CN101205202B - Substituted benzene urea compounds as well as preparation and uses thereof - Google Patents
Substituted benzene urea compounds as well as preparation and uses thereof Download PDFInfo
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- CN101205202B CN101205202B CN200610134973XA CN200610134973A CN101205202B CN 101205202 B CN101205202 B CN 101205202B CN 200610134973X A CN200610134973X A CN 200610134973XA CN 200610134973 A CN200610134973 A CN 200610134973A CN 101205202 B CN101205202 B CN 101205202B
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- 0 CC(C)=**Cc1c(*(*N)C(*(*)N)=C)cccc1 Chemical compound CC(C)=**Cc1c(*(*N)C(*(*)N)=C)cccc1 0.000 description 3
- FUALRGVCKMXEFW-UHFFFAOYSA-N CCC(CNC)C(C)=C Chemical compound CCC(CNC)C(C)=C FUALRGVCKMXEFW-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention disclsoes a replaced phenylurea compound and preparation and application thereof. The structure of the replaced phenylurea compound is shown as in the general formula I: see the specification for the definitions of various substituents. The replaced phenylurea compound of the invention has the broad-spectrum fungicidal activity, namely, and the invention can be used for controlling the diseases caused by a plurality of germs such as oomycetes, basidiomycetes, ascomycetes, and imperfect fungis, etc. on a plurality of crops. At the same time the compounds have very high biologicalactivity so as to enable the very good effects to be obtained under a very low level of dosages. Part of compounds of the invention also have very good disinsection and acaricidal activity and can beused for controlling the pests and mites on a plurality of crops.
Description
Technical field
The invention belongs to disinfectant use in agriculture and field of pesticides.Relate to substituted phenylurea compound and preparation thereof and application specifically.
Background technology
Following document was once reported the substituted phenylurea compound as sterilant and insecticidal/acaricidal agent: CN1154692A, CN1166829A, CN1171783A, CN1117080A, CN1824648A, JP 07295176A, WO9315046A, WO9903824A, WO2001084931A etc.
Before the present invention, we once applied for 5 Chinese patents, and were specific as follows:
1, CN1657522A (WO2005080344A1), this patent relates to the substituted azole derivative shown in the following general formula as desinsection, sterilant:
2, CN1616448A (WO2005044813A1), this patent relates to the Benzofurantone compound shown in the following general formula as desinsection, sterilant:
3, CN1869032A, this patent relates to a kind of coumarin kind compound shown in the following general formula as desinsection, sterilant:
Q is selected from one of following group:
4, CN1869034A, this patent relates to a kind of aryl ethers compounds shown in the following general formula as desinsection, sterilant:
Q is selected from one of group as follows:
5, application number is the Chinese patent of 200510046765.x, this patent relate to a kind of replacement shown in the following general formula to trifluoromethyl phenyl ether compound as desinsection, sterilant:
In the formula: Q is selected from Q as follows
1, Q
2, Q
3, Q
4Or Q
5
Though all disclosed compounds are similar to the The compounds of this invention structure division in the above-mentioned patent, exist significant different.
Summary of the invention
The object of the present invention is to provide a kind of substituted phenylurea compound that just can control various disease and pests under very little dosage, it can be applicable to agricultural and goes up to prevent and treat disease and the insect pest of crop.
Technical scheme of the present invention is as follows:
The invention provides a kind of substituted phenylurea compound, shown in general formula I:
In the formula:
R
1Be selected from hydrogen, C
1-C
3Alkyl, C
3-C
6Cycloalkyl, C
2-C
3Thiazolinyl, C
2-C
3Alkynyl, C
1-C
3Haloalkyl or C
1-C
3Alkoxyalkyl;
R
2Be selected from hydrogen, C
1-C
3Alkyl, C
3-C
6Cycloalkyl, C
2-C
3Thiazolinyl, C
2-C
3Alkynyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyalkyl, C
1-C
3Alkoxyl group, C
1-C
3Alkylthio, C
1-C
3Alkylamino or C
1-C
3Haloalkyl amino;
R
3Be selected from hydrogen, C
1-C
3Alkyl, C
3-C
6Cycloalkyl, C
2-C
3Thiazolinyl, C
2-C
3Alkynyl, C
1-C
3Haloalkyl or C
1-C
3Alkoxyalkyl;
Q is selected from any one substituting group of Q1-Q13 as follows:
Among the Q1: n=1-5; When n greater than 1 the time, R
4Can be identical or different, be selected from hydrogen, halogen, cyano group, nitro, C
1-C
12Alkyl, C
2-C
12Thiazolinyl, C
2-C
12Alkynyl, C
1-C
12Haloalkyl, C
1-C
12Alkoxyl group, C
1-C
12Alkylthio, C
1-C
12Alkane alkylsulfonyl, C
1-C
12Alkyl-carbonyl, C
1-C
12Alkoxy C
1-C
12Alkyl, C
1-C
12Alkoxy carbonyl, C
1-C
12Alkoxy carbonyl C
1-C
12Alkyl, C
1-C
12Halogenated alkoxy C
1-C
12Alkyl, any substituted-amino C
1-C
12Alkyl, the aryloxy that replaces arbitrarily, any fragrant C that replaces
1-C
12Alkyl oxy, the aryl that replaces arbitrarily, heteroaryl, any aryl C that replaces
1-C
12Alkyl, heteroaryl C
1-C
12Alkyl or heteroaryl C
1-C
12Alkoxyl group;
Among the Q2: R
5, R
6, R
7, R
8Be selected from hydrogen, halogen, cyano group, nitro, C respectively
1-C
12Alkyl, C
2-C
12Thiazolinyl, C
2-C
12Alkynyl, C
1-C
12Haloalkyl, C
1-C
12Alkoxyl group, C
1-C
12Alkylthio or C
1-C
12The alkane alkylsulfonyl;
Among the Q3: R
9, R
10, R
11Be selected from hydrogen, halogen, cyano group, nitro, C respectively
1-C
12Alkyl, C
2-C
12Thiazolinyl, C
2-C
12Alkynyl, C
1-C
12Haloalkyl, C
1-C
12Alkoxyl group, C
1-C
12Alkylthio, C
1-C
12Alkane alkylsulfonyl, C
1-C
12Alkyl-carbonyl, C
1-C
12Alkoxy C
1-C
12Alkyl, C
1-C
12Alkoxy carbonyl, C
1-C
12Alkoxy carbonyl C
1-C
12Alkyl, C
1-C
12Halogenated alkoxy C
1-C
12Alkyl, C
1-C
12Alkylamino, the aryloxy that replaces arbitrarily, any fragrant C that replaces
1-C
12Alkyl oxy, the aryl that replaces arbitrarily, heteroaryl, any aryl C that replaces
1-C
12Alkyl, heteroaryl C
1-C
12Alkyl, heteroaryl C
1-C
12Alkoxyl group, or R
9With R
10Be connected to five yuan or six-ring;
Among the Q4: R
12Be selected from halogen, C
1-C
12Alkyl, C
1-C
12Alkoxyl group, halo C
1-C
12Alkoxyl group, the aryl or the heteroaryl that do not replace or replace; R
13Be selected from hydrogen, halogen, cyano group or C
1-C
12Alkyl; X
1Be selected from O, S or NR
31R
31Be selected from hydrogen, C
1-C
12Alkyl, halo C
1-C
12Alkyl, C
1-C
12Alkoxy carbonyl or C
1-C
12Alkoxy carbonyl C
1-C
12Alkyl;
Among the Q5: R
14Be selected from halogen, cyano group, C
1-C
12Alkyl, halo C
1-C
12Alkyl, C
1-C
12Alkoxyl group, C
1-C
12Alkylamino or C
1-C
12Alkylthio; R
15Be selected from and have a CF at least
3The aryl or the heteroaryl that replace;
Among the Q6: R
16Be selected from C
1-C
12Alkyl, the phenyl that does not replace or replace; R
17Be selected from halogen;
Among the Q7: R
18, R
19, R
20, R
21Be selected from hydrogen, halogen, nitro, cyano group, C respectively
1-C
12Alkyl, halo C
1-C
12Alkyl, C
1-C
12Alkoxyl group, halo C
1-C
12Alkoxyl group or C
1-C
12Alkylthio;
Among the Q8: R
22Be selected from hydrogen, 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, the aryl or the heteroaryl that do not replace or replace; R
23Be selected from hydrogen, halogen, nitro, cyano group, CH
2CONH
2, CH
2CN, 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
12Alkane alkylsulfonyl, C
1-C
12Alkyl-carbonyl, C
1-C
12Alkoxy C
1-C
12Alkyl, C
1-C
12Alkoxy carbonyl or C
3-C
12Cycloalkyl;
Among the Q9: R
24Be selected from hydrogen, halogen, nitro, cyano group, C
1-C
12Alkyl, C
1-C
12Alkoxyl group, C
1-C
12Alkylthio, the aryl or the heteroaryl that do not replace or replace; R
25Be selected from hydrogen, halogen, cyano group, C
1-C
12Alkyl, C
1-C
12Alkoxyl group or C
1-C
12Alkylthio;
Among the Q10: R
26Be selected from hydrogen, halogen; R
27The phenyl that be selected from hydrogen, does not replace or replace; R
28Be selected from hydrogen, halogen, nitro, cyano group, C
1-C
12Alkyl, C
1-C
12Alkoxyl group, C
1-C
12Alkylthio, C
1-C
12Alkane alkylsulfonyl, the phenyl that does not replace or replace;
Among the Q11: R
29Be selected from hydrogen, halogen, nitro, cyano group, C
1-C
12Alkyl, halo C
1-C
12Alkyl, C
1-C
12Alkoxyl group, C
1-C
12Alkylthio, the phenyl that does not replace or replace;
Among the Q12: R
30Be selected from hydrogen, halogen, nitro, cyano group, C
1-C
12Alkyl, halo C
1-C
12Alkyl, C
1-C
12Alkoxyl group, C
1-C
12Alkylthio, the phenyl that does not replace or replace;
Among the Q13: R
32Be selected from hydrogen, halogen or C
1-C
12Alkyl; R
33Be selected from hydrogen or C
1-C
12Alkyl;
A is selected from O or S.
The present invention more preferably compound is: in the general formula I
R
1Be selected from hydrogen, C
1-C
3Alkyl, C
3-C
6Cycloalkyl, C
1-C
3Haloalkyl or C
1-C
3Alkoxyalkyl;
R
2Be selected from hydrogen, C
1-C
3Alkyl, C
3-C
6Cycloalkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyalkyl, C
1-C
3Alkoxyl group, C
1-C
3Alkylthio, C
1-C
3Alkylamino or C
1-C
3Haloalkyl amino;
R
3Be selected from hydrogen, C
1-C
3Alkyl, C
3-C
6Cycloalkyl, C
1-C
3Haloalkyl or C
1-C
3Alkoxyalkyl;
Q is selected from any one substituting group of Q1-Q13:
Among the Q1: n=1-5; When n greater than 1 the time, R
4Can be identical or different, be selected from hydrogen, halogen, cyano group, nitro, C
1-C
6Alkyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, C
1-C
6Alkane alkylsulfonyl, C
1-C
6Alkyl-carbonyl, C
1-C
6Alkoxy C
1-C
6Alkyl, C
1-C
6Alkoxy carbonyl, C
1-C
6Alkoxy carbonyl C
1-C
6Alkyl, C
1-C
6Alkylamino C
1-C
6Alkyl, aryl, aryloxy or heteroaryl unsubstituted or that further replaced by following group: 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 or C
1-C
6Alkyl-carbonyl;
Among the Q2: R
5, R
6, R
7, R
8Be selected from hydrogen, halogen, C respectively
1-C
6Alkyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio or C
1-C
6The alkane alkylsulfonyl;
Among the Q3: R
9, R
10, R
11Be selected from hydrogen, chlorine, bromine, fluorine, C respectively
1-C
6Alkyl, C
1-C
6Haloalkyl, C
1-C
6Alkyl-carbonyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, C
1-C
6Alkane alkylsulfonyl, C
1-C
6Alkoxy C
1-C
3Alkyl, C
1-C
3Halogenated alkoxy C
1-C
3Alkyl, C
1-C
3Alkylamino, phenyl, benzyl or pyridyl unsubstituted or that further replaced by following group: 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 R
9With R
10Be connected to five yuan or six-ring;
Among the Q4: R
12Be selected from halogen, C
1-C
6Alkyl, C
1-C
6Alkoxyl group, phenyl, pyridyl, furans, thiophene or thiazole unsubstituted or that further replaced by following group: 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, phenoxy group or rubigan; R
13Be selected from hydrogen, halogen, cyano group or C
1-C
6Alkyl; X
1Be selected from O or NR
31R
31Be selected from hydrogen, C
1-C
3Alkyl or halo C
1-C
3Alkyl;
Among the Q5: R
14Be selected from halogen, cyano group, C
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylamino or C
1-C
6Alkylthio; R
15Be selected from the phenyl of replacement, at least one is CF in its substituting group
3, other substituting group is selected from 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, phenoxy group or rubigan;
Among the Q6: R
16Be selected from C
1-C
6Alkyl, the unsubstituted or phenyl that replaces, its substituting group is selected from 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, phenoxy group or rubigan; R
17Be selected from halogen;
Among the Q7: R
18, R
19, R
20, R
21Be selected from hydrogen, halogen, nitro, C respectively
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
6Alkoxyl group or C
1-C
6Alkylthio;
Among the Q8: R
22Be selected from hydrogen, halogen, C
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
6Alkoxyl group, halo C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, phenyl, pyridyl unsubstituted or that further replaced by following group: 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, phenoxy group or rubigan; R
23Be selected from hydrogen, halogen, cyano group, C
1-C
6Alkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, C
1-C
6Alkane alkylsulfonyl, C
1-C
6Alkyl-carbonyl, C
1-C
6Alkoxy C
1-C
6Alkyl or C
3-C
6Cycloalkyl;
Among the Q9: R
24Be selected from hydrogen, C
1-C
6Alkyl, phenyl, pyridyl, pyrimidine, thiophene or thiazole unsubstituted or that further replaced by following group: 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, phenoxy group or rubigan; R
25Be selected from hydrogen, halogen, cyano group, C
1-C
6Alkyl, C
1-C
6Alkoxyl group or C
1-C
6Alkylthio;
Among the Q10: R
26Be selected from hydrogen or halogen; R
27Be selected from hydrogen, the unsubstituted or phenyl that replaces, its substituting group is selected from 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, phenoxy group or rubigan; R
28Be selected from hydrogen, halogen, nitro, cyano group, C
1-C
6Alkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, C
1-C
6Alkane alkylsulfonyl, the unsubstituted or phenyl that replaces, its substituting group is selected from 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, phenoxy group or rubigan;
Among the Q11: R
29 are selected from hydrogen, C
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, the unsubstituted or phenyl that replaces, its substituting group is selected from 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, halo C
1-C
6Alkylthio, C
1-C
6Alkane alkylsulfonyl, C
1-C
6Alkyl-carbonyl, phenoxy group or rubigan;
Among the Q12: R
30Be selected from hydrogen, C
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, the unsubstituted or phenyl that replaces, its substituting group is selected from 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, halo C
1-C
6Alkylthio, C
1-C
6Alkane alkylsulfonyl, C
1-C
6Alkyl-carbonyl, phenoxy group or rubigan;
Among the Q13: R
32Be selected from hydrogen, halogen or C
1-C
6Alkyl; R
33Be selected from hydrogen or C
1-C
6Alkyl;
A is selected from O or S.
Further preferred compound is: in the general formula I
R
1Be selected from hydrogen, C
1-C
3Alkyl, C
1-C
3Haloalkyl or C
1-C
3Alkoxyalkyl;
R
2Be selected from hydrogen, C
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyalkyl, C
1-C
3Alkoxyl group, C
1-C
3Alkylthio, C
1-C
3Alkylamino or C
1-C
3Haloalkyl amino;
R
3Be selected from hydrogen, C
1-C
3Alkyl or C
3-C
6Cycloalkyl;
Q is selected from any one substituting group of Q1-Q13:
Among the Q1: n=1-4; When n greater than 1 the time, R
4Can be identical or different, be selected from hydrogen, chlorine, bromine, fluorine, cyano group, nitro, C
1-C
6Alkyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio or C
1-C
6The alkane alkylsulfonyl;
Among the Q2: R
5, R
6, R
7, R
8Be selected from hydrogen, chlorine, bromine, fluorine, C respectively
1-C
6Alkyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio or C
1-C
6The alkane alkylsulfonyl;
Among the Q3: R
9, R
10, R
11Be selected from hydrogen, chlorine, bromine, fluorine, C respectively
1-C
6Alkyl, C
1-C
6Haloalkyl, C
1-C
6Alkyl-carbonyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, C
1-C
6Alkane alkylsulfonyl, C
1-C
6Alkoxy C
1-C
3Alkyl, C
1-C
3Halogenated alkoxy C
1-C
3Alkyl, C
1-C
3Alkylamino, phenyl, benzyl or pyridyl unsubstituted or that further replaced by following group: 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, or R
9With R
10Be connected to five yuan or six-ring;
Among the Q4: R
12Be selected from halogen, C
1-C
6Alkyl, phenyl, pyridyl, furans, thiophene or thiazole unsubstituted or that further replaced by following group: 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, phenoxy group or rubigan; R
13Be selected from hydrogen, chlorine or C
1-C
6Alkyl; X
1Be selected from O or NR
31R
31Be selected from hydrogen, methyl or sec.-propyl;
Among the Q5: R
14Be selected from chlorine, bromine, fluorine, cyano group, C
1-C
6Alkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylamino or C
1-C
6Alkylthio; R
15Be selected from the phenyl of replacement, at least one is CF for its substituting group
3, other substituting group is selected from 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, phenoxy group or rubigan;
Among the Q6: R
16Be selected from C
1-C
6Alkyl, the unsubstituted or phenyl that replaces, its substituting group is selected from 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, phenoxy group or rubigan; R
17Be selected from chlorine or bromine;
Among the Q7: R
18, R
19, R
20, R
21Be selected from hydrogen, chlorine, bromine, fluorine, nitro, C respectively
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
6Alkoxyl group or C
1-C
6Alkylthio;
Among the Q8: R
22Be selected from hydrogen, chlorine, C
1-C
6Alkyl, halo C
1-C
6Alkyl, phenyl or pyridyl unsubstituted or that further replaced by following group: halogen, nitro, cyano group, C
1-C
6Alkyl, halo C
1-C
6Alkyl or C
1-C
6Alkoxyl group; R
23Be selected from hydrogen, chlorine, cyano group, C
1-C
6Alkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkyl-carbonyl or C
3-C
6Cycloalkyl;
Among the Q9: R
24Be selected from hydrogen, C
1-C
6Alkyl, phenyl, pyridyl, pyrimidine, thiophene or thiazole unsubstituted or that further replaced by following group: halogen, nitro, cyano group, C
1-C
6Alkyl, halo C
1-C
6Alkyl or C
1-C
6Alkoxyl group; R
25Be selected from hydrogen, halogen, cyano group or C
1-C
6Alkyl;
Among the Q10: R
26Be selected from hydrogen or halogen; R
27Be selected from hydrogen, the unsubstituted or phenyl that replaces, its substituting group is selected from halogen, nitro, cyano group, C
1-C
6Alkyl, halo C
1-C
6Alkyl or C
1-C
6Alkoxyl group; R
28Be selected from hydrogen, halogen, cyano group, C
1-C
6Alkyl, C
1-C
6Alkoxyl group, C
1-C
6The phenyl of alkane alkylsulfonyl or replacement, its substituting group is selected from halogen, nitro, cyano group, C
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
6Alkoxyl group;
Among the Q11: R
29Be selected from hydrogen, C
1-C
6Alkyl, halo C
1-C
6Alkyl, the unsubstituted or phenyl that replaces, its substituting group is selected from C
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
6Alkoxyl group, halo C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, halo C
1-C
6Alkylthio or C
1-C
6The alkane alkylsulfonyl;
Among the Q12: R
30Be selected from hydrogen, C
1-C
6Alkyl, halo C
1-C
6Alkyl, the unsubstituted or phenyl that replaces, its substituting group is selected from C
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
6Alkoxyl group, halo C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, halo C
1-C
6Alkylthio or C
1-C
6The alkane alkylsulfonyl;
R among the Q13
32Be selected from hydrogen, halogen or C
1-C
6Alkyl; R
33Be selected from hydrogen or C
1-C
6Alkyl;
A is selected from O or S.
Further preferred again compound is: in the general formula I
R
1Be selected from CH
3Or CH
2F;
R
2Be selected from H, CH
3, OCH
3, NCH
3, CH
2CF
3Or NCH
2CF
3
R
3Be selected from H or CH
3
Q is selected from any one substituting group of Q1-Q13:
Among the Q1: n=2-4; R
4Can be identical or different, be selected from hydrogen, chlorine, fluorine, cyano group, nitro, C
1-C
6Alkyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, C
1-C
6The alkane alkylsulfonyl; For example, (R4) n is selected from 2,5-(CF
3)
2, 3,5-(CF
3)
2, 4-CN-3-CF
3, 4-NO
2-3-CF
3, 6-Cl-3-CF
3, 2-Cl-3-CF
3, 4-Cl-3-CF
3, 4-F-3-CF
3, 2-Cl-4-CF
3, 2-CH
3SO
2-4-CF
3, 3-Cl-4-CF
3, 2,6-Cl
2-4-CF
3, 2,6-(NO
2)
2-4-CF
3, 2-Cl-3,5-(CF
3)
2, 2-Cl-3-CN, 2-Cl-4-CN, 2-Cl-5-CN, 2-Cl-4-CH
3SO
2, 2-Cl-5-CH
3SO
2, 2-CN-3-Cl, 2-CN-3-CH
3SO
2, 2-NO
2-4-CH
3SO
2, 2-CH
3-4-i-C
3F
7, 2-Cl-4-i-C
3F
7, 2,6-Cl
2-4-i-C
3F
7, 2-OCHF
2-4-CF
3, 2,6-Cl
2-3-F-4-CF
3, 2-Cl-4-F-5-NH
2, 2-Cl-4-F-5-CF
3, 2-Cl-4-F-5-NHCO
2CH
3, 2-Cl-4-F-5-NO
2Or 2-Cl-4-F-5-NHCO
2CH
3
Among the Q2: R
5Be selected from hydrogen, chlorine or CF
3R
6Be selected from hydrogen, chlorine or CF
3R
7Be selected from hydrogen, chlorine, CH
3Or CF
3R
8Be selected from hydrogen, chlorine, CF
3, CON (CH
3)
2Or CH
3CH
2SO
2
Among the Q3: R
9, R
10, R
11Be selected from hydrogen, chlorine, bromine, fluorine, C respectively
1-C
6Alkyl, C
1-C
6Haloalkyl, C
1-C
6Alkyl-carbonyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, C
1-C
6Alkane alkylsulfonyl, C
1-C
6Alkoxy C
1-C
3Alkyl, C
1-C
3Halogenated alkoxy C
1-C
3Alkyl, C
1-C
3Alkylamino, phenyl, benzyl or pyridyl unsubstituted or that further replaced by following group: chlorine, bromine, fluorine, nitro, cyano group, C
1-C
3Alkyl, halo C
1-C
3Alkyl, C
1-C
3Alkoxyl group, halo C
1-C
3Alkoxyl group, C
1-C
3Alkylthio, or R
9With R
10Be connected to five yuan or six-ring;
Among the Q4: R
12Be selected from chlorine, bromine, fluorine, C
1-C
6Alkyl, unsubstituted or phenyl, pyridyl, furans, thiophene or the thiazole that can further be replaced by following group: halogen, nitro, cyano group, C
1-C
3Alkyl, halo C
1-C
3Alkyl, C
1-C
3Alkoxyl group, halo C
1-C
3Alkoxyl group, C
1-C
3Alkylthio, C
1-C
3Alkyl-carbonyl, phenoxy group or rubigan; R
13Be selected from hydrogen, chlorine or C
1-C
6Alkyl; X
1Be selected from O or NR
31R
31Be selected from hydrogen, methyl or sec.-propyl;
Among the Q5: R
14Be selected from chlorine, cyano group, CH
3, OCH
3, SCH
3, N (CH
3)
2R
15Be selected from the phenyl of replacement, its substituting group is selected from 2-CF
3, 3-CF
3, 4-CF
3, 2,5-(CF
3)
2, 3,5-(CF
3)
2, 4-CN-3-CF
3, 4-NO
2-3-CF
3, 6-Cl-3-CF
3, 2-Cl-3-CF
3, 4-Cl-3-CF
3, 4-F-3-CF
3, 2-Cl-4-CF
3, 2-SO
2CH
3-4-CF
3, 3-Cl-4-CF
3, 2,6-Cl
2-4-CF
3
Among the Q6: R
16Be selected from C
1-C
4Alkyl, the unsubstituted or phenyl that replaces, its substituting group is selected from chlorine, bromine, fluorine, nitro, cyano group, C
1-C
3Alkyl, halo C
1-C
3Alkyl, C
1-C
3Alkoxyl group, halo C
1-C
3Alkoxyl group, C
1-C
3Alkylthio, C
1-C
3Alkyl-carbonyl, phenoxy group or rubigan; R
17Be selected from chlorine or bromine;
Among the Q7: R
18, R
19, R
20, R
21Be selected from hydrogen, chlorine, bromine, fluorine, nitro, C respectively
1-C
4Alkyl, halo C
1-C
3Alkyl, C
1-C
3Alkoxyl group;
Among the Q8: R
22Be selected from hydrogen, chlorine, C
1-C
6Alkyl, halo C
1-C
6Alkyl, phenyl or pyridyl unsubstituted or that further replaced by following group: chlorine, bromine, fluorine, C
1-C
3Alkyl, halo C
1-C
3Alkyl or C
1-C
3Alkoxyl group; R
23Be selected from hydrogen, chlorine, cyano group, OCH
3, C
2H
5, CF
3, CO
2CH
3Or CO
2C
2H
5
Among the Q9: R
24Be selected from C
1-C
3Alkyl, phenyl, pyridyl, pyrimidine or thiazole unsubstituted or that further replaced by following group: chlorine, bromine, fluorine, cyano group, C
1-C
3Alkyl, halo C
1-C
3Alkyl or C
1-C
3Alkoxyl group; R
25Be selected from hydrogen, chlorine, cyano group or CH
3
Among the Q10: R
26Be selected from hydrogen or chlorine; R
27Be selected from hydrogen, the unsubstituted or phenyl that replaces, its substituting group is selected from chlorine, bromine, fluorine, nitro, cyano group, C
1-C
4Alkyl, halo C
1-C
3Alkyl or C
1-C
3Alkoxyl group; R
28Be selected from hydrogen, chlorine, bromine, fluorine, cyano group, C
1-C
3Alkyl, C
1-C
3Alkoxyl group, C
1-C
3Alkane alkylsulfonyl, the unsubstituted or phenyl that replaces, its substituting group is selected from chlorine, bromine, fluorine, nitro, cyano group, C
1-C
4Alkyl, halo C
1-C
3Alkyl or C
1-C
3Alkoxyl group;
Among the Q11: R
29Be selected from C
2H
5, CF
3, the unsubstituted or phenyl that replaces, its substituting group is selected from CF
3, OC
2H
5, SCH
3, OCF
3, SCF
3, SO
2CH
3, OCH
2CF
3, i-C
3H
7Or t-C
4H
9
Among the Q12: R
30Be selected from C
2H
5, CF
3, the unsubstituted or phenyl that replaces, its substituting group is selected from CF
3, OC
2H
5, SCH
3, OCF
3, SCF
3, SO
2CH
3, OCH
2CF
3, i-C
3H
7Or t-C
4H
9
R among the Q13
32Be selected from hydrogen, chlorine or methyl; R
33Be selected from hydrogen or methyl;
A is selected from O or S.
In the definition of the compound of Formula I that provides above, compile the following substituting group of used term general proxy:
Substituting group is alkyl, alkoxyl group, haloalkyl, halogenated alkoxy, halogen, nitro, CN, alkylthio, halogenated alkylthio, alkyl-carbonyl or the like in the pyridazine of the thiazole of the pyrimidine of the phenyl that replaces, the pyridyl of replacement, replacement, the pyrazoles of replacement, replacement, replacement De oxazole, replacement De isoxazole, replacement, the tonka bean camphor of replacement, and substituent number can be 1～5.
Halogen: refer to fluorine, chlorine, bromine and iodine.
Alkyl: straight or branched alkyl, for example methyl, ethyl, propyl group, sec.-propyl and the tertiary butyl.
Haloalkyl: the straight or branched alkyl, the hydrogen atom on these alkyl can partly or entirely be replaced by halogen, for example, haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl.
Alkoxyl group: the straight or branched alkyl is connected on the structure through the Sauerstoffatom key.
Halogenated alkoxy: the straight or branched alkoxyl group, the hydrogen atom on these alkoxyl groups can partly or entirely be replaced by halogen.For example, halogenated alkoxy such as chlorine methoxyl group, dichloro methoxyl group, trichlorine methoxyl group, fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, chlorine fluorine methoxyl group, trifluoro ethoxy.
Alkylthio: the straight or branched alkyl is connected on the structure through the sulphur atom key.
Halogenated alkylthio: the straight or branched alkylthio, the hydrogen atom on these alkylthios can partly or entirely be replaced by halogen atom.For example, halogenated alkylthio such as chloromethane sulfenyl, dichloromethane sulfenyl, trichloro-methylthio, fluorine methylthio group, difluoro methylthio group, trifluoromethylthio, chlorine fluorine methylthio group.
Thiazolinyl: straight or branched also can have two key, for example vinyl, allyl groups on any position.
Alkynyl: straight or branched also can have triple bond on any position, for example ethynyl, propargyl.
Aryl moiety in aryl and aralkyl, aryloxy and the aryloxy alkyl comprises phenyl and Nai Ji.
The indication heteroaryl is to contain one or more N, O, the heteroatomic 5 yuan of rings of S or 6 yuan of rings among the present invention.For example pyridine, furans, pyrimidine, pyrazine, pyridazine, triazine, quinoline, cumarone.
In compound of the present invention, because the two keys of carbon-to-carbon double bond or carbon-nitrogen connect different substituting groups and can form steric isomer (representing different configurations with Z and E respectively).The present invention includes the mixture of Z type isomer and E-isomer and any ratio thereof.
Can the present invention be described with the compound of listing in the following table, but not limit the present invention.
When Q in the general formula I was Q1 (phenyl ring of replacement), general formula was following structure, compound such as table 1.
Table 1
When Q in the general formula I was Q2 (pyridine of replacement), general formula was following structure, compound such as table 2.
Table 2
When Q in the general formula I was Q3 (tonka bean camphor of replacement), general formula was following structure, compound such as table 3.
Table 3
When Q in the general formula I was Q4 (5 replacements of pyrazoles Huo isoxazole), general formula was following structure, compound such as table 4.
Table 4
When Q in the general formula I was Q5 (imines), general formula was following structure, compound such as table 5.
Table 5
When Q in the general formula I was Q6 (pyridazinone), general formula was following structure, compound such as table 6.
Table 6
When Q in the general formula I was Q7 (benzothiazole or benzoxazoles), general formula was following structure, compound such as table 7.
Table 7
When Q in the general formula I was Q8 (4 replacements of thiazole or oxazole), general formula was following structure, compound such as table 8.
Table 8
When Q in the general formula I was Q9 (2 replacements of thiazole or oxazole), general formula was following structure, compound such as table 9.
Table 9
When Q in the general formula I was Q10 (replacement pyridazine), general formula was following structure, compound such as table 10.
Table 10
When Q was Q11 (replacement 1,2,4-thiadiazoles or 1,2,4-oxadiazoles) in general formula I, general formula was following structure, compound such as table 11.
Table 11
When Q was Q12 (replacement 1,3,4-thiadiazoles or 1,3,4-oxadiazoles) in general formula I, general formula was following structure, compound such as table 12.
Table 12
When Q in the general formula I was Q13 (3 replacements of pyrazoles), general formula was following structure, compound such as table 13.
Table 13
Technical scheme of the present invention also comprises the preparation method of compound of Formula I.
Compound of Formula I and steric isomer thereof are made by amine, hydrazine or the oxime reaction of Urethylane compounds shown in the general formula I I and replacement:
The definition of each group is the same in the general formula.
The optional tetrahydrofuran (THF) freely of The suitable solvent, toluene, dimethylbenzene, benzene, methyl alcohol etc.
Suitable temperature refers to room temperature to the solvent boiling point temperature, is generally 20～100 ℃.
Reaction times is 30 minutes to 20 hours, common 1～10 hour.
General formula I I compound and steric isomer thereof react under alkaline condition with reference to the CN1869034A method, by the compound of hydroxyl shown in the general formula III or sulfydryl and the benzyl halogen shown in the general formula I V and make:
Among the general formula I V, X
2Be leavings group, be selected from chlorine or bromine; The definition of other each groups is the same.
The optional tetrahydrofuran (THF) freely of The suitable solvent, acetonitrile, toluene, dimethylbenzene, benzene, N, dinethylformamide, methyl-sulphoxide, acetone or butanone etc.
The suitable optional potassium hydroxide freely of alkali, sodium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, triethylamine, pyridine, sodium methylate, sodium ethylate, sodium hydride, potassium tert.-butoxide or sodium tert-butoxide etc.
Suitable temperature refers to room temperature to the solvent boiling point temperature, is generally 20～100 ℃.
Reaction times is 30 minutes to 20 hours, common 1～10 hour.
Intermediate III can buy or make by currently known methods, specifically referring to CN1657522A, and CN1616448A, CN1869032A, CN1869034A, application number are the Chinese patent of 200510046765.x etc.
Compound shown in the general formula I V can be made by currently known methods, specifically referring to US4723034 and US5554578 etc.
Compound of the present invention have broad-spectrum sterilization activity-can be used for control on various crop by multiple germ diseases such as Oomycete, Basidiomycetes, ascomycetes and imperfect fungis, and because these compounds have very high biological activity makes just can obtain good effect under very low dosage.This compounds has systemic activity and can be used as the blade face and soil fungicides, can be applicable to the disease of preventing and treating on the various crop, for example: diseases such as cucumber downy mildew, gray mold of cucumber, powdery mildew of cucumber, early blight of tomato, tomato late blight, capsicum epidemic disease, downy mildew of garpe, fruit white rot of grape, ring rot of apple, alternaria leaf spot of apple, rice sheath blight disease, rice blast, wheat rust, speckled leaf blotch, wheat powdery mildew, sclerotinia rot of colza, corn southern leaf blight are all had good preventive effect.Part of compounds of the present invention also has good desinsection and acaricidal activity, can be used for preventing and treating insect and mite on the various crop.
The present invention also provides a kind of sterilization, insect-killing composition, contain upward acceptable carrier of compound of Formula I and agricultural in the composition, amount of application when the content of active ingredient depends on independent the use in the said composition, also depend on the mixed ratio and the synergism degree of a kind of compound and another kind of or above compound, simultaneously also relevant with the target fungi.Usually the weight percentage of active ingredient is the 0.5-90% of gross weight in the composition, and preferable is 5% to 85%.According to different preparation types, the active component content scope is different.Usually, liquid preparation contains 1-70% active substance by weight, preferably is 5-40%; Solid preparation contains the active substance of 5%-85% by weight, preferably is 10-40%; Suspension preparation contains the active substance of 10-60% by weight, preferably is 5-35%.
At least contain a kind of tensio-active agent in sterilization of the present invention, the insect-killing composition, the dispersion of active ingredient in water when being beneficial to use, and help making it can correctly be applied to plant.Selected tensio-active agent is known in those skilled in the art, comprises farming breast 500
#, farming breast 600
#, Nongru-700
#Farming breast 1601; the newborn OP-10 of farming; the newborn OX-2681 of farming; the newborn OX-2501 of farming; the agricultural newborn OX-635 of farming breast; farming breast 2201; the newborn 0201B of farming; the newborn 0203B of farming; condensation compound of methyl naphthalene sulfonic acid and formaldehyde; naphthalene sulfonic acidformaldehyde condensation product; the methanonaphthalene sodium sulfonate; to tertbutyl ether; N-methyl-oleoyl-Sodium taurine salt; the dibutyl naphthalene sulfonic acidformaldehyde condensation product; sodium laurylsulfate; alkyl alcohol polyoxyethylene groups ether sodium sulfate; alkyl sodium sulfonate; sodium alkyl naphthalene sulfonate; sorbitan fatty acid ester polyoxyethylene groups ether; xanthan gum; polyvinylpyrrolidone; neusilin; polyvinyl alcohol; polyoxyethylene glycol; carboxymethyl cellulose; bubble enemy etc.According to different dosage form, can also contain disintegrating agent known in those skilled in the art, wetting spreader-sticker, suspending agent etc. in the preparation.
Sterilization of the present invention, insect-killing composition also contain at least a an amount of solid or liquid diluent according to the formulation difference of being prepared.The appropriate liquid thinner comprises alkylbenzene, alkylnaphthalene, chlorinated aromatic hydrocarbons, aliphatic hydrocrbon, chloro aliphatic hydrocrbon, alcohols, ester class, ketone, and dimethyl formamide, dimethyl sulfoxide (DMSO) and N-methyl-pyrrolidone; Also have vegetables oil and methylcyclohexane.Mixtures of different liquids often is suitable for.Organic solvent also can be used as attached solubility promoter or antifreezing agent.Usually, be used to prepare that acceptable any solid diluent all can use on the agricultural of fungicide preparation.They can combine with active ingredient and be beneficial to active ingredient and be applied on the target and accepted by processed plant.Solid diluent commonly used such as diatomite, magnesium aluminum silicate, atlapulgite, kaolin, white carbon black, light calcium carbonate, ammonium sulfate, hexamethylene diamine, solid fertilizer, clay, polynite, gypsum, wilkinite and Zulkovsky starch etc.
Sterilization of the present invention, insect-killing composition can have no particular limits by the user before use through dilution or directly use.Its preparation can be by the preparation of common working method, is about to active substance and after liquid solvent and/or solid carrier mix, and adds in tensio-active agent such as emulsifying agent, dispersion agent, stablizer, wetting agent, tackiness agent, the defoamer etc. one or more again.
Sterilization of the present invention, insect-killing composition can be processed into acceptable forms on any agricultural on demand.For example can be suspension agent, aqueous emulsion, wettable powder, suspension concentrate, (water-dispersion) granula.The compound method of several formulations 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 makes 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 favorable dispersity.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%-40%) 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 drying, screening (pressing the screen cloth scope).Also former medicine, dispersion agent, disintegrating agent and wetting agent and solid diluent can be added in the sand mill, be medium milling with water, makes suspension agent, carries out spray drying granulation then, and formulation content is the 20%-30% granular product usually.
Composition of the present invention can be used by common method, as cast, injection, spraying, dusting, scatter or be fuming.Amount of application of the present invention is with weather condition or crop change of state.Time of application can be before or after infecting.This point is very important, because in fact the infection of Fa Shenging can not be realized immediately.The time length of protection is relevant with selected individualized compound, also relevant with many extraneous factors usually, and for example weather can slow down climatic influences usually by using suitable formulation.
By in composition, adding other one or more sterilant, make it can have the more activity of wide spectrum than independent compound of Formula I.In addition, but the fungicidal activity of other sterilant mutual-through types I compound has synergism.Also compound of Formula I and other sterilants can be used with, or use with another kind of sterilant and other sterilants simultaneously.
Embodiment
Following specific embodiment is used for further specifying the present invention, but the present invention is limited to these examples absolutely not.
Synthetic embodiment
Example 1: the preparation of compound 4-63
0.8 aqueous methylamine solution that digests compound II-1 and twice as high molar ratio was refluxed 5 hours in 50 ml methanol, concentrate back ethyl acetate extraction 2 times, the extract of merging washes with water 3 times, with saturated common salt washing 2 times, drying is filtered again, concentrate, get title compound 0.74 gram.Yield 93%.
Wherein, being prepared as follows of Compound I I-1:
According to synthetic method described in the CN1869034A, digest compound III-1 with 0.5 and be dissolved in 5 milliliters of N, in the dinethylformamide, add sodium hydride 0.17 gram, stirred 0.5 hour.Add 0.72 and digest compound IV-1,40 ℃ of oil baths were stirred 3 hours.After the TLC monitoring reaction finishes, reaction solution is poured in 50 milliliters of saturated aqueous common salts, divided with 60 milliliters of ethyl acetate to extract drying three times.Behind the precipitation, column chromatography purification gets oily product 0.56 gram, i.e. Compound I I-1.
Example 2: the preparation of compound 13-1
1 aqueous methylamine solution that digests compound II-2 (pyraclostrobin) and twice as high molar ratio was refluxed 5 hours in 60 ml methanol, concentrate back ethyl acetate extraction 2 times, the extract that merges washes with water 3 times, again with saturated common salt washing 2 times, dry, filter, concentrate, get title compound 0.94 gram.Yield 94%.
Other compounds of the present invention can make with preparation method provided by the invention.
The nuclear magnetic data of part of compounds (
1HNMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows:
Compound 2-3: fusing point 138-140 ℃.δppm?3.62(3H，s)，3.72(3H，s)，5.38(2H，s)，5.96(1H，bs)，7.40(2H，m)，7.62(2H，m).
Compound 4-63: fusing point 150-152 ℃.δppm?1.90(3H，s)，2.88(3H，d)，3.60(3H，s)，3.71(3H，s)，5.38(2H，s)，5.97(1H，bs)，7.35(5H，m)，7.42(3H，m)，7.70(1H，m)。
Compound 13-1: oily matter.δppm?2.89(3H，d)，3.68(3H，s)，5.39(2H，s)，5.94(1H，d)，5.95(1H，d)，7.35(5H，m)，7.54(2H，m)，7.63(1H，m)，7.68(1H，m)。
Example of formulations (each component add-on is weight percentage).
Embodiment 3:30% compound 2-3 wettable powder
Compound 2-3 50%
Sodium lauryl sulphate 2%
Sodium lignosulfonate 3%
Naphthalene sulfonic acidformaldehyde condensation product 5%
Light calcium carbonate complements to 100%
With thorough mixing such as compound 2-3, various tensio-active agent and solid diluents, after ultrafine crusher is pulverized, promptly obtain 30% wettable powder product.
Embodiment 4:20% compound 4-63 suspension agent
Compound 4-63 30%
Condensation compound of methyl naphthalene sulfonic acid and formaldehyde 3%
The newborn 0201B 2% of farming
Nongru-700
#1%
Xanthan gum 0.2%
Ethylene glycol 5%
Water complements to 100%
With water is medium, and compound 4-63, dispersion agent, suspending agent and antifreezing agent etc. are added in the sand mill, grinds, and makes suspension agent.
Embodiment 5:60% compound 2-3 water-dispersible granules
Compound 2-3 60%
Naphthalenesulfonic acid-formaldehyde condensate 12%
N-methyl-oleoyl-Sodium taurine salt 8%
Polyvinylpyrrolidone 2%
Carboxymethyl cellulose 2%
Kaolin complements to 100%
Compound 2-3 and powdery solid thinner, wetting spreader-sticker and tackiness agent etc. are mixed pulverizing, after adding water again and mediating, add in the tablets press that the certain specification screen cloth is housed and carry out granulation, and then drying, screening (pressing the screen cloth scope).
Embodiment 6:10% compound 13-1 aqueous emulsion
Compound 13-1 10%
Polyoxyethylene (n
20) styroyl
Phenolic group oleic acid ester 8%
Calcium dodecylbenzene sulphonate 16%
Piperonyl butoxide 15%
Pimelinketone 10%
Sorbyl alcohol 5%
Water complements to 100%
Compound 13-1, 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 favorable dispersity.
Embodiment 7:25% compound suspension agent
Compound 4-63 25%
The newborn 0201B 2.5% of farming
Farming breast 1,601 1%
Naphthalene sulfonic acidformaldehyde condensation product 2%
White carbon black 0.1%
Ethylene glycol 5%
Water complements to 100%
With water is medium, and compound 4-63, dispersion agent, suspending agent and antifreezing agent etc. are added in the sand mill, grinds, and makes suspension agent.
Embodiment 8:50% compound 2-3 wettable powder
Compound 2-3 20%
Methanonaphthalene sodium sulfonate 6%
Naphthalene sulfonic acidformaldehyde condensation product 3%
Sodium lauryl sulphate 2%
White carbon black 5%
Farming breast 600
#0.5%
Light calcium carbonate complements to 100%
With thorough mixing such as compound 2-3, various tensio-active agent and solid diluents, after ultrafine crusher is pulverized, promptly obtain 20% wettable powder product.
Biological activity determination
Example 9 fungicidal activities are measured
With The compounds of this invention the various fungus diseases of plant are tested.The method of test is as follows:
Adopt the potted plant measuring method of live body.The former medicinal small amount of acetone dissolving of testing compound is diluted to required concentration with the water that contains 0.1% tween 80.Spray pesticide carries out the disease inoculation after 24 hours to plant examination material.After the inoculation, plant is placed in the fixed temperature and humidity incubator, makes to infect and continue, wait to contrast abundant morbidity back (being generally week age) and carry out assessment surveys.The partial test result is as follows:
During 25ppm, compound 2-3,4-63,13-1 etc. are 100% to the preventive effect of rice blast, wheat powdery mildew, rice sheath blight disease.
During 25ppm, compound 13-1 etc. are 100% to the preventive effect of cucumber downy mildew, are 80% to the preventive effect of gray mold of cucumber.
Example 10 pesticide and miticide actilities are measured
With The compounds of this invention several insects and mite class have been carried out the insecticidal activity assay test.Method for measuring is as follows:
After the mixed solvent dissolving of testing compound with acetone/methanol (1: 1), be diluted to required concentration with the water that contains 0.1% tween 80.
With mythimna separata (Leucania separata), small cabbage moth (Plutella xylostella) and culex pipiens pollens (Culex pippens pallens) 2 instar larvaes, black peach aphid (Myzus persicae), (Tetranychus cinnabarinus is a target to carmine spider mite, adopt airbrush spray method and immersion method (culex pipiens pallens larvae) to carry out insecticidal activity assay, the pressure that the airbrush spraying is handled is that 10psi (is roughly equal to 0.7kg/cm
2), spouting liquid is 0.5ml.Handle the mortality ratio that 2-3 day is investigated target in the back.
The partial test result is as follows:
When liquor strength was 600ppm, compound 13-1 etc. reached more than 80% mythimna separata, small cabbage moth mortality ratio.
Claims (3)
1. substituted phenylurea compound, shown in general formula I:
In the formula:
Q is selected from any one substituting group as follows:
2. the application of the described compound of Formula I of claim 1 germ on the control crop.
3. fungicidal composition is characterized in that: contain compound of Formula I as claimed in claim 1 and agricultural goes up acceptable carrier, the weight percentage of active ingredient is 0.5-90% in the composition.
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