CN102464592B - Acyl benzylamine compound and use thereof - Google Patents
Acyl benzylamine compound and use thereof Download PDFInfo
- Publication number
- CN102464592B CN102464592B CN201010535133.0A CN201010535133A CN102464592B CN 102464592 B CN102464592 B CN 102464592B CN 201010535133 A CN201010535133 A CN 201010535133A CN 102464592 B CN102464592 B CN 102464592B
- Authority
- CN
- China
- Prior art keywords
- compound
- alkyl
- group
- halo
- integer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 C*c1n[n](*)cc1C*(C)C Chemical compound C*c1n[n](*)cc1C*(C)C 0.000 description 9
- JZBCGSYFWIYOQC-UHFFFAOYSA-N CNC(c(cccc1)c1NC(CCl)=C)=O Chemical compound CNC(c(cccc1)c1NC(CCl)=C)=O JZBCGSYFWIYOQC-UHFFFAOYSA-N 0.000 description 1
- ZFJWFLANVZAVOI-UHFFFAOYSA-N CNC(c(cccc1)c1NC(COc1ccc(CN)cc1)=O)=O Chemical compound CNC(c(cccc1)c1NC(COc1ccc(CN)cc1)=O)=O ZFJWFLANVZAVOI-UHFFFAOYSA-N 0.000 description 1
- KIMWOULVHFLJIU-UHFFFAOYSA-N CNC(c1ccccc1N)=O Chemical compound CNC(c1ccccc1N)=O KIMWOULVHFLJIU-UHFFFAOYSA-N 0.000 description 1
- XDJAAZYHCCRJOK-UHFFFAOYSA-N COc(cc1)ccc1C#N Chemical compound COc(cc1)ccc1C#N XDJAAZYHCCRJOK-UHFFFAOYSA-N 0.000 description 1
- WNJINNZMSVNKJD-UHFFFAOYSA-N Cc1nc(C(F)(F)F)c(C(Cl)=O)[s]1 Chemical compound Cc1nc(C(F)(F)F)c(C(Cl)=O)[s]1 WNJINNZMSVNKJD-UHFFFAOYSA-N 0.000 description 1
- JCPGDOSECCVZGJ-UHFFFAOYSA-N Cc1nc(C(F)(F)F)c(C(NCc(cc2)ccc2OCC(Nc(cccc2)c2C(NC)=O)=O)=O)[s]1 Chemical compound Cc1nc(C(F)(F)F)c(C(NCc(cc2)ccc2OCC(Nc(cccc2)c2C(NC)=O)=O)=O)[s]1 JCPGDOSECCVZGJ-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses an acyl benzylamine compound and a use thereof. The acyl benzylamine compound has wide-spectrum bactericidal activity and has a general structural formula shown in the formula I, wherein definitions of all substituent groups in the formula I are shown in the patent specification. The acyl benzylamine compound has wide-spectrum bactericidal activity, has effects of treating symptoms caused by cucumber downy mildew, corn rust and wheat powdery mildew, and especially, has excellent effects of preventing cucumber downy mildew and corn rust. The acyl benzylamine compound also has good effects of preventing and treating wheat powdery mildew. The acyl benzylamine compound has the advantages of high activity, low use amount and good safety.
Description
Technical field
The invention belongs to disinfectant use in agriculture field, be specifically related to a kind of acyl group benzylamine compound and application thereof.
Background technology
Germ is to crop, especially for the agricultural-food such as grain and fiber that can meet mankind's primary demand, as cotton, and paddy rice, corn, wheat, soybean etc. are caused very large infringement.When killing or suppress pathogen growth, avoiding or reducing the infringement of crop is a kind of effective way of improving agriculture production.Therefore need to continually develop more effective new type bactericide.Acyl group benzylamine compound uses as insecticidal/acaricidal agent as Tolfenpyrad (tolfenpyrad) [US 5039693], tebufenpyrad (tebufenpyrad) [US 4950668], CN1927860 etc. are many; CN1919838, WO2002083647 report compound has bactericidal and insecticidal activity, but as sterilant, use has no bibliographical information as the acyl group benzylamine compound of general structure of the present invention.
Summary of the invention
In order to meet the requirement in agricultural, the invention provides a kind of novel acyl group benzylamine compound and in agricultural, prevent and treat the application of germ.
Technical scheme of the present invention is as follows: (claim part is done after changing well more in the lump)
The invention provides a kind of acyl group benzylamine compound, as shown in general formula (I):
In formula:
R
1be selected from hydrogen or C
1-C
12alkyl; M is selected from 1 to 3 integer;
R
2be selected from halogen, cyano group, nitro, C
1-C
12alkyl, halo C
1-C
12alkyl, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
1-C
12alkylthio, C
1-C
12alkyl sulphonyl or R
5; N is selected from 0 to 4 integer;
Y is selected from O, S or NR
4;
R
3, R
4can be identical or different, be selected from respectively hydrogen, cyano group, C
1-C
12alkyl, halo C
1-C
12alkyl, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
3-C
6cycloalkyl, cyano group C
1-C
12alkyl, C
1-C
12alkylamino, halo C
1-C
12alkylamino, C
2-C
6dialkyl amido, C
2-C
12thiazolinyl, halo C
2-C
12thiazolinyl, C
2-C
12alkene oxygen base, halo C
2-C
12alkene oxygen base, C
2-C
12alkynyl, halo C
2-C
12alkynyl, C
2-C
12alkynyloxy group, halo C
2-C
12alkynyloxy group, C
1-C
12alkylthio, halo C
1-C
12alkylthio, C
1-C
12alkyl sulphonyl, C
1-C
12alkyl-carbonyl, halo C
1-C
12alkyl-carbonyl, halo C
1-C
12alkane alkylsulfonyl or R
5; Or,
When Y is selected from NR
4time, N R
4with R
3composition replaces or unsubstituted five yuan or six-ring, and described substituting group is selected from 1-2 C
1-C
4alkyl;
R
5be selected from unsubstituted or be independently selected from by 1-4 phenyl, benzyl or the heteroaryl that following group replaces: halogen, nitro, cyano group, C
1-C
12alkyl, halo C
1-C
12alkyl, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
1-C
12alkylthio, C
1-C
12alkyl-carbonyl or C
1-C
12alkoxy carbonyl;
(CHR
1) link position of mCONH and phenyl ring is selected from 2,3 or 4;
Q is selected from the C that does not replace or replaced by 1-4 following radicals
1-C
6alkyl, cyclopropyl or cyclohexyl: Cl, Br, F or C
1-C
4alkyl;
Or be selected from the anilino or the C that do not replace or replaced by 1-3 following radicals
2-C
4thiazolinyl: Cl, Br, F, C
1-C
4alkyl, C
3-C
6cycloalkyl, C
1-C
4haloalkyl, C
1-C
4alkoxyl group, C
1-C
4halogenated alkoxy or C
1-C
4alkoxy carbonyl;
Or be selected from the phenyl, benzene oxygen ethyl, benzene oxygen propyl group, pyridyl, pyrimidyl, piperidyl, piperazinyl, thiazolyl, isothiazolyl, thiadiazolyl group, oxazolyl, isoxazolyl, oxadiazolyl, triazolyl, thienyl, furyl, quinolyl, indyl, 3-pyrazolyl, 4-pyrazolyl or the 4-pyrazoles methyl that do not replace or replaced by 1-3 following radicals: halogen, CN, NO
2, C
1-C
4alkyl, C
3-C
6cycloalkyl, C
1-C
3haloalkyl, C
1-C
3alkoxyalkyl, C
1-C
3alkoxyl group, C
1-C
3halogenated alkoxy, COR
6, CO
2r
6, CON R
6r
7, NR
6r
7, NR
7cOR
6, NR
7cO
2r
6, SR
7, SOR
7, SO
2r
7, SO
2nR
6r
7or R
7;
R
6be selected from H or C
1-C
4alkyl;
R
7be selected from H, C
1-C
4alkyl, C
1-C
3haloalkyl, replacement or unsubstituted phenyl, described substituting group is selected from Cl, Br, F, CN, NO
2, C
1-C
4alkyl, CF
3, OCH
3, OCF
3or CO
2cH
3.
In the present invention, comparatively preferred compound is: in general formula (I)
R
1be selected from hydrogen or C
1-C
6alkyl; M is selected from 1 to 3 integer;
R
2be selected from halogen, cyano group, nitro, C
1-C
6alkyl, halo C
1-C
6alkyl, C
1-C
6alkoxyl group, halo C
1-C
6alkoxyl group, C
1-C
6alkylthio, C
1-C
6alkyl sulphonyl or R
5; N is selected from 0 to 4 integer;
Y is selected from O, S or NR
4;
R
3, R
4can be identical or different, be selected from respectively hydrogen, cyano group, C
1-C
6alkyl, halo C
1-C
6alkyl, C
1-C
6alkoxyl group, halo C
1-C
6alkoxyl group, C
3-C
6cycloalkyl, cyano group C
1-C
6alkyl, C
1-C
6alkylamino, halo C
1-C
6alkylamino, C
2-C
6dialkyl amido, C
3-C
6thiazolinyl, halo C
3-C
6thiazolinyl, C
3-C
6alkene oxygen base, halo C
3-C
6alkene oxygen base, C
3-C
6alkynyl, halo C
3-C
6alkynyl, C
3-C
6alkynyloxy group, C
1-C
6alkylthio, halo C
1-C
6alkylthio, C
1-C
6alkyl sulphonyl, C
1-C
6alkyl-carbonyl, halo C
1-C
6alkyl-carbonyl, halo C
1-C
6alkane alkylsulfonyl or R
5; Or,
When Y is selected from NR
4time, N R
4with R
3composition morpholine, piperazine, piperidines, pyrazoles, pyrroles or triazole ring;
R
5be selected from unsubstituted or by 1-4 be independently selected from phenyl that following group replaces, benzyl, pyridyl, pyrimidyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazoles base,, thiadiazolyl group, pyrazolyl, pyranyl, triazolyl or tetrazyl: halogen, nitro, cyano group, C
1-C
6alkyl, halo C
1-C
6alkyl, C
1-C
6alkoxyl group, halo C
1-C
6alkoxyl group, C
1-C
6alkylthio, C
1-C
6alkyl-carbonyl or C
1-C
6alkoxy carbonyl;
Q is selected from one of group as follows:
R
8be selected from H, Cl, Br, F, CN, NO
2, NH
2, CH
3, CH
2cH
3, the tertiary butyl, cyclopropyl, CF
3, CH
2cF
3, OCH
3, OCF
3, OCH
2cF
3, SO
2cH
3, CO
2cH
3, C
1-C
3alkyl amino-carbonyl, C
2-C
4the pyridyl of dialkyl amino carbonyl, not replacement or the phenyl replacing, replacement or replacement, described substituting group is selected from 1-3 following radicals: Cl, Br, F, CN, NO
2, CH
3, CH
2cH
3, the tertiary butyl, cyclopropyl, CHF
2, CF
3, CH
2cF
3, OCH
3, OCHF
2, OCF
3, OCH
2cF
3or SO
2cH
3;
R
9be selected from H, CH
3, CH
2cH
3, the tertiary butyl, CF
3, CH
2cF
3, the phenyl, the pyridyl that do not replace or replace that do not replace or replace, described substituting group is selected from 1-3 following group: Cl, Br, F, CN, NO
2, CH
3, CH
2cH
3, the tertiary butyl, cyclopropyl, CHF
2, CF
3, CH
2cF
3, OCH
3, OCHF
2, OCF
3, OCH
2cF
3or SO
2cH
3;
A is selected from 1 to 5 integer; B is selected from 1 to 4 integer; C is selected from 1 to 3 integer; D is selected from 1 to 2 integer.
The further preferred compound of the present invention is: in general formula (I)
R
1be selected from hydrogen or C
1-C
3alkyl; M is selected from 1 to 3 integer;
R
2be selected from halogen, cyano group, nitro, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, C
1-C
3alkylthio, C
1-C
4alkyl sulphonyl or R
5; N is selected from 0 to 3 integer;
Y is selected from O, S or NR
4;
R
3, R
4can be identical or different, be selected from respectively hydrogen, cyano group, C
1-C
6alkyl, halo C
1-C
6alkyl, C
1-C
6alkoxyl group, halo C
1-C
6alkoxyl group, C
3-C
6cycloalkyl, cyano group C
1-C
6alkyl, C
1-C
6alkylamino, halo C
1-C
6alkylamino, C
2-C
6dialkyl amido, C
3-C
6thiazolinyl, halo C
3-C
6thiazolinyl, C
3-C
6alkynyl, halo C
3-C
6alkynyl, C
1-C
6alkylthio, halo C
1-C
6alkylthio, C
1-C
6alkyl sulphonyl, C
1-C
6alkyl-carbonyl, halo C
1-C
6alkyl-carbonyl, halo C
1-C
6alkane alkylsulfonyl or R
5; Or,
When Y is selected from NR
4time, N R
4with R
3composition morpholine, piperazine, piperidines or pyrazole ring;
R
5be selected from unsubstituted or by 1-4 be independently selected from phenyl that following group replaces, benzyl, pyridyl, pyrimidyl, thiazolyl, oxazolyl, oxadiazoles base,, thiadiazolyl group, pyrazolyl, triazolyl or tetrazyl: halogen, nitro, cyano group, C
1-C
4alkyl, halo C
1-C
4alkyl, C
1-C
4alkoxyl group, halo C
1-C
4alkoxyl group, C
1-C
4alkylthio, C
1-C
4alkyl-carbonyl or C
1-C
4alkoxy carbonyl;
Q is selected from one of group as follows:
R
8be selected from H, Cl, Br, F, CN, NO
2, CH
3, CH
2cH
3, the tertiary butyl, cyclopropyl, CF
3, CH
2cF
3, OCH
3, OCF
3, OCH
2cF
3, SO
2cH
3, CO
2cH
3, do not replace or replace phenyl, do not replace or replace pyridyl, described substituting group is selected from 1-3 following radicals: Cl, Br, F, CN, NO
2, CH
3, CH
2cH
3, the tertiary butyl, cyclopropyl, CHF
2, CF
3, CH
2cF
3, OCH
3, OCHF
2, OCF
3, OCH
2cF
3or SO
2cH
3;
R
9be selected from H, CH
3, CH
2cH
3, the tertiary butyl, the phenyl that does not replace or replace, the pyridyl that do not replace or replace, described substituting group is selected from 1-3 following group: Cl, Br, F, CN, NO
2, CH
3, CH
2cH
3, the tertiary butyl, cyclopropyl, CF
3, CH
2cF
3, OCH
3,, OCF
3or SO
2cH
3;
A is selected from 1 to 5 integer; B is selected from 1 to 4 integer; C is selected from 1 to 3 integer; D is selected from 1 to 2 integer.
The present invention further preferred compound is: in general formula (I)
R
1be selected from hydrogen or methyl; M is selected from 1 to 3 integer;
R
2be selected from fluorine, chlorine, bromine, iodine, cyano group, nitro, C
1-C
4alkyl or halo C
1-C
4alkyl; N is selected from 0 to 3 integer;
Y is selected from O or NR
4;
R
3, R
4can be identical or different, be selected from respectively hydrogen, cyano group, C
1-C
5alkyl, halo C
1-C
5alkyl, C
1-C
5alkoxyl group, halo C
1-C
5alkoxyl group, C
3-C
6cycloalkyl, cyano group C
1-C
5alkyl, C
1-C
5alkylamino, halo C
1-C
5alkylamino, C
2-C
6dialkyl amido, C
3-C
5thiazolinyl, halo C
3-C
5thiazolinyl, C
3-C
5alkynyl, halo C
3-C
5alkynyl, C
1-C
5alkyl sulphonyl, C
1-C
5alkyl-carbonyl, halo C
1-C
5alkyl-carbonyl, halo C
1-C
5alkane alkylsulfonyl or R
5; Or,
When Y is selected from NR
4time, N R
4with R
3composition morpholine, piperazine or piperidine ring;
R
5be selected from unsubstituted or be independently selected from by 1-3 phenyl, benzyl, pyridyl, pyrimidyl, thiazolyl, oxazolyl or the pyrazolyl that following group replaces: fluorine, chlorine, bromine, nitro, cyano group, C
1-C
3alkyl, halo C
1-C
3alkyl, C
1-C
3alkoxyl group or halo C
1-C
3alkoxyl group;
Q is selected from one of group as follows:
R
8be selected from H, Cl, Br, F, CN, CH
3, CH
2cH
3, the tertiary butyl, cyclopropyl, CF
3, OCH
3, OCF
3, OCH
2cF
3, SO
2cH
3, the phenyl, the pyridyl that do not replace or replace that do not replace or replace, described substituting group is selected from 1-3 following group: Cl, Br, F, CN, NO
2, CH
3, CH
2cH
3, the tertiary butyl, CHF
2, CF
3, OCH
3, OCHF
2, OCF
3, OCH
2cF
3or SO
2cH
3;
R
9be selected from H, CH
3, CH
2cH
3, the tertiary butyl, the phenyl that does not replace or replace, the pyridyl that do not replace or replace, described substituting group is selected from 1-3 following group: Cl, Br, F, CN, NO
2, CH
3or CF
3;
A is selected from 1 to 4 integer; B is selected from 1 to 3 integer; C is selected from 1 to 2 integer; D is selected from 1 to 2 integer.
The present invention more further preferred compound is: in general formula (I)
R
1be selected from hydrogen or methyl; M is selected from 1 to 2 integer;
R
2be selected from fluorine, chlorine, bromine, iodine, cyano group, nitro, C
1-C
3alkyl or halo C
1-C
3alkyl; N is selected from 0 to 2 integer;
Y is selected from O or NR
4;
R
3, R
4can be identical or different, be selected from respectively hydrogen, C
1-C
5alkyl, C
1-C
5alkoxyl group, cyano group C
1-C
5alkyl, C
1-C
5alkylamino, C
2-C
6dialkyl amido, C
3-C
5thiazolinyl, C
3-C
5alkynyl, C
1-C
5alkyl sulphonyl, C
1-C
5alkyl-carbonyl or R
5; Or,
When Y is selected from NR
4time, N R
4with R
3composition morpholine, piperazine or piperidine ring;
R
5be selected from unsubstituted or be independently selected from by 1-2 phenyl, benzyl, pyridyl, pyrimidyl, thiazolyl or the pyrazolyl that following group replaces: fluorine, chlorine, bromine, nitro, cyano group, C
1-C
3alkyl, halo C
1-C
3alkyl, C
1-C
3alkoxyl group or halo C
1-C
3alkoxyl group;
Q is selected from one of group as follows:
R
8be selected from H, Cl, Br, F, CN, CH
3, CH
2cH
3, the tertiary butyl, CF
3, OCH
3, OCF
3, SO
2cH
3, the phenyl, the pyridyl that do not replace or replace that do not replace or replace, described substituting group is selected from 1-3 following group: Cl, Br, F, CN, NO
2, CH
3, CH
2cH
3, the tertiary butyl, CHF
2, CF
3, OCH
3, OCHF
2, OCF
3, or SO
2cH
3;
R
9be selected from H, CH
3, CH
2cH
3, the tertiary butyl, the phenyl that does not replace or replace, the pyridyl that do not replace or replace, described substituting group is selected from 1-3 following group: Cl, Br, F, CH
3or CF
3;
A is selected from 1 to 3 integer; B is selected from 1 to 2 integer; C is selected from 1 to 2 integer; D is selected from 1 to 2 integer.
The more preferred compound of the present invention is: in general formula (I)
R
1be selected from hydrogen or methyl; M is selected from 1;
R
2be selected from fluorine, chlorine, bromine or C
1-C
3alkyl; N is selected from 0 to 2 integer;
Y is selected from O or NR
4;
R
3, R
4can be identical or different, be selected from respectively hydrogen or C
1-C
3alkyl;
R
5be selected from unsubstituted or be independently selected from by 1-2 phenyl, benzyl, pyridine or the pyrimidyl that following group replaces: fluorine, chlorine, bromine, nitro, cyano group, C
1-C
3alkyl, halo C
1-C
3alkyl, C
1-C
3alkoxyl group or halo C
1-C
3alkoxyl group;
Q is selected from one of group as follows:
R
8be selected from H, Cl, Br, F, CN, CH
3, CH
2cH
3, CF
3, OCH
3, OCF
3, SO
2cH
3, the phenyl, the pyridyl that do not replace or replace that do not replace or replace, described substituting group is selected from 1-3 following group: Cl, Br, F, NO
2, CH
3, CH
2cH
3, CF
3or OCH
3;
R
9be selected from H, CH
3, the phenyl, the pyridyl that do not replace or replace that do not replace or replace, described substituting group is selected from 1-3 following group: Cl, Br, F or CH
3.
In the definition of general formula (I) compound providing, collect term General Definition used as follows above:
Halogen: refer to fluorine, chlorine, bromine or iodine.
Alkyl: straight or branched alkyl, for example methyl, ethyl, propyl group, sec.-propyl or the tertiary butyl.
Haloalkyl: straight or branched haloalkyl, the hydrogen atom on these alkyl can partly or entirely be replaced by halogen atom, for example, haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl or trifluoromethyl.
Alkoxyl group: straight chain, side chain or cyclisation alkoxyl group, for example methoxyl group, oxyethyl group, propoxy-, isopropoxy, tert.-butoxy or ring propoxy-.
Halogenated alkoxy: straight or branched halogenated alkoxy, hydrogen atom on these alkoxyl groups can partly or entirely be replaced by halogen atom, for example, haloalkyl such as chlorine methoxyl group, dichloro methoxyl group, trichlorine methoxyl group, fluorine methoxyl group, difluoro-methoxy or trifluoromethoxy.
Alkylthio: straight or branched alkyl, is connected in structure through sulphur atom key.
Halogenated alkylthio: straight or branched alkylthio, the hydrogen atom on these alkylthios can partly or entirely be replaced by halogen atom.For example, chloromethane sulfenyl, dichloromethane sulfenyl, trichloro-methylthio, fluorine methylthio group, difluoro methylthio group, trifluoromethylthio, chlorine fluorine methylthio group etc.
Thiazolinyl: straight or branched also can have two keys, for example vinyl or allyl group on any position.
Alkynyl: straight or branched also can have triple bond, for example ethynyl or propargyl on any position.
In the present invention, indication heteroaryl is containing one or more N, O, the heteroatomic five-ring of S or six-ring aryl.Such as pyridyl, pyrimidyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazoles base,, thiadiazolyl group, pyrazolyl, pyranyl, triazolyl or tetrazyl etc.
Technical scheme of the present invention also comprises a kind of intermediate phenylbenzylamine or its salt for the preparation of general formula (I) compound of novel structure, as shown in general formula (II):
In formula:
R
1be selected from hydrogen or C
1-C
12alkyl; M is selected from 1 to 3 integer;
R
2be selected from halogen, cyano group, nitro, C
1-C
12alkyl, halo C
1-C
12alkyl, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
1-C
12alkylthio, C
1-C
12alkyl sulphonyl or R
5; N is selected from 0 to 4 integer;
Y is selected from O, S or NR
4;
R
3, R
4can be identical or different, be selected from respectively hydrogen, cyano group, C
1-C
12alkyl, halo C
1-C
12alkyl, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
3-C
6cycloalkyl, cyano group C
1-C
12alkyl, C
1-C
12alkylamino, halo C
1-C
12alkylamino, C
2-C
6dialkyl amido, C
2-C
12thiazolinyl, halo C
2-C
12thiazolinyl, C
2-C
12alkene oxygen base, halo C
2-C
12alkene oxygen base, C
2-C
12alkynyl, halo C
2-C
12alkynyl, C
2-C
12alkynyloxy group, halo C
2-C
12alkynyloxy group, C
1-C
12alkylthio, halo C
1-C
12alkylthio, C
1-C
12alkyl sulphonyl, C
1-C
12alkyl-carbonyl, halo C
1-C
12alkyl-carbonyl, halo C
1-C
12alkane alkylsulfonyl or R
5; Or,
When Y is selected from NR
4time, N R
4with R
3composition replaces or unsubstituted five yuan or six-ring, and described substituting group is selected from 1-2 C
1-C
4alkyl;
R
5be selected from unsubstituted or be independently selected from by 1-4 phenyl, benzyl or the heteroaryl that following group replaces: halogen, nitro, cyano group, C
1-C
12alkyl, halo C
1-C
12alkyl, C
1-C
12alkoxyl group, halo C
1-C
12alkoxyl group, C
1-C
12alkylthio, C
1-C
12alkyl-carbonyl or C
1-C
12alkoxy carbonyl;
(CHR
1) link position of mCONH and phenyl ring is selected from 2,3 or 4.
Can comprise with the acid of the phenylbenzylamine salify shown in general formula of the present invention (II): carboxylic acid is acetic acid, propionic acid, butyric acid, oxalic acid, hexanodioic acid, dodecanedioic acid, lauric acid, stearic acid, trifluoroacetic acid, fumaric acid, toxilic acid, phenylformic acid or phthalic acid for example; Sulfonic acid is methylsulfonic acid, 1 for example, 3-the third disulfonic acid, tosic acid or Witco 1298 Soft Acid; And mineral acid for example hydrochloric acid, sulfuric acid, nitric acid or carbonic acid.
(CHR in general formula of the present invention (I) compound
1) link position of mCONH and phenyl ring can be selected from 2,3 or 4 of phenyl ring.
When 2 of phenyl ring are connected, shown in structural formula as I-1:
When 3 of phenyl ring are connected, shown in structural formula as I-2;
When 4 of phenyl ring are connected, shown in structural formula as I-3;
In general formula of the present invention (I) compound, because chiral carbon or nitrogen connect different groups or substituting group and can form steric isomer (representing different configurations with R and S respectively).Therefore, general formula of the present invention (I) compound has comprised R type isomer or S type isomer, and the mixture of any ratio.
In compound of Formula I of the present invention, the part concrete structure of Q group is in table 1; Work as CHR
1) link position of mCONH and phenyl ring is while being 2, R in phenyl ring
2concrete substituting group is in table 2; As (CHR
1) link position of mCONH and phenyl ring is while being 3, R
2concrete substituting group is in table 3; As (CHR
1) link position of mCONH and phenyl ring is while being 4, R
2concrete substituting group is referring to table 4; Y-R
3concrete substituting group is in table 5; In general formula (I), other substituting groups are as R
1, R
3, R
4, R
5, m and n definition the same.
Table 1
Table 2
| R 2 | R 2 | R 2 | R 2 | R 2 |
| 3-I | 3-Br | 6-OCH 3 | 3-CH 3-5-NO 2 | 6-CH 3-3，5-2Br |
| 3-CH 3 | 4-Br | 5-OCH 3 | 4-CH 3-3-NO 2 | 3-CF 3O-4，6-2Cl |
| 4-CH 3 | 5-Br | 3，5-2Cl | 4-CH 3-5-NO 2 | 4-CH 3-5-NO 2-3-Br |
| 5-CH 3 | 6-Br | 3，5-2Br | 5-CH 3-3-NO 2 | 3-CN-4，6-2Cl |
| 6-CH 3 | 5-I | 4-CH 3-5-Br | 6-CH 3-4-NO 2 | 3-CN-4-CH 3-6-Cl |
| 3-Cl | 5-F | 6-CH 3-5-CN | 6-CH 3-5-NO 2 | 3-CN-4-CF 3-6-Cl |
| 4-Cl | 6-F | 3，5，6-3Cl | 3-NO 2-5-Cl | 4-CH 3-5-CN-6-Cl |
| 5-Cl | 3-CN | 3-CH 2CH 3 | 3-NO 2-5-Br | 4-CF 3-5-CN-6-Cl |
| 6-Cl | 4-CN | 4-CH 2CH 3 | 5-NO 2-3-Br | 3-CF 3O-6-Cl |
| 3-CF 3 | 5-CN | 5-CH 2CH 3 | 5-CH 3-3-Br | 5-CN-3-Cl |
| 4-CF 3 | 6-CN | 6-CH 2CH 3 | 6-CH 3-5-Br | 5-CF 3-3，6-2Cl |
| 5-CF 3 | 3-NO 2 | 5-CF 3-3-Cl | 3-CH 3-5-Br | 5-CF 3-6-Cl |
| 6-CF 3 | 5-NO 2 | 5-CH 3-3-Cl | 3-CF 3-6-Cl | 3-CN-6-Cl |
| 6-I | 3-F | 4-F | 4-NO 2 | 6-NO 2 |
Table 3
| R 2 | R 2 | R 2 | R 2 | R 2 |
| 2-I | 2-Br | 6-OCH 3 | 4-CF 3 | 6-CH 3-4，5-2Br |
| 2-CH 3 | 4-Br | 5-OCH 3 | 4-CH 3-6-NO 2 | 2-NO 2 |
| 4-CH 3 | 5-Br | 2，5-2Cl | 6-CH 3-4-NO 2 | 5-CN-4，6-2Cl |
| 5-CH 3 | 6-Br | 2，5-2Br | 5-CH 3-5-Br | 6-CF 3 |
| 6-CH 3 | 5-I | 4-CH 3-5-Br | 6-CH 3-4Br | 5-CN-4-Cl |
| 2-Cl | 5-F | 6-CH 3-5-CN | 4-CH 3-5-Br | 5-CF 3-6-Cl |
| 4-Cl | 6-F | 4，5，6-3Cl | 4-CF 3-6-Cl | 2-CN-6-Cl |
| 5-Cl | 2-CN | 2-CH 2CH 3 | 5-CH 3-2-Cl | 4-CH 3-2-Cl |
| 6-Cl | 4-CN | 4-CH 2CH 3 | 4，5-2Cl | 5-CH 3-4-Cl |
| 2-CF 3 | 5-CN | 5-NO 2 | 5-CF 3 | 6-CN |
Table 4
| R 2 | R 2 | R 2 | R 2 | R 2 |
| 2-F | 2-C(CH 3) 2 | 3-CH 3 | 2，5-2CH 3 | 2-Cl-5-F |
| 3-F | 3-C(CH 3) 2 | 2，3-2CN | 3，6-2CH 3 | 2-Cl-5-Br |
| 5-F | 5-C(CH 3) 2 | 5，6-2CN | 5-CH 3-2-Br | 5-Cl-2-Br |
| 6-F | 2-CF 3 | 2，6-2CN | 5-CH 3-2-Cl | 2，5-2Cl |
| 2-Cl | 3-CF 3 | 3，6-2CN | 2，6-2Br | 5-CH 3-3-F |
| 3-Cl | 5-CF 3 | 2-F-5-Br | 3，6-2Br | 6-CH 3-3-Cl |
| 5-Cl | 6-CF 3 | 2-F-6-Cl | 2-CH 3-5-F | 2-CH 3-3-Br |
| 6-Cl | 2-OCH 3 | 2-CN-5-Cl | 5-CH 3-2-CN | 2-CH 3-3-F |
| 2-Br | 3-OCH 3 | 2-CN-5-Br | 2-CN | 2-CH 3-3-Cl |
| 3-Br | 5-OCH 3 | 5-CN-2-Cl | 3-CN | 2-CH 3-5-F |
| 5-Br | 3-OCF 3 | 5-CH 3-2-F | 5-CN | 2-CH 3-5-Cl |
| 6-Br | 5-OCF 3 | 2，3-2Br | 6-CN | 3-CH 3-2-Br |
| 2-I | 2，3-2F | 6-CH 3 | 2-NO 2 | 3-CH 3-5-Cl |
| 3-I | 5，6-2F | 2-C 2H 5 | 3-NO 2 | 3-CH 3-5-Br |
| 5-I | 3，5-2F | 5，6-2Cl | 5-NO 2 | 3-CH 3-5-I |
| 6-NO 2 | 2，3-2Cl | 2-CH 3 | 6-I | 2-CH 3-5-I |
| 3，6-2Cl | 2，6-2Cl | 5-CH 3 | 3，5-2Cl |
Table 5
Part preferred compound can illustrate the present invention by the particular compound of listing in table 6, table 7, table 8, but does not limit the present invention.
Table 6
Abridge in each table above Bn, Py, Ph represents respectively benzyl, pyridyl, phenyl, table 6R
2in row, "-" represents unsubstituted, and on phenyl ring, corresponding position is hydrogen.
Table 7
In table 7 (omission provides), compound number is 194-386, other each radicals R in table
1, R
2, Y-R
3, R
4, and the number of m, n is corresponding is same as in turn 1-193 compound in table 6.
Table 8
In table 8 (omission provides), compound number is 387-579, other each radicals R in table
1, R
2, Y-R
3, R
4, and the number of m, n is corresponding is same as in turn 1-193 compound in table 6.
General formula of the present invention (I) compound can be prepared in accordance with the following methods:
According to above-mentioned reaction equation, in the situation that having alkali or alkali-free to exist, make acyl chlorides (III) and phenylbenzylamine (II) reaction, described reaction is preferably used solvent to carry out at 0 to 100 DEG C, preferably 0 to 25 DEG C of temperature of reaction, reaction times is 30 minutes to 20 hours, preferably 0.5～10 hour.Described solvent is the solvent without direct impact on reaction, comprises aromatic hydrocarbons, as benzene, toluene and dimethylbenzene; Ketone, as acetone methylethylketone and mibk; Halohydrocarbon, as methylene dichloride, chloroform and ethylene dichloride; Lipid, as methyl acetate and ethyl acetate; And polar solvent, as tetrahydrofuran (THF), acetonitrile, diox, DMF, N-Methyl pyrrolidone, methyl-sulphoxide and pyridine.
Described alkali comprises metal hydride, as sodium hydride; Alkali metal hydroxide, as sodium hydroxide and potassium hydroxide; Alkaline carbonate, as sodium carbonate and salt of wormwood; Organic amine, as pyridine and triethylamine.
In order to separate (I) target compound after reaction, in the situation that using water-soluble solvent, remove described solvent under reduced pressure, in gained resistates, add water, use water-fast aromatic hydrocarbon, as benzene, toluene and dimethylbenzene; Halogenated alkane is as chloroform and methylene dichloride; And ester class, as ethyl acetate extracts above-mentioned resistates, and rinse extraction liquid with saturated sodium-chloride water solution, then use siccative as anhydrous magnesium sulfate or anhydrous sodium sulfate drying gained extraction liquid, then decompression desolventizes.In the time using water-immiscible solvent, in reaction mixture, add water, concussion separates, and with saturated sodium-chloride water solution flushing gained organic layer, then uses siccative as anhydrous magnesium sulfate or anhydrous sodium sulfate drying, and then decompression desolventizes.To the processing of gained residue purified, obtain the target compound being represented by general formula (I) by recrystallization, flushing and column chromatography.
As the intermediate of the synthetic target compound being represented by general formula (I), the acyl chlorides being represented by general formula (III), synthetic according to the method described in JP4069379.
Phenylbenzylamine compounds shown in general formula (II) is the key intermediate of preparation general formula of the present invention (I) compound, and its structure has no report before this, can prepare with the following method:
(1) preparation of phenylbenzylamine
Wherein, R
1, R
2, R
3, R
4, R
5, m and n and the defined same meaning of general formula (I).
Under the condition that has metal catalyst and ammoniacal liquor to exist, preferably with an organic solvent at 0 to 100 DEG C, make benzonitrile (IV) and hydrogen react, preferably 20 to 50 DEG C of this temperature of reaction; Reaction times is 30 minutes to 20 hours, preferably 0.5～10 hour.
As long as without directly impact, any organic solvent all can be used as the organic solvent of described reaction on described reaction.Described organic solvent comprises alcohols, as methyl alcohol, ethanol and Virahol; Aromatic hydrocarbon, as benzene.Toluene and dimethylbenzene; Ketone, as acetone, methylethylketone and mibk; Halohydrocarbon, as chloroform and methylene dichloride; Water; Ester class, as methyl acetate and ethyl acetate; Or polar solvent, as tetrahydrofuran (THF), acetonitrile, diox, DMF, N-Methyl pyrrolidone, methyl-sulphoxide and pyridine.
Described metal catalyst comprises Raney's nickel, palladium carbon and platinum oxide.
For separate type after reaction (II) target compound, described metal catalyst is removed by filter from gained reaction mixture, then remove solvent under reduced pressure,, refine and obtain pure products gains purification process with recrystallization, placement evaporation, flushing and column chromatography.
Can be according to currently known methods as US2001070671, J.Am.Chem.Soc.1960,82:2953 is by corresponding aminobenzoic acid derivative, halogen acyl chloride and hydroxybenzene nitrile synthesis of phenyl nitrile (IV).
(2) salt of synthesis of phenyl benzylamine by the following method:
Preferably use solvent at-5 to 50 DEG C, to make benzylamine (II) and acid-respons, preferably 0 to 25 DEG C of temperature, specifically with reference to CN1511142A.
Can comprise with the acid of the phenylbenzylamine salify being represented by general formula (II) of the present invention: carboxylic acid is acetic acid, propionic acid, butyric acid, oxalic acid, hexanodioic acid, dodecanedioic acid, lauric acid, stearic acid, trifluoroacetic acid, fumaric acid, toxilic acid, phenylformic acid or phthalic acid for example; Sulfonic acid is methylsulfonic acid, 1 for example, 3-the third disulfonic acid, tosic acid or Witco 1298 Soft Acid; And mineral acid for example hydrochloric acid, sulfuric acid, nitric acid or carbonic acid.
As long as without directly impact, any organic solvent all can be used as the organic solvent of described reaction on described reaction.Described organic solvent comprises aromatic hydrocarbon, as benzene, toluene or dimethylbenzene; Ketone, as acetone, methylethylketone or mibk; Halohydrocarbon, as chloroform or methylene dichloride; Water; Ester class, as methyl acetate or ethyl acetate; And polar solvent, as tetrahydrofuran (THF), acetonitrile, diox, DMF, N-Methyl pyrrolidone, methyl-sulphoxide or pyridine.
Adopt ordinary method to separate the salt that obtains phenylbenzylamine.
General formula of the present invention (I) compound has higher fungicidal activity to phytopathogen, can effectively control as sterilant the disease that oidium germ, Powdery Mildew germ, rust germ etc. cause.Therefore technical scheme of the present invention also comprises the purposes of general formula (I) compound control germ.Described phytopathogen has rice blast pathogen, Powdery Mildew germ, rust germ and oidium germ for instance, particularly cucumber downy mildew, rice blast, corn rust is had to good activity.Therefore, described compound can be used as the activeconstituents of the sterilant in the agricultural fields such as agricultural, gardening and flower culture, therefore general formula of the present invention (I) compound preferably agricultural and other field in for preventing and treating the application of phytopathogen.The phytopathogen that compound of the present invention can be prevented and treated is not limited to foregoing.
Due to good performance, above-claimed cpd can be advantageously used in protection agricultural and important crop, domestic animal and the breeding stock of horticulture, and the environment that often goes of the mankind avoids the injury of fungi.
For obtaining ideal effect, the consumption of compound changes because of various factors, for example formulation of the type of compound used therefor, protected crop, harmful organism, gradient of infection, weather condition, application method, employing.
The compound dosage that per hectare is 10 grams-1000 grams can provide sufficient control.
Another object of the present invention also relates to by using general formula (I) compound, the method for the plant pathogenic fungi in the environment that the crop that control agricultural and horticulture are important and/or domestic animal and breeding stock and/or the mankind often go.Especially, the consumption of compound changes in 10 grams-1000 grams of per hectares.
In order to be applied to agricultural, use containing the composition of one or more general formulas (I) compound normally useful.
Another object of the present invention relates to the fungicidal composition as activeconstituents containing one or more general formulas (I) compound, and in composition, the weight percentage of activeconstituents is 0.1-99%.In composition, also contain the upper acceptable carrier of agricultural, and conventionally contain tensio-active agent.Therefore, technical scheme of the present invention also comprises that said composition prevents and treats the purposes of germ in agricultural or other field as sterilant.
The type of service of composition can be dry powder, wettable powder, missible oil, microemulsion, paste, granule, solution, suspension agent etc.: concrete application is depended in the selection of types of compositions.
Composition is prepared with currently known methods, for example optional under the existence of tensio-active agent, by diluting or lytic activity material with solvent medium and/or solid diluent.
Available solid diluent or carrier are for example: silicon-dioxide, kaolin, wilkinite, talcum, diatomite, rhombspar, calcium carbonate, magnesium oxide, chalk, clay, synthetic silicate, attapulgite, sepiolite etc.
Beyond dewatering, available liquid diluent also comprises as aromatics organic solvent (mixture, the chlorobenzene etc. of dimethylbenzene or alkylbenzene), paraffin (petroleum fractions), alcohols (methyl alcohol, propyl alcohol, butanols, octanol, glycerine), ester class (ethyl acetate, isobutyl acetate etc.), ketone (pimelinketone, acetone, methyl phenyl ketone, isophorone, ethyl pentyl group ketone etc.), amides (DMF, N-Methyl pyrrolidone etc.).
Available tensio-active agent is sodium, calcium, triethylamine or the triethanolamine salt of polyoxyethylene ester, the sulfonated lignin etc. of alkylsulfonate, alkylaryl sulphonate, polyoxyethylene alkylphenol, sorbyl alcohol.
Composition also can containing special additive for specific object, for example, contain tackiness agent as gum arabic, polyvinyl alcohol, polyvinylpyrrolidone etc.
In above-mentioned composition, the concentration of activeconstituents can change according to the preparation type of activeconstituents, application target, envrionment conditions and employing in wide region.Activity component concentration scope is generally 0.1-99%, preferably 5-60%.
If needed, can to add in composition can with other activeconstituentss of general formula (I) compound compatibility, for example other miticide/sterilants, mycocide, plant-growth regulator, microbiotic, weedicide, fertilizer.
But the form of described composition is not limited in this, also can be by the compound of one or two or more array configuration using as activeconstituents.
The compound method of several frequently seen formulation is exemplified below:
The preparation of suspension agent: in common prescription, active component content is 5-35%.Taking water as medium, former medicine, dispersion agent, suspending agent and antifreezing agent etc. are added in sand mill, grind, make suspension agent.
The preparation of aqueous emulsion: former medicine, solvent and emulsifying agent are added together, make to be dissolved into even oil phase.Water, antifreezing agent etc. are mixed, become homogeneous water.Under high-speed stirring, water is joined to oil phase or oil phase is joined to water, form the aqueous emulsion of favorable dispersity.Aqueous emulsion active component content of the present invention is generally 5%-15%.For preparation emulsifiable concentrate, compound of the present invention is dissolvable in water one or several mixed solvents, then adds emulsifying agent to strengthen the dispersion effect of compound in water.
The preparation of wettable powder: by formula requirement, former medicine, various tensio-active agent and solid diluent etc. are fully mixed, after ultra-fine pulverizer disintegrating, obtain the wettable powder product of predetermined content (for example 10-60%).For preparation is suitable for spraying the wettable powder of use, compound of the present invention can be with the pressed powder of porphyrize as clay, inorganic silicate, carbonate and wetting agent, tackiness agent and/or dispersion agent composition mixture.
The preparation of water-dispersible granules: former medicine and powdery solid thinner, wetting spreader-sticker and tackiness agent etc. are carried out to co-grinding; add water again after kneading; add and in the tablets press that certain specification screen cloth is housed, carry out granulation, and then drying, screening (pressing screen cloth scope).Also former medicine, dispersion agent, disintegrating agent and wetting agent and solid diluent can be added in sand mill, taking water as medium milling, make suspension agent, then carry out spray drying granulation, formulation content is 20-30% granular product conventionally.
Embodiment
Following specific embodiment is used for further illustrating the present invention, but the present invention only limits to absolutely not these examples.
Synthetic example
Embodiment 1: the preparation of intermediate II-1
1).
Under stirring at room temperature, add on a small quantity 19.80g (0.067mol) solid phosgene to containing in the 150ml tetrahydrofuran solution of 13.70g (0.1mol) anthranilic acid in batches, within approximately 1.5 hours, add, continue stirring at room temperature reaction 2-3 hour, TLC monitors after completion of the reaction, remove solvent under reduced pressure, residuum adds in 80ml water, being stirred to excess phosgene decomposes completely, filter and water, the each 50ml washing of sherwood oil successively, obtain white solid 14.00g, yield 86.0%, fusing point 239-240 DEG C.
2).
Under stirring at room temperature, in the 100ml acetonitrile solution that contains 16.30g (0.1mol) benzoxazinone, slowly drip 40% aqueous methylamine solution, till while becoming clarification to solution, approximately drip 80ml first ammonia soln, drip and finish, continue room temperature reaction 0.5 hour, TLC monitors after completion of the reaction, decompression desolventizes, and water, the each 50ml washing of sherwood oil, obtain white solid 13.73g, yield 91.5%, fusing point 78-79 DEG C.
3).
Under stirring at room temperature, in the 50ml dichloromethane solution that contains 15.00g (0.1mol) anthranilamide and 12.10g (0.12mol) triethylamine, slowly drip the 30ml dichloromethane solution containing 12.40g (0.11mol) chloroacetyl chloride, within approximately 0.5 hour, drip off, continue room temperature reaction 2-3 hour, TLC monitoring reaction to terminal, decompression desolventizes, successively with 10% dilute hydrochloric acid, saturated sodium bicarbonate solution, water, the each 50ml washing of sherwood oil, obtain white solid 18.90g, yield is 83.4%, fusing point 155-157 DEG C.
4).
The adjacent chlor(o)acetamide yl-benzamide of 22.65g (0.1mol) and 14.29g (0.12mol) para hydroxybenzene nitrile add in 80ml butanone, add 27.60g (0.2mol) salt of wormwood, under stirring, be heated to reflux, reaction 4-5 hour, TLC monitoring reaction to terminal, removes solvent under reduced pressure, wash to obtain most of object with alkali, water, the each 50ml of sherwood oil successively, a small amount of resistates can obtain by column chromatography, obtains white solid 25.00g, yield 81.0%.
5).
By mixture stirring reaction 3-4 hour under hydrogen atmosphere, room temperature of 3.09g (0.01mol) intermediate (IV-1), Raney nickel (1.0g), 25% ammoniacal liquor 10ml and ethanol 50ml composition, TLC monitoring reaction to terminal, filtering Raney nickel, decompression desolventizes to obtain viscous liquid (II-1), cooling washing is white solid afterwards, obtain white solid 2.16g, yield is 69.00%, fusing point 114-116 DEG C.
Embodiment 2: the preparation of compound 23
Benzylamine (II-1) 0.313g (0.001mol) and triethylamine 0.12g (0.0012mol) are added in 20ml methylene dichloride, under stirring at room temperature, drip 0.17g (0.0011mol) 10ml dichloromethane solution (III-1), drip Bi Jixu stirring at room temperature reaction 1 hour, TLC monitoring reaction to terminal, by in reaction mixture impouring 30ml water, concussion separates organic layer, organic phase is used 10% dilute hydrochloric acid successively, saturated sodium bicarbonate aqueous solution, after the each 20ml washing of saturated common salt water washing, dry precipitation obtains product, wash to obtain white solid through ethyl acetate, column chromatography obtains sterling 0.38g, productive rate 87.5%, fusing point 168-169 DEG C.
Embodiment 3: the preparation of compound 62
Benzylamine (II-1) 0.313g (0.001mol) and triethylamine 0.12g (0.0012mol) are added in 20ml methylene dichloride, under stirring at room temperature, drip 0.22g (0.0011mol) 10ml dichloromethane solution (III-2), drip Bi Jixu stirring at room temperature reaction 1 hour, TLC monitoring reaction to terminal, by in reaction mixture impouring 30ml water, concussion separates organic layer, organic phase is used 10% dilute hydrochloric acid successively, saturated sodium bicarbonate aqueous solution, after the each 20ml washing of saturated common salt water washing, dry precipitation obtains product, wash to obtain white solid through ethyl acetate, column chromatography obtains sterling 0.39g, productive rate 82.0%, fusing point 154-156 DEG C.
Embodiment 4: the preparation of compound 133
Benzylamine (II-1) 0.313g (0.001mol) and triethylamine 0.12g (0.0012mol) are added in 20ml methylene dichloride, under stirring at room temperature, drip 0.27g (0.0011mol) 10ml dichloromethane solution (III-3), drip Bi Jixu stirring at room temperature reaction 1 hour, TLC monitoring reaction to terminal, by in reaction mixture impouring 30ml water, concussion separates organic layer, organic phase is used 10% dilute hydrochloric acid successively, saturated sodium bicarbonate aqueous solution, after the each 20ml washing of saturated common salt water washing, dry precipitation obtains product, ethyl acetate is washed to obtain white solid, column chromatography obtains sterling 0.41g, productive rate 78.2%, fusing point 173-174 DEG C.
Embodiment 5: the preparation of compound 150
Benzylamine (II-1) 0.313g (0.001mol) and triethylamine 0.12g (0.0012mol) are added in 20ml methylene dichloride, under stirring at room temperature, drip containing 0.21g (0.0011mol) 10ml dichloromethane solution (III-4), drip Bi Jixu stirring at room temperature reaction 1 hour, TLC monitoring reaction to terminal, by in reaction mixture impouring 30ml water, concussion separates organic layer, organic phase is successively through 10% dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution, after the each 50ml washing of saturated aqueous common salt, dry precipitation obtains product, ethyl acetate is washed to obtain white solid, column chromatography obtains sterling 0.41g, productive rate 86.0%.Fusing point 178-180 DEG C.
Other compounds of general formula (I) can make by preparation method provided by the invention.
Part of compounds fusing point (melting point apparatus is not proofreaied and correct) and nuclear magnetic data (
1hNMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows:
Compound 1: fusing point 147-149 DEG C.δppm 1.15-1.30(6H，m)，1.50-1.53(1H，d)，1.91-1.97(1H，m)，3.74(3H，s)，4.35-4.37(2H，d)，5.21(2H，s)，5.79(1H，s)，6.44-6.46(1H，d)，7.02-7.05(2H，m)，7.21-7.26(2H，m)，7.50-7.55(1H，m)，7.75-7.77(2H，m)，、8.28-8.31(1H，m)。
Compound 8: fusing point 173-175 DEG C.δppm 0.67-0.69(3H，d)，1.01-1.03(3H，d)，2.40(1H，m)，2.76-2.80(1H，d)，3.72(3H，s)，4.18-4.42(2H，m)，5.16(2H，s)，5.80(1H，s)，6.95-6.97(2H，m)，7.09-7.11(2H，m)，7.50(1H，m)，7.73-7.74(2H，m)，8.30(1H，m)。
Compound 10: fusing point 199-200 DEG C.δppm 3.74(3H，s)，4.57-4.59(2H，d)，5.22(2H，s)，6.40(1H，s)，7.03-7.06(2H，m)，7.26-7.32(3H，m)，7.39-7.52(5H，m)，7.75-7.79(4H，m)，、8.27(1H，m)。
Compound 13: fusing point 167-168 DEG C.δppm 3.72(3H，s)，4.59-4.61(2H，d)，，5.18(2H，s)，6.51(1H，s)，7.03-7.06(2H，m)，7.27-7.39(5H，m)，7.48-7.53(1H，m)，7.64-7.76(2H，m)，8.27-8.29(1H，d)。
Compound 23: fusing point 168-169 DEG C.δppm 3.74(3H，s)，4.62-4.63(2H，d)，5.18(2H，s)，7.04-7.14(4H，m)，7.25-7.34(4H，m)，7.46-7.54(2H，m)，7.73-7.77(2H，m)，8.13(1H，m)，8.29-8.31(1H，m)。
Compound 27: fusing point 187-189 DEG C.δppm 3.76(3H，s)，4.62(2H，d)，5.22(2H，s)，7.10(2H，m)，7.26-7.30(6H，m)，7.80(2H，m)，8.30(1H，d)。
Compound 33: fusing point 225-226 DEG C.δppm 3.73(3H，s)，4.60-4.61(2H，d)，5.20(2H，s)，6.24(1H，s)，6.90-6.95(2H，m)，7.03-7.06(2H，m)，7.30-7.37(3H，m)，7.49-7.53(1H，m)，7.71-7.77(2H，m)，8.27-8.29(1H，d)。
Compound 38: fusing point 182-183 DEG C.δppm 2.38(3H，s)，3.71(3H，s)，4.56-4.57(2H，d)，，5.17(2H，s)，6.43(1H，s)，7.01-7.04(2H，m)，7.19-7.31(5H，m)，7.48-7.53(1H，m)，7.66-7.76(4H，m)，8.27-8.29(1H，m)。
Compound 44: fusing point 163-164 DEG C.δppm 2.27(3H，s)，3.63(2H，s)，3.73(3H，s)，4.32-4.34(2H，d)，5.15(2H，s)，5.60(1H，s)，6.96-6.99(2H，m)，7.10-7.26(6H，m)，7.49-7.54(1H，m)，7.69-7.77(2H，m)，8.28-8.30(1H，m)。
Compound 47: fusing point 163-164 DEG C.δppm 2.38(3H，s)，3.73(3H，s)，4.58-4.59(2H，d)，5.18(2H，s)，7.02-7.05(2H，m)，7.26-7.32(4H，m)，7.49-7.61(3H，m)，7.69-7.77(2H，m)，8.28-8.30(1H，m)。
Compound 55: fusing point 200-201 DEG C.δppm 3.73(3H，s)，4.56-4.58(2H，d)，5.19(2H，s)，6.10(1H，s)，7.03-7.06(2H，m)，7.27-7.32(2H，m)，7.51-7.55(4H，m)，7.72-7.74(4H，m)，8.30(1H，m)。
Compound 59: fusing point 118-119 DEG C.δppm 2.97-3.06(6H，d)，4.58-4.60(4H，m)，7.00-7.03(1H，m)，7.14-7.17(1H，m)，7.26-7.28(2H，m)，7.31-7.34(2H，m)，7.53-7.59(4H，m)，7.69-7.71(1H，m)，8.38(1H，m)，9.98(1H，s)。
Compound 62: fusing point 154-156 DEG C.δppm 2.97-3.06(6H，d)，4.58-4.60(4H，m)，7.00-7.03(1H，m)，7.14-7.17(1H，m)，7.26-7.28(2H，m)，7.31-7.34(2H，m)，7.53-7.59(4H，m)，7.69-7.71(1H，m)。
Compound 70: fusing point 149-150 DEG C.δppm 3.73(3H，s)，3.91-3.92(6H，m)，4.56-4.58(2H，d)，，5.18(2H，s)，6.40(1H，s)，6.82-6.85(1H，m)，7.02-7.05(2H，m)，7.27-7.31(3H，m)，7.45-7.51(2H，m)，7.69-7.76(2H，m)，8.28-8.30(1H，d)。
Compound 74: fusing point 178-179 DEG C.δppm 3.74(3H，s)，3.87-3.88(9H，m)，4.57-4.59(2H，d)，5.18(2H，s)，7.01-7.06(4H，m)，7.26-7.32(2H，m)，7.70(1H，m)，7.71(2H，m)，8.30(1H，m)。
Compound 79: fusing point 205-207 DEG C.δppm 3.05(3H，s)，3.74(3H，s)，4.60-4.61(2H，d)，5.22(2H，s)，6.45(1H，s)，7.05-7.08(2H，m)，7.26-7.34(2H，m)，7.52-7.55(1H，m)，7.74-7.78(2H，m)，7.81-7.87(2H，m)，7.97(1H，s)，8.27-8.29(1H，d)。
Compound 83: fusing point 171-173 DEG C.δppm 3.74(3H，s)，4.27(2H，m)，5.21(2H，s)，6.40(1H，s)，6.88(4H，m)，7.35-7.61(10H，m)，7.77(2H，m)，8.27(1H，m)。
Compound 88: fusing point 202-204 DEG C.δppm 3.72(3H，s)，3.87(3H，s)，4.61-4.63(2H，d)，4.17(2H，s)，6.20(1H，s)，7.02-7.09(3H，m)，7.27-7.28(1H，m)，7.31-7.37(2H，m)，7.44-7.48(1H，m)，7.71(2H，m)，8.26(1H，d)。
Compound 95: fusing point 168-170 DEG C.δppm 3.74(3H，s)，4.49-4.51(2H，m)，4.55(2H，s)，5.18(2H，s)，6.82-6.84(1H，m)，7.03-7.06(3H，m)，7.20-7.27(4H，m)，7.38-7.39(1H，m)，7.52(1H，m)，7.70-7.77(2H，m)，8.29-8.31(1H，d)。
Compound 101: fusing point 194-195 DEG C.δppm 3.74-3.77(3H，s)，4.60-4.62(2H，d)，5.22-5.24(2H，s)，6.80(1H，s)，7.05-7.08(2H，m)，7.27-7.36(3H，m)，7.52-7.55(1H，m)，7.74-7.77(2H，m)，8.10-8.14(1H，m)，8.27-8.30(1H，m)，8.44-8.46(1H，m)。
Compound 105: fusing point 206-208 DEG C.δppm 3.74(3H，s)，4.61(2H，d)，5.20(2H，s)，6.77(1H，s)，7.04-7.07(2H，m)，7.26-7.49(3H，m)，7.51-7.52(1H，m)，7.72-7.77(1H，m)，7.89-7.93(1H，m)，8.12-8.14(1H，m)，8.45-8.46(1H，m)。
Compound 108: fusing point is 118-120 DEG C.δppm 1.37-1.41(3H，t)，2.62(3H，s)，4.24-4.27(2H，q)，4.57-4.59(2H，d)，5.21(2H，s)，6.59(1H，s)，7.07-7.10(2H，m)，7.26-7.31(2H，m)，7.38-7.40(2H，m)，7.58(1H，m)，8.07-8.11(2H，m)，8.74-8.75(1H，m)。
Compound 112: fusing point 208-210 DEG C.δppm 3.72(3H，s)，4.56-4.58(2H，d)，5.18(2H，s)，6.59(1H，s)，7.02-7.05(2H，m)，7.27-7.30(3H，m)，7.38-7.41(1H，m)，7.49-7.54(1H，m)，7.69-7.77(2H，m)，8.08-8.10(1H，m)，8.26-8.29(1H，m)，8.74-8.75(1H，s)。
Compound 118: fusing point 177-178 DEG C.δppm 3.73(3H，s)，4.58-4.60(2H，d)，5.20(2H，s)，6.20(1H，s)，7.04-7.07(2H，m)，7.26-7.32(3H，m)，7.51-7.56(2H，m)，7.73-7.77(2H，m)，8.26-8.28(1H，d)，8.82(1H，s)。
Compound 122: fusing point 182-183 DEG C.δppm 3.73(3H，)，4.53-4.54(2H，d)，5.19(2H，s)，6.10(1H，s)，7.03-7.06(2H，m)，7.28-7.30(3H，m)，7.52(1H，m)，7.73-7.78(2H，m)，8.30(1H，m)，8.57(1H，s)。
Compound 129: fusing point 157-159 DEG C.δppm 3.73(3H，s)，4.54-4.56(2H，d)，5.18(2H，s)，6.50(1H，s)，6.66(1H，s)，7.03-7.06(2H，m)，7.14-7.15(1H，m)，7.28-7.31(3H，m)，7.51(1H，m)，7.66-7.77(2H，m)，8.29-8.31(1H，m)。
Compound 133: fusing point 173-174 DEG C.δppm 2.71(3H，s)，3.73(3H，s)，4.53-4.54(2H，d)，5.18(2H，s)，6.43(1H，s)，7.03-7.06(2H，m)，7.26-7.29(2H，m)，7.50(1H，m)，7.70(2H，m)，8.30(1H，d)。
Compound 138: fusing point 214-216 DEG C.δppm 3.62(3H，s)，3.80-4.00(2H，m)，5.28(2H，s)，7.14-7.24(4H，m)，7.54(3H，m)，7.64-7.67(3H，m)，7.81-7.82(3H，m)，8.14(1H，m)，8.50-8.52(1H，m)。
Compound 142: fusing point 170-172 DEG C.δppm 1.16-1.21(3H，t)，2.68-2.70(2H，q)，3.79(3H，s)，4.55-4.57(2H，m)，5.08(2H，s)，6.96-7.03(3H，m)，7.25-7.35(1H，m)，7.51(2H，m)，7.71-7.80(21H，m)，8.26(1H，m)，9.98(1H，s)。
Compound 143: fusing point 207-208 DEG C.δppm 1.16-1.21(3H，t)，2.59(3H，s)，2.70-2.73(2H，q)，3.84(3H，s)，4.47-4.49(2H，m)，4.63(2H，s)，6.99-7.02(2H，m)，7.14(1H，m)，7.30-7.33(2H，m)，7.52-7.58(1H，m)，7.70-7.76(2H，m)，8.04-8.08(1H，m)，8.72-8.78(1H，m)。
Compound 144: fusing point 129-130 DEG C.δppm 1.14-1.19(3H，t)，1.83-1.85(3H，d)，2.66-2.68(2H，q)，3.71(3H，s)，3.80(3H，s)，4.50-4.52(2H，d)，5.50-5.58(1H，m)，6.94-6.97(3H，m)，7.24-7.28(2H，m)，7.42-7.55(1H，m)，7.72-7.73(2H，m)，8.25-8.30(1H，m)。
Compound 145: fusing point 130-132 DEG C.δppm 1.34-1.38(3H，t)，2.29(3H，s)，2.68-2.71(2H，q)，3.81(3H，s)，4.30-4.33(2H，m)，4.56-4.58(3H，m)，4.66(2H，s)，6.99-7.02(4H，m)，7.22-7.26(2H，m)，7.33-7.35(1H，m)，7.80(1H，m)，9.92(1H，s)。
Compound 146: fusing point 113-114 DEG C.δppm 1.15-1.20(3H，t)，2.67-2.70(2H，q)，3.73(3H，s)，3.79(3H，s)，4.53-4.55(2H，d)，5.18(2H，s)，7.01-7.04(3H，m)，7.27-7.33(2H，m)，7.52(1H，m)，7.72-7.74(2H，m)，8.30(1H，m)。
Compound 150: fusing point 178-180 DEG C.δppm 3.74(3H，s)，4.02-4.03(3H，s)，4.51-4.53(2H，d)，5.20(2H，s)，6.15(1H，s)，7.03-7.06(2H，d)，7.27-7.29(3H，m)，7.52(1H，m)，7.69-7.77(3H，m)，8.27-8.30(1H，m)。
Compound 152: fusing point 179-180 DEG C.δppm 3.74(3H，s)，3.91(3H，s)，4.54-4.56(2H，d)，5.20(2H，s)，6.30(1H，s)，7.03-7.06(2H，d)，7.27-7.30(2H，m)，7.49-7.54(1H，m)，7.71-7.77(2H，m)，8.27-8.30(1H，m)。
Compound 159: fusing point 156-158 DEG C.δppm 1.58(3H，m)，3.94(3H，s)，4.30(2H，m)，4.40(2H，m)，5.19(2H，s)，6.80-7.20(6H，m)，7.30-7.40(3H，m)，7.42-7.58(3H，m)，7.70-7.80(1H，m)，7.82-8.00(1H，m)。
Compound 165: fusing point 137-138 DEG C.δppm 0.98-1.00(3H，m)，2.39(3H，s)，3.74(3H，s)，3.90(3H，s)，4.50-4.52(2H，d)，4.92(2H，s)，5.19(2H，s)，7.04-7.07(2H，m)，7.52-7.55(2H，m)，7.72-7.78(3H，m)，8.30(1H，m)。
Compound 193: fusing point 98-99 DEG C.δppm 3.91-3.93(8H，m)，3.99(6H，m)，4.62-4.64(4H，m)，6.30-6.35(2H，m)，7.21-7.27(4H，m)，7.38-7.41(3H，m)。
Example of formulations (each component add-on is weight percentage, is metered into after active compound folding hundred)
Example 6:30% wettable powder
Compound 23 30%
Sodium lauryl sulphate 2%
Sodium lignosulfonate 3%
Naphthalene sulfonic acidformaldehyde condensation product 5%
Light calcium carbonate complements to 100%
Compound 23 and other components are fully mixed, after ultra-fine pulverizer disintegrating, obtain 30% wettable powder product.
Example 7:40% suspension concentrates
Compound 152 40%
Ethylene glycol 10%
Nonoxynol-9 6%
Sodium lignosulfonate 10%
Carboxymethyl cellulose 1%
37% formalin 0.2%
75% silicone oil water miscible liquid 0.8%
Water complements to 100%
Compound 152 and other components are fully mixed, the suspension concentrates obtaining thus, dilute with water gained suspension agent can obtain the diluent of any desired concn.
Example 8:60% water-dispersible granules
Compound 138 60%
Naphthalenesulfonic acid-formaldehyde condensate 12%
N-methyl-N-oleoyl-Sodium taurine salt 8%
Polyvinylpyrrolidone 2%
Carboxymethyl cellulose 2%
Kaolin complements to 100%
By compound 138 and other component co-grindings, then after adding water and mediating, add in the tablets press of 10-100 eye mesh screen and carry out granulation, and then drying, screening (pressing screen cloth scope).
Biological activity determination embodiment
Example 9: greenhouse pot culture biological activity (cucumber downy mildew)
Test adopts potted plant seedling assay method.Select the potted plant cucumber seedling of growth neat and consistent to cut off vegetative point and retain two true leaves, carry out foliar spray processing according to design concentration with the compounds of this invention, separately establish the blank of spray clear water, 3 repetitions.Process latter second day inoculation cucumber downy mildew spore suspension, after inoculation, place phytotron (temperature: 25 DEG C of daytimes, 20 DEG C of nights, relative humidity: 95～100%) moisturizing is cultivated, and places greenhouse (25 DEG C ± 1 DEG C) normal management after 24 hours.Inoculate latter 7 days investigation prevention effects, disease scale, with reference to National Standard of the People's Republic of China " pesticide field efficacy medicine test criterion ", calculates prevention effect with disease index.
Partial test result is as follows:
When liquor strength is 400ppm, 13,23,95,138,143 and 152 pairs of cucumber downy mildew preventive effects of compound reach 100%;
When liquor strength is 100ppm, 13,23,95,138,143 and 152 pairs of cucumber downy mildew preventive effects of compound reach 50%.
Example 10: greenhouse pot culture biological activity (wheat powdery mildew)
Test adopts potted plant seedling assay method.Select the potted plant seedling of 2 leaf phase wheat of growth neat and consistent, carry out foliar spray processing according to design concentration with the compounds of this invention, separately establish the blank of spray clear water, 3 repetitions.Process latter second day spore and shake off method inoculation, postvaccinal crop is put greenhouse (25 DEG C ± 1 DEG C) normal management.Seven days " Invest, Then Investigate "s of medication, disease scale, with reference to National Standard of the People's Republic of China " pesticide field efficacy medicine test criterion ", calculates prevention effect with disease index.
Partial test result is as follows:
When liquor strength is 400ppm, compound 62 reaches 100% to wheat powdery mildew preventive effect;
Example 11: greenhouse pot culture biological activity (corn rust)
Test adopts potted plant seedling assay method.Select the potted plant seedling of 2-3 leaf phase corn of growth neat and consistent, carry out foliar spray processing according to design concentration with the compounds of this invention, separately establish the blank of spray clear water, 3 repetitions.Process latter second day inoculation corn rust spore suspension, after inoculation, place phytotron (temperature: 25 DEG C of daytimes, 20 DEG C of nights, relative humidity: 95～100%) moisturizing is cultivated, and places greenhouse (25 DEG C ± 1 DEG C) normal management after 24 hours.10d investigation prevention effect after inoculation, disease scale, with reference to National Standard of the People's Republic of China " pesticide field efficacy medicine test criterion ", calculates prevention effect with disease index.
Partial test result is as follows:
When liquor strength is 400ppm, 62,193 pairs of corn rust preventive effects of compound reach 100%.
Claims (7)
1. an acyl group benzylamine compound, structure is as shown in (I) general formula:
In formula:
R
1be selected from hydrogen or methyl; M is selected from 1;
R
2be selected from C
1-C
4alkyl; N is selected from 0 to 3 integer;
Y is selected from O or NR
4;
R
3, R
4can be identical or different, be selected from respectively hydrogen or C
1-C
5alkyl; Or,
When Y is selected from NR
4time, NR
4with R
3composition morpholine, piperazine or piperidine ring;
Q is selected from one of group as follows:
R
8be selected from H, Cl, Br, F, CH
3, CH
2cH
3, CF
3, OCH
3or pyridyl;
R
9be selected from CH
3or CH
2cH
3;
A is selected from 1 to 4 integer; D is selected from 1 to 2 integer.
2. compound according to claim 1, is characterized in that: in general formula (I)
R
1be selected from hydrogen; M is selected from 1;
R
2be selected from C
1-C
3alkyl; N is selected from 0 to 2 integer;
Y is selected from O or NR
4;
R
3, R
4can be identical or different, be selected from respectively hydrogen or C
1-C
5alkyl; Or,
When Y is selected from NR
4time, NR
4with R
3composition morpholine ring;
Q is selected from one of group as follows:
R
8be selected from H, Cl, Br, F, CH
3, CH
2cH
3, CF
3, OCH
3or pyridyl;
R
9be selected from CH
3;
A is selected from 1 to 3 integer; D is selected from 1 to 2 integer.
3. compound according to claim 2, is characterized in that: in general formula (I)
R
1be selected from hydrogen; M is selected from 1;
R
2be selected from C
1-C
3alkyl; N is selected from 0 to 2 integer;
Y is selected from O or NR
4;
R
3, R
4can be identical or different, be selected from respectively hydrogen or C
1-C
3alkyl;
Q is selected from one of group as follows:
R
8be selected from H, Cl, Br, F, CH
3, CH
2cH
3, CF
3, OCH
3or pyridyl;
R
9be selected from CH
3.
4. prepare intermediate phenylbenzylamine or its salt of general formula (I) compound, as shown in general formula (II):
In formula:
R
1be selected from hydrogen or methyl; M is selected from 1;
R
2be selected from C
1-C
4alkyl; N is selected from 0 to 3 integer;
Y is selected from O or NR
4;
R
3, R
4can be identical or different, be selected from respectively hydrogen or C
1-C
5alkyl; Or,
When Y is selected from NR
4time, N R
4with R
3composition morpholine, piperazine or piperidine ring.
5. a purposes of preventing and treating germ according to the acyl group benzylamine compound as shown in general formula (I) claimed in claim 1 in agriculture field.
6. a fungicidal composition, is characterized in that: containing just like general formula (I) compound described in any one in claim 1-3 as active ingredient, in composition, the weight percentage of active ingredient is 0.1-99%.
7. in agriculture field, prevent and treat the purposes of germ according to composition claimed in claim 6 for one kind.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010535133.0A CN102464592B (en) | 2010-11-03 | 2010-11-03 | Acyl benzylamine compound and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010535133.0A CN102464592B (en) | 2010-11-03 | 2010-11-03 | Acyl benzylamine compound and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102464592A CN102464592A (en) | 2012-05-23 |
| CN102464592B true CN102464592B (en) | 2014-09-03 |
Family
ID=46068755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010535133.0A Active CN102464592B (en) | 2010-11-03 | 2010-11-03 | Acyl benzylamine compound and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102464592B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11771088B2 (en) | 2015-11-18 | 2023-10-03 | Monsanto Technology Llc | Insecticidal compositions and methods |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672101A (en) * | 2013-11-26 | 2015-06-03 | 中国中化股份有限公司 | o-chloroacetylamino benzoyl methylamine preparation method |
| CN103980203B (en) * | 2014-05-20 | 2015-11-18 | 浙江金伯士药业有限公司 | A kind of novel preparation method of carnosine |
| CN106973990B (en) * | 2016-01-19 | 2019-12-10 | 中国科学院上海有机化学研究所 | fumigation method for preventing and controlling entomophthora in grains |
| CN116239500A (en) * | 2023-03-13 | 2023-06-09 | 中国农业大学 | High-activity abscisic acid functional analogue (I) and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0207253D0 (en) * | 2002-03-27 | 2002-05-08 | Syngenta Participations Ag | Chemical compounds |
| EP1792901A1 (en) * | 2005-11-22 | 2007-06-06 | Bayer CropScience S.A. | N-(1-alkyl-2-phenylethyl)-carboxamide derivatives and use thereof as fungicides |
-
2010
- 2010-11-03 CN CN201010535133.0A patent/CN102464592B/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11771088B2 (en) | 2015-11-18 | 2023-10-03 | Monsanto Technology Llc | Insecticidal compositions and methods |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102464592A (en) | 2012-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1210766A (en) | 1-(n-heterocyclic containing)-3-carboxy-4-halogen- phenyl derivatives | |
| US5169855A (en) | Piperidine ether derivatives as psychotropic drugs or plant fungicides | |
| CN102464592B (en) | Acyl benzylamine compound and use thereof | |
| CN102239166A (en) | Substituted 1-(thiazolyl)- and 1-(isothiazolyl)pyrazole-4-yl-acetic acids, method for the production thereof and the use thereof as herbicides and plant growth regulators | |
| CN104822674B (en) | 1,2,4-triazine-3,5-dione-6-carboxamides and use thereof as herbicide | |
| CN103221395A (en) | Insecticidal compounds | |
| EP0034945B1 (en) | N-phenylpyrazole derivatives | |
| CN106467537A (en) | A kind of substituted amides compound and purposes | |
| CN102336744B (en) | Substituted triazoline ether ketone class compound and application thereof as bactericide as well as insecticide and acaricide | |
| CA3134907A1 (en) | Amide compounds and preparation method therefor and use thereof | |
| CN102336743B (en) | Triazoline ketone ether-substituted compound and application thereof | |
| CN110054596A (en) | A kind of substitution furodiazole compound and its application | |
| AU2011203504A1 (en) | Animal ectoparasite-controlling agent | |
| CN102993100B (en) | Substituted pyrazole (sulphur) ketone compound and application thereof | |
| CN102464618B (en) | Pyrazolecarboxamide compound and application thereof | |
| CN106715403A (en) | Bicyclic arylcarboxylic acid amides and their use as herbicides | |
| JPH04124178A (en) | Heterocyclic compound and herbicide containing the same | |
| AU2011203501A1 (en) | Animal ectoparasite-controlling agent | |
| AU2011203502A1 (en) | Animal ectoparasite-controlling agent | |
| US4044013A (en) | 1,2-Dialkylpyrazolium compounds having 3-(or 3,5-) nitrogen-containing heterocyclic group | |
| CN102993189B (en) | Hydrazone-containing triazolinone compounds and uses thereof | |
| AU615280B2 (en) | Novel thiadiazines, process for production thereof, and insecticidal and acaricidal agents comprising the thiadiazines | |
| CN101768088A (en) | Phthalic acid derivative and agricultural and horticultural pesticide and application method thereof | |
| CN104177340A (en) | Novel quinazoline (sulfur) ketone compound and application | |
| CN102464622B (en) | Substituted pyrimidine ammine compound and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160121 Address after: 110021 Liaodong Road, Tiexi District, Liaoning, No. 8-1, No. Patentee after: SHENYANG SINOCHEM PESTICIDE CHEMICAL RESEARCH AND DEVELOPMENT CO., LTD. Address before: 100031 Beijing, Xicheng District, the door of the revitalization of the main street, No. 28 Patentee before: Sinochem Corporation Patentee before: Shenyang Research Institute of Chemical Industry |