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CN1187810A - New hydroximic acid derivatives - Google Patents

New hydroximic acid derivatives Download PDF

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Publication number
CN1187810A
CN1187810A CN96194830A CN96194830A CN1187810A CN 1187810 A CN1187810 A CN 1187810A CN 96194830 A CN96194830 A CN 96194830A CN 96194830 A CN96194830 A CN 96194830A CN 1187810 A CN1187810 A CN 1187810A
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China
Prior art keywords
alkyl
group
compound
cycloalkyl
haloalkyl
Prior art date
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Pending
Application number
CN96194830A
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Chinese (zh)
Inventor
桐尾佳惠
前田贵子
佐佐木则雄
外岛德重
泽井伸光
布鲁斯·米利根
约瑟夫·佩雷斯
让－彼埃尔·沃尔斯
丹尼尔·B·甘特
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Bayer CropScience SA
Original Assignee
Rhone Poulenc Agrochimie SA
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Publication date
Application filed by Rhone Poulenc Agrochimie SA filed Critical Rhone Poulenc Agrochimie SA
Priority to CN96194830A priority Critical patent/CN1187810A/en
Publication of CN1187810A publication Critical patent/CN1187810A/en
Pending legal-status Critical Current

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Abstract

Hydroximic acid derivatives of general formula (I), wherein G is either G1 or G2 or G3 or G4 of the formula: R5OC=C(COOR4)-, R5ON=C(COOR4)-, R5ON=C(CONR6R7)-, R5OC=C(CONR6R7)-, X1, X2, X3 are H, halo, HO, mercapto, nitro, SCN, azido, CN, alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, cyanoalkoxy, alkylthio, haloalkylthio, cyanoalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, cycloalkyl, halocycloalkyl group, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio, alkynylthio, amino, alkylamino, dialkylamino, acylamino, alkoxycarbonyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, N-alkylsulfamoyl, N,N-dialkylsulfamoyl, R1, R2 are H or alkyl, haloalkyl, cycloalkyl, halocycloalkyl, cyano, alkoxyalkyl, alkoxycarbonyl; or R1 and R2 can form together a divalent radical R3 is H or alkyl, haloalkyl, cycloalkyl, halocycloalkyl, alkenyl, alkynyl, alkoxyalkyl, alkylthioalkyl, cyanoalkyl, haloalkoxyalkyl, dialkylaminoalkyl, optionally substituted phenyl, optionally substituted benzyl, W is O, S, SO or SO2 R4, R5 are alkyl, R6, R7 are H or alkyl.

Description

New hydroxamic acid derivatives
The present invention relates to be used for the new hydroxamic acid derivatives of plant protection.The invention still further relates to fungicidal and Arthropodicidal dompositions, also relate to these compounds and prevent and treat fungal diseases of plants and kill arthropodan method based on these compounds.
The hydroxamic acid derivatives that is used to prevent and treat fungal disease is known by EP463488 and EP370629.
An object of the present invention is to provide the new hydroxamic acid derivatives of a class, more selection is so just arranged on available product.Have more available product,, and make that according to the particular problem that is intended to solve fungal disease being made control preferably becomes possibility, this desirable really so that various activity profiles are arranged.
Another object of the present invention provides new hydroxamic acid derivatives, and this hydroxamic acid derivatives is being handled fungal disease and killed the performance that improvement is arranged aspect the arthropods of crop.
Another object of the present invention provides such compound, and this compound is particularly handled at the fungal disease of rice, cereal class, fruit tree and vegetables, grape and sugar beet on the control in field of fungal disease, has the spectrum of use of improvement.
Have now found that by being described in product of the present invention hereinafter, above-mentioned purpose can realize whole or in part.
Compound provided by the invention is the hydroxamic acid derivatives of general formula (I): Wherein: G is the G of following formula 1Or G 2Or G 3Or G 4
X 1, X 2, X 3Be hydrogen or halogen atom independently; Hydroxyl, sulfydryl, nitro, thiocyano, azido-, cyano group;
-alkyl or haloalkyl, cyano group alkyl, alkoxyl group, halogenated alkoxy, cyano alkoxy, alkylthio, haloalkyl thio, cyano group alkylthio, alkyl sulphinyl, haloalkyl sulfinyl, alkyl sulphonyl, halogenated alkyl sulfonyl, these alkyl or alkoxyl group are rudimentary group;
-cycloalkyl or halogenated cycloalkyl, thiazolinyl, alkynyl, alkenyloxy, alkynyloxy group, alkenylthio group, alkynes sulfenyl, these alkyl or alkenyl or alkynyl are rudimentary group;
-amino, alkylamino, dialkyl amido, kharophen,
-lower alkoxycarbonyl,
-N-alkyl-carbamoyl,
-N, N-dialkyl amido formyl radical,
-N-alkylsulfamoyl group,
-N, the N-dialkyl sulfamine,
R 1, R 2Be hydrogen atom or alkyl or haloalkyl, cycloalkyl or halogenated cycloalkyl, cyano group, alkoxyalkyl, alkoxy carbonyl independently; Or R 1And R 2Can form divalent group together, as alkylidene group, these alkyl or alkoxyl group or alkylidene group are rudimentary group,
R 3Be hydrogen atom or alkyl or haloalkyl, cycloalkyl or halogenated cycloalkyl, alkenyl, alkynyl, alkoxyalkyl, alkyl-thio-alkyl, cyano group alkyl, halogenated alkoxy alkyl, dialkylaminoalkyl, the optional phenyl that replaces or the optional benzyl that replaces, these alkyl or alkoxyl group or alkenyl or alkynyl are rudimentary group
W is oxygen or sulphur atom, SO and SO 2,
R 4, R 5Be low alkyl group,
R 6, R 7Be hydrogen atom or low alkyl group independently.
In formula (I) compound, according to each the difference of configuration of 2 two keys, and have 4 kinds of different steric isomers (E, E or E, Z or Z, E or Z, Z).The name of E or Z can be with corresponding title cis (syn) and trans (anti), or cis (cis) and trans (trans) replace.These names are known in the art.Specifically, in the such name of EZ, EE or ZE or ZZ, first letter is meant the configuration of G group, and second decides the configuration that letter is meant the hydroxyl oximido.
In some cases, a plurality of optical activity carbon also can be arranged.
Formula (I) and the present invention comprise that also the solid of these compounds leads structure body (comprising enantiomorph), they or isolating or in mixture.
In this article, general term has following connotation:
Halogen atom is meant fluorine, chlorine, bromine or iodine atom;
The adjective " rudimentary " of definition organic group is meant that group is up to 6 carbon atoms;
Alkyl group can be a straight or branched;
The name of " hydroxamic acid derivatives " comprise actual " hydroxamic acid derivatives " (having the O-C=N-O group) and " sulfo-hydroxamic acid derivatives " (having S-C=N-O) both.
The more specifically example that can be used for group of the present invention is:
Low alkyl group such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, neo-pentyl, tert-pentyl, hexyl,
Low-grade cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
Lower alkoxy such as methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, pentyloxy,
Lower alkylthio such as methylthio group, ethylmercapto group, propyl dithiocarbamate, isopropylthio, butyl sulfo-, amyl group sulfo-,
Low-grade halogenated alkyl such as chloromethyl, brooethyl, difluoromethyl, dichloromethyl, trifluoromethyl, 1-chloroethyl, 2-iodine ethyl, 3-chloropropyl, 2-methyl-2-chloropropyl,
Elementary halogenated alkoxy such as trifluoromethoxy, difluoro-methoxy, chlorine difluoro-methoxy, 2-chloroethoxy, 1,1,2,2-tetrafluoro oxyethyl group, 3-chlorine propoxy-, 2,2, the 2-trifluoro ethoxy,
Alkoxy carbonyl such as methoxycarbonyl, ethoxycarbonyl, the different third oxygen carbonyl,
Rudimentary dialkylamino such as dimethylamino, ethyl methylamino-, diethylin, dipropyl amino, diisopropylaminoethyl; It also comprises such group, as pyrrolidyl, piperidino-(1-position only), morpholino.
Some object lessons of compound by general formula (I) representative of the present invention are shown in Table 1, wherein X 3=R 2=H, G=G 1Or G 2Or G 3Or G 4Each abbreviation that is used for this table is defined as follows:
Me is a methyl; Et is an ethyl; N-Pr is a n-propyl; I-Pr is a sec.-propyl; CPr is a cyclopropyl;
Table 1
??N° ????G ????R1，R2 ????X1，X2 ????R3 ????W ????R5 ????R4 ?R6，R7
????1 ????G1 ????H；H ????H，H ????H ????O ????Me ????Me
????2 ????G2 ????H；H ????H，H ????H ????O ????Me ????Me
????3 ????G3 ????H；H ????H，H ????H ????O ????Me ?Me；H
????4 ????G1 ????H；H ????H，H ????Me ????O ????Me ????Me
????5 ????G2 ????H；H ????H，H ????Me ????O ????Me ????Me
????6 ????G3 ????H；H ????H，H ????Me ????O ????Me ?Me；H
????7 ????G1 ????H；H ????H，H ????Et ????O ????Me ????Me
????8 ????G2 ????H；H ????H，H ????Et ????O ????Me ????Me
????9 ????G3 ????H；H ????H，H ????Et ????O ????Me ?Me；H
????10 ????G1 ????H；H ????H，H ????iPr ????O ????Me ????Me
????11 ????G2 ????H；H ????H，H ????iPr ????O ????Me ????Me
????12 ????G3 ????H；H ????H，H ????iPr ????O ????Me ?Me；H
????13 ????G1 ????Me；H ????H，H ????H ????O ????Me ????Me
????14 ????G2 ????Me；H ????H，H ????H ????O ????Me ????Me
????15 ????G3 ????Me；H ????H，H ????H ????O ????Me ?Me；H
????16 ????G1 ????Me；H ????H，H ????Me ????O ????Me ????Me
????17 ????G2 ????Me；H ????H，H ????Me ????O ????Me ????Me
????18 ????G3 ????Me；H ????H，H ????Me ????O ????Me ?Me；H
????19 ????G1 ????Me；H ????H，H ????Et ????O ????Me ????Me
????20 ????G2 ????Me；H ????H，H ????Et ????O ????Me ????Me
????21 ????G3 ????Me；H ????H，H ????Et ????O ????Me ?Me；H
????22 ????G1 ????Me；H ????H，H ????iPr ????O ????Me ????Me
????23 ????G2 ????Me；H ????H，H ????iPr ????O ????Me ????Me
????24 ????G3 ????Me；H ????H，H ????iPr ????O ????Me ?Me；H
????25 ????G1 ????H；H ????H，H ????iPr ????S ????Me ????Me
????26 ????G1 ????H；H ????2-F ????H ????O ????Me ????Me
????27 ????G1 ????H；H ????2-Cl ????H ????O ????Me ????Me
????28 ????G1 ????H；H ????2-Me ????H ????O ????Me ????Me
????29 ????G1 ????H；H ????2-CF3 ????H ????O ????Me ????Me
????30 ??G1 ??H；H ??2-CH 3O ??H ??O ??Me ??Me
????31 ??G1 ??H；H ??2-CN ??H ??O ??Me ??Me
????32 ??G1 ??H；H ??3-F ??H ??O ?Me ?Me
????33 ??G1 ??H；H ??3-Cl ??H ??O ??Me ??Me
????34 ??G1 ??H；H ??3-Me ??H ??O ??Me ??Me
????35 ??G1 ??H；H ??3-CF 3 ??H ??O ??Me ??Me
????36 ??G1 ??H；H ??3-CH 3O ??H ??O ??Me ??Me
????37 ??G1 ??H；H ??3-CN ??H ??O ??Me ??Me
????38 ??G1 ??H；H ??4-F ??H ??O ??Me ??Me
????39 ??G1 ??H；H ??4-Cl ??H ??O ??Me ??Me
????40 ??G1 ??H；H ??4-Me ??H ??O ??Me ??Me
????41 ??G1 ??H；H ??4-CF 3 ??H ??O ??Me ??Me
????42 ??G1 ??H；H ??4-CH 3O ??H ??O ??Me ??Me
????43 ??G1 ??H；H ??4-CN ??H ??O ??Me ??Me
??44 ??G1 ??H；H ??2，4-(F)2 ??H ??O ??Me ??Me
????45 ??G2 ??H；H ??2-F ??H ??O ??Me ??Me
????46 ??G2 ??H；H ??2-Cl ??H ??O ??Me ??Me
????47 ??G2 ??H；H ??2-Me ??H ??O ??Me ??Me
????48 ??G2 ??H；H ??2-CF 3 ??H ??O ??Me ??Me
????49 ??G2 ??H；H ??2-CH 3O ??H ??O ??Me ??Me
????50 ??G2 ??H；H ??2-CN ??H ??O ??Me ??Me
????51 ??G2 ??H；H ??3-F ??H ??O ??Me ??Me
????52 ??G2 ??H；H ??3-Cl ??H ??O ??Me ??Me
????53 ??G2 ??H；H ??3-Me ??H ??O ??Me ??Me
????54 ??G2 ??H；H ??3-CF 3 ??H ??O ??Me ??Me
????55 ??G2 ??H；H ??3-CH 3O ??H ??O ??Me ??Me
????56 ??G2 ??H；H ??3-CN ??H ??O ??Me ??Me
????57 ??G2 ??H；H ??4-F ??H ??O ??Me ??Me
????58 ??G2 ??H；H ??4-Cl ??H ??O ??Me ??Me
????59 ??G2 ??H；H ??4-Me ??H ??O ??Me ??Me
????60 ??G2 ??H；H ??4-CF 3 ??H ??O ??Me ??Me
????61 ??G2 ??H；H ??4-CH 3O ??H ??O ??Me ??Me
????62 ??G2 ??H；H ????4-CN ????H ??O ?Me ?Me
????63 ??G2 ??H；H ????2，4-(F)2 ????H ????O ?Me ?Me
????64 ??G3 ??H；H ????2-F ????H ??O ?Me ?Me；H
????65 ??G3 ??H；H ????2-Cl ????H ??O ?Me ?Me；H
????66 ??G3 ??H；H ????2-Me ????H ??O ?Me ?Me；H
????67 ??G3 ??H；H ????2-CF 3 ????H ??O ?Me ?Me；H
????68 ??G3 ??H；H ????2-CH 3O ????H ??O ?Me ?Me；H
????69 ??G3 ??H；H ????2-CN ????H ??O ?Me ?Me；H
????70 ??G3 ??H；H ????3-F ????H ??O ?Me ?Me；H
????71 ??G3 ??H；H ????3-Cl ????H ??O ?Me ?Me；H
????72 ??G3 ??H；H ????3-Me ????H ??O ?Me ?Me；H
????73 ??G3 ??H；H ????3-CF 3 ????H ??O ?Me ?Me；H
????74 ??G3 ??H；H ????3-CH 3O ????H ??O ?Me ?Me；H
????75 ??G3 ??H；H ????3-CN ????H ??O ?Me ?Me；H
????76 ??G3 ??H；H ????4-F ????H ????O ?Me ?Me；H
????77 ??G3 ??H；H ????4-Cl ????H ??O ?Me ?Me；H
????78 ??G3 ??H；H ????4-Me ????H ??O ?Me ?Me；H
????79 ??G3 ??H；H ????4-CF 3 ????H ??O ?Me ?Me；H
????80 ??G3 ??H；H ????4-CH 3O ????H ??O ?Me ?Me；H
????81 ??G3 ??H；H ????4-CN ????H ??O ?Me ?Me；H
????82 ??G3 ??H；H ??2，4-(F)2 ??H ??O ?Me ?Me；H
????83 ??G1 ??Me；H ????2-F ????H ??O ?Me ?Me
????84 ??G1 ??Me；H ????2-Cl ????H ??O ?Me ?Me
????85 ??G1 ??Me；H ????2-Me ????H ??O ?Me ?Me
????86 ??G1 ??Me；H ????2-CF 3 ????H ??O ?Me ?Me
????87 ??G1 ??Me；H ????2-CH 3O ????H ??O ?Me ?Me
????88 ??G1 ??Me；H ????2-CN ????H ??O ?Me ?Me
????89 ??G1 ??Me；H ????3-F ????H ??O ?Me ?Me
????90 ??G1 ??Me；H ????3-Cl ????H ??O ?Me ?Me
????91 ??G1 ??Me；H ????3-Me ????H ??O ?Me ?Me
????92 ??G1 ??Me；H ????3-CF 3 ????H ??O ?Me ?Me
????93 ??G1 ??Me；H ????3-CH 3O ????H ????O ?Me ?Me
94 ??G1 ??Me；H ????3-CN ????H ????O ?Me ?Me
95 ??G1 ??Me；H ????4-F ????H ????O ?Me ?Me
96 ??G1 ??Me；H ????4-Cl ????H ????O ?Me ?Me
97 ??G1 ??Me；H ????4-Me ????H ????O ?Me ?Me
98 ??G1 ??Me；H ????4-CF 3 ????H ????O ?Me ?Me
99 ??G1 ??Me；H ????4-CH 3O ????H ????O ?Me ?Me
100 ??G1 ??Me；H ????4-CN ????H ????O ?Me ?Me
101 ??G1 ??Me；H ????2，4-(F)2 ????H ????O ?Me ?Me
102 ??G2 ??Me；H ????2-F ????H ????O ?Me ?Me
103 ??G2 ??Me；H ????2-Cl ????H ????O ?Me ?Me
104 ??G2 ??Me；H ????2-Me ????H ????O ?Me ?Me
105 ??G2 ??Me；H ????2-CF 3 ????H ????O ?Me ?Me
106 ??G2 ??Me；H ????2-CH 3O ????H ????O ?Me ?Me
107 ??G2 ??Me；H ????2-CN ????H ????O ?Me ?Me
108 ??G2 ??Me；H ????3-F ????H ????O ?Me ?Me
109 ??G2 ??Me；H ????3-Cl ????H ????O ?Me ?Me
11O ??G2 ??Me；H ????3-Me ????H ????O ?Me ?Me
111 ??G2 ??Me；H ????3-CF 3 ????H ????O ?Me ?Me
112 ??G2 ??Me；H ????3-CH 3O ????H ????O ?Me ?Me
113 ??G2 ??Me；H ????3-CN ????H ????O ?Me ?Me
114 ??G2 ??Me；H ????4-F ????H ????O ?Me ?Me
115 ??G2 ??Me；H ????4-Cl ????H ????O ?Me ?Me
116 ??G2 ??Me；H ????4-Me ????H ????O ?Me ?Me
117 ??G2 ??Me；H ????4-CF 3 ????H ????O ?Me ?Me
118 ??G2 ??Me；H ????4-CH 3O ????H ????O ?Me ?Me
119 ??G2 ??Me；H ????4-CN ????H ????O ?Me ?Me
120 ??G2 ??Me；H ????2，4-(F)2 ????H ????O ?Me ?Me
121 ??G3 ??Me；H ????2-F ????H ????O ?Me ??Me；H
122 ??G3 ??Me；H ????2-Cl ????H ????O ?Me ?Me；H
123 ??G3 ??Me；H ????2-Me ????H ????O ?Me ?Me；H
124 ??G3 ??Me；H ????2-CF 3 ????H ????O ?Me ?Me；H
125 ????G3 ????Me；H ????2-CH 3O ????H ????O ?Me ?Me；H
126 ????G3 ????Me；H ????2-CN ????H ????O ????Me ?Me；H
127 ????G3 ????Me；H ????3-F ????H ????O ????Me ?Me；H
128 ????G3 ????Me；H ????3-Cl ????H ????O ???Me ?Me；H
129 ????G3 ????Me；H ????3-Me ????H ????O ???Me ?Me；H
130 ????G3 ????Me；H ????3-CF 3 ????H ????O ???Me ?Me；H
131 ????G3 ????Me；H ????3-CH 3O ????H ????O ????Me ?Me；H
132 ????G3 ????Me；H ????3-CN ????H ????O ????Me ?Me；H
133 ????G3 ????Me；H ????4-F ????H ????O ????Me ?Me；H
134 ????G3 ????Me；H ????4-Cl ????H ????O ????Me ?Me；H
135 ????G3 ????Me；H ????4-Me ????H ????O ????Me ?Me；H
136 ????G3 ????Me；H ????4-CF 3 ????H ????O ?????Me ?Me；H
137 ????G3 ????Me；H ????4-CH 3O ????H ????O ???Me ?Me；H
138 ????G3 ????Me；H ????4-CN ????H ????O ????Me ?Me；H
139 ????G3 ????Me；H ????2，4-(F)2 ????H ????O ????Me ?Me；H
140 ????G1 ????H；H ????2-F ????Me ????O ????Me ????Me
141 ????G1 ????H；H ????2-Cl ????Me ????O ????Me ????Me
142 ????G1 ????H；H ????2-Me ????Me ????O ????Me ????Me
143 ????G1 ????H；H ????2-CF 3 ????Me ????O ????Me ????Me
144 ????G1 ????H；H ????2-CH 3O ????Me ????O ????Me ????Me
145 ????G1 ????H；H ????2-CN ????Me ????O ????Me ????Me
146 ????G1 ????H；H ????3-F ????Me ????O ????Me ????Me
147 ????G1 ????H；H ????3-Cl ????Me ????O ????Me ????Me
148 ????G1 ????H；H ????3-Me ????Me ????O ????Me ????Me
149 ????G1 ????H；H ????3-CF 3 ????Me ????O ????Me ????Me
150 ????G1 ????H；H ????3-CH 3O ????Me ????O ????Me ????Me
151 ????G1 ????H；H ????3-CN ????Me ????O ????Me ????Me
152 ????G1 ????H；H ????4-F ????Me ????O ????Me ????Me
153 ????G1 ????H；H ????4-Cl ????Me ????O ????Me ????Me
154 ????G1 ????H；H ????4-Me ????Me ????O ????MMe ????Me
155 ????G1 ????H；H ????4-CF 3 ????Me ????O ????Me ????Me
156 ????G1 ????H；H ????4-CH 3O ????Me ????O ????Me ????Me
157 ????G1 ????H；H ????4-CN ????Me ????O ????Me ????Me
158 ??G1 ??H；H ??2，4-(F)2 ??Me ??O ?Me ?Me
159 ??G2 ??H；H ??2-F ??Me ??O ?Me ?Me
160 ??G2 ??H；H ??2-Cl ??Me ??O ?Me ?Me
161 ??G2 ??H；H ??2-Me ??Me ??O ?Me ?Me
162 ??G2 ??H；H ??2-CF 3 ??Me ??O ?Me ?Me
163 ??G2 ??H；H ??2-CH 3O ??Me ??O ?Me ?Me
164 ??G2 ??H；H ??2-CN ??Me ??O ?Me ?Me
165 ??G2 ??H；H ??3-F ??Me ??O ?Me ?Me
166 ??G2 ??H；H ??3-Cl ??Me ??O ?Me ?Me
167 ??G2 ??H；H ??3-Me ??Me ??O ?Me ?Me
168 ??G2 ??H；H ??3-CF 3 ??Me ??O ?Me ?Me
169 ??G2 ??H；H ??3-CH 3O ??Me ??O ?Me ?Me
170 ??G2 ??H；H ??3-CN ??Me ??O ?Me ?Me
171 ??G2 ??H；H ??4-F ??Me ??O ?Me ?Me
172 ??G2 ??H；H ??4-Cl ??Me ??O ?Me ?Me
173 ??G2 ??H；H ??4-Me ??Me ??O ??Me ??Me
174 ??G2 ??H；H ??4-CF 3 ??Me ??O ?Me ?Me
175 ??G2 ??H；H ??4-CH 3O ??Me ??O ?Me ?Me
176 ??G2 ??H；H ??4-CN ??Me ??O ?Me ?Me
177 ??G2 ??H；H ??2，4-(F)2 ??Me ??O ?Me ?Me
178 ??G3 ??H；H ??2-F ??Me ??O ?Me ?Me；H
179 ??G3 ??H；H ??2-Cl ??Me ??O ?Me ?Me；H
180 ??G3 ??H；H ??2-Me ??Me ??O ?Me ?Me；H
181 ??G3 ??H；H ??2-CF 3 ??Me ??O ?Me ?Me；H
182 ??G3 ??H；H ??2-CH 3O ??Me ??O ?Me ?Me；H
183 ??G3 ??H；H ??2-CN ??Me ??O ?Me ?Me；H
184 ??G3 ??H；H ??3-F ??Me ??O ?Me ?Me；H
185 ??G3 ??H；H ??3-Cl ??Me ??O ?Me ?Me；H
186 ??G3 ??H；H ??3-Me ??Me ??O ?Me ?Me；H
187 ??G3 ??H；H ??3-CF 3 ??Me ??O ?Me ?Me；H
188 ??G3 ??H；H ??3-CH 3O ??Me ??O ?Me ?Me；H
189 ??G3 ??H；H ??3-CN ??Me ??O ?Me ?Me；H
?190 ??G3 ??H；H ????4-F ??Me ??O ?Me ?Me；H
?191 ??G3 ??H；H ????4-Cl ??Me ??O ?Me ?Me；H
?192 ??G3 ??H；H ????4-Me ??Me ??O ?Me ?Me；H
?193 ????G3 ????H；H ????4-CF 3 ??Me ??O ?Me ?Me；H
?194 ??G3 ??H；H ????4-CH 3O ??Me ??O ?Me ?Me；H
?195 ??G3 ??H；H ????4-CN ??Me ??O ?Me ?Me；H
?196 ??G3 ??H；H ????2，4-(F)2 ??Me ??O ?Me ?Me；H
?197 ??G1 ??Me；H ????2-F ??Me ??O ?Me ?Me
?198 ??G1 ??Me；H ????2-Cl ??Me ??O ?Me ?Me
?199 ??G1 ??Me；H ????2-Me ??Me ??O ?Me ?Me
?200 ??G1 ??Me；H ????2-CF 3 ??Me ??O ?Me ?Me
?201 ??G1 ??Me；H ????2-CH 3O ??Me ??O ?Me ?Me
?202 ??G1 ??Me；H ????2-CN ??Me ??O ?Me ?Me
?203 ??G1 ??Me；H ????2-Br ??Me ??O ?Me ?Me
?204 ??G1 ??Me；H ????2-MeS ??Me ??O ?Me ?Me
?205 ??G1 ??Me；H ????2-CF 3O ??Me ??O ?Me ?Me
?206 ??G1 ??Me；H ????2-CF 3S ??Me ??O ?Me ?Me
?207 ??G1 ??Me；H ????2-NO 2 ??Me ??O ?Me ?Me
?208 ??G1 ??Me；H ????2-Et ??Me ??O ?Me ?Me
?209 ??G1 ??Me；H ????2-MeOC(O) ??Me ??O ?Me ?Me
?21O ??G1 ??Me；H ????2-(Me) 2N ??Me ??O ?Me ?Me
?211 ??G1 ??Me；H ????3-F ??Me ??O ?Me ?Me
?212 ??G1 ??Me；H ????3-Cl ??Me ??O ?Me ?Me
?213 ??G1 ??Me；H ????3-Me ??Me ??O ?Me ?Me
?214 ??G1 ??Me；H ????3-CF 3 ??Me ??O ?Me ?Me
?215 ??G1 ??Me；H ????3-CH 3O ??Me ??O ?Me ?Me
?216 ??G1 ??Me；H ????3-CN ??Me ??O ?Me ?Me
?217 ??G1 ??Me；H ????3-Br ??Me ??O ?Me ?Me
?218 ??G1 ??Me；H ????3-MeS ??Me ??O ?Me ?Me
?219 ??G1 ??Me；H ????3-CF 3O ??Me ??O ?Me ?Me
?220 ??G1 ??Me；H ????3-CF 3S ??Me ??O ?Me ?Me
?221 ??G1 ??Me；H ????3-NO 2 ??Me ??O ?Me ?Me
?222 ??G1 ??Me；H ????3-Et ??Me ??O ?Me ?Me
?223 ?G1 ?Me；H ???3-MeOC(O) ??Me ??O ?Me ?Me
?224 ?G1 ?Me；H ???3-(Me)2N ??Me ??O ?Me ?Me
?225 ?G1 ?Me；H ???4-F ??Me ??O ?Me ?Me
?226 ?G1 ?Me；H ???4-Cl ??Me ??O ?Me ?Me
?227 ?G1 ?Me；H ???4-Me ??Me ??O ?Me ?Me
?228 ?G1 ?Me；H ???4-CF 3 ??Me ??O ?Me ?Me
?229 ?G1 ?Me；H ???4-CH 3O ??Me ??O ?Me ?Me
?230 ?G1 ?Me；H ???4-CN ??Me ??O ?Me ?Me
?231 ?G1 ?Me；H ???4-Br ??Me ??O ?Me ?Me
?232 ?G1 ?Me；H ???4-MeS ??Me ??O ?Me ?Me
?233 ?G1 ?Me；H ???4-CF 3O ??Me ??O ?Me ?Me
?234 ?G1 ?Me；H ???4-CF 3S ??Me ??O ?Me ?Me
?235 ?G1 ?Me；H ???4-NO 2 ??Me ??O ?Me ?Me
?236 ?G1 ?Me；H ???4-Et ??Me ??O ?Me ?Me
?237 ?G1 ?Me；H ???4-MeOC(O) ??Me ??O ?Me ?Me
?238 ?G1 ?Me；H ???4-(Me) 2N ??Me ??O ?Me ?Me
?239 ?G1 ?Me；H ???2，3-(F) 2 ??Me ??O ?Me ?Me
?240 ?G1 ?Me；H ???2，4-(F) 2 ??Me ??O ?Me ?Me
?241 ?G1 ?Me；H ???2，5-(F) 2 ??Me ??O ?Me ?Me
?242 ?G1 ?Me；H ???2，6-(F) 2 ??Me ??O ?Me ?Me
?243 ?G1 ?Me；H ???3，4-(F) 2 ??Me ??O ?Me ?Me
?244 ?G1 ?Me； H ???3，5-(F) 2 ??Me ??O ?Me ?Me
?245 ?G1 ?Me；H ???2，3-(Me) 2 ??Me ??O ?Me ?Me
?246 ?G1 ?Me；H ???2，4-(Me) 2 ??Me ??O ?Me ?Me
?247 ?G1 ?Me；H ???2，5-(Me) 2 ??Me ??O ?Me ?Me
?248 ?G1 ?Me；H ???2，6-(Me) 2 ??Me ??O ?Me ?Me
?249 ?G1 ?Me；H ???3，4-(Me) 2 ??Me ??O ?Me ?Me
?250 ?G1 ?Me；H ???3，5-(Me) 2 ??Me ??O ?Me ?Me
?251 ?G1 ?Me；H ???2，4-(F) 2 ??Me ??O ?Me ?Me
?252 ?G2 ?Me；H ???2-F ??Me ??O ?Me ?Me
?253 ?G2 ?Me；H ???2-Cl ??Me ??O ?Me ?Me
?254 ?G2 ?Me；H ????2-Me ??Me ??O ?Me ?Me
?255 ?G2 ?Me；H ????2-CF 3 ??Me ??O ?Me ?Me
?256 ?G2 ?Me；H ????2-CH 3O ??Me ??O ?Me ?Me
?257 ?G2 ?Me；H ????2-CN ????Me ????O ?Me ?Me
?258 ?G2 ?Me；H ????3-F ??Me ??O ?Me ?Me
?259 ?G2 ?Me；H ????3-Cl ??Me ??O ?Me ?Me
?260 ?G2 ?Me；H ????3-Me ??Me ??O ?Me ?Me
?261 ?G2 ?Me；H ????3-CF 3 ??Me ??O ?Me ?Me
?262 ?G2 ?Me；H ????3-CH 3O ??Me ??O ?Me ?Me
?263 ?G2 ?Me；H ????3-CN ??Me ??O ?Me ?Me
?264 ?G2 ?Me；H ????4-F ??Me ??O ?Me ?Me
?265 ?G2 ?Me；H ????4-Cl ??Me ??O ?Me ?Me
?266 ?G2 ?Me；H ????4-Me ??Me ??O ?Me ?Me
?267 ?G2 ?Me；H ????4-CF 3 ??Me ??O ?Me ?Me
?268 ?G2 ?Me；H ???4-CH 3O ??Me ??O ?Me ?Me
?269 ?G2 ?Me；H ????4-CN ??Me ??O ?Me ?Me
?270 ?G2 ?Me；H ????2，4-(F) 2 ??Me ??O ?Me ?Me
?271 ?G3 ?Me；H ????2-F ??Me ??O ?Me ?Me；H
?272 ?G3 ?Me；H ????2-Cl ??Me ??O ?Me ?Me；H
?273 ?G3 ?Me；H ????2-Me ??Me ??O ?Me ?Me；H
?274 ?G3 ?Me；H ????2-CF 3 ??Me ??O ?Me ?Me；H
?275 ?G3 ?Me；H ????2-CH 3O ??Me ??O ?Me ?Me；H
?276 ?G3 ?Me；H ????2-CN ??Me ??O ?Me ?Me；H
?277 ?G3 ?Me；H ????3-F ??Me ??O ?Me ?Me；H
?278 ?G3 ?Me；H ????3-Cl ??Me ??O ?Me ?Me；H
?279 ?G3 ?Me；H ????3-Me ??Me ??O ?Me ?Me；H
?280 ?G3 ?Me；H ????3-CF 3 ??Me ??O ?Me ?Me；H
?281 ?G3 ?Me；H ????3-CH 3O ??Me ??O ?Me ?Me；H
?282 ?G3 ?Me；H ????3-CN ??Me ??O ?Me ?Me；H
?283 ?G3 ?Me；H ????4-F ??Me ??O ?Me ?Me；H
?284 ?G3 ?Me；H ????4-Cl ??Me ??O ??Me ??Me；H
??285 ?G3 ?Me；H ????4-Me ??Me ??O ??Me ??Me；H
?286 ?G3 ?Me；H ?4-CF 3 ?Me ?O ?Me ?Me；H
?287 ?G3 ?Me；H ?4-CH 3O ?Me ?O ?Me ?Me；H
?288 ?G3 ?Me；H ?4-CN ?Me ?O ?Me ?Me；H
?289 ?G3 ?Me；H ?2，4-(F) 2 ?Me ?O ?Me ?Me；H
?290 ?G1 ?Me；H ?2-F ?Et ?O ?Me ?Me
?291 ?G1 ?H；H ?2-Cl ?Et ?O ?Me ?Me
?292 ?G1 ?H；H ?2-Me ?Et ?O ?Me ?Me
?293 ?G1 ?H；H ?2-CF 3 ?Et ?O ?Me ?Me
?294 ?G1 ?H；H ?2-CH 3O ?Et ?O ?Me ?Me
?295 ?G1 ?H；H ?2-CN ?Et ?O ?Me ?Me
?296 ?G1 ?H；H ?3-F ?Et ?O ?Me ?Me
?297 ?G1 ?H；H ?3-Cl ?Et ?O ?Me ?Me
?298 ?G1 ?H；H ?3-Me ?Et ?O ?Me ?Me
?299 ?G1 ?H；H ?3-CF 3 ?Et ?O ?Me ?Me
?300 ?G1 ?H；H ?3-CH 3O ?Et ?O ?Me ?Me
?301 ?G1 ?H；H ?3-CN ?Et ?O ?Me ?Me
?302 ?G1 ?H；H ?4-F ?Et ?O ?Me ?Me
?303 ?G1 ?H；H ?4-Cl ?Et ?O ?Me ?Me
?304 ?G1 ?H；H ?4-Me ?Et ?O ?Me ?Me
?305 ?G1 ?H；H ?4-CF 3 ?Et ?O ?Me ?Me
?306 ?G1 ?H；H ?4-CH 3O ?Et O ?Me ?Me
?307 ?G1 ?H；H ?4-CN ?Et ?O ?Me ?Me
?308 ?G1 ?H；H ?2，4-(F) 2 ?Et ?O ?Me ?Me
?309 ?G2 ?H；H ?2-F ?Et ?O ?Me ?Me
?310 ?G2 ?H；H ?2-Cl ?Et ?O ?Me ?Me
?311 ?G2 ?H；H ?2-Me ?Et ?O ?Me ?Me
?312 ?G2 ?H；H ?2-CF 3 ?Et ?O ?Me ?Me
?313 ?G2 ?H；H ?2-CH 3O ?Et ?O ?Me ?Me
?314 ?G2 ?H；H ?2-CN ?Et ?O ?Me ?Me
?315 ?G2 ?H；H ?3-F ?Et ?O ?Me ?Me
?316 ?G2 ?H；H ?3-Cl ?Et ?O ?Me ?Me
?317 ?G2 ?H；H ?3-Me ?Et ?O ?Me ?Me
?318 ?G2 ?H；H ?3-CF 3 ?Et ?O ?Me ?Me
?319 ?G2 ?H；H ?3-CH 3O ?Et ?O ?Me ?Me
?320 ?G2 ?H；H ?3-CN ?Et ?O ?Me ?Me
?321 ?G2 ?H；H ?4-F ?Et ?O ?Me ?Me
?322 ?G2 ?H；H ?4-Cl ?Et ?O ?Me ?Me
?323 ?G2 ?H；H ?4-Me ?Et ?O ?Me ?Me
?324 ?G2 ?H；H ?4-CF 3 ?Et ?O ?Me ?Me
?325 ?G2 ?H；H ?4-CH 3O ?Et ?O ?Me ?Me
?326 ?G2 ?H；H ?4-CN ?Et ?O ?Me ?Me
?327 ?G2 ?H；H ?2，4-(F) 2 ?Et ?O ?Me ?Me
?328 ?G3 ?H；H ?2-F ?Et ?O ?Me ?Me；H
?329 ?G3 ?H；H ?2-Cl ?Et ?O ?Me ?Me；H
?330 ?G3 ?H；H ?2-Me ?Et ?O ?Me ?Me；H
?331 ?G3 ?H；H ?2-CF 3 ?Et ?O ?Me ?Me；H
?332 ?G3 ?H；H ?2-CH 3O ?Et ?O ?Me ?Me；H
?333 ?G3 ?H；H ?2-CN ?Et ?O ?Me ?Me；H
?334 ?G3 ?H；H ?3-F ?Et ?O ?Me ?Me；H
?335 ?G3 ?H；H ?3-Cl ?Et ?O ?Me ?Me；H
?336 ?G3 ?H；H ?3-Me ?Et ?O ?Me ?Me；H
?337 ?G3 ?H；H ?3-CF 3 ?Et ?O ?Me ?Me；H
?338 ?G3 ?H；H ?3-CH3O ?Et ?O ?Me ?Me；H
?339 ?G3 ?H；H ?-CN ?Et ?O ?Me ?Me；H
?340 ?G3 ?H；H ?4-F ?Et ?O ?Me ?Me；H
?341 ?G3 ?H；H ?4-Cl ?Et ?O ?Me ?Me；H
?342 ?G3 ?H；H ?4-Me ?Et ?O ?Me ?Me；H
?343 ?G3 ?H；H ?4-CF3 ?Et ?O ?Me ?Me；H
?344 ?G3 ?H；H ?4-CH3O ?Et ?O ?Me ?Me；H
?345 ?G3 ?H；H ?4-CN ?Et ?O ?Me ?Me；H
?346 ?G3 ?H；H ?2，4-(F)2 ?Et ?O ?Me ?Me；H
?347 ?G1 ?Me；H ?2-F ?Et ?O ?Me ?Me
?348 ?G1 ?Me；H ?2-Cl ?Et ?O ?Me ?Me
?349 ?G1 ?Me；H ?2-Me ?Et ?O ?Me ?Me
?350 ?G1 ?Me；H ????2-CF3 ????Et ????O ?Me ?Me
?351 ?G1 ?Me；H ????2-CH3O ????Et ????O ?Me ?Me
?352 ?G1 ?Me；H ????2-CN ????Et ????O ?Me ?Me
?353 ?G1 ?Me；H ????3-F ????Et ????O ?Me ?Me
?354 ?G1 ?Me；H ????3-Cl ????Et ????O ?Me ?Me
?355 ?G1 ?Me；H ????3-Me ????Et ????O ?Me ?Me
?356 ?G1 ?Me；H ????3-CF3 ????Et ????O ?Me ?Me
?357 ?G1 ?Me；H ????3-CH3O ????Et ????O ?Me ?Me
?358 ?G1 ?Me；H ????3-CN ????Et ????O ?Me ?Me
?359 ?G1 ?Me；H ????4-F ????Et ????O ?Me ?Me
?360 ?G1 ?Me；H ????4-Cl ????Et ????O ??Me ??Me
?361 ??G1 ??Me；H ????4-Me ????Et ????O ?Me ?Me
?362 ?G1 ?Me；H ????4-CF3 ????Et ????O ?Me ?Me
?363 ?G1 ?Me；H ????4-CH3O ????Et ????O ?Me ?Me
?364 ?G1 ?Me；H ????4-CN ????Et ????O ?Me ?Me
?365 ?G1 ?Me；H ????2，4-(F)2 ????Et ????O ?Me ?Me
?366 ?G2 ?Me；H ????2-F ????Et ????O ?Me ?Me
?367 ?G2 ?Me；H ????2-Cl ????Et ????O ?Me ?Me
?368 ?G2 ?Me；H ????2-Me ????Et ????O ?Me ?Me
?369 ?G2 ?Me；H ????2-CF3 ????Et ????O ?Me ?Me
?370 ?G2 ?Me；H ????2-CH3O ????Et ????O ?Me ?Me
?371 ?G2 ?Me；H ????2-CN ????Et ????O ?Me ?Me
?372 ?G2 ?Me；H ????3-F ????Et ????O ?Me ?Me
?373 ?G2 ?Me；H ????3-Cl ????Et ????O ?Me ?Me
?374 ?G2 ?Me；H ????3-Me ????Et ????O ?Me ?Me
?375 ?G2 ?Me；H ????3-CF3 ????Et ????O ?Me ?Me
?376 ?G2 ?Me；H ????3-CH3O ????Et ????O ?Me ?Me
?377 ?G2 ?Me；H ????3-CN ????Et ????O ??Me ??Me
?378 ??G2 ??Me；H ????4-F ????Et ????O ?Me ?Me
?379 ?G2 ?Me；H ????4-Cl ????Et ????O ?Me ?Me
?380 ?G2 ?Me；H ????4-Me ????Et ????O ?Me ?Me
?381 ?G2 ?Me；H ????4-CF3 ????Et ????O ?Me ?Me
?382 ?G2 ?Me；H ??4-CH3O ??Et ??O ?Me ?Me
?383 ?G2 ?Me；H ??4-CN ??Et ??O ?Me ?Me
?384 ?G2 ?Me；H ??2，4-(F)2 ??Et ??O ?Me ?Me
?385 ?G3 ?Me；H ??2-F ??Et ??O ?Me ?Me；H
?386 ?G3 ?Me；H ??2-Cl ??Et ??O ?Me ?Me；H
?387 ?G3 ?Me；H ??2-Me ??Et ??O ?Me ?Me；H
?388 ?G3 ?Me；H ??2-CF3 ??Et ??O ?Me ?Me；H
?389 ?G3 ?Me；H ??2-CH3O ??Et ??O ?Me ?Me；H
?390 ?G3 ?Me；H ??2-CN ??Et ??O ?Me ?Me；H
?391 ?G3 ?Me；H ??3-F ??Et ??O ?Me ?Me；H
?392 ?G3 ?Me；H ??3-Cl ??Et ??O ?Me ?Me；H
?393 ?G3 ?Me；H ??3-Me ??Et ??O ?Me ?Me；H
?394 ?G3 ?Me；H ??3-CF3 ??Et ??O ?Me ?Me；H
?395 ?G3 ?Me；H ??3-CH3O ??Et ??O ?Me ?Me；H
?396 ?G3 ?Me；H ??3-CN ??Et ??O ?Me ?Me；H
?397 ?G3 ?Me；H ??4-F ??Et ??O ?Me ?Me；H
?398 ?G3 ?Me；H ??4-Cl ??Et ??O ?Me ?Me；H
?399 ?G3 ?Me；H ??4-Me ??Et ??O ?Me ?Me；H
?400 ?G3 ?Me；H ??4-CF3 ??Et ??O ?Me ?Me；H
?401 ?G3 ?Me；H ??4-CH3O ??Et ??O ?Me ?Me；H
?402 ?G3 ?Me；H ??4-CN ??Et ??O ?Me ?Me；H
?403 ?G3 ?Me；H ??2，4-(F)2 ??Et ??O ?Me ?Me；H
?404 ?G1 ?Me；H ??2-F ??iPr ??O ?Me ?Me
?405 ?G1 ?Me；H ??2-Cl ??iPr ??O ?Me ?Me
?406 ?G1 ?H；H ??2-Me ??iPr ??O ?Me ?Me
?407 ?G1 ?H；H ??2-CF3 ??iPr ??O ?Me ?Me
?408 ?G1 ?H；H ??2-CH3O ??iPr ??O ?Me ?Me
?409 ?G1 ?H；H ??2-CN ??iPr ??O ?Me ?Me
?410 ?G1 ?H；H ??3-F ??iPr ??O ?Me ?Me
?411 G1 ?H；H ??3-Cl ??iPr ??O ?Me ?Me
?412 ?G1 ?H；H ??3-Me ??iPr ??O ?Me ?Me
?413 ?G1 ?H；H ??3-CF3 ??iPr ??O ?Me ?Me
?414 ?G1 ?H；H ????3-CH3O ????iPr ????O ?Me ?Me
?415 ?G1 ?H；H ????3-CN ????iPr ????O ?Me ?Me
?416 ?G1 ?H；H ????4-F ????iPr ????O ?Me ?Me
?417 ?G1 ?H；H ????4-Cl ????iPr ????O ?Me ?Me
?418 ?G1 ?H；H ????4-Me ????iPr ????O ?Me ?Me
?419 ?G1 ?H；H ????4-CF3 ????iPr ????O ?Me ?Me
?420 ?G1 ?H；H ????4-CH3O ????iPr ????O ?Me ?Me
?421 ?G1 ?H；H ????4-CN ????iPr ????O ?Me ?Me
?422 ?G1 ?H；H ????2，4-(F)2 ????iPr ????O ?Me ?Me
?423 ?G2 ?H；H ????2-F ????iPr ????O ?Me ?Me
?424 ?G2 ?H；H ????2-Cl ????iPr ????O ?Me ?Me
?425 ?G2 ?H；H ????2-Me ????iPr ????O ?Me ?Me
?426 ?G2 ?H；H ????2-CF3 ????iPr ????O ?Me ?Me
?427 ?G2 ?H；H ????2-CH3O ????iPr ????O ?Me ?Me
?428 ?G2 ?H；H ????2-CN ????iPr ????O ?Me ?Me
?429 ?G2 ?H；H ????3-F ????iPr ????O ?Me ?Me
?430 ?G2 ?H；H ????3-Cl ????iPr ????O ?Me ?Me
?431 ?G2 ?H；H ????3-Me ????iPr ????O ?Me ?Me
?432 ?G2 ?H；H ????3-CF3 ????iPr ????O ?Me ?Me
?433 ?G2 ?H；H ????3-CH3O ????iPr ????O ?Me ?Me
?434 ?G2 ?H；H ????3-CN ????iPr ????O ?Me ?Me
?435 ?G2 ?H；H ????4-F ????iPr ????O ?Me ?Me
?436 ?G2 ?H；H ????4-Cl ????iPr ????O ?Me ?Me
?437 ?G2 ?H；H ????4-Me ????iPr ????O ?Me ?Me
?438 ?G2 ?H；H ????4-CF3 ????iPr ????O ?Me ?Me
?439 ?G2 ?H；H ????4-CH3O ????iPr ????O ?Me ?Me
?440 ?G2 ?H；H ????4-CN ????iPr ????O ?Me ?Me
?441 ?G2 ?H；H ????2，4-(F)2 ????iPr ????O ?Me ?Me
?442 ?G3 ?H；H ????Z-F ????iPr ????O ?Me ?Me；H
?443 ?G3 ?H；H ????2-Cl ????iPr ????O ?Me ?Me；H
?444 ?G3 ?H；H ????2-Me ????iPr ????O ?Me ?Me；H
?445 ?G3 ?H；H ????2-CF3 ????iPr ????O ??Me ??Me；H
??446 ?G3 ?H；H ????2-CH3O ??iPr ??O ?Me ?Me；H
?447 ?G3 ?H；H ????2-CN ??iPr ??O ?Me ?Me；H
?448 ?G3 ?H；H ????3-F ??iPr ??O ?Me ?Me；H
?449 ?G3 ?H；H ????3-Cl ??iPr ??O ?Me ?Me；H
?450 ?G3 ?H；H ????3-Me ??iPr ??O ?Me ?Me；H
?451 ?G3 ?H；H ????3-CF3 ??iPr ??O ?Me ?Me；H
?452 ?G3 ?H；H ????3-CH3O ??iPr ??O ?Me ?Me；H
?453 ?G3 ?H；H ????3-CN ??iPr ??O ?Me ?Me；H
?454 ?G3 ?H；H ????4-F ??iPr ??O ?Me ?Me；H
?455 ?G3 ?H；H ????4-Cl ??iPr ??O ?Me ?Me；H
?456 ?G3 ?H；H ????4-Me ??iPr ??O ?Me ?Me；H
?457 ?G3 ?H；H ????4-CF3 ??iPr ??O ?Me ?Me；H
?458 ?G3 ?H；H ????4-CH3O ??iPr ??O ?Me ?Me；H
?459 ?G3 ?H；H ????4-CN ??iPr ??O ?Me ?Me；H
?460 ?G3 ?H；H ????2，4-(F)2 ??iPr ??O ?Me ?Me；H
?461 ?G1 ?Me；H ????2-F ??iPr ??O ?Me ?Me
?462 ?G1 ?Me；H ????2-Cl ??iPr ??O ?Me ?Me
?463 ?G1 ?Me；H ????2-Me ??iPr ??O ?Me ?Me
?464 ?G1 ?Me；H ????2-CF3 ??iPr ??O ?Me ?Me
?465 ?G1 ?Me；H ????2-CH3O ??iPr ??O ?Me ?Me
?466 ?G1 ?Me；H ????2-CN ??iPr ??O ?Me ?Me
?467 ?G1 ?Me；H ????3-F ??iPr ??O ?Me ?Me
?468 ?G1 ?Me；H ????3-Cl ??iPr ??O ?Me ?Me
?469 ?G1 ?Me；H ????3-Me ??iPr ??O ?Me ?Me
?470 ?G1 ?Me；H ????3-CF3 ??iPr ??O ?Me ?Me
?471 ?G1 ?Me；H ????3-CH3O ??iPr ??O ?Me ?Me
?472 ?G1 ?Me；H ????3-CN ??iPr ??O ?Me ?Me
?473 ?G1 ?Me；H ????4-F ??iPr ??O ?Me ?Me
?474 ?G1 ?Me；H ????4-Cl ??iPr ??O ?Me ?Me
?475 ?G1 ?Me；H ????4-Me ??iPr ??O ?Me ?Me
?476 ?G1 ?Me；H ????4-CF3 ??iPr ??O ?Me ?Me
?477 ?G1 ?Me；H ????4-CH3O ??iPr ??O ?Me ?Me
?478 ?G1 ?Me；H ????4-CN ??iPr ??O ?Me ?Me
?479 ?G1 ?Me；H ????2，4-(F)2 ??iPr ??O ?Me ?Me
?480 ?G2 ?Me；H ????2-F ??iPr ??O ?Me ?Me
?481 ?G2 ?Me；H ????2-Cl ??iPr ??O ?Me ?Me
?482 ?G2 ?Me；H ????2-Me ??iPr ??O ?Me ?Me
?483 ?G2 ?Me；H ????2-CF3 ??iPr ??O ?Me ?Me
?484 ?G2 ?Me；H ????2-CH3O ??iPr ??O ?Me ?Me
?485 ?G2 ?Me；H ????2-CN ??iPr ??O ?Me ?Me
?486 ?G2 ?Me；H ????3-F ??iPr ??O ?Me ?Me
?487 ?G2 ?Me；H ????3-Cl ??iPr ??O ?Me ?Me
?488 ?G2 ?Me；H ????3-Me ??iPr ??O ?Me ?Me
?489 ?G2 ?Me；H ????3-CF3 ??iPr ??O ?Me ?Me
?490 ?G2 ?Me；H ????3-CH3O ??iPr ??O ?Me ?Me
?491 ?G2 ?Me；H ????3-CN ??iPr ??O ?Me ?Me
?492 ?G2 ?Me；H ????4-F ??iPr ??O ?Me ?Me
?493 ?G2 ?Me；H ????4-Cl ??iPr ??O ?Me ?Me
?494 ?G2 ?Me；H ????4-Me ??iPr ??O ?Me ?Me
?495 ?G2 ?Me；H ????4-CF3 ??iPr ??O ?Me ?Me
?496 ?G2 ?Me；H ????4-CH3O ??iPr ??O ?Me ?Me
?497 ?G2 ?Me；H ????4-CN ??iPr ??O ?Me ?Me
?498 ?G2 ?Me；H ????2，4-(F)2 ??iPr ??O ?Me ?Me
?499 ?G3 ?Me；H ????2-F ??iPr ??O ?Me ?Me；H
?500 ?G3 ?Me；H ????2-Cl ??iPr ??O ?Me ?Me；H
?501 ?G3 ?Me；H ????2-Me ??iPr ??O ?Me ?Me；H
?502 ?G3 ?Me；H ????2-CF3 ??iPr ??O ?Me ?Me；H
?503 ?G3 ?Me；H ????2-CH3O ??iPr ??O ?Me ?Me；H
?504 ?G3 ?Me；H ????2-CN ??iPr ??O ?Me ?Me；H
?505 ?G3 ?Me；H ????3-F ??iPr ??O ?Me ?Me；H
?506 ?G3 ?Me；H ????3-Cl ??iPr ??O ?Me ?Me；H
?507 ?G3 ?Me；H ????3-Me ??iPr ??O ?Me ??Me；H
??508 ?G3 ?Me；H ????3-CF3 ??iPr ??O ?Me ?Me；H
?509 ?G3 ?Me；H ????3-CH3O ??iPr ??O ?Me ?Me；H
?510 ?G3 ?Me；H ????3-CN ??iPr ??O ?Me ?Me；H
?511 ?G3 ?Me；H ????4-F ??iPr ??O ?Me ?Me；H
?512 ?G3 ?Me；H ????4-Cl ??iPr ??O ?Me ?Me；H
?513 ?G3 ?Me；H ????4-Me ??iPr ??O ?Me ?Me；H
?514 ?G3 ?Me；H ????4-CF3 ??iPr ??O ?Me ?Me；H
?515 ?G3 ?Me；H ????4-CH3O ??iPr ??O ?Me ?Me；H
?516 ?G3 ?Me；H ????4-CN ??iPr ??O ?Me ?Me；H
?517 ?G3 ?Me；H ????2，4-(F)2 ??iPr ??O ?Me ?Me；H
?518 ?G1 ?H；H ????2-F ??cPr ??O ?Me ?Me
?519 ?G1 ?H；H ????2-Cl ??cPr ??O ?Me ?Me
?520 ?G1 ?H；H ????2-Me ??cPr ??O ?Me ?Me
?521 ?G1 ?H；H ????2-CF3 ??cPr ??O ?Me ?Me
?522 ?G1 ?H；H ????2-CH3O ??cPr ??O ?Me ?Me
?523 ?G1 ?H；H ????2-CN ??cPr ??O ?Me ?Me
?524 ?G1 ?H；H ????3-F ??cPr ??O ?Me ?Me
?525 ?G1 ?H；H ????3-Cl ??cPr ??O ?Me ?Me
?526 ?G1 ?H；H ????3-Me ??cPr ??O ?Me ?Me
?527 ?G1 ?H；H ????3-CF3 ??cPr ??O ?Me ?Me
?528 ?G1 ?H；H ????3-CH3O ??cPr ??O ?Me ?Me
?529 ?G1 ?H；H ????3-CN ??cPr ??O ?Me ?Me
?530 ?G1 ?H；H ????4-F ??cPr ??O ?Me ?Me
?531 ?G1 ?H；H ????4-Cl ??cPr ??O ?Me ?Me
?532 ?G1 ?H；H ????4-Me ??cPr ??O ?Me ?Me
?533 ?G1 ?H；H ????4-CF3 ??cPr ??O ?Me ?Me
?534 ?G1 ?H；H ????4-CH3O ??cPr ??O ?Me ?Me
?535 ?G1 ?H；H ????4-CN ??cPr ??O ?Me ?Me
?536 ?G1 ?H；H ????2，4-(F)2 ??cPr ??O ?Me ?Me
?537 ?G2 ?H；H ????2-F ??cPr ??O ?Me ?Me
?538 ?G2 ?H；H ????2-Cl ??cPr ??O ?Me ?Me
?539 ?G2 ?H；H ????2-Me ??cPr ??O ?Me ?Me
?540 ?G2 ?H；H ????2-CF3 ??cPr ??O ?Me ?Me
?541 ?G2 ?H；H ????2-CH3O ??cPr ??O ?Me ?Me
?542 ?G2 ?H；H ????2-CN ??cPr ??O ?Me ?Me
?543 ?G2 ?H；H ????3-F ??cPr ??O ?Me ?Me
?544 ?G2 ?H；H ????3-Cl ??cPr ??O ?Me ?Me
?545 ?G2 ?H；H ????3-Me ??cPr ??O ?Me ?Me
?546 ?G2 ?H；H ????3-CF3 ??cPr ??O ?Me ?Me
?547 ?G2 ?H；H ????3-CH3O ??cPr ??O ?Me ?Me
?548 ?G2 ?H；H ????3-CN ??cPr ??O ?Me ?Me
?549 ?G2 ?H；H ????4-F ??cPr ??O ?Me ?Me
?550 ?G2 ?H；H ????4-Cl ??cPr ??O ?Me ?Me
?551 ?G2 ?H；H ????4-Me ??cPr ??O ?Me ?Me
?552 ?G2 ?H；H ????4-CF3 ??cPr ??O ?Me ?Me
?553 ?G2 ?H；H ????4-CH3O ??cPr ??O ?Me ?Me
?554 ?G2 ?H；H ????4-CN ??cPr ??O ?Me ?Me
?555 ?G2 ?H；H ????2，4-(F)2 ??cPr ??O ?Me ?Me
?556 ?G3 ?H；H ????2-F ??cPr ??O ?Me ?Me；H
?557 ?G3 ?H；H ????2-Cl ??cPr ??O ?Me ?Me；H
?558 ?G3 ?H；H ????2-Me ??cPr ??O ?Me ?Me；H
?559 ?G3 ?H；H ????2-CF3 ??cPr ??O ?Me ?Me；H
?560 ?G3 ?H；H ????2-CH3O ??cPr ??O ?Me ?Me；H
?561 ?G3 ?H；H ????2-CN ??cPr ??O ?Me ?Me；H
?562 ?G3 ?H；H ????3-F ??cPr ??O ?Me ?Me；H
?563 ?G3 ?H；H ????3-Cl ??cPr ??O ?Me ?Me；H
?564 ?G3 ?H；H ????3-Me ??cPr ??O ?Me ?Me；H
?565 ?G3 ?H；H ????3-CF3 ??cPr ??O ?Me ?Me；H
?566 ?G3 ?H；H ????3-CH3O ??cPr ??O ?Me ?Me；H
?567 ?G3 ?H；H ????3-CN ??cPr ??O ?Me ?Me；H
?568 ?G3 ?H；H ????4-F ??cPr ??O ?Me ?Me；H
?569 ?G3 ?H；H ????4-Cl ??cPr ??O ?Me ?Me；H
?570 ?G3 ?H；H ????4-Me ??cPr ??O ?Me ?Me；H
?571 ?G3 ?H；H ????4-CF3 ??cPr ??O ?Me ?Me；H
?572 ?G3 ?H；H ????4-CH3O ??cPr ??O ?Me ?Me；H
?573 ?G3 ?H；H ????4-CN ??cPr ??O ?Me ?Me；H
?574 ?G3 ?H；H ????2，4-(F)2 ????cPr ????O ?Me ?Me；H
?575 ?G1 ?Me；H ????2-F ????cPr ????O ?Me ?Me
?576 ?G1 ?Me；H ????2-Cl ????cPr ????O ?Me ?Me
?577 ?G1 ?Me；H ????2-Me ????cPr ????O ?Me ?Me
?578 ?G1 ?Me；H ????2-CF3 ????cPr ????O ?Me ?Me
?579 ?G1 ?Me；H ????2-CH3O ????cPr ????O ?Me ?Me
?580 ?G1 ?Me；H ????2-CN ????cPr ????O ?Me ?Me
?581 ?G1 ?Me；H ????3-F ????cPr ????O ?Me ?Me
?582 ?G1 ?Me；H ????3-Cl ????cPr ????O ?Me ?Me
?583 ?G1 ?Me；H ????3-Me ????cPr ????O ?Me ?Me
?584 ?G1 ?Me；H ????3-CF3 ????cPr ????O ?Me ?Me
?585 ?G1 ?Me；H ????3-CH3O ????cPr ????O ?Me ?Me
?586 ?G1 ?Me；H ????3-CN ????cPr ????O ?Me ?Me
?587 ?G1 ?Me；H ????4-F ????cPr ????O ?Me ?Me
?588 ?G1 ?Me；H ????4-Cl ????cPr ????O ?Me ?Me
?589 ?G1 ?Me；H ????4-Me ????cPr ????O ?Me ?Me
?590 ?G1 ?Me；H ????4-CF3 ????cPr ????O ?Me ?Me
?591 ?G1 ?Me；H ????4-CH3O ????cPr ????O ?Me ?Me
?592 ?G1 ?Me；H ????4-CN ????cPr ????O ?Me ?Me
?593 ?G1 ?Me；H ????2，4-(F)2 ????cPr ????O ?Me ?Me
?594 ?G2 ?Me；H ????2-F ????cPr ????O ?Me ?Me
?595 ?G2 ?Me；H ????2-Cl ????cPr ????O ?Me ?Me
?596 ?G2 ?Me；H ????2-Me ????cPr ????O ?Me ?Me
?597 ?G2 ?Me；H ????2-CF3 ????cPr ????O ?Me ?Me
?598 ?G2 ?Me；H ????2-CH3O ????cPr ????O ?Me ?Me
?599 ?G2 ?Me；H ????2-CN ????cPr ????O ?Me ?Me
?600 ?G2 ?Me；H ????3-F ????cPr ????O ?Me ?Me
?601 ?G2 ?Me；H ????3-Cl ????cPr ????O ?Me ?Me
?602 ?G2 ?Me；H ????3-Me ????cPr ????O ?Me ?Me
?603 ?G2 ?Me；H ????3-CF3 ????cPr ????O ?Me ?Me
?604 ?G2 ?Me；H ????3-CH3O ????cPr ????O ??Me ??Me
??605 ??G2 ??Me；H ????3-CN ????cPr ????O ?Me ?Me
?606 ?G2 ?Me；H ????4-F ????cPr ????O ?Me ?Me
?607 ?G2 ?Me；H ????4-Cl ????cPr ????O ?Me ?Me
?608 ?G2 ?Me；H ????4-Me ????cPr ????O ?Me ?Me
?609 ?G2 ?Me；H ????4-CF3 ????cPr ????O ?Me ?Me
?610 ?G2 ?Me；H ????4-CH3O ????cPr ????O ?Me ?Me
?611 ?G2 ?Me；H ????4-CN ????cPr ????O ?Me ?Me
?612 ?G2 ?Me；H ????2，4-(F)2 ????cPr ????O ?Me ?Me
?613 ?G3 ?Me；H ????2-F ????cPr ????O ?Me ?Me；H
?614 ?G3 ?Me；H ????2-Cl ????cPr ????O ?Me ?Me；H
?615 ?G3 ?Me；H ????2-Me ????cPr ????O ?Me ?Me；H
?616 ?G3 ?Me；H ????2-CF3 ????cPr ????O ?Me ?Me；H
?617 ?G3 ?Me；H ????2-CH3O ????cPr ????O ?Me ?Me；H
?618 ?G3 ?Me；H ????2-CN ????cPr ????O ?Me ?Me；H
?619 ?G3 ?Me；H ????3-F ????cPr ????O ?Me ?Me；H
?620 ?G3 ?Me；H ????3-Cl ????cPr ????O ?Me ?Me；H
?621 ?G3 ?Me；H ????3-Me ????cPr ????O ?Me ?Me；H
?622 ?G3 ?Me；H ????3-CF3 ????cPr ????O ?Me ?Me；H
?623 ?G3 ?Me；H ????3-CH3O ????cPr ????O ?Me ?Me；H
?624 ?G3 ?Me；H ????3-CN ????cPr ????O ?Me ?Me；H
?625 ?G3 ?Me；H ????4-F ????cPr ????O ?Me ?Me；H
?626 ?G3 ?Me；H ????4-Cl ????cPr ????O ?Me ?Me；H
?627 ?G3 ?Me；H ????4-Me ????cPr ????O ?Me ?Me；H
?628 ?G3 ?Me；H ????4-CF3 ????cPr ????O Me ?Me；H
?629 ?G3 ?Me；H ????4-CH3O ????cPr ????O ?Me ?Me；H
?630 ?G3 ?Me；H ????4-CN ????cPr ????O ?Me ?Me；H
?631 ?G3 ?Me；H ????2，4-(F)2 ????cPr ????O ?Me ?Me；H
?632 ?G1 ?H；H ????H，H ????H ????S ?Me ?Me
?633 ?G1 ?H；H ????H，H ????Me ????S ?Me ?Me
?634 ?G1 ?H；H ????H，H ????Et ????S ?Me ?Me
?635 ?G2 ?H；H ????H，H ????H ????S ?Me ?Me
?636 ?G2 ?H；H ????H，H ????Me ????S ?Me ?Me
??637 ?G2 ?H；H ????H，H ????Et ????S ?Mc ?Me
?638 ?G3 ?H；H ????H，H ????H ????S ?Me ?Me；H
?639 ?G3 ?H；H ????H，H ????Me ????S ?Me ?Me；H
?640 ?G3 ?H；H ????H，H ????Et ????S ?Me ?Me；H
?641 ?G1 ?H；H ????H，H ????H ????SO ?Me ?Me
?642 ?G1 ?H；H ????H，H ????Me ????SO ?Me ?Me
?643 ?G1 ?H；H ????H，H ????Et ????SO ?Me ?Me
?644 ?G2 ?H；H ????H，H ????H ????SO ?Me ?Me
?645 ?G2 ?H；H ????H，H ????Me ????SO ?Me ?Me
?646 ?G2 ?H；H ????H，H ????Et ????SO ?Me ?Me
?647 ?G3 ?H；H ????H，H ????H ????SO ?Me ?Me；H
?648 ?G3 ?H；H ????H，H ????Me ????SO ?Me ?Me；H
?649 ?G3 ?H；H ????H，H ????Et ????SO ?Me ?Me；H
?650 ?G1 ?H；H ????H，H ????H ????SO2 ?Me ?Me
?651 ?G1 ?H；H ????H，H ????Me ????SO2 ?Me ?Me
?652 ?G1 ?H；H ????H，H ????Et ????SO2 ?Me ?Me
?653 ?G2 ?H；H ????H，H ????H ????SO2 ?Me ?Me
?654 ?G2 ?H；H ????H，H ????Me ????SO2 ?Me ?Me
?655 ?G2 ?H；H ????H，H ????Et ????SO2 ?Me ?Me
?656 ?G3 ?H；H ????H，H ????H ????SO2 ?Me ?Me；H
?657 ?G3 ?H；H ????H，H ????Me ????SO2 ?Me ?Me；H
?658 ?G3 ?H；H ????H，H ????Et ????SO2 ?Me ?Me；H
?659 ?G1 ?H；H ????H，H ????cPr ????O ?Me ?Me
?660 ?G2 ?H；H ????H，H ????cPr ????O ?Me ?Me
?661 ?G3 ?H；H ????H，H ????cPr ????O ?Me ?Me；H
?662 ?G1 ?Me；H ????H，H ????cPr ????O ?Me ?Me
?663 ?G2 ?Me；H ????H，H ????cPr ????O ?Me ?Me
?664 ?G3 ?Me；H ????H，H ????cPr ????O ?Me ?Me；H
For fungicidal application and Arthropodicidal application, the preferred compound of formula (I) is such compound, wherein:
When G is G 1Or G 2The time, R 4It is methyl; R 5It is methyl; Or
When G is G 3Or G 4The time, R 5It is methyl; R 6Be methyl and R 7Be hydrogen.
A preferred insecticides is R wherein 3It is the compound of hydrogen atom, low alkyl group or cycloalkyl.
A preferred insecticides is R wherein 1Be hydrogen atom or low alkyl group or cycloalkyl, cyano group, carbalkoxy, haloalkyl and R 2It is the compound of hydrogen or methyl.
A preferred insecticides is X wherein 3Be H and X 1Or X 2It is the compound of alkyl, cyano group, halogen, haloalkyl, alkoxyl group or halogenated alkoxy.
A preferred insecticides is the compound that the two keys of two in as indicated earlier the formula (I) are the E configuration.
A particularly preferred class mycocide is such formula (I) compound, wherein X 1Be methyl or hydrogen, X 2And X 3Be hydrogen; R 1Be hydrogen or methyl; R 2Be hydrogen; R 3Be hydrogen or low alkyl group; W is a Sauerstoffatom.
The The compounds of this invention that is characterized as above-mentioned general formula (I) can prepare by following method A or B or at least a of C or D.Normally itself is known to be used for the production method of reagent of these methods, and is described in usually in the prior art, and these descriptions can be concrete, also can be to describe to such degree, are to be used for the present invention, and those skilled in the art can make amendment.Can be used for determining the prior art of the suitable details of reagent production method by those skilled in the art, be found in the database that chemical general handbook and " chemical abstracts " and the open to the public or public can using a computer.
Method A
According to flow process (1), exist down at acid binding agent (that is, the organic or inorganic alkaline reagents), choose wantonly in the presence of solvent, make formula (II) compound (novel hydroxamic acid esters) and the reaction of formula (III) compound, can prepare formula (I) compound: [flow process (1)] R wherein 1, R 2, R 3, W, X 1, X 2, X 3, G is identical with the definition in the above-mentioned general formula [I]; V is a halogen atom.
Temperature of reaction is normally-80 ℃ to 150 ℃ or to the boiling temperature of solvent for use.As the solvent of this reaction, arbitrary inert solvent can use with starting material, and this inert solvent is aliphatic hydrocrbon such as pentane, hexane, heptane, octane for example; Aromatic hydrocarbons such as benzene,toluene,xylene, halogeno-benzene; Ethers such as ether, diisopropyl ether, tetrahydrofuran (THF), dioxane, glycol dimethyl ether; Halohydrocarbon such as methylene dichloride, chloroform and ethylene dichloride; Ester class such as methyl acetate, ethyl acetate; Nitrile such as acetonitrile, propionitrile; Dimethyl formamide, dimethyl sulfoxide (DMSO), water.Also can use those skilled in the art to think the The suitable solvent mixture.Reaction times is depended on reaction conditions, normally 0.1 to 24 hour reaction times.
As acid binding agent (being also referred to as alkaline reagents), that can mention has, the oxyhydroxide of basic metal or alkaline-earth metal for example, and hydride, carbonate or supercarbonate are as sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide; Yellow soda ash, salt of wormwood, cesium carbonate, lime carbonate, sodium bicarbonate, saleratus, cesium bicarbonate; Sodium hydride, potassium hydride KH, cesium hydride; And organic bases, particularly nitrogenous alkali, as pyridine derivate, for example pyridine or N, N-lutidine; Alkylamine, for example, triethylamine; Diaza derivatives, for example diazabicylo undecylene and diazabicyclooctane.
The ratio of formula (III) compound and formula (II) compound does not have strict restriction.Yet, be that the mol ratio of formula (III) compound and formula (II) compound is 0.5 to 2, in preferred 0.9 to 1.1 the scope usually easily.
By known method itself, for example extraction, recrystallization, chromatogram can be with formula (I) compound separation (as long as need or think useful) and the purifying of gained.
Starting material in the reaction of flow process (I) are hydroxamic acid or sulfo-hydroxamic acid derivs of formula (II).They can be for example by following flow process (2) or (3) preparation, although preparation be there is no concrete restriction.[flow process (2)]
Figure A9619483000311
[flow process (3)]
Figure A9619483000321
R wherein 1, R 2, R 3, W, X 1, X 2, X 3, G is identical with the definition in the above-mentioned general formula (I); Y is halogen atom, alkylsulfonyloxy or aryl-sulfonyl oxygen; U is halogen atom or hydroxyl, alkoxyl group, amino or O-C (=O) R ' 3Group, R ' 3With R 3Definition identical, similar or different, halogen atom preferably, and the compound of formula V is an acyl halide.
According to flow process (2); in the presence of acid conjugate matter or dewatering agent; choose wantonly in the presence of the solvent that also is useful on reagent; make the hydroxylamine derivative and logical formula V compound (for example carboxylic acid or acyl halide or the acid anhydrides) reaction of general formula (IV), can prepare the hydroxamic acid or the sulfo-hydroxamic acid derivs of formula (II).
The general reaction conditions that can be used for flow process (2) reaction is similar or identical with the reaction conditions that is used to describe reaction formula (1), and this puts different except also replacing acid binding agent with dewatering agent.As dewatering agent, also can use carboxylic acid or acid anhydrides, for example diacetyl oxide or propionic anhydride.Operation is known according to the explanation of flow process (2) method, and is found in " HOUBEN-WEYL, organic chemistry method " [HOUBEN-WEYL, Methoden der organischen Chemie], E5 volume, 1144-1149 page or leaf.
According to reaction process (3), choose wantonly in the presence of the solvent that also is useful on reagent, make the hydroxamic acid derivs reaction of the benzyl derivative and the general formula (VII) of general formula (VI), can prepare the hydroxamic acid derivs of formula (II).
The general reaction conditions that is used for reaction process (3) reaction is with to be used to describe the reaction conditions that flow process (1) reacts similar or identical.Operation is known according to the explanation of the method for flow process (3), and is found in " HOUBEN-WEYL, organic chemistry method " [HOUBEN-WEYL, Methoden derorganischen Chemie], E5 volume, 1148-1149 page or leaf.
Wherein the stereochemistry of G group is formula (III) the halogeno-benzyl derivative (it be above the starting material in the reaction process 1) of Z or E, can be by known method itself, or by its related manufacturing processes preparation.These compounds and relevant detailed production method are known in the art.For example be found in european patent application 426460,398692,617014,585751,487409,535928 or German patent application 4305502.Other benzyl derivative of formula (III) also can be by using or the known method preparation of improvement itself.
The sulfo-hydroxamic acid derivs of formula (II), wherein R 1, R 2, R 3, X 1, X 2, X 3Identical with the definition in the general formula (I) above, and W is sulphur, also is a part of the present invention.They can be according to being described in (or being similar to) " (HOUBEN-WEYL, the organic chemistry method " [HOUBEN-WEYL, Methoden der organischen Chemie], the 5th volume, 1279-1280 and " synthesizing " [Synthesis], 1984, the method among the 829-831 prepares by using vulcanizing agent such as thiophosphoric anhydride or " Lawesson reagent " sulfuration hydroxamic acid.[flow process (4)]
Method B:
(wherein G is G to the compound of being represented by general formula (I) 3Or G 4) can be according to following reaction process, (it is that wherein G is G to through type I-1 compound 1Or G 2Formula I compound) with methylamine reaction and prepare:
Figure A9619483000332
R wherein 1, R 2, R 3, R 4, R 5, W, X 1, X 2, X 3Identical with the aforementioned definitions in the general formula (I), and Z is N or CH.
Temperature of reaction is normally-50 ℃ to 100 ℃, or the boiling temperature of solvent for use.Reaction is preferably carried out in as methyl alcohol or ethanol or Virahol at alcoholic solvent.
The ratio of formula (I-1) compound and methylamine does not have strict restriction.Yet being to use methylamine usually easily is 1 to 5 than formula (I-1) compound, the mol ratio in preferred 1.1 to 2 scopes.
Method C
General formula (I) compound by method A preparation is the Z stereochemistry of the hydroxyl oximido part of this molecule usually and mainly.By in solvent, preferably heating under UV (UV-light) irradiation and/or in the presence of acid catalyst can be prepared E isomer by Z isomer.Till making this reaction carry out when Z isomer changes into E isomer and reaches suitable required transformation efficiency.Temperature of reaction usually at 0 ℃ to the boiling spread of solvent.As the solvent of this reaction, arbitrary inert solvent all can use with starting material, and solvent is aliphatic hydrocarbon such as pentane, hexane, heptane, octane for example; Aromatic hydrocarbons such as benzene,toluene,xylene, chlorobenzene; Ethers such as ether, diisopropyl ether, tetrahydrofuran (THF), dioxane, glycol dimethyl ether; Halohydrocarbon such as methylene dichloride, chloroform and ethylene dichloride; Alcohols such as methyl alcohol, ethanol, Virahol; Ester class such as methyl acetate, ethyl acetate; Nitrile such as acetonitrile, propionitrile; Dimethyl formamide, dimethyl sulfoxide (DMSO), water.Also can use those skilled in the art to think the The suitable solvent mixture.
Solvent is aromatic solvent preferably, for example toluene or dimethylbenzene or ether such as diisopropyl ether.
Preferably anhydrous haloid acid of acid such as HCl; Or hydroxy acid, as acetate, propionic acid; Or sulfonic acid, as methylsulfonic acid, tosic acid or sulfuric acid.
Method D
(wherein W is SO or SO to formula I compound 2, and R 1, R 2, R 3, X 1, X 2, X 3, G can be with definition above identical) can be in inert solvent, by the oxygenant oxidation wherein W be that the compound of Formula I of sulphur prepares.Catalyzer exists down, and oxygenant can use organic or inorganic superoxide such as metachloroperbenzoic acid, hydroperoxide, inorganic chlorine oxide compound or oxygen.Following flow process has been described this type of reaction.
Substituting group in this flow process still have with the front formula in identical general sense.
The invention provides the method for control at the fungal diseases of plants in a certain place, this method comprises the compound of using the formula (I) of significant quantity to it.
The invention still further relates to processing and be subjected to maybe can be subjected to the method for the harmful raise crop that influences of fungi, it is characterized in that, use the compound of the formula (I) of effective dose to this thing.Effective dose is interpreted as being enough to prevent and treat or root out the amount of the fungi that exists on these raise crops.Yet, different according to the type of the fungi that for example is intended to prevent and treat, crop, weather condition and used compound, the dosage of use can change in wide scope.
In fact, under the situation of foliage applying, compound is 1 to 1000ppm, and to use in preferred 1 to 500ppm the concentration range be favourable.When the place that is intended to handle, to 10 kilograms/hectare (Kg/ha), preferred 10 gram/hectares are to 1 kilogram/hectare at 5 gram/hectares (g/ha), and more preferably the dosage in the scope of 50 to 500 gram/hectares to use compound of the present invention be favourable.For crop zone or the non-crop zone, above-mentioned consumption is an ideal for foliage applying.
Under the situation of soil application, in this using, think in the most of infiltration of the activeconstituents soil that therefore advise higher dosage, this dosage is at 0.01 to 100 kilogram/hectare, in preferred 0.2 to 20 kilogram/hectare scope.More preferably, the significant quantity scope of active compound is about 0.01 kilogram/hectare to about 2 kilograms/hectare.
Fungal disease is interpreted as, by plant pathogenic fungi, and the disease that causes of the plant pathogenic fungi of Oomycete, Ascomycetes and Basidiomycetes particularly.
The compound of formula (I) demonstrates good prevention effect to the following plants disease:
Rice blast (Pyricularia orgzae), rice sheath blight disease (Rhizoctonia solani), Helminthosporium of brown spot of rice (Cochliobolus miyabeanus),
Various host crops such as cereal class comprise barley, wheat, Powdery Mildew on the oat etc. (Erysiphegraminis), spot blight (Septoria tritici and Septoria nodorum), net blotch (Pyrenophorateres), leaf rust (Puccinia recondita), crown hull sugar (Puccinia coronata), eye spot (Pseudocercosporella herpotrichoides), stripe rust (Puccinia striiformis), the late blight of potato and tomato late blight (Phytophthora infestans) and other crop, the oidium of each kind of plant such as cucumber downy mildew (Pseudoperonospora cubensis), downy mildew of garpe (Plasmoporaviticola); Scab of apple (Venturia inaequalis); Apple zonate spot (Alternaria mali); Sand pear black spot (Alternaria kikuchiana); Melanose of citrus (Diaporthe citri); Alternaria spot and blight of garden radish (Alternaria brassicae); Beet cercospora leaf spot (Cercospora beticola); Powdery mildew of cucumber (Erysiphecichoracearum); Soybean rust (Uromyces appendiculatus).
The present invention also provides the arthropods of control in a certain place, particularly insect or mite, and nematode, and the method for worm or protozoon harmful organism, this method comprise to be used or the compound of the formula (I) of the significant quantity of offeing medicine.
Compound of the present invention can be used for the control through foliage applying, or through the control of the systemic action of other harmful arthropod, the especially insect of feeding plant over-ground part.The control of blade face insect also comprises the using of roots of plants or plant seed, and absorbs the over-ground part that moves to plant in subsequently.
The compounds of this invention can be used for preventing and treating soil insect such as corn cutworm (corn cutworm), termite (especially for the protection buildings), root maggot, wireworm, root weevil, borer, cutworm, Phylloxera or grub.They also can be used to provide the active or activity of anti-mite of anti-plant pathogeny line insect such as root knot nematode (root-knotnematode), packing nematode (cystnematodes), the large-scale needlework worm of mulberry, scab nematode (lesion ematode) or Ditylenchus dipsaci (stem nematode) or sweet potato stem nematode (bulb nematode).During control soil pest (for example corn cutworm), The compounds of this invention advantageously is applied to significant quantity or mixes the soil of planting or being intended to kind of plant, or is applied to the root of seed or growing plant.
In the public health field, the many insects of control, the aspect that does not does not particularly prevent and treat unclean fly or other Diptera pest such as housefly, stable fly, stratiomyiid, horn fly, deerfly, horsefly, midge, midge, blackfly or mosquito, The compounds of this invention is particularly useful.
The compounds of this invention can be used for following application and is used for following harmful organism comprising arthropods, particularly insect or mite; Nematode or worm or protozoon harmful organism.As previously mentioned, the invention provides through using or formula (I) compound of effective dosage and the method for the harmful organism that prevents and treats in a certain place, this method comprises handles this place.
When arthropods, particularly insect of control plant or the practical application of mite or nematode harmful organism, for example, method comprises to the matrix of plant or its growth uses the significant quantity The compounds of this invention.
The method of control harmful organism also comprises the blade face of using or handling plant, and the arthropods of dividing with control infringement plant shoot is insect or mite, fungi or nematode especially.In addition, provide with the method for The compounds of this invention control harmful organism and prevented and treated away from infringement of using the site or feeding plant harmful organism partly, for example get the insect of food blade, when for example being applied to plant roots or being applied to plant seed before plantation, this class insect is to be able to be prevented and treated through the systemic action of active compound.Moreover The compounds of this invention can reduce the infringement of harmful organism to plant by food refusal or repellent action.
The compounds of this invention and valuable especially in the protection in following field: land for growing field crops with the method for its control harmful organism; feed; the plantation; the greenhouse; orchard or vineyard; ornamental plant; or plantation trees or forest-tree; for example: the cereal class is (as corn; wheat; rice or jowar); cotton; tobacco; vegetables are (as beans; the rape crop; melon; lettuce; green onion; tomato or green pepper class); field crop is (as potato; sugar beet; peanut; soybean; or rape); sugarcane; lawn or fodder crop are (as corn; jowar; clover); plantation crops is (as tea; coffee; cocoa; banana; palm; coconut; rubber or spice crop); orchard or oranges and tangerines garden are (as nut or drupe; Citrus; Kiwifruit; avocado; mango; olive or walnut); grape; ornamental plant; shrub in flowers or vegetables or greenhouse or garden or the park, or forest; forest-tree in plantation or the nursery (comprising fallen leaves and evergreen tree).The cereal class is the preferred crop of implementing the inventive method.
They are not subjected to aspect the infringement of sawfly for example or beetle or termite at protection timber (felling of having, regenerated, timber storage or that processed) also be valuable.
They are not subjected to aspect moth, beetle, the infringement of acarid trox purposes is arranged also at protection storage product.Described storage product such as cereal, fruit, nut, spices or tobacco, no matter be former state, ground or combined prod.Also can protect the animal product of storage such as natural or changed skin, hair, knitting wool or the feather (for example carpet or fabric) of profile, make it not to be subjected to the infringement of moth or beetle; Can also protect meat, fish or the cereal of storage, make it not to be subjected to the infringement of moth, mite or fly.
In addition, The compounds of this invention and application method thereof can be propagated or as the arthropods of the media of the people or the disease of domestic animals, worm or protozoon aspect are valuable especially in control.These kinds comprise above-mentioned those and tick, mite, lice, flea, midge and that bite, myiosis or disgusting fly class.The compounds of this invention in control is present in domestic host animal body or in its skin or on get food or suck aspect arthropods, worm or the protozoon of animal blood particularly useful.For reaching this purpose, The compounds of this invention can per os, without intestines, through skin or topical.
The invention provides a kind of insect-killing composition, it comprises acceptable carrier on the compound of one or more formula (I) and the agricultural chemicals; Said composition also can comprise acceptable surfactant on the agricultural chemicals.
Another theme of the present invention is the desinsection fungicide composition, fungicide composition particularly, they contain with agricultural go up acceptable solid or liquid vehicle and same on agricultural the acceptable surfactant blended, as the compound of one or more formula (I) of active substance.Specifically, can use inertia and conventional carrier and conventional surfactants.
These compounds can be processed into the formulation that is generally used for mycocide, for example pulvis, granule, but wettable powder flowing agent or the like.
In addition, these compounds are by with mixing such as other agricultural chemicals, chemical fertilizer, soil redeposition such as other agricultural chemicals such as mycocide, sterilant, miticide, weedicide, plant-growth regulator or use and use.
As the carrier or the thinner of reagent, that can mention has for example normally used solid or a liquid vehicle.
As solid carrier, having of can mentioning is the potter's clay of representative with kaolinite, montmorillonite, illite, polygroskite etc. for example, and pyrophyllite, attapulgite, sepiolite, kaolinite, montmorillonite, vermiculite, mica, talcum etc. are arranged or rather; Other inorganic substance such as gypsum, lime carbonate, rhombspar, diatomite, magnesian lime, phosphatic rock, zeolite, silicic anhydride and synthetic calcium silicate; Derive from the organic substance of plant such as soyflour, tobacco powder, walnut powder, flour, wood sawdust, starch, crystal fibre element etc.; Synthetic or natural high moleculer eompound such as coumarone resin, petroleum resin, Synolac, polyvinyl chloride, polyalkylene glycol, ketone resin, ester gum,   glue and Agate glue; Wax such as carnauba wax and beeswax; Urea etc.
As what liquid vehicle can be mentioned for example paraffin or naphthenic hydrocarbon such as kerosene, mineral oil, spindle oil and white oil arranged; Aromatic hydrocarbons such as dimethylbenzene, ethylbenzene, isopropyl benzene and methylnaphthalene; Hydrochloric ether such as trieline, chlorobenzene, ortho-chlorotolu'ene etc.; Ethers such as dioxane, tetrahydrofuran (THF) etc.; Ketone such as acetone, methylethylketone, diisobutyl ketone, pimelinketone, methyl phenyl ketone, isophorone etc.; Ester class such as ethyl acetate, pentyl acetate, acetate glycol ester, acetate binaryglycol ester, dibutyl maleinate, ethyl succinate etc.; Alcohols such as methyl alcohol, n-hexyl alcohol, ethylene glycol, Diethylene Glycol, hexalin, phenylcarbinol etc.; Ether alcohol class such as ethylene glycol ethyl ether, diethylene glycol ether, Diethylene Glycol butyl ether; Polar solvent such as dimethyl formamide, dimethyl sulfoxide (DMSO) etc.; Water; Or the like;
In addition, also can use other auxiliary agent, be used for emulsification, dispersion, wetting, sprawl and bonding activeconstituents, regulate the disintegration ability, stabilizing active ingredient improves liquidity, anticorrosion freeze proof or the like purpose.
All nonionics, negatively charged ion, positively charged ion and amphoterics all can be used as tensio-active agent of the present invention, but normally used be nonionic and/or anion surfactant.
Suitable ionic surfactant pack is for example drawn together by polymerization, and oxyethane is added to that higher alcohols such as lauryl alcohol, stearyl alcohol, oleyl alcohol etc. are gone up and the compound that obtains; By polymerization, oxyethane is added to that alkylphenol such as isooctyl phenol, nonyl phenol etc. are gone up and the compound that obtains; By polymerization, oxyethane is added on alkyl naphthol such as butyl naphthols, the octyl group naphthols and the compound that obtains; By polymerization, oxyethane is added to that higher fatty acid such as palmitinic acid, stearic acid, oleic acid etc. are gone up and the compound that obtains; The high-grade aliphatic ester of polyvalent alcohol such as anhydrous sorbitol etc.; With by polymerization, oxyethane added on it and the compound that obtains; By segment copolymerization, oxyethane added on the propylene oxide and the compound that obtains.
The anion surfactant that is fit to comprises for example alkyl sulfuric ester salt such as sodium lauryl sulphate, oleyl alcohol sulfuric ester amine salt etc.; Alkylsulfonate such as dioctyl sodium sulphosuccinate, the own sodium sulfonate of 2-ethyl etc.; Arylsulphonate such as isopropyl naphthalene sodium sulfonate, sodium methylene bis-naphthalene sulfonate, sodium lignosulfonate, Sodium dodecylbenzene sulfonate etc.
Moreover, be the performance improve preparation and the purpose that increases the effectiveness of mycocide, can also use macromolecular compound such as casein, gelatin, albumin, glue, Sulfite lignin, alginate, carboxymethyl cellulose, methylcellulose gum, Natvosol, polyvinyl alcohol etc. with mycocide of the present invention.
According to the difference of purpose, and to formulation, use site etc. and take in, can be used alone or in combination above-mentioned carrier and various auxiliary agent aptly.
Content of effective in the mycocide of the present invention in the thus obtained various formulation can be according to the difference of formulation difference to some extent, but can be, in preferred 1 to 60% the scope by weight by weight 0.1 to 99%.
Under the situation of wettable powder, mycocide contains and for example is generally one or more bioactive agent composition of 10 to 90% by weight, and remainder comprises solid carrier, dispersion agent and wetting agent.If desired, can be to wherein adding protective colloid agent and defoamer etc.
Under the situation of granule, mycocide contains and for example is generally one or more activeconstituents of 1 to 35% by weight, and remainder is solid carrier, tensio-active agent etc.Activeconstituents or with the solid carrier uniform mixing, or adhere to the surface of solid carrier equably or be adsorbed onto on its surface, and the particulate diameter can be in about scope of 0.2 to 1.5mm.
Under the situation of missible oil, mycocide contains and for example is generally by weight and 5 to 30% one or more activeconstituents and 5 to 20% emulsifying agent roughly by weight, and remainder is made up of liquid vehicle.If desired, can be to wherein adding spreading agent and corrosion inhibitor or the like.
Under the situation of flowing agent, it is one or more activeconstituents of 5 to 50% and 3 to 10% dispersion and wetting agent by weight usually by weight that mycocide for example contains, and remainder is made up of water.If desired, can be to wherein adding protective colloid agent sanitas, defoamer etc.
Hydroxamic acid derivatives of the present invention can directly use or use after being processed into above-mentioned various formulation.
Provide the following example and be for The compounds of this invention, composition and method are described, but not be intended to limit described invention.The method that biological Examples explanation the present invention uses.
In these embodiments, compound is according to last table numbering.When the stereochemistry of structure when being known, as above-mentioned indicated, use compound number, and then be letter e or Z, with this geometric configuration that indicates the two keys of C=G earlier, be only the geometric configuration of hydroxyl oximido then.When isolating steric isomer, and its stereochemistry is used the numeral corresponding to chemical formula when still uncertain, and then is lowercase (a or b), or then is that alphabetical MP or LP determine compound.Letter MP or LP are meant thin-layer chromatography polarity higher or lower
Embodiment 1: compound 2
(2 and methods for using them A prepare N-benzyloxy methane amide by flow process)
(4.63g 37mmol) is dissolved in 89% the formic acid (80ml), and remains in temperature under 50 to 60 ℃ the situation, to wherein being added dropwise to the 30ml diacetyl oxide with the O-benzyl hydroxylamine.Diacetyl oxide finishes, and solution was at room temperature stirred 2 hours.With organic layer washing, dry and with solvent evaporation.Residue silica gel chromatography purifying obtains 3.05g N-benzyloxy methane amide (yield: 60%) afterwards.The proton N MR spectrum of this compound is 4.82bs, 4.93bs (2H); 7.20-7.47m (5H); 7.93bs, 8.30bs (1H) (solvent: DCl 3).
(1g 6.6mmol) is dissolved in the 15ml dimethyl formamide with N-benzyloxy methane amide.After being cooled to 0 ℃, (0.34g 8.5mmol), and stirred 30 minutes under uniform temp to wherein adding 60% sodium hydride.This reaction soln is restir 40 minutes at room temperature, and to wherein be added dropwise to 2-(2-brooethyl) phenyl-2-methoxyimino methyl acetate of being dissolved in the dimethyl formamide (8ml) (2.85g, 6.6mmol).
After at room temperature stirring one day, reaction soln is poured in the 20ml water, and used ethyl acetate extraction.Organic phase washes with water and is dry.Behind the evaporative removal solvent, residue silica gel chromatography purifying obtains 0.40g2-(2-benzyloxy imino-methoxymethyl phenyl)-2-methoxyimino methyl acetate (yield: 14%).The proton N MR spectrum of this compound is 3.81s (3H), 4.01s (3H), 4.85s (2H), 5.01s (2H), 6.48s (1H), 7.12-7.19m (1H), 7.23-7.52m (8H).
Embodiment 2: and compound 4 (E, Z)
(preparing N-benzyloxy ethanamide) by flow process 3 with method A
Under the ice bath cooling, (11.68g, (21.9g is in dimethyl formamide solution 0.292mol) (200ml) 0.292mol) to join acetohydroxamic acid with 60% sodium hydride.After at room temperature stirring 1 hour, (50g 0.292mol), and is allowed to condition under the room temperature reaction 24 hours to wherein adding bromotoluene.Reaction soln is poured in the 500ml water, and used ethyl acetate extraction.Organic layer washes with water and is dry.Behind the evaporative removal solvent, residue silica gel chromatography purifying obtains 31.3gN-benzyloxy ethanamide (yield: 65%).The proton spectra of this compound are: 1.85s (3H); 4.89bs (2H); 7.37s (5H); 8.30bs, 8.81bs (1H) (solvent: CDCl 3).
With N-benzyloxy ethanamide (1.65g, 10ml dimethyl formamide solution 10mmol) cools off with ice bath, (0.4g 10mmol), and stirred 10 minutes to wherein adding 60% sodium hydride.(2.85g behind 20ml dimethyl formamide solution 10mmol), allows this solution at room temperature react 15 hours to be added dropwise to 2-2-bromomethylphenyl-3-methoxy acrylate.Reaction finishes, and reaction soln is poured in the 200ml water, and used ethyl acetate extraction.Organic layer washes with water, and dry.Behind the evaporative removal solvent, residue silica gel chromatography purifying obtains 0.34g 2-[2-(1-benzyloxy imino-ethyl) oxygen aminomethyl phenyl]-3-methoxy-methyl acrylate (yield: 9.2%).Proton N MR spectrum is: 1.79s (3H); 3.67s (3H); 3.77s (3H); 5.01s (2H); 5.04s (2H); 7.10-7.50m (9H); 7.57s (1H) (solvent: CDCl 3).
Embodiment 3: and compound 7 (E, Z)
(preparing N-benzyloxy propionic acid amide) by flow process 3 with method A
With the propionyl hydroxamic acid (4.5g, 50mmol), bromotoluene (8.55g, 50mmol), salt of wormwood (7.6g, 55mmol) and the mixture of acetonitrile (50ml) at room temperature stirred 50 hours.Reaction finishes, and reaction soln is filtered, and evaporative removal solvent, residue silica gel chromatography purifying obtains N-benzyloxy propionic acid amide (8.5g, yield: 100%).The proton N MR spectrum of this compound is: 1.14t (3H); 2.08b (2H); 4.89b (2H); 7.38s (5H); 8.10b (1H) (solvent: CDCl 3).
With N-benzyloxy propionic acid amide (1.8g, 10mmol), 2-2-bromomethylphenyl-3-methoxy acrylate (2.85g, 10mmol), salt of wormwood (1.66g, 12mmol), 4-N, the mixture reflux of N-dimethyl-aminopyridine (0.1g) and acetonitrile (20ml) 7 hours.Reaction finishes, and reaction soln is filtered, and evaporative removal solvent, residue silica gel chromatography purifying obtains 2-[2-{ (1-benzyloxy imino-propyl group) oxygen methyl } phenyl]-3-methoxy-methyl acrylate (1.00g, yield: 26%).Proton N MR composes 1.04t (3H); 2.21q (2H); 3.67s (3H); 3.73s (3H); 5.01s (2H); 5.10s (2H); 7.13-7.45m (9H); 7.45s (1H) (solvent: CDCl 3).
Embodiment 4 (flow process 4):
At room temperature, 18g (0.1mol) O-benzyl propionyl hydroxamic acid and 40g (0.1mol) Lawesson reagent were stirred 1 hour 30 minutes in 200ml THF (abbreviation of tetrahydrofuran (THF)).The ammoniacal liquor that adds 500ml 1.2N.The water extracted with diethyl ether.Water neutralizes with dense HCl afterwards, uses extracted with diethyl ether, through dried over mgso and evaporating solvent, produces the colorless oil of 12.5g (64%), need not to be further purified just and can use; NMR:1.20t (3H), 2.45g (2H), 4.3bs (1H), 5.15s (2H), 7.20-7.45m (5H).
Prepare similar compound (Rf is the known coefficient of these compounds transfer ability on thin-layer chromatography) according to following table.
The O-dibenzylsulfide is for benzoyl hydroxamate 30%, liquid, Rf=0.8 (ethyl acetate/hexane 20/80)
The O-dibenzylsulfide is for acetohydroxamic acid 27%, liquid, Rf=0.8 (ethyl acetate/hexane 20/80)
The different propionyl hydroxamic acid of O-benzyl formyl sulfo- 37%, liquid, Rf=0.9 (ethyl acetate/hexane 20/80)
Embodiment 5:(method A; W=5) compound 634a
With as above the preparation N-benzyloxy thiopropionamide (1.2g, 6mmol), 2-2-bromomethylphenyl-3-methoxy acrylate (1.7g, 6mmol) and salt of wormwood (1g, 7mmol) at room temperature the stirring spend the night.Reaction mixture is filtered, and evaporative removal solvent, residue silica gel chromatography purifying obtains 2-[2-{ (1-benzyloxy imino-propyl group) sulphomethyl } phenyl]-3-methoxy-methyl acrylate (1.6g, yield 67%).Proton N MR spectrum: 1.12t (3H); 2.36g (2H); 3.67s (3H); 3.77s (3H); 3.95s (2H); 5.12s (2H); 7.15-7.50m (9H); 7.59s (1H) (solvent: CDCl 3).
Other compound uses the mode similar to embodiment 1 to 5 to prepare.They are shown in Table 2.
Table 2
Compound number The NMR spectrum is based on proton (ppm), in CDCl 3Make in the solvent.S=s is unimodal; D=is bimodal; T=three peaks; Q=four peaks and | the m=multimodal
4 1.79s (3H), 3.67s (3H), 3.77s (3H), 5.01s (2H), 5.04s (2H), 7.10-7.50m (9H), 7.57s (1H)
5 (EZ) 1.82s (3H) 3.83s (3H), 4.01s (3H), 5.00s (2H), 5.02s (2H), 7.13-7.49m (9H)
16 1.56d (3H), 1.75s (3H) 3.68s (3H), 3.79s (3H), 5.05-5.10m (3H), 7.12-7.40m (9H), 7.58s (1H)
17 1.51d, 1.55d (3H), 1.77s (3H), 3.84s3.87s (3H), 3.95s4.03s (3H), 4.7-4.9m (1H), 5.02-5.10m (2H), 7.14-7.53m (9H)
8 (EZ) 1.05t (3H) .2.14q, 2.51q (2H), 3.82s (3H), 3.98s (3H), 4.99s (2H), 5.08s (2H), 7.1 6-7.47m (9H)
1 3.67s (3H), 3.77s (3H), 4.94s (2H), 5.01s (2H), 6.49s (1H), 7.20-7.48m (9H), 7.58s (1H)
7 (EZ) 1.04t (3H), 2.21q (2H), 3.67s (3H), 3.73s (3H), 5.01s (2H), 5.10s (2H), 7.13-7.45m (9H), 7.54s (1H)
2 3.81s (3H), 4.01s (3H), 4.89s (3H), 5.01s (2H), 6.48s (1H), 7.12-7.19m (1H), 7.23-7.52m (8H)
148 1.79s (3H), 2.35s (3H), 3.67s (3H), 3.75s (3H), 5.04s (2H), 5.04s (2H), 7.00-7.50m (8H), 7.57s (1H)
167 1.82s, 2.19s (3H), 2.32s, 2.36s (3H), 3.83s, 3.86s (3H), 4.02s (3H), 4.69s, 4.97s (2 H), 5.02s, 5.15s (2H), 7.01-7.53m (8H)
154 1.78s (3H) 2.35s (3H) 3.67s (3H), 3.77s (3H) 4.97s (2H), 5.03s (2H), 7.08-7.20m (3H), 7.25-7.35m (4H), 7.43-7.49m (1H) 7.57s (1H)
173 1.81s, 2.16s (3H), 2.33s, 2.34s (3H), 3.83s, 3.86s (3H), 4.01s (3H), 4.68s, 4.95s (2 H), 5.01s, 5.14s (2H), 7.10-7.19m (3H), 7.24-7.57m (5H)
142 (E Z) 1.81s (3H), 2.39s (3H), 3.67s (3H), 3.76s (3H), 5.02s (2H), 5.04s (2H), 7.09 7.41m (7H), 7.45-7.56m (1H), 7.56s (1H)
161 ????1.83s(3H)，2.38s(3H)，3.82s(3H)，4.00s(3H)，5.01s(4H)，7.07-7.53m(8H)
141 ????1.82s(3H)，3.68s(3H)，3.79s(3H)，5.07s(2H)，5.13s(2H)，7.10- 7.41m(6H)，7.46-7.57m(2H)，7.59s(1H)
160 ????1.84s(3H)，3.84s(3H)，4.02s(3H)，5.05s(2H)，5.11s(2H)，7.12- 7.30m(3H)，7.31-7.59m(5H)
144 ????1.80s(3H)，3.68s(3H)，3.78s(3H)，3.83s(3H)，5.06s(2H)，5.08s(2H)，6.83- 7.00m(2H)，7.10-7.16m(1H)，7.22-7.44m(4H)，7.48-7.55m(1H)，7.57s(1H)
163 ????1.82s(3H)，3.83s(3H)，3.84s(3H)，4.02s(3H)，5.04s(2H)，5.07s(2H)，6.81- 7.00m(2H)，7.11-7.58m(6H)
143(E ?Z) ????1.82s(3H)，3.67s(3H)，3.79s(3H)，5.08s(2H)，5.23s(2H)，7.13- 7.18m(1H)，7.23-7.31m(3H)，7.53-7.68m(4H)，7.59s(1H)
149(E Z) ????1.80s(3H)，3.68s(3H)，3.90s(3H)，5.04s(2H)，5.05s(2H)，7.13- 7.15m(1H)，7.30-7.768m(7H)，7.59s(1H)，
8(ZE) ????1.10t(3H)，2.46q(2H)，3.85s(3H)，3.96s(3H)，4.94s(2H)，5.18s(2H)，7.25- 7.41m(8H)，7.40d(1H)
8(ZZ) ????1.06t(3H)，2.17q(2H)，3.88s(3H)，5.03s(2H)，5.44s(2H)，7.26- 7.43m(8H)，7.63d(1H)
10(EZ) ????1.06d(6H)；2.42h(1H)；3.64s(6H)；4.97s(2H)；5.21s(2H)；7.00- 7.47m(9H)；7.48s(1H)
659(E Z) ????0.50-0.60m(2H)；0.62-0.70m(2H)；1.35m(1H)； 3.62s(6H)；4.96s(2H)；5.20(2H)；7.10-7.55m(9H)；7.51s(1H)
634a ????1.12t(3H)；2.36q(2H)；3.67s(3H)；3.77s(3H)；3.95s(2H)；5.12s(2H)；7.15- 7.50m(9H)；7.59s(1H)
634b ????1.09t(3H)；2.43q(2H)；3.69s(3H)；3.78s(3H)；4.02bs(2H)；5.09s(2H)；7.05- 7.40m(9H)；7.56s(1H)
633a 2.04s (3H); 3.66s (3H); 3.77s (3H); 3.95s (2H); 5.10s (2H); 7.05-7.50m (9H); 7.59s (1H); Fusing point; 80 ℃
633b ????1.89s(3H)；3.67s(3H)；3.78s(3H)；3.81s(2H)；5.11s(2H)；7.05- 7.45m(9H)；7.58s(1H)
25 ????1.09d(6H)；2.58h(1H)；3.67s(3H)；3.75s(3H)；3.98s(2H)；5.13s(2H)；7.00- 7.40m(9H)；7.57s(1H)
632 ????3.66s(3H)；3.78s(3H)；3.88s(2H)；5.12s(2H)；5.29s(1H)；7.10- 7.45m(9H)；7.59s(1H)
637a 1.11t (3H); 2.35q (2H); 3.81s (3H); 3.92s (2H); 4.02s (3H); 5.12s (2H); 7.10-7.50m (9H); Fusing point: 53 ℃
637b ????1.07t(3H)；2.42q(2H)；3.86s(3H)；3.95s(2H)；4.03s(3H)；5.08s(2H)；7.10- 7.45m(9H)
Embodiment 6
Have E, the compound 7:(7 (EE) of the two key configurations of E) preparation method C
Compound 7 (EZ) (266g) is dissolved in toluene (21.) and being heated to reflux 2 hours.Behind the evaporating solvent,, produce compound 7 (E, E) glue of (72g) by silica gel chromatography purifying resistates.Prepare following compounds according to same method.Under some situation, need uv irradiating or acetic acid catalysis.
Compound number NMR spectrum (as above definition)
9(E，E) ????1.05t(3H)；2.14q(2H)；2.81d(3H)；3.89s(3H)；4.97s(2H)；5.77s(2H )；6.71bd(1H)；7.16-7.20m(1H)；7.3O-7.45m(8H)
5(E，E) ????1.92s(3H)，3.84s(3H)，4.00s(3H)，4.86s(2H)，4.93s(2H)，7.18- 7.43m(9H)
142(E，E) ????2.22s(3H)，2.66s(3H)，3.95s(3H)，4.03s(3H)，5.15s(2H)，5.23s(2H) ，7.40-7.80m(8H)，7.82s(1H)
143(E，E) ????1.99s(3H)，3.66s(3H)，3.73s(3H)，4.85s(2H)，5.15s(2H)，7.13- 7.17m(1H)7.22-7.43m(5H)7.52s(1H)?7.52-7.70m(2H)
149(E，E) ????1.97s(3H)3.67s(3H)，3.74s(3H)，4.84s(2H)，4.98s(2H)，7.13- 7.16m(1H)，7.29-7.62m(7H)，7.53s(1H)
8(E，E) ????1.04t(3H)，2.38q(2H)，3.83s(3H)，4.0Os(3H)，4.84s(2H)，4.91s(2H) ，7.15-7.20m(1H)，7.22-7.45m(7H)
7(E，E) ????1.05(t，3H)，2.40(q，2H)，3.66(s，3H)，3.73(s，3H)，4.85(s， 2H)，4.92(2，2H)，7.10-7.50(m，9H)，7.55(s，1H)
16(E，E) ????1.50(d，3H)，1.97(s，3H)，3.65(s，3H)，3.68(s，3H)，4.80(s， 2H)，5.03(q，1H)，7.05-7.45(m，9H)，7.48(s，1H)
10(E，E) ????1.03d(6H)；3.30h(1H)；3.64s(3H)；3.66s(3H)； 4.84s(2H)；4.91(2H)；7.05-7.45m(9H)；7.51s(1H)
659(EE) ????0.65-0.75m(2H)；0.85-0.95m(2H)；2.20-2.35m(1H)； 3.68s(3H)；3.75s(3H)；4.81s(2H)；4.98s(2H)；7.10- 7.45m(9H)；7.52s(1H)
Embodiment 7 compounds 642 and 651 (W=SO, SO 2) preparation method D
3-methoxyl group-2-(2-(N-benzyloxy) acetimidoyl sulfinyl aminomethyl phenyl)-methyl acrylate and 3-methoxyl group-2-(2-(N-benzyloxy) acetimidoyl alkylsulfonyl aminomethyl phenyl)-methyl acrylate.
????642 ?1.94s(3H)；3.68s(3H)；3.76s(3H)；4.43s(2H)；5.25s(2H)；7.15- 7.45m(9H)；7.56s(1H)
????651 ?2.04s(3H)；3.66s(3H)；3.72s(3H)；3.97s(2H)；5.11s(2H)；7.10- 7.40m(9H)；7.55s(1H)
At room temperature, (0.5g is 1.6mmol) with 0.39g (1.6mmol) metachloroperbenzoic acid in methylene dichloride reaction 4 days to make 3-methoxyl group-2-(2-(N-benzyloxy) acetimidoyl sulphomethyl phenyl)-methyl acrylate.Reaction finish and column chromatography (20AcOEt-80 hexane) after, isolate the compound 642 and 651 of 0.05g and 0.05g, be oily matter.
Embodiment 8: method B compound 3
With 2-(2-benzyloxy imino-methoxymethyl phenyl)-(200mg 0.6mmol) is dissolved in the 8ml methyl alcohol 2-methoxyimino methyl acetate (compound 2), to wherein adding 40% methylamine (230mg, 2.9mmol) aqueous solution.Stir after 1 day, in reaction soln, add entry, evaporative removal methyl alcohol, and use ethyl acetate extraction.Organic phase washes with water and is dry.Behind the evaporative removal solvent, the residue silica gel chromatography obtains 0.18g N-methyl 2-(2-benzyloxy imino-methoxymethyl phenyl)-2-methoxyimino acetic amide (compound 3, yield 90%).The proton N MR spectrum of this compound is: 2.81s (3H); 3.89s (3H); 4.91s (2H); 5.00s (2H); 6.52s (1H); 6.82bd (1H); 7.15-7.21m (1H); 7.23-7.47m (8H) (solvent: CDCl 3).
With the compound of the same procedure preparation that is described in above-mentioned preparation embodiment in table 3.
Table 3
Compound number Aforesaid NMR spectrum
????9 ?1.05t(3H)，2.14q，2.41q(2H)，2.82d(3H)，3.90s，3.96s(3H)，4.01s(3 ????H)，4.78s，5.01s(2H)，7.20-7.55m(9H)
????3 ????2.81s(3H)，3.89s(3H)，4.91s(2H)，5.00s(2H)，6.52s(1H)，6.82bd(1 H)，7.15-7.21m(1H)，7.23-747m(8H)
????192 ????1.82s，2.06s(3H)，2.35s，2.36s(3H)，2.79d，2.82d(3H)，3.91s，4.01s( 3H)，4.72s，4.94s(2H)，4.99s，5.02s(2H)，6.77bd(1H)，7.13- 7.54m(8H)
????179 ????1.84s(3H)，2.85s(3H)，3.91s(3H)，5.06s(2H)，5.11s(2H)，6.81bd(1 H)，7.15-7.29m(3H)，7.31-7.53m(5H)
????182 ????1.84s(3H)，2.82s(3H)，3.84s(3H)，3.86s(3H)，5.04s(2H)，5.05s(2H) ，6.82-6.99m(3H)，7.18-7.46m(6H)
????640a 1.11t (3H); 2.35q (2H); 2.89d (3H); 3.94s (5H); 5.12s (2H); 6.7-6.85bs (1H); 7.10-7.50m (9H); Fusing point: 83 °
????640b ????1.08t(3H)；2.42q(2H)；290d(3H)；3.94s(5H)；5.08s(2H)；6.65- 6.75bs(1H)；7.10-7.45m(9H)
Several formulations of activeconstituents of the present invention prepare according to the following example.All " parts " are by weight, unless otherwise.
Formulation embodiment 1 (emulsifiable concentrate formulation)
11 10 parts of compounds
45 parts of dimethylbenzene
7 parts of calcium dodecylbenzene sulphonates
13 parts of polyoxyethylene styryl phenyl ethers
25 parts of dimethyl formamides
Said mixture is mixed equably and dissolve, obtain 100 parts of emulsifiable concentrate formulations.
Formulation embodiment 2 (wettable powder agent prescription)
16 20 parts of compounds
70 parts in diatomite
5 parts of Calcium Lignosulphonate 99.99 mins
5 parts of naphthene sulfonic acid-formaldehyde condensation products
Said mixture is mixed, grinds, obtains 100 parts of wettable powders.
Formulation embodiment 3 (granule prescription)
43 5 parts of compounds
50 parts of montmorillonites
42 parts in talcum
2 parts of Sodium Lignosulphonates
1 part of polyoxyethylene alkylaryl ether
Said mixture is mixed, add a spot of water and mediate, and use the tablets press granulation, obtain 100 parts of granule prescriptions.
Biological Examples (rice blast control test)
(cultivar: Koshihikari) kind is seeded in the plastic cup, and cultivates for 3 weeks in the greenhouse with rice.To be diluted with water to 200ppm according to the missible oil of formulation embodiment 1, and to the whole surface spray of rice strain.Spray after one day, spray once again with the aqueous spore suspension of Pyricularia oryzae.Then the rice strain is placed in the humidification darkroom under 25 ℃ one day, moves in the greenhouse then.After spraying 7 days for the second time, count the average scab number on every blade, compare with the average scab number of the sub-district of not spraying.
Under these conditions, the compound of observing good (at least 80%) or provide protection fully has: 2,3,4,5 (EZ); 5 (EE), 7 (EE), 8 (EE), 9,16; 17,141,142 (EZ), 142 (EE), 143 (EZ); 143 (EE), 144,148,149 (EZ); 149 (EE), 154,160,161; 163,173,179,182.
Biological Examples 2 (sheath and culm blight of rice control test)
Sowing seed rice (Cultivar: Koshihikari), and in the greenhouse, cultivate 4-6 week.When the 5th leaf launches, will be diluted with water to 200ppm according to the missible oil of formulation embodiment 1, and spraying (25ml/6 strain) will comprehensively be done in the rice strain.After air-dry, the mycelium of Rhizoctonia solani Kuhn is inoculated in rice seedlings in the bottom of rice strain.It is in 100% and 28 ℃ the culturing room that these rice strains are moved to humidity.After 3 days, count the average scab number on the every leaf, and according to experimental example 1 in the standard described, estimate prevention effect.Test-results is shown in Table 4.
Under these conditions, observe good (at least 80%) or fully the compound that uses of protection 5 (EZ) are arranged, 8 (EE), 142 (EZ), 143 (EE), 144,160,173,182.
Biological Examples 3
Cause the in vivo test of the Puccinia recondita (Puccinia recondita) of wheat leaf rust.
By the following mixture of fine grinding, prepare the aqueous suspensions that is intended to the active substance tested with following component:
Active substance: 60mg
Acetone: 5ml
Tensio-active agent tween 80 (oleic acid ester of the polyoxyethylene derivative of anhydrous sorbitol) dilute with water little molehill to concentration is 10%:0.3ml.
The water polishing is to 60ml.
This aqeous suspension of dilute with water afterwards is to obtaining required active material concentration.
Be seeded in the 50/50 peat/volcanic ash matrix in the little basin and in the wheat (kind: Scipion), when its 10cm is high, handle of 12 ℃ of cultivations with above-mentioned aqeous suspension spraying.
After 24 hours, with aqeous suspension (100000 spores/cm of spore 3) being sprayed on the wheat: this suspension is obtained by susceptible wheat seeding.Afterwards wheat is placed the raising chamber 24 hours of about 20 ℃ and 100% relative humidity, placed afterwards under the 60% relative humidity condition 7 to 14 days.
After the infection between the 8th day and the 15th day, by with untreated control relatively, the state of an illness of range estimation wheat seeding.
Under these conditions, under the dosage of 0.1g/l, the compound of observing good (at least 75%) or provide protection fully has: 1,3,4; 5 (EE), 7 (EE), 8 (EZ), 8 (EE), 8 (ZE); 8 (ZZ), 9 (EE), 25,16 (EE), 17; 141,14 (EZ), 142 (EE), 148,149 (EE); 154,167,179,633; 634,637,640,651.
Dosage 1g/l in this test conditions is equivalent to the dosage that the g/ha with the 1kg/ha order of magnitude represents.
Biological Examples 4:
Cause the in vivo test of the wheat septoria (Septoria tritici) of wheat leaf rot.
(be diluted to 10% by oleic acid ester with 60mg active substance and acetone (5ml) and tensio-active agent-tween 80; 0.3ml) grind together, obtaining the test active substance aqeous suspension of concentration 1g/l, water transfers to 60ml with volume afterwards.
These aqeous suspension dilute with waters obtain required active material concentration.
The wheat seeding (kind Scipion) that is seeded in 50/50 peat/volcanic ash matrix and grows in the greenhouse under 10-12 ℃ of temperature was handled with aforesaid active substance suspension spray in its 1 leaf phase (approximately 10cm height).
Handle with the aqueous solution spraying that does not contain active substance with the wheat seeding that compares.
Handle after 24 hours, (500000 spores/ml) spraying infect wheat seeding by using the aqueous spore suspension of gathering from 7 age in days cultures.
After the infection, wheat seeding placed 18 ℃ wet environment.By comparing, estimate after 20 days in inoculation with the contrast wheat seeding.
Under these conditions, under the dosage of 0.1g/l, the compound of observing good (at least 75%) or provide protection fully has: 2,3,5 (EE), 7 (EZ); 7 (EE), 8 (EZ), 8 (EE), 8 (ZE), 8 (ZZ), 9 (EE); 10 (EZ), 10 (EE), 25,16 (EE), 17,142 (EZ); 142 (EE), 143 (EZ), 143 (EE), 149 (EZ), 149 (EE); 154,167,632,633,634; 637,640,651,659 (EE), 659 (EZ).
Dosage 1g/l in this test conditions is equivalent to the dosage that the g/ha with the 1kg/ha order of magnitude represents.
Biological Examples 5
Cause the in vivo test of the clever withered septoria musiva (Septoria nodorum) of wheat glume blight.
By 60mg active substance and acetone (5ml) and tween 80 (are diluted to 10%; 0.3ml) grind together, obtaining concentration is the test active substance aqeous suspension of 1g/l, water transfers to 60ml with volume afterwards.
These aqeous suspension dilute with waters obtain required active material concentration.
The wheat seeding (kind Scipion) that is seeded in 50/50 peat/volcanic ash matrix and grows in the greenhouse under 10-12 ℃ of temperature was handled with aforesaid active substance suspension spray in its 1 leaf phase (approximately 10cm height).
Handle with the aqueous solution spraying that does not contain active substance with the wheat seeding that compares.
Handle after 24 hours, (500000 spores/ml) spraying infect wheat seeding by using the aqueous spore suspension of gathering from 7 age in days cultures.
After the infection, wheat seeding placed 18 ℃ wet environment.By comparing, estimate after 20 days in inoculation with the contrast wheat seeding.
Under these conditions, under the dosage of 0.1g/l, the change of observing good (at least 75%) or complete provide protection contains thing to be had: 4,5 (EE), 7 (EZ), 7 (EE); 8 (EZ), 8 (EE), 8 (ZE), 8 (ZZ), 9 (EE), 10 (EZ); 10 (EE), 25,16 (EE), 17,141,142 (EZ); 142 (EE), 143 (EZ), 143 (EE), 149 (EZ), 149 (EE), 154; 179,632,633,634,637; 640,642,651,659 (EE), 659 (EZ).
Dosage 1g/l in this test conditions is equivalent to the dosage that the g/ha with the 1kg/ha order of magnitude represents.
Experimental example 6
Cause the in vivo test of the Erisyphe graminis var.hordei of barley powdery mildew.
(water is rare to 10% by fine grinding active substance (60mg) and acetone (5ml) and tween 80; 0.3ml) prepare the as above active substance aqeous suspension that is intended to test of composition.
These aqeous suspensioies are diluted with water to and obtain required active material concentration.
Be seeded in the 50/50 peat/volcanic ash matrix in the little basin and, when its 10cm is high, handle with above-mentioned aqeous suspension spraying the barley (kind Express) of 12 ℃ of cultivations.
After 24 hours, dust, plant is inoculated with dried conidium.
Afterwards barley is placed 60% relative humidity and 20 ℃ following 10 days.By making comparisons, estimated in back 10 days in inoculation with untreated control.
Under these conditions, under the dosage of 0.1g/l, the compound of observing good (at least 75%) or provide protection fully has: 4,5 (EE), 7 (EE), 8 (EZ); 8 (EE), 8 (ZE), 8 (ZZ), 9 (EE), 10 (EZ), 10 (EE); 25,16 (EE), 141,142 (EZ), 142 (EE); 143 (EZ), 143 (EE), 149 (EZ), 148,149 (EZ); 149 (EE), 154,179,632,634; 637,640,642,659 (EE), 659 (EZ).
The dosage of 1g/l in this test is equivalent to the dosage that the g/ha with the 1kg/ha order of magnitude represents.
Experimental example 7
Cause the in vivo test of net blotch of barley Dreschlera teres.
(be diluted with water to 10% by fine grinding active substance (60mg) and acetone (5ml) and tween 80; 0.3ml), prepare the as above active substance aqeous suspension that is intended to test of composition.
These aqeous suspension dilute with waters are to obtain required active material concentration.
Be seeded in the 50/50 peat/volcanic ash matrix in the little basin and the barleys of under 12 ℃, cultivating, when its 10cm is high, handle with above-mentioned aqeous suspension spraying.
After 24 hours, with aqeous suspension (1,000 000 spores/cm of spore 2) be sprayed on the barley; This suspension is obtained by susceptible Herba Hordei Vulgaris.Afterwards barley is placed roughly the culturing room 24 hours of 20 ℃ and 100% relative humidity, placed afterwards under 60% relative humidity 7-10 days.By comparing, between the 8th day to the 11st day, the state of an illness of wheat seeding is estimated with untreated control.
Under these conditions, under the dosage of 0.1g/l, the compound of observing good (at least 75%) or provide protection fully has: 1,3,4; 5 (EE), 7 (EE), 8 (EZ), 8 (EE), 8 (ZE); 8 (ZZ), 9 (EE), 10 (EE), 16 (EE), 17; 142 (EZ), 142 (EE), 143 (EZ), 143 (EE), 148; 149 (EE), 154,167,632,633; 634,637,640,651,659 (EZ).
Dosage 1g/l under this test conditions is equivalent to the dosage that the g/ha with the 1kg/ha order of magnitude represents.
Arthropodicidal application of compound method
Carried out adopting the following representative test program of The compounds of this invention, determined The compounds of this invention, comprised pesticidal use and the activity of aphid, caterpillar, fly, cockroach and corn cutworm some insect.The concrete kind of test is as follows:
Belong to, plant popular name
Aphis gossypii cotten aphid
Spodoptera eridania subtropics mythimna separata
Musca domestica housefly
Periplaneta americana periplaneta americana
Diabrotica undecimpunctata melon 11 asterophyllite first
Preparation:
According to following method the test compound preparation is used.
For cotten aphid, subtropics mythimna separata and melon 11 asterophyllite first, test compound is joined in the solution of dimethyl formamide, acetone, emulsifying agent (alkyl aryl polyether alcohol organic sulfonic acid ester) and water, prepare solution or suspension, the result gets the test compound of 500ppm concentration.
For the housefly test, usefulness 20% aqueous sucrose solution is by weight adjusted above-mentioned water-acetone-DMF-emulsifier solution, forms the test compound of 250ppm concentration.
For melon 11 asterophyllite first, above-mentioned water-acetone-DMF-emulsifier solution is adjusted to 6.75ppm handles ratio.
Test method
Then the insecticidal activity of test compound under specific concentrations (concentration is in ppm by weight (part/percentage) or kg/ha (kilogram/hectare)) of above-mentioned preparation done evaluation.
Cotten aphid: respectively the cotten aphid of adult and nymph is cultivated on potted plant little watercress or cotton.The plant that will infect 100-150 aphid with 500ppm test compound preparation is wetting to downward drip state.As untreated control, also use the extremely downward drip state of the water-acetone-DMF-emulsifier solution that does not contain test compound to the plant that infects.The plant of handling was deposited three days, afterwards the dead aphid number of counting.
Subtropics mythimna separata: the beans leaf is wetting to downward drip state with 500ppm test compound preparation.As untreated control, also use the water-acetone-DMF-emulsifier solution that does not contain test compound to downward drip state to the beans foliar spray.With 5 or 6 select at random two age the subtropics mythimna separata put into the plastic containers that each all has dried processing blade.With container closure, and placed five days.Even, be considered to dead by promoting to move an individual long larva when stimulating.
Housefly: the adult housefly that uses four to six ages in days.Make it inactive with carbon dioxide narcosis.Prepare a bait cup, contain 250ppm test compound preparation/sucrose solution and absorbent tampons pad in the cup.As untreated control, then in a similar manner, with the water-acetone-DMF-emulsifying agent-sucrose solution that does not contain test compound.Before putting into the housefly that 12-25 only anaesthetizes, the bait cup is put into cage.24 hours postevaluation mortality ratio.
Corn cutworm: corn seed is put into glass jar, and cover the dry sand loam.Use the 500ppm test compound, make soil concentration reach 6.75ppm.As untreated control, use the water-acetone-DMF-emulsifier solution of aliquot sample in a similar manner.Cultivate after 24 hours,, and insert about 25 corn cutworm ovum mixing with soil.Infect after eight days,, estimate mortality ratio with Berlese funnel extraction method.
Periplaneta americana: in the cylinder that contains 1-2ml 500ppm test preparation, add the dog food bottle.As untreated control,, use the water-acetone that does not the contain test compound-DMF-emulsifier solution of aliquot with similar mode.After 48 hours, the cockroach nymph is added in the cylinder.Infect the back the 1st day and the 5th day, and estimated the contact and the mortality ratio of ingesting.Test-results:
With some compounds in the aforesaid method evaluation scope of the invention.The activity of anti-above-mentioned one or more insect of following compounds in the table 4 reaches 100% mortality ratio.
Table 4
Compound number Cotten aphid The subtropics mythimna separata Housefly Periplaneta americana Melon 11 asterophyllite first
????5(EZ) ????X ????X
????16 ????X ????X ????X
????16(EE) ????X ????X
????8(EZ) ????X ????X
????9 ????X ????X ????X ????X
????9(EE) ????X
????7(EZ) ????X ????X ????X
????7(EE) ????X ????X ????X
????142(EZ) ????X ????X ????X

Claims (19)

1. the hydroxamic acid derivatives of general formula (I) Wherein: G is the G of following formula 1Or G 2Or G 3Or G 4:
Figure A9619483000022
X 1, X 2, X 3Be hydrogen or halogen atom independently; Hydroxyl, sulfydryl, nitro, thiocyano, azido-, cyano group;
-alkyl or haloalkyl, cyano group alkyl, alkoxyl group, halogenated alkoxy, cyano alkoxy, alkylthio, haloalkyl thio, cyano group alkylthio, alkyl sulphinyl, haloalkyl sulfinyl, alkyl sulphonyl, halogenated alkyl sulfonyl, these alkyl or alkoxyl group are rudimentary group;
-cycloalkyl or halogenated cycloalkyl, thiazolinyl, alkynyl, alkene oxygen base, alkynyloxy group, thiazolinyl sulfo-, alkynes sulfo-, these alkyl or alkenyls or alkynyl are rudimentary group;
-amino, alkylamino, dialkylamino, kharophen,
-lower alkoxycarbonyl,
-N-alkyl-carbamoyl,
-N, N-dialkyl amido formyl radical,
-N-alkylsulfamoyl group,
-N, the N-dialkyl sulfamine,
R 1, R 2Be hydrogen atom or alkyl or haloalkyl, cycloalkyl or halogenated cycloalkyl, cyano group, alkoxyalkyl, alkoxy carbonyl independently; Or R 1And R 2Can form divalent group together, as alkylidene group, these alkyl or alkoxyl group or alkylidene group are rudimentary group,
R 3Be hydrogen atom or alkyl or haloalkyl, cycloalkyl or halogenated cycloalkyl, thiazolinyl, alkynyl, alkoxyalkyl, alkylthio alkyl, cyano group alkyl, halogenated alkoxy alkyl, dialkylaminoalkyl, the optional phenyl that replaces or the optional benzyl that replaces, these alkyl or alkoxyl group or alkenyl or alkynyl are rudimentary group
W is oxygen or sulphur atom, SO and SO 2,
R 4, R 5Be low alkyl group,
R 6, R 7Be hydrogen atom or low alkyl group independently.
2. according to the hydroxamic acid derivatives of claim 1, wherein alkyl has 6 carbon atoms of as many as.
3. according to each hydroxamic acid derivatives of aforementioned claim, wherein:
When G is G 1Or G 2The time, R 4It is methyl; R 5It is methyl; Or
When G is G 3Or G 4The time, R 5It is methyl; R 6Be methyl and R 7Be hydrogen.
4. according to each hydroxamic acid derivatives of aforementioned claim, wherein:
R 3Be hydrogen atom, low alkyl group or cycloalkyl, and/or
R 1Be hydrogen atom or low alkyl group or cycloalkyl, cyano group, alkoxy carbonyl, haloalkyl and/or
R 2Be hydrogen or methyl and/or
X 3Be H and/or
X 1Or X 2Be alkyl, cyano group, halogen, haloalkyl, alkoxyl group, halogenated alkoxy.
5. according to each hydroxamic acid derivatives of aforementioned claim, wherein the two keys of two in the formula as shown in claim 1 (I) are the E configuration.
6. according to each hydroxamic acid derivatives of aforementioned claim, X wherein 1Be methyl or hydrogen; X 2And X 3Be hydrogen; R 1Be hydrogen or methyl; R 2Be hydrogen; R 3Be hydrogen or low alkyl group; W is a Sauerstoffatom.
7. can be used for preparing each the midbody compound of compound of aforementioned claim, it is the compound of the general formula (II) of S for W wherein, R wherein 1, R 2, R 3, X 1, X 2, X 3With define in each of aforementioned claim identical.
8. each method of compound for preparing aforementioned claim comprises the compound that makes general formula (II) and the compound reaction of general formula (III),
Figure A9619483000042
R wherein 1, R 2, R 3, W, X 1, X 2, X 3, G is identical with the definition in the general formula (I) above; V is a halogen atom.
9. the method for preparing compound according to Claim 8, wherein reaction is in the presence of acid binding agent, choosing wantonly is having in the presence of the solvent and/or at-80 ℃ to 150 ℃ or to the temperature of the boiling point of solvent, and/or at the ratio of the compound of the compound of formula (III) and formula (II) 0.5 to 2, carry out under the condition in preferred 0.9 to 1.1 scope.
10. preparation comprises according to following reaction formula according to each the method for compound of claim 1 to 6, and general formula (I-1) compound and methylamine are reacted,
R wherein 1, R 2, R 3, R 4, R 5, W, X 1, X 2, X 3With defined identical in each of aforementioned claim, and Z is N or CH.
11. preparation is according to the method for the compound of claim 10, wherein temperature of reaction is the boiling temperature of-50 ℃ to 100 ℃ or solvent, and/or the mol ratio of the compound of methylamine and formula (I-1) is 1 to 5, in preferred 1.1 to 2 the scope.
12. preparation according to claim 1 to 6 each compound and partly be the stereochemical method of E at the hydroxyl oximido of molecule, the hydroxyl oximido that identical chemical formula and this molecule are wherein arranged partly is that the stereochemical compound of Z is in solvent, preferably heating under the UV irradiation and/or in the presence of acid catalyst changes into E isomer until Z isomer and reaches suitable required transformation efficiency.
13. preparation is according to each the method for compound of claim 1 to 6, the W in its Chinese style (I) is SO or SO 2Method, wherein, making W wherein is that the respective compound of sulphur is used oxidizer treatment in inert solvent.
14. a pesticide composition, it comprises the arbitrary compound according to claim 1 to 6 as active substance, as acceptable liquid vehicle on the agricultural and/or on agricultural same acceptable surfactant.
15. according to the pesticide composition of claim 14, it is mycocidal and comprises 0.1 to 99%w/w, preferred 1 to 60% activeconstituents.
16. a processing has been subjected to maybe can be subjected to the method for the raise crop that fungal disease influences, it is characterized in that, to each the compound according to claim 1 to 6 of this crop applying effective dose.
17. the method according to claim 16 is characterized in that, under the situation of foliage applying, effective dose is 1 to 10000ppm, and/or preferred 1 to 500ppm scope, and applicating ratio is 5g/ha to 10kg/ha, preferred 10g/ha to 1kg/ha, or more preferably 50 to 500g/ha.
18. the method according to claim 17 is characterized in that, under the situation of soil application, effective dose is to 100kg/ha, in preferred 0.01 to 2kg/ha the scope 0.01.
19. according to the method for claim 16 to 18, medicament is to be applied to the cereal class.
CN96194830A 1995-04-17 1996-03-29 New hydroximic acid derivatives Pending CN1187810A (en)

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JP90733/95 1995-04-17
WOPCT/EP95/02984 1995-07-27
JP194670/95 1995-07-31
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CN96194830A CN1187810A (en) 1995-04-17 1996-03-29 New hydroximic acid derivatives

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108495843A (en) * 2016-01-29 2018-09-04 住友化学株式会社 The manufacturing method of thiocarbonyl compound
CN112844854A (en) * 2020-12-21 2021-05-28 矿冶科技集团有限公司 Flotation collector for copper oxide ores and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108495843A (en) * 2016-01-29 2018-09-04 住友化学株式会社 The manufacturing method of thiocarbonyl compound
CN112844854A (en) * 2020-12-21 2021-05-28 矿冶科技集团有限公司 Flotation collector for copper oxide ores and preparation method thereof
CN112844854B (en) * 2020-12-21 2024-06-04 矿冶科技集团有限公司 Flotation collector for copper oxide ore and preparation method thereof

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