CN102464592A - Acyl benzylamine compound and use thereof - Google Patents
Acyl benzylamine compound and use thereof Download PDFInfo
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- CN102464592A CN102464592A CN2010105351330A CN201010535133A CN102464592A CN 102464592 A CN102464592 A CN 102464592A CN 2010105351330 A CN2010105351330 A CN 2010105351330A CN 201010535133 A CN201010535133 A CN 201010535133A CN 102464592 A CN102464592 A CN 102464592A
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- alkoxyl group
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- 0 CCC1=CC=C[C@@]2C1=C2* Chemical compound CCC1=CC=C[C@@]2C1=C2* 0.000 description 10
- RWZYAGGXGHYGMB-UHFFFAOYSA-N Nc1ccccc1C(O)=O Chemical compound Nc1ccccc1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 1
- TXJUTRJFNRYTHH-UHFFFAOYSA-N O=C(c(cccc1)c1N1)OC1=O Chemical compound O=C(c(cccc1)c1N1)OC1=O TXJUTRJFNRYTHH-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 the 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 agricultural-food such as grain that can satisfy human primary demand and fibers, like cotton, and paddy rice, corn, wheat, soybean etc. are caused very big infringement.Kill or suppress that the germ growth is avoided the time or the infringement that reduces crop is a kind of effective way of improving agriculture prodn.Therefore need continually develop more effective new type bactericide.Acyl group benzylamine compound such as azoles insect amide (tolfenpyrad) [US 5039693], tebufenpyrad (tebufenpyrad) [US 4950668], CN1927860 etc. are many to be used as insecticidal/acaricidal agent; CN1919838, WO2002083647 report compound has bactericidal and insecticidal activity, but as the acyl group benzylamine compound of general structure of the present invention as sterilant use do not see bibliographical information.
Summary of the invention
In order to satisfy the requirement on the agricultural, the invention provides a kind of novel acyl group benzylamine compound and on agricultural the control germ application.
Technical scheme of the present invention is following: (claim is done after partly changing well more in the lump)
The present invention provides a kind of acyl group benzylamine compound, shown in general formula (I):
In the formula:
R
1Be selected from hydrogen or C
1-C
12Alkyl; M is selected from 1 to 3 integer;
R
2Be selected from halogen, cyanic acid, 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
5N 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 hydrogen, cyanic acid, C respectively
1-C
12Alkyl, halo C
1-C
12Alkyl, C
1-C
12Alkoxyl group, halo C
1-C
12Alkoxyl group, C
3-C
6Naphthenic base, cyanic acid 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
5Perhaps,
When Y is selected from NR
4The time, N R
4With R
3Form replacement or unsubstituted five yuan or six-ring, described substituting group is selected from 1-2 C
1-C
4Alkyl;
R
5Be selected from unsubstituted or independently be selected from the substituted phenyl of following group, benzyl or heteroaryl: halogen, nitro, cyanic acid, C by 1-4
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 not and replaces or by 1-4 the substituted C of following radicals
1-C
6Alkyl, cyclopropyl or cyclohexyl: Cl, Br, F or C
1-C
4Alkyl;
Perhaps be selected from not and replace or by 1-3 substituted anilino of following radicals or C
2-C
4Thiazolinyl: Cl, Br, F, C
1-C
4Alkyl, C
3-C
6Naphthenic base, C
1-C
4Haloalkyl, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy or C
1-C
4Alkoxy carbonyl;
Perhaps be selected from not and replace or by 1-3 the substituted phenyl of following radicals, benzene oxygen ethyl, benzene oxygen propyl group, pyridyl, pyrimidyl, piperidyl, piperazinyl, thiazolyl, isothiazolyl, thiadiazolyl group 、 oxazolyl 、 isoxazolyl 、 oxadiazole base, triazolyl, thienyl, furyl, quinolyl, indyl, 3-pyrazolyl, 4-pyrazolyl or 4-pyrazoles methyl: halogen, CN, NO
2, C
1-C
4Alkyl, C
3-C
6Naphthenic base, 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
Comparatively preferred compound is among the present invention: in the 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, cyanic acid, 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
5N 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 hydrogen, cyanic acid, C respectively
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
6Alkoxyl group, halo C
1-C
6Alkoxyl group, C
3-C
6Naphthenic base, cyanic acid 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
5Perhaps,
When Y is selected from NR
4The time, N R
4With R
3Form morpholine, piperazine, piperidines, pyrazoles, pyrroles or triazole ring;
R
5Be selected from unsubstituted or by 1-4 independently be selected from the substituted phenyl of following group, benzyl, pyridyl, pyrimidyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazoles base,, thiadiazolyl group, pyrazolyl, pyranyl, triazolyl or tetrazyl: halogen, nitro, cyanic acid, 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
4Dialkyl amino carbonyl, do not replace or substituted phenyl, do not replace or substituted 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, CF
3, CH
2CF
3, do not replace or substituted phenyl, do not replace or substituted pyridyl, 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 the 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, cyanic acid, 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
5N 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 hydrogen, cyanic acid, C respectively
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
6Alkoxyl group, halo C
1-C
6Alkoxyl group, C
3-C
6Naphthenic base, cyanic acid 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
5Perhaps,
When Y is selected from NR
4The time, N R
4With R
3Form morpholine, piperazine, piperidines or pyrazoles ring;
R
5Be selected from unsubstituted or by 1-4 independently be selected from the substituted phenyl of following group, benzyl, pyridyl, pyrimidyl, thiazolyl, oxazolyl, oxadiazoles base,, thiadiazolyl group, pyrazolyl, triazolyl or tetrazyl: halogen, nitro, cyanic acid, 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 substituted phenyl, do not replace or substituted 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, do not replace or substituted phenyl, do not replace or substituted pyridyl, 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 further preferred compound of the present invention is: in the 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, cyanic acid, 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 hydrogen, cyanic acid, C respectively
1-C
5Alkyl, halo C
1-C
5Alkyl, C
1-C
5Alkoxyl group, halo C
1-C
5Alkoxyl group, C
3-C
6Naphthenic base, cyanic acid 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
5Perhaps,
When Y is selected from NR
4The time, N R
4With R
3Form morpholine, piperazine or piperidine ring;
R
5Be selected from unsubstituted or independently be selected from the substituted phenyl of following group, benzyl, pyridyl, pyrimidyl, thiazolyl, oxazolyl or pyrazolyl: fluorine, chlorine, bromine, nitro, cyanic acid, C by 1-3
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, do not replace or substituted phenyl, do not replace or substituted pyridyl, 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, do not replace or substituted phenyl, do not replace or substituted pyridyl, 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 further preferred again compound of the present invention is: in the 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, cyanic acid, 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 hydrogen, C respectively
1-C
5Alkyl, C
1-C
5Alkoxyl group, cyanic acid 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
5Perhaps,
When Y is selected from NR
4The time, N R
4With R
3Form morpholine, piperazine or piperidine ring;
R
5Be selected from unsubstituted or independently be selected from the substituted phenyl of following group, benzyl, pyridyl, pyrimidyl, thiazolyl or pyrazolyl: fluorine, chlorine, bromine, nitro, cyanic acid, C by 1-2
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, do not replace or substituted phenyl, do not replace or substituted pyridyl, 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, do not replace or substituted phenyl, do not replace or substituted pyridyl, 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 the 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 hydrogen or C respectively
1-C
3Alkyl;
R
5Be selected from unsubstituted or independently be selected from the substituted phenyl of following group, benzyl, pyridine or pyrimidyl: fluorine, chlorine, bromine, nitro, cyanic acid, C by 1-2
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, do not replace or substituted phenyl, do not replace or substituted pyridyl, 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, do not replace or substituted phenyl, do not replace or substituted pyridyl, described substituting group is selected from 1-3 following group: Cl, Br, F or CH
3
In the definition of the general formula that provides above (I) compound, it is following to compile used term General Definition:
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: the straight or branched haloalkyl, the Wasserstoffatoms 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; Wasserstoffatoms 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: the straight or branched alkyl is connected on the structure through the sulphur atom key.
Halogenated alkylthio: the straight or branched alkylthio, the Wasserstoffatoms 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 key, for example vinyl or allyl groups on any position.
Alkynyl: straight or branched also can have triple bond on any position, for example ethynyl or propargyl.
The indication heteroaryl is to contain one or more N, O, the heteroatomic five-ring of S or six-ring aryl among the present invention.For example 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 midbody phenylbenzylamine or its salt of being used to prepare general formula (I) compound of novel structure, shown in general formula (II):
In the formula:
R
1Be selected from hydrogen or C
1-C
12Alkyl; M is selected from 1 to 3 integer;
R
2Be selected from halogen, cyanic acid, 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
5N 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 hydrogen, cyanic acid, C respectively
1-C
12Alkyl, halo C
1-C
12Alkyl, C
1-C
12Alkoxyl group, halo C
1-C
12Alkoxyl group, C
3-C
6Naphthenic base, cyanic acid 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
5Perhaps,
When Y is selected from NR
4The time, N R
4With R
3Form replacement or unsubstituted five yuan or six-ring, described substituting group is selected from 1-2 C
1-C
4Alkyl;
R
5Be selected from unsubstituted or independently be selected from the substituted phenyl of following group, benzyl or heteroaryl: halogen, nitro, cyanic acid, C by 1-4
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 salifiable acid of phenylbenzylamine shown in the general formula of the present invention (II): carboxylic acid is acetate, propionic acid, butyric acid, oxalic acid, hexanodioic acid, dodecanedioic acid, LAURIC ACID 99 MIN, Triple Pressed Stearic Acid, trifluoroacetic acid, fumaric acid, toxilic acid, phenylformic acid or phthalic acid for example; Sulfonic acid is methylsulfonic acid, 1 for example, 3-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 the structural formula as I-1:
When 3 of phenyl ring are connected, shown in the structural formula as I-2;
When 4 of phenyl ring are connected, shown in the 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.
The part concrete structure of Q group is seen table 1 in the compound of Formula I of the present invention; Work as CHR
1) when the link position of mCONH and phenyl ring is 2, R in the phenyl ring
2Concrete substituting group is seen table 2; As (CHR
1) when the link position of mCONH and phenyl ring is 3, R
2Concrete substituting group is seen table 3; As (CHR
1) when the link position of mCONH and phenyl ring is 4, R
2Concrete substituting group is referring to table 4; Y-R
3Concrete substituting group is seen table 5; Other substituting groups such as R in the general formula (I)
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
The part preferred compound can be explained the present invention with the particular compound of listing in table 6, table 7, the table 8, but does not limit the present invention.
Table 6
More than in each table abridge Bn, Py, Ph represent benzyl, pyridyl, phenyl respectively, table 6R
2"-" expression unsubstituted in the row, promptly corresponding position is a hydrogen on the phenyl ring.
Table 7
Compound number is 194-386 in the table 7 (omission provides), other each radicals R in the table
1, R
2, Y-R
3, R
4, and the number of m, n is corresponding is same as 1-193 compound in the table 6 in order.
Table 8
Compound number is 387-579 in the table 8 (omission provides), other each radicals R in the table
1, R
2, Y-R
3, R
4, and the number of m, n is corresponding is same as 1-193 compound in the table 6 in order.
General formula of the present invention (I) compound can prepare according to following method:
According to above-mentioned reaction equation, under the situation that has alkali or alkali-free to exist, make the reaction of acyl chlorides (III) and phenylbenzylamine (II); Said reaction preferably uses solvent under 0 to 100 ℃, to carry out; Preferred 0 to 25 ℃ of temperature of reaction, the reaction times is 30 minutes to 20 hours, preferred 0.5～10 hour.Said solvent is that reaction is not had the directly solvent of influence, comprises aromatic hydrocarbons, like benzene, toluene and YLENE; Ketone is like acetone methylethylketone and mibk; Halohydrocarbon is like methylene dichloride, chloroform and ethylene dichloride; Lipid is like methyl acetate and ETHYLE ACETATE; And polar solvent, like THF, acetonitrile 、 diox, N, dinethylformamide, N-Methyl pyrrolidone, methyl-sulphoxide and pyridine.
Described alkali comprises metal hydride, like sodium hydride; Alkali metal hydroxide is like sodium hydroxide and Pottasium Hydroxide; Alkaline carbonate is like yellow soda ash and salt of wormwood; Organic amine is like pyridine and triethylamine.
In order after reaction, to separate (I) target compound, under the situation of using water-soluble solvent, remove said solvent under reduced pressure, in the gained resistates, add water, use water-fast aromatic hydrocarbon, like benzene, toluene and YLENE; Halogenated alkane such as chloroform and methylene dichloride; And the ester class, like the above-mentioned resistates of ethyl acetate extraction, and wash extraction liquid with saturated sodium-chloride water solution, use siccative such as anhydrous magnesium sulfate or anhydrous sodium sulfate drying gained extraction liquid again, decompression desolventizes then.When using water-immiscible solvent, then in reaction mixture, add water, concussion separates, and with saturated sodium-chloride water solution flushing gained organic layer, uses siccative such as anhydrous magnesium sulfate or anhydrous sodium sulfate drying again, and decompression desolventizes then.Through recrystallization, flushing and column chromatography the gained residue purified is handled, obtained target compound by general formula (I) expression.
As the midbody that synthesizes by the target compound of general formula (I) expression,, synthetic according to the method described in the JP4069379 by the acyl chlorides of general formula (III) expression.
Phenylbenzylamine compounds shown in the general formula (II) is the key intermediate of preparation general formula of the present invention (I) compound, and its structure is not appeared in the newspapers before this, available following method preparation:
(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 under 0 to 100 ℃, make benzonitrile (IV) and hydrogen react preferred 20 to 50 ℃ of this temperature of reaction; Reaction times is 30 minutes to 20 hours, preferred 0.5～10 hour.
As long as said reaction is not had direct influence, any organic solvent all can be used as the organic solvent of said reaction.Described organic solvent comprises alcohols, like methyl alcohol, ethanol and Virahol; Aromatic hydrocarbon is like benzene.Toluene and YLENE; Ketone is like acetone, methylethylketone and mibk; Halohydrocarbon is like chloroform and methylene dichloride; Water; The ester class is like methyl acetate and ETHYLE ACETATE; Perhaps polar solvent is like THF, acetonitrile 、 diox, N, dinethylformamide, N-Methyl pyrrolidone, methyl-sulphoxide and pyridine.
Said metal catalyst comprises Raney's nickel, palladium carbon and platinum oxide.
For separate type after reaction (II) target compound; Said metal catalyst is removed by filter from the gained reaction mixture; Remove solvent then under reduced pressure, to the gains purification process, make with extra care and obtain pure products with recrystallization, placement evaporation, flushing and column chromatography.
Can be according to currently known methods such as US2001070671, J.Am.Chem.Soc.1960,82:2953 is through corresponding aminobenzoic acid derivative, halogen acyl chloride and hydroxybenzene nitrile synthesis of phenyl nitrile (IV).
(2) can be through the salt of following method synthesis of phenyl benzylamine:
The preferred solvent that uses makes benzylamine (II) and acid-respons under-5 to 50 ℃, 0 to 25 ℃ of preferred temperature is specifically with reference to CN1511142A.
Can comprise with the salifiable acid of phenylbenzylamine by general formula (II) expression of the present invention: carboxylic acid is acetate, propionic acid, butyric acid, oxalic acid, hexanodioic acid, dodecanedioic acid, LAURIC ACID 99 MIN, Triple Pressed Stearic Acid, trifluoroacetic acid, fumaric acid, toxilic acid, phenylformic acid or phthalic acid for example; Sulfonic acid is methylsulfonic acid, 1 for example, 3-third disulfonic acid, tosic acid or Witco 1298 Soft Acid; Reach mineral acid for example hydrochloric acid, sulfuric acid, nitric acid or carbonic acid.
As long as said reaction is not had direct influence, any organic solvent all can be used as the organic solvent of said reaction.Described organic solvent comprises aromatic hydrocarbon, like benzene, toluene or YLENE; Ketone is like acetone, methylethylketone or mibk; Halohydrocarbon is like chloroform or methylene dichloride; Water; The ester class is like methyl acetate or ETHYLE ACETATE; And polar solvent, like THF, acetonitrile 、 diox, N, dinethylformamide, 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 the disease that oidium germ, Powdery Mildew germ, rust germ etc. cause as sterilant.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 good active.Therefore, said compound can be used as the activeconstituents of the sterilant in agricultural fields such as agricultural, gardening and flower culture, and therefore general formula of the present invention (I) compound preferably is used to prevent and treat the application of phytopathogen in agricultural and other field.The phytopathogen that compound of the present invention can be prevented and treated is not limited to foregoing.
Because good performance, above-claimed cpd can be advantageously used in protection agricultural and important crop, domestic animal and the kind poultry of horticulture, and the human environment that often goes avoids the injury of fungi.
For obtaining ideal effect, the consumption of compound changes because of various factors, for example the formulation of the type of compound used therefor, protected crop, harmful organism, gradient of infection, weather condition, application method, employing.
The compound dosage of per hectare 10 grams-1000 grams can provide sufficient control.
Another object of the present invention also relates to through using general formula (I) compound, the method for the plant pathogenic fungi in crop that control agricultural and horticulture are important and/or domestic animal and kind poultry and/or the human environment that often goes.Especially, the consumption of compound changes in per hectare 10 grams-1000 grams.
In order to be applied to agricultural, it is normally useful that use contains one or more general formulas (I) compound compositions.
Another object of the present invention relates to and contains the fungicidal compsn of one or more general formulas (I) compound as activeconstituents, and the weight percentage of activeconstituents is 0.1-99% in the compsn.Also contain agricultural in the compsn and go up acceptable carrier, and contain tensio-active agent usually.Therefore, technical scheme of the present invention comprises that also said composition prevents and treats the purposes of germ as sterilant in agricultural or other field.
The type of service of compsn 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.
Compsn is for example chosen wantonly in the presence of tensio-active agent with the currently known methods preparation, through diluting or the lytic activity material with solvent medium and/or solid diluent.
Available solid diluent or carrier for example are: silicon-dioxide, kaolin, wilkinite, talcum, zeyssatite, rhombspar, lime carbonate, Natural manganese dioxide, chalk, clay, synthetic silicate, attapulgite, sepiolite etc.
Beyond dewatering; The available liquid diluent also comprises like aromatics organic solvent (mixture of YLENE or korenyl, chlorobenzene etc.), paraffin (petroleum fractions), alcohols (methyl alcohol, propyl alcohol, butanols, octanol, glycerine); Ester class (ETHYLE ACETATE, isobutyl acetate etc.); Ketone (pimelinketone, acetone, methyl phenyl ketone, isophorone, ethyl pentyl group ketone etc.), amides (N, dinethylformamide, N-Methyl pyrrolidone etc.).
The available tensio-active agent is sodium, calcium, triethylamine or the triethanolamine salt of polyoxyethylene ester, sulfonated lignin of AS, alkylaryl sulphonate, polyoxyethylene alkylphenol, sorbyl alcohol etc.
Compsn also can contain special additive and be used for specific purpose, for example contains tackiness agent such as gum arabic, Z 150PH, Vinylpyrrolidone polymer etc.
The concentration of activeconstituents can be according to the preparation type of activeconstituents, application target, envrionment conditions and employing and in wide region, change in the above-mentioned compsn.The activity component concentration scope is generally 0.1-99%, preferred 5-60%.
If desired, can in compsn, add can be compatible with general formula (I) compound other activeconstituentss, for example other miticide/sterilants, mycocide, plant-growth regulator, microbiotic, weedicide, fertilizer.
But the form of said compsn is not limited in this, also can be with one or both or polymorphic compound with as activeconstituents.
The compound method of several frequently seen formulation is exemplified below:
The preparation of suspension agent: active component content is 5-35% in the common prescription.With water is medium, and former medicine, dispersion agent, suspending agent and antifreezing agent etc. are added in the sand mill, grinds, and processes suspension agent.
The preparation of aqueous emulsion: former medicine, solvent added with emulsifying agent be in the same place, make and be dissolved into even oil phase.Water, antifreezing agent etc. is mixed, becomes the homogeneous water.Under high-speed stirring, water is joined oil phase or oil phase is joined water, form the aqueous emulsion of good dispersibility.Aqueous emulsion active component content of the present invention is generally 5%-15%.Be the preparation emulsifiable concentrate, compound of the present invention is dissolvable in water a kind of or several mixed solvents, adds emulsifying agent again and strengthens the dispersion effect of compound in water.
The preparation of wettable powder:,, after ultrafine crusher is pulverized, promptly obtain the wettable powder product of predetermined content (for example 10-60%) with thorough mixing such as former medicine, various tensio-active agent and solid diluents by the prescription requirement.For preparation is suitable for spraying the wettable powder of usefulness, compound of the present invention can with pressed powder such as clay, inorganic silicate, carbonate and wetting agent, tackiness agent and/or the dispersion agent composition mixture of porphyrize.
The preparation of water-dispersible granules: former medicine and powdery solid thinner, wetting spreader-sticker and tackiness agent etc. are mixed pulverizing; After adding the water kneading again; Add in the tablets press that the certain specification screen cloth is housed and carry out granulation, and then through dry, screening (pressing the screen cloth scope).Also can former medicine, dispersion agent, disintegrating agent and wetting agent and solid diluent be added in the sand mill, be medium milling with water, processes suspension agent, carries out spray drying granulation then, and formulation content is the 20-30% granular product usually.
Embodiment
Following specific embodiment is used for further specifying the present invention, but the present invention only limits to these examples absolutely not.
Synthetic embodiment
Embodiment 1: the preparation of intermediate II-1
1).
In the 150ml tetrahydrofuran solution that contains 13.70g (0.1mol) anthranilic acid, add 19.80g (0.067mol) solid phosgene under the stirring at room on a small quantity in batches, added in about 1.5 hours, continue stirring at room reaction 2-3 hour; After the TLC monitoring reaction finishes, remove solvent under reduced pressure, residuum adds in the 80ml water; Be stirred to excess phosgene and decompose fully, filter and water, each 50ml washing of sherwood oil successively, get white solid 14.00g; Yield 86.0%, fusing point 239-240 ℃.
2).
In the 100ml acetonitrile solution that contains 16.30g (0.1mol) benzoxazinone, slowly drip 40% aqueous methylamine solution under the stirring at room, when solution becomes is clarified till, drip 80ml first ammonia soln approximately; Drip and finish, continued room temperature reaction 0.5 hour, after the TLC monitoring reaction finishes; Decompression desolventizes, and water, each 50ml washing of sherwood oil get white solid 13.73g; Yield 91.5%, fusing point 78-79 ℃.
3).
In the 50ml dichloromethane solution that contains 15.00g (0.1mol) anthranilamide and 12.10g (0.12mol) triethylamine, slowly drip the 30ml dichloromethane solution that contains 12.40g (0.11mol) chloroacetyl chloride under the stirring at room; Dripped off in about 0.5 hour; Continued room temperature reaction 2-3 hour, the TLC monitoring reaction to terminal, decompression desolventizes; Successively with 10% Hydrogen chloride, saturated sodium bicarbonate solution, water, each 50ml washing of sherwood oil; Get white solid 18.90g, yield is 83.4%, fusing point 155-157 ℃.
4).
22.65g (0.1mol) adjacent chlor(o)acetamide yl-benzamide and 14.29g (0.12mol) para hydroxybenzene nitrile add in the 80ml butanone, add 27.60g (0.2mol) salt of wormwood, are heated to backflow under stirring; Reacted 4-5 hour, the TLC monitoring reaction removes solvent under reduced pressure to terminal; Successively with alkali, water, each 50ml of sherwood oil wash most of object; Small amount of residue can obtain through column chromatography, gets white solid 25.00g, yield 81.0%.
5).
The mixture that 3.09g (0.01mol) midbody (IV-1), Raney nickel (1.0g), 25% ammoniacal liquor 10ml and ethanol 50ml are formed under hydrogen atmosphere, room temperature stirring reaction 3-4 hour; The TLC monitoring reaction to terminal, filtering Raney nickel, the decompression desolventize viscous liquid (II-1); Cooling washing back is a white solid; Get white solid 2.16g, yield is 69.00%, fusing point 114-116 ℃.
Embodiment 2: the preparation of compound 23
Benzylamine (II-1) 0.313g (0.001mol) and triethylamine 0.12g (0.0012mol) are added in the 20ml methylene dichloride, drip 0.17g (0.0011mol) 10ml dichloromethane solution (III-1) under the stirring at room, drip Bi Jixu stirring at room reaction 1 hour; The TLC monitoring reaction to terminal; In reaction mixture impouring 30ml water, organic layer is told in concussion, and organic phase gets product with 10% Hydrogen chloride, saturated sodium bicarbonate aqueous solution, each 20ml washing after drying precipitation of saturated common salt water washing successively; Through ETHYLE ACETATE wash white solid; Column chromatography gets pure article 0.38g, productive rate 87.5%, fusing point 168-169 ℃.
Embodiment 3: the preparation of compound 62
Benzylamine (II-1) 0.313g (0.001mol) and triethylamine 0.12g (0.0012mol) are added in the 20ml methylene dichloride, drip 0.22g (0.0011mol) 10ml dichloromethane solution (III-2) under the stirring at room, drip Bi Jixu stirring at room reaction 1 hour; The TLC monitoring reaction to terminal; In reaction mixture impouring 30ml water, organic layer is told in concussion, and organic phase gets product with 10% Hydrogen chloride, saturated sodium bicarbonate aqueous solution, each 20ml washing after drying precipitation of saturated common salt water washing successively; Through ETHYLE ACETATE wash white solid; Column chromatography gets pure article 0.39g, productive rate 82.0%, fusing point 154-156 ℃.
Embodiment 4: the preparation of compound 133
Benzylamine (II-1) 0.313g (0.001mol) and triethylamine 0.12g (0.0012mol) are added in the 20ml methylene dichloride, drip 0.27g (0.0011mol) 10ml dichloromethane solution (III-3) under the stirring at room, drip Bi Jixu stirring at room reaction 1 hour; The TLC monitoring reaction to terminal; In reaction mixture impouring 30ml water, organic layer is told in concussion, and organic phase gets product with 10% Hydrogen chloride, saturated sodium bicarbonate aqueous solution, each 20ml washing after drying precipitation of saturated common salt water washing successively; ETHYLE ACETATE wash white solid; Column chromatography gets pure article 0.41g, productive rate 78.2%, fusing point 173-174 ℃.
Embodiment 5: the preparation of compound 150
Benzylamine (II-1) 0.313g (0.001mol) and triethylamine 0.12g (0.0012mol) are added in the 20ml methylene dichloride; Dropping contains 0.21g (0.0011mol) 10ml dichloromethane solution (III-4) under the stirring at room, drips Bi Jixu stirring at room reaction 1 hour, and the TLC monitoring reaction to terminal; In reaction mixture impouring 30ml water; Organic layer is told in concussion, and organic phase gets product through 10% Hydrogen chloride, saturated sodium bicarbonate aqueous solution, each 50ml washing after drying precipitation of saturated aqueous common salt successively, ETHYLE ACETATE wash white solid; Column chromatography gets pure article 0.41g, productive rate 86.0%.Fusing point 178-180 ℃.
Other compounds of general formula (I) can make with preparation method provided by the invention.
Part of compounds fusing point (the fusing point appearance 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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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 ℃.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)。
FORMULATION EXAMPLE (each component add-on is weight percentage, is metered into behind the active compound folding hundred)
Instance 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%
With compound 23 and other component thorough mixing, after ultrafine crusher is pulverized, promptly obtain 30% wettable powder product.
Instance 7:40% suspension concentrates
Compound 152 40%
Terepthaloyl moietie 10%
Nonoxynol-9 6%
Sodium lignosulfonate 10%
CMC 99.5 1%
37% formalin 0.2%
75% silicone oil water miscible liquid 0.8%
Water complements to 100%
With compound 152 and other component thorough mixing, the suspension concentrates that obtains thus, dilute with water gained suspension agent can obtain the diluent of any desired concn.
Instance 8:60% water-dispersible granules
Compound 138 60%
Naphthalenesulfonic acid-formaldehyde condensate 12%
N-methyl-N-oleoyl-Sodium taurine salt 8%
Vinylpyrrolidone polymer 2%
CMC 99.5 2%
Kaolin complements to 100%
Compound 138 and other components mixed pulverize, after adding water again and mediating, add in the tablets press of 10-100 eye mesh screen and carry out granulation, and then through dry, screening (pressing the screen cloth scope).
Biological activity determination embodiment
Instance 9: greenhouse pot culture biological activity (cucumber downy mildew)
Potted plant seedling assay method is adopted in test.The potted plant cucumber seedling of selection growth neat and consistent cuts off vegetative point and keeps two true leaves, carries out foliar spray with The compounds of this invention according to design concentration and handles, and other establishes the blank of spray clear water, 3 repetitions.Handle back second day inoculation cucumber downy mildew spore suspension, the inoculation back place phytotron (temperature: 25 ℃ of daytimes, 20 ℃ of nights, relative humidity: 95～100%) cultivation of preserving moisture, place greenhouse (25 ℃ ± 1 ℃) normal management after 24 hours.Inoculate back 7 days investigation prevention effects, the disease classification is calculated control effect with reference to State Standard of the People's Republic of China " pesticide field efficacy medicine test criterion " with disease index.
The partial test result is following:
When liquor strength was 400ppm, 13,23,95,138,143 and 152 pairs of cucumber downy mildew preventive effects of compound reached 100%;
When liquor strength was 100ppm, 13,23,95,138,143 and 152 pairs of cucumber downy mildew preventive effects of compound reached 50%.
Instance 10: greenhouse pot culture biological activity (wheat powdery mildew)
Potted plant seedling assay method is adopted in test.Select the potted plant seedling of 2 leaf phase wheats of growth neat and consistent, carry out foliar spray with The compounds of this invention according to design concentration and handle, other establishes the blank of spray clear water, 3 repetitions.Handle back second day spore and shake off the method inoculation, postvaccinal crop is put greenhouse (25 ℃ ± 1 ℃) normal management.Seven days " Invest, Then Investigate "s of medication, disease classification calculate control effect with reference to State Standard of the People's Republic of China " pesticide field efficacy medicine test criterion " with disease index.
The partial test result is following:
When liquor strength was 400ppm, 62 pairs of wheat powdery mildew preventive effects of compound reached 100%;
Instance 11: greenhouse pot culture biological activity (corn rust)
Potted plant seedling assay method is adopted in test.Select the potted plant seedling of 2-3 leaf phase corn of growth neat and consistent, carry out foliar spray with The compounds of this invention according to design concentration and handle, other establishes the blank of spray clear water, 3 repetitions.Handle back second day inoculation corn rust spore suspension, the inoculation back place phytotron (temperature: 25 ℃ of daytimes, 20 ℃ of nights, relative humidity: 95～100%) cultivation of preserving moisture, place greenhouse (25 ℃ ± 1 ℃) normal management after 24 hours.Inoculation back 10d investigation prevention effect, the disease classification is calculated control effect with reference to State Standard of the People's Republic of China " pesticide field efficacy medicine test criterion " with disease index.
The partial test result is following:
When liquor strength was 400ppm, 62,193 pairs of corn rust preventive effects of compound reached 100%.
Claims (10)
1. acyl group benzylamine compound, structure is shown in (I) general formula:
In the formula:
R
1Be selected from hydrogen or C
1-C
12Alkyl; M is selected from 1 to 3 integer;
R
2Be selected from halogen, cyanic acid, 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
5N 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 hydrogen, cyanic acid, C respectively
1-C
12Alkyl, halo C
1-C
12Alkyl, C
1-C
12Alkoxyl group, halo C
1-C
12Alkoxyl group, C
3-C
6Naphthenic base, cyanic acid 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
5Perhaps,
When Y is selected from NR
4The time, N R
4With R
3Form replacement or unsubstituted five yuan or six-ring, described substituting group is selected from 1-2 C
1-C
4Alkyl;
R
5Be selected from unsubstituted or independently be selected from the substituted phenyl of following group, benzyl or heteroaryl: halogen, nitro, cyanic acid, C by 1-4
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 not and replaces or by 1-4 the substituted C of following radicals
1-C
6Alkyl, cyclopropyl or cyclohexyl: Cl, Br, F or C
1-C
4Alkyl;
Perhaps be selected from not and replace or by 1-3 substituted anilino of following radicals or C
2-C
4Thiazolinyl: Cl, Br, F, C
1-C
4Alkyl, C
3-C
6Naphthenic base, C
1-C
4Haloalkyl, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy or C
1-C
4Alkoxy carbonyl;
Perhaps be selected from not and replace or by 1-3 the substituted phenyl of following radicals, benzene oxygen ethyl, benzene oxygen propyl group, pyridyl, pyrimidyl, piperidyl, piperazinyl, thiazolyl, isothiazolyl, thiadiazolyl group 、 oxazolyl 、 isoxazolyl 、 oxadiazole base, triazolyl, thienyl, furyl, quinolyl, indyl, 3-pyrazolyl, 4-pyrazolyl or 4-pyrazoles methyl: halogen, CN, NO
2, C
1-C
4Alkyl, C
3-C
6Naphthenic base, 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
2. acyl group benzylamine compound according to claim 1 is characterized in that: in the 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, cyanic acid, 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
5N 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 hydrogen, cyanic acid, C respectively
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
6Alkoxyl group, halo C
1-C
6Alkoxyl group, C
3-C
6Naphthenic base, cyanic acid 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
5Perhaps,
When Y is selected from NR
4The time, N R
4With R
3Form morpholine, piperazine, piperidines, pyrazoles, pyrroles or triazole ring;
R
5Be selected from unsubstituted or by 1-4 independently be selected from the substituted phenyl of following group, benzyl, pyridyl, pyrimidyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazoles base,, thiadiazolyl group, pyrazolyl, pyranyl, triazolyl or tetrazyl: halogen, nitro, cyanic acid, 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
4Dialkyl amino carbonyl, do not replace or substituted phenyl, do not replace or substituted 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, CF
3, CH
2CF
3, do not replace or substituted phenyl, do not replace or substituted pyridyl, 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.
3. compound according to claim 2 is characterized in that: in the 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, cyanic acid, 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
5N is selected from the integer of O to 3;
Y is selected from O, S or NR
4
R
3, R
4Can be identical or different, be selected from hydrogen, cyanic acid, C respectively
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
6Alkoxyl group, halo C
1-C
6Alkoxyl group, C
3-C
6Naphthenic base, cyanic acid 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
5Perhaps,
When Y is selected from NR
4The time, N R
4With R
3Form morpholine, piperazine, piperidines or pyrazoles ring;
R
5Be selected from unsubstituted or by 1-4 independently be selected from the substituted phenyl of following group, benzyl, pyridyl, pyrimidyl, thiazolyl, oxazolyl, oxadiazoles base,, thiadiazolyl group, pyrazolyl, triazolyl or tetrazyl: halogen, nitro, cyanic acid, 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 substituted phenyl, do not replace or substituted 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, do not replace or substituted phenyl, do not replace or substituted pyridyl, 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.
4. compound according to claim 3 is characterized in that: in the 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, cyanic acid, 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 hydrogen, cyanic acid, C respectively
1-C
5Alkyl, halo C
1-C
5Alkyl, C
1-C
5Alkoxyl group, halo C
1-C
5Alkoxyl group, C
3-C
6Naphthenic base, cyanic acid 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
5Perhaps,
When Y is selected from NR
4The time, N R
4With R
3Form morpholine, piperazine or piperidine ring;
R
5Be selected from unsubstituted or independently be selected from the substituted phenyl of following group, benzyl, pyridyl, pyrimidyl, thiazolyl, oxazolyl or pyrazolyl: fluorine, chlorine, bromine, nitro, cyanic acid, C by 1-3
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, do not replace or substituted phenyl, do not replace or substituted pyridyl, 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, do not replace or substituted phenyl, do not replace or substituted pyridyl, 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.
5. compound according to claim 4 is characterized in that: in the 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, cyanic acid, 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 hydrogen, C respectively
1-C
5Alkyl, C
1-C
5Alkoxyl group, cyanic acid 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
5Perhaps,
When Y is selected from NR
4The time, N R
4With R
3Form morpholine, piperazine or piperidine ring;
R
5Be selected from unsubstituted or independently be selected from the substituted phenyl of following group, benzyl, pyridyl, pyrimidyl, thiazolyl or pyrazolyl: fluorine, chlorine, bromine, nitro, cyanic acid, C by 1-2
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, do not replace or substituted phenyl, do not replace or substituted pyridyl, 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, do not replace or substituted phenyl, do not replace or substituted pyridyl, 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.
6. compound according to claim 5 is characterized in that: in the 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 hydrogen or C respectively
1-C
3Alkyl;
R
5Be selected from unsubstituted or independently be selected from the substituted phenyl of following group, benzyl, pyridine or pyrimidyl: fluorine, chlorine, bromine, nitro, cyanic acid, C by 1-2
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, do not replace or substituted phenyl, do not replace or substituted pyridyl, 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, do not replace or substituted phenyl, do not replace or substituted pyridyl, described substituting group is selected from 1-3 following group: Cl, Br, F or CH
3
7. midbody phenylbenzylamine or its salt for preparing general formula (I) compound, shown in general formula (II):
In the formula:
R
1Be selected from hydrogen or C
1-C
12Alkyl; M is selected from 1 to 3 integer;
R
2Be selected from halogen, cyanic acid, 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
5N 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 hydrogen, cyanic acid, C respectively
1-C
12Alkyl, halo C
1-C
12Alkyl, C
1-C
12Alkoxyl group, halo C
1-C
12Alkoxyl group, C
3-C
6Naphthenic base, cyanic acid 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
5Perhaps,
When Y is selected from NR
4The time, N R
4With R
3Form replacement or unsubstituted five yuan or six-ring, described substituting group is selected from 1-2 C
1-C
4Alkyl;
R
5Be selected from unsubstituted or independently be selected from the substituted phenyl of following group, benzyl or heteroaryl: halogen, nitro, cyanic acid, C by 1-4
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.
8. purposes of in agricultural or other field, preventing and treating germ according to the described acyl group benzylamine compound shown in general formula (I) of claim 1.
9. fungicidal compsn, it is characterized in that: contain just like any described general formula (I) compound is as active ingredient among the claim 1-6, the weight percentage of active ingredient is 0.1-99% in the compsn.
10. purposes of in agricultural or other field, preventing and treating germ according to the described compsn of claim 9.
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980203A (en) * | 2014-05-20 | 2014-08-13 | 浙江金伯士药业有限公司 | New preparation method of carnosine |
| CN104672101A (en) * | 2013-11-26 | 2015-06-03 | 中国中化股份有限公司 | o-chloroacetylamino benzoyl methylamine preparation method |
| CN106973990A (en) * | 2016-01-19 | 2017-07-25 | 中国科学院上海有机化学研究所 | A kind of fumigating method for being used to prevent and treat grain entomophthora |
| EP3377486A4 (en) * | 2015-11-18 | 2019-09-04 | Monsanto Technology LLC | Insecticidal compositions and methods |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1642963A (en) * | 2002-03-27 | 2005-07-20 | 辛根塔参与股份公司 | Siliconated phenyl amides derivatives useful as microbiocide |
| WO2007060164A1 (en) * | 2005-11-22 | 2007-05-31 | Bayer Cropscience Sa | N-(1-alkyl-2-phenylethyl)-carboxamide derivatives and use thereof as fungicides |
-
2010
- 2010-11-03 CN CN201010535133.0A patent/CN102464592B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1642963A (en) * | 2002-03-27 | 2005-07-20 | 辛根塔参与股份公司 | Siliconated phenyl amides derivatives useful as microbiocide |
| WO2007060164A1 (en) * | 2005-11-22 | 2007-05-31 | Bayer Cropscience Sa | N-(1-alkyl-2-phenylethyl)-carboxamide derivatives and use thereof as fungicides |
Cited By (8)
| 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 |
| CN103980203A (en) * | 2014-05-20 | 2014-08-13 | 浙江金伯士药业有限公司 | New preparation method of carnosine |
| 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 |
| EP3377486A4 (en) * | 2015-11-18 | 2019-09-04 | Monsanto Technology LLC | Insecticidal compositions and methods |
| US10827755B2 (en) | 2015-11-18 | 2020-11-10 | Monsanto Technology Llc | Insecticidal compositions and methods |
| CN106973990A (en) * | 2016-01-19 | 2017-07-25 | 中国科学院上海有机化学研究所 | A kind of fumigating method for being used to prevent and treat grain entomophthora |
| 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 |
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|---|---|
| CN102464592B (en) | 2014-09-03 |
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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 |