, 2, the 6-dimethoxy, 2,3, the 6-trimethoxy, 2,4, the 6-trimethoxy, 2, the 6-diethoxy, 2,3, the 6-triethoxy, 2,4, the 6-triethoxy, 2,3,4, the 6-tetramethyl-, 2,3,5, the 6-tetramethyl-, 2,3,4,5, the 6-pentamethyl-, 2,3,4, the 6-tetramethoxy, 2,3,5, the 6-tetramethoxy, 2,3,4,5, the 6-pentamethoxyl, 2,3,4, the 6-tetraethoxy, 2,3,5, the 6-tetraethoxy, 2,3,4,5,6-five oxyethyl groups, 2, the 6-dicyano, 2,3, the 6-tricyano, 2,4, the 6-tricyano, 2, the 6-dinitrobenzene, 2, the 6-phenylbenzene, 2,6-two phenoxy groups, 2, the 6-dibenzyl, 2,6-two (trifluoromethyl), 2,3,6-three (trifluoromethyl), 2,4,6-three-(trifluoromethyl), 2,3,4,6-four (trifluoromethyl), 2,3,5,6-four (trifluoromethyl), 2,3,4,5,6-five (trifluoromethyl), 2,6-pair-(trifluoromethoxy), 2,3,6-three (trifluoromethoxy), 2,4,6-three (trifluoromethoxy), 2,3,4,5-four (trifluoromethoxy), 2,3,4,6-four-(trifluoromethoxy), 2,3,5,6-four (trifluoromethoxy), 2,3,4,5,6-five (trifluoromethoxy), 2 bromo-6-chlorine, 2-bromo-6-fluorine, 2-bromo-6-(trifluoromethyl), 2-bromo-6-methyl, 2-bromo-6-methoxyl group, 2-bromo-6-(trifluoromethoxy), 2-bromo-6-cyano group, 2-chloro-6 fluorine, 2-chloro-6-(trifluoromethyl), 2-chloro-6-methyl, 2-chloro-6-methoxyl group, 2 chloro-6-trifluoromethoxies), 2-chloro-6-cyano group, 2-fluoro-6-(trifluoromethyl), 2-fluorine 6-methyl, 2-fluoro-6-methoxyl group, 2-fluoro-6-(trifluoromethoxy), 6-cyano group-2-fluorine, 2 methyl-6-(trifluoromethyl), 6-methoxyl group-2-methyl, 2-methyl-6-(trifluoromethoxy), 6 cyano group-2-methyl, 3,6-two chloro-2-fluorine, 3-chloro-2, the 6-difluoro, 4-chloro-2, the 6-difluoro, 2 bromo-3, the 6-dichloro, 2,3-two bromo-6-chlorine, 3-chloro-2, the 6-dibromo, 2,6-two chloro-3 fluorine, 2,3-two chloro-6-fluorine, 2-chloro-3, the 6-difluoro, 3-bromo-2, the 6-dichloro, 3-bromine 2, the 6-fluorine, 3-bromo-6-chloro-2-fluorine, 2-bromo-5-chloro-6-fluorine, 2,6-two bromo-3 fluorine, 2,5-two bromo-6-fluorine, 2,4-two chloro-6-fluorine, 2,6-chloro-4-fluorine, 2,4, two chloro-6-bromines, 2,6-two chloro-4-bromines, 2,4-two fluoro-6-chlorine, 2,4-two fluoro-6-bromines, 2,6-two fluoro-4-bromines, 2,4-two bromo-6-fluorine, 2,4-two bromo-6-chlorine, 2,6-two bromo-4 chlorine, 2,6-two bromo-4-fluorine, 2,4-two chloro-6-methyl, 2,6-two chloro-4-methyl, 2-chlorine 4, the 6-dimethyl, 4-chloro-2, the 6-dimethyl, 2,4-two fluoro-6-methyl, 2,6-two fluoro-4-methyl, 2 fluoro-4, the 6-dimethyl, 4-fluoro-2, the 6-dimethyl, 2,4-two bromo-6-methyl, 2,6-two bromo-4 methyl, 2-bromo-4, the 6-dimethyl, 4-bromo-2, the 6-dimethyl, 2,4-two chloro-6-methoxyl groups, 2,6 two chloro-4-methoxyl groups, 2-chloro-4, the 6-dimethoxy, 4-chloro-2, the 6-dimethoxy, 2,4-two fluoro-6 methoxyl groups, 2,6-two fluoro-4-methoxyl groups-, 2-fluoro-4, the 6-dimethoxy, 4-fluoro-2, the 6-dimethoxy, 2,4-two bromo-6-methoxyl groups, 2,6-two bromo-4-methoxyl groups, 4-bromo-2, the 6-dimethoxy, 4-bromine 2, the 6-dimethoxy, 2,4-two chloro-6-(trifluoromethyl), 2,6-two chloro-4-(trifluoromethyl), 2 chloro-4,6-two (trifluoromethyl), 4-chloro-2,6-two (trifluoromethyl), 2,4-two fluoro-6 (trifluoromethyl), 2,6-two fluoro-4-(trifluoromethyl), 2-fluoro-4,6-two (trifluoromethyl), 4-fluoro-2,6-two (trifluoromethyl), 2,4-two bromo-6-(trifluoromethyl), 2,6-two bromo-4-(trifluoromethyl), 2-bromo-4,6-two (trifluoromethyl), 4-bromo-2,6-two (trifluoromethyl), 2-chloro-4,6-two (trifluoromethoxy), 4-chloro-2,6-two (trifluoromethoxy), 2,4-difluoro 6-(trifluoromethoxy), 2,6-two fluoro-4-(trifluoromethoxy), 2-fluoro-4,6-two (trifluoromethoxy), 4-fluoro-2,6-two (trifluoromethoxy), 2,4-two bromo-6-(trifluoromethoxy), 2,6 two bromo-4-(trifluoromethoxy), 2-bromo-4,6-two (trifluoromethoxy), 4-bromo-2,6-two (trifluoromethoxy), 4,6-two chloro-2-nitros, 4,6-two bromo-2-nitros, 4,6-two fluoro-2-nitros, 2,6-two chloro-4-nitros, 2-bromo-3,4, the 6-trichlorine, 6-fluoro-2,4, the 5-trichlorine, 6-chlorine 2,4, the 5-tribromo, 6-fluoro-2,4, the 5-tribromo, 2-bromo-3,4, the 6-trifluoro, 2-chloro-3,4, the 6-trifluoro, 6-methyl-2,4, the 5-trichlorine, 6-methyl-2,4, the 5-tribromo, 6-methyl-2,4, the 5-trifluoro, 6-(trifluoromethyl)-2,4, the 5-trichlorine, 6-(trifluoromethyl)-2,4, the 5-tribromo, 2-(three fluoro-methyl)-3,4, the 6-trifluoro, 6-(trifluoromethoxy)-2,4, the 5-tribromo, 2-(trifluoromethoxy) 3,4, the 6-trifluoro, 6-(trifluoromethoxy)-2,4, the 5-trichlorine, 2-bromo-3,5, the 6-trichlorine, 6 fluoro-2,3, the 5-trichlorine, 6-chloro-2,3, the 5-tribromo, 6-fluoro-2,3, the 5-tribromo, 2-bromine 3,5, the 6-trifluoro, 2-chloro-3,5, the 6-trifluoro, 6-methyl-2,3, the 5-trichlorine, 6-methyl-2,3,5 tribromos, 2-methyl-3,5, the 6-trifluoro, 2,3,5-three chloro-6-trifluoromethyls, 2,3,5-three bromo-6-(trifluoromethyl), 3,5,6-three fluoro-2-(trifluoromethyl), 3,5,6-three chloro-2-trifluoromethoxies, 2,3,5-three bromo-6-trifluoromethoxies, 3,5,6-three fluoro-2-trifluoromethoxies, 4 bromo-2,3,5, the 6-tetrachloro, 4-fluoro-2,3,5, the 6-tetrachloro, 4-chloro-2,3,5, the 6-tetrabromo-, 4-fluoro-2,3,5, the 6-tetrabromo, 4-chloro-2,3,5, the 6-tetrafluoro, 4-bromo-2,3,5, the 6-tetrafluoro, 2-bromo-3,4,5, the 6-tetrachloro, 6-fluoro-2,3,4, the 5-tetrachloro-, 2-chloro-3,4,5,6 tetrafluoros, 2-bromo-3,4,5, the 6-tetrafluoro, 2-chloro-3,4,5, the 6-tetrabromo, 2-fluoro-3,4,5, the 6-tetrabromo, 4-methyl-2,3,5, the 6-tetrachloro, 4-methyl-2,3,5, the 6-tetrabromo, 4-methyl 2,3,5, the 6-tetrafluoro, 2,3,5,6-tetrachloro-4-(trifluoromethyl), 2,3,5,6-tetrabromo-4-(trifluoromethyl), 2,3,5,6-tetrafluoro-4-(trifluoromethyl), 2,3,5,6-tetrachloro-4-(trifluoromethoxy), 2,3,5,6-tetrabromo-4-(trifluoromethoxy), 2,3,5,6-tetrafluoro-4-(trifluoromethoxy), 6-methyl-2,3,4, the 5-tetrachloro, 6-methyl-2,3,4, the 5-tetrabromo, 2 methyl-3,4,5, the 6-tetrafluoro, 2,3,4,5-tetrachloro-6-(trifluoromethyl), 2,3,4,5-tetrabromo 6-(trifluoromethyl), 3,4,5,6-tetrafluoro-2-(trifluoromethyl), 2,3,4,5-tetrachloro-6 (trifluoromethoxy), 2,3,4,5-tetrabromo-6-(trifluoromethoxy) and 3,4,5,6-tetrafluoro-2-(trifluoromethoxy).

The term heterocycle refer to be selected from 3-or 4-pyridyl, 5-pyrimidyl, 3-pyridazinyl replacement 6 yuan of unsaturated rings or be selected from 5 yuan of unsaturated rings of 3-thienyl, 3-furyl, 3-pyrryl, 4-isoxazolyl, 4-isothiazolyl or 4-pyrazolyl, wherein two positions adjacent with cyclopropyl rings all are substituted on the heterocycle, and this ring is independently selected from following substituting group replacement by 2-4: (C ₁-C ₄) alkyl, (C ₃-C ₇) cycloalkyl, trihalomethyl group, three halogenated methoxies, halogen, cyano group, (C ₁-C ₄) alkoxy carbonyl, nitro, phenyl and phenoxy group.The term heterocycle refers to that also that replace or unsubstituted 6 yuan unsaturatedly contain 1,2 or 3 heteroatoms, preferred 1,2 or 3 heteroatomic ring that is independently selected from oxygen, nitrogen and sulphur, or 5 yuan unsaturatedly contain 1,2 or 3 heteroatoms, preferred 1 or 2 heteroatomic ring that is independently selected from oxygen, nitrogen and sulphur, wherein said heterocycle is not substituted or is replaced by 1-3 substituting group, and wherein at least one and cyclopropyl ring key position adjacent are the hydrogen substituting group on the heterocycle.The heterocyclic example includes but not limited to 2-, 3-or 4-pyridyl, pyrazinyl, 4-or 5-pyrimidyl, pyridazinyl, pyrazoles, imidazolyl, 2 or 3-thienyl, 2 or 3-furyl, 3-pyrryl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazole base and thiadiazolyl group.These rings can be chosen wantonly and are independently selected from following substituting group by 1-3 at the most and replace: (C ₁-C ₄) alkyl, (C ₃-C ₇) cycloalkyl, trihalomethyl group, halogen, cyano group, (C ₁-C ₄) alkoxy carbonyl, nitro, phenyl and phenoxy group.

The term aryl alkyl is used to describe a kind of group, and wherein alkyl chain is 1-10 carbon atom and can is side chain or straight chain, preferably straight chain, the wherein terminal portions of the aryl moiety of above definition formation arylalkyl part.Partly optional benzyl, styroyl, hydrocinnamyl and the benzene butyl part of typical arylalkyl for replacing.

On the phenyl ring at least one be attached to the typical benzyl moiety that the methylene radical position adjacent on the cyclopropyl rings replaced by hydrogen and include but not limited to 2-benzyl chloride base, 3-benzyl chloride base, 4-benzyl chloride base, the 2-luorobenzyl, the 3-luorobenzyl, the 4-luorobenzyl, the 2-bromobenzyl, the 3-bromobenzyl, the 4-bromobenzyl, the 2-trifluoromethyl benzyl, the 3-trifluoromethyl benzyl, 4 trifluoromethyl benzyls, the 2-methyl-benzyl, the 3-methyl-benzyl, 4-methyl-benzyl 2, the 3-difluorobenzyl, 2, the 3-dichloro benzyl, 2, the 3-dibromo-benzyl, 2, the 3-dimethyl benzyl, 2, the 4-difluorobenzyl, 2, the 4-dichloro benzyl, 2, the 4-dibromo-benzyl, 2, the 4-dimethyl benzyl, 2, the 5-difluorobenzyl, 2, the 5-dichloro benzyl, 2, the 5-dibromo-benzyl, 2, the 5-dimethyl benzyl, 3, the 4-difluorobenzyl, 3, the 4-dichloro benzyl, 3, the 4-dibromo-benzyl, 3, the 4-dimethyl benzyl, 3, the 5-difluorobenzyl, 3, the 5-dichloro benzyl, 3, the 5-dibromo-benzyl, 3, the 5-dimethyl benzyl, 2,3, the 4-trifluoro-benzyl, 2,3,4-trichlorine benzyl, 2,3,4-three bromobenzyls and 3,4,5 trichlorine benzyls.Two include but not limited to 2, the 6-dichloro benzyl with all substituted typical benzyl moiety of methylene radical position adjacent that is attached on the cyclopropyl rings on the phenyl ring, 2,3,6-trichlorine benzyl, 2,4,6-trichlorine benzyl, 2, the 6-difluorobenzyl, 2,3, the 6-luorobenzyl, 2,4, the 6-trifluoro-benzyl, 2, two (trifluoromethyl) benzyls of 6-, 2,3,6-three (trifluoromethyl) benzyl, 2,4,6-three (trifluoromethyl) benzyl, 2,3,4,6-tetrachloro benzyl, 2,3,5,6-tetrachloro benzyl, 2,3,4,5,6-pentachloro-benzyl, 2,3,4,6-tetrabromo benzyl, 2,3,5,6-tetrabromo benzyl, 2,3,4,5, the 6-pentabromobenzyl, 2,3,4, the 6-ptfe benzyl, 2,3,5,6-ptfe benzyl and 2,3,4,5, the 6-PFBBR.On the phenyl ring at least one be attached to the styroyl that the ethyl part position adjacent on the cyclopropyl rings replaced by hydrogen and partly include but not limited to 2-(2-chloro-phenyl-) ethyl, 2-(3-chloro-phenyl-) ethyl, 2-(4-chloro-phenyl-) ethyl, 2-(2-fluorophenyl) ethyl, 2-(3-fluorophenyl) ethyl, 2-(4-fluoro-phenyl) ethyl, 2-(2-aminomethyl phenyl) ethyl, 2-(3-aminomethyl phenyl) ethyl, 2-(4-aminomethyl phenyl)-ethyl, 2-(4-trifluoromethyl) ethyl, 2-(2, the 4-dichlorophenyl) ethyl and 2-(3,5 Dimethoxyphenyl) ethyl.Two partly include but not limited to 2-(2, the 6-dichlorophenyl) ethyl with all substituted typical styroyl of ethyl part position adjacent that is attached on the cyclopropyl rings on the phenyl ring, 2-(2,3,6 trichlorophenyl) ethyl, 2-(2,4, the 6-trichlorophenyl) ethyl, 2-(2, the 6-difluorophenyl) ethyl, 2-(2,3, the 6-trifluorophenyl) ethyl, 2-(2,4, the 6-trifluorophenyl) ethyl, 2-(2, the 6-3,5-dimethylphenyl) ethyl, 2-(2,3, the 6-trimethylphenyl) ethyl, 2-(2,4, the 6-trimethylphenyl) ethyl, 2-(2, two (trifluoromethyl) phenyl of 6-) ethyl, 2-(2,3,6-three (trifluoromethyl) phenyl) ethyl, 2-(2,4,6-three (trifluoromethyl) phenyl) ethyl, 2-(2, the 6-Dimethoxyphenyl) ethyl, 2-(2,3, the 6-trimethoxyphenyl) ethyl and 2-(2,4, the 6-trimethoxyphenyl) ethyl.At least one is partly included but not limited to the 3-phenyl propyl with the propyl group part position adjacent that is bonded on the cyclopropyl rings by the typical hydrocinnamyl that hydrogen replaces on the phenyl ring, 3-(2-chloro-phenyl-) propyl group, 3-(3-chloro-phenyl-)-propyl group, 3-(4-chloro-phenyl-) propyl group, 3-(2, the 4-dichlorophenyl) propyl group, 3-(2-fluorophenyl)-propyl group, 3-(3-fluorophenyl) propyl group, 3-(4-fluorophenyl) propyl group, 3-(2-aminomethyl phenyl)-propyl group, 3-(3-aminomethyl phenyl) propyl group, 3-(4-aminomethyl phenyl) propyl group, 3-(4-trifluoromethyl-phenyl) propyl group, 3-(2, the 4-dichlorophenyl) propyl group and 3-(3, the 5-3,5-dimethylphenyl) propyl group.Two partly include but not limited to 3-(2 with all substituted typical hydrocinnamyl of propyl group part position adjacent that is attached on the cyclopropyl rings on the phenyl ring, the 6-dichlorophenyl) propyl group, 3-(2,3, the 6-trichlorophenyl) propyl group, 3-(2,4, the 6-trichlorophenyl) propyl group, 3-(2, the 6-difluorophenyl) propyl group, 3-(2,3, the 6-trifluorophenyl) propyl group, 3-(2,4, the 6-trifluorophenyl) propyl group, 3-(2, the 6-3,5-dimethylphenyl) propyl group, 3-(2,3, the 6-trimethylphenyl) propyl group, 3-(2,4, the 6-trimethylphenyl) propyl group and 3-(2, two (trifluoromethyl) phenyl of 6-) propyl group.On the phenyl ring at least one be attached to the typical benzene butyl that the butyl part position adjacent on the cyclopropyl rings replaced by hydrogen and partly include but not limited to 4-phenyl butyl, 4-(2-chloro-phenyl) butyl, 4-(3-chloro-phenyl-) butyl, 4-(4-chloro-phenyl-) butyl, 4-(2-fluorophenyl)-butyl, 4-(3-fluorophenyl) butyl, 4-(4-fluorophenyl) butyl, 4-(2-aminomethyl phenyl) butyl, 4-(3-aminomethyl phenyl) butyl, 4-(4-aminomethyl phenyl) butyl and 4-(2,4 dichloro benzene base) butyl.Two partly include but not limited to 4-(2 with all substituted typical benzene butyl of butyl part position adjacent that is attached on the cyclopropyl rings on the phenyl ring, the 6-dichlorophenyl) butyl, 4-(2,3, the 6-trichlorophenyl) butyl, 4-(2,4, the 6-trichlorophenyl) butyl, 4-(2, the 6-difluorophenyl) butyl, 4-(2,3, the 6-trifluorophenyl) butyl, 4-(2,4, the 6-trifluorophenyl)-butyl, 4-(2, the 6-3,5-dimethylphenyl) butyl, 4-(2,3, the 6-trimethylphenyl) butyl, 4-(2,4, the 6-trimethylphenyl) butyl and 4-(2, two (trifluoromethyl) phenyl of 6-) butyl.

Halogen or halo comprise iodine, fluorine, bromine and chlorine.

Can prepare the E/Z isomer mixture of the compound of general formula I.These isomer can be separated into independent component by ordinary method.The cyclopropane of the replacement of formula I can prepare cis and trans-isomer(ide) mixture, and described mixture can be separated into independent component by ordinary method.Independent isomeric compound and composition thereof all forms the present invention, and can be used as mycocide and sterilant.

Compound, enantiomorph, salt and title complex that an embodiment preferred of the present invention is formula I, wherein A, R ₄And R ₅Be hydrogen; R ₁And R ₂Be (C independently ₁-C ₄) alkyl; R ₇Be phenyl, phenylalkyl or heterocycle, so be substituted with cyclopropyl ring key position adjacent on phenyl ring and the heterocycle; And R ₆Be selected from hydrogen, (C ₁-C ₁₂) alkyl, halo (C ₁-C ₁₂) alkyl, (C ₃-C ₇) cycloalkyl, halo (C ₃-C ₇) cycloalkyl, (C ₂-C ₈) alkenyl, halo (C ₂-C ₈) alkenyl, (C ₂-C ₈) alkynyl and halo (C ₂-C ₈) alkynyl.

Compound, enantiomorph, salt and title complex that a preferred embodiment of the present invention is formula I, wherein A, R ₄And R ₅Be hydrogen; R ₁And R ₂Be (C independently ₁-C ₄) alkyl; R ₆Be hydrogen or (C ₁-C ₁₂) alkyl; And R ₇Be 2,6-di-substituted-phenyl, 2,3,6-tri-substituted phenyl or 2,4,6-tri-substituted phenyl.

Compound, enantiomorph, salt and title complex that further preferred embodiment of the present invention is formula I, wherein A, R ₄And R ₅Be hydrogen; R ₁And R ₂Be CH ₃R ₆Be hydrogen or (C ₁-C ₄) alkyl; And R ₇Be 2,6-dihalogenated phenyl, 2,3,6 trihalogenated benzene bases or 2,4,6-trihalogenated benzene base.

Second embodiment preferred of the present invention is for being compound, enantiomorph, salt and the title complex of formula I, wherein A, R ₄And R ₅Be hydrogen; R ₁And R ₂Be (C independently ₁-C ₄) alkyl; R ₇Be phenyl, phenylalkyl or heterocycle, wherein at least one and cyclopropyl ring key position adjacent are the hydrogen substituting group on phenyl or the heterocycle; And R ₆Be hydrogen, (C ₁-C ₁₂) alkyl, halo (C ₁-C ₁₂) alkyl, (C ₃-C ₇) cycloalkyl, halo (C ₃-C ₇) cycloalkyl, (C ₂-C ₈) alkenyl, halo (C ₂-C ₈) alkenyl, (C ₂-C ₈) alkynyl or halo (C ₂-C ₈) alkynyl.

The of the present invention second preferred embodiment is for being compound, enantiomorph, salt and the title complex of formula I, wherein A, R ₄And R ₅Be hydrogen; R ₁And R ₂Be CH ₃R ₇Be the phenyl of phenyl, 2-replacement, the phenyl that 3-replaces, the phenyl, 2 that 4-replaces, the dibasic phenyl 2 of 3-, the dibasic phenyl of 4-, 2,5 dibasic phenyl, 3, the dibasic phenyl of 4-, 3,5-is dibasic, 2,3,4-trisubstd phenyl, 2,3,5-trisubstd phenyl, 2,4,5-trisubstd phenyl, 3,4,5-trisubstd phenyl or 2,3,4, the quaternary phenyl of 5-; And R ₆Be hydrogen, (C ₁(C ₁-C ₄) alkyl or halo (C ₁-C ₄) alkyl.

The of the present invention second further preferred embodiment is for being compound, enantiomorph, salt and the title complex of formula I, wherein A, R ₄With Rs be hydrogen; R ₁And R ₂Be CH ₃R ₇Be phenyl, 2-halogenophenyl, 3-halogenophenyl, 4-halogenophenyl, 2,3-dihalogenated phenyl 2,4-dihalogenated phenyl, 2,5-dihalogenated phenyl, 3,4-dihalogenated phenyl, 3,5-dihalogenated phenyl, 2,3,4-trihalogenated benzene base, 2,3,5-trihalogenated benzene base, 2,4,5-trihalogenated benzene base or 3,4,5-trihalogenated benzene base and R ₆Be hydrogen or (C ₁-C ₄) alkyl.

The most preferred embodiment of the present invention is compound, enantiomorph, salt and the title complex of formula II, wherein R ₇Be 2,6-dichlorophenyl, 2,3,6-trichlorophenyl or 2,4,6-trichlorophenyl.

Compound, enantiomorph, salt and title complex that another the most preferred embodiment of the present invention is formula II ', wherein R ₇Be phenyl, 2-chloro-phenyl-, 3-chloro-phenyl-, 4-chloro-phenyl-, 2-fluorophenyl, 3-fluorophenyl or 4-fluorophenyl, and R ₆Be CH ₃

In the compound of the typical formula I that the present invention includes, A, R ₄And R ₅Be hydrogen, and R ₁Be methyl; Described compound comprises the compound about formula III shown in the table 1, wherein R ₂, R ₆And R ₇Define as table 1. Formula III

Formula III

Table 2Compound R ₂ R ₆ R ₇2.1 H H 2-pyridine radicals 2.2 H H 3-pyridine radicals 2.3 H H 4-pyridine radicals 2.4 H H 2-pyrazinyl 2.5 H H 4-pyrimidine radicals 2.6 H H 5-pyrimidine radicals 2.7 H H 3-pyridazinyl 2.8 H H 4-pyridazinyl 2.9 H H 2-furyl 2.1 H H 3-furyl 2.11 H H 2-thienyl 2.12 H H 3-thienyl 2.13 CH₃H 2-pyridine radicals 2.14 CH₃H 3-pyridine radicals 2.15 CH₃H 4-pyridine radicals 2.16 CH₃H 2-pyrazinyl 2.17 CH₃H 4-pyrimidine radicals 2.18 CH₃H 5-pyrimidine radicals 2.19 CH₃H 3-pyridazinyl 2.20 CH₃H 4-pyridazinyl 2.21 CH₃H 2-furyl 2.22 CH₃H 3-furyl 2.23 CH₃H 2-thienyl 2.24 CH₃H 3-thienyl 2.25 CH₃ H 1-CH ₃-3-(1H)- 2.26 CH ₃ H 1-CH ₃-4-(1H)- 2.27 CH ₃H 5-(1H)-pyrazolyl 2.28 CH₃H 4-(1H)-imidazole radicals 2.29 CH₃H 5-(1H)-imidazole radicals 2.30 CH₃H 5-(1H)-pyrazolyl 2.31 CH₃H 3-isothiazolyl 2.32 CH₃H 4-isothiazolyl 2.33 CH₃H 5-isothiazolyl 2.34 CH₃H 4-thiazolyl 2.35 CH₃H 5-thiazolyl 2.36 CH₃H 3-isoxazolyl 2.37 CH₃H 4-isoxazolyl 2.38 CH₃H 5-isoxazolyl 2.39 CH₃H 4-oxazolyl 2.40 CH₃H 5-oxazolyl 2.41 CH₃H 1-methyl-2-(1H)-2.42 CH₃H 1-methyl-3-(1H)-2.43 CH₃H 2-quinolyl 2.44 CH₃H 3-quinolyl 2.45 CH₃H 4-quinolyl 2.46 CH₃H 3-Cl-pyridine-2-base 2.47 CH₃H 2-Cl-pyridin-3-yl 2.48 CH₃H 2-Cl-pyridin-4-yl 2.49 CH₃H 4-Cl-furans-2-base 2.50 CH₃H 2-Cl-furans-3-base 2.51 CH₃ CH ₃2-pyridine radicals 2.52 CH₃ CH ₃3-pyridine radicals 2.53 CH₃ CH ₃4-pyridine radicals 2.54 CH₃ CH ₃2-furyl 2.55 CH₃ CH ₃3-furyl 2.56 CH₃ CH ₃2-thienyl 2.57 CH₃ CH ₃3-thienyl 2.58 C₂H ₅H 2-pyridine radicals 2.59 C₂H ₅H 3-pyridine radicals 2.60 C₂H ₅H 4-pyridine radicals 2.61 C₂H ₅ CH ₃2-furyl 2.62 C₂H ₅ CH ₃3-furyl 2.63 C₂H ₅ CH ₃2-thienyl 2.64 C₂H ₅ CH ₃The positive C of 3-thienyl 2.65₃H ₇The positive C of H 2-pyridine radicals 2.66₃H ₇The positive C of H 3-pyridine radicals 2.67₃H ₇The positive C of H 4-pyridine radicals 2.68₃H ₇ CH ₃The positive C of 2-furyl 2.69₃H ₇ CH ₃The positive C of 3-furyl 2.70₃H ₇ CH ₃The positive C of 2-thienyl 2.71₃H ₇ CH ₃The positive C of 3-thienyl 2.72₄H ₉The positive C of H 2-pyridine radicals 2.73₄H ₉The positive C of H 3-pyridine radicals 2.74₄H ₉The positive C of H 4-pyridine radicals 2.75₄H ₉ CH ₃The positive C of 2-furyl 2.76₄H ₉ CH ₃The positive C of 3-furyl 2.77₄H ₉ CH ₃The positive C of 2-thienyl 2.78₄H ₉ CH ₃The different C of 3-thienyl 2.79₄H ₉H 2-pyridine radicals 2.80 different C₄H ₉H 3-pyridine radicals 2.81 different C₄H ₉H 4-pyridine radicals 2.82 different C₄H ₉ CH ₃The different C of 2-furyl 2.83₄H ₉ CH ₃The different C of 3-furyl 2.84₄H ₉ CH ₃The different C of 2-thienyl 2.85₄H ₉ CH ₃3-thienyl 2.86 cyclopropyl H 2-pyridine radicals 2.87 cyclopropyl H 3-pyridine radicals 2.88 cyclopropyl H 4-pyridine radicals 2.89 cyclopropyl CH₃2-furyl 2.90 cyclopropyl CH₃3-furyl 2.91 cyclopropyl CH₃2-thienyl 2.92 cyclopropyl CH₃3-thienyl 2.93 CN H 2-pyridine radicals 2.94 CN H 3-pyridine radicals 2.95 CN H 4-pyridine radicals 2.96 CN CH₃2-furyl 2.97 CN CH₃3-furyl 2.98 CN CH₃2-thienyl 2.99 CN CH₃3-thienyl 2.100 CF₃H 2-pyridine radicals 2.101 CF₃H 3-pyridine radicals 2.102 CF₃H 4-pyridine radicals 2.105 CF₃ CH ₃2-thienyl 2.106 CF₃ CH ₃3-thienyl 2.107 CH₃ C ₂H ₅2-pyridine radicals 2.108 CH₃ C ₂H ₅3-pyridine radicals 2.109 CH₃ C ₂H ₅4-pyridine radicals 2.110 CH₃ C ₂H ₅2-furyl 2.111 CH₃ C ₂H ₅3-furyl 2.112 CH₃ C ₂H ₅2-thienyl 2.113 CH₃ C ₂H ₅3-thienyl 2.114 CH₃Positive C₃H ₇2-pyridine radicals 2.115 CH₃Positive C₃H ₇3-pyridine radicals 2.116 CH₃Positive C₃H ₇4-pyridine radicals 2.117 CH₃Positive C₃H ₇2-furyl 2.118 CH₃Positive C₃H ₇3-furyl 2.119 CH₃Positive C₄H ₉2-pyridine radicals 2.120 CH₃Positive C₄H ₉3-pyridine radicals 2.121 CH₃Positive C₄H ₉4-pyridine radicals 2.122 CH₃Positive C₄H ₉2-thienyl 2.123 CH₃Positive C₄H ₉3-thienyl 2.124 CH₃Different C₄H ₉2-pyridine radicals 2.125 CH₃Different C₄H ₉3-pyridine radicals 2.126 CH₃Different C₄H ₉4-pyridine radicals 2.127 CH₃Different C₄H ₉2-thienyl 2.128 CH₃Different C₄H ₉3-thienyl 2.129 CH₃Cyclopropyl 2-pyridine radicals 2.130 CH₃Cyclopropyl 3-pyridine radicals 2.131 CH₃Cyclopropyl 4-pyridine radicals 2.132 CH₃Cyclopropyl 2-thienyl 2.133 CH₃Cyclopropyl 3-thienyl 2.134 CF₃ CH ₃2-pyridine radicals 2.135 CF₃ CH ₃3-pyridine radicals 2.136 CF₃ CH ₃4-pyridine radicals 2.134 CF₃ CH ₃2-furyl 2.135 CF₃ CH ₃3-furyl 2.136 CF₃ CH ₃2-thienyl 2.137 CF₃ CH ₃3-thienyl 2.138 CF₃ C ₂H ₅2-pyridine radicals 2.139 CF₃ C ₂H ₅3-pyridine radicals 2.140 CF₃ C ₂H ₅4-pyridine radicals 2.141 CF₃ C ₂H ₅2-furyl 2.142 CF₃ C ₂H ₅3-furyl 2.143 CF₃ C ₂H ₅2-thienyl 2.144 CF₃ C ₂H ₅The 3-thienyl

2.145 CN CH ₃The 2-pyridyl

2.146 CN CH ₃The 3-pyridyl

2.147 CN CH ₃The 4-pyridyl

2.148 CN CH ₃The 2-furyl

2.149 CN CH ₃The 3-furyl

2.150 CN CH ₃The 2-thienyl

2.151 CN CH ₃The 3-thienyl

2.152 CN C ₂H ₅The 2-pyridyl

2.153 CN C ₂H ₅The 3-pyridyl

2.154 CN C ₂H ₅The 4-pyridyl

2.155 CN C ₂H ₅The 2-furyl

2.156 CN C ₂H ₅The 3-furyl

2.157 CN C ₂H ₅The 2-thienyl

2.158 CN C ₂H ₅The 3-thienyl

In the compound of the typical formula I that the present invention comprises, A, R ₄And R ₅Be hydrogen, and R ₁Be methyl; Described compound comprises the compound about formula III shown in the table 3, wherein R ₂, R ₆And R ₇Define as table 3. Formula III

Table 3Compound R ₂ R ₆ R ₇ 3.1 H H 2，6-Cl(Ph) 3.2 H H 2，3，6-Cl(Ph) 3.3 H H 2，4，6-Cl(Ph) 3.4 H H 2，6-Br(Ph) 3.5 H H 2，3，6-Br(Ph) 3.6 H H 2，4，6-Br(Ph) 3.7 H H 2，6-F(Ph) 3.8 H H 2，3，6-F(Ph) 3.9 H H 2，4，6-F(Ph) 3.10 H H 2，6-CH ₃(Ph) 3.11 H H 2，3，6-CH ₃(Ph) 3.12 H H 2，4，6-CH ₃(Ph) 3.13 H H 2，6-CH ₃O(Ph) 3.14 H H 2，3，6-CH ₃O(Ph) 3.15 H H 2，4，6-CH ₃O(Ph) 3.16 CH ₃ H 2，6-Cl(Ph) 3.17 CH ₃ H 2，3，6-Cl(Ph) 3.18 CH ₃ H 2，4，6-Cl(Ph) 3.19 CH ₃ H 2，6-Br(Ph) 3.20 CH ₃ H 2，3，6-Br(Ph) 3.21 CH ₃ H 2，4，6-Br(Ph) 3.22 CH ₃ H 2，6-F(Ph) 3.23 CH ₃ H 2，3，6-F(Ph) 3.24 CH ₃ H 2，4，6-F(Ph) 3.25 CH ₃ H 2，6-CH ₃(Ph) 3.26 CH ₃ H 2，3，6-CH ₃(Ph) 3.27 CH ₃ H 2，4，6-CH ₃(Ph) 3.28 CH ₃ H 2，6-CH ₃O(Ph) 3.29 CH ₃ H 2，3，6-CH ₃O(Ph) 3.30 CH ₃ H 2，4，6-CH ₃O(Ph) 3.31 CH ₃ H 2，6-NO ₂(Ph) 3.32 CH ₃ H 2，6-CN(Ph) 3.33 CH ₃ H 2，3，6-CN(Ph) 3.34 CH ₃ H 2，4，6-CN(Ph) 3.35 CH ₃ H 2，6-Ph(Ph) 3.36 CH ₃ H 2，3，6-PhPh) 3.37 CH ₃ H 2，4，6-Ph(Ph) 3.38 CH ₃ H 2，6-PhO(Ph) 3.39 CH ₃ H 2，3，6-PhO(Ph) 3.40 CH ₃ H 2，4，6-PhO(Ph) 3.41 CH ₃ H 2，6-CF ₃(Ph) 3.42 CH ₃ H 2，3，6-CF ₃(Ph) 3.43 CH ₃ H 2，4，6-CF ₃(Ph) 3.44 CH ₃ H 2，6-CF ₃O(Ph) 3.45 CH ₃ H 2，3，6-CF ₃O(Ph) 3.46 CH ₃ H 2，4，6-CF ₃O(Ph) 3.47 CH ₃ H 2，3，4，6-Cl(Ph) 3.48 CH ₃ H 2，3，5，6-Cl(Ph) 3-49 CH ₃ H 2，3，4，5，6-Cl(Ph) 3.50 CH ₃ H 2，3，4，6-Ph(Ph) 3.51 CH ₃ H 2，3，5，6-Ph(Ph) 3.52 CH ₃ H 2，3，4，5，6-Ph(Ph) 3.53 CH ₃ H 2，3，4，6-PhO(Ph) 3.54 CH ₃ H 2，3，5，6-PhO(Ph) 3.55 CH ₃ H 2，3，4，5，6-PhO(Ph) 3.56 CH ₃ H 2，3，4，6-Br(Ph) 3.57 CH ₃ H 2，3，5，6-Br(Ph) 3.58 CH ₃ H 2，3，4，5，6-Br(Ph) 3.59 CH ₃ H 2，3，4，6-F(Ph) 3.60 CH ₃ H 2，3，5，6-F(Ph) 3.61 CH ₃ H 2，3，4，5，6-F(Ph) 3.62 CH ₃ H 2，3，4，6-CH ₃(Ph) 3.63 CH ₃ H 2，3，5，6-CH ₃(Ph) 3.64 CH ₃ H 2，3，4，5，6-CH ₃(Ph) 3.65 CH ₃ H 2，3，4，6-C ₂H ₅(Ph) 3.66 CH ₃ H 2，3，5，6-C ₂H ₅(Ph) 3.67 CH ₃ H 2，3，4，5，6-C ₂H ₅(Ph) 3.68 CH ₃ H 2，3，4，6-CH ₃O(Ph) 3.69 CH ₃ H 2，3，5，6-CH ₃O(Ph) 3.70 CH ₃ H 2，3，4，5，6-CH ₃O(Ph) 3.71 CH ₃ H 2，3，4，6-CF ₃(Ph) 3.72 CH ₃ H 2，3，5，6-CF ₃(Ph) 3.73 CH ₃ H 2，3，4，5，6-CF ₃(Ph) 3.74 CH ₃ H 2，3，4，6-CF ₃O(Ph) 3.75 CH ₃ H 2，3，5，6-CF ₃O(Ph) 3.76 CH ₃ H 2，3，4，5，6-CF ₃O(Ph) 3.77 CH ₃ H 2，3，4，6-CN(Ph) 3.78 CH ₃ H 2，3，5，6-CN(Ph) 3.79 CH ₃ H 2，3，4，5，6-CN(Ph) 3.80 CH ₃ H 2-Br-6-Cl(Ph) 3.81 CH ₃ H 2-Br-6-F(Ph) 3.82 CH ₃ H 2-Br-6-CH ₃(Ph) 3.83 CH ₃ H 2-Br-6-CF ₃(Ph) 3.84 CH ₃ H 2-Br-6-CH ₃O(Ph) 3.85 CH ₃ H 2-Br-6-CF ₃O(Ph) 3.86 CH ₃ H 2-Br-6-CN(Ph) 3.87 CH ₃ H 2-Cl-6-F(Ph) 3.88 CH ₃ H 2-Cl-6-CH ₃(Ph) 3.89 CH ₃ H 2-Cl-6-CF ₃(Ph) 3.90 CH ₃ H 2-Cl-6-CH ₃O(Ph) 3.91 CH ₃ H 2-Cl-6-CF ₃O(Ph) 3.92 CH ₃ H 2-Cl-6-CN(Ph) 3.93 CH ₃ H 2-F-6-CH ₃(Ph) 3.94 CH ₃ H 2-F-6-CF ₃(Ph) 3.95 CH ₃ H 2-F-6-CH ₃O(Ph) 3.96 CH ₃ H 2-F-6-CF ₃O(Ph) 3.97 CH ₃ H 6-CN，-F(Ph) 3.98 CH ₃ H 2-CH ₃-6-CF ₃(Ph) 3.99 CH ₃ H 6-CH ₃O-2-CH ₃(Ph) 3.100 CH ₃ H 2-CH ₃-6-CF ₃O(Ph) 3.101 CH ₃ H 6-CN-2OMe(Ph) 3.102 CH ₃ H 6-CN-2-CH ₃(Ph) 3.103 CH ₃ H 3，6-Cl-2-F(Ph) 3.104 CH ₃ H 3Cl-2，6-F(Ph) 3.105 CH ₃ H 4-Cl-2，6-F(Ph) 3.106 CH ₃ H 2-Br-3，6-Cl(Ph) 3.107 CH ₃ H 2，3-Br-6-Cl(Ph) 3.108 CH ₃ H 3-Cl-2，6-Br(Ph) 3.109 CH ₃ H 2，6-Cl-3-F(Ph) 3.110 CH ₃ H 2，3-Cl-6-F(Ph) 3.111 CH ₃ H 2-Cl-3，6-F(Ph) 3.112 CH ₃ H 3-Br-2，6-Cl(Ph) 3.113 CH ₃ H 3-Br-2，6-F(Ph) 3.114 CH ₃ H 3-Br-6Cl-2-F(Ph) 3.115 CH ₃ H 2-Br-5-Cl-6-F(Ph) 3.116 CH ₃ H 2，6-Br-3-F(Ph) 3.117 CH ₃ H 2，5-Br-6-F(Ph) 3.118 CH ₃ H 2，4-Cl-6F(Ph) 3.119 CH ₃ H 2，6-Cl-4F(Ph) 3.120 CH ₃ H 2，4-Cl-6-Br(Ph) 3.121 CH ₃ H 2，6-Cl-4-Br(Ph) 3.122 CH ₃ H 2，4-F-6-Cl(Ph) 3.123 CH ₃ H 2，4-F-6-Br(Ph) 3.124 CH ₃ H 2，6-F-4-Br(Ph) 3.125 CH ₃ H 2，4-Br-6-F(Ph) 3.126 CH ₃ H 2，4-Br-6-Cl(Ph) 3.127 CH ₃ H 2，6-Br-4-Cl(Ph) 3.128 CH ₃ H 2，6-Br-4-F(Ph) 3.129 CH ₃ H 2，4-Cl-6-CH ₃(Ph) 3.130 CH ₃ H 2，6-Cl-4-CH ₃(Ph) 3.131 CH ₃ H 2-Cl-4，6-(CH ₃) ₂(Ph) 3.132 CH ₃ H 4-Cl-2，6-(CH ₃) ₂(Ph) 3.133 CH ₃ H 2，4-F-6-CH ₃(Ph) 3.134 CH ₃ H 2，6-F-4-CH ₃(Ph) 3.135 CH ₃ H 2-F-4，6-(CH，)，(Ph) 3.136 CH ₃ H 4-F-2，6-(CH ₃) ₂(Ph) 3.137 CH H 2，4-Br-6-CH ₃(Ph) 3.138 CH ₃ H 2，6-Br-4-CH ₃(Ph) 3.139 CH ₃ H 2-Br-4，6-(CH ₃) ₂(Ph) 3.140 CH ₃ H 4-Br-2，6-(CH ₃) ₂(Ph) 3.141 CH H 2，4-Cl-6-CF ₃(Ph) 3.142 CH ₃ H 2，6-Cl-4-CF ₃(Ph) 3.143 CH ₃ H 2-Cl-4，6-(CF ₃) ₂(ph) 3.144 CH ₃ H 4-Cl-2，6-(CF ₃) ₂(Ph) 3.145 CH ₃ H 2，4-F-6-CF ₃(Ph) 3.146 CH ₃ H 2，6-F-4-CF ₃(Ph) 3.147 CH H 2-F-4，6-(CF ₃) ₂(Ph) 3.148 CH ₃ H 4-F-2，6-(CF ₃) ₂(Ph) 3.149 CH ₃ H 2，4-Br-6-CF ₃(Ph) 3.150 CH ₃ H 2，6-Br-4-CF ₃(Ph) 3.137 CH ₃ H 2-Br-4，6-(CF ₃) ₂(Ph) 3.138 CH ₃ H 4-Br-2，46-(CF ₃) ₂(Ph) 3.139 CH ₃ H 2，4-Cl-6-CF ₃O(Ph) 3.140 CH ₃ H 2，6-Cl-4-CF ₃O(Ph) 3.141 CH ₃ H 2-Cl-4，6-(CF ₃O) ₂(Ph) 3.142 CH ₃ H 4-Cl-2，6-(CF ₃O) ₂(Ph) 3.143 CH ₃ H 2，4-F-6-CF ₃O(Ph) 3.144 CH ₃ H 2，6-F-4-CF ₃O(Ph) 3.145 CH ₃ H 2-F-4，6-(CF ₃O) ₂(Ph) 3.146 CH ₃ H 4-F-2，6-(CF ₃O) ₂(Ph) 3.147 CH ₃ H 2，3-F-6-CF ₃O(Ph) 3.148 CH ₃ H 2，6-F-3-CF ₃O(Ph) 3.149 CH ₃ H 2-F-3，6-(CF ₃O)(Ph) 3.150 CH ₃ H 3-F-2，6-(CF ₃O) ₂(Ph) 3.151 CH ₃ H 2-Br-3，4，6-Cl(Ph) 3.152 CH ₃ H 6-F-2，4，5-Cl(Ph) 3.153 CH ₃ H 6-Cl-2，4，5-Br(Ph) 3.154 CH ₃ H 6-F-2，4，5-Br(Ph) 3.155 CH ₃ H 2-Br-3，4，6-F(Ph) 3.156 CH ₃ H 2-Cl-3，4，6-F(Ph) 3.157 CH ₃ H 6-CH ₃-2，4，5-Cl(Ph) 3.158 CH ₃ H 6-CH ₃-2，4，5-Br(Ph) 3.159 CH ₃ H 6-CH ₃-2，4，5-F(Ph) 3.160 CH ₃ H 6-CF ₃-2，4，5-Cl(Ph) 3.161 CH ₃ H 6-CF ₃-2，4，5-Br(Ph) 3.162 CH ₃ H 6-CF ₃-2，4，5-F(Ph) 3.163 CH ₃ H 6-CF ₃O-2，4，5-Cl(Ph) 3.164 CH ₃ H 6-CF ₃O-2，4，5-Br(Ph) 3.165 CH ₃ H 6-CF ₃O-2，4，5-F(Ph) 3.166 CH ₃ H 2-Br-3，5，6-Cl(Ph) 3.167 CH ₃ H 2-Br-3，5，6-F(Ph) 3.168 CH ₃ H 2-Cl-3，5，6-F(Ph) 3.169 CH ₃ H 6-F-2，3，5-Cl(Ph) 3.170 CH ₃ H 6-Cl-2，3，5-Br(Ph) 3.171 CH ₃ H 6-F-2，3，5-Br(Ph) 3.172 CH ₃ H 6-CH ₃-2，3，5-Cl(Ph) 3.173 CH ₃ H 6-CH ₃-2，3，5-Br(Ph) 3.174 CH ₃ H 2-CH ₃-3，5，6-F(Ph) 3.175 CH ₃ H 6-CF ₃-2，3，5-Cl(Ph) 3.176 CH ₃ H 6-CF ₃-2，3，5-Br(Ph) 3.177 CH ₃ H 2-CF ₃-3，5，6-F(Ph) 3.178 CH ₃ H 6-CF ₃O-2，3，5-Cl(Ph) 3.179 CH ₃ H 6-CF ₃O-2，3，5-Br(Ph) 3.180 CH ₃ H 2-CF ₃O-3，5，6-F(Ph) 3.172 CH ₃ H 4-Br-2，3，5，6-Cl(Ph) 3.173 CH ₃ H 4-F-2，3，5，6-Cl(Ph) 3.174 CH ₃ H 4-Cl-2，3，5，6-Br(Ph) 3.175 CH ₃ H 4-F-2，3，5，6-Br(Ph) 3.176 CH ₃ H 4-Cl-2，3，5，6-FPh) 3.177 CH ₃ H 4-Br-2，3，5，6-F(Ph) 3.178 CH ₃ H 2-Br-3，4，5，6-Cl(Ph) 3.179 CH ₃ H 2-F-3，4，5，6-Cl(Ph) 3.180 CH ₃ H 2-Cl-3，4，5，6-F(Ph) 3.181 CH ₃ H 2-Br-3，4，5，6-F(Ph) 3.182 CH ₃ H 6-Cl-2，3，4，5-Br(Ph) 3.183 CH ₃ H 6-F-2，3，4，5-Br(Ph) 3.184 CH ₃ H 4-CH ₃-2，3，5，6-CI(Ph) 3.185 CH ₃ H 4-CH ₃-2，3，5，6-Br(Ph) 3.186 CH ₃ H 4-CH ₃-2，3，5，6-F(Ph) 3.187 CH ₃ H 4-CF ₃-2，3，5，6-Cl(Ph) 3.188 CH ₃ H 4-CF ₃-2，3，5，6-Br(Ph) 3.189 CH ₃ H 4-CF ₃-2，3，5，6-F(Ph) 3.190 CH ₃ H 4-CH ₃O-2，3，5，6-Cl(Ph) 3.191 CH ₃ H 4-CF ₃O-2，3，5，6-Br(Ph) 3.192 CH ₃ H 4-CF ₃O-2，3，5，6-F(Ph) 3.193 CH ₃ H 4-CF ₃O-2，3，5，6-Cl(Ph) 3.194 CH ₃ H 6-CH ₃-2，3，4，5-Cl(Ph) 3.195 CH ₃ H 6-CH ₃-2，3，4，5-BrPh) 3.196 CH ₃ H 2-CH ₃-3，4，5，6-F(Ph) 3.197 CH ₃ H 6-CF ₃O-2，3，4，5-Cl(Ph) 3.198 CH ₃ H 6-CF ₃O-2，3，4，5-BrPh) 3.199 CH ₃ H 2-CF ₃O-3，4，5，6-F(Ph) 3.200 CH ₃ CH ₃ 2，6-Cl(Ph) 3.201 CH ₃ CH ₃ 2，3，6-Cl(Ph) 3.202 CH ₃ CH ₃ 2，4，6-Cl(Ph) 3.203 CH ₃ CH ₃ 2，6-Br(Ph) 3.204 CH ₃ CH ₃ 2，3，6-Br(Ph) 3.205 CH ₃ CH ₃ 2，4，6-Br(Ph) 3.206 CH ₃ CH ₃ 2，6-F(Ph) 3.207 CH ₃ CH ₃ 2，3，6-F(Ph) 3.208 CH ₃ CH ₃ 2，4，6-F(Ph) 3.209 CH ₃ CH ₃ 2，6-CH ₃(Ph) 3.210 CH ₃ CH ₃ 2，3，6-CH ₃(Ph) 3.211 CH ₃ C ₂H ₅ 2，4，6-CH ₃(Ph) 3.212 CH ₃Positive C₃H ₇ 2，6-Cl(Ph) 3.213 CH ₃Different C₃H ₇ 2，3，6-Cl(Ph) 3.214 CH ₃Positive C₄H ₉ 2，4，6-Cl(Ph) 3.215 CH ₃Different C₄H ₉ 2，6-Cl(Ph) 3.216 CH ₃ CH ₂＝CH 2，3，6-Cl(Ph) 3.217 CH ₃ CH ₃CH＝CH 2，4，6-Cl(Ph) 3.218 CN H 2，6-Cl(Ph) 3.219 CN CH ₃ 2，3，6-Cl(Ph) 3.220 CN C ₂H ₅2,4,6-Cl (Ph), the 3.221 positive C of CN₃H ₇2,6-Cl (Ph), the 3.222 different C of CN₃H ₇2,3,6-Cl (Ph), the 3.223 positive C of CN₄H ₉2,4,6-Cl (Ph), the 3.224 different C of CN₄H ₉ 2，6-Cl(Ph) 3.225 CN CH ₂＝CH 2，3，6-Cl(Ph) 3.226 CN CH ₃CH＝CH 2，4，6-Cl(Ph) 3.227 CF ₃ H 2，6-Cl(Ph) 3.228 CF ₃ CH ₃ 2，3，6-Cl(Ph) 3.229 CF ₃ C ₂H ₅ 2，4，6-Cl(Ph) 3.230 CF ₃Positive C₃H ₇ 2，6-Cl(Ph)

3.231 CF ₃Different C ₃H ₇2,3,6-Cl (Ph)

In the compound of the typical formula I that the present invention comprises, A, R ₄And R ₅Be hydrogen, X is CH, and Z is O, and R ₁Be methyl; Described compound comprises the compound about formula III shown in the table 4, wherein R ₂, R ₆And R ₇Define as table 4. Formula III

Table 4Compound R ₂ R ₆ R ₇4.1 H H 2,4-Cl-pyridin-3-yl 4.2 H H 2,4-F-pyridin-3-yl 4.3 H H 2-Cl-4-F-pyridin-3-yl 4.4 H H 2,4-(CH₃) ₂-pyridin-3-yl 4.5 H H 3,5-Cl-pyridin-4-yl 4.6 H H 3,5-F-pyridin-4-yl 4.7 H H 3-Cl-5-F-pyridin-4-yl 4.8 H H 3,5-(CH₃) ₂-pyridin-4-yl 4.9 H H 4,6-Cl-pyrimidine-5-base 4.10 H H 4,6-F-pyrimidine-5-base 4.11 H H 4,6-(CH₃) ₂-pyrimidine-5-base 4.12 H H 4-Cl-6-F-pyrimidines-5-base 4.13 CH₃H 2,4-Cl-pyridin-3-yl 4.14 CH₃H 2,4-F-pyridin-3-yl 4.15 CH₃H 2-Cl-4-F-pyridin-3-yl 4.16 CH₃ H 2，4-(CH ₃) ₂-pyridin-3-yl 4.17 CH₃H 3,5-Cl-pyridin-4-yl 4.18 CH₃H 3,5-F-pyridin-4-yl 4.19 CH₃H 3-Cl-5-F-pyridin-4-yl 4.20 CH₃ H 3，5-(CH ₃) ₂-pyridin-4-yl 4.21 CH₃H 4,6-Cl-pyrimidine-5-base 4.22 CH₃H 4,6-F-pyrimidine-5-base 4.23 CH₃ H 4，6-(CH ₃) ₂-pyrimidine-5-base 4.24 CH₃H 4-Cl-6-F-pyrimidine-5-base 4.25 CH₃H 3,5-Cl-pyridazine-4-base 4.26 CH₃H 3,5-F-pyridazine-4-base 4.27 CH₃H 3,5-Br-pyridazine-4-base 4.28 CH₃ H 3，5-(CH ₃) ₂-pyridazine-4-base 4.29 CH₃H 3-Cl-5-F-pyridazine-4-base 4.30 CH₃H 5-Cl-3-F-pyridazine-4-base 4.31 CH₃H 3-Br-5-Cl-pyridazine-4-base 4.32 CH₃H 5-Br-3-Cl-pyridazine-4-base 4.33 CH₃H 2,4-Cl-thiene-3-yl-4.34 CH₃H 2,4-F-thiene-3-yl-4.35 CH₃ CH ₃2-Cl-4-F-thiene-3-yl-4.36 CH₃ CH ₃2-F-4-Cl-thiene-3-yl-4.37 CH₃ CH ₃ 2，4-(CH ₃) ₂-thiene-3-yl-4.38 CH₃ CH ₃2,4,5-Cl-thiene-3-yl-, 4.39 CH₃ CH ₃2,4,5-F-thiene-3-yl-, 4.40 CH₃ CH ₃ 2，4，5-CH ₃-thiene-3-yl-4.41 CH₃ CH ₃2,4-Cl-furans-3-base 4.42 CH₃ CH ₃2,4-F-furans-3-base 4.43 CH₃ CH ₃2-Cl-4F-furans-3-base 4.44 CH₃ CH ₃2-F-4Cl-furans-3-base 4.45 CH₃ CH ₃ 2，4-(CH ₃) ₂-furans-3-base 4.46 CH₃ CH ₃2,4,5-Cl-furans-3-base 4.47 CH₃ CH ₃2,4,5-F-furans-3-base 4.48 CH₃ CH ₃ 2，4，5-CH ₃-furans-3-base 4.49 CH₃ CH ₃ 2，4-Cl-1-CH ₃-1H-pyrroles-3-base 4.50 CH₃ CH ₃ 2，4-F-1-CH ₃-1H-pyrroles-3-base 4.51 CH₃ CH ₃ 2-Cl-4F-1-CH ₃-1H-pyrroles-3-base 4.52 CH₃ CH ₃ 2-F-4C ₁-1-CH ₃-1H-pyrroles-3-base 4.53 CH₃ CH ₃3,5-Cl-isoxazole-4-base, 4.54 CH₃ CH ₃3,5-F-isoxazole-4-base, 4.55 CH₃ CH ₃3,5-Br-isoxazole-4-base, 4.56 CH₃ CH ₃ 3，5-CH ₃-isoxazole-4-base 4.57 CH₃ CH ₃ 3，5-CH ₃O-isoxazole-4-base 4.58 CH₃ CH ₃ 3，5-CF ₃O-isoxazole-4-base 4.50 CH₃ CH ₃3,5-Cl-isothiazole-4-base 4.60 CH₃ CH ₃3,5-F-isothiazole-4-base 4.61 CH₃ CH ₃3,5-Br-isothiazole-4-base 4.62 CH₃ CH ₃ 3，5-CH ₃-isothiazole-4-base 4.63 CH₃ CH ₃ 3，5-CH ₃O-isothiazole-4-base 4.64 CH₃ CH ₃ 3，5-CF ₃O-isothiazole-4-base 4.66 CH₃ CH ₃ 3，5-Cl-1-CH ₃-1H-pyrazoles-4-base 4.67 CH₃ CH ₃ 3，5-F-1-CH ₃-1H-pyrazoles-4-base 4.68 CH₃ CH ₃ 3，5-Br-1-CH ₃-1H-pyrazoles-4-base 4.69 CH₃ CH ₃ 3-Cl-5F-1-CH ₃-1H-pyrazoles-4-base 4.70 CH₃ CH ₃2,4-Cl-pyridine-3-base 4.71 CH₃ C ₂H ₅2,4-F-pyridine-3-base 4.72 CH₃Positive C₃H ₇2-Cl-4-F-pyridine-3-base 4.73 CH₃Different C₃H ₇ 2，4-(CH ₃) ₂-pyridine-3-base 4.74 CH₃Positive C₄H ₉3,5-Cl-pyridine-4-base 4.75 CH₃Different C₄H ₉3,5-F-pyridine-4-base 4.76 CH₃ CH ₂=CH 3-Cl-5-F-pyridine-4-base 4.77 CN CH₃CH=CH 2,4-Cl-pyridine-3-base 4.78 CN CH₃2,4-F-pyridine-3-base 4.79 CN CH₃2-Cl-4-F-pyridine-3-base 4.80 CN CH₃ 2，4-(CH ₃) ₂-pyridine-3-base 4.81 CN CH₃3,5-Cl-pyridine-4-base 4.82 CN CH₃3,5-F-pyridine-4-base 4.83 CN CH₃3-Cl-5-F-pyridine-4-base 4.84 CN CH₃4,6-Cl-pyrimidine-5-base 4.85 CN CH₃4,6-F-pyrimidine-5-base 4.86 CN CH₃2,4-Cl-thiophene-3-base 4.87 CN CH₃2,4-F-thiophene-3-base 4.88 CN CH₃2-Cl-4-F-thiophene-3-base 4.89 CN CH₃2-F-4-Cl-thiophene-3-base 4.90 CN CH₃ 2，4-(CH ₃) ₂-thiophene-3-base 4.89 CN CH₃2,4,5-Cl-thiophene-3-base 4.90 CN CH₃2,4,5-F-thiophene-3-base 4.91 CN CH₃ 2，4，5-CH ₃-thiophene-3-base 4.92 CN C₂H ₅2,4-Cl-pyridine-3-base 4.93 positive C of CN₃H ₇2,4-Cl-pyridine-3-base 4.94 different C of CN₃H ₇2,4-Cl-thiophene-3-base 4.95 positive C of CN₄H ₉2,4-F-thiophene-3-base 4.96 different C of CN₄H ₉2-Cl-4-F-thiophene-3-base 4.97 CN CH₂=CH 2-F-4-Cl-thiophene-3-base 4.98 CN CH₃CH＝CH 2，4-(CH ₃) ₂-thiophene-3-base 4.99 CF₃ CH ₃2,4-Cl-pyridine-3-base 4.100 CF₃ CH ₃2,4-F-pyridine-3-base 4.101 CF₃ CH ₃2,4-Cl-thiophene-3-base 4.102 CF₃ CH ₃2,4-F-thiophene-3-base 4.103 CF₃ CH ₃2-Cl-4-F-thiophene-3-base 4.104 CF₃ CH ₃2-F-4-Cl-thiophene-3-base 4.105 CF₃ CH ₃ 2，4-(CH ₃) ₂-thiophene-3-base 4.106 CF₃ CH ₃3,5-Cl-isothiazole-4-base 4.107 CF₃ CH ₃3,5-F-isothiazole-4-base 4.108 CF₃Positive C₃H ₇2,4-Cl-pyridine-3-base 4.109 CF₃Different C₃H ₇2,4-F-pyridine-3-base 4.110 CF₃Positive C₄H ₉3,5-Cl-pyridine-4-base 4.111 CF₃Different C₄H ₉3,5-F-pyridine-4-base

4.112 CF ₃CH ₂=CH 2, the 4-Cl-pyridin-3-yl

4.113 CF ₃CH ₃CH=CH 2, the 4-F-pyridin-3-yl

Used Ph is interpreted as phenyl among the table 1-4.

Prepare compound of the present invention according to following synthetic route.Route A has described the preparation of the compound of formula (I '), wherein A and R ₁-R ₇As show 1-4 definition.With cyclopropyl oxime (V) and the suitable benzyl derivative (IV) (wherein Z is halogen such as bromine, chlorine or iodine) that replaces, preferred benzyl bromide reaction.The oxime that the cyclopropyl of representing with the logical formula V of suitable alkaline purification under the room temperature replaces adds benzyl bromide (IV) then to form negatively charged ion.The typical alkali that uses is metal hydride such as sodium hydride, alkoxide such as sodium methylate, hydroxide bases such as sodium hydride or potassium hydroxide and alkali base such as yellow soda ash and salt of wormwood.The typical solvent that uses with hydride is N, dinethylformamide (DMF) and tetrahydrofuran (THF) (THF); And use with hydroxide bases DMF, THF, methyl ethyl ketone (MEK) and acetone; With use with alkali base solvent such as DMF, acetone and MEK.

Shown in route A, C (R ₂N-O key among the)=N-O-appears at the E position and (supposes

Be large-substituent).Should be realized that the mixture that to produce Z isomer.When producing isomer, they are specified isomer A (higher R on the thin-layer chromatography _f) and isomer B (lower R on the thin-layer chromatography _f).Can determine which isomer, A or B have E or Z geometry by routine techniques such as X ray crystallization or by spectrography such as NMR (Nuclear Magnetic Resonance) spectrum.For compound of the present invention, isomer A has been designated as E oxidation imines configuration, and isomer B is a Z oxidation imines configuration.

Route A

At alkali, preferred NaOH or KOH exist down, at solvent, use methyl N-(2 2-bromomethylphenyl)-N-alkoxy amino manthanoate to carry out alkylation and the compound of preparation formula I in preferred acetone or the methyl ethyl ketone.Particularly, as described in route A (wherein Z is a bromine), methyl N-(2-2-bromomethylphenyl)-N-methoxyl group carbamate (IV) and oxime (V) reaction are obtained the compound of formula I '.As US 5,650,434 is described, prepares N-(2-2-bromomethylphenyl)-N-alkoxy amino methyl-formiate, particularly N-(2-2-bromomethylphenyl)-N-methoxyl group Urethylane (IV, wherein Z is a bromine) in proper order with 4 steps shown in the route B.As described in the above-mentioned european patent application, Ortho Nitro Toluene and ammonium chloride reacted in the presence of zinc obtain N-2-methyl oxyamine (XI), as at Organic Synthesis Collective VolumeIII (organic synthesis collection the 3rd volume), the 668th page is described.With methyl-chloroformate the oxyamine acidylate is obtained N-hydroxyl amino methyl-formiate (XII); this compound uses that alkylation obtains (XIII) such as methyl-sulfate (R is a methyl); with this compound in standard conditions; under the N-bromine succinimide in tetracol phenixin, bromination obtains intermediate product benzyl bromide (XIV) in the presence of catalyzer such as benzoyl peroxide.

Route B

As shown in the route C, can extremely reflux in room temperature by corresponding ring third aldehydes or ketones (X) and hydroxy amine hydrochloric acid salt, under the preferred room temperature, in The suitable solvent such as methyl alcohol and ethanol, reaction obtains the oxime of logical formula V in the presence of suitable alkali such as sodium hydroxide, salt of wormwood or pyridine.At March, Advanced Organic Chemistry (Advanced Organic Chemistry), the 4th edition, 906-907 and and described in the bibliography with the generality of the synthetic oxime of oxyamine and described.When the oxime that obtains as the general formula (III) of cis or anti-oxime mixture of isomers, it can be separated into independent isomer and as described in route A and B, carry out alkylation.When the mixture of the oxime that in route A and B, uses general formula (III), can the compound separation of formula VI, VII and IX be become their independent isomer by the conventional chromatogram technology.

Route C

By routine techniques preparation ring third aldehydes or ketones (X).With the acyl group cyclopropane that reactant salt in unsaturated intermediate product XI (route D) and the sulphur that is prepared in the presence of alkali by dimethyl oxidation sulfonium salt obtains replacing, X is shown in route D.At Trost and Melvin, Sulfur Ylids (sulphur In Salt, press of institute, New York, NY 1975 and Block, Reactions of Organosulfur Compounds (reaction of organosulfur compound), the 91-123 page or leaf, press of institute, the chemistry of sulphur inner salt has been described in New York among the NY 1978.The typical reaction conditions that is formed the sulphur inner salt by dimethyl oxidation sulfonium salt closes use alkali such as oxyhydroxide, metal hydride and alkoxide, and described alkali is in solvent such as glycol dimethyl ether, methyl-sulphoxide and the water, and this depends on used alkali.Be reflected under 0-20 ℃, carry out under preferred 10-15 ℃, preferably use the alkali metal hydroxide in methyl-sulphoxide.Usually, in the presence of powdered sodium hydroxide, at room temperature prepare dimethyl oxidation sulfonium methyl (methylide) by the trimethylammonium sulfoxonium iodide in methyl-sulphoxide.(XI) is added drop-wise to inner salt with undersaturated aldehydes or ketones, and at room temperature stirs.

Route D

α, beta-unsaturated aldehyde or ketone XI can be by conventional condensation technology preparations.At March, Advanced Organic Chemistry (Advanced Organic Chemistry), the 4th edition, α has extensively been described, beta-unsaturated aldehyde or ketone (enones) synthetic in 937-955 page or leaf and the bibliography thereof.For example, Organic Reactions (organic reaction), the 16th volume has been described the general aldol condensation of ketone and aldehyde.For the intermediate product of formula XI of the present invention, ketone and aldehyde are R usually ₇COR ₆(XII) and R ₂COCH ₂R ₃(XIII), R wherein ₂, R ₃, R ₆And R ₇Definition as described above.Work as R ₆During for hydrogen, aldehyde R ₇CHO (XIV) is phenyl aldehyde (aryl CHO) or the heterocyclic aldehydes that replaced by 2-5 substituting group, wherein in formula I, all is substituted with cyclopropyl ring key position adjacent on aryl and heterocycle.The phenyl aldehyde of these replacements or heterocyclic aldehydes are available commercially or are prepared by routine techniques.With aldehyde R ₇CHO (XIV) and ketone R ₂COCH ₂R ₃, XIII, (shown in route E) reaction obtains intermediate product ketone XV.Usually with ketone R ₂COCH ₂R ₃Be dissolved in the hydroxylic solvent,, in this solvent, drip aldehyde R as methyl alcohol or ethanol ₇CHO adds alkali or selectable aldehyde solution in alkali aqueous solution then.The typical alkali that uses can be alkali metal hydroxide, as hydrated barta, potassium hydroxide or sodium hydroxide, and drips under 0-35 ℃, preferably at room temperature carries out.When by acetone (R ₂Be methyl and R ₃Being hydrogen) when deriving ketone, solvent can be an acetone, adds R in this solvent ₇COR ₆, add hydroxide aqueous solution then.Preferably aldehyde is dissolved in acetone: in the solvent mixture of water (1: 5), in this mixture, add alkali when at room temperature stirring.

Route E

Work as R ₆When being not hydrogen, R ₇COR ₆(XII) be ketone aryl COR ₆Or heterocyclic ketone, described group is replaced by 2-5 substituting group, wherein in formula I, on aryl and heterocycle, all be substituted with cyclopropyl ring key position adjacent, perhaps aryl or heterocycle are not substituted or are replaced by 1-4 substituting group, wherein in formula I on aryl or the heterocycle at least one and cyclopropyl ring key position adjacent be hydrogen.About R wherein ₆Be not the compound of the formula I of hydrogen, according to United States Patent (USP) 3,950, the 20th row described method in 427, the 17 hurdles prepares intermediate product unsaturated aldehyde and ketone XI, to obtain E diastereomer (R behind purifying shown in route F ₇R at XI ₂The trans position of CO).In typical preparation, with ketone such as R ₇COR ₆React in the presence of potassium tert.-butoxide with the trans 3-oxyethyl group ethyl crotonate in dimethyl formamide, carry out acid hydrolysis and decarboxylation then and obtain XI.Crotonate, XVI can be by ordinary method by the ethyl Acetolon preparation that replaces.

Route F

Selectively, can prepare α by cyclopropyl nitrile XIV, β-unsaturated cyclopropyl ketone X, the described cyclopropyl nitrile XIV Cyclopropanated preparation by vinyl cyanide XVIII is as described in the route G.Can pass through at March, Advanced Organic Chemistry is (high Organic chemistry), the 4th edition, the conventional synthetic method preparation described in 937-955 and the bibliography thereof is at the vinyl cyanide XVIII raw material shown in the route G.For example, with carbonitrile derivatives R ₃CH ₂CN and ketone or aldehyde R ₇COR ₆Condensation obtains vinyl cyanide XIII in the presence of alkali.Usually nitrile is dissolved in solvent such as the second alcohol and water, in this solvent, adds aldehydes or ketones, add alkali then.Used typical alkali can be alkali metal hydroxide, as hydrated barta, potassium hydroxide or sodium hydroxide, at room temperature stirs the mixture usually.

As described in route D, obtain cyclopropyl nitrile XVII with sulphur inner salt processing vinyl cyanide XVIII.By in nitrile, adding organo-metallic hydrolysis and cyclopropyl nitrile XVII is converted into cyclopropyl ketone then.For example, with standard Grignard reagent R ₂MgX or organolithium reagent R ₂Li is added to nitrile functionality so that ketone X to be provided.At March, Advanced Organic Chemistry is (high Organic chemistry), the 4th edition, the addition reaction of nitrile has been described in the reference of 935-936 page or leaf and citation thereof.Can as using diisobutyl aluminium hydride (DiBAL) cyclopropyl nitrile XVII be converted into cyclopropyl aldehyde X ' (R wherein by the standard method of reducing ₂Be H).At March, Advanced Organic Chemistry (Advanced Organic Chemistry), the 4th edition, described by nitrile reducing in the reference of 919-920 page or leaf and citation thereof and formed aldehyde.

Route G

Route H has shown compound directly synthetic of formula VII or IX.Can be by functionalized cyclopropyl ketone or aldehyde and the XIX condensation of amino oxygen intermediate product and the direct compound of preparation formula VII or IX.At United States Patent (USP) 5,194, the preparation of amino oxygen intermediate product XIX has been described in 662.Prepare the amino oxygen intermediate product in proper order with 2 steps by the following method:, obtain XIX with the hydrazine processing with N-hydroxyphthalimide alkylation IV (wherein X is N).Amino oxygen intermediate product XIX and ketone or aldehyde X condensation are obtained VII, shown in route B, handle this compound and obtain IX.

Route H

Can prepare compound of the present invention according to following method.

Embodiment 1

The preparation of E and Z amino oxygen isomer: ((E) and (Z)-(1-is (anti-for N-methoxyl group-N-[2- Formula-2-phenycyclopropyl) phenyl amino oxygen methyl ethylidene))] preparation of Urethylane

The compound 1.11A and the 1.11B of table 1

The preparation of trans-2-phenycyclopropyl methyl ketone

Pack in the 2000ml round-bottomed flask of being furnished with magnetic stirrer 150g trimethylammonium sulfoxonium iodide (0.685moles, 1.0eq.), the 28g sodium hydroxide powder (0.685moles, 1.0eq.) and 1000ml DMSO.Disposable adding 100g is trans-4-phenyl-3-butene-2-ketone (0.685moles) after, clog flask and at room temperature stirred 15 minutes.Under the room temperature reactant was stirred 5 minutes, pour 500ml water then into, and with 3 * 200ml extracted with diethyl ether.Use 2 * 200ml water and 200ml salt water washing ether extract successively, use anhydrous MgSO ₄Drying is filtered and stripping, separates 94g yellow liquid (86% productive rate) then, is using 300MHz ¹When H NMR analyzes this product trans with target product-the 2-Cyclopropyl Methyl Ketone is consistent.

300MHz， ¹H，CDCl ₃，TMS＝0ppm)：1.3(m，1H)，1.7(m，1H)，2.2(m，1H)，2.3(s，3H)，2.6(m，1H)，7.1(d，2H)，7.2-7.4(m，3H)。

E and Z imine isomer: (E) and (Z) N-methoxyl group-N-(2-((anti-form-1-2-phenyl ring Propyl group) phenyl amino oxygen methyl ethylidene))] Urethylane

Add N-methoxyl group-N-[2-(amino oxygen methyl) phenyl in the 20ml vial] Urethylane (600mg, 2.65mmol), trans-the 2-Cyclopropyl Methyl Ketone (400mg, 2.4mmol) and MeOH (15ml).Under the room temperature mixture stirring of gained is spent the night.By GC and TLC monitoring reaction process.When reacting completely, add entry, make extraction treatment with ether then.Obtain 300mg isomer A by the silicagel column purifying crude product that uses 70: 30 hexane/ethyl acetate solvent mixtures, for (methyl-N-methoxyl group-N-[2-((E)-(1-(trans-2-phenyl ring propyl group) ethylidene) amino oxygen methyl) phenyl] carbamate and 270mg isomer B, be methyl N-methoxyl group-N-[2-((Z)-(1-(trans-2-phenyl ring propyl group)-ethylidene) amino oxygen methyl) phenyl] carbamate, total points is 65% from productive rate.

NMR isomer A:(E)-and isomer: 300MHz, 1H, CDCl ₃, TMS=0ppm): 1.1-1.2 (m, 1H), 1.35-1.45 (m, 1H), 1.75-1.80 (m, 1H), 1.84 (s, 3H), 3.74 (s, 3H), 3.77 (s, 3H), 5.12 (s, 2H), 7.05-7.6 (m, 9H).

NMR isomer B:(Z)-isomer: 300MHz, ₁H, CDCl ₃, TMS=0ppm): 1.2-1.4 (m, 2H), 1.68 (s, 3H), 2.2-2.3 (m, 1H), 1.65-1.75 (m, 1H), 3.65 (s, 3H), 3.72 (s, 3H), 5.11 (s, 2H), 7.0-7.5 (m, 9H) .3.72 (s, 3H), 5.11 (s, 2H), 7.0-7.5 (m, 9H).

N-methoxyl group-N-[2-(amino as intermediate product used in the embodiment of the invention The oxygen methyl) phenyl] preparation of Urethylane

N-methoxyl group-N-[2-(O-phthalic imidine oxygen methyl) phenylcarbamic acid methyl esters

Pack into 8.4g (0.0512moles) N-hydroxyphthalimide, 2.1g (0.0521moles) sodium hydroxide powder and 500ml DMF in the anhydrous 1000ml round-bottomed flask of being furnished with magnetic stirrer and nitrogen inlet.Under the room temperature dark red solution was stirred 20 minutes disposable then adding 20g (0.0512moles) 70% pure N-(2-2-bromomethylphenyl)-N-methoxyl group Urethylane.Under the room temperature reactant stirred and spend the night, impouring 500ml water and stir 1 hour so that white solid to be provided is collected this solid by vacuum filtration, water and hexane wash then.40 ℃ of following vacuum-drying brown solid are spent the night.Separation 17.1g N-methoxyl group-N-methyl [2-(O-phthalic imidine oxygen methyl) phenyl } carbamate, be a kind of pale yellow solid, isolated yield is 94%.

300MHz? ¹H?NMR(CDCl ₃，tms＝0ppm)3.76(s，3H)；3.78(s，3H)；5.25(s，2H)；7.4(m，3H)，7.8(m，5H)。

N-methoxyl group-N-[2-(amino oxygen methyl) phenyl] preparation of Urethylane

Pack in the 250ml round-bottomed flask of being furnished with magnetic stirrer 5g (0.0195moles) N-methoxyl group-N-methyl [2-(O-phthalimide methyl) phenyl] carbamate, 100ml anhydrous methanol and 1.08g (0.0215moles) hydrazine monohydrate.Clogging flask also at room temperature stirs reactant 2 hours.Remove by filter the solid of gained, and rotation stripping filtrate.Pulp resistates in the 150ml anhydrous ether, filtering also, stripping obtains 4.1g N-methoxyl group-N[2-(amino oxygen methyl) phenyl] Urethylane, be a kind of thick yellow liquid, it preserved until needs down in-20 ℃ further synthesize that isolated yield is 93%.

300MHz? ¹H?NMR(CDCl ₃，tms＝0ppm)3.75(s，3H)；3.78(s，3H)；4.75(s，2H)；5.2(bs，2H)，7.35(m，3H)；7.4(m，1H)。

The preparation of N-(2-2-bromomethylphenyl)-N-methoxyl group Urethylane

The preparation of N-2-aminomethyl phenyl oxyamine

Be enclosed in 28.6g (1.0eq., 0.21moles) Ortho Nitro Toluene and 28.7g (2.1eq, 0.44moles) zinc powder bits in the 200ml ethanol in the 1L 3 neck round-bottomed flasks.Reaction soln is heated to 45 ℃, use adds funnel and be added in 13.5g in the 120ml water (1.2eq., 0.25moles) ammonium chloride are 50 ℃-55 ℃ with ice bath control exothermic temperature scope.Analyze monitoring reaction and after 30 minutes, add 7.2g (0.11mole) zinc bits again by glc, be added in 3.3g (0.06moles) ammonium chloride in the 10ml water then.45 minutes aftertreatment reactants by celite vacuum filtration reaction mixture, with the wet block of 50ml washing with alcohol, and obtain orange oil with rotatory evaporator except that desolvating under 30 ℃.300ml ether and 200ml water are added this oil.Separate organic phase, and, use NaCl to destroy emulsion, use anhydrous MgSO with 3 * 200ml water washing ₄Drying, and under 30 ℃, remove ether with rotatory evaporator and obtain the 16.1g product, for a kind of orange oil (62.3% productive rate), it is directly used in next step.

The preparation of N-hydroxy-n-2-aminomethyl phenyl Urethylane

Be enclosed in 16.1g (1.0eq., 0.13moles) N-2-aminomethyl phenyl oxyamine and 16.8g (1.5eq., 0.20moles) sodium bicarbonate bits in the 40ml methylene dichloride in the 250ml 3 neck round-bottomed flasks that under nitrogen atmosphere, stir.(1.05eq, 0.37moles) the methyl-chloroformate bits are added to mixture with 13.1g with valinche under-5 ℃ to+5 ℃.Add the back and under 0 ℃, reaction mixture was stirred 30 minutes, use the GC monitoring reaction then.After 45 minutes, add 100ml methylene dichloride and 100ml water termination reaction, cool off with ice bath simultaneously.With additional 100ml methylene dichloride and treatment reaction thing.Separate organic phase,, and under 30 ℃, obtain the 21.3g crude product except that desolvating, be a kind of orange viscous solid with rotatory evaporator with 3 * 200ml water washing.Grind with the 40ml hexane, and after, obtain the 15.35g product, be a kind of beige solid (65.3% productive rate) with the solid of 3 * 20ml hexane wash gained with the crushing of mortar and mortar.

300MHz, ¹H, CDCl ₃, TMS=0ppm): 2.31 (s, 3H), 3.76 (s, 3H), 7.25-7.26 (m, 4H) and 7.78-7.81 (br, 1H).

The preparation of N-methoxyl group-N-2-aminomethyl phenyl Urethylane

Be enclosed in the 15.25g (1.0eq. in the 30ml methylene dichloride in the 250ml 3 neck round-bottomed flasks that under nitrogen atmosphere, stir, 84.25mmoles) N-hydroxy-n-2-aminomethyl phenyl Urethylane and 17.4g (1.5eq., 0.126moles) the salt of wormwood bits, cause solid mass almost to form immediately.In reaction mixture, add other 150ml methylene dichloride, and press the tongue cutter that big block is divided into agglomerate.Add 12.74g (1.2eq, 0.101moles) methyl-sulfate bits and in the reaction mixture at 40 ℃ of following heated mixt.With the reaction of TLC monitoring after 1 hour and 3 hours, and after 1 hour, add 1.2g (9.5mmole) methyl-sulfate bits.After 3 hours by with in the reactant impouring 250ml water and the termination reaction mixture.Processing reaction thing by the following method: be added to 150 methylene dichloride in the terminated reactant and distribute organic phase,, use anhydrous magnesium sulfate drying with 250ml water washing 3 times.Obtain the 20.8g crude product with rotatory evaporator except that desolvating under 45 ℃, be light brown oil, this oil contains methyl-sulfate.With 10% ammonium hydroxide washing 1.5g crude product, remove methyl-sulfate and obtain the 0.9g product.In 250ml ether, handle the crude product that 19.3g contains the remnants of methyl-sulfate,, use anhydrous magnesium sulfate drying with 3 * 200ml, 10% ammonium hydroxide, 3 * 200ml water washing.Obtain 12.4g and 0.9g with rotatory evaporator except that desolvating under 45 ℃, total amount is that N-methoxyl group-N-2-aminomethyl phenyl Urethylane of 13.3g is a kind of brown/orange oil (81.1% productive rate).

300MHz， ¹H，CDCl ₃，TMS＝0ppm)：2.29(s，3H)，3.73(s，3H)，3.78(s，3H)，7.26(m，4H)

N-2-2-bromomethylphenyl-N-methoxyl group Urethylane

Past at N ₂Be enclosed in 70ml CCl in the 500ml 3 neck round-bottomed flasks under the atmosphere ₄In 12.0g (1.0eq, 61.5mm) N-methoxyl group-N-2-aminomethyl phenyl Urethylane, 12.0g (1.1eq, 67.7mmoles) N-bromine succinimide (NBS) is considered to be worth doing, 36 milligrams of (mg.) 2,2-azepine two (2-methyl propionitriles) (AIBN), and at 77 ℃ down with high-intensity lamp reflux 10 hours.During this period, add other 300mg AIBN and other 3g NBS.The vacuum filtration reaction mixture with 200ml 2.5% acid S-WAT, 200ml 2.5% sodium bicarbonate, 2 * 200ml water washing filtrate, and is used anhydrous magnesium sulfate drying.Obtain the 16.0g product with rotatory evaporator except that desolvating under 40 ℃, be a kind of orange oil (71% purity, 68.0% productive rate).

300MHz， ¹H，CDCl ₃，TMS＝0ppm)：3.79(s，3H)，3.80(s，3H)，4.5(s，2H)，7.2-7.4(m，4H)

Embodiment 2

Preparation E amino oxygen isomer: N-methoxyl group-N-[2-(E-(1-(trans-(2-(4 '- Fluorophenyl)-and the 2-methyl) cyclopropyl) ethylidene) the amino oxygen methyl) phenyl] Urethylane The compound 1.58A of table 1

The preparation of 4-(4-fluorophenyl)-3-amylene-2-ketone

A) The preparation of ethyl-trans-3-oxyethyl group crotonate

Pack into 81.5g (0.626moles) methyl aceto acetate, 95g (0.64moles) triethyl orthoformate and 20 vitriol oils (catalyzer) in the anhydrous 500ml round-bottomed flask of being furnished with magnetic stirrer and nitrogen inlet.Under the room temperature reactant stirring is spent the night.The GC analysis revealed complete reaction of aliquots containig has a principal reaction product.Add excessive slightly (about 40) quinoline with neutralisation of sulphuric acid.The distillation reaction thing obtains 94g ethyl-trans-3-oxyethyl group crotonate under 15mm Hg (85-90 ℃) then, is a kind of clarifying colourless liquid, the crystallization when leaving standstill of this liquid, and isolated yield is 95%.

300MHz? ¹H?NMR(CDCl ₃，tms＝0ppm)1.3(t，3H)；1.33(t，3H)；2.3(s，3H)；3.8(q，2H)；4.14(q，2H)，5.0(s，1H)

B) The preparation of 4-(4-fluorophenyl)-3-amylene-2-ketone

Pack in the 3000ml round-bottomed flask of being furnished with mechanical stirrer, nitrogen inlet and additional funnel 100g (0.72moles) 4 '-acetyl fluoride benzene, 115g (0.72moles) ethyl-trans-3-oxyethyl group crotonate and 500mls anhydrous dimethyl formamide.Then toward disposable adding 89g (0.79g) potassium tert.-butoxide of this solution and 250ml DMF.At room temperature under nitrogen atmosphere, reactant was stirred two days altogether then.Then with reaction mixture impouring 1000ml water, and with 3 * 200ml extracted with diethyl ether aqueous solution to remove any unreacted raw material.With the dense HCl aqueous solution of 6N watery distillate is acidified to pH2 and forms yellow solid then, filter and collect this solid, water, hexane wash and dry air.This solid is resuspended in the dense HCl aqueous solution of 500ml6N, and heated 1 hour down in 50 ℃.TLC and GC analysis revealed do not have not residue of raw material, and form a kind of new product.Mixture aqueous solution is cooled to room temperature, then with its impouring 500ml water, and with 3 * 200ml extracted with diethyl ether.With 2 * 200ml water, 100ml salt water washing ether extract, use anhydrous magnesium sulfate drying, filtration and stripping obtain 82g 4-(4-fluorophenyl)-3-amylene-2-ketone, are a kind of lark liquid, it is 95% trans, 5% cis mixtures of isomers, and overall yield is 65%.

300MHz? ¹H?NMR(CDCl ₃，，tms＝0ppm)2.3(s，3H)；2.5(s，3H)；6.5(s，1H)；7.1(t，2H)，7.5(m，2H)。

The preparation of anti-form-1-methyl isophthalic acid-(4-fluorophenyl)-2-ethanoyl-cyclopropane

Toward the 2000ml round-bottomed flask of being furnished with mechanical stirrer, nitrogen inlet and adding funnel pack into 112g (0.51g) trimethylammonium sulfoxonium iodide, 20.4g (0.51moles) sodium hydroxide powder and the anhydrous DMSO of 500ml.Under the room temperature mixture was stirred 1 hour, be added in 82g (0.0461moles) 4-(4-the fluorophenyl)-3-amylene-2-ketone among the 100ml DMSO then fast.Under the room temperature reactant was stirred 3 days, then with its impouring 200ml frozen water, and with 3 * 200ml extracted with diethyl ether." filtered through silica gel and stripping obtain the thick lark oil of 97g, and this oil is distilled down step by step in 0.2mmHg with 2 * 100ml water, 100ml salt water washing ether extract, to use anhydrous magnesium sulfate drying, by 2.Merge the purest cut and obtain 74g lark liquid, it is about 88% that GC analyzes this purity liquid, remains some accessory impurity.Using 90% hexane/10% ethyl acetate that this material is carried out silica gel chromatography then handles.Merge pure fraction and obtain 37g anti-form-1-methyl isophthalic acid-(4-fluorophenyl)-2-ethanoyl-cyclopropane, be a kind of colourless liquid, isolated yield is 42%.

300MHz’H?NMR(CDCl ₃，tms＝0ppm)1.4(m，1H)；1.45(s，3H)；1.6(m，1H)；2.25(m，1H)，2.35(s，3H)；7.0(t，2H)；7.35(m，2H)

N-methoxyl group-N-[2-(E-(1-(trans-(2-(4 '-fluorophenyl)-2-methyl) cyclopropyl) Ethylidene) phenyl amino oxygen methyl)] preparation of Urethylane

Pack in the 50ml round-bottomed flask of being furnished with magnetic stirrer and nitrogen inlet methyl N-methoxyl group-N-[2-(amino oxygen methyl) phenyl of 0.6g (0.0031moles) anti-form-1-methyl isophthalic acid-(4-fluorophenyl)-2-ethanoyl-cyclopropane and 0.82g (0.0035moles)] carbamate.This mixture is dissolved in the 20ml anhydrous methanol, and adds 2 Glacial acetic acid as catalyzer.Under the room temperature this flask stirred and spend the night, impouring 100ml water then, and with 3 * 100ml extracted with diethyl ether.With 2 * 100ml water, 100ml salt water washing ether extract, use anhydrous magnesium sulfate drying, filtration and stripping obtain the thick brown oil of 1.3g, with 20% ethyl acetate/80% hexane it are carried out silica gel chromatography and handle.Merge pure fraction and stripping and obtain 0.72g N-methoxyl group-N-[2-(E-(1-(trans-(2-(4 '-fluorophenyl)-2-methyl) cyclopropyl) ethylidene) amino oxygen methyl) phenyl] Urethylane, be a kind of clarifying lark liquid, isolated yield is 58%.

300MHz? ¹H?NMR(CDCl ₃，tms＝0ppm)1.1(m，1H)；1.2(s，3H)；1.35(m，1H)；1.85(m，1H)；2.1(s，3H)；3.75(s，3H)；3.8(s，3H)；5.15(s，2H)；7.1(t，2H)，7.35(m，2H)；7.4(m，3H)；7.5(m，1H)

Embodiment 3

Preparation E amino oxygen isomer: ((1-is (trans for E-for N-methoxyl group-N-[2- -2-(2 ', 6 '-dichlorophenyl) cyclopropyl) phenyl amino oxygen methyl ethylidene))] carboxylamine The compound 3.16A of methyl esters table 1

The preparation of 4-(2, the 6-dichlorophenyl)-3-butene-2-ketone

The 26.5g (0.15moles) 2 that packs in the 1000ml round-bottomed flask that is equipped with mechanical stirrer and nitrogen inlet, 6-dichlorobenzaldehyde, 125ml acetone, 600ml water and 9.3g (0.23moles) sodium hydroxide.Under the room temperature mixture was stirred 12 hours.Analyze aliquots containig by GC and show complete reaction.By the solid of vacuum filtration collection gained, with 100ml water, 100ml hexane wash, and 40 ℃ of following vacuum-dryings 3 hours.Separate the 31.4g title compound, 4-(2, the 6-dichlorophenyl)-3-butene-2-ketone is a kind of lark solid, and isolated yield is 98%.

300MHz， ¹H，CDCl ₃，TMS＝0ppm)：2.43(s，3H)；6.80(d，1H)；7.18-7.38(m，1H)；7.4(d，2H)；7.6(d，1H)。

The preparation of anti-form-1-(2.6 dichlorophenyl)-2-ethanoyl-cyclopropane

Toward being furnished with magnetic stirrer, nitrogen inlet and adding pack in the 1000ml round-bottomed flask of funnel 33.2g (0.151moles) trimethylammonium sulfoxonium iodide, 6.1g (0.151moles) sodium hydroxide powder and 300ml DMSO.Under the room temperature mixture was stirred 1 hour, and disposable apace then adding 4-(2, the 6-dichlorophenyl)-3-butene-2-ketone (32.3g, 0.151moles).At room temperature reactant was stirred 10 minutes then, impouring 200ml frozen water subsequently, and with 3 * 100ml extracted with diethyl ether.With 2 * 100ml water, the water washing of 100ml salt, use anhydrous MgSO ₄Drying is by 2 " filtered through silica gel, and obtain the thick lark oil of 31.7g with the rotatory evaporator vacuum concentration, this oil carries out the silica gel chromatography processing with 90% hexane, 10% ethyl acetate.Merge pure fraction and obtain 27.9g anti-form-1-(2,6 dichlorophenyl)-2-ethanoyl-cyclopropane with the rotatory evaporator vacuum concentration, be a kind of free-pouring lark liquid, productive rate is 81%.

300MHz， ¹H，CDCl ₃，TMS＝0ppm)：1.4-1.48(m，1H)；1.78-1.86(m，1H)；2.21-2.30(m，1H)；2.34-2.4(m，1H)；2.41(s，3H)，7.2(m，1H)，7.3(d，2H)。

E amino oxygen isomer: ((1-is (trans for E-for methyl N-methoxyl group-N-[2- -2-(2 ', 6 '-dichlorophenyl) cyclopropyl) phenyl amino oxygen methyl ethylidene))] carboxylamine The preparation of ester

Method according to embodiment 2; use 0.6g (0.00262moles) anti-form-1-(2; 6 dichlorophenyls)-and 2-ethanoyl cyclopropane and 0.7g (0.00288moles) N-methoxyl group-N-[2-(amino oxygen methyl) phenyl] Urethylane obtains 0.6g N-methoxyl group N-[2-((1-is (trans-2-(2 ' for E-; 6 '-dichlorophenyl) phenyl amino oxygen methyl cyclopropyl) ethylidene))] Urethylane, isolated yield is 53%.

300MHz? ¹H?NMR(CDCl ₃，tms＝0ppm)1.2(m，1H)；1.6(m，1H)；1.85(m，1H)；1.9(s，3H)；2.2(m，1H)；3.75(s，3H)；3.8(s，3H)；5.15(s，2H)；7.1(t，2H)，7.35(d，2H)；7.4(m，2H)；7.55(m，1H)

Embodiment 4

Preparation E and Z amino oxygen isomer: ((1-is (trans for E and Z-for N-methoxyl group-N-[2- -2-(4 '-chloro-phenyl-) cyclopropyl) phenyl amino oxygen methyl ethylidene))] Urethylane The compound 1.14A and the 1.14B of table 1

The preparation of 4-(4-chloro-phenyl-)-3-butene-2-ketone

Pack in the 250ml round-bottomed flask 2g (0.0142moles) 4-chlorobenzaldehyde, 10.5ml acetone (0.142moles), 50ml ethanol and 10ml water.After stirring about 1 minute, add 0.27g hydrated barta (0.00142moles), and at room temperature the mixture stirring of gained is spent the night.When reaction is finished, add entry, carry out extraction treatment with ether then.Vacuum is removed ether solvents, and obtains 2.3g 4-(4-chloro-phenyl-)-3-butene-2-ketone, is a kind of brown oil.

The preparation of anti-form-1-(4-chloro-phenyl-)-2-ethanoyl-cyclopropane

100ml DMSO, 3.10g (0.014moles) trimethylammonium sulfoxonium iodide and 0.56g NaOH (0.014moles) pack in the 250ml round-bottomed flask.Mixture with gained under the room temperature stirred 1 hour.Under the room temperature mixture was stirred 1 hour disposable apace then adding 2.3g 4-(4-chloro-phenyl-) 3-butene-2-ketone (0.0128moles).Under the room temperature with the mixture restir of gained 5 minutes, and by the GLC monitoring reaction.When reacting completely, add entry, carry out extraction treatment with ether then.Remove ether solvents under the vacuum and obtain 1.8 grams instead

Formula-1-(4-chloro-phenyl-)-2-ethanoyl-cyclopropane is a kind of brown oil.

E and Z amino oxygen isomer: N-methoxyl group-N-[2-(E and Z-(1-(trans-2-(4 '- Chloro-phenyl-) phenyl amino oxygen methyl cyclopropyl) ethylidene))] preparation of Urethylane

Method according to embodiment 2; use 0.96g (0.0049moles) anti-form-1-(4-chloro-phenyl-)-2-ethanoyl cyclopropane and 1.3g (0.0055moles) N-methoxyl group-N-[2-(amino oxygen methyl) phenyl] Urethylane; elution order with silica gel chromatographic column (20% ethyl acetate, 80% hexane) obtains 0.42g isomer A:N-methoxyl group-N-[2-(E-(1-(trans-2-(4 '-chloro-phenyl-) cyclopropyl) ethylidene) amino oxygen methyl) phenyl] Urethylane and 0.34g isomer B:N-methoxyl group-N-[2-(Z-(1-(trans-2-(4 '-chloro-phenyl-) cyclopropyl) ethylidene) amino oxygen methyl) phenyl] Urethylane.Isolated yield is respectively 21% and 17%.

NMR: isomer A (E amino oxygen isomer) 300MHz ¹H NMR (CDCl ₃, tms=0ppm) 1.1 (m, 1H); 1.5 (m, 1H); 1.8 (m, 1H); 1.85 (s, 3H); 2.2 (m, 1H); 3.7 (s, 3H); 3.75 (s, 3H); 5.1 (s, 2H); 7.0 (d, 2H), 7.2 (d, 2H); 7.4 (m, 3H); 7.5 (m, 1H)

NMR: isomer B (Z amino oxygen isomer) 300MHz ¹H NMR (CDCl ₃, tms=0ppm) 1.1 (m, 1H); 1.3 (m, 1H); 1.65 (s, 3H); 2.2 (m, 1H); 2.7 (m, 1H); 3.65 (s, 3H); 3.7 (s, 3H); 5.1 (s, 2H); 7.0 (d, 2H), 7.3 (d, 2H); 7.4 (m, 3H); 7.5 (m, 1H)

Embodiment 5

Test multiple compound of the present invention to Fungicidally active in the body of following disease.Compound is dissolved in 1: 1 mixture of acetone and methyl alcohol, then the concentration of 2: 1: 1 mixtures (by volume) of water, acetone and methyl alcohol dilution to obtain suiting.Solution is sprayed onto on the plant and dry 2 hours.Inoculate plant with fungal spore then.Each test is used and is sprayed with control plant suitable solvent and that inoculated.About these protection tests, first day inoculation plant after with compound treatment of the present invention.Other technical problem of each test as described below, the test-results of all cpds as herein described represents to various fungies that with compound number # dosage is the 150g/ hectare.These results are disease control percentage of comparing with untreated control group, wherein 100 are evaluated as complete control disease, and 0 control for being evaluated as no disease.The following fungal spore of will testing is applied to test plant:

Wheat leaf rust (WLR)

In the greenhouse, went up cultivation Puccinia recondita (Puccinia recondita) (f sp.Tritici) 12 days in the wheat (Cultivar Fielder) in 7 day age.Spore is collected on the aluminium foil by blade, sieved the purification spore that sieves, stored dry with 250 microns openings.The exsiccant spore used in 1 month.Prepare spore suspension with the exsiccant uredospore, every milliliter of Soltrol oil adds 20mg (9.5 hundred ten thousand spore).Suspension is scattered in gelatine capsule (each capsular capacity is 0.7ml), this capsule monkshood oil fogger.Every plate has 20, and 7 day age Cultivar is housed is 2 square inches jar of Fielder wheat plant, and every plate uses a capsule, waits at least 15 minutes so that oil is evaporated from blade, then plant is placed 24 hours in the Dew chamber.Subsequently plant is placed in the greenhouse, after 12 days disease is estimated.

Wheat glume blight (SNW)

In 20 ℃ of incubators, clever withered septoria musiva (Septoria nodorum) culture on the Czapek-Dox V-8 syrup agar plate was placed 12 hours under illumination, placed in the dark 12 hours, totally 2 weeks.In deionized water, vibrate the aqeous suspension that the part that has fungal material can obtain spore, filter by Cheese cloth.The concentration that the aqeous suspension that contains spore is diluted to spore is every milliliter 3.0 * 10 ⁶Individual spore.With the Devilbiss spraying gun inoculum is scattered on 1 all big wheat plants (Cultivar Fielder), described wheat plant sprayed with fungicide compound in advance.Postvaccinal plant is placed on 20 ℃ Dew chamber, alternately under illumination, placed 12 hours, placed totally 4 days in the dark 12 hours.Then postvaccinal rice shoot was moved in the controlled environment chamber of 20 ℃ and humidity 80% hatching 2 days.With percentage inverse amplification factor record disease controlling valu.

Wheat powdery mildew (WPM)

In temperature being controlled at 18 ℃ chamber, going up in wheat rice shoot (Cultivar Fielder) and to cultivate standing grain powdery mildew (Erysiphe graminis) (f.sp.Tritici).The vibration culturing plants makes the Powdery Mildew spore inoculating on 7 days stem and leaf of Wheat, and this rice shoot sprayed with fungicide compound in advance.Postvaccinal rice shoot is placed on temperature is controlled in 18 ℃ the chamber, irrigate.Inoculate 7 days postevaluation disease control percentage ratio.With percentage inverse amplification factor record disease controlling valu.

Powdery mildew of cucumber (CPM)

In the greenhouse, Siberian cocklebur monofilament shell bacterium (Sphaerotheca fulginea) is placed on the cucumber plant (Cultivar Bush Champion cross-fertilize seed), 5-10 sheet severe infections the cucumber leaf of Powdery Mildew be placed in the glass jar that 500ml water is housed, wherein every 100ml water contains 1 tween 80 (polyoxyethylene list oleate), with the preparation inoculum.Vibrating liquid and leaf filter inoculum by Cheese cloth, with the spray bottle atomizer it are atomized on plant.The counting of spore is 100,000 spores/ml.Plant is positioned over the greenhouse to be infected and inoculates.Inoculate and after 7 days plant is marked, the controlling valu of record disease is as control percentage ratio.

Tomato late blight (TLB)

The culture of phytophthora infestan (Phytophthora infestans) is placed 2-3 week in the agar of the pea modification of green.Water washes out spore from agar, and is scattered in the Devilbiss spraying gun on the leaf of big Pitio hybridization tomato plant of 3 weeks, and this plant was handled with the The compounds of this invention agent that will test in advance.Postvaccinal plant is positioned in 20 ℃ the Dow cell infected 24 hours.Then plant being moved to temperature is 20 ℃, and the controlled environment of humidity 90% is indoor.Disease control situation to plant after 5 days is estimated.

Rice blast (RB)

The culture of Pyricularia oryzae is placed 2-3 week in potato dextrose agar.The water that contains 1 tween 80 with every 100ml water is with spore flush away from agar.Aqueous spore suspension filters by two layers of Cheese cloth, and the spore counting is adjusted to every ml water 5 * 10 ⁵With the Devilbiss spraying gun spore suspension is sprayed on 12 the biggest rice plants (Cultivar M-201).Postvaccinal plant placed in 20 ℃ Dew chamber made its infection in 36 hours.Infect the back plant of inoculation is moved to the greenhouse.Disease control rate to plant after 6 days counts.The disease controlling valu is with the control percentage registration.

Cucumber charcoal seasonal febrile diseases (CA)

In the dark, under 22 ℃, fungal pathogens Curcurbitaceae hair disc spore (Colletotrichum lagenarium) was cultivated 8-14 days in potato dextrose agar (PDA).The spore that makes C.lagmarium with the surface of distilled water flushing plate is by separating among the PDA, and described water is by the yeast extract modification of 05%v/w.The outside surface of fungal colony is pulverized with blunt utensil, to being discharged in the water surrounding to most of sporocyst.Filter spore suspension by Cheese cloth, add the water that more contains yeast extract and regulate the counting of spore until obtaining 3 * 10 ⁶Spore/ml water.Chemically treated cucumber plant is 15 days big (a Cultivar Bush Champion hybrid).Use the hand held pump spray bottle, spore suspension is sprayed at the last leaf surface of plant until overflowing.Plant is placed on the moist cell (12 hours bright, and 12 hours dark) that fluorescence illuminates, totally 48 hours.After this period of infection, plant was placed 3 days in the growth cell of 25 ℃ and 80% humidity.Estimate the disease control of handling plant then.Record disease controlling valu is control percentage ratio.

Tomato incipient wilting disease (TEB)

Make target chain lattice spore (Alternaria solani) culture under room temperature and fluorescence (12 hours bright, 12 hours dark), 2 weeks of growth on V-8 juice agar plate.Be used in the surface of the exuberant agar plate of 0.5% yeast extract solution in the distilled water and obtain the suspension of spore.Scrape the agar plate surface lightly so that spore is released in the liquid with blunt plastic tool.Filter spore suspension by Cheese cloth, spore concentration is adjusted to the every ml of about 80,000 spores.When handling with experimental compound, about 18 days of tomato (Cultivar Patio cross-fertilize seed) is big.After processing, crop was placed in the greenhouse 1 day.After during this, adopt the Devilbiss spraying gun to inoculate freshly prepd spore suspension to plant.Spore suspension is applied to the upper surface of leaf.After the inoculation, plant is placed on indoor the carrying out of 20 ℃ Dew infected in 24 hours.Then crop is transferred in the growth room of 22 ℃ and 80% humidity, continues 3 days.The disease controlling valu is recorded as control percentage ratio.

During with the anti-wheat leaf rust of 150 gram/hectares test, compound 1.11A shows 95% control; And when testing with 100 gram/hectares, compound 1.11B, 1.14A, 1.58A and 3.16A show 95% or better control.

When with the anti-wheat glume blight of 100 gram hectare tests, compound 1.14A, 1.58A and 3.16A show 95% or better control.

When with 150 gram hectare test resist powdery mildew of wheat, compound 1.11A shows 95% control, and when testing with 100 gram/hectares, and compound 1.11B, 1.14A, 1.58A and 3.16A show 80% or better control.

When with the anti-powdery mildew of cucumber of 150 gram hectare tests, compound 1.11A shows 85% control, and when testing with 100 gram/hectares, and compound 1.14A, 1.58A and 3.16A show 80% or better control.

When with the anti-tomato late blight of 150 gram hectare tests, compound 1.11A shows 100% or better control.

When with 150 gram hectare test blast resistings, compound 1.11A shows 95% control, and when testing with 100 gram/hectares, and compound 1.14A, 1.58A and 3.16A show 95% or better control.

When with the anti-cucumber charcoal seasonal febrile diseases of 150 gram hectare tests, compound 1.11A shows 90% control, and when testing with 100 gram/hectares, and compound 1.14A, 1.58A and 3.16A show 80% or better control.

When with the anti-tomato incipient wilting of 150 gram hectare tests when sick, compound 1.11A shows 80% control, and when testing with 100 gram/hectares, and compound 1.14A, 1.58A and 3.16A show 95% or better control.

The present invention can be used as agricultural fungicides, and can be used for the leaf of various spots such as seed, soil or plant to be protected.

The compounds of this invention can be according to ordinary method as mycocidal sprays, as large vol hydraulic atomizing, small volume spraying, air blast spraying, the aerosol spray of routine with dust.The disease that plant that the thinning ratio of using and using is handled than the type that depends on equipment used, the method for using, needs and needs are controlled.The amount of application of common compound of the present invention is extremely approximately 50kg of the about 0.005kg of per hectare, and preferably approximately 0.025kg is to about 25kg activeconstituents.

As seed protectant, the amount of coated toxic agent is normally used than being extremely approximately 20g of the about 0.05g of 100kg seed on the seed, and preferably approximately 0.05g is to about 4g, and more preferably about 0.1g is 1g extremely approximately.As soil mycocide, can dope chemical soil or be applied to soil surface usually, use than being extremely approximately 20kg of the about 0.02kg of per hectare, preferably approximately 0.05kg is to about 10kg, and more preferably about 0.1kg is 5kg extremely approximately.As blade mycocide, usually toxic agent is applied to growing plants, use than being extremely approximately 10kg of the about 0.01kg of per hectare, preferably approximately 0.02kg is to about 5kg, and more preferably about 0.25kg is 1kg extremely approximately.

Because The compounds of this invention demonstrates Fungicidally active, these compounds can be used in combination so that broad spectrum of activity to be provided with other known mycocide.Suitable mycocide includes but not limited to US5, cited mycocide (especially referring to the 14th and 15 hurdles) in 252,594.Other known mycocide that can be used in combination with The compounds of this invention is dimethomorph, white urea cyanogen, thifluzamide, the metalaxyl of barking, ofurace, the spirit of M 9834, Evil frost, Propamocarb, ester bacterium abdomen, fenpiclonil, fludioxonil, phonetic mould glue, phonetic collarium Jiao, Evil bacterium azoles, fluquinconazole, miconazole, spiroxamine, carpropamid, azoxystrobin, kresoxim-methyl, metominostrobin and trifIoxystrobino.

The compounds of this invention can be used with the whole bag of tricks well.Because these compounds have the Fungicidally active of wide spectrum, they can be used for the storage of some cereal, also can be as the cereal that comprises wheat, barley and rye, the mycocide of paddy rice, peanut, soybean and grape also can be used as the mycocide of meadow, fruit, nut, orchard and golf course.

The example of the disease that The compounds of this invention can be prevented and treated comprises that the length of corn and barley is wriggled and embrace to belong to a disease, the Powdery Mildew of wheat and barley, the leaf rust of wheat and stem rust, speckle of barley and leaf rust, the early blight of tomato, the late blight of tomato, leaf spot morning of peanut, uncinula necator, black rot of grape, apple scab, apple mildew, powdery mildew of cucumber, the brown root rot of fruit, grey mold is stiff rotten sick, the soybean Powdery Mildew, cucumber charcoal eqpidemic disease, the withered septoria musiva disease of wheat grain husk, paddy rice strand rot and rice blast.

Also can comprise known agricultural chemical compound according to composition of the present invention and preparation.The activity profile of this expansion preparation, and may improve its synergy.Suitable sterilant known in the art is referring to US5, and 075,471, especially referring to the 14th and 15 hurdles.

The compounds of this invention can composition or the form of preparation use.The example of the preparation of composition and preparation is seen american chemical society publication " Pestcidal FormulationResearch " (1969), Advances in Chemistry Series No.86, editor Wade Van Valkenburg; Marcel Dekker, Inc.publication " Pesticide Formulations ", (1973), Wade Van Valkenburg edits.In these compositions and preparation, chemical substance and conventional inertia agricultural acceptable (be plant compatible and/or the agricultural chemicals inert) all kinds of solid carrier materials or liquid carrier material commonly used in farm chemicals diluent or extender such as pesticide composition or the preparation." the agricultural carrier of accepting " is meant any material of dissolving, dispersive of activeconstituents in composition, and these materials do not reduce the effectiveness of activeconstituents, and itself does not have tangible destruction to the plant or the agricultural environment of soil, equipment, needs.If desired, can be used in combination for example assistant agent of tensio-active agent, stablizer, foam reducing composition and anti-drift agent.

According to the present invention, composition and examples of formulations are the aqueous solution and dispersion agent, oil solution and oil dispersant, paste, the pulvis that dusts, wettable powder, missible oil, flowing agent, granula, bait, inverse emulsion, aerosol composition and the stifling candle of using.Wettable powder, paste, flowing agent and missible oil are concentrate formulations, dilute with water before use or when using.In these preparations,, if desired, can add suitable tensio-active agent with liquid or solid carrier proliferation compound.Bait contains food usually or other can attract the material of insect, wherein comprises a kind of The compounds of this invention at least.

Specifically, under the situation of leaf spray agent, require comprising the assistant agent that uses in the agricultural practice, as wetting agent, spreading agent, dispersion agent, thickening material, tackiness agent etc. usually.The inventory of these assistant agents commonly used in this area all has been discussed in a lot of documents, for example referring to John W.McCutcheon, Inc.publication " Detergents and Emulsifiers, Annual. ".

Active compound of the present invention can use separately; but perhaps can use with the form of mixture another kind of and/or that form with the dispersible carrier of these solids and/or liquid and/or with other known compatible promoting agent; described promoting agent, particularly plant protection product such as other sterilant, miticide, nematocides, mycocide, sterilant, rodenticide, weedicide, fertilizer, plant-growth regulator, synergistic agent.

In composition of the present invention, the amount of active compound is about 0.0001-99wt%.For the composition that is suitable for storing or transporting, the amount of activeconstituents is preferably about 0.5-90wt% of mixture, more preferably about 1-75wt%.Be suitable for directly using or the amount of the common contained active compound of composition that use in the land for growing field crops is the 0.0001-95wt% of mixture preferably approximately 0.0005-90wt%, more preferably about 0.001-75wt%.The ratio of all right compound of said composition and carrier is described.The weight ratio of The compounds of this invention (active compound/carrier) scope can be 99 in these materials: 1-1: 4, more preferably 10: 1-1: 3.

Usually, can be dissolved in some solvent such as acetone, methyl alcohol, ethanol, dimethyl formamide, pyridine or methyl-sulphoxide to The compounds of this invention, these solution dilutable waters.The concentration range of solution can be about 1%-90%, and preferable range is about 5%-50%.

For cream preparation, The compounds of this invention is dissolved in the suitable organic solvent or the mixture of solvent, wherein also have emulsifying agent so that compound fully disperses in water.The concentration of activeconstituents is generally 10-90% in the missible oil, and the concentration of the missible oil that can flow may be up to 75%.

Wettable powder is suitable for spraying, can be by the solid of compound and fine dispersion such as clay, inorganic silicate and carbonate and silicon-dioxide be mixed, and in this mixture, dope wetting agent, thickening material and/or dispersion agent prepare.The concentration range of activeconstituents is generally 20%-99% in these preparations, preferred 40%-75%.Typical wettable powder is to prepare by the compound of 50 parts of formula I, 45 parts of synthetic precipitated silicas and 5 parts of wooden sodium sulfonates are mixed.In another preparation of above-mentioned wettable powder, with the synthetic sedimentary aqueous silicon dioxide of clay replacement of high mountain range scholar's type (Barden), in another this type of preparation, 25% silicon-dioxide replaces with synthetic aluminosilicate sodium solid.

Pulvis is to prepare by compound is mixed with the inert solid of fine dispersion, and described solid can be organic or inorganic in nature.Employed for this purpose material comprises plant powder, silicon-dioxide, silicate, carbonate and clay.The common method of preparation pulvis is the carrier dilution wettable powder with fine dispersion.Usually preparation contains the enriching agent of the pulvis of 20% to 80% activeconstituents, and it is diluted to 1% to 10% working concentration.

Except that mentioned component, preparation of the present invention also can contain material commonly used in other this type of preparation.For example, can be lubricant such as calcium stearate or Magnesium Stearate adding wettable powder or mixture to be prepared.In addition, for example can add " tackiness agent ", with the bond properties between the surface of improving agricultural chemicals and will protect as polyvinyl alcohol-derivatived cellulose or other colloidalmaterial such as casein.

Claims

1. the salt of the compound of following formula and they, title complex, enantiomorph, steric isomer and composition thereof:

Wherein:

R ₁Be (C ₁-C ₁₂) alkyl or halo (C ₁-C ₁₂) alkyl;

R ₃Be hydrogen;

Wherein:

B) R ₇Be aryl, arylalkyl, heterocycle or heterocycle (C ₁-C ₄) alkyl, wherein aryl or heterocycle are not substituted or are replaced by 1-4 substituting group, and wherein at least one and cyclopropyl ring key position adjacent are hydrogen on aryl or the heterocycle; And R ₆Be hydrogen, (C ₁-C ₁₂) alkyl, halo (C ₁-C ₁₂) alkyl, (C ₃-C ₇) cycloalkyl, halo (C ₃-C ₇) cycloalkyl, (C ₂-C ₈) alkenyl, halo (C ₂-C ₈) alkenyl, (C ₂-C ₈) alkynyl, halo (C ₂-C ₈) alkynyl, halogen, cyano group or (C ₁-C ₄) alkoxy carbonyl.

2. the compound of claim 1, wherein R ₁And R ₂Be CH ₃, and R ₆Be hydrogen or (C ₁-C ₁₂) alkyl.

3. the compound of claim 1, wherein R ₁And R ₂Be CH ₃, R ₆Be hydrogen or (C ₁-C ₁₂) alkyl, and R ₇Be 2,6-dichlorophenyl, 2,6-difluorophenyl, 2,6-dibromo phenyl, 2, two (trifluoromethyl) phenyl, 2,3 of 6-, 6-trichlorophenyl, 2,3,6-trifluorophenyl, 2,3,6-tribromo phenyl, 2,3,6-three (trifluoromethyl) phenyl, 2,4,6-trichlorophenyl, 2,4,6-trifluorophenyl, 2,4,6-tribromo phenyl or 2,4,6-three (trifluoromethyl) phenyl, and R ₆Be hydrogen.

4. the compound of claim 1, wherein this compound be N-methyl-2-[2-((anti-form-1-(2-N-methoxyl group-N-methyl-N-[2-((anti-form-1-(2-(2 ', 6 '-dichlorophenyl) cyclopropyl) ethylidene) amino oxygen methyl) phenyl] carbamate.

5. the compound of claim 1, wherein R ₁And R ₂Be CH ₃, R ₆Be hydrogen or (C ₁-C ₁₂) alkyl, and R ₇Be phenyl, 2-chloro-phenyl-, 3-chloro-phenyl-, 4-chloro-phenyl-, 4-fluorophenyl, 4-bromophenyl, 2-(trifluoromethyl)-phenyl, 2,4 dichloro benzene base, 2,4 difluorobenzene base, 2,4-dibromo phenyl or 2, two (trifluoromethyl) phenyl of 4-, and R ₆Be (C ₁-C ₁₂) alkyl.

6. the compound of claim 5, wherein R ₇Be phenyl, 4-chloro-phenyl-or 4-fluorophenyl, and R ₆Be CH ₃

7. the compound of claim 1, wherein this compound is N-methoxyl group-N-methyl-N-[2-((anti-form-1-(2-(4 '-fluorophenyl-2-methyl) cyclopropyl) ethylidene) amino oxygen methyl) phenyl] carbamate.

8. a method for preparing the compound of claim 4, wherein R ₆Be (C ₁-C ₁₂) alkyl, described method comprises step: make N-methoxyl group-N-methyl (E)-2-(amino oxygen methyl) phenylcarbamate and 1-aryl-1-(C ₁-C ₁₂) alkyl-2-(C (=O) (CH ₃)) cyclopropane or 1-heteroaryl-1-(C ₁-C ₁₂) alkyl-2-(C (=O) (CH ₃)) the cyclopropane reaction.

9. fungicide composition that is used for the controlling plant pathogenic epiphyte, described composition comprise the compound of acceptable carrier and claim 1 on the agronomy, and wherein the ratio of carrier and compound is 99: 1-1: 2.

10. method that is used for the controlling plant pathogenic epiphyte, described method comprise the spot that the compound of claim 1 is applied to needs control, and wherein application rate is the 0.005-50 kg/ha.