Triazole derivatives as well as insecticide and acaricide

Abstract

A novel triazole derivative for use in an insecticide or an acaricide has a general formula [I]: ##STR1## (wherein R.sup.1 is an alkyl group, X is a hydrogen atom, a halogen atom, an alkyl group or the like, n is an integer of 1-5, Y is an alkenyl group, an alkynyl group, an alkoxyalkyl group or the like) and controls various injurious insects and mites, particularly mites and aphids without damaging crops.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to novel triazole derivatives as well as insecticide and acaricide containing the same as an active ingredient.

2. Description of the Related Art

Japanese Patent laid open No. 56-154464 and DE-A-363-1511 disclose that various triazole derivatives develop insecticidal and acaricidal activities. However, it can not be said that the insecticidal and acaricidal activities of these compounds described in these specifications are satisfactory.

Up to the present, various compounds such as organophosphorus compound, organotin compound and the like have been used for the control of pests in farm and garden crops and mites. However, these compounds have been used over many years, so that the above injurious insects have a resistance to chemicals to a certain extent and it recently becomes difficult to control these insects. Particularly, this tendency is conspicuous in lepidopteran injurious insects, mites and aphids and becomes serious. As a result, it is demanded to develop new types of insecticide and acaricide having a different function.

SUMMARY OF THE INVENTION

The inventors have made various studies in order to create novel insecticides and acaricides having a very high effect against wide injurious pests and capable of safely using, which have never been found in the conventional technique, in the development of the insecticide and acaricide having a function different from that of the conventional ones.

Further, the inventors have synthesized various triazole derivatives and examined their physiological activities. As a result, the inventors have found that novel triazole derivatives having a general formula [I] as mentioned later have an excellent effect against wide injurious pests in farm and garden crops, particularly lepidopteran injurious insects, mites and aphids and also develop a very high effect against eggs and larvae of mites and larvae of aphids having a resistance to the conventional chemicals, and the invention has been accomplished.

According to the invention, there is the provision of a triazole derivative having the following general formula [I]: ##STR2## [wherein R.sup.1 is an alkyl group, X is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, a nitro group, a cyano group or a trifluoromethyl group, n is an integer of 1-5 provided that when n is 2 or more, X may be an optional combination of same or different atoms or groups, and Y is an alkenyl group, an alkynyl group, an alkoxyalkyl group, an alkoxyalkoxy group, an alkylthioalkyl group, a cycloalkyl group, a cycloalkylalkoxy group, a cycloalkylalkyl group, a cycloalkylalkenyl group, a cycloalkylalkynyl group, a trialkylsilylalkyl group, a trialkylsilylalkoxy group, an alkyl group having a carbon number of not less than 7, an alkoxy group having a carbon number of not less than 7, an alkylthio group having a carbon number of not less than 7, an alkylsulfinyl group having a carbon number of not less than 7, an alkylsulfonyl group having a carbon number of not less than 7 or a group represented by the following general formula (1): ##STR3## (wherein A is an oxygen atom, a sulfur atom, a lower alkylene group, a lower alkyleneoxy group, an oxy-lower alkylene group or a lower alkyleneoxyalkylene group, k is 0 or 1, Q is CH- group or a nitrogen atom, R.sup.2 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, trifluoromethyl group or trifluoromethoxy group, m is an integer of 1-5 provided that when m is 2 or more, R.sup.2 may be an optional combination of same or different atoms or groups)].

Furthermore, the invention provides an insecticide or an acaricide containing the above triazole derivative as an active ingredient.

Throughout the specification, the term "lower" means that the carbon number in the group added with this term is not more than 6.

Further, the term "alkyl group" means a straight or branched-chain alkyl group having a carbon number of 1-30, which includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isoamyl group, neopentyl group, n-hexyl group, isohexyl group, 3,3-dimethylbutyl group, n-heptyl group, 5-methylhexyl group, 4-methylhexyl group, 3-methylhexyl group, 4,4-dimethylpentyl group, n-octyl group, 6-methylheptyl group, n-nonyl group, 7-methyloctyl group, n-decyl group, 8 methylnonyl group, n-undecyl group, 9-methyldecyl group, n-dodecyl group, 10-methylundecyl group, n-tridecyl group, 11-methyldodecyl group, n-tetradecyl group, 12-methyltridecyl group, n-pentadecyl group, 13-methyl-tetradecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group and the like.

The terms "alkoxy group", "alkylthio group", "alkylsulfinyl group" and "alkylsulfonyl group" are (alkyl)--O-- group, (alkyl)--S-- group, (alkyl)--SO-- group, and (alkyl)--SO.sub.2 group in which the alkyl portion has the same meaning as mentioned above, respectively.

The term "halogen atom" means fluorine, chlorine, bromine and iodine.

The term "alkenyl group" means a straight or branched-chain alkenyl group having a carbon number of 2-20, which includes, for example, vinyl group, propenyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, 3-methyl-1-butenyl group, 4-methyl-1-pentenyl group and the like.

The term "alkynyl group" means a straight or branched-chain alkynyl group having a carbon number of 2-20, which includes, for example, ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group, 3,3-dimethyl-1-butynyl group, 4-methyl-1-pentynyl group, 3-methyl-1-pentynyl group, 5-methyl-1-hexynyl group, 4-methyl-1-hexynyl group, 3-methyl-1-hexynyl group, heptynyl group, octynyl group, nonynyl group, decynyl group, undecynyl group, dodecynyl group, tridecynyl group, tetradecynyl group, pentadecynyl group, hexadecynyl group and the like.

The term "cycloalkyl group" means a cycloalkyl group having a carbon number of 3-12, which includes, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like.

The term "cycloalkylalkyl group" means a cycloalkylalkyl group having a carbon number of 6-12, which includes, for example, cyclopentylmethyl group, cyclohexylmethyl group, cyclopentylethyl group, cyclohexylethyl group, cyclopentylpropyl group, cyclohexylpropyl group, cyclohexylpentyl group and the like.

The term "cycloalkylalkoxy group" means a (cycloalkylalkyl)--O-- group in which the cycloalkylalkyl portion has the same meaning as mentioned above.

The term "cycloalkylalkenyl group" means a cycloalkylalkenyl group having a carbon number of 5-12, which includes, for example, cyclopentylvinyl group, cyclohexylvinyl group, 3-cyclopentyl-1-propenyl group, 3-cyclohexyl-1-propenyl group, 5-cyclohexyl-1-pentenyl group and the like.

The term "cycloalkylalkynyl group" means a cycloalkylalkynyl group having a carbon number of 5-12, which includes, for example, cyclopentylethynyl group, cyclohexylethynyl group, 3-cyclopentyl-1-propynyl group, 3-cyclohexyl-1-propynyl group and the like.

The term "tri(lower alkyl)silyl lower alkyl group" includes, for example, trimethylsilylmethyl group, dimethylethylsilylmethyl group, butyldimethylsilylmethyl group and the like.

The term "tri(lower alkyl)silyl lower alkoxy group" means [tri(lower alkyl)silyl lower alkyl]--O--group in which the tri(lower alkyl)silyl lower alkyl portion has the same meaning as mentioned above.

The term "lower alkylene group" means a straight or branched-chain alkylene group having a carbon number of 1-4, which includes, for example, --CH.sub.2 --, --CH.sub.2 CH.sub.2 --, --CH(CH.sub.3)--, --CH.sub.2 CH.sub.2 CH.sub.2 --, --CH(CH.sub.3)CH.sub.2 --, --C(CH.sub.3).sub.2 --, --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 --, --CH(CH.sub.3)CH.sub.2 CH.sub.2 --, --CH.sub.2 CH(CH.sub.3)CH.sub.2 -- and the like.

The term "lower alkyleneoxy group" means -(lower alkylene)--O-- group in which the lower alkylene portion has the same meaning as mentioned above.

The term "oxy-lower alkylene group" means --O-- (lower alkylene)-- group in which the lower alkylene portion has the same meaning as mentioned above.

The term "lower alkyleneoxyalkylene group" means --(lower alkylene)--O--(lower alkylene)-- group in which the lower alkylene portion has the same meaning as mentioned above.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

As a preferable compound according to the invention, there are mentioned compounds having the general formula [I] wherein R.sup.1 is a straight or branched-chain alkyl group having a carbon number of 1-6, preferably methyl group, X is a hydrogen atom, a halogen atom, a straight or branched-chain alkyl group having a carbon number of 1-4, a nitro group, a cyano group or trifluoromethyl group, n is an integer of 1-3 provided that when n is 2 or 3, X may be an optional combination of same or different atoms or groups, Y is a straight or branched-chain alkyl group having a carbon number of 7-20, a cycloalkyl group having a carbon number of 3-12, a cycloalkylalkyl group having a carbon number of 6-12, a straight or branched-chain alkoxy group having a carbon number of 7-16, a cycloalkylalkoxy group having a carbon number of 7-12, a straight or branched-chain alkylthio group having a carbon number of 7-16, an alkylsulfinyl group, an alkylsulfonyl group, a straight or branched-chain alkenyl group having a carbon number of 3-16, a cycloalkylalkenyl group having a carbon number of 5-12, a straight or branched-chain alkynyl group having a carbon number of 3-16, a cycloalkylalkynyl group having a carbon number of 5-12, a tri(lower alkyl)silyl lower alkyl group, a tri(lower alkyl)silyl lower alkoxy group or a group represented by the formula (1) (wherein A is an oxygen atom, a sulfur atom, a lower alkylene group having a carbon number of 1-4, methyleneoxy group or oxymethylene group, k is 0 or 1, Q is CH- group or a nitrogen atom, R.sup.2 is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, trifluoromethyl group or trifluoromethoxy group, and m is an integer of 1-3 provided that when m is 2 or 3, R.sup.2 may be an optional combination of same or different atoms or groups).

Concrete examples of the compounds having the general formula [I] according to the invention are shown in Tables 1 to 10. Moreover, the compound No. is referred in subsequent description.

TABLE 1______________________________________ ##STR4##Compound Melting point (.degree.C.) orNo. R.sup.1 Xn Y refractive index (n.sub.D.sup.20)______________________________________ 1 CH.sub.3 H 4-C.sub.7 H.sub.15 1.5819 2 CH.sub.3 2-F 4-C.sub.7 H.sub.15 1.5650 3 CH.sub.3 2-Cl 4-C.sub.7 H.sub.15 1.5816 4 CH.sub.3 2-Br 4-C.sub.7 H.sub.15 1.5924 5 CH.sub.3 2-I 4-C.sub.7 H.sub.15 1.6025 6 CH.sub.3 2,3,4,5,6-F.sub.5 4-C.sub.7 H.sub.15 1.5252 7 CH.sub.3 2-CH.sub.3 4-C.sub.7 H.sub.15 1.5803 8 CH.sub.3 2-OCH.sub.3 4-C.sub.7 H.sub.15 1.5840 9 CH.sub.3 2-SCH.sub.3 4-C.sub.7 H.sub.15 1.600310 CH.sub.3 2-CN 4-C.sub.7 H.sub.15 50.0-53.511 CH.sub.3 2-NO.sub.2 4-C.sub.7 H.sub.15 1.578012 CH.sub.3 2-CF.sub.3 4-C.sub.7 H.sub.15 1.540713 CH.sub.3 2-Cl 4-C.sub.8 H.sub.17 1.580014 CH.sub.3 2,6-F.sub.3 4-C.sub.8 H.sub.17 1.553215 CH.sub.3 2-Cl, 6-F 4-C.sub.8 H.sub.17 1.565216 CH.sub.3 2-Cl 4-C.sub.9 H.sub.19 1.576617 CH.sub.3 2-Cl, 6-F 4-C.sub.9 H.sub.19 1.561218 CH.sub.3 2,6-F.sub.2 4-C.sub.9 H.sub.19 1.551819 CH.sub.3 2,6-Cl.sub.2 4-C.sub.9 H.sub.19 1.569820 CH.sub.3 2-F 4-C.sub.10 H.sub.21 1.559521 CH.sub.3 2-Cl 4-C.sub.10 H.sub.21 1.570822 CH.sub.3 2-Br 4-C.sub.10 H.sub.21 1.578023 CH.sub.3 2-I 4-C.sub.10 H.sub.21 1.587524 CH.sub.3 2-CH.sub.3 4-C.sub.10 H.sub.21 48.0-50.0______________________________________ TABLE 2______________________________________Compound Melting point (.degree.C.) orNo. R.sup.1 Xn Y refractive index (n.sub.D .sup.20)______________________________________25 CH.sub.3 2-OCH.sub.3 4-C.sub.10 H.sub.21 1.564926 CH.sub.3 2-SCH.sub.3 4-C.sub.10 H.sub.2127 CH.sub.3 2-CN 4-C.sub.10 H.sub.21 37.0-40.028 CH.sub.3 2-NO.sub.2 4-C.sub.10 H.sub.21 55.0-58.029 CH.sub.3 2-CF.sub.3 4-C.sub.10 H.sub.21 56.0-57.030 CH.sub.3 2-Cl, 6-F 4-C.sub.10 H.sub.21 1.557031 CH.sub.3 2,6-F.sub.2 4-C.sub.10 H.sub.21 1.548232 CH.sub.3 2,6-Cl.sub.2 4-C.sub.10 H.sub.21 1.567833 CH.sub.3 2,4,6-F3 4-C.sub.10 H.sub.21 1.534034 CH.sub.3 2-Cl 4-C.sub.11 H.sub.23 52.0-54.035 CH.sub.3 2-Cl, 6-F 4-C.sub.11 H.sub.23 1.549536 CH.sub.3 2,6-Cl.sub.2 4-C.sub.11 H.sub.23 58.0-60.037 CH.sub.3 2,6-F.sub.2 4-C.sub.11 H.sub.23 1.543738 CH.sub.3 2-Cl 4-C.sub.12 H.sub.25 62.0-63.039 CH.sub.3 2-Cl, 6-F 4-C.sub.12 H.sub.25 51.0-52.040 CH.sub.3 2,6-F.sub.2 4-C.sub.12 H.sub.25 43.0-49.541 CH.sub.3 2,6-Cl.sub.2 4-C.sub.12 H.sub.25 53.0-54.542 CH.sub.3 2-Cl 4-C.sub.13 H.sub.27 55.0-57.043 CH.sub.3 2-C1, 6-F 4-C.sub.13 H.sub.27 43.0-47.044 CH.sub.3 2,6-F.sub.2 4-C.sub.13 H.sub.27 37.0-40.045 CH.sub.3 2,6-Cl.sub.2 4-C.sub.13 H.sub.27 52.0-55.046 CH.sub.3 2-Cl 4-C.sub.14 H.sub.29 66.0-67.547 CH.sub.3 2-Cl, 6-F 4-C.sub.14 H.sub.29 56.0-58.048 CH.sub.3 2,6-F.sub.2 4-C.sub.14 H.sub.29 61.0-62.549 CH.sub.3 2,6-Cl.sub.2 4-C.sub.14 H.sub.29 47.0-49.050 CH.sub.3 2-Cl 4-C.sub.15 H.sub.31 62.0-65.051 CH.sub.3 2-C1, 6-F 4-C.sub.15 H.sub.31 61.0-63.052 CH.sub.3 2,6-F.sub.2 4-C.sub.15 H.sub.31 54.0-56.0______________________________________ TABLE 3__________________________________________________________________________Com- Melting point (.degree.C.)pound or refractiveNo. R.sup.1 Xn Y index (n.sub.D .sup.20)__________________________________________________________________________53 CH.sub.3 2, 6-Cl.sub.2 4-C.sub.15 H.sub.31 61.5-64.054 CH.sub.3 2-Cl 4-C.sub.16 H.sub.33 70.0-73.055 CH.sub.3 2-Cl, 6-F 4-C.sub.16 H.sub.33 65.0-67.056 CH.sub.3 2,6-F.sub.2 4-C.sub.16 H.sub.33 55.0-57.057 CH.sub.3 2,6-Cl.sub.2 4-C.sub.16 H.sub.33 69.5-71.058 CH.sub.3 2-Cl 4-C.sub.17 H.sub.3559 CH.sub.3 2-C1, 6-F.sub. 4-C.sub.17 H.sub.3560 CH.sub.3 2,6-F.sub.2 4-C.sub.17 H.sub.3561 CH.sub.3 2-Cl 4-C.sub.18 H.sub.3762 CH.sub.3 2-Cl, 6-F 4-C.sub.18 H.sub.3763 CH.sub.3 2,6-F.sub.2 4-C.sub.18 H.sub.3764 C.sub.2 H.sub.5 2-Cl, 6-F 4-C.sub.12 H.sub.25 43.0-45.065 CH(CH.sub.3).sub.2 2-Cl 4-C.sub.12 H.sub.2566 CH(CH.sub.3).sub.2 2-Cl, 6-F 4-C.sub.12 H.sub.25 63.0-66.067 CH.sub.3 2-Cl 4-CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 64.0-67.068 CH.sub.3 2-Cl, 6-F 4-CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 1.561469 CH.sub.3 2,6-F.sub.2 4-CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 1.557870 CH.sub.3 2-Cl 4-CH.sub.2 CH.sub.2 CH.sub.2 CH(C.sub.2 H.sub.5)CH.sub.3 1.593571 CH.sub.3 2-Cl, 6-F 4-CH.sub.2 CH.sub.2 CH.sub.2 CH(C.sub.2 H.sub.5)CH.sub.3 1.575972 CH.sub.3 2-Cl 4-CH.sub.2 CH.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3 1.587973 CH.sub.3 2-Cl, 6-F 4-CH.sub.2 CH.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3 1.569374 CH.sub.3 2-Cl 4-CH.sub.2 CH.sub.2 CH.sub.2 C(CH.sub.3).sub.375 CH.sub.3 2-Cl, 6-F 4-CH.sub.2 CH.sub.2 CH.sub.2 C(CH.sub.3).sub.376 CH.sub.3 2,6-F.sub.2 4-CH.sub.2 CH.sub.2 CH.sub.2 C(CH.sub.3).sub.377 CH.sub.3 2-Cl 4-OC.sub.8 H.sub.17 58.0-59.578 CH.sub.3 2-Cl 4-O(CH.sub.2).sub.4 CH(CH.sub.3).sub.279 CH.sub.3 2-Cl, 6-F 4-O(CH.sub.2).sub.4 CH(CH.sub.3).sub.2__________________________________________________________________________ TABLE 4______________________________________Com- Melting pointpound (.degree.C.) or refractiveNo. R.sup.1 Xn Y index (n.sub.D.sup.20)______________________________________80 CH.sub.3 2-Cl ##STR5## 83.0-86.081 CH.sub.3 2-Cl, 6-F ##STR6## 83.0-85.082 CH.sub.3 2-Cl 4-OC.sub.10 H.sub.21 67.5-69.083 CH.sub.3 2-Cl, 6-F 4-OC.sub.10 H.sub.21 55.0-57.084 CH.sub.3 2,6-F.sub.2 4-OC.sub.10 H.sub.21 1.539985 CH.sub.3 2,6-Cl.sub.2 4-OC.sub.10 H.sub.21 60.0-64.086 CH.sub.3 2-Cl 4-OC.sub.12 H.sub.25 73.5-75.087 CH.sub.3 2-Cl, 6-F 4-OC.sub.12 H.sub.25 59.0-61.088 CH.sub.3 2-Cl 4-SC.sub.8 H.sub.1789 CH.sub.3 2-Cl, 6-F 4-SC.sub.8 H.sub.1790 CH.sub.3 2-Cl 4-SOC.sub.8 H.sub.1791 CH.sub.3 2-Cl 4-SO.sub.2 C.sub.8 H.sub.1792 CH.sub.3 2-Cl 4-OCH.sub.2 CH.sub.2 OCH.sub.393 CH.sub.3 2-Cl 4-CH.sub.2 OC.sub.4 H.sub.9 1.585094 CH.sub.3 2-Cl 4-CH.sub.2 OC.sub.10 H.sub. 2195 CH.sub.3 2-Cl, 6-F 4-CH.sub.2 OC.sub.10 H.sub.2196 CH.sub.3 2-Cl, 6-F 4-CH.sub.2 SC.sub.3 H.sub.7 1.602397 CH.sub.3 2-Cl 4-CHCHCH.sub.3 1.641098 CH.sub.3 2-Cl 4-CHCHC.sub.10 H.sub.2199 CH.sub.3 2-Cl, 6-F 4-CHCHC.sub.10 H.sub.21100 CH.sub.3 2-Cl 4-CCCH.sub.3 93.5-95.0101 CH.sub.3 2-Cl, 6-F 4-CCCH.sub.3 124.0-126.5102 CH.sub.3 2-Cl 2-CCC.sub.2 H.sub.5 1.6249103 CH.sub.3 2-Cl 4-CCC.sub.2 H.sub.5 1.6478104 CH.sub.3 2,6-F.sub.2 4-CCC.sub.2 H.sub.5 1.6158______________________________________ TABLE 5__________________________________________________________________________Compound Melting point (.degree.C.) orNo. R.sup.1 Xn Y refractive index (n.sub.D.sup.20)__________________________________________________________________________105 CH.sub.3 2-Cl, 6-F 4-CCC.sub.2 H.sub.5 1.6244106 CH.sub.3 2-Cl 3-CCC.sub.3 H.sub.7 1.6265107 CH.sub.3 2-Cl 4-CCC.sub.3 H.sub.7 1.5380108 CH.sub.3 2,6-F2 4-CCC.sub.3 H.sub.7 1.6018109 CH.sub.3 2-Cl, 6-F 4-CCC.sub.3 H.sub.7 1.6175110 CH.sub.3 2-Cl 4-CCCH.sub.2 CH(CH.sub.3).sub.2 82.0-84.0111 CH.sub.3 2-Cl 3-CCC.sub.4 H.sub.9 1.6191112 CH.sub.3 2-Cl, 6-F 3-CCC.sub.4 H.sub.9 1.6121113 CH.sub.3 2-Cl 4-C CC.sub.4 H.sub.9 1.6273114 CH.sub.3 2-Cl, 6-F 4-CCC.sub.4 H.sub.9 1.6110115 CH.sub.3 2,6-F.sub.2 4-CCC.sub.4 H.sub.9116 CH.sub.3 2,6-Cl.sub.2 4-CCC.sub.4 H.sub.9117 CH.sub.3 2-Cl 3-CCC.sub.5 H.sub.11 1.6010118 CH.sub.3 2-Cl, 6-F 3-CCC.sub.5 H.sub.11 1.5947119 CH.sub.3 2-Cl 4-CCC.sub.5 H.sub.11 1.6224120 CH.sub.3 2-Cl, 6-F 4-CCC.sub.5 H.sub.11 1.6052121 CH.sub.3 2,6-F.sub.2 4-CCC.sub.5 H.sub.11122 CH.sub.3 2,6-Cl.sub.2 4-CCC.sub.5 H.sub.11123 CH.sub.3 2-Cl, 6-F 4-C CC.sub.6 Hl.sub.3124 CH.sub.3 2,6-F.sub.2 4-CCC.sub.6 Hl.sub.3125 CH.sub.3 2,6-Cl.sub.2 4-CCC.sub.6 Hl.sub.3126 CH.sub.3 2-Cl 4-CCC.sub.8 H.sub.17 1.5852127 CH.sub.3 2-Cl, 6-F 4-CCC.sub.8 H.sub.17 60.5-64.0128 CH.sub.3 2-Cl ##STR7## 79.5-82.0129 CH.sub.3 2-Cl ##STR8##__________________________________________________________________________ TABLE 6__________________________________________________________________________Compound Melting point (.degree.C.) orNo. R.sup.1 Xn Y refractive index (n.sub.D .sup.20)__________________________________________________________________________130 CH.sub.3 2-Cl ##STR9## 116.0-118.0131 CH.sub.3 2-Cl, 6-F ##STR10## 88.5-90.0132 CH.sub.3 2-Cl ##STR11##133 CH.sub.3 2-Cl, 6-F ##STR12##134 CH.sub.3 2-Cl ##STR13## 65.0-69.0135 CH.sub.3 2-Cl, 6-F ##STR14## 53.0-57.0136 CH.sub.3 2-Cl ##STR15## 118.0-121.0137 CH.sub.3 2-Cl, 6-F ##STR16## 100.0-103.0138 CH.sub.3 2-Cl ##STR17##139 CH.sub.3 2-Cl ##STR18##140 CH.sub.3 2-Cl, 6-F ##STR19##141 CH.sub.3 2-Cl 4-CH.sub.2 CH.sub.2 Si(CH.sub.3).sub.3 79.0-81.0142 CH.sub.3 2-Cl, 6-F 4-CH.sub.2 CH.sub.2 Si(CH.sub.3).sub.3 1.5728143 CH.sub.3 2-Cl 4-OCH.sub.2 Si(CH.sub.3).sub.3 55.0-57.0144 CH.sub.3 2-Cl, 6-F 4-OCH.sub.2 Si(CH.sub.3).sub.3 1.5730145 C.sub.2 H.sub.5 2-Cl, 6-F 4-C.sub.16 H.sub.33 56.0-59.0146 CH.sub.3 2,6-F2 ##STR20## not measurable147 CH.sub.3 2-Cl 4-CCCH(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3 1.6171148 CH.sub.3 2-Cl 3-C.sub.8 H.sub.17 1.5810149 CH.sub.3 2-Cl, 6-F 3-C.sub.8 H.sub.17 1.5586150 CH.sub.3 2-Cl 3-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3 1.5803151 CH.sub.3 2-Cl, 6-F 3-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3 1.5499152 CH.sub.3 2-Cl 3-OC.sub.8 H.sub.17 1.5789153 CH.sub.3 2-Cl, 6-F 3-OC.sub.8 H.sub. 17 1.559__________________________________________________________________________ TABLE 7__________________________________________________________________________ ##STR21##Compound Substitution Melting point (.degree.C.) orNo. R.sup.1 Xn position A R.sup.2 m refractive index (n.sub.D .sup.20)__________________________________________________________________________154 CH.sub.3 2-Cl 4- -- H 152.0-154.5155 CH.sub.3 2,6-F.sub.2 4- -- 4-C.sub.3 H.sub.7 112.0-116.0156 CH.sub.3 2-Cl 4- -- 4-C.sub.3 H.sub.7 111.5-114.0157 CH.sub.3 2-Cl, 6-F 4- -- 4-C.sub.3 H.sub.7 158.0-160.5158 CH.sub.3 2-Cl 4- -- 4-C.sub.6 H.sub.13 112.0-114.0159 CH.sub.3 2-Cl, 6-F 4- -- 4-C.sub.6 H.sub.13 93.0.95.0160 CH.sub.3 2,6-F.sub.2 4- -- 4-C.sub.6 H.sub.13 96.0-98.0161 CH.sub.3 2,6-Cl.sub.2 4- -- 4-C.sub.6 H.sub.13 96.0-97.5162 CH.sub.3 2-Cl 4- -- 4-Cl 142.0-143.0163 CH.sub.3 2-Cl 4- -- 4-OCH.sub.3 137.0-141.0164 CH.sub.3 2-Cl 4- -- 3-CH.sub.3 137.0-139.0165 CH.sub.3 2-Cl 4- CH.sub.2 H 68.0-71.0166 CH.sub.3 2-Cl, 6-F 4- CH.sub.2 H 1.6248167 CH.sub.3 2-Cl 4- CH.sub.2 4-Cl168 CH.sub.3 2-Cl, 6-F 4- CH.sub.2 4-Cl169 CH.sub.3 2-Cl 4- CH.sub.2 4-C.sub.4 H.sub.9170 CH.sub.3 2-Cl, 6-F 4- CH.sub.2 4-C.sub.4 H.sub.9171 CH.sub.3 2-Cl 4- CH.sub.2 CH.sub.2 H 68.0-69.0172 CH.sub.3 2-Cl, 6-F 4- CH.sub.2 CH.sub.2 H 160.0-162.0173 CH.sub.3 2-Cl 4- CH.sub.2 O H 99.0-102.0174 CH.sub.3 2-Cl, 6-F 4- CH.sub.2 O H 103.0-106.0175 CH.sub.3 2-Cl 4- OCH.sub.2 H 83.0-87.0176 CH.sub.3 2-Cl, 6-F 4- OCH.sub.2 H 143.0-153.0__________________________________________________________________________ TABLE 8__________________________________________________________________________Com- Substi-pound tution Melting point (.degree.C.) orNo. R.sup.1 Xn position A R.sup.2 m refractive index (n.sub.D .sup.20)__________________________________________________________________________177 CH.sub.3 2-Cl 4- CH.sub.2 OCH.sub.2 H178 CH.sub.3 2-Cl, 6-F 4- CH.sub.2 OCH.sub.2 H179 CH.sub.3 2-Cl 3- O H 1.6354180 CH.sub.3 2-Cl 4- O H 106.0-108.0181 CH.sub.3 2-Cl, 6-F 4- O H 165.0-168.o182 CH.sub.3 2,6-F.sub.2 4- O H 85.0-89.0183 CH.sub.3 2-Cl 4- O 4-CH.sub.3 not measurable184 CH.sub.3 2-Cl, 6-F 4- O 4-CH.sub.3 not measurable185 CH.sub.3 2-Cl 4- O 4-C.sub.4 H.sub.9186 CH.sub.3 2-Cl, 6-F 4- O 4-C.sub.4 H.sub.9187 CH.sub.3 2-Cl 4- O 2-Cl188 CH.sub.3 2-Cl, 6-F 4- O 2-Cl189 CH.sub.3 2-Cl 4- O 2-Cl, 4-CF.sub.3190 CH.sub.3 2-Cl, 6-F 4- O 2-Cl, 4-CF.sub.3191 CH.sub.3 2-Cl 4- -- 4-CH.sub.3 151.0-154.0192 CH.sub.3 2-Cl, 6-F 4- -- 4-CH.sub.3 207.0-211.0193 CH.sub.3 2-Cl 4- -- 4-OCF.sub.3 119.0-122.0194 CH.sub.3 2-Cl, 6-F 4- -- 4-OCF.sub.3 114.0-116.0195 CH.sub.3 2-Cl 4- -- 4-CF.sub.3 155.0-159.0196 CH.sub.3 2-Cl, 6-F 4- -- 4-CF.sub.3 146.0-149.0197 CH.sub.3 2-Cl 4- -- 3,4-Cl.sub.12198 CH.sub.3 2-Cl, 6-F 4- -- 3,4-Cl.sub.12199 CH.sub.3 2-Cl 4- -- 2,4-Cl.sub.12200 CH.sub.3 2-Cl, 6-F 4- -- 2,4-Cl.sub.12201 CH.sub.3 2-Cl 4- CH.sub.2 O 4-CH.sub.3 135.0-138.0202 CH.sub.3 2-Cl, 6-F 4- CH.sub.2 O 4-CH.sub.3 149.0-152.0203 CH.sub.3 2-Cl 4- CH.sub.2 O 4-C.sub.4 H.sub.9204 CH.sub.3 2-Cl, 6-F 4- CH.sub.2 O 4-C.sub.4 H.sub.9205 CH.sub.3 2-Cl 4- OCH.sub.2 4-CH.sub.3 108.0-110.0206 CH.sub.3 2-Cl, 6-F 4- OCH.sub.2 4-CH.sub.3 150.0-155.0207 CH.sub.3 2-Cl 4- OCH.sub.2 2,3,4,5,6-F.sub.5208 CH.sub.3 2-Cl, 6-F 4- OCH.sub.2 2,3,4,5,6-F.sub.5209 CH.sub.3 2-Cl 4- O 4-C.sub.8 H.sub.15 1.6060__________________________________________________________________________ TABLE 9__________________________________________________________________________Com- Substi-pound tution Melting point (.degree.C.) orNo. R.sup.1 Xn position A R.sup.2 m refractive index (n.sub.D .sup.20)__________________________________________________________________________210 CH.sub.3 2-Cl, 6-F 4- O 4-C.sub.6 H.sub.13 1.5891211 CH.sub.3 2-Cl 4- O 3,4-Cl.sub.2 115.0-118.0212 CH.sub.3 2-Cl, 6-F 4- O 3,4-Cl.sub.2 103.0-106.0213 CH.sub.3 2-Cl 4- O 2,4-Cl.sub.2 not measurable214 CH.sub.3 2-Cl, 6-F 4- O 2,4-Cl.sub.2 not measurable215 CH.sub.3 2-Cl, 6-F 4- -- 4-OCH.sub.3 191.0-192.0216 CH.sub.3 2-Cl 4- -- 4-OC.sub.4 H.sub.9 118.0-121.0217 CH.sub.3 2-Cl, 6-F 4- -- 4-OC.sub.4 H.sub.9 141.0-144.0218 CH.sub.3 2-Cl, 6-F 4- -- 3-CH.sub.3 131.0-134.0219 CH.sub.3 2-Cl, 6-F 4- -- 4-Cl 105.0-107.0220 CH.sub.3 2-Cl 4- CH.sub.2 CH.sub.2 4-CH.sub. 3 95.0-97.0221 CH.sub.3 2-Cl, 6-F 4- CH.sub.2 CH.sub.2 4-CH.sub.3 188.0-192.0222 CH.sub.3 2-Cl 4- O 3,5-Cl.sub.2 105.0-108.0223 CH.sub.3 2-Cl 4- O 3,5-Cl.sub.2 121.0-123.0224 CH.sub.3 2-Cl, 6-F 4- O 4-Cl not measurable__________________________________________________________________________ TABLE 10__________________________________________________________________________ ##STR22##Compound Substitution Melting point (.degree.C.) orNo. R.sup.1 Xn position A R.sup.2 m refractive index (n.sub.D .sup.20)__________________________________________________________________________225 CH.sub.3 2-Cl 4- O H226 CH.sub.3 2-Cl, 6-F 4- O H227 CH.sub.3 2-Cl 4- O 5-CF.sub.3 not measurable228 CH.sub.3 2-Cl, 6-F 4- O 5-CF.sub.3 107.0-109.0229 CH.sub.3 2-Cl 4- O 3-Cl, 5-CF.sub.3 not measurable230 CH.sub.3 2-Cl, 6-F 4- O 3-Cl, 5-CF.sub.3 not measurable231 CH.sub.3 2-Cl 4- S 3-Cl, 5-CF.sub.3232 CH.sub.3 2-Cl 4- CH.sub.2 O H233 CH.sub.3 2-Cl, 6-F 4- CH.sub.2 O H__________________________________________________________________________

The compounds according to the invention can be produced by the following methods. However, it is not intended to restrict the invention to these methods.

Production Method A

The compounds of the general formula [I] according to the invention can be obtained by reacting an alkyl N-acyl(thio) imidate derivative of a general formula [II] with a hydrazine derivative of a general formula [III] in an inert solvent according to the following reaction formula (1): ##STR23## (wherein W is a sulfur atom or an oxygen atom, L is an alkyl group having a carbon number of 1-4 and R.sup.1, X, n and Y have the same meaning as mentioned above).

As the solvent, use may be made of any solvent not obstruction the reaction, which includes, for example, an alcohol such as methanol, ethanol or the like; an ether such as diethyl ether, tetrahydrofuran, dioxane, diglyme or the like; an aromatic hydrocarbon such as benzene, toluene, chlorobenzene or the like; an aliphatic hydrocarbon such as pentane, hexane, petroleum ether or the like; a halogenated hydrocarbon such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride or the like; a nitrile such as acetonitrile or the like; an aprotic polar solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide or the like; water and a mixture thereof.

In general, the compound of the general formula [III] is used in an amount of 1.0-5.0 moles per 1 mole of the compound of the general formula [II].

The reaction temperature is optional within a range of 0.degree. C. to a boiling point of the solvent, but is preferably 0.degree. C.-50.degree. C.. The reaction time is dependent upon the kind of compounds used, but is usually 1-72 hours.

A concrete example of this reaction is disclosed, for example, in Synthesis, page 483 (1983).

The compound of the general formula [II] as a starting material can be produced by the following method.

Production Method B

The compound of the general formula [II] can be obtained by reacting compounds of general formulae [IV] and [V] in an inert solvent in the presence of a base according to the following reaction formula (2): ##STR24## (wherein a derivative of the general formula [IV] may be an acid addition salt (e.g. a salt with boron tetra-fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide or the like), Z is a halogen atom, and L, W, X, n and Y have the same meaning as mentioned above).

As the base, use may be made of an inorganic base such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide or the like; and an organic base such as diethylamine, triethylamine, diisopropylethylamine, pyridine, 4-N,N-dimethylamino pyridine or the like.

As the solvent, use may be made of a ketone such as acetone, methyl ethyl ketone or the like; an ether such as diethyl ether, tetrahydrofuran, dioxane, diglyme or the like; an aromatic hydrocarbon such as benzene, toluene, chlorobenzene or the like; an aliphatic hydrocarbon such as pentane, hexane, petroleum ether or the like; a halogenated hydrocarbon such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride or the like; a nitrile such as acetonitrile or the like; an aprotic polar solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide or the like; and a mixture thereof.

In general, the compound of the general formula [V] is used in an amount of 0.8-1.3 moles per 1 mole of the compound of the general formula [IV]. The amount of the base used is 1.0-2.0 moles per 1 mole of the compound of the general formula [IV].

The reaction time is dependent upon the kind of the compounds used, but is usually within a range of 1-24 hours. The reaction temperature is within a range of 0.degree. C. to a boiling point of the solvent.

Production Method C

The compound of the general formula [I] according to the invention can be obtained by reacting an N-(phenylsulfonyl) benzohydrazonoyl chloride derivative of a general formula [VI] with a benzonitrile derivative of a general formula [VII] in an inert solvent in the presence of Lewis acid according to the following reaction formula (3): ##STR25## (wherein R.sup.1, X, n and Y have the same meaning as mentioned above, and R.sup.3 is benzene or benzene substituted with an alkyl group having a carbon number of 1-4).

As the solvent, use may be made of any solvent not obstruction the reaction, which includes, for example, an ether such as diethyl ether, tetrahydrofuran, dioxane, diglyme or the like; an aromatic hydrocarbon such as benzene, toluene, chlorobenzene, dichlorobenzene or the like; an aliphatic hydrocarbon such as pentane, hexane, petroleum ether or the like; a halogenated hydrocarbon such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride or the like; a non-protonic polar solvent such as nitrobenzene, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide or the like; and a mixture thereof.

As the Lewis acid, use may be made of aluminum bromide, aluminium chloride, ferric chloride, boron trifluoride, titanium tetrachloride and the like.

In general, the amount of the compound of the general formula [VII] used is 1.0-2.0 moles per 1 mole of the compound of the general formula [VI], and the amount of Lewis acid used is 1.0-2.0 moles per 1 mole of the compound of the general formula [VI].

The reaction temperature is optionally within a range of 0.degree. C. to a boiling point of the solvent, but is preferably within a range of 50.degree.-180.degree. C. The reaction time is dependent upon the kind of the compounds used, but is usually within a range of 15 minutes to 8 hours.

A concrete example of this reaction is disclosed, for example, in Bulletin of the Chemical Society of Japan, vol. 56, pages 547-548 (1983).

Production Method D

The compound of the general formula [I] according to the invention can be obtained by reacting an N-(phenylsulfonyl) benzamidrazone derivative of a general formula [VIII] with a benzoylhalide derivative of the general formula [V] in the absence of a solvent or in an inert solvent according to the following reaction formula (4): ##STR26## (wherein R.sup.1, R.sup.3, X, n, Y and Z have the same meaning as mentioned above).

As the solvent, use may be made of any solvent not obstruction the reaction, which includes, for example, an ether such as diethyl ether, tetrahydrofuran, dioxane, diglyme or the like; an aromatic hydrocarbon such as benzene, toluene, chlorobenzene or the like; an aliphatic hydrocarbon such as pentane, hexane, petroleum ether or the like; a halogenated hydrocarbon such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride or the like; an aprotic polar solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, 1-methyl-2-pyrolidinone or the like; and a mixture thereof.

In general, the amount of the compound of the general formula [V] used is 1.0-2.0 moles per 1 mole of the compound of the general formula [VIII].

The reaction temperature is optionally within a range of 0.degree. C. to a boiling point of the solvent, but is preferably within a range of 50.degree.-250.degree. C. The reaction time is dependent upon the kind of the compounds used, but is usually within a range of 30 minutes to 5 hours.

A concrete example of this reaction is disclosed, for example, in Bulletin of the Chemical Society of Japan, vol. 56, page 548 (1983).

The compound of the general formula [VIII] as a starting material can be produced by the following method.

Production Method E

The compound of the general formula [VIII] can be obtained by reacting the compound of the general formula [VI] with ammonia gas in an inert solvent according to the following reaction formula (5): ##STR27## (wherein R.sup.1, R.sup.3, X and n have the same meaning as mentioned above).

As the solvent, use may be made of any solvent not obstruction the reaction, which includes, for example, an ether such as diethyl ether, tetrahydrofuran, dioxane, diglyme or the like; an aromatic hydrocarbon such as benzene, toluene, chlorobenzene or the like; an aliphatic hydrocarbon such as pentane, hexane, petroleum ether or the like; a halogenated hydrocarbon such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, diclorobenzene or the like; an aprotic polar solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide or the like; and a mixture thereof.

In general, the amount of ammonia gas used is 5.0-10.0 moles per 1 mole of the compound of the general formula [VI].

The reaction temperature is optionally within a range of 0.degree. C. to a boiling point of the solvent, but is preferably within a range of 20.degree.-150.degree. C. The reaction time is dependent upon the kind of the compounds used, but is usually within a range of 1-24 hours.

A concrete example of this reaction is disclosed, for example, in Bulletin of the Chemical Society of Japan, vol. 56, pages 545-548 (1983).

The invention will be described concretely with reference to the following production examples, formulation examples and applications.

PRODUCTION EXAMPLE 1

3-(2-chloro-6-fluorophenyl)-1-methyl-5-(4-octylphenyl)-1H-1,2,4-triazole (Compound No. 15)

In 100 ml of toluene were dissolved 2.20 g of ethyl 2 chloro-6-fluorobenzimidate and 1.10 g of triethylamine, to which was added dropwise 2.53 g of 4-octylbenzoyl chloride within a temperature range of 5.degree.-10.degree. C. with stirring and then stirred at room temperature for 1 hour and further refluxed under heating for 2 hours. After the cooling to room temperature, the resulting reaction solution was added with 100 ml of toluene, washed with a diluted hydrochloric acid and further with a saline solution, and thereafter the resulting toluene layer was dried over anhydrous magnesium sulfate.

The toluene layer was added with 3.00 g of monomethylhydrazine and stirred at room temperature for 8 hours. After the completion of the reaction, the reaction mixture was washed with a diluted hydrochloric acid solution and further with a saturated saline solution, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure. The resulting concentrate was purified through a chromatography of silica gel column using a mixed solution of hexane and ethyl acetate as a developing solvent to obtain 1.34 g of the given compound (n.sub.D.sup.20 =1.5652).

______________________________________NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value) 0.77 (3H, t) 1.00-1.79 (12H, m) 2.57 (2H, t) 3.95 (3H, s) 6.83-7.67 (7H, m)______________________________________

PRODUCTION EXAMPLE 2

3-(2-chlorophenyl)-1-methyl-5-[4-(6-methylhexyl)phenyl]-1H-1,2,4-triazole (Compound No. 67)

A mixture of 2.06 g of N-methyl-N-phenylsulfonyl-2-chlorobenzohydrazonoyl chloride, 1.30 g of 4-(6-methylhexyl) benzonitrile, 0.93 g of anhydrous aluminum chloride and 5 ml of o-dichlorobenzene was stirred in an oil bath at a temperature of 140.degree. C. for 30 minutes. After the cooling, the resulting solution was dissolved in 200 ml of chloroform, washed with diluted hydrochloric acid solution, diluted sodium hydroxide aqueous solution and saline water in this order, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure. The resulting concentrate was purified through a chromatography of silica gel column using a mixed solution of hexane and ethyl acetate as a developing solvent to obtain 1.52 g of the given compound (melting point: 64.0.degree.-67.0.degree. C.).

______________________________________NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value) 0.86 (6H, d) 1.15-1.80 (7H, m) 2.67 (2H, t) 4.00 (3H, s) 7.17-8.00 (8H, m)______________________________________

PRODUCTION EXAMPLE 3

3-(2-chlorophenyl)-1-methyl-5-(4-tridecylphenyl)-1H-1,2,4-triazole (Compound No. 42)

A mixture of 0.82 g of N-methyl-N-phenylsulfonyl-2-chlorobenzohydrazonoyl chloride, 0.70 g of 4-tridecylbenzonitrile, 0.4 g of anhydrous aluminium chloride and 3 ml of o-dichlorobenzene was stirred in an oil bath at a temperature of 140.degree. C. for 30 minutes. After the cooling, the resulting solution was dissolved in 100 ml of chloroform, washed with diluted hydrochloric acid solution, diluted sodium hydroxide solution and saline water in this order, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure. The resulting concentrate was purified through a chromatography of silica gel column using a mixed solution of hexane and ethyl acetate as a developing solvent to obtain 0.70 g of the given compound (melting point: 55.0.degree.-57.0.degree. C.).

______________________________________NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value) 0.67-1.80 (25H, m) 2.67 (2H, t) 4.00 (3H, s) 7.16-8.03 (8H, m)______________________________________

PRODUCTION EXAMPLE 4

3(2-chlorophenyl)-1-methyl-5-(4-pentadecylphenyl)-1H-1,2,4-triazole (Compound No. 50)

A mixture of 3.24 g of N-methyl-N-phenylsulfonyl-2-chlorobenzamidrazone and 3.50 g of 4-pentadecylbenzoyl chloride was stirred in an oil bath at a temperature of 170.degree.-180.degree. C. for 4 hours. After the cooling, the resulting solution was added with water and extracted with ethyl acetate (200 ml.times.2) and the extracted organic layer was washed with saline water, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure. The resulting concentrate was purified through a chromatography of silica gel column using a mixed solution of hexane and ethyl acetate as a developing solvent and washed with n-hexane to obtain 0.34 g of the given compound (melting point: 62.0.degree.-65.0.degree. C.).

______________________________________NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value) 0.77-1.73 (29H, m) 1.67 (2H, m) 4.00 (3H, s) 7.17-7.97 (8H, m)______________________________________

PRODUCTION EXAMPLE 5

5-(4-decyloxyphenyl)-3-(2,6-dichlorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 85)

A mixture of 1.10 g of N-methyl-N-phenylsulfonyl-2,6-dichlorobenzohydrazonoyl chloride, 0.70 g of 4-decyloxybenzonitrile, 0.4 g of anhydrous aluminium chloride and 3 ml of o-dichlorobenzene was stirred in an oil bath at a temperature of 140.degree. C. for 30 minutes. After the cooling, the resulting solution was dissolved in 100 ml of chloroform, washed with diluted hydrochloric acid solution, diluted sodium hydroxide solution and saline water in this order, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure. The resulting concentrate was purified through a chromatography of silica gel column using a mixed solution of hexane and ethyl acetate as a developing solvent to obtain 0.40 g of the given compound (melting point: 60.0.degree.-64.0.degree. C.).

______________________________________NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value) 0.77-1.90 (19H, m) 3.98 (2H, t) 4.04 (3H, s) 6.88-7.73 (7H, m)______________________________________

PRODUCTION EXAMPLE 6

3-(2-chloro-6-fluorophenyl)-5-[4-(3-chloro-5-trifluoromethylpyridin-2-yloxy)phenyl]-1-methyl-1H-1,2,4-triazole (Compound No. 188)

A mixture of 1.30 g of N-methyl-N-phenylsulfonyl-2-chloro-6-fluorobenzohydrazonoyl chloride, 1.00 g of 4-(3-chloro-5-trifluoromethylpyridin-2-yloxy)benzonitrile, 0.50 g of anhydrous aluminum chloride and 3 ml of o-dichlorobenzene was stirred in an oil bath at a temperature of 140.degree. C. for 30 minutes. After the cooling, the resulting solution was dissolved in 100 ml of chloroform, washed with diluted hydrochloric acid solution, diluted sodium hydroxide solution and saline water in this order, dried over anhydrous magnesium sulfate and concentrated under a reduced pressure. The resulting concentrate was purified through a chromatography of silica gel column using a mixed solution of hexane and ethyl acetate as a developing solvent to obtain 0.70 g of the given compound (measurement of n.sub.D.sup.20 was impossible). NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value)

______________________________________ 4.07 (3H, s) 6.75-8.58 (9H, m)______________________________________

PRODUCTION EXAMPLE 7

N-methyl-N-phenylsulfonyl-2-chlorobenzamidrazone

In 100 ml of N,N-dimethylformamide was dissolved 17.2 g of N-methyl-N-phenylsulfonyl-2-chlorobenzhydrazonoyl chloride, which was stirred at 60.degree.-70.degree. C. for 3 hours while introducing ammonia gas thereinto. After the cooling, the reaction solution was dissolved in 500 ml of ethyl acetate, washed with water, dried on anhydrous magnesium sulfate and concentrated under a reduced pressure. The resulting crystal was washed with n-hexane to obtain 15.4 g of the given compound (melting point 94.0.degree.-96.0.degree. C.).

______________________________________NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value) 2.75 (3H, s) 5.80 (2H, s) 7.10-8.00 (9H, m)______________________________________

The insecticide and acaricide according to the invention contain the triazole derivative represented by the general formula (I) as an active ingredient.

When the triazole compounds according to the invention are used as an active ingredient for insecticides and acaricides, these compounds themselves may be used alone, or may be compounded with a carrier, a surfactant, a dispersing agent, an adjuvant or the like usually used in the formulation to form dusts, wettable powder, emulsion, fine powder, granulates or the like.

As the carrier used in the formulation, mention may be made of a solid carrier such as zeeklite, talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, calcium hydroxide, quartz sand, ammonium sulfate, urea or the like; and a liquid carrier such as isopropyl alcohol, xylene, cyclohexane, methylnaphthalene or the like.

As the surfactant and dispersing agent, mention may be made of a metal salt of alkylbenzene sulfonic acid, a metal salt of dinaphtylmethane disulfonic acid, a sulfuric acid ester of alcohol, alkylarylsulfonate, lignin sulfonate, polyoxyethylene glycol ether, polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan monoalkylate and the like.

As the adjuvant, mention may be made of carboxymethylcellulose, polyethylene glycol, gum arabi and the like.

In use, the compound according to the invention is directly applied or sprayed by diluting to a proper concentration.

The insecticide and acaricide according to the invention may be used by spraying onto stem and leaves, by applying to soil, by applying to a nursery box, by spraying onto water surface or the like.

In the formulation, the amount of the active ingredient used may be selected in accordance with the use purpose, but it is properly selected within a range of 0.05-20% by weight, preferably 0.1-10% by weight in case of the dusts or granules. In case of the emulsion or wettable powder, the amount of the active ingredient is properly selected within a range of 0.5-80% by weight, preferably 1-60% by weight.

The amount of the insecticide and acaricide applied is dependent upon the kind of the compound used as an active ingredient, injurious insect to be controlled, tendency and degree of insect injury, environmental condition, kind of formulation used and the like. When the insecticide and acaricide according to the invention are directly used as dusts or granules, the amount of the active ingredient is properly selected within a range of 0.05 g-5 kg, preferably 0.1-1 kg per 10 are. Furthermore, when they are used in form of a liquid as emulsion or wettable powder, the amount of the active ingredient is properly selected within a range of 0.1-5000 ppm, preferably 1-1000 ppm.

Moreover, the insecticide and acaricide according to the invention may be used by mixing with other insecticide, fungicide, fertilizer, plant growth regulator and the like.

The formulation will concretely be described with respect to typical examples. In this case, the kind of the compounds and additives and the compounding ratio are not limited to these examples and may be varied within wide ranges. Moreover, % is by weight otherwise specified. FORMULATION EXAMPLE 1

Emulsion

An emulsion was prepared by uniformly dissolving 30% of compound No. 55, 20% of cyclohexanone, 11% of polyoxyethylene alkylaryl ether, 4% of calcium alkylbenzenesulfonate and 35% of methylnaphthalene.

FORMULATION EXAMPLE 2

Wettable powder

A wettable powder was prepared by uniformly mixing and pulverizing 40% of compound No. 38, 15% of diatomaceous earth, 15% of clay, 25% of white carbon, 2% of sodium dinaphthylmethane disulfonate and 3% of sodium lignin sulfonate. FORMULATION EXAMPLE 3

Dust

A dust was prepared by uniformly mixing and pulverizing 2% of compound No. 120, 5% of diatomaceous earth and 93% of clay.

FORMULATION EXAMPLE 4

Granules

A mixture of 5% of compound No. 71, 2% of sodium salt of lauryl alcohol sulfuric acid ester, 5% of sodium lignin sulfonate, 2% of carboxymethyl cellulose and 86% of clay was uniformly pulverized and added with 20 parts by kneaded, shaped into granules of 14-32 mesh through an extrusion type granulating machine and dried to form granules.

The triazole derivatives according to the invention are effective to control planthoppers such as brown planthopper, white-backed planthopper, small brown planthopper and the like; leafhoppers such as green rice leafhopper, tea green leafhopper and the like; aphids such as cotton aphid, green peach aphid, cabbage aphid and the like; whiteflies such as greenhouse whitefly and the like; hemipteran injurious insects such as mulberry scale, corbett rice bug and the like; lepidopteran injurious insects such as diamond-back moth, lima-bean cutworm, tobacco cutworm and the like; dipteran injurious insects such as house maggot, mosquito and the like; elytron injurious insects such as rice plant weevil, soy bean weevil, cucurbit leaf beetle and the like; orthopteran injurious insects such as american cockroach, steam fly and the like; mites such as two-spotted spider mite, kanzawa spider mite, citrus red mite and the like; and mites having an increased resistance to organotin, synthesized pyrethroid and organophosphorus chemicals.

Particularly, they develop a very excellent effect of controlling mites such as two-spotted spider mite, kanzawa spider mite, citrus red mite and the like.

The effect of the compounds according to the invention will be described with respect to the following test examples. Moreover, the following compounds were used as a comparative chemical, wherein a comparative chemical a is a compound described in Japanese Patent laid open No. 56-154464, and a comparative chemical b is a commercial product usually used for the control of mites.

COMPARATIVE CHEMICAL A

3,5-bis(o-chlorophenyl)-1-methyl-1H-1,2,4-triazole

COMPARATIVE CHEMICAL B

Hexythiazox (common name)

Test Example 1

Insecticidal test for diamond-back moth

The wettable powder prepared according to Formulation Example 2 was diluted with water so that the concentration of the active ingredient was 500 ppm. Cabbage leaves were immersed in the resulting diluted solution, dried in air and then placed in a vinyl chloride cup of 60 ml capacity. Ten larvae of 3rd instar diamond-back moth were released in the cup and thereafter a cover was placed thereon. Then, the cup was placed in a thermostatic chamber of 25.degree. C. for 6 days, and the number of larvae died was counted to calculate the percentage of mortality. The test was carried out by double series. Moreover, the comparative chemical A was used for the comparison. The results are shown in Table 11.

TABLE 11______________________________________Compound No. Mortality (%)______________________________________17 10018 9030 10031 9535 9537 10039 9043 10047 9068 9071 100114 95120 100137 90Comparative 20chemical A______________________________________

TEST EXAMPLE 2

Insecticidal test for larvae of cotton aphid

The wettable powder prepared according to Formulation Example 2 was diluted with water so that the concentration of the active ingredient was 100 ppm. In the resulting diluted solution were immersed cucumber seedlings previously inoculated with larvae of cotton aphid and then subjected to a drying treatment in air. After the treatment, the cucumber seedlings were placed in a thermostatic chamber of 25.degree. C. for 3 days and then the number of larvae died was counted to calculate the percentage of mortality. The test was carried out by double series. The results are shown in Table 12.

TABLE 12______________________________________Compound CompoundNo. Mortality (%) No. Mortality (%)______________________________________ 3 100 103 10013 100 104 10014 100 105 10015 100 106 10017 100 107 10019 100 108 10030 100 109 10035 100 111 10039 100 112 10047 100 113 10051 100 114 10055 100 117 10068 100 118 10069 100 119 10071 100 120 10084 100 127 10087 100 131 10093 100 137 10096 100 179 10097 100 180 100100 100 229 100101 100______________________________________

TEST EXAMPLE 3

Ovicidal test for eggs of two-spotted spider mite

Female adults of two-spotted spider mite were placed on three leaf discs of kidney bean (diameter: 15 mm) and oviposited over 24 hours, and thereafter these adults were removed therefrom. The wettable powder prepared according to Formulation Example 2 was diluted with water so that the concentration of the active ingredient was 0.16 ppm. In the resulting diluted solution were immersed these leaf discs for 10 seconds. After the treatment, the leaf discs were placed in a thermostatic chamber of 25.degree. C. for 7 days and then the number of unhatched eggs was counted to calculate the percentage of ovicidal activity. The test was carried out by double series. Moreover, the comparative chemicals A and B were used for the comparison. The results are shown in Table 13.

TABLE 13______________________________________ Ovicidal activityCompound No. (%)______________________________________21 10030 10034 10035 10038 10039 9542 10043 9547 10050 10051 10054 10055 100Comparative 24chemical AComparative 95chemical B______________________________________

TEST EXAMPLE 4

Ovicidal test for eggs of chemical-resistant kanzawa spider mite

Female adults of kanzawa spider mite having a resistance to commercially available chemicals were placed on three lead disc of kidney bean (diameter: 15 mm) and oviposited over 2 days, and thereafter these adults were removed therefrom. The wettable powder prepared according to Formulation Example 2 was diluted with water so that the concentration of the active ingredient was 4 ppm. In the resulting diluted solution were immersed these leaf discs for 10 seconds. After the treatment, the leaf discs were placed in a thermostatic chamber of 25.degree. C. for 7 days and then the number of unhatched eggs was counted to calculate the percentage of ovicidal activity. The test was carried out by double series. Moreover, the comparative chemicals A and B were used for the comparison. The results are shown in Table 14.

TABLE 14______________________________________Compound Ovicidal Compound OvicidalNo. activity (%) No. activity (%)______________________________________ 3 100 53 9013 100 55 10014 100 56 10015 100 57 9021 100 84 9030 100 106 10034 100 108 9035 100 110 10036 100 111 9537 100 112 10038 100 117 10039 100 118 10040 100 155 10041 100 156 10042 100 157 10043 100 180 10044 100 181 10046 90 182 10048 100 Comparative 3151 100 chemical A52 95 Comparative 0 chemical B______________________________________

TEST EXAMPLE 5

Insecticidal test for larvae of chemical-resistant kanzawa spider mite

Female adults of kanzawa spider mite having a resistance to commercially available chemicals were placed on three leaf discs of kidney bean (diameter: 15 mm) and oviposited over 2 days, and thereafter these adults were removed therefrom. Then, these leaf discs were placed in a thermostatic chamber of 25.degree. C. for 5 days and the number of hatched larvae was counted. Separately, the wettable powder prepared according to Formulation Example 2 was diluted with water so that the concentration of the active ingredient was 20 ppm. After these leaf discs were sprayed with the resulting diluted solution, they were placed in a thermostatic chamber of 25.degree. C. for 7 days and then the number of living adults was counted to calculate the percentage of mortality on the hatched larvae. The test was carried out by double series. Moreover, the comparative chemicals A and B were used for the comparison. The results are shown in Table 15.

TABLE 15______________________________________Compound CompoundNo. Mortality (%) No. Mortality (%)______________________________________ 3 100 41 10013 100 42 10014 100 43 10015 100 44 10016 100 45 10017 100 46 10018 100 47 10021 100 48 10030 100 49 10031 100 50 10032 100 51 10034 100 52 10035 100 53 10036 100 55 10037 100 56 10038 100 Comparative 5539 100 chemical A40 100 Comparative 25 chemical B______________________________________

TEST EXAMPLE 6

Ovicidal test for eggs of citrus red mite

Female adults of citrus red mite were placed on two laminae of citrus fruit (diameter: 10 mm) and oviposited over 2 days, and thereafter these adults were removed therefrom. The wettable powder prepared according to Formulation Example 2 was diluted with water so that the concentration of the active ingredient was 4 ppm. In the resulting diluted solution were immersed these laminae for 10 seconds. After the treatment, the laminae were placed in a thermostatic chamber of 25.degree. C. for 7 days and then the number of unhatched eggs was counted to calculate the percentage of ovidcidal activity. The test was carried out by double series. Moreover, the comparative chemicals A and B were used for the comparison. The results are shown in Table 16.

TABLE 16______________________________________Compound No. Ovicidal activity (%)______________________________________ 3 9516 9017 10018 10021 9530 10031 10032 10034 10035 10036 9537 10038 10039 10040 9043 10044 10047 9548 10052 10097 95106 100Comparative 33chemical AComparative 90chemical B______________________________________

Claims

1. A triazole derivative having the following formula: ##STR28## wherein R.sup.1 is alkyl (C.sub.1 -C.sub.6) group, x is a hydrogen atom, a halogen atom, an alkyl (C.sub.1 -C.sub.6) group, an alkoxy (C.sub.1 -C.sub.6) group, an alkylthio (C.sub.1 -C.sub.6) group, a nitro group, a cyano group or a trifluoromethyl group, n is an integer of 1-5 provided that when n is 2 or more, X may be an optional combination of same or different atoms or groups and Y is an alkyl (C.sub.7 -C.sub.20) group, an alkoxy (C.sub.7 -C.sub.20) group, an alkylthio (C.sub.7 -C.sub.20) group, an alkylsulfinyl (C.sub.7 -C.sub.20) group, an alkylsulfonyl (C.sub.7 -C.sub.20) group, an alkenyl (C.sub.2 -C.sub.20) group, an alkynyl (C.sub.2 -C.sub.20) group, an alkoxy (C.sub.1 -C.sub.12) alkyl (C.sub.1 -C.sub.6) group, an alkoxy (C.sub.1 -C.sub.6) alkoxy (C.sub.1 -C.sub.6) group, an alkylthio (C.sub.1 -C.sub.6) alkyl (C.sub. 1 -C.sub.6) group, a cycloalkyl (C.sub.3 -C.sub.12) group, a cycloalkyl (C.sub.3 -C.sub.12) alkyl (C.sub.1 -C.sub.6) group, a cycloalkyl (C.sub.3 -C.sub.12) alkoxy (C.sub.1 -C.sub.6) group, a cycloalkyl (C.sub.3 -C.sub.12) alkenyl (C.sub.2 -C.sub.6) group, a cycloalkyl (C.sub.3 -C.sub.12) alkynyl (C.sub.2 -C.sub.6) group, a trialkyl (C.sub.1 -C.sub.4) silyalkyl (C.sub.1 -C.sub.4) group, a trialkyl (C.sub.1 -C.sub.4) silyalkoxy (C.sub.1 -C.sub.4) group or a group represented by the following formula (1): ##STR29## (wherein A is an oxygen atom, a sulfur atom, an alkylene (C.sub.1 -C.sub.4) group, an alkyleneoxy (C.sub.1 -C.sub.4) group, an oxyalkylene (C.sub.1 -C.sub.4) group or an alkyleneoxy (C.sub.1 -C.sub.4) alkylene (C.sub.1 -C.sub.4) group, k is 0 or 1, Q is --CH.dbd. group, R.sup.2 is a hydrogen atom, a halogen atom, an alkyl (C.sub.1 -C.sub.6) group, an alkoxy (C.sub.1 -C.sub.6) group, a trifluoromethyl group or a trifluoromethoxy group and m is an integer of 1-5 provided that when m is 2 or more, R.sup.2 may be an optional combination of same or different atoms or groups.)

2. The triazole derivative according to claim 1, wherein said R.sup.1 is a straight or branched-chain alkyl (C.sub.1 -C.sub.6) group, X is a hydrogen atom, a halogen atom, a straight or branched-chain alkyl (C.sub.1 -C.sub.4) group, a nitro group, a cyano group or a trifluoromethyl group, n is an integer of 1-3 provided that when n is 2 or 3, X may be an optional combination of same or different atoms or groups, Y is a straight or branched-chain alkyl (C.sub.7 -C.sub.16) group, a cycloalkyl (C.sub.3 -C.sub.12) group, a cycloalkyl (C.sub.3 -C.sub.6) alkyl (C.sub.1 -C.sub.6) group, a straight or branched-chain alkoxy (C.sub.10 -C.sub.12) group, a cycloalkyl (C.sub.3 -C.sub.6) alkoxy (C.sub.1 -C.sub.6) group, a straight or branched-chain alkylthio (C.sub.8)-C.sub.12) group, an alkylsulfinyl (C.sub.8 -C.sub.12) group, an alkylsulfonyl (C.sub.8 -C.sub.12) group, a straight or branched-chain alkenyl (C.sub.8 -C.sub.12) group, a cycloalkyl (C.sub.3 -C.sub.6) alkenyl (C.sub.2 -C.sub.6) group, a straight or branched-chain alkynyl (C.sub.3 -C.sub.12) group, a cycloalkyl (C.sub.3 -C.sub.6) alkynyl (C.sub.2 -C.sub.6) group, a tris silyalkyl (C.sub.1 -C.sub.4) group, a tris silylalkoxy (C.sub.1 -C.sub.4) group or a group represented by said formula (1) (wherein A is an oxygen atom, a sulfur atom, an alkylene (C.sub.1 -C.sub.2) group, an alkyleneoxy (C.sub.1 -C.sub.2) group or an oxyalkylene (C.sub.1 -C.sub.2) group, k is 0 or 1, Q is --CH.dbd. group, R.sup.2 is a hydrogen atom, a halogen atom, an alkyl (C.sub.1 -C.sub.6) group, an alkoxy (C.sub.1 -C.sub.4) group, a trifluoromethyl group or a trifluoromethoxy group and m is an integer of 1-3 provided that when m is 2 or 3, R.sup.2 may be an optional combination of same or different atoms or groups.)

3. The triazole derivative according to claim 1, wherein said R.sup.1 is methyl gruop , X is halogen atom, n is 1 or 2 provided that when n is 2, X may be an optional combination of same or different atoms and Y is an alkyl (C.sub.10 -C.sub.16) group.

4. The triazole derivative according to claim 1, wherein aid R.sup.1 is methyl group, X is a chlorine atom or a fluorine atom , n is 1 or 2 provided that when n is 2, X may be an optional combination of same or different atoms and Y is a dodecyl group or a tris(methyl)silylmethoxy group.

5. The triazole derivative according to claim 1, wherein said Y is an alkoxy (C.sub.1 -C.sub.12) alkyl (C.sub.1 -C.sub.6) group, an alkoxy (C.sub.1 -C.sub.6) alkoxy (C.sub.1 -C.sub.6) group or an alkylthio (C.sub.1 -C.sub.6) alkyl (C.sub.1 -C.sub.6) group.

6. The triazole derivative according to claim 1, wherein said Y is a group represented by said formula (1) (wherein A is an oxygen atom, a sulfur atom, an alkylene (C.sub.1 -C.sub.4) group, an alkyleneoxy (C.sub.1 -C.sub.4) group, an oxyalkylene (C.sub.1 -C.sub.4) group or an alkyleneoxy (C.sub.1 -C.sub.4) alkylene (C.sub.1 -C.sub.4) group, k is 0 or 1, Q is --CH.dbd. group, R.sup.2 is a hydrogen atom, a halogen atom, an alkyl (C.sub.1 -C.sub.6) group, an alkoxy (C.sub.1 -C.sub.6) group, a trifluoromethyl group or a trifluoromethoxy group and m is an integer of 1-3 provided that when m is 2 or more, R.sup.2 may be an optional combination of same or different atoms or groups.

7. The triazole derivative according to claim 1, wherein said R.sup.1 is methyl group, X is a chlorine atom or a fluorine atom, n is 1 or 2 provided that when n is 2, X may be an optional combination of same or different atoms and Y is a group represented by said formula (1) (wherein A is an oxygen atom, a methylene group, a methyleneoxy group or an oxymethylene group, k is 0 or 1, Q is --CH.dbd. group, R.sup.2 is a hydrogen atom, a chlorine atom, a fluorine atom, an alkyl (C.sub.1 -C.sub.4) group, an alkoxy (C.sub.1 -C.sub.4) group, a trifluoromethyl group or a trifluoromethoxy group, m is 1 or 2 provided that when m is 2, R.sup.2 may be an optional combination of same or different atoms or groups.

8. An insecticidal and acaricidal composition comprising an insecticidally and acaricidally effective amount of triazole derivative as defined in claim 1 and a carrier.

9. An insecticidal and acaricidal composition comprising an insecticidally and acaricidally effective amount of triazole derivative as defined in claim 2 and a carrier.

10. An insecticidal and acaricidal composition comprising an insecticidally and acaricidally effective amount of triazole derivative as defined in claim 3 and a carrier.

11. An insecticidal and acaricidal composition comprising an insecticidally and acaricidally effective amount of triazole derivative as defined in claim 4 and a carrier.

12. An insecticidal and acaricidal composition comprising an insecticidally and acaricidally effective amount of triazole derivative as defined in claim 5 and a carrier.

13. An insecticidal and acaricidal composition comprising an insecticidally and acaricidally effective amount of triazole derivative as defined in claim 6 and a carrier.

14. An insecticidal and acaricidal composition comprising an insecticidally and acaricidally effective amount of triazole derivative as defined in claim 7 and a carrier.

15. A method of killing insects, aphids or mites or their eggs or larvae, comprising applying to a site infested or liable to infestation therewith an insecticidally and acaricidally effective amount of triazole derivative as defined in claim 1.

16. A method of killing insects, aphids or mites or their eggs or larvae, comprising applying to a site infested or liable to infestation therewith an insecticidally and acaricidally effective amount of triazole derivative as defined in claim 2.

17. A method of killing insects, aphids or mites or their eggs or larvae, comprising applying to a site infested or liable to infestation therewith an insecticidally and acaricidally effective amount of triazole derivative as defined in claim 3.

18. A method of killing insects, aphids or mites or their eggs or larvae, comprising applying to a site infested or liable to infestation therewith an insecticidally and acaricidally effective amount of triazole derivative as defined in claim 4.

19. A method of killing insects, aphids or mites or their eggs or larvae, comprising applying to a site infested or liable to infestation therewith an insecticidally and acaricidally effective amount of triazole derivative as defined in claim 5.

20. A method of killing insects, aphids or mites or their eggs or larvae, comprising applying to a site infested or liable to infestation therewith an insecticidally and acaricidally effective amount of triazole derivative as defined in claim 6.

21. A method of killing insects, aphids or mites or their eggs or larvae, comprising applying to a site infested or liable to infestation therewith an insecticidally and acaricidally effective amount of triazole derivative as defined in claim 7.