CN101119972B - Aromatic ether compounds, and preparation and usage thereof - Google Patents

Aromatic ether compounds, and preparation and usage thereof Download PDF

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CN101119972B
CN101119972B CN200680005095XA CN200680005095A CN101119972B CN 101119972 B CN101119972 B CN 101119972B CN 200680005095X A CN200680005095X A CN 200680005095XA CN 200680005095 A CN200680005095 A CN 200680005095A CN 101119972 B CN101119972 B CN 101119972B
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nch
compound
alkoxy
hydrogen
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CN101119972A (en
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刘长令
李淼
李志念
耿丽文
张弘
周德锋
崔东亮
罗艳梅
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Shenyang Sinochem Agrochemicals R&D Co Ltd
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ZHONGHUA CO Ltd CHINA
Shenyang Research Institute of Chemical Industry Co Ltd
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Abstract

The present invention discloses an aryl ether composition and the preparation and application thereof. The structure is showed as the general formula I, and the definition of each substituent is in the instruction book. The aryl ether composition of the invention has a broad-spectrum activity, can be used to prevent and control the disease which is caused by a plurality of germs of oomycetes, basidiomycetes, sac fungus and fungi imperfecti, etc. in a plurality of crops. Part composition of the invention also has a certain pesticide and miticide activity, and can be used to prevent and cure the destructive insect and acarid on a plurality of crops.

Description

A kind of aryl ethers compounds and preparation thereof and application
Technical field
The invention belongs to disinfectant use in agriculture and field of pesticides.Relate to a kind of aryl ethers compounds and preparation thereof and application specifically.
Background technology
Natural product methoxy acrylate compound is the compound of known biologically active.Disclose wide-spectrum bactericide Strobilurin (pyraclostrobin) among patent US5869517, US6054592, CN1154692, the CN1308065 etc., its chemical structure is as follows:
Strobilurin (pyraclostrobin)
Following compound with fungicidal activity is disclosed among the patent DE19548786:
Figure G68545537150141000D000012
The compound with fungicidal activity shown in the following general formula is disclosed among the patent WO9933812:
" agricultural chemicals journal " (Nongyaoxue Xuebao, 2004,6 (1), 17-21) the compound shown in the following general formula of report with fungicidal activity:
Figure G68545537150141000D000014
Before the present invention, we had once submitted the application of Chinese patent (CN1657524A) and PCT patent (WO2005080344A), related to the substituted azole derivative shown in the following general formula as desinsection, sterilant:
Figure G68545537150141000D000021
In the formula: X 1Be selected from CH or N; X 2Be selected from O, S or NR 7R 7Be selected from hydrogen or (C 1-C 12) alkyl; X 3Be selected from O, S or NR 8R 8Be selected from hydrogen, C 1-C 12Alkyl, halo C 1-C 12Alkyl, C 1-C 12Alkoxy carbonyl, C 1-C 12Alkoxy carbonyl C i-C 12Alkyl; R 1, R 2Be selected from hydrogen, C respectively 1-C 12Alkyl or halo C 1-C 12Alkyl; A 1Be selected from N and CR 9A 2Be selected from N and CR 10A 3Be selected from N and CR 11Work as A 1When being selected from N, A 2Be selected from CR 10, A 3Be selected from CR 11Work as A 2When being selected from N, A 1Be selected from CR 9, A 3Be selected from CR 11Work as A 3When being selected from N, A 1Be selected from CR 9, A 2Be selected from CR 10R 3Be selected from hydrogen, halogen atom, C 1-C 12Alkyl, halo C 1-C 12Alkyl or C 1-C 12Alkoxyl group; R 4, R 5, R 6, R 9, R 10, R 11Can be identical or different, be selected from hydrogen, halogen atom, nitro, cyano group, CONH respectively 2, 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, 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, heteroaryl C 1-C 12Alkoxyl group.
Above patent (application) though in all disclosed compounds and The compounds of this invention structural similitude, exist significant different.
Summary of the invention
The object of the present invention is to provide a kind of aryl ethers compounds that just can control various disease and pests under very low dose of, it can be applicable to agricultural and goes up disease and insect pest with the control crop.
Technical scheme of the present invention is as follows:
The invention provides a kind of aryl ethers compounds, shown in general formula I:
Figure G68545537150141000D000022
In the formula:
X 1Be selected from O, S or NR 2
X 2Be selected from CH 2Or
Figure G68545537150141000D000023
Work as X 2Be selected from
Figure G68545537150141000D000031
The time, the 4-position of pyrimidine links to each other with oxygen, and 6-position oxygen links to each other with phenyl ring;
R 1Be selected from hydrogen, halogen atom, nitro, cyano group, CONH 2, 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, C 1-C 12Alkoxy carbonyl C 1-C 12Alkyl, C 1-C 12Halogenated alkoxy C 1-C 12Alkyl, replacement or unsubstituted amido C 1-C 12Alkyl;
R 2Be 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;
Q is selected from one of group as follows:
Figure G68545537150141000D000032
When Q is selected from Q 1, Q 2, Q 3Or Q 5, X 2=CH 2The time, Ar is selected from and replaces or unsubstituted quinary heteroaryl; Work as Q=Q 1,
Figure G68545537150141000D000033
Or work as Q=Q 4, X 2=CH 2The time, Ar is selected from and replaces or unsubstituted aryl, heteroaryl; Substituting group is selected from halogen atom, CN, nitro, C 1-C 6Alkyl, C 1-C 6Alkoxyl group, C 1-C 6Alkylthio, C 1-C 6Alkane alkylsulfonyl, C 1-C 6Alkoxy carbonyl, C 1-C 6The aryl of halogenated alkoxy, replacement or the aryloxy of replacement;
And steric isomer.
Comparatively preferred compound is among the present invention: in the general formula I
X 1Be selected from O, S or NR 2
X 2Be selected from CH 2Or
Figure G68545537150141000D000034
R 1Be selected from hydrogen, halogen atom, nitro, cyano group, CONH 2, CH 2CONH 2, CH 2CN, 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 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 6Halogenated alkoxy C 1-C 6Alkyl, replacement or unsubstituted amido C 1-C 6Alkyl;
R 2Be selected from hydrogen, C 1-C 6Alkyl, halo C 1-C 6Alkyl, C 1-C 6Alkoxy carbonyl or C 1-C 6Alkoxy carbonyl C 1-C 6Alkyl;
When Q is selected from Q 1, Q 2, Q 3Or Q 5, X 2=CH 2The time, Ar is selected from and replaces or unsubstituted quinary heteroaryl; Work as Q=Q 1,
Figure G68545537150141000D000035
Or work as Q=Q 4, X 2=CH 2The time, Ar is selected from and replaces or unsubstituted aryl, heteroaryl; Substituting group is selected from halogen atom, CN, nitro, C 1-C 6Alkyl, C 1-C 6Alkoxyl group, C 1-C 6Alkylthio, C 1-C 6Alkane alkylsulfonyl, C 1-C 6Alkoxy carbonyl, C 1-C 6The phenyl of halogenated alkoxy, replacement or the phenoxy group of replacement.
Further preferred compound is: in the general formula I
X 1Be selected from O or NR 2
X 2Be selected from CH 2Or
Figure G68545537150141000D000041
R 1Be selected from hydrogen, halogen atom, nitro, cyano group, CONH 2, CH 2CONH 2, CH 2CN, 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 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 6Halogenated alkoxy C 1-C 6Alkyl, replacement or unsubstituted amido C 1-C 3Alkyl;
R 2Be selected from hydrogen, C 1-C 6Alkyl, halo C 1-C 6Alkyl, C 1-C 3Alkoxy carbonyl or C 1-C 6Alkoxy carbonyl C 1-C 3Alkyl;
When Q is selected from Q 1, Q 2, Q 3Or Q 5, X 2=CH 2The time, Ar is selected from and replaces or unsubstituted furans, thiophene or thiazole; Work as Q=Q 1,
Figure G68545537150141000D000042
Or work as Q=Q 4, X 2=CH 2The time, Ar is selected from and replaces or unsubstituted phenyl, pyridyl, furans, thiophene or thiazole; Substituting group is selected from halogen atom, CN, nitro, C 1-C 6Alkyl, C 1-C 6Alkoxyl group, C 1-C 6Alkylthio, C 1-C 6Alkane alkylsulfonyl, C 1-C 6The phenyl of halogenated alkoxy, replacement or the phenoxy group of replacement.
Further preferred compound is: in the general formula I
X 1Be selected from O or NR 2
X 2Be selected from CH 2Or
R 1Be selected from hydrogen, chlorine, bromine, fluorine, nitro, cyano group, CH 2CN or C 1-C 6Alkyl;
R 2Be selected from hydrogen, C 1-C 3Alkyl, halo C 1-C 3Alkyl, C 1-C 3Alkoxy carbonyl or C 1-C 3Alkoxy carbonyl C 1-C 3Alkyl;
Work as Q=Q 1, Q 2, Q 3Or Q 5, X 2=CH 2The time, Ar is selected from and replaces or unsubstituted furans, thiophene or thiazole; Work as Q=Q 1,
Figure G68545537150141000D000044
Or work as Q=Q 4, X 2=CH 2The time, Ar is selected from and replaces or unsubstituted phenyl, pyridyl, furans, thiophene or thiazole; Substituting group is selected from halogen atom, CN, nitro, C 1-C 6Alkyl, C 1-C 6Alkoxyl group, C 1-C 6Alkylthio, C 1-C 6Halogenated alkoxy, chlorophenyl or chloro phenoxy group.
Further preferred again compound is: in the general formula I
X 1Be selected from O or NR 2
X 2Be selected from CH 2Or
Figure G68545537150141000D000045
R 1Be selected from hydrogen or methyl;
R 2Be selected from hydrogen, methyl or sec.-propyl;
Work as Q=Q 1, Q 2, Q 3Or Q 5, X 2=CH 2The time, Ar is selected from and replaces or not substituted furan or thiophene; Work as Q=Q 1,
Figure G68545537150141000D000051
Or work as Q=Q 4, X 2=CH 2The time, Ar is selected from and replaces or unsubstituted phenyl, pyridyl, furans or thiophene; Substituting group is selected from halogen atom, C 1-C 3Alkyl, C 1-C 3Alkoxyl group, C 1-C 3Alkylthio or C 1-C 3Halogenated alkoxy.
In the definition of the compound of Formula I that provides above, compile the following substituting group of used term general proxy:
Not replacing all substituting groups of expression all is hydrogen.
Substituting group is C in the amido that replaces 1-C 3Alkyl, C 1-C 3Alkoxyl group, halo C 1-C 3Alkyl, halo C 1-C 3Alkoxyl group, halogen, nitro or CN or the like, substituent number can be 1～2.
Substituting group is alkyl, alkoxyl group, haloalkyl, halogenated alkoxy, halogen, nitro or CN or the like in the phenyl that replaces, benzyl, phenoxy group, the benzyloxy, and substituent number can be 1～5.
Halogen: refer to fluorine, chlorine, bromine or iodine.
Alkyl: straight or branched alkyl, for example methyl, ethyl, propyl group, sec.-propyl or the tertiary butyl.
Haloalkyl: the straight or branched 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 or 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 or trifluoro ethoxy.
Alkenyl: straight or branched also can have two key, for example vinyl or allyl groups on any position.The substituted alkenyl base comprises the aromatic yl alkenyl of any replacement.
Alkynyl: straight or branched also can have triple bond on any position, for example ethynyl or propargyl.Substituted alkynyl comprises the sweet-smelling alkynyl of any replacement.
Aryl moiety in aryl and aralkyl, aromatic yl alkenyl, sweet-smelling alkynyl, aryloxy and the aryloxy alkyl comprises phenyl or naphthyl.
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 or cumarone.
In compound of the present invention, because carbon-to-carbon double bond is connected different substituting groups and can forms steric isomer (representing different configurations with Z and E respectively) with the two keys of carbon-nitrogen.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 1, but not limit the present invention.
Table 1
Figure G68545537150141000D000052
Numbering X 1 X 2 R 1 Ar Q
1 NCH 3 CH 2 H C 6H 5 Q 4
2 NCH 3 CH 2 H 4-Cl-C 6H 4 Q 4
3 NCH 3 CH 2 H 4-F-C 6H 4 Q 4
4 NCH 3 CH 2 H 4-NO 2-C 6H 4 Q 4
5 NCH 3 CH 2 H 4-CF 3-C 6H 4 Q 4
6 NCH 3 CH 2 H 4-CN-C 6H 4 Q 4
7 NCH 3 CH 2 H 4-CH 3CO 2-C 6H 4 Q 4
8 NCH 3 CH 2 H 4-CH 3S-C 6H 4 Q 4
9 NCH 3 CH 2 H 4-CF 3O-C 6H 4 Q 4
10 NCH 3 CH 2 H 2，4-2Cl-C 6H 3 Q 4
11 NCH(CH 3) 2 CH 2 H 4-Cl-C 6H 4 Q 4
12 NCH 3 CH 2 H 4-CH 3O-C 6H 4 Q 4
13 NCH 3 CH 2 H 2-Cl-4-F-C 6H 3 Q 4
14 NCH 3 CH 2 H 3-Cl-C 6H 4 Q 4
15 NCH 3 CH 2 H 4-Br-C 6H 4 Q 4
16 NCH 3 CH 2 H 4-CH 3-C 6H 4 Q 4
17 NCH 3 CH 2 H 4-C 2H 5-C 6H 4 Q 4
18 NCH 3 CH 2 H 4-CF 3CH 2O-C 6H 4 Q 4
19 NCH 3 CH 2 H 4-PhO-C 6H 4 Q 4
20 NCH 3 CH 2 H 2-Cl-C 6H 4 Q 4
21 NCH 3 CH 2 H 6-Cl-Pyridin-3-yl Q 4
22 NCH 3 CH 2 H 6-F-Pyridin-3-yl Q 4
23 NCH 3 CH 2 H 6-CF 3O-Pyridin-3-yl Q 4
24 NCH 3 CH 2 H 6-CF 3-Pyridin-3-yl Q 4
25 NCH 3 CH 2 H 6-CH 3O-Pyridin-3-yl Q 4
26 NCH 3 CH 2 H 6-CF 3CH 2O-Pyridin-3-yl Q 4
27 NCH 3 CH 2 H 4-(4-Cl-Ph)-C 6H 4 Q 4
28 NCH 3 CH 2 H Thiophen-2-yl Q 4
29 NCH 3 CH 2 H 5-Cl-Thiophen-2-yl Q 4
30 NCH 3 CH 2 H Thiazol-2-yl Q 4
31 NCH 3 CH 2 H Furan-2-yl Q 4
32 NCH 3 CH 2 Cl C 6H 5 Q 4
33 NCH 3 CH 2 Cl 4-Cl-C 6H 4 Q 4
34 NCH 3 CH 2 Cl 4-F-C 6H 4 Q 4
35 NCH 3 CH 2 Cl 4-NO 2-C 6H 4 Q 4
36 NCH 3 CH 2 Cl 4-CF 3-C 6H 4 Q 4
37 NCH 3 CH 2 Cl 4-CN-C 6H 4 Q 4
38 NCH 3 CH 2 Cl 4-CH 3CO 2-C 6H 4 Q 4
39 NCH 3 CH 2 Cl 4-CH 3S-C 6H 4 Q 4
40 NCH 3 CH 2 Cl 4-CF 3O-C 6H 4 Q 4
41 NCH 3 CH 2 Cl 2，4-2Cl-C 6H 3 Q 4
42 NCH(CH 3) 2 CH 2 Cl 4-Cl-C 6H 4 Q 4
43 NCH 3 CH 2 Cl 4-CH 3O-C 6H 4 Q 4
44 NCH 3 CH 2 Cl 2-Cl-4-F-C 6H 3 Q 4
45 NCH 3 CH 2 Cl 3-Cl-C 6H 4 Q 4
46 NCH 3 CH 2 Cl 4-Br-C 6H 4 Q 4
47 NCH 3 CH 2 Cl 4-CH 3-C 6H 4 Q 4
48 NCH 3 CH 2 Cl 4-C 2H 5-C 6H 4 Q 4
49 NCH 3 CH 2 Cl 4-CF 3CH 2O-C 6H 4 Q 4
50 NCH 3 CH 2 Cl 4-PhO-C 6H 4 Q 4
51 NCH 3 CH 2 Cl 2-Cl-C 6H 4 Q 4
52 NCH 3 CH 2 Cl 6-Cl-Pyridin-3-yl Q 4
53 NCH 3 CH 2 Cl 6-F-Pyridin-3-yl Q 4
54 NCH 3 CH 2 Cl 6-CF 3O-Pyridin-3-yl Q 4
55 NCH 3 CH 2 Cl 6-CF 3-Pyridin-3-yl Q 4
56 NCH 3 CH 2 Cl 6-CH 3O-Pyridin-3-yl Q 4
57 NCH 3 CH 2 Cl 6-CF 3CH 2O-Pyridin-3-yl Q 4
58 NCH 3 CH 2 Cl 4-(4-Cl-Ph)-C 6H 4 Q 4
59 NCH 3 CH 2 Cl Thiophen-2-yl Q 4
60 NCH 3 CH 2 Cl 5-Cl-Thiophen-2-yl Q 4
61 NCH 3 CH 2 Cl Thiazol-2-yl Q 4
62 NCH 3 CH 2 Cl Furan-2-yl Q 4
63 NCH 3 CH 2 CH 3 C 6H 5 Q 4
64 NCH 3 CH 2 CH 3 4-Cl-C 6H 4 Q 4
65 NCH 3 CH 2 CH 3 4-F-C 6H 4 Q 4
66 NCH 3 CH 2 CH 3 4-NO 2-C 6H 4 Q 4
67 NCH 3 CH 2 CH 3 4-CF 3-C 6H 4 Q 4
68 NCH 3 CH 2 CH 3 4-CN-C 6H 4 Q 4
69 NCH 3 CH 2 CH 3 4-CH 3CO 2-C 6H 4 Q 4
70 NCH 3 CH 2 CH 3 4-CH 3S-C 6H 4 Q 4
71 NCH 3 CH 2 CH 3 4-CF 3O-C 6H 4 Q 4
72 NCH 3 CH 2 CH 3 2，4-2Cl-C 6H 3 Q 4
73 NCH(CH 3) 2 CH 2 CH 3 4-Cl-C 6H 4 Q 4
74 NCH 3 CH 2 CH 3 4-CH 3O-C 6H 4 Q 4
75 NCH 3 CH 2 CH 3 2-Cl-4-F-C 6H 3 Q 4
76 NCH 3 CH 2 CH 3 3-Cl-C 6H 4 Q 4
77 NCH 3 CH 2 CH 3 4-Br-C 6H 4 Q 4
78 NCH 3 CH 2 CH 3 4-CH 3-C 6H 4 Q 4
79 NCH 3 CH 2 CH 3 4-C 2H 5-C 6H 4 Q 4
80 NCH 3 CH 2 CH 3 4-CF 3CH 2O-C 6H 4 Q 4
81 NCH 3 CH 2 CH 3 4-PhO-C 6H 4 Q 4
82 NCH 3 CH 2 CH 3 2-Cl-C 6H 4 Q 4
83 NCH 3 CH 2 CH 3 6-Cl-Pyridin-3-yl Q 4
84 NCH 3 CH 2 CH 3 6-F-Pyridin-3-yl Q 4
85 NCH 3 CH 2 CH 3 6-CF 3O-Pyridin-3-yl Q 4
86 NCH 3 CH 2 CH 3 6-CF 3-Pyridin-3-yl Q 4
87 NCH 3 CH 2 CH 3 6-CH 3O-Pyridin-3-yl Q 4
88 NCH 3 CH 2 CH 3 6-CF 3CH 2O-Pyridin-3-yl Q 4
89 NCH 3 CH 2 CH 3 4-(4-Cl-Ph)-C 6H 4 Q 4
90 NCH 3 CH 2 CH 3 Thiophen-2-yl Q 4
91 NCH 3 CH 2 CH 3 5-Cl-Thiophen-2-yl Q 4
92 NCH 3 CH 2 CH 3 Thiazol-2-yl Q 4
93 NCH 3 CH 2 CH 3 Furan-2-yl Q 4
94 O CH 2 H C 6H 5 Q 4
95 O CH 2 H 4-Cl-C 6H 4 Q 4
96 O CH 2 H 4-F-C 6H 4 Q 4
97 O CH 2 H 4-NO 2-C 6H 4 Q 4
98 O CH 2 H 4-CF 3-C 6H 4 Q 4
99 O CH 2 H 4-CN-C 6H 4 Q 4
100 O CH 2 H 4-CH 3CO 2-C 6H 4 Q 4
101 O CH 2 H 4-CH 3S-C 6H 4 Q 4
102 O CH 2 H 4-CF 3O-C 6H 4 Q 4
103 O CH 2 H 2，4-2Cl-C 6H 3 Q 4
104 O CH 2 H 4-CH 3O-C 6H 4 Q 4
105 O CH 2 H 2-Cl-4-F-C 6H 3 Q 4
106 O CH 2 H 3-Cl-C 6H 4 Q 4
107 O CH 2 H 4-CH 3-C 6H 4 Q 4
108 O CH 2 H 4-Br-C 6H 4 Q 4
109 O CH 2 H 4-C 2H 5-C 6H 4 Q 4
110 O CH 2 H 4-CF 3CH 2O-C 6H 4 Q 4
111 O CH 2 H 4-PhO-C 6H 4 Q 4
112 O CH 2 H 2-Cl-C 6H 4 Q 4
113 O CH 2 H 6-Cl-Pyridin-3-yl Q 4
114 O CH 2 H 6-F-Pyridin-3-yl Q 4
115 O CH 2 H 6-CF 3O-Pyridin-3-yl Q 4
116 O CH 2 H 6-CF 3-Pyridin-3-yl Q 4
117 O CH 2 H 6-CH 3O-Pyridin-3-yl Q 4
118 O CH 2 H 6-CF 3CH 2O-Pyridin-3-yl Q 4
119 O CH 2 H 4-(4-Cl-Ph)-C 6H 4 Q 4
120 O CH 2 H Thiophen-2-yl Q 4
121 O CH 2 H 5-Cl-Thiophen-2-yl Q 4
122 O CH 2 H Thiazol-2-yl Q 4
123 O CH 2 H Furan-2-yl Q 4
124 O CH 2 Cl C 6H 5 Q 4
125 O CH 2 Cl 4-Cl-C 6H 4 Q 4
126 O CH 2 Cl 4-F-C 6H 4 Q 4
127 O CH 2 Cl 4-NO 2-C 6H 4 Q 4
128 O CH 2 Cl 4-CF 3-C 6H 4 Q 4
129 O CH 2 Cl 4-CN-C 6H 4 Q 4
130 O CH 2 Cl 4-CH 3CO 2-C 6H 4 Q 4
131 O CH 2 Cl 4-CH 3S-C 6H 4 Q 4
132 O CH 2 Cl 4-CF 3O-C 6H 4 Q 4
133 O CH 2 Cl 2，4-2Cl-C 6H 3 Q 4
134 O CH 2 Cl 4-CH 3O-C 6H 4 Q 4
135 O CH 2 Cl 2-Cl-4-F-C 6H 3 Q 4
136 O CH 2 Cl 3-Cl-C 6H 4 Q 4
137 O CH 2 Cl 4-CH 3-C 6H 4 Q 4
138 O CH 2 Cl 4-Br-C 6H 4 Q 4
139 O CH 2 Cl 4-C 2H 5-C 6H 4 Q 4
140 O CH 2 Cl 4-CF 3CH 2O-C 6H 4 Q 4
141 O CH 2 Cl 4-PhO-C 6H 4 Q 4
142 O CH 2 Cl 2-Cl-C 6H 4 Q 4
143 O CH 2 Cl 6-Cl-Pyridin-3-yl Q 4
144 O CH 2 Cl 6-F-Pyridin-3-yl Q 4
145 O CH 2 Cl 6-CF 3O-Pyridin-3-yl Q 4
146 O CH 2 Cl 6-CF 3-Pyridin-3-yl Q 4
147 O CH 2 Cl 6-CH 3O-Pyridin-3-yl Q 4
148 O CH 2 Cl 6-CF 3CH 2O-Pyridin-3-yl Q 4
149 O CH 2 Cl 4-(4-Cl-Ph)-C 6H 4 Q 4
150 O CH 2 Cl Thiophen-2-yl Q 4
151 O CH 2 Cl 5-Cl-Thiophen-2-yl Q 4
152 O CH 2 Cl Thiazol-2-yl Q 4
153 O CH 2 Cl Furan-2-yl Q 4
154 O CH 2 CH 3 C 6H 5 Q 4
155 O CH 2 CH 3 4-Cl-C 6H 4 Q 4
156 O CH 2 CH 3 4-F-C 6H 4 Q 4
157 O CH 2 CH 3 4-NO 2-C 6H 4 Q 4
158 O CH 2 CH 3 4-CF 3-C 6H 4 Q 4
159 O CH 2 CH 3 4-CN-C 6H 4 Q 4
160 O CH 2 CH 3 4-CH 3CO 2-C 6H 4 Q 4
161 O CH 2 CH 3 4-CH 3S-C 6H 4 Q 4
162 O CH 2 CH 3 4-CF 3O-C 6H 4 Q 4
163 O CH 2 CH 3 2，4-2Cl-C 6H 3 Q 4
164 O CH 2 CH 3 4-CH 3O-C 6H 4 Q 4
165 O CH 2 CH 3 2-Cl-4-F-C 6H 3 Q 4
166 O CH 2 CH 3 3-Cl-C 6H 4 Q 4
167 O CH 2 CH 3 4-CH 3-C 6H 4 Q 4
168 O CH 2 CH 3 4-Br-C 6H 4 Q 4
169 O CH 2 CH 3 4-C 2H 5-C 6H 4 Q 4
170 O CH 2 CH 3 4-CF 3CH 2O-C 6H 4 Q 4
171 O CH 2 CH 3 4-PhO-C 6H 4 Q 4
172 O CH 2 CH 3 2-Cl-C 6H 4 Q 4
173 O CH 2 CH 3 6-Cl-Pyridin-3-yl Q 4
174 O CH 2 CH 3 6-F-Pyridin-3-yl Q 4
175 O CH 2 CH 3 6-CF 3O-Pyridin-3-yl Q 4
176 O CH 2 CH 3 6-CF 3-Pyridin-3-yl Q 4
177 O CH 2 CH 3 6-CH 3O-Pyridin-3-yl Q 4
178 O CH 2 CH 3 6-CF 3CH 2O-Pyridin-3-yl Q 4
179 O CH 2 CH 3 4-(4-Cl-Ph)-C 6H 4 Q 4
180 O CH 2 CH 3 Thiophen-2-yl Q 4
181 O CH 2 CH 3 5-Cl-Thiophen-2-yl Q 4
182 O CH 2 CH 3 Thiazol-2-yl Q 4
183 O CH 2 CH 3 Furan-2-yl Q 4
184 NCH 3 M H C 6H 5 Q1
185 NCH 3 M H 4-Cl-C 6H 4 Q 1
186 NCH 3 M H 4-F-C 6H 4 Q 1
187 NCH 3 M H 4-NO 2-C 6H 4 Q 1
188 NCH 3 M H 4-CF 3-C 6H 4 Q 1
189 NCH 3 M H 4-CN-C 6H 4 Q 1
190 NCH 3 M H 4-CH 3CO 2-C 6H 4 Q 1
191 NCH 3 M H 4-CH 3S-C 6H 4 Q 1
192 NCH 3 M H 4-CF 3O-C 6H 4 Q 1
193 NCH 3 M H 2，4-2Cl-C 6H 3 Q 1
194 NCH(CH 3) 2 M H 4-Cl-C 6H 4 Q 1
195 NCH 3 M H 4-CH 3O-C 6H 4 Q 1
196 NCH 3 M H 2-Cl-4-F-C 6H 3 Q 1
197 NCH 3 M H 3-Cl-C 6H 4 Q 1
198 NCH 3 M H 4-Br-C 6H 4 Q 1
199 NCH 3 M H 4-CH 3-C 6H 4 Q 1
200 NCH 3 M H 4-C 2H 5-C 6H 4 Q 1
201 NCH 3 M H 4-CF 3CH 2O-C 6H 4 Q 1
202 NCH 3 M H 4-PhO-C 6H 4 Q 1
203 NCH 3 M H 2-Cl-C 6H 4 Q 1
204 NCH 3 M H 6-Cl-Pyridin-3-yl Q 1
205 NCH 3 M H 6-F-Pyridin-3-yl Q 1
206 NCH 3 M H 6-CF 3O-Pyridin-3-yl Q 1
207 NCH 3 M H 6-CF 3-Pyridin-3-yl Q 1
208 NCH 3 M H 6-CH 3O-Pyridin-3-yl Q 1
209 NCH 3 M H 6-CF 3CH 2O-Pyridin-3-yl Q 1
210 NCH 3 M H 4-(4-Cl-Ph)-C 6H 4 Q 1
211 NCH 3 M H Thiophen-2-yl Q 1
212 NCH 3 M H 5-Cl-Thiophen-2-yl Q 1
213 NCH 3 M H Thiazol-2-yl Q 1
214 NCH 3 M H Furan-2-yl Q 1
215 NCH 3 M Cl C 6H 5 Q 1
216 NCH 3 M Cl 4-Cl-C 6H 4 Q 1
217 NCH 3 M Cl 4-F-C 6H 4 Q 1
218 NCH 3 M Cl 4-NO 2-C 6H 4 Q 1
219 NCH 3 M Cl 4-CF 3-C 6H 4 Q 1
220 NCH 3 M Cl 4-CN-C 6H 4 Q 1
221 NCH 3 M Cl 4-CH 3CO 2-C 6H 4 Q 1
222 NCH 3 M Cl 4-CH 3S-C 6H 4 Q 1
223 NCH 3 M Cl 4-CF 3O-C 6H 4 Q 1
224 NCH 3 M Cl 2，4-2Cl-C 6H 3 Q 1
225 NCH(CH 3) 2 M Cl 4-Cl-C 6H 4 Q 1
226 NCH 3 M Cl 4-CH 3O-C 6H 4 Q 1
227 NCH 3 M Cl 2-Cl-4-F-C 6H 3 Q 1
228 NCH 3 M Cl 3-Cl-C 6H 4 Q 1
229 NCH 3 M Cl 4-Br-C 6H 4 Q 1
230 NCH 3 M Cl 4-CH 3-C 6H 4 Q 1
231 NCH 3 M Cl 4-C 2H 5-C 6H 4 Q 1
232 NCH 3 M Cl 4-CF 3CH 2O-C 6H 4 Q 1
233 NCH 3 M Cl 4-PhO-C 6H 4 Q 1
234 NCH 3 M Cl 2-Cl-C 6H 4 Q 1
235 NCH 3 M Cl 6-Cl-Pyridin-3-yl Q 1
236 NCH 3 M Cl 6-F-Pyridin-3-yl Q 1
237 NCH 3 M Cl 6-CF 3O-Pyridin-3-yl Q 1
238 NCH 3 M Cl 6-CF 3-Pyridin-3-yl Q 1
239 NCH 3 M Cl 6-CH 3O-Pyridin-3-yl Q 1
240 NCH 3 M Cl 6-CF 3CH 2O-Pyridin-3-yl Q 1
241 NCH 3 M Cl 4-(4-Cl-Ph)-C 6H 4 Q 1
242 NCH 3 M Cl Thiophen-2-yl Q 1
243 NCH 3 M Cl 5-Cl-Thiophen-2-yl Q 1
244 NCH 3 M Cl Thiazol-2-yl Q 1
245 NCH 3 M Cl Furan-2-yl Q 1
246 NCH 3 M CH 3 C 6H 5 Q 1
247 NCH 3 M CH 3 4-Cl-C 6H 4 Q 1
248 NCH 3 M CH 3 4-F-C 6H 4 Q 1
249 NCH 3 M CH 3 4-NO 2-C 6H 4 Q 1
250 NCH 3 M CH 3 4-CF 3-C 6H 4 Q 1
251 NCH 3 M CH 3 4-CN-C 6H 4 Q 1
252 NCH 3 M CH 3 4-CH 3CO 2-C 6H 4 Q 1
253 NCH 3 M CH 3 4-CH 3S-C 6H 4 Q 1
254 NCH 3 M CH 3 4-CF 3O-C 6H 4 Q 1
255 NCH 3 M CH 3 2，4-2Cl-C 6H 3 Q 1
256 NCH(CH 3) 2 M CH 3 4-Cl-C 6H 4 Q 1
257 NCH 3 M CH 3 4-CH 3O-C 6H 4 Q 1
258 NCH 3 M CH 3 2-Cl-4-F-C 6H 3 Q 1
259 NCH 3 M CH 3 3-Cl-C 6H 4 Q 1
260 NCH 3 M CH 3 4-Br-C 6H 4 Q 1
261 NCH 3 M CH 3 4-CH 3-C 6H 4 Q 1
262 NCH 3 M CH 3 4-C 2H 5-C 6H 4 Q 1
263 NCH 3 M CH 3 4-CF 3CH 2O-C 6H 4 Q 1
264 NCH 3 M CH 3 4-PhO-C 6H 4 Q 1
265 NCH 3 M CH 3 2-Cl-C 6H 4 Q 1
266 NCH 3 M CH 3 6-Cl-Pyridin-3-yl Q 1
267 NCH 3 M CH 3 6-F-Pyridin-3-yl Q 1
268 NCH 3 M CH 3 6-CF 3O-Pyridin-3-yl Q 1
269 NCH 3 M CH 3 6-CF 3-Pyridin-3-yl Q 1
270 NCH 3 M CH 3 6-CH 3O-Pyridin-3-yl Q 1
271 NCH 3 M CH 3 6-CF 3CH 2O-Pyridin-3-yl Q 1
272 NCH 3 M CH 3 4-(4-Cl-Ph)-C 6H 4 Q 1
273 NCH 3 M CH 3 Thiophen-2-yl Q 1
274 NCH 3 M CH 3 5-Cl-Thiophen-2-yl Q 1
275 NCH 3 M CH 3 Thiazol-2-yl Q 1
276 NCH 3 M CH 3 Furan-2-yl Q 1
277 O M H C 6H 5 Q 1
278 O M H 4-Cl-C 6H 4 Q 1
279 O M H 4-F-C 6H 4 Q 1
280 O M H 4-NO 2-C 6H 4 Q 1
281 O M H 4-CF 3-C 6H 4 Q 1
282 O M H 4-CN-C 6H 4 Q 1
283 O M H 4-CH 3CO 2-C 6H 4 Q 1
284 O M H 4-CH 3S-C 6H 4 Q 1
285 O M H 4-CF 3O-C 6H 4 Q 1
286 O M H 2，4-2Cl-C 6H 3 Q 1
287 O M H 4-CH 3O-C 6H 4 Q 1
288 O M H 2-Cl-4-F-C 6H 3 Q 1
289 O M H 3-Cl-C 6H 4 Q 1
290 O M H 4-Br-C 6H 4 Q 1
291 O M H 4-CH 3-C 6H 4 Q 1
292 O M H 4-C 2H 5-C 6H 4 Q 1
293 O M H 4-CF 3CH 2O-C 6H 4 Q 1
294 O M H 4-PhO-C 6H 4 Q 1
295 O M H 2-Cl-C 6H 4 Q 1
296 O M H 6-Cl-Pyridin-3-yl Q 1
297 O M H 6-F-Pyridin-3-yl Q 1
298 O M H 6-CF 3O-Pyridin-3-yl Q 1
299 O M H 6-CF 3-Pyridin-3-yl Q 1
300 O M H 6-CH 3O-Pyridin-3-yl Q 1
301 O M H 6-CF 3CH 2O-Pyridin-3-yl Q 1
302 O M H 4-(4-Cl-Ph)-C 6H 4 Q 1
303 O M H Thiophen-2-yl Q 1
304 O M H 5-Cl-Thiophen-2-yl Q 1
305 O M H Thiazol-2-yl Q 1
306 O M H Furan-2-yl Q 1
307 O M Cl C 6H 5 Q 1
308 O M Cl 4-Cl-C 6H 4 Q 1
309 O M Cl 4-F-C 6H 4 Q 1
310 O M Cl 4-NO 2-C 6H 4 Q 1
311 O M Cl 4-CF 3-C 6H 4 Q 1
312 O M Cl 4-CN-C 6H 4 Q 1
313 O M Cl 4-CH 3CO 2-C 6H 4 Q 1
314 O M Cl 4-CH 3S-C 6H 4 Q 1
315 O M Cl 4-CF 3O-C 6H 4 Q 1
316 O M Cl 2，4-2Cl-C 6H 3 Q 1
317 O M Cl 4-CH 3O-C 6H 4 Q 1
318 O M Cl 2-Cl-4-F-C 6H 3 Q 1
319 O M Cl 3-Cl-C 6H 4 Q 1
320 O M Cl 4-Br-C 6H 4 Q 1
321 O M Cl 4-CH 3-C 6H 4 Q 1
322 O M Cl 4-C 2H 5-C 6H 4 Q 1
323 O M Cl 4-CF 3CH 2O-C 6H 4 Q 1
324 O M Cl 4-PhO-C 6H 4 Q 1
325 O M Cl 2-Cl-C 6H 4 Q 1
326 O M Cl 6-Cl-Pyridin-3-yl Q 1
327 O M Cl 6-F-Pyridin-3-yl Q 1
328 O M Cl 6-CF 3O-Pyridin-3-yl Q 1
329 O M Cl 6-CF 3-Pyridin-3-yl Q 1
330 O M Cl 6-CH 3O-Pyridin-3-yl Q 1
331 O M Cl 6-CF 3CH 2O-Pyridin-3-yl Q 1
332 O M Cl 4-(4-Cl-Ph)-C 6H 4 Q 1
333 O M Cl Thiophen-2-yl Q 1
334 O M Cl 5-Cl-Thiophen-2-yl Q 1
335 O M Cl Thiazol-2-yl Q 1
336 O M Cl Furan-2-yl Q 1
337 O M CH 3 C 6H 5 Q 1
338 O M CH 3 4-Cl-C 6H 4 Q 1
339 O M CH 3 4-F-C 6H 4 Q 1
340 O M CH 3 4-NO 2-C 6H 4 Q 1
341 O M CH 3 4-CF 3-C 6H 4 Q 1
342 O M CH 3 4-CN-C 6H 4 Q 1
343 O M CH 3 4-CH 3CO 2-C 6H 4 Q 1
344 O M CH 3 4-CH 3S-C 6H 4 Q 1
345 O M CH 3 4-CF 3O-C 6H 4 Q 1
346 O M CH 3 2，4-2Cl-C 6H 3 Q 1
347 O M CH 3 4-CH 3O-C 6H 4 Q 1
348 O M CH 3 2-Cl-4-F-C 6H 3 Q 1
349 O M CH 3 3-Cl-C 6H 4 Q 1
350 O M CH 3 4-Br-C 6H 4 Q 1
351 O M CH 3 4-CH 3-C 6H 4 Q 1
352 O M CH 3 4-C 2H 5-C 6H 4 Q 1
353 O M CH 3 4-CF 3CH 2O-C 6H 4 Q 1
354 O M CH 3 4-PhO-C 6H 4 Q 1
355 O M CH 3 2-Cl-C 6H 4 Q 1
356 O M CH 3 6-Cl-Pyridin-3-yl Q 1
357 O M CH 3 6-F-Pyridin-3-yl Q 1
358 O M CH 3 6-CF 3O-Pyridin-3-yl Q 1
359 O M CH 3 6-CF 3-Pyridin-3-yl Q 1
360 O M CH 3 6-CH 3O-Pyridin-3-yl Q 1
361 O M CH 3 6-CF 3CH 2O-Pyridin-3-yl Q 1
362 O M CH 3 4-(4-Cl-Ph)-C 6H 4 Q 1
363 O M CH 3 Thiophen-2-yl Q 1
364 O M CH 3 5-Cl-Thiophen-2-yl Q 1
365 O M CH 3 Thiazol-2-yl Q 1
366 O M CH 3 Furan-2-yl Q 1
367 NCH 3 CH 2 H Thiophen-2-yl Q 1
368 NCH 3 CH 2 H 5-Cl-Thiophen-2-yl Q 1
369 NCH 3 CH 2 H Thiazol-2-yl Q 1
370 NCH 3 CH 2 H Furan-2-yl Q 1
371 NCH 3 CH 2 Cl Thiophen-2-yl Q 1
372 NCH 3 CH 2 Cl 5-Cl-Thiophen-2-yl Q 1
373 NCH 3 CH 2 Cl Thiazol-2-yl Q 1
374 NCH 3 CH 2 Cl Furan-2-yl Q 1
375 NCH 3 CH 2 CH 3 Thiophen-2-yl Q 1
376 NCH 3 CH 2 CH 3 5-Cl-Thiophen-2-yl Q 1
377 NCH 3 CH 2 CH 3 Thiazol-2-yl Q 1
378 NCH 3 CH 2 CH 3 Furan-2-yl Q 1
379 O CH 2 H Thiophen-2-yl Q 1
380 O CH 2 H 5-Cl-Thiophen-2-yl Q 1
381 O CH 2 H Thiazol-2-yl Q 1
382 O CH 2 H Furan-2-yl Q 1
383 O CH 2 Cl Thiophen-2-yl Q 1
384 O CH 2 Cl 5-Cl-Thiophen-2-yl Q 1
385 O CH 2 Cl Thiazol-2-yl Q 1
386 O CH 2 Cl Furan-2-yl Q 1
387 O CH 2 CH 3 Thiophen-2-yl Q 1
388 O CH 2 CH 3 5-Cl-Thiophen-2-yl Q 1
389 O CH 2 CH 3 Thiazol-2-yl Q 1
390 O CH 2 CH 3 Furan-2-yl Q 1
391 NCH 3 CH 2 H Thiophen-2-yl Q 2
392 NCH 3 CH 2 H 5-Cl-Thiophen-2-yl Q 2
393 NCH 3 CH 2 H Thiazol-2-yl Q 2
394 NCH 3 CH 2 H Furan-2-yl Q 2
395 NCH 3 CH 2 Cl Thiophen-2-yl Q 2
396 NCH 3 CH 2 Cl 5-Cl-Thiophen-2-yl Q 2
397 NCH 3 CH 2 Cl Thiazol-2-yl Q 2
398 NCH 3 CH 2 Cl Furan-2-yl Q 2
399 NCH 3 CH 2 CH 3 Thiophen-2-yl Q 2
400 NCH 3 CH 2 CH 3 5-Cl-Thiophen-2-yl Q 2
401 NCH 3 CH 2 CH 3 Thiazol-2-yl Q 2
402 NCH 3 CH 2 CH 3 Furan-2-yl Q 2
403 O CH 2 H Thiophen-2-yl Q 2
404 O CH 2 H 5-Cl-Thiophen-2-yl Q 2
405 O CH 2 H Thiazol-2-yl Q 2
406 O CH 2 H Furan-2-yl Q 2
407 O CH 2 Cl Thiophen-2-yl Q 2
408 O CH 2 Cl 5-Cl-Thiophen-2-yl Q 2
409 O CH 2 Cl Thiazol-2-yl Q 2
410 O CH 2 Cl Furan-2-yl Q 2
411 O CH 2 CH 3 Thiophen-2-yl Q 2
412 O CH 2 CH 3 5-Cl-Thiophen-2-yl Q 2
413 O CH 2 CH 3 Thiazol-2-yl Q 2
414 O CH 2 CH 3 Furan-2-yl Q 2
415 NCH 3 CH 2 H Thiophen-2-yl Q 3
416 NCH 3 CH 2 H 5-Cl-Thiophen-2-yl Q 3
417 NCH 3 CH 2 H Thiazol-2-yl Q 3
418 NCH 3 CH 2 H Furan-2-yl Q 3
419 NCH 3 CH 2 Cl Thiophen-2-yl Q 3
420 NCH 3 CH 2 Cl 5-Cl-Thiophen-2-yl Q 3
421 NCH 3 CH 2 Cl Thiazol-2-yl Q 3
422 NCH 3 CH 2 Cl Furan-2-yl Q 3
423 NCH 3 CH 2 CH 3 Thiophen-2-yl Q 3
424 NCH 3 CH 2 CH 3 5-Cl-Thiophen-2-yl Q 3
425 NCH 3 CH 2 CH 3 Thiazol-2-yl Q 3
426 NCH 3 CH 2 CH 3 Furan-2-yl Q 3
427 O CH 2 H Thiophen-2-yl Q 3
428 O CH 2 H 5-Cl-Thiophen-2-yl Q 3
429 O CH 2 H Thiazol-2-yl Q 3
430 O CH 2 H Furan-2-yl Q 3
431 O CH 2 Cl Thiophen-2-yl Q 3
432 O CH 2 Cl 5-Cl-Thiophen-2-yl Q 3
433 O CH 2 Cl Thiazol-2-yl Q 3
434 O CH 2 Cl Furan-2-yl Q 3
435 O CH 2 CH 3 Thiophen-2-yl Q 3
436 O CH 2 CH 3 5-Cl-Thiophen-2-yl Q 3
437 O CH 2 CH 3 Thiazol-2-yl Q 3
438 O CH 2 CH 3 Furan-2-yl Q 3
439 NCH 3 CH 2 H 2-CH 3O-C 6H 4 Q 4
440 NCH 3 CH 2 H 2，5-2CH 3-Thiophen-3-yl Q 4
441 NCH 3 CH 2 H 2，5-2CH 3-Thiophen-3-yl Q 1
442 NCH 3 CH 2 H 2，5-2CH 3-Thiophen-3-yl Q 2
443 NCH 3 CH 2 H 2，4-2CH 3-C 6H 3 Q 4
444 NCH 3 CH 2 H 3，4-2CH 3-C 6H 3 Q 4
445 NCH 3 CH 2 H 2，5-2CH 3-C 6H 3 Q 4
446 NCH 3 CH 2 H 2，6-2CH 3-C 6H 3 Q 4
447 NCH 3 CH 2 CH 3 2，4-2CH 3-C 6H 3 Q 4
448 NCH 3 CH 2 CH 3 3，4-2CH 3-C 6H 3 Q 4
449 NCH 3 CH 2 CH 3 2，5-2CH 3-C 6H 3 Q 4
450 NCH 3 CH 2 CH 3 2，6-2CH 3-C 6H 3 Q 4
In the table
Figure G68545537150141000D000181
The present invention also comprises the preparation method of compound of Formula I.
Compound of Formula I and steric isomer thereof are reacted under alkaline condition by the azole compounds of the hydroxyl shown in the general formula III and the benzyl halogen shown in the general formula I V and make:
Among the general formula I V, R is a leavings group, is 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 be obtained according to the currently known methods condensation by intermediate II and (replacement) hydrazine, azanol, and intermediate II can buy or make by currently known methods, specifically referring to US3781438, CN1257490 and WO9615115 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 of 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, cucumber anthracnose, 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 desinsection, fungicidal composition, and the compound and the agricultural that contain general formula I in the said composition go up acceptable carrier, and the weight percentage of active ingredient is 0.1-99% in the composition.
The present invention also provides preparation of compositions method as defined above: the compound of general formula I is mixed with carrier.This composition can be for containing the mixture of simplification compound of the present invention or several compounds.
Carrier system in the present composition satisfies the material of following condition: being convenient to be applied to pending site after it and activeconstituents are prepared, for example can be plant, seed or soil; Perhaps help storing, transport or operation.Carrier can be solid or liquid, comprises the material that is generally gas but has been compressed into liquid, and used carrier all can use in preparation desinsection, fungicidal composition usually.
Suitable solid carrier comprises natural or synthetic clay or silicate, for example diatomite, talcum, attapulgite, pure aluminium silicate (kaolin), montmorillonite, mica; Lime carbonate; Calcium sulfate; Ammonium sulfate; Synthetic silicon oxide, synthetic calcium silicate or pure aluminium silicate; Element such as carbon, sulphur; Natural or synthetic resin such as coumarone resin, polyvinyl chloride, styrene polymer or multipolymer; Solid polystream phenol; Pitch; Wax such as beeswax, paraffin.
Suitable liquid vehicle comprises water; Alcohol is as Virahol, ethanol; Ketone such as acetone, methyl ethyl ketone, methyl isopropyl Ketone, cyclohexyl ketone; Ether; Aromatic hydrocarbons such as benzene,toluene,xylene; Petroleum fractions such as kerosene, mineral oil; Hydrochloric ether such as tetracol phenixin, tetrachloroethylene, trieline.Usually, these mixtures of liquids also are suitable.
Desinsection, fungicidal composition are processed into the form of enriched material usually and are used for transportation with this, by the user it are diluted before using.Having of a spot of supporting surfactant helps dilution.Like this, according to having preferably tensio-active agent of a kind of carrier in the composition of the present invention at least.For example composition can contain at least two kinds of carriers, and wherein at least a is tensio-active agent.
Tensio-active agent can be emulsifying agent, dispersion agent or wetting agent; It can be non-ionic or the ionic tensio-active agent.The example of suitable tensio-active agent comprises the sodium salt or the calcium salt of polyacrylic acid and lignosulfonic acid; Contain the lipid acid of at least 12 carbon atoms or the condenses of aliphatic amide or acid amides and oxyethane and/or propylene oxide in the molecule.The condenses of glycol, sorbyl alcohol, sucrose or pentaerythritol fatty ester and these esters and oxyethane and/or propylene oxide; Fatty Alcohol(C12-C14 and C12-C18) or alkylphenol such as paraoctyl phenol or to the condenses of octyl group cresylol and oxyethane and/or propylene oxide; The vitriol of these condensation products and sulfonate; In molecule, contain the sulfuric acid of 10 carbon atoms or the basic metal or the alkaline earth salt of sulphonate at least, particular certain cancers, sulfuric acid laurate sodium for example, the secondary alkyl ester sodium of sulfuric acid, the sulfonated castor oil sodium salt, alkyl aryl sulfonic acid ester sodium is as pelopon A.
The example of composition of the present invention can be wettable powder, pulvis, granule or liquor, emulsible enriching agent, emulsion, suspension enriching agent, aerosol or smoke substance.Wettable powder contains 25,50 or 75% weight activeconstituents usually, and usually except that solid inert carrier, also contains the dispersion agent of 3-10% weight, and if needs to add stablizer and/or other additive such as the permeate agent or the tackiness agent of 0-10% weight.Pulvis may be molded to the pulvis enriching agent that has the composition similar to wettable powder but do not have dispersion agent usually, further with the solid carrier dilution, is contained the composition of 0.5-10% weight active ingredient usually again.Granula is prepared into usually has 10 to 100 order (1.676-0.152mm) sizes, and available agglomerating or implantttion technique preparation.Usually granula contains the activeconstituents of 0.5-75% weight and 0-10% weight additive such as stablizer, tensio-active agent, slowly-releasing modifying agent.So-called " dry powder can flow " is by the relatively little granulometric composition with relative high density activeconstituents.Outside but emulsion concentrate desolventizes, when needs, contain cosolvent usually, 1-50%W/V activeconstituents, other additives of 2-20%W/V emulsifying agent and 0-20%W/V such as stablizer, permeate agent and corrosion inhibitor.The suspension enriching agent contains other additive of dispersion agent, 0.1-10% weight of activeconstituents, the 0.5-15% weight of 10-75% weight such as defoamer, corrosion inhibitor, stablizer, permeate agent usually Or tackiness agent.
Water dispersant and emulsion, for example by dilute with water according to the composition that wettable powder of the present invention or enriched material obtain, also list the scope of the invention in.Said emulsion can have water-in-oil or two types of oil-in-water.
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 further specifies the present invention.
Synthetic embodiment
Example 1: the preparation of compound 2
Figure G68545537150141000D000202
2.12 grams are dissolved in 10 ml methanol reflux to the chlorobenzoyl methyl acetate.Drip excessive slightly methyl hydrazine, refluxed 3 hours.After the TLC monitoring reaction finishes, concentrate, crystal is separated out in cooling.Filter, wash crystal with small amount of methanol.Drying gets 1.5 gram crystal 3-(4-chloro-phenyl-)-1-methyl-5-pyrazoles alcohol, i.e. compounds (III-1).
Above-mentioned crystal 0.5 gram is dissolved in 5 milliliters of N, in the dinethylformamide, adds sodium hydride 0.17 gram, stirred 0.5 hour.Add compound (IV-1) 0.72 gram, 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, and promptly compound 2.
Nuclear magnetic data ( 1HNMR, 300MHz, interior mark TMS, solvent C DCl 3) as follows:
δppm?3.75(6H，s)，3.81(3H，s)，5.20(2H，s)，5.86(1H，s)，7.35(2H，d)，7.44(3H，m)，7.54(1H，m)，7.69(2H，m)。
Example 2: the preparation of compound 21
Figure G68545537150141000D000211
60% sodium hydride, 0.15 gram is joined in the reaction flask, after washing with sherwood oil, add 5 milliliters of N, dinethylformamide, add compound (III-2) 1.0 grams that make according to patent CN1257490A method then, stirring at room adds compound (IV-1) 1.40 gram after 2 minutes, 60 ℃ of following stirring reactions 2 hours.After the TLC monitoring reaction finishes, reaction solution is poured in 50 milliliters of saturated aqueous common salts, divided with 100 milliliters of ethyl acetate to extract drying three times.Behind the precipitation, column chromatography purification gets oily product 0.95 gram, and promptly compound 21.
Nuclear magnetic data ( 1HNMR, 300MHz, interior mark TMS, solvent C DCl 3) as follows:
δppm?3.75(3H，s)，3.76(3H，s)，3.82(3H，s)，5.21(2H，s)，5.89(1H，s)，7.33(1H，d)，7.45(3H，m)，7.58(1H，d)，8.06(1H，d)，8.68(1H，s)。
Example 3: the preparation of compound 89
Figure G68545537150141000D000212
With reference to patent US3781438 reported method, 2 grams are dissolved in the methyl alcohol the toluyl methyl acetate, and add excessive slightly oxammonium hydrochloride, the sodium hydroxide of equimolar amount, reflux is 3 hours then.The TLC monitoring reaction Hou Jiashui that finishes, ethyl acetate extraction, dry, concentrate solid 4-aminomethyl phenyl isoxzzole-5-alcohol, i.e. compound (III-3).
Digest compound (III-3) with 1 and be dissolved in N, in the dinethylformamide, add sodium hydride 0.45 gram, stirred 0.5 hour.Add compound (IV-1) 1.7 grams, 50 ℃ of oil baths were stirred 6 hours.After the TLC monitoring reaction finishes, reaction solution is poured in 50 milliliters of saturated aqueous common salts, divided with 100 milliliters of ethyl acetate to extract drying three times.Behind the precipitation, column chromatography purification gets oily product 1.5 grams, and promptly compound 89.
Example 4: the preparation of compound 121
Figure G68545537150141000D000213
In 15 milliliters of N, the mixing solutions in the dinethylformamide is heated to 70-80 ℃, stirs 7 hours with compound (III-1) 1.0 grams, compound (N-2) (with reference to patent WO 9807707, WO 9208703 preparations) 1.7 grams and 2.1 gram Anhydrous potassium carbonates.After the TLC monitoring reaction finishes, reaction solution is poured in 100 milliliters of saturated aqueous common salts, divided with 100 milliliters of ethyl acetate to extract drying three times.Behind the precipitation, column chromatography purification gets oily product 1.1 grams, and promptly compound 121.
Other compounds are synthetic with reference to aforesaid method.
The physico-chemical property of the compound of Formula I shown in the part table 1 and nuclear magnetic data ( 1HNMR, 300MHz, interior mark TMS, solvent C DCl 3) as follows:
Compound 1: oily matter.δppm?3.75(6H，s)，3.81(3H，s)，5.19(2H，s)，5.86(1H，s)，7.40(5H，m)，7.60(1H，m)，7.68(2H，d)。
Compound 8: fusing point is 98-100 ℃.δppm?2.47(3H，s)，3.73(3H，s)，3.75(3H，s)，3.81(3H，s)，5.18(2H，s)，5.83(1H，s)，7.24(1H，m)，7.42(3H，m)，7.65(3H，m)。
Compound 10: fusing point is 89-91 ℃.δppm3.75(6H，s)，3.79(3H，s)，5.20(2H，s)，6.07(1H，s)，7.24(2H，d)，7.42(4H，m)，7.58(1H，m)，7.75(1H，d)。
Compound 11: oily matter.δppm?1.45(6H，s)，3.60(3H，s)，3.66(3H，s)，4.94(2H，s)，7.22(3H，m)，7.30(3H，m)，7.47(3H，m)。
Compound 12: oily matter.δppm?3.73(3H，s)，3.75(3H，s)，3.81(3H，s)，3.82(3H，s)，5.18(2H，s)，5.79(1H，s)，6.90(2H，m)，7.42(3H，m)，7.61(1H，m)，7.66(2H，m)。
Compound 15: fusing point is 90-92 ℃.δppm3.73(3H，s)，3.75(3H，s)，3.81(3H，s)，5.18(2H，s)，5.83(1H，s)，7.43(3H，m)，7.47(1H，m)，7.50(1H，m)，7.60(3H，m)。
Compound 16: fusing point is 93-95 ℃.δppm 2.36(3H，s)，3.74(3H，s)，3.76(3H，s)，3.82(3H，s)，5.19(2H，s)，5.83(1H，s)，7.19(2H，d)，7.42(3H，m)，7.63(3H，d)。
Compound 17: oily matter.δppm?1.27(3H，t)，1.89(3H，s)，2.70(2H，q)，3.62(3H，s)，3.78(6H，s)5.32(2H，s)，7.22(2H，m)，7.28(2H，m)，7.40(3H，m)，7.70(1H，m)。
Compound 20: oily matter.δppm?3.57(6H，s)，3.79(6H，s)，5.26(2H，s)，5.73(1H，s)，7.37(6H，m)，7.50(1H，m)，7.69(1H，d)。
Compound 26: fusing point is 114-116 ℃.δppm?3.75(6H，s)，3.81(3H，s)，4.79(2H，t)，5.21(2H，s)，5.83(1H，s)，7.44(3H，m)，7.58(1H，d)，8.06(1H，dd)，8.44(1H，s)。
Compound 28: oily matter.δppm?3.72(3H，s)，3.75(3H，s)，3.82(3H，s)，5.17(2H，s)，5.78(1H，s)，6.43(1H，dd)，6.58(1H，m)，7.41(4H，m)，7.59(1H，m)。
Compound 29: oily matter.δppm?3.69(3H，s)，3.74(3H，s)，3.81(3H，s)，5.16(2H，s)，5.70(1H，s)，6.82(1H，m)，6.98(1H，m)，7.42(3H，m)，7.56(1H，m)。
Compound 31: oily matter.δppm?3.73(3H，s)，3.76(3H，s)，3.82(3H，s)，5.18(2H，s)，5.78(1H，s)，7.01(1H，m)，7.20(1H，m)，7.24(1H，d)，7.42(3H，m)，7.60(1H，m)。
Compound 63: fusing point is 66-68 ℃.δppm?1.90(3H，s)，3.62(3H，s)，3.79(6H，s)，5.32(2H，s)，7.30(2H，d)，7.42(6H，m)，7.72(1H，d)，7.60(3H，m)。
Compound 64: oily matter.δppm?1.68(3H，s)，3.60(3H，s)，3.79(6H，s)，5.30(2H，s)，7.25(2H，d)，7.42(5H，m)，7.72(1H，d)。
Compound 74: oily matter.δppm?1.88(3H，s)，3.61(3H，s)，3.78(3H，s)，3.79(3H，s)，3.86(3H，s)，5.32(2H，s)，6.99(2H，m)，7.22(2H，m)，7.40(3H，m)，7.69(1H，m)。
Compound 78: oily matter.δppm?1.89(3H，s)，2.05(3H，s)，3.61(3H，s)，3.78(6H，s)，5.31(2H，s)，7.22(2H，d)，7.29(1H，d)，7.38(3H，m)，7.71(1H，m)。
Compound 107: oily matter.δppm?2.39(3H，s)，3.74(3H，s)，3.76(3H，s)，3.83(3H，s)，5.32(2H，s)，5.56(1H，s)，7.24(2H，d)，7.42(3H，m)，7.63(3H，d)。
Compound 185: oily matter.δppm?3.61(3H，s)，3.78(6H，s)，6.41(2H，s)，7.20(1H，m)，7.35(5H，m)，7.42(1H，m)，7.72(2H，d)，8.50(1H，s)。
Compound 194: oily matter.δppm?1.50(6H，s)，3.61(3H，s)，3.77(6H，s)，6.32(1H，s)，7.40(1H，s)，7.20(1H，m)，7.34(6H，m)，7.48(1H，s)，7.74(2H，d)，8.50(1H，s)。
Compound 199: fusing point is 142-144 ℃.δppm?2.37(3H，s)，3.61(3H，s)，3.77(6H，s)，6.39(2H，dd)，7.19(3H，d)，7.38(2H，m)，7.42(1H，m)，7.46(1H，s)，7.68(2H，d)，8.50(1H，s)。
Compound 204: oily matter.δppm?3.62(3H，s)，3.78(6H，s)，6.43(2H，m)，7.19(1H，d)，7.38(4H，m)，7.48(1H，s)，8.08(1H，d)，8.50(1H，s)，8.78(1H，s)。
Compound 367: fusing point is 130-132 ℃.δppm?3.69(3H，s)，3.71(3H，s)，3.84(3H，s)，5.03(2H，s)，5.72(1H，s)，6.43(1H，dd)，6.61(1H，dd)，7.17(1H，m)，7.38(3H，m)，7.48(1H，m)，7.61(1H，s)。
Compound 368: fusing point is 92-94 ℃.δppm?3.65(3H，s)，3.71(3H，s)，3.83(3H，s)，5.01(2H，s)，5.62(1H，s)，6.81(1H，d)，6.98(1H，d)，7.20(1H，m)，7.37(2H，m)，7.48(1H，m)，7.60(1H，s)。
Compound 370: fusing point is 96-98 ℃.δppm?3.69(3H，s)，3.71(3H，s)，3.84(3H，s)，5.03(2H，s)，5.70(1H，s)，7.02(1H，m)，7.21(2H，m)，7.27(1H，m)，7.29(2H，m)，7.38(1H，m)，7.61(1H，s)。
Compound 391: fusing point is 127-130 ℃.δppm 3.65(3H，s)，3.85(3H，s)，4.06(3H，s)，5.00(2H，s)，5.86(1H，s)，7.02(1H，m)，7.21(3H，m)，7.48(3H，m)。
Compound 392: oily matter.δppm?3.72(3H，s)，3.84(3H，s)，4.04(3H，s)，5.02(2H，s)，5.60(1H，m)，6.94(1H，m)，7.21(1H，m)，7.46(4H，m)。
Compound 394: fusing point is 88-90 ℃.δppm?3.68(3H，s)，3.85(3H，s)，4.06(3H，s)，5.01(2H，s)，5.73(1H，s)，6.42(1H，m)，6.62(2H，m)，7.25(1H，m)，7.41(2H，m)，7.46(1H，m)。
Compound 415: fusing point is 139-141 ℃.δppm?2.92(3H，d)，3.64(3H，s)，3.96(3H，s)，5.00(2H，s)，5.74(1H，s)，6.79(1H，bs)，7.02(1H，m)，7.22(3H，m)，7.45(2H，m)，7.49(1H，m)。
Compound 418: oily matter.δppm?2.89(3H，d)，3.42(3H，s)，3.94(3H，s)，5.16(2H，s)，6.43(1H，m)，6.79(1H，bs)，6.96(1H，m)，7.25(3H，m)，7.46(3H，m)。
Compound 439: oily matter.δppm?3.75(3H，s)，3.77(3H，s)，3.81(3H，s)，3.88(3H，s)，5.20(2H，s)，6.10(1H，s)，6.94(2H，m)，7.26(1H，m)，7.42(3H，m)，7.61(1H，m)，7.87(1H，m)。
Compound 440: oily matter.δppm?2.39(3H，s)，2.52(3H，s)，3.74(6H，s)，3.80(3H，s)，5.18(2H，s)，5.65(1H，s)，6.92(1H，s)，7.42(3H，m)，7.48(1H，m)。
Compound 441: oily matter.δppm?2.39(3H，s)，2.51(3H，s)，3.66(3H，s)，3.69(3H，s)，3.81(3H，s)，5.00(2H，s)，6.56(1H，s)，6.86(1H，s)，7.20(1H，m)，7.35(2H，m)，7.50(1H，m)，7.58(1H，s)。
Compound 442: oily matter.δppm?3.63(3H，s)，3.73(3H，s)，3.85(3H，s)，3.92(3H，s)，4.05(3H，s)，5.00(2H，s)，5.67(1H，s)，6.79(2H，m)，6.92(2H，m)，7.25(1H，m)。
Example of formulations (add-on of active ingredient is metered into after rolling over hundred in the prescription, and all percentage compositions are weight percentage)
Example 5 35% missible oil
Compound 2 (content 97.2%) 35%
Phosphorous acid 10%
Ethoxylated glycerol three acid esters 15%
Pimelinketone complements to 100%
Phosphorous acid is dissolved in the pimelinketone, adds compound 2 and ethoxylated glycerol three acid esters then, obtain transparent solution.
Example 660% wettable powder
Compound 64 (content 98.4%) 60%
Dodecyl sodium naphthalene sulfonate 2%
Sodium lignosulfonate 9%
Kaolin complements to 100%
Compound 64, dodecyl sodium naphthalene sulfonate, sodium lignosulfonate and kaolin (being solid) are mixed, in pulverizer, pulverize, reach standard up to particle.
Example 7 30% aq suspensions
Compound 121 (content 96.8%) 30%
Dodecyl sodium naphthalene sulfonate 4%
Hemicellulose 2%
Propylene oxide 8%
Water complements to 100%
Compound 121 is pulverized in (1mm pearl) in ball mill with 80% and the dodecyl sodium naphthalene sulfonate of answering amount of water.Hemicellulose and propylene oxide are dissolved in all the other water of 20%, stir then to add said components.
Example 8 25% suspension-emulsion enriched materials
Compound 11 (content 96.2%) 25%
The epoxy first and second alkane epoxy propane copolymers 2.5%
Dodecyl alcohol polyoxyethylene glycol phosphoric acid ester 4%
Oxyethyl group tri-glyceride 2%
Calcium dodecylbenzene sulphonate 1.5%
Pimelinketone 30%
The alkylaryl cut complements to 100%
With compound 11 be dissolved in 80% should add (pimelinketone and alkylaryl cut) in the quantity of solvent, add emulsifying agent (dodecyl alcohol polyoxyethylene glycol phosphoric acid ester, oxyethyl group tri-glyceride and calcium dodecylbenzene sulphonate) and dispersion agent (2.5 parts of epoxy first and second alkane epoxy propane copolymers) then, mixture is thoroughly stirred.Mixture is pulverized in ball mill (1mm pearl), and then adds all the other solvents of 20%.
Biological activity determination
Example 9 fungicidal activities are measured
With The compounds of this invention the multiple fungal disease of plant has been carried out determination of activity.Test method is as follows:
Provide protection and therapeutic action are measured and are adopted potted plant assay method.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.Provide protection is measured and at first medicine liquid spray is handled on the plant examination material, carries out the disease inoculation after 24 hours.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.Pathogenic bacteria is then at first inoculated in therapeutic action, and the processing of spraying after 4 days is waited to contrast abundant morbidity back (spraying was handled the back 3-4 days) and carried out assessment surveys.
The partial test result is as follows:
Under 500mg/L dosage, compound 16 grades are 100% to the preventive effect of wheat powdery mildew (BLumeria graminis), and compound 1,15,26,185,367 reaches more than 80%.
Under 500mg/L dosage, compound 1,8,15,194,367,415 etc. are 100% to the preventive effect of cucumber downy mildew (Pseudoperonospora cubenis), and compound 11,391 is 90%.
Under 500mg/L dosage, compound 21 grades are 100% to the preventive effect of gray mold of cucumber (Botrytis cinerea) and wheat powdery mildew.
When 500mg/L, compound 10,20,63,78 etc. are 100% to the preventive effect of cucumber downy mildew and wheat powdery mildew.
Compound 15,20,63,78 preventive effect to cucumber downy mildew under 25mg/L dosage is 100%, and the preventive effect to wheat powdery mildew under 12.5mg/L dosage reaches more than 95%.
Compound 63 is under 100mg/L dosage, and (Colletotrichum lagenarium) has 100% prevention effect to cucumber anthracnose, and preventive effect still is 100% during 1.56mg/L.
Compound 63 removes rice blast (Pyricularia oryzae), tomato late blight (Phytophthora infestans), cucumber downy mildew, wheat powdery mildew, cucumber anthracnose, outside powdery mildew of cucumber (Sphaerotheca fuliginea) and rice sheath blight disease (Rhizoctonia solani) are effective, to scab of cucumber (Cladosporium cucumerinum), canker of apple fruit (Valsa mali), sclerotinia rot of colza (Sclerotinia sclerotiorum) also has active preferably, to leaf muld of tomato (Fulvia fulva), corn southern leaf blight (Helminthosporium maydis), wheat scab (Fusarium graminearum) shows certain activity.
The test-results that compound 63 is prevented and treated rice sheath blight disease and wheat powdery mildew sees the following form 2～4.
Table 2 compound 63 is prevented and treated the test-results of rice sheath blight disease
Table 3 compound 63 control wheat powdery mildew test-results
Figure G68545537150141000D000252
Table 4 compound 63 control wheat powdery mildew test-results
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 pipienspallens) 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 of back 2 days investigation targets.
The partial test result is as follows:
When liquor strength was 600mg/L, compound 15,21,63,64 etc. reached more than 85% mythimna separata, small cabbage moth, black peach aphid, culex pipiens pollens mortality ratio.
Compound 15 is 90% to the black peach aphid mortality ratio under 200mg/L dosage, and compound 63 is 100% to the small cabbage moth mortality ratio under 200mg/L dosage.

Claims (8)

1. aryl ethers compounds, shown in general formula I:
Figure FSB00000096443900011
In the formula:
X 1Be selected from NR 2
X 2Be selected from CH 2
R 1Be selected from hydrogen, halogen atom, nitro, cyano group, CONH 2, 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, C 1-C 12Alkoxy carbonyl C 1-C 12Alkyl, C 1-C 12Halogenated alkoxy C 1-C 12Alkyl, amido C 1-C 12Alkyl;
R 2Be 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;
Q is selected from Q 4:
Figure FSB00000096443900012
Ar is selected from and replaces or unsubstituted phenyl, pyridyl, furans, thiophene or thiazole, and its substituting group is selected from halogen atom, C 1-C 6Alkyl, C 1-C 6Alkoxyl group, C 1-C 6Alkylthio or C 1-C 6Halogenated alkoxy.
2. compound according to claim 1 is characterized in that: in the general formula I
X 1Be selected from NR 2
X 2Be selected from CH 2
R 1Be selected from hydrogen, halogen atom, nitro, cyano group, CONH 2, CH 2CONH 2, CH 2CN, 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 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 6Halogenated alkoxy C 1-C 6Alkyl, amido C 1-C 6Alkyl;
R 2Be selected from hydrogen, C 1-C 6Alkyl, halo C 1-C 6Alkyl, C 1-C 6Alkoxy carbonyl or C 1-C 6Alkoxy carbonyl C 1-C 6Alkyl;
Q＝Q 4；
Ar is selected from and replaces or unsubstituted phenyl, pyridyl, furans, thiophene or thiazole, and its substituting group is selected from halogen atom, C 1-C 6Alkyl, C 1-C 6Alkoxyl group, C 1-C 6Alkylthio or C 1-C 6Halogenated alkoxy.
3. compound according to claim 2 is characterized in that: in the general formula I
X 1Be selected from NR 2
X 2Be selected from CH 2
R 1Be selected from hydrogen, chlorine, bromine, fluorine, nitro, cyano group, CH 2CN or C 1-C 6Alkyl;
R 2Be selected from hydrogen, C 1-C 3Alkyl, halo C 1-C 3Alkyl, C 1-C 3Alkoxy carbonyl or C 1-C 3Alkoxy carbonyl C 1-C 3Alkyl;
Q＝Q 4；
Ar is selected from and replaces or unsubstituted phenyl, pyridyl, furans, thiophene or thiazole, and its substituting group is selected from halogen atom, C 1-C 6Alkyl, C 1-C 6Alkoxyl group, C 1-C 6Alkylthio or C 1-C 6Halogenated alkoxy.
4. compound according to claim 3 is characterized in that: in the general formula I
X 1Be selected from NR 2
X 2Be selected from CH 2
R 1Be selected from hydrogen or methyl;
R 2Be selected from hydrogen, methyl or sec.-propyl;
Q＝Q 4；
Ar is selected from and replaces or unsubstituted phenyl, pyridyl, furans or thiophene, and its substituting group is selected from 1-2 halogen, C 1-C 3Alkyl, C 1-C 3Alkoxyl group, C 1-C 3Alkylthio or C 1-C 3Halogenated alkoxy.
5. preparation method according to the described compound of Formula I of claim 1 is characterized in that: the compound of general formula I is reacted under alkaline condition by the azole compounds of the hydroxyl shown in the formula III and the benzyl halogen shown in the formula IV and makes:
Figure FSB00000096443900021
In the formula, R is a leavings group, is selected from chlorine or bromine; X 1, X 2, R 1, Ar, Q as defined in claim 1.
6. the described compound of Formula I of claim 1 is in the application that prevents and treats pest on crop.
7. the application of the described compound of Formula I of claim 1 germ on the control crop.
8. a desinsection, fungicidal composition is characterized in that containing compound as claimed in claim 1 and agricultural goes up acceptable carrier, and the weight percentage of active ingredient is 1-99% in the composition.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1030749A (en) * 1987-02-09 1989-02-01 帝国化学工业公司 The method for preparing Fungicidal compounds
CN1046275C (en) * 1993-02-23 1999-11-10 巴斯福股份公司 Ortho-substituted 2-methoxyiminophenylacetic acid methylamides
CN1100761C (en) * 1996-06-06 2003-02-05 陶氏益农有限责任公司 Benzyloxy substituted aromatics and their use as fungicides and insecticides
CN100427481C (en) * 2005-05-26 2008-10-22 沈阳化工研究院 An arylether kind compound and its preparation and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1030749A (en) * 1987-02-09 1989-02-01 帝国化学工业公司 The method for preparing Fungicidal compounds
CN1046275C (en) * 1993-02-23 1999-11-10 巴斯福股份公司 Ortho-substituted 2-methoxyiminophenylacetic acid methylamides
CN1100761C (en) * 1996-06-06 2003-02-05 陶氏益农有限责任公司 Benzyloxy substituted aromatics and their use as fungicides and insecticides
CN100427481C (en) * 2005-05-26 2008-10-22 沈阳化工研究院 An arylether kind compound and its preparation and application

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