JPH0873446A - Heterocyclic compound and insecticide/miticide - Google Patents

Abstract

PURPOSE: To obtain a highly safe new heterocyclic compound useful as an insecticide/miticide and low in the toxicity to fishes and the animals living in the Temperate Zone. CONSTITUTION: This compound is expressed by formula I [A is hydroxyl, an alkenyloxy, of formula II (R3 is a halogen, 1-5C alkyl, etc.; (j) is 0-4; W is O, S, NH, etc.; (m) is 0-4; (n) is 0-5], e.g. 2-(2,6-difluorophenyl)-4-(4-t- butoxyphenyl)-5,6-dihydro-4H-1,3-oxazine The compound of formula I is obtained by reaction of a compound of formula III using a dehydrogenating agent (e.g. dialkylazodicarboxylate) and a deoxygenating agent (e.g. triphenylphosphine) in a solvent such as THF at-20 deg.C to the boiling point of the solvent (in the case that Z is 0). This compound is effective for controlling esp. Aphis, armyworm, mite, etc., being also useful as an antifoulant for preventing aquatic organisms from sticking to underwater contact objects such as ship bottoms or fishnets.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel heterocyclic compound and an insecticide / acaricide.

[0002]

2. Description of the Related Art Conventionally, a large number of insecticides and acaricides have been used, but their efficacy is insufficient, their use is limited due to drug resistance problems, and they are harmful to plants. However, it is difficult to say that it is a satisfactory control agent because it may cause pollution, or may be highly toxic to human livestock and fish. Therefore, there is a demand for the development of a drug that can be used safely with few such drawbacks.

The following documents (1) to (4) disclose the compounds similar to the compound of the present invention, but there is no description of biological activity. Zh. Org. Khim, 18 , 178 (198
2) (CA 96 (21) 181222Z)

Embedded image Gazz. Chim. Ital. , 104 , 118
1 (1974)

[Chemical 9] r ₁ ; Me, Et, Ph: r ₂ ; H, Me: r ₃ ; H,
NO ₂ Ital. 927515 (patented) (CA86,
55459n) (polymeric monomer)

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a pest control agent which has a reliable effect and can be used safely.

The present invention is a pest control agent comprising a heterocyclic compound represented by the formula 10 and one or more of the compounds as an active ingredient.

[0006]

[Chemical 10]

[Wherein A is a chemical formula 11, a chemical formula 12, a chemical formula 13,
Chemical formula 14, Chemical formula 15, R ₄ —W ′, hydroxy group, alkenyloxy group, alkynyloxy group and naphthyl group, preferably bulky chemical formulas 11 to 15 and R ₄ —.
Represents any one selected from the group consisting of W '.

[0008]

[Chemical 11]

[0009]

[Chemical 12]

[0010]

[Chemical 13]

[0011]

Embedded image

[0012]

[Chemical 15]

B is a C ₁ -C ₅ alkyl group or C ₁ -C
₅ represents a haloalkyl group, W is O, S, NH, C
H _2, CH ₂ O or a single bond, Y is a halogen atom, C _1-5 alkyl or C _1-5 alkoxy group, preferably represents a halogen atom, Z is O or S,
W'represents -CC- (ethynylene group). R ₁ represents a hydrogen atom or a C ₁ -C ₅ alkyl group, R ₂ represents a halogen atom, a C ₁ -C ₅ alkyl group, a C ₁ -C ₅ haloalkyl group, a C ₁ -C ₅ alkoxy group, C ₁ -C ₅ haloalkoxy group, C ₁ -C ₅ alkylthio group, C ₁ -C ₅ alkylsulfonyl group, C ₁ -C ₅ alkylamino group, C ₁
Represents a -C ₅ dialkylamino group, a nitro group, a nitrile group, a carboxy group or a C ₁ -C ₅ alkoxycarbonyl group, and R ₃ represents a halogen atom, a C ₁ -C ₅ alkyl group, C
₃ -C ₇ cycloalkyl group, C ₁ -C ₅ haloalkyl group, optionally substituted with a phenyl group which may have a substituent C ₁ -C ₅ alkoxy group, C ₁ -C ₅ haloalkoxy group, Nitro group (may be substituted with a halogen atom, a C ₁ -C ₅ alkyl group or a C ₁ -C ₅ alkoxy group)
Represents a phenyl group or a phenoxy group (which may be substituted with a halogen atom, a C ₁ -C ₅ alkyl group or a C ₁ -C ₅ alkoxy group), and R ₄ represents a tri C ₁ -C ₅ alkylsilyl group or a substituted group. Represents a phenyl group which may be present. m is 0-
Represents an integer of 4, R ₂ may be the same or different when 2 or more, n represents an integer of 0-5, and Y is 2 or more
May be the same or different, j represents an integer of 0-4, and when 2 or more, R ₃ may be the same or different;
k represents an integer of 0-5, and when it is 2 or more, R ₃ may be the same or different. ]

Further, the substituent of the phenyl group of the C ₁ -C ₅ alkoxy group substituted by the phenyl group which may have a substituent of R ₃ is, for example, fluorine, chlorine, bromine,
Halogen atom such as iodine, methyl, ethyl, propyl,
Examples thereof include linear or branched C ₁ -C ₅ alkyl groups such as isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, isopentyl and the like. In the present invention, when the number of substituents is 2 or more, the substituents may be the same or different. The compound of the present invention can be synthesized, for example, by the following production method.

[0015]

Embedded image

The above reaction is carried out in an inert solvent such as water, benzene, tetrahydrofuran, acetonitrile, N, N-dimethylformamide or the like, optionally using a deoxidizing agent such as triethylamine, pyridine or sodium hydroxide, or if desired concentrated sulfuric acid. , A cyclohexylcarbodiimide or the like is used, and the temperature is from -20 ° C. to the boiling point of the solvent used for 30 minutes to several tens of hours.

[0017]

[Chemical 17]

The above reaction is carried out by using a dehydrogenating agent such as dialkylazodicarboxylate and a deoxidizing agent such as triphenylphosphine in an inert solvent such as tetrahydrofuran or benzene, if desired, from a solvent used from -20 ° C. A compound in which Z is an oxygen atom is obtained by performing the reaction at a temperature up to the boiling point for 30 minutes to several tens of hours. Further, a compound in which Z is a sulfur atom can be obtained by using Lawesson's reagent, phosphorus pentasulfide or the like as the dehydrating agent.

[0019]

[Chemical 18]

[Wherein M is a halogen atom or RSO
₃ (R is a C ₁ -C ₆ alkyl group such as methyl, or p
-Represents a phenyl group which may have a substituent such as a tolyl group. ) Is represented. The above reaction is carried out by using a halogenating agent such as thionyl chloride, phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, or R in an inert solvent such as benzene, tetrahydrofuran or chloroform.
-SO ₂ Cl and a base such as triethylamine, pyridine, sodium hydroxide and sodium carbonate at -20 ° C
From 30 minutes to several 1 at temperatures up to the boiling point of the solvent used
It will be held for 0 hours.

[0021]

[Chemical 19]

In the next reaction, solvent-free or water, alcohol, tetrahydrofuran, benzene, chloroform,
In an inert solvent such as N, N-dimethylformamide, acetonitrile, dioxane, or dichloromethane, if desired, a base such as sodium hydride, sodium hydroxide, sodium carbonate, triethylamine or pyridine, or a dehydrating agent such as sulfuric acid or phosphorus pentoxide may be used. It is carried out at a temperature from -20 ° C to the boiling point of the solvent used for several minutes to several tens hours. When Lawesson's reagent, phosphorus pentasulfide or the like is used as a dehydrating agent, a compound in which X is a sulfur atom can be obtained. The compound of the present invention can also be produced by appropriately selecting the following reaction formula or a reaction similar to a known one, depending on the kind of the substituent.

[0023]

Embedded image

In any case of carrying out the reaction, the desired product can be obtained by carrying out a usual post-treatment after the completion of the reaction. The structure of the compound of the present invention was determined by IR, NMR, Mass and the like. The compound of the present invention has geometric isomers of cis and trans as shown in Chemical formula 21, which are all included in the present invention.

[0025]

[Chemical 21]

[0026]

The present invention will be described in more detail with reference to the following examples. (Example 1)

[0027]

[Chemical formula 22]

N- [1- (4-t-butoxyphenyl)
-3-Hydroxypropyl] -2,6-difluorobenzamide 0.45 g and triethylamine 0.14 g
Was dissolved in 10 ml of tetrahydrofuran, 0.14 g of methanesulfonyl chloride was added at 10 ° C., and the mixture was reacted at room temperature. After 2 hours, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, filtered, and concentrated under reduced pressure to obtain the desired N-
0.5 g of [1- (4-t-butoxyphenyl) -3- (methylsulfonyloxy) propyl] -2,6-difluorobenzamide was obtained.

[0029]

[Chemical formula 23]

N- [1- (4-t-butoxyphenyl)
-3- (Methylsulfonyloxy) propyl] -2,
6-difluorobenzamide 0.5 g DMF 10 ml
Dissolve in 60% sodium hydride at 10 ° C 0.05
g was added. After stirring at room temperature for 3 hours, the reaction solution was added to ice water, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained residue is separated and purified by a silica gel column to obtain the desired 2-
0.33 g of (2,6-difluorophenyl) -4- (4-t-butoxyphenyl) -5,6-dihydro-4H-1,3-oxazine (Compound No. 141) was obtained. (Example 2)

[0031]

[Chemical formula 24]

2- (2,6-difluorophenyl) -4
-(4-Hydroxyphenyl) -5,6-dihydro-4
5.0 g of H-1,3-oxazine was added to dichloromethane 10
After dissolving in 0 ml and cooling to −70 ° C., 2.6 g of trifluoromethanesulfonic acid was added, and isobutene 1.
9 g were blown in in a few minutes. After 3 hours, the reaction solution was neutralized with triethylamine and then gradually returned to room temperature. The reaction solution was poured into ice water, the organic layer was separated, washed with water, dried over magnesium sulfate, and separated by filtration. The residue obtained by distilling off dichloromethane under reduced pressure was separated and purified by a silica gel column to give the desired 2- (2,6-difluorophenyl) -4- (4-
t-butoxyphenyl) -5,6-dihydro-4H-
There were obtained 3.6 g of 1,3-oxazine. (Example 3)

[0033]

[Chemical 25]

2- (2,6-difluorophenyl) -4
-(2-chloro-4-hydroxyphenyl) -5,6-
1.5 g of dihydro-4H-1,3-oxazine in DMF
Dissolve in 20 ml, at room temperature 0.7 g potassium carbonate,
1.1 g of 2,3-dichloro- (5-trifluoromethyl) pyridine was added, and the mixture was heated at 70 ° C for 1 hour. The reaction mixture was added to ice water, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained residue is separated and purified by a silica gel column to give the desired 2- (2,6-difluorophenyl) -4- {2-.
Chloro-4- (3-chloro-5-trifluoromethylpyridin-2-yloxy) phenyl) -5,6-dihydro-4H-1,3-oxazine (Compound No. 209)
1.7 g was obtained. (Example 4)

[0035]

[Chemical formula 26]

2- (2,6-difluorophenyl) -4
-(3-chloro-4-hydroxyphenyl) -5,6-
After dissolving 1.0 g of dihydro-4H-1,3-oxazine in 10 ml of dichloromethane and cooling to -70 ° C,
0.46 g of trifluoromethanesulfonic acid was added, and 5.2 g of isobutene was blown in for a few minutes. After 1 hour, the reaction solution was neutralized with triethylamine and then gradually returned to room temperature. The reaction solution was poured into ice water, the organic layer was separated, washed with water, dried over magnesium sulfate, and separated by filtration. The residue obtained by distilling off dichloromethane under reduced pressure was separated and purified by a silica gel column to give the desired 2- (2,6-difluorophenyl).
-4- (3-chloro-4-t-butoxyphenyl)-
0.5 g of 5,6-dihydro-4H-1,3-oxazine (Compound No. 67) was obtained. (Reference example 1)

[0037]

[Chemical 27]

4.0 g of 3- (4-benzyloxy-2-chlorophenyl) -4,5-dihydroisoxazoline
Is dissolved in 40 ml of tetrahydrofuran, and BF is added under ice cooling.
1.9 ml of ₃ · Et ₂ O, 1 of BH ₃ · (CH ₃ ) ₂ S
1.9 ml of 0 molar solution was added and the mixture was refluxed for 3 hours. After cooling the reaction solution, 15 ml of a 5N sodium hydroxide aqueous solution was added, and the mixture was refluxed again for 1 hour. After cooling the reaction solution, the organic layer was separated and concentrated under reduced pressure, and the obtained crystals were recrystallized from n-hexane to give the desired 3- (4-benzyloxy-2-chlorophenyl) -3-amino-1. 4 g of propanol are obtained. (Reference example 2)

[0039]

[Chemical 28]

4.0 g of 3- (4-benzyloxy-2-chlorophenyl) 3-amino-1-propanol and 1.4 g of triethylamine were added to 40 m of tetrahydrofuran.
It was dissolved in 1, and 2.7 g of 2,6-difluorobenzoyl chloride was added under stirring with ice cooling, and the mixture was reacted at room temperature. After 1 hour, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained residue was separated and purified by a silica gel column to obtain the target N- [1- (4-benzyloxy-2-chlorophenyl) -3-hydroxypropyl] -2,6-difluorobenzamide 5.2. . (Reference example 3)

[0041]

[Chemical 29]

N- [1- (4-benzyloxy-2-chlorophenyl) -3-hydroxypropyl] -2,6-
Difluorobenzamide (5.2 g) and triethylamine (1.5 g) were dissolved in tetrahydrofuran (50 ml), and methanesulfonyl chloride (1.7 g) was added thereto under ice-cooling stirring.
After dropping in 0 minutes, the mixture was reacted overnight at room temperature. The reaction mixture is poured into ice water, extracted with chloroform, washed with water, dried over magnesium sulfate, filtered, and concentrated under reduced pressure to give the desired N- [1- (4-benzyloxy-2
6.0 g of -chlorophenyl-3- (methylsulfonyloxy) propyl] -2,6-difluorobenzamide was obtained. (Example 5)

[0043]

[Chemical 30]

6.0 g of N- [1- (4-benzyloxy-2-chlorophenyl-3- (methylsulfonyloxy) propyl] -2,6-difluorobenzamide was dissolved in 60 ml of dioxane, and 1.3 g of triethylamine was added. The reaction mixture was poured into ice water, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, filtered and concentrated under reduced pressure to obtain the desired 2- (2,6).
-Difluorophenyl) -4- (4-benzyloxy-
2-chlorophenyl) -5,6-dihydro-4H-1,
4.8 g of 3-oxazine (Compound No. 1347) was obtained. (Reference example 4)

[0045]

[Chemical 31]

2- (2,6-difluorophenyl) -4
-(4-benzyloxy-2-chlorophenyl) -5,
2.0 g of 6-dihydro-4H-1,3-oxazine and 10 ml of cyclohexene were dissolved in 20 ml of ethyl alcohol, and 0.1 g of 20% palladium hydroxide carbon was added at room temperature, followed by refluxing for 30 minutes. The reaction solution is filtered through Celite,
Then, it is washed with ethyl acetate, washed with water, dried over magnesium sulfate, filtered, and concentrated under reduced pressure to obtain the desired 2-
(2,6-Difluorophenyl) -4- (4-hydroxy-2-chlorophenyl) -5,6-dihydro-4H-
1.4 g of 1,3-oxazine was obtained. (Example 6)

[0047]

[Chemical 32]

2- (2,6-difluorophenyl) -4
-(4-Hydroxy-2-chlorophenyl) -5,6-
After dissolving 1.0 g of dihydro-4H-1,3-oxazine in 10 ml of dichloromethane and cooling to -40 ° C, 0.5 g of trifluoromethanesulfonic acid was added, and 5.5 g of isobutene was blown in for several minutes. After 1 hour, the reaction solution was neutralized with triethylamine and gradually returned to room temperature. The reaction solution was poured into ice water, washed with water, dried over magnesium sulfate, and then filtered. The solvent was evaporated under reduced pressure and the obtained residue was separated and purified by silica gel column chromatography to give the desired 2- (2,6-difluorophenyl) -4.
-(2-chloro-4-t-butoxyphenyl) -5,6
-0.5 g of dihydro-4H-1,3-oxazine (Compound No. 2) was obtained. Representative examples of the compounds of the present invention including the above-mentioned examples are shown in Table 1.

[0049]

[Table 1001]

[0050]

[Table 1002]

[0051]

[Table 1003]

[0052]

[Table 1004]

[0053]

[Table 1005]

[0054]

[Table 1006]

[0055]

[Table 1007]

[0056]

[Table 100]

[0057]

[Table 1009]

[0058]

[Table 1010]

[0059]

[Table 1011]

[0060]

[Table 1012]

[0061]

[Table 1013]

[0062]

[Table 1014]

[0063]

[Table 1015]

[0064]

[Table 1016]

[0065]

[Table 1017]

[0066]

[Table 1018]

[0067]

[Table 1019]

[0068]

[Table 1020]

[0069]

[Table 1021]

[0070]

[Table 1022]

[0071]

[Table 1023]

[0072]

[Table 1024]

[0073]

[Table 1025]

[0074]

[Table 1026]

[0075]

[Table 1027]

[0076]

[Table 1028]

[0077]

[Table 1029]

[0078]

[Table 1030]

[0079]

[Table 1031]

[0080]

[Table 1032]

[0081]

[Table 1033]

[0082]

[Table 1034]

[0083]

[Table 1035]

[0084]

[Table 1036]

[0085]

[Table 1037]

[0086]

[Table 1038]

[0087]

[Table 1039]

[0088]

[Table 1040]

[0089]

[Table 1041]

[0090]

[Table 1042]

[0091]

[Table 1043]

[0092]

[Table 1044]

[0093]

[Table 1045]

[0094]

[Table 1046]

[0095]

[Table 1047]

[0096]

[Table 1048]

[0097]

[Table 1049]

[0098]

[Table 1050]

[0099]

[Table 1051]

[0100]

[Table 1052]

[0101]

[Table 1053]

[0102]

[Table 1054]

[0103]

[Table 1055]

[0104]

[Table 1056]

[0105]

[Table 1057]

[0106]

[Table 1058]

[0107]

[Table 1059]

[0108]

[Table 1060]

[0109]

[Table 1061]

[0110]

[Table 1062]

[0111]

[Table 1063]

[0112]

[Table 1064]

[0113]

[Table 1065]

[0114]

[Table 1066]

[0115]

[Table 1067]

[0116]

[Table 1068]

[0117]

[Table 1069]

[0118]

[Table 1070]

[0119]

[Table 1071]

[0120]

[Table 1072]

[0121]

[Table 1073]

[0122]

[Table 1074]

[0123]

[Table 1075]

[0124]

[Table 1076]

[0125]

[Table 1077]

[0126]

[Table 1078]

[0127]

[Table 1079]

[0128]

[Table 1080]

[0129]

[Table 1081]

[0130]

[Table 1082]

[0131]

[Table 1083]

[0132]

[Table 1084]

[0133]

[Table 1085]

[0134]

[Table 1086]

[0135]

[Table 1087]

[0136]

[Table 1088]

[0137]

[Table 1089]

[0138]

[Table 1090]

[0139]

[Table 1091]

[0140]

[Table 1092]

[0141]

[Table 1093]

[0142]

[Table 1094]

[0143]

[Table 1095]

[0144]

[Table 1096]

[0145]

[Table 1097]

[0146]

[Table 1098]

[0147]

[Table 1099]

[0148]

[Table 1100]

[0149]

[Table 1101]

[0150]

[Table 1102]

[0151]

[Table 1103]

[0152]

[Table 1104]

[0153]

[Table 1105]

[0154]

[Table 1106]

[0155]

[Table 1107]

[0156]

[Table 1108]

[0157]

[Table 1109]

[0158]

[Table 1110]

[0159]

[Table 1111]

[0160]

[Table 1112]

[0161]

[Table 1113]

[0162]

[Table 1114]

[0163]

[Table 1115]

[0164]

[Table 1116]

[0165]

[Table 1117]

[0166]

[Table 1118]

[0167]

[Table 1119]

[0168]

[Table 1120]

[0169]

[Table 1121]

[0170]

[Table 1122]

[0171]

[Table 1123]

[0172]

[Table 1124]

[0173]

[Table 1125]

[0174]

[Table 1126]

[0175]

[Table 1127]

[0176]

[Table 1128]

[0177]

[Table 1129]

[0178]

[Table 1130]

[0179]

[Table 1131]

[0180]

[Table 1132]

[0181]

[Table 1133]

[0182]

[Table 1134]

[0183]

[Table 1135]

[0184]

[Table 1136]

[0185]

[Table 1137]

[0186]

[Table 1138]

[0187]

[Table 1139]

[0188]

[Table 1140]

[0189]

[Table 1141]

[0190]

[Table 1142]

[0191]

[Table 1143]

[0192]

[Table 1144]

[0193]

[Table 1145]

[0194]

[Table 1146]

[0195]

[Table 1147]

[0196]

[Table 1148]

[0197]

[Table 1149]

[0198]

[Table 1150]

[0199]

[Table 1151]

[0200]

[Table 1152]

[0201]

[Table 1153]

[0202]

[Table 1154]

[0203]

[Table 1155]

[0204]

[Table 1156]

[0205]

[Table 1157]

[0206]

[Table 1158]

[0207]

[Table 1159]

[0208]

[Table 1160]

[0209]

[Table 1161]

[0210]

[Table 1162]

[0211]

[Table 1163]

[0212]

[Table 1164]

[0213]

[Table 1165]

[0214]

[Table 1166]

[0215]

[Table 1167]

[0216]

[Table 1168]

[0219]

[Table 1169]

[0218]

[Table 1170]

[0219]

[Table 1171]

[0220]

[Table 1172]

[0221]

[Table 1173]

[0222]

[Table 1174]

[0223]

[Table 1175]

[0224]

[Table 1176]

[0225]

[Table 1177]

[0226]

[Table 1178]

[0227]

[Table 1179]

[0228]

[Table 1180]

[0229]

[Table 1181]

[0230]

[Table 1182]

[0231]

[Table 1183]

[0232]

[Table 1184]

[0233]

[Table 1185]

[0234]

[Table 1186]

[0235]

[Table 1187]

[0236]

[Table 1188]

[0237]

[Table 1189]

[0238]

[Table 1190]

[0239]

[Table 1191]

[0240]

[Table 1192]

[0241]

[Table 1193]

[0242]

[Table 1194]

[0243]

[Table 1195]

[0244]

[Table 1196]

[0245]

[Table 1197]

NMR spectrum data of compound: [Compound No. 209] δ _TMS (CDCl ₃ ) (ppm): 1.92 (m, 1)
H), 2.55 (m, 1H), 4.44 (m, 2H),
5.18 (m, 1H), 6.96 (m, 2H), 7.1
0-7.60 (m, 4H), 7.99 (d, 1H),
8.28 (d, 1H)

[Compound No. 210] δ _TMS (CDCl ₃ ) (ppm): 1.98 (m, 1
H), 2.56 (m, 1H), 4.45 (m, 2H),
5.12 (m, 1H), 6.95 (m, 2H), 7.1
8 to 7.42 (m, 3H), 7.55 (d, 1H),
7.99 (d, 1H), 8.38 (d, 1H)

[Compound No. 212] δ _TMS (CDCl ₃ ) (ppm): 1.97 (m, 1
H), 2.36 (m, 1H), 2.40 (s, 3H),
4.40 (m, 2H), 5.01 (m, 1H), 6.8
1-7.07 (m, 4H), 7.22-7.43 (m,
2H), 7.98 (d, 1H), 8.28 (d, 1H)

[Compound No. 216] δ _TMS (CDCl ₃ ) (ppm): 1.43 (t, 3)
H), 1.97 (m, 1H), 2.46 (m, 1H),
4.06 (m, 2H), 4.37 (m, 2H), 5.1
3 (m, 1H), 6.67 to 7.00 (m, 4H),
7.25 to 7.45 (m, 2H), 7.97 (d, 1
H), 8.28 (d, 1H)

[Compound No. 340] δ _TMS (CDCl ₃ ) (ppm): 2.00 (m, 1
H), 2.49 (m, 1H), 4.45 (m, 2H),
5.10 (m, 1H), 6.93-7.08 (m, 3
H), 7.27-7.43 (m, 2H), 8.00
(D, 1H), 8.24 (d, 1H)

[Compound No. 347] δ _TMS (CDCl ₃ ) (ppm): 2.04 (m, 1)
H), 2.40 (m, 1H), 4.42 (m, 2H),
4.79 (m, 1H), 6.96 (m, 2H), 7.2
9-7.42 (m, 1H), 7.45 (s, 2H),
8.00 (d, 1H), 8.20 (d, 1H)

[Compound No. 348] δ _TMS (CDCl ₃ ) (ppm): 2.05 (m, 1
H), 2.40 (m, 1H), 4.40 (m, 2H),
4.85 (q, 1H), 6.93 (m, 2H), 7.1
6 (d, 2H), 7.32 (m, 1H), 7.45
(D, 2H), 7.96 (d, 1H), 8.25 (d,
1H)

[Compound No. 361] δ _TMS (CDCl ₃ ) (ppm): 2.10 (m, 1
H), 2.40 (m, 1H), 4.42 (m, 2H),
4.87 (m, 1H), 7.00-7.51 (m, 7
H), 7.98 (d, 1H), 8.28 (d, 1H)

[Compound No. 585] δ _TMS (CDCl ₃ ) (ppm): 1.42 (d, 3)
H), 1.50 (m, 1H), 2.57 (m, 1H),
4.68 (m, 2H), 5.18 (m, 1H), 6.9
5 (m, 2H), 7.08-7.67 (m, 4H),
7.99 (d, 1H), 8.29 (d, 1H)

[Compound No. 633] δ _TMS (CDCl ₃ ) (ppm): 1.41 (d, 3)
H), 2.12 (m, 2H), 4.37 (m, 1H),
4.97 (m, 1H), 6.97 (m, 2H), 7.1
3-7.47 (m, 5H), 7.99 (d, 1H),
8.28 (d, 1H)

[Compound No. 646] δ _TMS (CDCl ₃ ) (ppm): 1.40 (d, 3)
H), 1.70 (m, 1H), 2.34 (m, 1H),
4.62 (m, 1H), 4.80 (m, 1H), 6.9
1 (m, 2H), 7.10-7.50 (m, 5H),
7.98 (d.1H), 8.25 (d.1H)

[Compound No. 1007] δ _TMS (CDCl ₃ ) (ppm): 1.28 (s, 9
H), 1.88 (m, 1H), 2.50 (m, 1H),
4.39 (m, 2H), 5.10 (m, 1H), 6.9
5 (m, 2H), 7.29-7.55 (m, 4H)

[Compound No. 1060] δ _TMS (CDCl ₃ ) (ppm): 1.31 (s, 9
H), 1.37 (d, 3H), 2.30 (m, 1H),
4.57 (m, 1H), 4.82 (m, 1H), 6.9
0 (m, 2H), 7.20-7.42 (m, 5H)

[Compound No. 1086] δ _TMS (CDCl ₃ ) (ppm): 1.30 (s, 9)
H), 2.06 (m, 1H), 2.37 (m, 1H),
4.38 (m, 2H), 4.79 (m, 1H), 6.9
3 (m, 2H)

[Compound No. 1199] δ _TMS (CDCl ₃ ) (ppm): 1.37 (s, 9
H), 2.10 (m, 1H), 2.43 (m, 1H),
4.45 (m, 2H), 4.95 (m, 1H), 6.9
5 (m, 2H), 7.27-7.63 (m, 9H)

[Compound No. 1207] δ _TMS (CDCl ₃ ) (ppm): 2.08 (m, 1
H), 2.38 (m, 1H), 4.40 (m, 2H),
4.82 (m, 1H), 6.94 (m, 2H), 7.2
1-7.54 (m, 8H)

[Compound No. 1208] δ _TMS (CDCl ₃ ) (ppm): 2.03 (m, 1
H), 2.48 (m, 1H), 4.40 (m, 2H),
4.82 (m, 1H), 6.94 (m, 2H), 7.2
2-7.60 (m, 7H), 7.68 (d, 1H)

[Compound No. 1214] δ _TMS (CDCl ₃ ) (ppm): 2.08 (m, 1
H), 2.42 (m, 1H), 4.41 (m, 2H),
4.88 (m, 1H), 6.93 (m, 2H), 7.2
2-7.56 (m, 7H), 7.72 (d, 1H)

[Compound No. 1215] δ _TMS (CDCl ₃ ) (ppm): 2.09 (m, 1)
H), 2.40 (m, 1H), 4.42 (m, 2H),
4.85 (m, 1H), 6.95 (m, 2H), 7.2
3-7.63 (m, 8H)

[Compound No. 1255] δ _TMS (CDCl ₃ ) (ppm): 1.35 (s, 9)
H), 2.08 (m, 1H), 2.42 (m, 1H),
4.42 (m, 2H), 4.90 (m, 1H), 6.9
5 (m, 2H), 7.29-7.65 (m, 9H)

[Compound No. 1261] δ _TMS (CDCl ₃ ) (ppm): 0.25 (s, 9
H), 1.97 (m, 1H), 2.35 (m, 1H),
4.37 (m, 2H), 4.80 (m, 1H), 6.9
3 (m, 2H), 7.23 to 7.50 (m, 5H)

[Compound No. 1347] δ _TMS (CDCl ₃ ) (ppm): 1.85 (m, 1
H), 2.45 (m, 1H), 4.39 (m, 2H),
5.04 (s, 2H), 5.08 (m, 1H), 6.8
8 to 7.45 (m, 11H)

[Compound No. 1351] δ _TMS (CDCl ₃ ) (ppm): 1.48 (s, 9
H), 1.92 (m, 1H), 2.39 (m, 1H),
3.85 (s, 3H), 4.35 (m, 2H), 5.0
3 (m, 1H), 6.89-7.00 (m, 3H),
7.25-7.40 (m, 2H)

[Compound No. 1353] δ _TMS (CDCl ₃ ) (ppm): 1.42 (t, 3)
H), 1.50 (s, 9H), 1.89 (m, 1H),
2.36 (m, 1H), 4.08 (m, 2H), 4.3
7 (m, 2H), 5.03 (m, 1H), 6.92
(S, 1H), 7.22-7.65 (m, 5H)

[Compound No. 1364] δ _TMS (CDCl ₃ ) (ppm): 1.40 (s, 9
H), 2.02 (m, 1H), 2.32 (m, 1H),
2.47 (m, 1H), 4.35 (m, 2H), 4.7
0 (d, 2H), 4.75 (m, 1H), 6.92
(M, 2H), 7.11-7.39 (m, 4H)

[Compound No. 1377] δ _TMS (CDCl ₃ ) (ppm): 2.15 (m, 1
H), 2.42 (m, 1H), 4.42 (m, 2H),
5.00 (m, 1H), 7.20-7.93 (m, 9
H)

The compound of the present invention can be used for controlling agricultural pests, sanitary pests, storage pests, clothing pests, house pests and the like, and has an insecticidal, nymphicidal, larvicidal and ovicidal action. The following are typical examples. Lepidopteran pest,
For example, Hasmonyoto, Spodoptera litura, Tamanagaga, Atomidae, Tamanaginuwaba, Kokonaga, Chanococa montana, Chamomaki, Peach mosquito, Nashihime Shinkui, Mikanhamogiga, Chanohosuga, Meadowagai corn, corned moth, corned moth, corned moths , Heliotis genus, Helicoverpa genus, Agrotis genus, squid, codling moth, cotton bollworm, etc., Hemiptera pests, for example, green peach aphid, cotton aphid, black lice aphid, warbler beetle aphid, nematode beetle, yam beetle bug , Scale insect, whitefly, whitefly, tobacco whitefly, whitefly, nashigumbai, brown planthopper, himehime Biunka, Sejirounka,
Pests of the order Coleoptera, such as leafhoppers, leaf beetle, urchin beetle, Colorado potato beetle, rice weevil, elephant beetle, azuki bean weevil, beetle beetle, genus chafer, diablotica genus, mosquito larva, mosquito larvae, scorpionopsis, staghorn beetle, asclepias serrata, larvae, ascendant, ascendantia, ascendantia, ascendantia, ascendantia, moss, and moss. Dictyostelium, Boll Weevils, etc., Diptera pests, such as house flies, fleas flies, sentinic flies, sea flies, mandarin fruit flies, rice flies, rice leaf flies, Drosophila melanogaster, mosquitoes, etc. Thysanoptera, teal thrips, etc., pests of the order Hymenoptera, for example, househopper, yellow hornet, turnip, etc., orthoptera Insects, for example, German cockroaches, American cockroaches, Black cockroaches, Black locusts, etc., Pteridae, such as house termites, Yamato termites, etc., Insecta, such as, for example, human fleas, lice pests, for example, human lice, mites, for example , Mite mites, kanzawa mites, citrus mites, apple mites, citrus mites, apple rust mites, mite dust mites, brevi palpas, eotetranicus, robined mites,
Phytoparasitic nematodes such as Physcomitrella patens, Dermatophagoides farinae, Dermatophagoides farinae, Haemaphysalis longicornis, and the like, such as Sweet potato Nematode nematode, Negaresenchuu nematode, Soybean cyst nematode, Rice gingale nematode, pine wood nematode and the like. Among the above-mentioned pests, pests to which the compound of the present invention is particularly preferably applied are cotton aphids, armyworm, mites and the like.

Further, in recent years, many insect pests such as diamondback moth, planthopper, leafhopper, aphid have developed resistance to organophosphorus agents, carbamate agents and acaricides, causing a problem of insufficient efficacy of these agents. A drug effective for pests and mites is desired. The compound of the present invention is a drug having an excellent insecticidal and acaricidal effect not only on susceptible strains but also on organic phosphorus agents, carbamate agents, pyrethroids and acaricide-resistant strains of pests and mites. Further, the compound of the present invention has no phytotoxicity, has low toxicity to fish poisons and warm-blooded animals, and is a highly safe drug. The compound of the present invention can also be used as an antifouling agent for preventing aquatic organisms from adhering to underwater contact substances such as ship bottoms and fishnets.

[0274]

[Means for Solving the Problems]

[Insecticidal and acaricidal agent] When the compound of the present invention thus obtained is actually applied, it can be used in a pure form without adding other components, and it is used as a pesticide. The obtained form, that is, a wettable powder, a granule, a powder, an emulsion, an aqueous solution, a suspension, a flowable form and the like can be used. When a solidifying agent is intended as an additive and a carrier, soybean grains, vegetable powder such as wheat flour, diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, mineral fine powder such as clay, benzoic acid Soda, urea,
Organic and inorganic compounds such as Glauber's salt are used. For the purpose of liquid dosage form, kerosene, petroleum fractions such as xylene and solvent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil, water. Etc. are used as a solvent. If necessary, a surfactant may be added in order to obtain a uniform and stable form in these preparations. The wettable powder, emulsion and flowable agent thus obtained are diluted with water to a predetermined concentration to give a suspension or emulsion, and the powder and granules are used as they are for spraying on plants.

Needless to say, the compounds of the present invention are sufficiently effective alone, but they may be used in combination with one or more of various fungicides, insecticides / miticides or synergists. I can.

Typical examples of fungicides, insecticides, acaricides and plant growth regulators which can be used by mixing with the compound of the present invention are shown below. Bactericides: captan, folpet, thiuram, diram, zineb, manneb, mancozeb, propineb, polycarbamate, chlorothalonil, quintozen, captaphor, iprodione, prosaimidone, vinclozolin, fluoroimide, cymoxanil, mepronil, flutolanil, pencyclone, oxycarboxin, Fosetyl aluminum, propamocurve, triadimefon,
Triadimenol, Propiconazole, Diclobutrazol, Bitertanol, Hexaconazole, Microbutanyl, Flucyrazole, Etaconazole, Fluotrimazole, Flutriafen, Penconazole, Diniconazole, Cyproconazole, Fenalimol, Triflumizole, Prochloraz, Imazalil, pefurazoate, tridemorph, fenpropimorph, triphorin, butiobate, pyrifenox, anilazine, polyoxine, metalaxyl, oxadixyl, furaraxyl, isoprothiolane, probenazole, pyrrolnitrin, blasticidin S, kasugamycin, validamycin, dihydrostrenoptomycin, sulfate. , Carbendazim, thiophanate methyl, hymexazole, basic copper chloride Basic copper sulfate, fentin acetate, triphenyltin hydroxide, Sierra preparative Fen benthiavalicarb,
Metasulfocarb, quinomethionate, vinapacryl,
Lecithin, baking soda, dithianon, zinocap, phenaminosulf, diclomedine, guazatine, dodine, IBP,
Edifenphos, mepanipyrim, fermzone, trichlamide, metasulfocarb, fluazinam, etquinolac, dimethomorph, pyroquilon, teclophthalam,
Fusalide, phenazine oxide, thiabendazole,
Tricyclazole, vinclozolin, cimoxanil, cyclobutanyl, guazatine, propamocarb hydrochloride, oxolinic acid.

Insecticides and acaricides: Organophosphorus and carbamate insecticides: fenthion, fenitrothion, diazinon, chlorpyrifos, ES
P, bamidothion, fentoate, dimethoate, formothion, marathon, trichlorfon, thiomethone,
Phosmet, dichlorvos, acephate, EPBP,
Methyl parathion, oxydimethone methyl, ethione,
Salithion, cyanophos, isoxathion, pyridafenthion, phosalone, methithione, sulprophos, chlorfenbinphos, tetrachlorbinphos, dimethylvinphos, propaphos, isofenphos, ethylthiomethone, profenophos, pyraclofos, monocrotophos, azinphosmethyl, aldicarb, mesomil, thiodicarb, Carbofuran, Carbosulfan, Benfuracarb, Fratiocarb, Propoxur, BPMC,
MTMC, MIPC, carbaryl, pirimicarb, etiophencarb, phenoxycarb.

Pyrethroid insecticides: permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropatrine, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propasulin, phenothrin, prothrin, fluvalinate, cyfluthrin, cyhalothrin, flucitrinate, eth. Fenprox, cycloprothrin, tromethrin, silafluofen, profenprox, acrinathrin, etc.

Benzoylurea-based and other insecticides: diflubenzuron, chlorfluazuron, hexaflumuron, triflumuron, tetrabenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, methoprene, cartap, thiocyclam, bensultap. , Benzoepin, diafenthiuron, imidacloprid, acetamiprid, nitenpyram, fipronil, nicotine sulfate, rotenone, methaaldehyde, machine oil, microbial pesticides such as BT and insect pathogenic virus. Nematicides: fenamiphos, fosthiazate, etc. Acaricide: chlorbenzilate, phenisobromolate, dicofol, amitraz, BPPS, benzomate,
Hexthiazox, fenbutatin oxide, polynactin, quinomethionate, CPCBS, tetradiphone, avermectin, milbemectin, clofentezine, cyhexatin, pyridaben, fenpyroximate, tebufenpyrad, pyrimidifen, phenothiocarb, dienochlor and the like. Plant growth regulators: gibberellins (eg gibberellin A ₃ , gibberellin A ₄ , gibberellin A ₇ ) IAA, NA
A. etc.

[0280]

【Example】

[Insecticidal / Acaricide] Next, examples of the composition of the present invention will be shown, but the additives and the addition ratios should not be limited to these examples, and can be widely varied. . Parts in the formulation examples indicate parts by weight.

Example 5 Emulsion Compound of the present invention 10 parts Alkylphenyl polyoxyethylene 5 parts Dimethylformamide 50 parts Xylene 35 parts The above components are mixed and dissolved, and diluted with water before use and sprayed as an emulsion.

Example 6 Wettable powder Compound of the present invention 10 parts Higher alcohol sulfate ester 5 parts Diatomaceous earth 80 parts Silica 5 parts The above components are mixed and ground into fine powder, which is diluted with water before use and sprayed as a suspension.

Example 7 Dust agent Compound of the present invention 5 parts Talc 94.7 parts Silica 0.3 parts

Example 8 Granules Compound of the present invention 5 parts Clay 73 parts Bentonite 20 parts Dioctyl sulfosuccinate sodium salt 1 part Sodium phosphate 1 part The above is granulated and applied as it is when used.

[0285]

【The invention's effect】

Test Example 1 Efficacy against cotton aphid Adults of cotton aphid were inoculated into cucumbers seeded in three-spots and 10 days after germination. Remove the adult one day later,
According to the emulsion formulation shown in Example 5 of the above drug, the compound concentration of cucumber parasitized by nymphs born was 125.
A chemical solution diluted with water to a ppm was sprayed. It was placed in a thermostatic chamber at a temperature of 25 ° C. and a humidity of 65%, and the insecticidal rate was investigated 6 days later. The results are shown in Table 2.

[0286]

[Table 201]

[0287]

[Table 202]

Test Example 2 Efficacy against armyworm The compound was diluted with water to a compound concentration of 125 ppm according to the wettable powder formulation shown in Example 6 of the drug. Immerse corn leaves in the solution for 30 seconds, air dry,
The leaves were placed in a petri dish containing five third-instar larvae of armyworm. The glass cover was placed and placed in a thermostatic chamber at a temperature of 25 ° C. and a humidity of 65%, and the insecticidal rate was examined after 5 days. It is 2 repetitions. The results are shown in Table 3.

[0289]

[Table 3]

Test Example 3 Efficacy against Nite Mite [0290] Seventeen adult female adults of Nymphalid mite resistant to organophosphorus agents were inoculated on the first true leaves 7 to 10 days after germination of kidney beans sown in two-spots. According to the wettable powder formulation shown in Example 6 of the drug, a drug solution diluted with water to a compound concentration of 125 ppm was sprayed. It was placed in a temperature-controlled room at a temperature of 25 ° C. and a humidity of 65%, 3 days after spraying, the adults were removed, and the eggs laid during these 3 days were examined on the 11th day to see if they could develop into adults, The acaricidal effectiveness was calculated. The results are shown in Table 4. In addition, the acaricidal effectiveness was calculated by the following formula.

[0291]

[Equation 1]

[0292]

[Table 401]

[0293]

[Table 402]

[0294]

[Table 403]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location C07D 417/12 213 (72) Inventor Tatsumi Suzuki 345 Takada, Yanagicho, Odawara-shi, Kanagawa Nippon Soda Co., Ltd. Odawara Research Center (72) Inventor Renpei Hatano 345 Yanagicho Takada, Odawara, Kanagawa Japan Soda Co., Ltd. Odawara Research Center (72) Inventor Atsushi Yamamoto 345 Takayanagi, Odawara, Kanagawa Pref. (72) Inventor Jun Mitsui, 62-1 Sakabe, Haibara-cho, Haibara-gun, Shizuoka Prefecture, within the Harahara Agricultural Research Institute, Nippon Soda Co., Ltd. (72) Takao Iwasa, 345, Yanagicho, Takada, Odawara, Kanagawa Prefecture

Claims (2)

[Claims] 1. A heterocyclic compound represented by formula 1. Embedded image [In the formula, A is chemical formula 2, chemical formula 3, chemical formula 4, chemical formula 5, chemical formula 6, R _4-
It represents any one selected from the group consisting of W ', a hydroxy group, an alkenyloxy group, an alkynyloxy group and a naphthyl group. Embedded image [Chemical 3] [Chemical 4] [Chemical 5] [Chemical 6] B represents a C ₁ -C ₅ alkyl group or a C ₁ -C ₅ haloalkyl group, and W represents O, S, NH, CH ₂ , CH.
₂ O or a single bond, Y is a halogen atom, C
_1-5 alkyl group or C _1-5 alkoxy group, Z
Represents O or S, and W'represents -CC- (ethynylene). R ₁ represents a hydrogen atom or a C ₁ -C ₅ alkyl group, R ₂ represents a halogen atom, a C ₁ -C ₅ alkyl group, a C ₁ -C ₅ haloalkyl group, a C ₁ -C ₅ alkoxy group, C ₁ -C ₅ haloalkoxy groups, C ₁ -C ₅ alkylthio groups, C ₁ -C ₅ alkylsulfonyl groups, C ₁ -C
₅ alkylamino groups, C ₁ -C ₅ dialkylamino groups,
Nitro group, nitrile group, carboxy group or C ₁ -C ₅
Represents an alkoxycarbonyl group, wherein R ₃ is substituted with a halogen atom, a C ₁ -C ₅ alkyl group, a C ₃ -C ₇ cycloalkyl group, a C ₁ -C ₅ haloalkyl group, or a phenyl group which may have a substituent. Optionally substituted C ₁ -C ₅ alkoxy group, C ₁ -C ₅ haloalkoxy group, nitro group, (may be substituted with halogen atom, C ₁ -C ₅ alkyl group or C ₁ -C ₅ alkoxy group ) Represents a phenyl group or a phenoxy group (which may be substituted with a halogen atom, a C ₁ -C ₅ alkyl group or a C ₁ -C ₅ alkoxy group), R ₄
Represents a tri C ₁ -C ₅ alkylsilyl group or an optionally substituted phenyl group. m represents an integer of 0-4, 2
In the above case, R ₂ may be the same or different, and n is 0.
Represents an integer of -5, when 2 or more, Y may be the same or different, and j represents an integer of 0-4, and when 2 or more, R
₃ may be the same or different, k represents an integer of 0-5, and when ₃ or more, R ₃ may be the same or different. ] 2. An insecticidal and acaricidal agent which comprises, as an active ingredient, one or more heterocyclic compounds represented by the formula (7). [Chemical 7] [In the formula, A, Y, Z, R ₁ , R ₂ , m and n have the same meanings as described above. ]