CN101205187B - Substituted aryl ethers compounds as well as preparation and uses thereof - Google Patents
Substituted aryl ethers compounds as well as preparation and uses thereof Download PDFInfo
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- CN101205187B CN101205187B CN2006101349744A CN200610134974A CN101205187B CN 101205187 B CN101205187 B CN 101205187B CN 2006101349744 A CN2006101349744 A CN 2006101349744A CN 200610134974 A CN200610134974 A CN 200610134974A CN 101205187 B CN101205187 B CN 101205187B
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- ZMYWBTSKPSHRJR-UHFFFAOYSA-N CC[IH]1=C(C)C=C(NBr)N=C1 Chemical compound CC[IH]1=C(C)C=C(NBr)N=C1 ZMYWBTSKPSHRJR-UHFFFAOYSA-N 0.000 description 1
- GGFJPYWUQCOYLQ-UHFFFAOYSA-N Cc1ncnc(OC)c1 Chemical compound Cc1ncnc(OC)c1 GGFJPYWUQCOYLQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the field of the agricultural pesticides and fungicides, in particular discloses a replaced aryl ether compounds and the preparation and application. The replaced aryl ether compounds of the invention are shown as the general formula (I), wherein Ar represents Ar-1 or Ar-2. The general formula (I) compounds of the invention have the broad-spectrum activity--the compounds have very favorable control effects on the diseases such as the grape downy mildew, rice sheath blight, rice-blast disease, tomato late blight, powdery mildew, cucumber powdery mildew, cucumber downy mildew, cucumber gray mold, etc. The compounds of the invention simultaneously have very good insecticidal activity, have effects on a plurality of pests such as the armyworm, the diamondback moth, etc. and are very suitable for the integrated control of the pests on various crops.
Description
Technical field
The invention belongs to agricultural insecticidal, sterilant field, relate to substituted aryl ethers compounds and preparation thereof and application particularly.
Background technology
The methoxy acrylate compound is the compound of known biologically active.The patent of report and document are a lot of as CN1030749A, CN1188394A, EP335519A, US4829085, US4914128, US5145980, US5157144, US5334748, US5395854, US5548078, US2004029944A, WO9515083A, WO9517818A, WO9823155A, WO9823156A, WO9703950A, WO2003087032A; Tetrahedron (1999), 55 (37), 11343-11364; Nippon Noyaku Gakkaishi (1998), 23 (2), 107-112; Shionogi Kenkyusho Nenpo (1997), 47,33-57 etc.
Known commercial kind is also a lot, and the structure and the title of part commercialization kind are as follows:
Applicant of the present invention discloses following general formula compound in for " replacement to trifluoromethyl phenyl ether compound and preparation and application ", the Chinese patent application of application number 200510046765.x in denomination of invention:
In the formula: Q is selected from Q as follows
1, Q
2, Q
3, Q
4Or Q
5
A is selected from CH
2Or
When
The time, the 4-position of pyrimidine links to each other with oxygen, and 6-position oxygen links to each other Q=Q with phenyl ring
1X is 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 amido 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.
Although the compound patent and the commercialization kind of a lot of similar are arranged, substituted aryl ethers compounds involved in the present invention is not concrete open.
Summary of the invention
The object of the present invention is to provide a kind of substituted aryl ethers compounds 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 aryl ethers compounds, shown in general formula (I):
In the formula:
Ar represents Ar-1 or Ar-2:
Q is selected from Q as follows
1, Q
2, Q
3, Q
4Or Q
5:
X is selected from O or S;
R
1-R
5In the following several ways:
Work as R
1, R
2, R
3One of be CF
3The time, other substituting groups are 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
12Halogenated alkoxy, C
1-C
12Halogenated alkylthio, C
1-C
12Alkane alkylsulfonyl, C
1-C
12Haloalkane 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 or any substituted-amino C
1-C
12Alkyl;
Work as R
3Be CF
3, R
1During for chlorine, R
5Be selected from fluorine, cyano group, nitro, C
2-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
12Halogenated alkoxy, C
1-C
12Halogenated alkylthio, C
1-C
12Alkane alkylsulfonyl, C
1-C
12Haloalkane 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 or any substituted-amino C
1-C
12Alkyl; R
2, R
4Be 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
12Halogenated alkoxy, C
1-C
12Halogenated alkylthio, C
1-C
12Alkane alkylsulfonyl, C
1-C
12Haloalkane 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 or any substituted-amino C
1-C
12Alkyl;
Work as R
3Be i-C
3F
7The time, other substituting groups are 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
12Halogenated alkoxy, C
1-C
12Halogenated alkylthio, C
1-C
12Alkane alkylsulfonyl, C
1-C
12Haloalkane 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 or any substituted-amino C
1-C
12Alkyl;
X
1Be selected from N or CH;
X
2, X
3Be selected from N or C-R respectively; Wherein R is 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
12Halogenated alkoxy, C
1-C
12Halogenated alkylthio or C
1-C
12The alkane alkylsulfonyl;
R
6, R
7Be 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
12Halogenated alkoxy, C
1-C
12Halogenated alkylthio or C
1-C
12The alkane alkylsulfonyl;
And steric isomer.
Comparatively preferred compound is among the present invention: in the general formula (I)
Q is selected from Q
1, Q
2, Q
3, Q
4Or Q
5
X is selected from O or S;
R
1-R
5In the following several ways:
Work as R
1, R
2, R
3One of be CF
3The time, other substituting groups are selected from hydrogen, halogen, cyano group, nitro, C respectively
1-C
6Alkyl, C
2-C
6Thiazolinyl, C
2-C
6Alkynyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, C
1-C
6Halogenated alkoxy, C
1-C
6Halogenated alkylthio, C
1-C
6Alkane alkylsulfonyl, C
1-C
6Haloalkane 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
6Halogenated alkoxy C
1-C
6Alkyl or any substituted-amino C
1-C
6Alkyl;
Work as R
3Be CF
3, R
1During for chlorine, R
5Be selected from fluorine, cyano group, nitro, C
2-C
6Alkyl, C
2-C
6Thiazolinyl, C
2-C
6Alkynyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, C
1-C
6Halogenated alkoxy, C
1-C
6Halogenated alkylthio, C
1-C
6Alkane alkylsulfonyl, C
1-C
6Haloalkane 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
6Halogenated alkoxy C
1-C
6Alkyl or any substituted-amino C
1-C
6Alkyl; R
2, R
4Be selected from hydrogen, halogen, cyano group, nitro, C respectively
1-C
6Alkyl, C
2-C
6Thiazolinyl, C
2-C
6Alkynyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, C
1-C
6Halogenated alkoxy, C
1-C
6Halogenated alkylthio, C
1-C
6Alkane alkylsulfonyl, C
1-C
6Haloalkane 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
6Halogenated alkoxy C
1-C
6Alkyl or any substituted-amino C
1-C
6Alkyl;
Work as R
3Be i-C
3F
7The time, other substituting groups are selected from hydrogen, halogen, cyano group, nitro, C respectively
1-C
6Alkyl, C
2-C
6Thiazolinyl, C
2-C
6Alkynyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, C
1-C
6Halogenated alkoxy, C
1-C
6Halogenated alkylthio, C
1-C
6Alkane alkylsulfonyl, C
1-C
6Haloalkane 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
6Halogenated alkoxy C
1-C
6Alkyl or any substituted-amino C
1-C
6Alkyl;
X
1Be selected from N or CH;
X
2, X
3Be selected from N or C-R respectively; Wherein R is selected from hydrogen, halogen, cyano group, nitro, C
1-C
6Alkyl, C
2-C
6Thiazolinyl, C
2-C
6Alkynyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, C
1-C
6Halogenated alkoxy, C
1-C
6Halogenated alkylthio or C
1-C
6The alkane alkylsulfonyl;
R
6, R
7Be selected from hydrogen, halogen, cyano group, nitro, C respectively
1-C
6Alkyl, C
2-C
6Thiazolinyl, C
2-C
6Alkynyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, C
1-C
6Halogenated alkoxy, C
1-C
6Halogenated alkylthio or C
1-C
6The alkane alkylsulfonyl.
Further preferred compound is: in the general formula (I)
Q is selected from Q
1, Q
2, Q
3Or Q
4
X is selected from O or S;
R
1-R
5In the following several ways:
Work as R
1, R
2, R
3One of be CF
3The time, other substituting groups are selected from hydrogen, halogen, cyano group, nitro, C respectively
1-C
6Alkyl, C
2-C
6Thiazolinyl, C
2-C
6Alkynyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, C
1-C
6Halogenated alkoxy, C
1-C
6Halogenated alkylthio, C
1-C
6Alkane alkylsulfonyl or C
1-C
6The haloalkane alkylsulfonyl;
Work as R
3Be CF
3, R
1During for chlorine, R
5Be selected from fluorine, cyano group, nitro, C
2-C
6Alkyl, C
2-C
6Thiazolinyl, C
2-C
6Alkynyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, C
1-C
6Halogenated alkoxy, C
1-C
6Halogenated alkylthio, C
1-C
6Alkane alkylsulfonyl or C
1-C
6The haloalkane alkylsulfonyl; R
2, R
4Be selected from hydrogen, halogen, cyano group, nitro, C respectively
1-C
6Alkyl, C
2-C
6Thiazolinyl, C
2-C
6Alkynyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, C
1-C
6Halogenated alkoxy, C
1-C
6Halogenated alkylthio, C
1-C
6Alkane alkylsulfonyl or C
1-C
6The haloalkane alkylsulfonyl;
Work as R
3Be i-C
3F
7The time, other substituting groups are selected from hydrogen, halogen, cyano group, nitro, C respectively
1-C
6Alkyl, C
2-C
6Thiazolinyl, C
2-C
6Alkynyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, C
1-C
6Alkylthio, C
1-C
6Halogenated alkoxy, C
1-C
6Halogenated alkylthio, C
1-C
6Alkane alkylsulfonyl or C
1-C
6The haloalkane alkylsulfonyl;
X
1Be selected from N or CH;
X
2, X
3Be selected from N or C-R respectively; Wherein R is 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
6Halogenated alkoxy or C
1-C
6Halogenated alkylthio;
R
6, R
7Be selected from hydrogen, halogen, cyano group, nitro, C
1-C
6Alkyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group or C
1-C
6Alkylthio.
Further preferred again compound is: in the general formula (I)
Q is selected from Q
1, Q
2, Q
3Or Q
4
X is selected from O or S;
R
1-R
5In the following several ways:
Work as R
1, R
2, R
3One of be CF
3The time, other substituting groups are selected from hydrogen, chlorine, bromine, fluorine, cyano group, nitro, C respectively
1-C
6Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Alkylthio, C
1-C
3Halogenated alkoxy, C
1-C
3Halogenated alkylthio, C
1-C
3Alkane alkylsulfonyl or C
1-C
3The haloalkane alkylsulfonyl;
Work as R
3Be CF
3, R
1During for chlorine, R
5Be selected from fluorine, cyano group, nitro, C
2-C
6Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Alkylthio, C
1-C
3Halogenated alkoxy, C
1-C
3Halogenated alkylthio, C
1-C
3Alkane alkylsulfonyl or C
1-C
3The haloalkane alkylsulfonyl; R
2, R
4Be selected from hydrogen, chlorine, bromine, fluorine, cyano group, nitro, C respectively
1-C
6Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Alkylthio, C
1-C
3Halogenated alkoxy, C
1-C
3Halogenated alkylthio, C
1-C
3Alkane alkylsulfonyl or C
1-C
3The haloalkane alkylsulfonyl;
Work as R
3Be i-C
3F
7The time, other substituting groups are selected from hydrogen, chlorine, bromine, fluorine, cyano group, nitro, C respectively
1-C
6Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Alkylthio, C
1-C
3Halogenated alkoxy, C
1-C
3Halogenated alkylthio, C
1-C
3Alkane alkylsulfonyl or C
1-C
3The haloalkane alkylsulfonyl;
X
1Be selected from N or CH;
X
2, X
3Be selected from N or C-R respectively; Wherein R is selected from hydrogen, chlorine, cyano group, nitro, C
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group or C
1-C
3Halogenated alkoxy;
R
6, R
7Be selected from hydrogen, chlorine, cyano group, C respectively
1-C
6Alkyl or C
1-C
6Haloalkyl.
Further preferred compound is: in the general formula (I)
Q is selected from Q
1, Q
2, Q
3Or Q
4
X is selected from O;
R
1-R
5In the following several ways:
Work as R
1, R
2, R
3One of be CF
3The time, other substituting groups are selected from hydrogen, chlorine, fluorine, methyl, cyano group, nitro, OCF respectively
3, SCF
3, SO
2CH
3, SO
2CF
3Or i-C
3F
7
Work as R
3Be CF
3, R
1During for chlorine, R
5Be selected from fluorine, cyano group, nitro, OCF
3, SCF
3, SO
2CH
3, SO
2CF
3, i-C
3F
7Or CF
3, R
2, R
4Be selected from hydrogen, chlorine, fluorine, cyano group, nitro, OCF respectively
3, SCF
3, SO
2CH
3, SO
2CF
3, i-C
3F
7Or CF
3
Work as R
3Be i-C
3F
7The time, other substituting groups are selected from hydrogen, chlorine, fluorine, methyl, cyano group, nitro, OCF respectively
3, SCF
3, SO
2CH
3, SO
2CF
3Or i-C
3F
7
X
1Be selected from N or CH;
X
2, X
3Be selected from N or C-R respectively; Wherein R is selected from hydrogen, chlorine, cyano group, nitro, CF
3Or OCH
2CF
3
R
6, R
7Be selected from hydrogen, chlorine, cyano group or CF respectively
3
In the definition of the general formula that provides above (I) compound, compile the following substituting group of used term general proxy:
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 atom, 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 atom.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.
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.
In the 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 geometrical isomer (representing different configurations with Z and E respectively).General formula of the present invention (I) compound comprises the Z type isomer and the E-isomer mixture of Z type isomer and E-isomer and any ratio thereof.
The compound of listing in following table 1 and the table 2 but does not limit the present invention in order to explanation the present invention.
Table 1
| Numbering | X | R 1 | R 2 | R 3 | R 4 | R 5 | Q |
| 1 | O | CF 3 | SO 2CH 3 | H | H | H | Q 1 |
| 2 | O | CF 3 | CN | H | H | H | Q 1 |
| 3 | O | CF 3 | NO 2 | H | H | H | Q 1 |
| 4 | O | CF 3 | SO 2CF 3 | H | H | H | Q 1 |
| 5 | O | CF 3 | OCF 3 | H | H | H | Q 1 |
| 6 | O | CF 3 | SCF 3 | H | H | H | Q 1 |
| 7 | O | CF 3 | F | H | H | H | Q 1 |
| 8 | O | CF 3 | Cl | H | H | H | Q 1 |
| 9 | O | CF 3 | H | SO 2CH 3 | H | H | Q 1 |
| 10 | O | CF 3 | H | CN | H | H | Q 1 |
| 11 | O | CF 3 | H | NO 2 | H | H | Q 1 |
| 12 | O | CF 3 | H | SO 2CF 3 | H | H | Q 1 |
| 13 | O | CF 3 | H | OCF 3 | H | H | Q 1 |
| 14 | O | CF 3 | H | SCF 3 | H | H | Q 1 |
| 15 | O | CF 3 | H | F | H | H | Q 1 |
| 16 | O | CF 3 | H | Cl | H | H | Q 1 |
| 17 | O | CF 3 | H | H | SO 2CH 3 | H | Q 1 |
| 18 | O | CF 3 | H | H | CN | H | Q 1 |
| 19 | O | CF 3 | H | H | NO 2 | H | Q 1 |
| 20 | O | CF 3 | H | H | SO 2CF 3 | H | Q 1 |
| 21 | O | CF 3 | H | H | OCF 3 | H | Q 1 |
| 22 | O | CF 3 | H | H | SCF 3 | H | Q 1 |
| 23 | O | CF 3 | H | H | F | H | Q 1 |
| 24 | O | CF 3 | H | H | Cl | H | Q 1 |
| 25 | O | CF 3 | H | H | H | SO 2CH 3 | Q 1 |
| 26 | O | CF 3 | H | H | H | CN | Q 1 |
| 27 | O | CF 3 | H | H | H | NO 2 | Q 1 |
| 28 | O | CF 3 | H | H | H | SO 2CF 3 | Q 1 |
| 29 | O | CF 3 | H | H | H | OCF 3 | Q 1 |
| 30 | O | CF 3 | H | H | H | SCF 3 | Q 1 |
| 31 | O | CF 3 | H | H | H | F | Q 1 |
| 32 | O | CF 3 | H | H | H | Cl | Q 1 |
| 33 | O | SO 2CH 3 | CF 3 | H | H | H | Q 1 |
| 34 | O | CN | CF 3 | H | H | H | Q 1 | |
| 35 | O | NO 2 | CF 3 | H | H | H | Q 1 | |
| 36 | O | SO 2CF 3 | CF 3 | H | H | H | Q 1 | |
| 37 | O | OCF 3 | CF 3 | H | H | H | Q 1 | |
| 38 | O | SCF 3 | CF 3 | H | H | H | Q 1 | |
| 39 | O | F | CF 3 | H | H | H | Q 1 | |
| 40 | O | Cl | CF 3 | H | H | H | Q 1 | |
| 41 | O | H | CF 3 | SO 2CH 3 | H | H | Q 1 | |
| 42 | O | H | CF 3 | CN | H | H | Q 1 | |
| 43 | O | H | CF 3 | NO 2 | H | H | Q 1 | |
| 44 | O | H | CF 3 | SO 2CF 3 | H | H | Q 1 | |
| 45 | O | H | CF 3 | OCF 3 | H | H | Q 1 | |
| 46 | O | H | CF 3 | SCF 3 | H | H | Q 1 | |
| 47 | O | H | CF 3 | F | H | H | Q 1 | |
| 48 | O | H | CF 3 | H | SO 2CH 3 | H | Q 1 | |
| 49 | O | H | CF 3 | H | CN | H | Q 1 | |
| 50 | O | H | CF 3 | H | NO 2 | H | Q 1 | |
| 51 | O | H | CF 3 | H | SO 2CF 3 | H | Q 1 | |
| 52 | O | H | CF 3 | H | OCF 3 | H | Q? 1 | |
| 53 | O | H | CF 3 | H | SCF 3 | H | Q 1 | |
| 54 | O | H | CF 3 | H | F | H | Q 1 | |
| 55 | O | H | CF 3 | H | Cl | H | Q 1 | |
| 56 | O | H | CF 3 | H | H | SO 2CH 3 | Q 1 | |
| 57 | O | H | CF 3 | H | H | CN | Q 1 | |
| 58 | O | H | CF 3 | H | H | NO 2 | Q 1 | |
| 59 | O | H | CF 3 | H | H | SO 2CF 3 | Q 1 | |
| 60 | O | H | CF 3 | H | H | OCF 3 | Q 1 | |
| 61 | O | H | CF 3 | H | H | SCF 3 | Q 1 | |
| 62 | O | H | CF 3 | H | H | F | Q 1 | |
| 63 | O | H | CF 3 | H | H | Cl | Q 1 | |
| 64 | O | SO 2CH 3 | H | CF 3 | H | H | Q 1 | |
| 65 | O | CN | H | CF 3 | H | H | Q 1 | |
| 66 | O | NO 2 | H | CF 3 | H | H | Q 1 | |
| 67 | O | SO 2CF 3 | H | CF 3 | H | H | Q 1 | |
| 68 | O | OCF 3 | H | CF 3 | H | H | Q 1 | |
| 69 | O | SCF 3 | H | CF 3 | H | H | Q 1 | |
| 70 | O | F | H | CF 3 | H | H | Q 1 | |
| 71 | O | H | SO 2CH 3 | CF 3 | H | H | Q 1 | |
| 72 | O | H | CN | CF 3 | H | H | Q 1 | |
| 73 | O | H | NO 2 | CF 3 | H | H | Q 1 | |
| 74 | O | H | SO 2CF 3 | CF 3 | H | H | Q 1 | |
| 75 | O | H | OCF 3 | CF 3 | H | H | Q 1 | |
| 76 | O | H | SCF 3 | CF 3 | H | H | Q 1 | |
| 77 | O | H | F | CF 3 | H | H | Q 1 |
| 78 | O | H | Cl | CF 3 | H | H | Q 1 |
| 79 | O | Cl | CF 3 | H | CF 3 | H | Q 1 |
| 80 | O | Cl | CF 3 | H | SO 2CH 3 | H | Q 1 |
| 81 | O | Cl | CF 3 | H | CN | H | Q 1 |
| 82 | O | Cl | CF 3 | H | NO 2 | H | Q 1 |
| 83 | O | Cl | CF 3 | H | SO 2CF 3 | H | Q 1 |
| 84 | O | Cl | CF 3 | H | OCF 3 | H | Q 1 |
| 85 | O | Cl | CF 3 | H | SCF 3 | H | Q 1 |
| 86 | O | Cl | CF 3 | H | F | H | Q 1 |
| 87 | O | Cl | CF 3 | H | Cl | H | Q 1 |
| 88 | O | Cl | H | CF 3 | H | CF 3 | Q 1 |
| 89 | O | Cl | H | CF 3 | H | SO 2CH 3 | Q 1 |
| 90 | O | Cl | H | CF 3 | H | CN | Q 1 |
| 91 | O | Cl | H | CF 3 | H | NO 2 | Q 1 |
| 92 | O | Cl | H | CF 3 | H | SO 2CF 3 | Q 1 |
| 93 | O | Cl | H | CF 3 | H | OCF 3 | Q 1 |
| 94 | O | Cl | H | CF 3 | H | SCF 3 | Q 1 |
| 95 | O | Cl | H | CF 3 | H | F | Q 1 |
| 96 | O | NO 2 | H | CF 3 | H | NO 2 | Q 1 |
| 97 | O | CN | Cl | H | H | H | Q 1 |
| 98 | O | CN | SO 2CH 3 | H | H | H | Q 1 |
| 99 | O | CN | SO 2CF 3 | H | H | H | Q 1 |
| 100 | O | Cl | CN | H | H | H | Q 1 |
| 101 | O | H | CN | H | H | Cl | Q 1 |
| 102 | O | Cl | H | CN | H | H | Q 1 |
| 103 | O | NO 2 | H | SO 2CH 3 | H | H | Q 1 |
| 104 | O | NO 2 | H | SO 2CF 3 | H | H | Q 1 |
| 105 | O | Cl | H | SO 2CH 3 | H | H | Q 1 |
| 106 | O | Cl | H | SO 2CF 3 | H | H | Q 1 |
| 107 | O | H | SO 2CH 3 | H | H | Cl | Q 1 |
| 108 | O | H | SO 2CF 3 | H | H | Cl | Q 1 |
| 109 | O | H | H | i-C 3F 7 | H | H | Q 1 |
| 110 | O | Cl | H | i-C 3F 7 | H | H | Q 1 |
| 111 | O | F | H | i-C 3F 7 | H | H | Q 1 |
| 112 | O | CH 3 | H | i-C 3F 7 | H | H | Q 1 |
| 113 | O | CF 3 | H | i-C 3F 7 | H | H | Q 1 |
| 114 | O | CH 3O | H | i-C 3F 7 | H | H | Q 1 |
| 115 | O | CN | H | i-C 3F 7 | H | H | Q 1 |
| 116 | O | NO 2 | H | i-C 3F 7 | H | H | Q 1 |
| 117 | O | Br | H | i-C 3F 7 | H | H | Q 1 |
| 118 | O | C 2H 5 | H | i-C 3F 7 | H | H | Q 1 |
| 119 | O | CF 3O | H | i-C 3F 7 | H | H | Q 1 |
| 120 | O | CH 3S | H | i-C 3F 7 | H | H | Q 1 |
| 121 | O | SO 2CH 3 | H | i-C 3F 7 | H | H | Q 1 |
| 122 | O | SCF 3 | H | i-C 3F 7 | H | H | Q 1 |
| 123 | O | Cl | H | i-C 3F 7 | H | Cl | Q 1 |
| 124 | O | Cl | H | i-C 3F 7 | H | F | Q 1 |
| 125 | O | Cl | H | i-C 3F 7 | H | CH 3 | Q 1 |
| 126 | O | Cl | H | i-C 3F 7 | H | CF 3 | Q 1 |
| 127 | O | Cl | H | i-C 3F 7 | H | CH 3O | Q 1 |
| 128 | O | Cl | H | i-C 3F 7 | H | CN | Q 1 |
| 129 | O | Cl | H | i-C 3F 7 | H | NO 2 | Q 1 |
| 130 | O | Cl | H | i-C 3F 7 | H | Br | Q 1 |
| 131 | O | CF 3 | SO 2CH 3 | H | H | H | Q 2 |
| 132 | O | CF 3 | CN | H | H | H | Q 2 |
| 133 | O | CF 3 | NO 2 | H | H | H | Q 2 |
| 134 | O | CF 3 | SO 2CF 3 | H | H | H | Q 2 |
| 135 | O | CF 3 | OCF 3 | H | H | H | Q 2 |
| 136 | O | CF 3 | SCF 3 | H | H | H | Q 2 |
| 137 | O | CF 3 | F | H | H | H | Q 2 |
| 138 | O | CF 3 | Cl | H | H | H | Q 2 |
| 139 | O | CF 3 | H | SO 2CH 3 | H | H | Q 2 |
| 140 | O | CF 3 | H | CN | H | H | Q 2 |
| 141 | O | CF 3 | H | NO 2 | H | H | Q 2 |
| 142 | O | CF 3 | H | SO 2CF 3 | H | H | Q 2 |
| 143 | O | CF 3 | H | OCF 3 | H | H | Q 2 |
| 144 | O | CF 3 | H | SCF 3 | H | H | Q 2 |
| 145 | O | CF 3 | H | F | H | H | Q 2 |
| 146 | O | CF 3 | H | Cl | H | H | Q 2 |
| 147 | O | CF 3 | H | H | SO 2CH 3 | H | Q 2 |
| 148 | O | CF 3 | H | H | CN | H | Q 2 |
| 149 | O | CF 3 | H | H | NO 2 | H | Q 2 |
| 150 | O | CF 3 | H | H | SO 2CF 3 | H | Q 2 |
| 151 | O | CF 3 | H | H | OCF 3 | H | Q 2 |
| 152 | O | CF 3 | H | H | SCF 3 | H | Q 2 |
| 153 | O | CF 3 | H | H | F | H | Q 2 |
| 154 | O | CF 3 | H | H | Cl | H | Q 2 |
| 155 | O | CF 3 | H | H | H | SO 2CH 3 | Q 2 |
| 156 | O | CF 3 | H | H | H | CN | Q 2 |
| 157 | O | CF 3 | H | H | H | NO 2 | Q 2 |
| 158 | O | CF 3 | H | H | H | SO 2CF 3 | Q 2 |
| 159 | O | CF 3 | H | H | H | OCF 3 | Q 2 |
| 160 | O | CF 3 | H | H | H | SCF 3 | Q 2 |
| 161 | O | CF 3 | H | H | H | F | Q 2 |
| 162 | O | CF 3 | H | H | H | Cl | Q 2 |
| 163 | O | SO 2CH 3 | CF 3 | H | H | H | Q 2 |
| 164 | O | CN | CF 3 | H | H | H | Q 2 |
| 165 | O | NO 2 | CF 3 | H | H | H | Q 2 |
| 166 | O | SO 2CF 3 | CF 3 | H | H | H | Q 2 |
| 167 | O | OCF 3 | CF 3 | H | H | H | Q 2 |
| 168 | O | SCF 3 | CF 3 | H | H | H | Q 2 |
| 169 | O | F | CF 3 | H | H | H | Q 2 |
| 170 | O | Cl | CF 3 | H | H | H | Q 2 |
| 171 | O | H | CF 3 | SO 2CH 3 | H | H | Q 2 |
| 172 | O | H | CF 3 | CN | H | H | Q 2 |
| 173 | O | H | CF 3 | NO 2 | H | H | Q 2 |
| 174 | O | H | CF 3 | SO 2CF 3 | H | H | Q 2 |
| 175 | O | H | CF 3 | OCF 3 | H | H | Q 2 |
| 176 | O | H | CF 3 | SCF 3 | H | H | Q 2 |
| 177 | O | H | CF 3 | F | H | H | Q 2 |
| 178 | O | H | CF 3 | H | SO 2CH 3 | H | Q 2 |
| 179 | O | H | CF 3 | H | CN | H | Q 2 |
| 180 | O | H | CF 3 | H | NO 2 | H | Q 2 |
| 181 | O | H | CF 3 | H | SO 2CF 3 | H | Q 2 |
| 182 | O | H | CF 3 | H | OCF 3 | H | Q 2 |
| 183 | O | H | CF 3 | H | SCF 3 | H | Q 2 |
| 184 | O | H | CF 3 | H | F | H | Q 2 |
| 185 | O | H | CF 3 | H | Cl | H | Q 2 |
| 186 | O | H | CF 3 | H | H | SO 2CH 3 | Q 2 |
| 187 | O | H | CF 3 | H | H | CN | Q 2 |
| 188 | O | H | CF 3 | H | H | NO 2 | Q 2 |
| 189 | O | H | CF 3 | H | H | SO 2CF 3 | Q 2 |
| 190 | O | H | CF 3 | H | H | OCF 3 | Q 2 |
| 191 | O | H | CF 3 | H | H | SCF 3 | Q 2 |
| 192 | O | H | CF 3 | H | H | F | Q 2 |
| 193 | O | H | CF 3 | H | H | Cl | Q 2 |
| 194 | O | SO 2CH 3 | H | CF 3 | H | H | Q 2 |
| 195 | O | CN | H | CF 3 | H | H | Q 2 |
| 196 | O | NO 2 | H | CF 3 | H | H | Q 2 |
| 197 | O | SO 2CF 3 | H | CF 3 | H | H | Q 2 |
| 198 | O | OCF 3 | H | CF 3 | H | H | Q 2 |
| 199 | O | SCF 3 | H | CF 3 | H | H | Q 2 |
| 200 | O | F | H | CF 3 | H | H | Q 2 |
| 201 | O | H | SO 2CH 3 | CF 3 | H | H | Q 2 |
| 202 | O | H | CN | CF 3 | H | H | Q 2 |
| 203 | O | H | NO 2 | CF 3 | H | H | Q 2 |
| 204 | O | H | SO 2CF 3 | CF 3 | H | H | Q 2 |
| 205 | O | H | OCF 3 | CF 3 | H | H | Q 2 |
| 206 | O | H | SCF 3 | CF 3 | H | H | Q 2 |
| 207 | O | H | F | CF 3 | H | H | Q 2 |
| 208 | O | H | Cl | CF 3 | H | H | Q 2 |
| 209 | O | Cl | CF 3 | H | CF 3 | H | Q 2 |
| 210 | O | Cl | CF 3 | H | SO 2CH 3 | H | Q 2 |
| 211 | O | Cl | CF 3 | H | CN | H | Q 2 |
| 212 | O | Cl | CF 3 | H | NO 2 | H | Q 2 |
| 213 | O | Cl | CF 3 | H | SO 2CF 3 | H | Q 2 |
| 214 | O | Cl | CF 3 | H | OCF 3 | H | Q 2 |
| 215 | O | Cl | CF 3 | H | SCF 3 | H | Q 2 |
| 216 | O | Cl | CF 3 | H | F | H | Q 2 |
| 217 | O | Cl | CF 3 | H | Cl | H | Q 2 |
| 218 | O | Cl | H | CF 3 | H | CF 3 | Q 2 |
| 219 | O | Cl | H | CF 3 | H | SO 2CH 3 | Q 2 |
| 220 | O | Cl | H | CF 3 | H | CN | Q 2 |
| 221 | O | Cl | H | CF 3 | H | NO 2 | Q 2 |
| 222 | O | Cl | H | CF 3 | H | SO 2CF 3 | Q 2 |
| 223 | O | Cl | H | CF 3 | H | OCF 3 | Q 2 |
| 224 | O | Cl | H | CF 3 | H | SCF 3 | Q 2 |
| 225 | O | Cl | H | CF 3 | H | F | Q 2 |
| 226 | O | NO 2 | H | CF 3 | H | NO 2 | Q 2 |
| 227 | O | CN | Cl | H | H | H | Q 2 |
| 228 | O | CN | SO 2CH 3 | H | H | H | Q 2 |
| 229 | O | CN | SO 2CF 3 | H | H | H | Q 2 |
| 230 | O | Cl | CN | H | H | H | Q 2 |
| 231 | O | H | CN | H | H | Cl | Q 2 |
| 232 | O | Cl | H | CN | H | H | Q 2 |
| 233 | O | NO 2 | H | SO 2CH 3 | H | H | Q 2 |
| 234 | O | NO 2 | H | SO 2CF 3 | H | H | Q 2 |
| 235 | O | Cl | H | SO 2CH 3 | H | H | Q 2 |
| 236 | O | Cl | H | SO 2CF 3 | H | H | Q 2 |
| 237 | O | H | SO 2CH 3 | H | H | Cl | Q 2 |
| 238 | O | H | SO 2CF 3 | H | H | Cl | Q 2 |
| 239 | O | H | H | i-C 3F 7 | H | H | Q 2 |
| 240 | O | Cl | H | i-C 3F 7 | H | H | Q 2 |
| 241 | O | F | H | i-C 3F 7 | H | H | Q 2 |
| 242 | O | CH 3 | H | i-C 3F 7 | H | H | Q 2 |
| 243 | O | CF 3 | H | i-C 3F 7 | H | H | Q 2 |
| 244 | O | CH 3O | H | i-C 3F 7 | H | H | Q 2 |
| 245 | CN | H | i-C 3F 7 | H | H | Q 2 | |
| 246 | O | NO 2 | H | i-C 3F 7 | H | H | Q 2 |
| 247 | O | Br | H | i-C 3F 7 | H | H | Q 2 |
| 248 | O | C 2H 5 | H | i-C 3F 7 | H | H | Q 2 |
| 249 | O | CF 3O | H | i-C 3F 7 | H | H | Q 2 |
| 250 | O | CH 3S | H | i-C 3F 7 | H | H | Q 2 |
| 251 | O | SO 2CH 3 | H | i-C 3F 7 | H | H | Q 2 |
| 252 | O | SCF 3 | H | i-C 3F 7 | H | H | Q 2 |
| 253 | O | Cl | H | i-C 3F 7 | H | Cl | Q 2 |
| 254 | O | Cl | H | i-C 3F 7 | H | F | Q 2 |
| 255 | O | Cl | H | i-C 3F 7 | H | CH 3 | Q 2 |
| 256 | O | Cl | H | i-C 3F 7 | H | CF 3 | Q 2 |
| 257 | O | Cl | H | i-C 3F 7 | H | CH 3O | Q 2 |
| 258 | O | Cl | H | i-C 3F 7 | H | CN | Q 2 |
| 259 | O | Cl | H | i-C 3F 7 | H | NO 2 | Q 2 |
| 260 | O | Cl | H | i-C 3F 7 | H | Br | Q 2 |
| 261 | O | CF 3 | SO 2CH 3 | H | H | H | Q 3 |
| 262 | O | CF 3 | CN | H | H | H | O 3 |
| 263 | O | CF 3 | NO 2 | H | H | H | Q 3 |
| 264 | O | CF 3 | SO 2CF 3 | H | H | H | O 3 |
| 265 | O | CF 3 | OCF 3 | H | H | H | Q 3 |
| 266 | O | CF 3 | SCF 3 | H | H | H | O 3 |
| 267 | O | CF 3 | F | H | H | H | Q 3 |
| 268 | O | CF 3 | Cl | H | H | H | O 3 |
| 269 | O | CF 3 | H | SO 2CH 3 | H | H | Q 3 |
| 270 | O | CF 3 | H | CN | H | H | O 3 |
| 271 | O | CF 3 | H | NO 2 | H | H | Q 3 |
| 272 | O | CF 3 | H | SO 2CF 3 | H | H | O 3 |
| 273 | O | CF 3 | H | OCF 3 | H | H | Q 3 |
| 274 | O | CF 3 | H | SCF 3 | H | H | O 3 |
| 275 | O | CF 3 | H | F | H | H | Q 3 |
| 276 | O | CF 3 | H | Cl | H | H | O 3 |
| 277 | O | CF 3 | H | H | SO 2CH 3 | H | Q 3 |
| 278 | O | CF 3 | H | H | CN | H | O 3 |
| 279 | O | CF 3 | H | H | NO 2 | H | Q 3 |
| 280 | O | CF 3 | H | H | SO 2CF 3 | H | O 3 |
| 281 | O | CF 3 | H | H | OCF 3 | H | Q 3 |
| 282 | O | CF 3 | H | H | SCF 3 | H | O 3 |
| 283 | O | CF 3 | H | H | F | H | Q 3 |
| 284 | O | CF 3 | H | H | Cl | H | O 3 |
| 285 | O | CF 3 | H | H | H | SO 2CH 3 | Q 3 |
| 286 | O | CF 3 | H | H | H | CN | O 3 |
| 287 | O | CF 3 | H | H | H | NO 2 | Q 3 |
| 288 | O | CF 3 | H | H | H | SO 2CF 3 | O 3 |
| 289 | O | CF 3 | H | H | H | OCF 3 | Q 3 |
| 290 | O | CF 3 | H | H | H | SCF 3 | O 3 |
| 291 | O | CF 3 | H | H | H | F | Q 3 |
| 292 | O | CF 3 | H | H | H | Cl | O 3 |
| 293 | O | SO 2CH 3 | CF 3 | H | H | H | Q 3 |
| 294 | O | CN | CF 3 | H | H | H | O 3 |
| 295 | O | NO 2 | CF 3 | H | H | H | Q 3 |
| 296 | O | SO 2CF 3 | CF 3 | H | H | H | O 3 |
| 297 | O | OCF 3 | CF 3 | H | H | H | Q 3 |
| 298 | O | SCF 3 | CF 3 | H | H | H | O 3 |
| 299 | O | F | CF 3 | H | H | H | Q 3 |
| 300 | O | Cl | CF 3 | H | H | H | O 3 |
| 301 | O | H | CF 3 | SO 2CH 3 | H | H | Q 3 |
| 302 | O | H | CF 3 | CN | H | H | O 3 |
| 303 | O | H | CF 3 | NO 2 | H | H | Q 3 |
| 304 | O | H | CF 3 | SO 2CF 3 | H | H | O 3 |
| 305 | O | H | CF 3 | OCF 3 | H | H | Q 3 |
| 306 | O | H | CF 3 | SCF 3 | H | H | O 3 |
| 307 | O | H | CF 3 | F | H | H | Q 3 |
| 308 | O | H | CF 3 | SO 2CH 3 | H | O 3 | |
| 309 | O | H | CF 3 | H | CN | H | Q 3 |
| 310 | O | H | CF 3 | H | NO 2 | H | O 3 |
| 311 | O | H | CF 3 | H | SO 2CF 3 | H | Q 3 |
| 312 | O | H | CF 3 | H | OCF 3 | H | O 3 |
| 313 | O | H | CF 3 | H | SCF 3 | H | Q 3 |
| 314 | O | H | CF 3 | H | F | H | O 3 |
| 315 | O | H | CF 3 | H | Cl | H | Q 3 |
| 316 | O | H | CF 3 | H | H | SO 2CH 3 | O 3 |
| 317 | O | H | CF 3 | H | H | CN | Q 3 |
| 318 | O | H | CF 3 | H | H | NO 2 | O 3 |
| 319 | O | H | CF 3 | H | H | SO 2CF 3 | Q 3 |
| 320 | O | H | CF 3 | H | H | OCF 3 | O 3 |
| 321 | O | H | CF 3 | H | H | SCF 3 | Q 3 |
| 322 | O | H | CF 3 | H | H | F | O 3 |
| 323 | O | H | CF 3 | H | H | Cl | Q 3 |
| 324 | O | SO 2CH 3 | H | CF 3 | H | H | O 3 |
| 325 | O | CN | H | CF 3 | H | H | Q 3 |
| 326 | O | NO 2 | H | CF 3 | H | H | O 3 |
| 327 | O | SO 2CF 3 | H | CF 3 | H | H | Q 3 |
| 328 | O | OCF 3 | H | CF 3 | H | H | O 3 |
| 329 | O | SCF 3 | H | CF 3 | H | H | Q 3 |
| 330 | O | F | H | CF 3 | H | H | O 3 |
| 331 | O | H | SO 2CH 3 | CF 3 | H | H | Q 3 |
| 332 | O | H | CN | CF 3 | H | H | O 3 |
| 333 | O | H | NO 2 | CF 3 | H | H | Q 3 |
| 334 | O | H | SO 2CF 3 | CF 3 | H | H | O 3 |
| 335 | O | H | OCF 3 | CF 3 | H | H | Q 3 |
| 336 | O | H | SCF 3 | CF 3 | H | H | O 3 |
| 337 | O | H | F | CF 3 | H | H | Q 3 |
| 338 | O | H | Cl | CF 3 | H | H | O 3 |
| 339 | O | Cl | CF 3 | H | CF 3 | H | Q 3 |
| 340 | O | Cl | CF 3 | H | SO 2CH 3 | H | O 3 |
| 341 | O | Cl | CF 3 | H | CN | H | Q 3 |
| 342 | O | Cl | CF 3 | H | NO 2 | H | O 3 |
| 343 | O | Cl | CF 3 | H | SO 2CF 3 | H | Q 3 |
| 344 | O | Cl | CF 3 | H | OCF 3 | H | O 3 |
| 345 | O | Cl | CF 3 | H | SCF 3 | H | Q 3 |
| 346 | O | Cl | CF 3 | H | F | H | O 3 |
| 347 | O | Cl | CF 3 | H | Cl | H | Q 3 |
| 348 | O | Cl | H | CF 3 | H | CF 3 | O 3 |
| 349 | O | Cl | H | CF 3 | H | SO 2CH 3 | Q 3 |
| 350 | O | Cl | H | CF 3 | H | CN | O 3 |
| 351 | O | Cl | H | CF 3 | H | NO 2 | Q 3 |
| 352 | O | Cl | H | CF 3 | H | SO 2CF 3 | O 3 |
| 353 | O | Cl | H | CF 3 | H | OCF 3 | Q 3 |
| 354 | O | Cl | H | CF 3 | H | SCF 3 | O 3 |
| 355 | O | Cl | H | CF 3 | H | F | Q 3 |
| 356 | O | NO 2 | H | CF 3 | H | NO 2 | O 3 |
| 357 | O | CN | Cl | H | H | H | Q 3 |
| 358 | O | CN | SO 2CH 3 | H | H | H | O 3 |
| 359 | O | CN | SO 2CF 3 | H | H | H | Q 3 |
| 360 | O | Cl | CN | H | H | H | O 3 |
| 361 | O | H | CN | H | H | Cl | Q 3 |
| 362 | O | Cl | H | CN | H | H | O 3 |
| 363 | O | NO 2 | H | SO 2CH 3 | H | H | Q 3 |
| 364 | O | NO 2 | H | SO 2CF 3 | H | H | O 3 |
| 365 | O | Cl | H | SO 2CH 3 | H | H | Q 3 |
| 366 | O | Cl | H | SO 2CF 3 | H | H | O 3 |
| 367 | O | H | SO 2CH 3 | H | H | Cl | Q 3 |
| 368 | O | H | SO 2CF 3 | H | H | Cl | O 3 |
| 369 | O | H | H | i-C 3F 7 | H | H | Q 3 |
| 370 | O | Cl | H | i-C 3F 7 | H | H | O 3 |
| 371 | O | F | H | i-C 3F 7 | H | H | Q 3 |
| 372 | O | CH 3 | H | i-C 3F 7 | H | H | O 3 |
| 373 | O | CF 3 | H | i-C 3F 7 | H | H | Q 3 |
| 374 | O | CH 3O | H | i-C 3F 7 | H | H | O 3 |
| 375 | O | CN | H | i-C 3F 7 | H | H | Q 3 |
| 376 | O | NO 2 | H | i-C 3F 7 | H | H | O 3 |
| 377 | O | B r | H | i-C 3F 7 | H | H | Q 3 |
| 378 | O | C 2H 5 | H | i-C 3F 7 | H | H | O 3 |
| 379 | O | CF 3O | H | i-C 3F 7 | H | H | Q 3 |
| 380 | O | CH 3S | H | i-C 3F 7 | H | H | O 3 |
| 381 | O | SO 2CH 3 | H | i-C 3F 7 | H | H | Q 3 |
| 382 | O | SCF 3 | H | i-C 3F 7 | H | H | O 3 |
| 383 | O | Cl | H | i-C 3F 7 | H | Cl | Q 3 |
| 384 | O | Cl | H | i-C 3F 7 | H | F | O 3 |
| 385 | O | Cl | H | i-C 3F 7 | H | CH 3 | Q 3 |
| 386 | O | Cl | H | i-C 3F 7 | H | CF 3 | O 3 |
| 387 | O | Cl | H | i-C 3F 7 | H | CH 3O | Q 3 |
| 388 | O | Cl | H | i-C 3F 7 | H | CN | O 3 |
| 389 | O | Cl | H | i-C 3F 7 | H | NO 2 | Q 3 |
| 390 | O | Cl | H | i-C 3F 7 | H | Br | O 3 |
| 391 | O | CF 3 | SO 2CH 3 | H | H | H | Q 4 |
| 392 | O | CF 3 | CN | H | H | H | O 4 |
| 393 | O | CF 3 | NO 2 | H | H | H | Q 4 |
| 394 | O | CF 3 | SO 2CF 3 | H | H | H | O 4 |
| 395 | O | CF 3 | OCF 3 | H | H | H | Q 4 |
| 396 | O | CF 3 | SCF 3 | H | H | H | O 4 |
| 397 | O | CF 3 | F | H | H | H | Q 4 |
| 398 | O | CF 3 | Cl | H | H | H | O 4 |
| 399 | O | CF 3 | H | SO 2CH 3 | H | H | Q 4 |
| 400 | O | CF 3 | H | CN | H | H | O 4 |
| 401 | O | CF 3 | H | NO 2 | H | H | Q 4 |
| 402 | O | CF 3 | H | SO 2CF 3 | H | H | O 4 |
| 403 | O | CF 3 | H | OCF 3 | H | H | Q 4 |
| 404 | O | CF 3 | H | SCF 3 | H | H | O 4 |
| 405 | O | CF 3 | H | F | H | H | Q 4 |
| 406 | O | CF 3 | H | Cl | H | H | O 4 |
| 407 | O | CF 3 | H | H | SO 2CH 3 | H | Q 4 |
| 408 | O | CF 3 | H | H | CN | H | O 4 |
| 409 | O | CF 3 | H | H | NO 2 | H | Q 4 |
| 410 | O | CF 3 | H | H | SO 2CF 3 | H | O 4 |
| 411 | O | CF 3 | H | H | OCF 3 | H | Q 4 |
| 412 | O | CF 3 | H | H | SCF 3 | H | O 4 |
| 413 | O | CF 3 | H | H | F | H | Q 4 |
| 414 | O | CF 3 | H | H | Cl | H | O 4 |
| 415 | O | CF 3 | H | H | H | SO 2CH 3 | Q 4 |
| 416 | O | CF 3 | H | H | H | CN | O 4 |
| 417 | O | CF 3 | H | H | H | NO 2 | Q 4 |
| 418 | O | CF 3 | H | H | H | SO 2CF 3 | O 4 |
| 419 | O | CF 3 | H | H | H | OCF 3 | Q 4 |
| 420 | O | CF 3 | H | H | H | SCF 3 | O 4 |
| 421 | O | CF 3 | H | H | H | F | Q 4 |
| 422 | O | CF 3 | H | H | H | Cl | O 4 |
| 423 | O | SO 2CH 3 | CF 3 | H | H | H | Q 4 |
| 424 | O | CN | CF 3 | H | H | H | O 4 |
| 425 | O | NO 2 | CF 3 | H | H | H | Q 4 |
| 426 | O | SO 2CF 3 | CF 3 | H | H | H | O 4 |
| 427 | O | OCF 3 | CF 3 | H | H | H | Q 4 |
| 428 | O | SCF 3 | CF 3 | H | H | H | O 4 |
| 429 | O | F | CF 3 | H | H | H | Q 4 |
| 430 | O | Cl | CF 3 | H | H | H | O 4 |
| 431 | O | H | CF 3 | SO 2CH 3 | H | H | Q 4 |
| 432 | O | H | CF 3 | CN | H | H | O 4 |
| 433 | O | H | CF 3 | NO 2 | H | H | Q 4 |
| 434 | O | H | CF 3 | SO 2CF 3 | H | H | O 4 |
| 435 | O | H | CF 3 | OCF 3 | H | H | Q 4 |
| 436 | O | H | CF 3 | SCF 3 | H | H | O 4 |
| 437 | O | H | CF 3 | F | H | H | Q 4 |
| 438 | O | H | CF 3 | SO 2CH 3 | H | O 4 | |
| 439 | O | H | CF 3 | H | CN | H | Q 4 |
| 440 | O | H | CF 3 | H | NO 2 | H | O 4 |
| 441 | O | H | CF 3 | H | SO 2CF 3 | H | Q 4 |
| 442 | O | H | CF 3 | H | OCF 3 | H | O 4 |
| 443 | O | H | CF 3 | H | SCF 3 | H | Q 4 |
| 444 | O | H | CF 3 | H | F | H | O 4 |
| 445 | O | H | CF 3 | H | Cl | H | Q 4 |
| 446 | O | H | CF 3 | H | H | SO 2CH 3 | O 4 |
| 447 | O | H | CF 3 | H | H | CN | Q 4 |
| 448 | O | H | CF 3 | H | H | NO 2 | O 4 |
| 449 | O | H | CF 3 | H | H | SO 2CF 3 | Q 4 |
| 450 | O | H | CF 3 | H | H | OCF 3 | O 4 |
| 451 | O | H | CF 3 | H | H | SCF 3 | Q 4 |
| 452 | O | H | CF 3 | H | H | F | O 4 |
| 453 | O | H | CF 3 | H | H | Cl | Q 4 |
| 454 | O | SO 2CH 3 | H | CF 3 | H | H | O 4 |
| 455 | O | CN | H | CF 3 | H | H | Q 4 |
| 456 | O | NO 2 | H | CF 3 | H | H | O 4 |
| 457 | O | SO 2CF 3 | H | CF 3 | H | H | Q 4 |
| 458 | O | OCF 3 | H | CF 3 | H | H | O 4 |
| 459 | O | SCF 3 | H | CF 3 | H | H | Q 4 |
| 460 | O | F | H | CF 3 | H | H | O 4 |
| 461 | O | H | SO 2CH 3 | CF 3 | H | H | Q 4 |
| 462 | O | H | CN | CF 3 | H | H | O 4 |
| 463 | O | H | NO 2 | CF 3 | H | H | Q 4 |
| 464 | O | H | SO 2CF 3 | CF 3 | H | H | O 4 | |
| 465 | O | H | OCF 3 | CF 3 | H | H | Q 4 | |
| 466 | O | H | SCF 3 | CF 3 | H | H | O 4 | |
| 467 | O | H | F | CF 3 | H | H | Q 4 | |
| 468 | O | Cl | CF 3 | H | H | O 4 | ||
| 469 | O | Cl | CF 3 | H | CF 3 | H | Q 4 | |
| 470 | O | Cl | CF 3 | H | SO 2CH 3 | H | O 4 | |
| 471 | O | Cl | CF 3 | H | CN | H | Q 4 | |
| 472 | O | Cl | CF 3 | H | NO 2 | H | O 4 | |
| 473 | O | Cl | CF 3 | H | SO 2CF 3 | H | Q 4 | |
| 474 | O | Cl | CF 3 | H | OCF 3 | H | O 4 | |
| 475 | O | Cl | CF 3 | H | SCF 3 | H | Q 4 | |
| 476 | O | Cl | CF 3 | H | F | H | O 4 | |
| 477 | O | Cl | CF 3 | H | Cl | H | Q 4 | |
| 478 | O | Cl | H | CF 3 | H | CF 3 | O 4 | |
| 479 | O | Cl | H | CF 3 | H | SO 2CH 3 | Q 4 | |
| 480 | O | Cl | H | CF 3 | H | CN | O 4 | |
| 481 | O | Cl | H | CF 3 | H | NO 2 | Q 4 | |
| 482 | O | Cl | H | CF 3 | H | SO 2CF 3 | O 4 | |
| 483 | O | Cl | H | CF 3 | H | OCF 3 | Q 4 | |
| 484 | O | Cl | H | CF 3 | H | SCF 3 | O 4 | |
| 485 | O | Cl | H | CF 3 | H | F | Q 4 | |
| 486 | O | NO 2 | H | CF 3 | H | NO 2 | O 4 | |
| 487 | O | CN | Cl | H | H | H | Q 4 | |
| 488 | O | CN | SO 2CH 3 | H | H | H | O 4 | |
| 489 | O | CN | SO 2CF 3 | H | H | H | Q 4 | |
| 490 | O | Cl | CN | H | H | H | O 4 | |
| 491 | O | H | CN | H | H | Cl | Q 4 | |
| 492 | O | Cl | H | CN | H | H | O 4 | |
| 493 | O | NO 2 | H | SO 2CH 3 | H | H | Q 4 | |
| 494 | O | NO 2 | H | SO 2CF 3 | H | H | O 4 | |
| 495 | O | Cl | H | SO 2CH 3 | H | H | Q 4 | |
| 496 | O | Cl | H | SO 2CF 3 | H | H | O 4 | |
| 497 | O | H | SO 2CH 3 | H | H | Cl | Q 4 | |
| 498 | O | H | SO 2CF 3 | H | H | Cl | O 4 | |
| 499 | O | H | H | i-C 3F 7 | H | H | Q 4 | |
| 500 | O | Cl | H | i-C 3F 7 | H | H | O 4 | |
| 501 | O | F | H | i-C 3F 7 | H | H | Q 4 | |
| 502 | O | CH 3 | H | i-C 3F 7 | H | H | O 4 | |
| 503 | O | CF 3 | H | i-C 3F 7 | H | H | Q 4 | |
| 504 | O | CH 3O | H | i-C 3F 7 | H | H | O 4 | |
| 505 | O | CN | H | i-C 3F 7 | H | H | Q 4 | |
| 506 | O | NO 2 | H | i-C 3F 7 | H | H | O 4 | |
| 507 | O | Br | H | i-C 3F 7 | H | H | Q 4 |
| 508 | O | C 2H 5 | H | i-C 3F 7 | H | H | O 4 |
| 509 | O | CF 3O | H | i-C 3F 7 | H | H | Q 4 |
| 510 | O | CH 3S | H | i-C 3F 7 | H | H | O 4 |
| 511 | O | SO 2CH 3 | H | i-C 3F 7 | H | H | Q 4 |
| 512 | O | SCF 3 | H | i-C 3F 7 | H | H | O 4 |
| 513 | O | Cl | H | i-C 3F 7 | H | Cl | Q 4 |
| 514 | O | Cl | H | i-C 3F 7 | H | F | O 4 |
| 515 | O | Cl | H | i-C 3F 7 | H | CH 3 | Q 4 |
| 516 | O | Cl | H | i-C 3F 7 | H | CF 3 | O 4 |
| 517 | O | Cl | H | i-C 3F 7 | H | CH 3O | Q 4 |
| 518 | O | Cl | H | i-C 3F 7 | H | CN | O 4 |
| 519 | O | Cl | H | i-C 3F 7 | H | NO 2 | Q 4 |
| 520 | O | Cl | H | i-C 3F 7 | H | Br | O 4 |
| 521 | O | H | CF 3 | Cl | H | H | Q 1 |
| 522 | O | H | CF 3 | Cl | H | H | O 2 |
| 523 | O | H | CF 3 | Cl | H | H | O 3 |
| 524 | O | H | CF 3 | Cl | H | H | O 4 |
Table 2
| Numbering | X | X 1 | X2 | X 3 | R 6 | R 7 | Q |
| 525 | O | N | C-H | C-H | CF 3 | CN | Q 1 |
| 526 | O | N | C-CF 3 | C-H | CF 3 | H | Q 1 |
| 527 | O | N | C-H | C-CF 3 | H | CF 3 | Q 1 |
| 528 | O | N | C-OCH 2CF 3 | C-CF 3 | H | H | Q 1 |
| 529 | O | N | C-H | C-CF 3 | CF 3 | H | Q 1 |
| 530 | O | N | C-OCH 2CF 3 | C-CF 3 | H | CF 3 | Q 1 |
| 531 | O | N | C-CN | C-H | CF 3 | H | Q 1 |
| 532 | O | N | C-Cl | C-H | CF 3 | CN | Q 1 |
| 533 | O | N | C-CF 3 | C-H | CF 3 | Cl | Q 1 |
| 534 | O | N | C-Cl | C-H | Cl | Cl | Q 1 |
| 535 | O | C-H | N | C-H | H | CF 3 | Q 1 |
| 536 | O | N | C-Cl | C-H | Cl | Cl | Q 2 |
| 537 | O | N | C-H | C-H | CF 3 | CN | Q 2 |
| 538 | O | N | C-CF 3 | C-H | CF 3 | H | Q 2 |
| 539 | O | N | C-H | C-CF 3 | H | CF 3 | Q 2 |
| 540 | O | N | C-OCH 2CF 3 | C-CF 3 | H | H | Q 2 |
| 541 | O | N | C-H | C-CF 3 | CF 3 | H | Q 2 |
| 542 | O | N | C-OCH 2CF 3 | C-CF 3 | H | CF 3 | Q 2 |
| 543 | O | N | C-CN | C-H | CF 3 | H | Q 2 |
| 544 | O | N | C-Cl | C-H | CF 3 | CN | Q 2 |
| 545 | O | N | C-CF 3 | C-H | CF 3 | Cl | Q 2 |
| 546 | O | C-H | N | C-H | H | CF 3 | Q 2 |
| 547 | O | N | C-H | C-H | CF 3 | CN | Q 3 |
| 548 | O | N | C-CF 3 | C-H | CF 3 | H | Q 3 |
| 549 | O | N | C-H | C-CF 3 | H | CF 3 | Q 3 |
| 550 | O | N | C-OCH 2CF 3 | C-CF 3 | H | H | Q 3 |
| 551 | O | N | C-H | C-CF 3 | CF 3 | H | Q 3 |
| 552 | O | N | C-OCH 2CF 3 | C-CF 3 | H | CF 3 | Q 3 |
| 553 | O | N | C-CN | C-H | CF 3 | H | Q 3 |
| 554 | O | N | C-Cl | C-H | CF 3 | CN | Q 3 |
| 555 | O | N | C-CF 3 | C-H | CF 3 | Cl | Q 3 |
| 556 | O | C-H | N | C-H | H | CF 3 | Q 3 |
| 557 | O | N | C-H | C-H | CF 3 | CN | Q 4 |
| 558 | O | N | C-CF 3 | C-H | CF 3 | H | Q 4 |
| 559 | O | N | C-H | C-CF 3 | H | CF 3 | Q 4 |
| 560 | O | N | C-OCH 2CF 3 | C-CF 3 | H | H | Q 4 |
| 561 | O | N | C-H | C-CF 3 | CF 3 | H | Q 4 |
| 562 | O | N | C-OCH 2CF 3 | C-CF 3 | H | CF 3 | Q 4 |
| 563 | O | N | C-CN | C-H | CF 3 | H | Q 4 |
| 564 | O | N | C-Cl | C-H | CF 3 | CN | Q 4 |
| 565 | O | N | C-CF 3 | C-H | CF 3 | Cl | Q 4 |
| 566 | O | C-H | N | C-H | H | CF 3 | Q 4 |
| 567 | O | N | C-Cl | C-Cl | Cl | Cl | Q 1 |
| 568 | O | N | C-Cl | C-Cl | Cl | Cl | Q 2 |
| 569 | S | N | C-Cl | C-Cl | Cl | Cl | Q 1 |
| 570 | S | N | C-Cl | C-Cl | Cl | Cl | Q 2 |
| 571 | S | N | C-Cl | C-H | Cl | Cl | Q 1 |
| 572 | S | N | C-Cl | C-H | Cl | Cl | Q 2 |
Technical scheme of the present invention also comprises the preparation method of general formula (I) compound:
Q is selected from Q in general formula (I) compound
1, Q
2, Q
4Or Q
5The time, react under alkaline condition, in organic solvent by the benzyl halogen shown in compound shown in the general formula (II) and the general formula (III) and to make.Reaction formula is as follows:
In the formula: A is a leavings group, is selected from halogen (chlorine, bromine or iodine); The definition of other each groups is the same.
React the optional tetrahydrofuran (THF) freely of used appropriate solvent, acetonitrile, toluene, dimethylbenzene, benzene, N, N dimethyl formamide, methyl-sulphoxide, acetone or butanone etc.
The optional potassium hydroxide freely of suitable alkali, sodium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, triethylamine, pyridine, sodium hydride, sodium methylate, sodium ethylate, 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.
When Q was selected from Q3 in general formula (I) compound, reaction formula was as follows:
The definition of each group is the same in the general formula.
The suitable solvent can be selected from tetrahydrofuran (THF), toluene, dimethylbenzene, benzene or 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.
Compound shown in the general formula (II) partly has commercially available, also can be according to the similar approach preparation of introducing among the patent USP4548640.
Compound shown in the general formula (III) can be made by currently known methods, referring to USP4723034, USP5554578.
General formula of the present invention (I) compound has broad spectrum of activity---and this compounds all has good preventive effect to diseases such as downy mildew of garpe, rice sheath blight disease, rice blast, tomato late blight, wheat powdery mildew, powdery mildew of cucumber, cucumber downy mildew, gray molds of cucumber.Compound of the present invention has excellent insecticidal activity simultaneously, and is effective to various pests such as mythimna separata, small cabbage moth etc., is very suitable for the integrated control to various pest on crop.
The present invention also provides a kind of sterilization, insect-killing composition, contain upward acceptable carrier of general formula (I) compound 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 that preferable is 5%-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 5% to 85% active substance 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.Sterilization of the present invention, the selected tensio-active agent of insect-killing composition are known in those skilled in the art, comprise 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 have the more activity of wide spectrum than independent general formula (I) compound.In addition, but the fungicidal activity of other sterilant mutual-through type (I) compounds has synergism.Also general formula (I) compound and other sterilants can be used with, or use with another kind of sterilant and other sterilants simultaneously.
Embodiment
Below concrete example be used for further specifying the present invention, but do not limit the present invention, the present invention is limited to these examples absolutely not.
Synthetic embodiment
Example 1: the preparation of compound 40
Under the room temperature, to contain 0.8 gram Anhydrous potassium carbonate, 0.39 digests compound (II-1), 0.4 and digests compound (III-1) in 20 milliliters of N, the reflux stirring reaction is 5 hours in the mixed solution of dinethylformamide, reaction mixture is poured in the frozen water into ethyl acetate extraction 3 times, combining extraction liquid, saturated common salt washing 3 times, drying is filtered, concentrating under reduced pressure, getting faint yellow solid is thick product.Mixed solution (1: 8) column chromatography with ethyl acetate and sherwood oil obtains title compound 0.51 gram, fusing point 84-86 ℃.Yield 70.5%.
Nuclear magnetic data (
1HNMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows:
δppm 3.71(3H，s)，3.84(3H，s)，5.10(2H，s)，7.01(1H，m)，7.20(1H，m)，7.25(1H，m)，7.35(2H，m)，7.56(1H，m)，7.62(1H，s)。
Example 2: the preparation of compound 193
Under the room temperature, to contain 0.8 gram Anhydrous potassium carbonate, 0.39 digests compound (II-2), 0.42 and digests compound (III-2) in 20 milliliters of N, the mixed solution reflux stirring reaction of dinethylformamide 5 hours is poured reaction mixture in the frozen water into, ethyl acetate extraction 3 times, combining extraction liquid, saturated common salt washing 3 times, drying is filtered, concentrating under reduced pressure, getting faint yellow solid is thick product.Mixed solution (1: 8) column chromatography with ethyl acetate and sherwood oil obtains title compound 0.53 gram, fusing point 92-94 ℃.Yield 73.2%.
Nuclear magnetic data (
1HNMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows:
δppm?3.86(3H，s)，4.04(3H，s)，5.06(2H，s)，7.06(1H，d)，7.15(1H，m)，7.23(1H，m)，7.44(3H，m)，7.58(1H，m)。
Example 3: the preparation of compound 323
With 0.60 aqueous methylamine solution stirred overnight at room temperature in 50 milliliters of tetrahydrofuran (THF)s of digesting compound 193 and twice as high molar ratio, concentrate back ethyl acetate extraction 2 times, the extract that merges washes with water 3 times, again with saturated common salt washing 2 times, drying is filtered, and concentrates, get title compound 0.53 gram, fusing point 132-134 ℃.Yield 88.5%.
Nuclear magnetic data (
1HNMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows:
δppm?2.92(3H，s)，3.92(3H，s)，5.12(2H，s)，6.95(1H，d)，7.24(1H，m)，7.42(3H，m)，7.54(1H，d)，7.62(1H，s).
Other compounds of the present invention can be synthetic with reference to aforesaid method.
The nuclear magnetic data of the compound of Formula I shown in part table 1 and the table 2 (
1HNMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows:
Compound 63: fusing point 72-78 ℃.Compound 521: oily matter.δppm?3.71(3H，s)，3.84(3H，s)，5.10(1H，s)，7.02(1H，m)，7.12(1H，m)，7.20(1H，m)，7.35(2H，m)，7.47(1H，m)，7.56(1H，m)，7.64(1H，s).
Compound 170: fusing point 100-102 ℃.δppm?3.86(3H，s)，4.04(3H，s)，5.06(2H，s)，7.04(1H，m)，7.21(2H，m)，7.29(1H，m)，7.43(2H，m)，7.60(1H，m).
Compound 521: oily matter.δppm?3.71(3H，s)，3.83(3H，s)，4.98(1H，s)，6.97(1H，m)，7.19(2H，m)，7.34(3H，m)，7.46(1H，m)，7.60(1H，s).
Compound 522: oily matter.δppm?3.88(3H，s)，4.00(3H，s)，4.96(2H，s)，6.95(1H，m)，7.23(2H，m)，7.47(4H，m).
Compound 523: oily matter.δppm?2.90(3H，d)，3.94(3H，s)，4.97(2H，s)，6.80(1H，d)，6.96(1H，m)，7.20(2H，m)，7.34(1H，m)，7.40(2H，m)，7.46(1H，m).
Compound 534: fusing point 112-114 ℃.δppm?3.69(3H，s)，3.83(3H，s)，5.32(2H，s)，7.17(1H，m)，7.34(2H，m)，7.58(2H，m)，7.69(1H，s).
Compound 536: fusing point 108-111 ℃.δppm?3.85(3H，s)，4.04(3H，s)，5.30(2H，s)，7.20(1H，m)，7.42(2H，m)，7.59(1H，m)，7.69(1H，s).
Example of formulations (each component add-on is weight percentage).
Embodiment 4:30% compound 40 wettable powders
Compound 40 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 40, various tensio-active agent and solid diluents, after ultrafine crusher is pulverized, promptly obtain 30% wettable powder product.
Embodiment 5:20% compound 63 suspension agents
Compound 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 63, dispersion agent, suspending agent and antifreezing agent etc. are added in the sand mill, grinds, and makes suspension agent.
Embodiment 6:60% compound 323 water-dispersible granules
Compound 323 60%
Naphthalenesulfonic acid-formaldehyde condensate 12%
N-methyl-oleoyl-Sodium taurine salt 8%
Polyvinylpyrrolidone 2%
Carboxymethyl cellulose 2%
Kaolin complements to 100%
Compound 323 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 7:10% compound 521 aqueous emulsions
Compound 521 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 521, 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 8:25% compound suspension agent
Compound 534 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 534, dispersion agent, suspending agent and antifreezing agent etc. are added in the sand mill, grinds, and makes suspension agent.
Embodiment 9:50% compound 536 wettable powders
Compound 536 20%
Industry methyl naphthalene sulfonic acid sodium 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 536, various tensio-active agent and solid diluents, after ultrafine crusher is pulverized, promptly obtain 20% wettable powder product.
Biological activity determination
Example 10 fungicidal activities are measured
With The compounds of this invention the multiple fungal disease of plant has been carried out the fungicidal activity test.The method of test is as follows:
Adopt the potted plant measuring method of live body.The former medicinal acetone solution of testing compound (acetone consumption be liquid to be measured 10%) 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 it susceptible, wait to contrast abundant morbidity back (being generally week age) and carry out assessment surveys.
Partial test result following (all dosage are all in effective constituent):
Preventive effect to wheat powdery mildew: during 25ppm, compound 534,536 is 100%; 6.25ppm the time, compound 323,523 is 100%, compound 521,522 reaches more than 90%.
Preventive effect to cucumber downy mildew: during 400ppm, compound 170,193 is 100%; During 25ppm, compound 523,534,536 is 100%; 12.5ppm the time, compound 323 is 100%.
Preventive effect to gray mold of cucumber: during 25ppm, compound 193 is 80%.
Preventive effect to rice blast: during 25ppm, compound 534,536 is 100%; 8.3ppm the time, compound 170,193,522,523 is 100%; 0.9ppm the time, compound 323 is 100%.
Preventive effect to the late blight of potato: during 25ppm, compound 323,534 is 100%, 523 to be 98%; 12.5ppm the time, compound 323 still reaches 98%.
Preventive effect to rice sheath blight disease: during 25ppm, compound 534,536 is 100%.
Example 11 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 pippenspallens) 2 instar larvaes, black peach aphid (Myzus persicae), carmine spider mite (Tetranychus cinnabarinus) is target, 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.
Investigation and result's statistics (all dosage are all in effective constituent):
When liquor strength was 600ppm, compound 523 grades reached 80% to the mythimna separata mortality ratio.
When liquor strength was 600ppm, compound 534 grades reached 80% to the small cabbage moth mortality ratio.
Claims (5)
1. substituted aryl ethers compounds, shown in general formula (I):
In the formula: Ar represents Ar-1 or Ar-2:
Q is selected from Q as follows
1, Q
2Or Q
3:
X is selected from O;
R
2Be selected from CF
3R
1, R
3, R
5Be selected from hydrogen, chlorine, bromine, fluorine or cyano group respectively; R
4Be selected from hydrogen or chlorine;
X
1Be selected from N;
X
2, X
3Be selected from C-R respectively; Wherein R is selected from hydrogen or chlorine;
R
6, R
7Be selected from chlorine respectively.
2. compound according to claim 1 is characterized in that: in the general formula (I)
Q is selected from Q
1, Q
2Or Q
3
X is selected from O;
R
2Be selected from CF
3R
1, R
3, R
5Be selected from hydrogen or chlorine; R
4Be selected from hydrogen;
X
1Be selected from N;
X
2Be selected from C-Cl; X
3Be selected from C-H;
R
6, R
7Be selected from chlorine respectively.
3. the described general formula of claim 1 (I) compound is in the application of control pest on crop.
4. the application of the described general formula of claim 1 (I) compound germ on the control crop.
5. a sterilization, insect-killing composition is characterized in that: contain the described general formula of claim 1 (I) compound and agricultural goes up acceptable carrier, the weight percentage of active ingredient is 0.5-90% in the composition.
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| WO2010089267A2 (en) | 2009-02-05 | 2010-08-12 | Basf Se | Method for producing 2-halogenomethylphenyl acetic acid derivatives |
| JP2013502412A (en) * | 2010-04-21 | 2013-01-24 | オスコテク インコーポレイテッド | α-Arylmethoxyacrylate derivative, process for preparing the same and pharmaceutical composition containing the same |
| CN104430343B (en) * | 2013-09-24 | 2017-02-15 | 沈阳中化农药化工研发有限公司 | Application of substituted ether and thioether compound as plant virus resisting agent |
| CN104803929B (en) * | 2014-01-28 | 2017-11-14 | 沈阳中化农药化工研发有限公司 | A kind of substituted oximinoether kind compound and application thereof |
| CN109053463B (en) * | 2018-08-03 | 2021-04-20 | 兰州大学 | Method for converting diaryl ether into N-cyclohexyl aniline compound |
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| JP2897789B2 (en) * | 1990-11-16 | 1999-05-31 | 塩野義製薬株式会社 | Alkoxyiminoacetic acid amide compounds and their use as agricultural fungicides |
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| CN1031227A (en) * | 1987-07-11 | 1989-02-22 | 先灵农业化学品公司 | Acrylate fungicides |
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