Triazole derivatives, insecticide, acaricide and methods thereof

�TECHNICAL FIELD!
This invention relates to triazole derivatives, insecticides and acaricides containing them as an active ingredient, and methods thereof.
�BACKGROUND ART!
As a prior art including compounds similar to the compound according to the invention in the chemical structure, there have hitherto been known the specification of JP-A-56-154464 and technical report RD 278004. They disclose that the compounds have insecticidal and acaricidal activities. However, it can not be said that the compounds described in the above opened specification and technical report are sufficient in the insecticidal and acaricidal activities.
�DISCLOSURE OF INVENTION!
The inventors have synthesized various triazole derivatives in order to develop novel and useful insecticide and acraricide and made various studies with respect to physiological activity thereof. As a result, it has been found that the compounds according to the invention have very excellent insecticidal and acaricidal activities against harmful insects and harmful mites as compared with the compounds concretely described in the specification of JP-A-56-154464 and technical report RD 278004. Particularly, it has been found that they are characterized by having plural substituent groups on a benzene ring substituted in 5-position of a triazole ring and have a very excellent insecticidal activity against mites such as two-spotted spider mite, Kanzawa spider mite, citrus red mite and the like; aphids such as cotton aphid and the like; and lepidoptera pests such as diamond-back moth and the like, and as a result the invention has been accomplished.
The invention lies in a triazole derivative represented by a 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 optionally be same or different combination, Y is a halogen atom, a nitro group, an alkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxyalkoxy group, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, an alkylthioalkyl group, an alkylsulfinylalkyl group, an alkylsulfonylalkyl group, a cycloalkyl group, a cycloalkylalkyl group, a cycloalkylalkenyl group, a cycloalkylalkynyl group, a haloalkyl group, a haloalkoxy group, a trialkylsilylalkyl group, a trialkylsilylalkoxy group, an alkenyl group, an alkenyloxy group, an alkynyl group, an alkynyloxy group or a group represented by a general formula ##STR3## (wherein A is an oxygen atom, a sulfur atom, a lower alkylene group, a lower alkyleneoxy group, an oxy lower alkylene group, a lower alkyleneoxy lower alkylene group, a lower alkylenethio group, a thio lower alkylene group, a vinylene group or an ethynylene group, k is 0 or 1, Q is a methine group or a nitrogen atom, R.sup.2 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a trifluoromethyl group or a trifluoromethoxy group, j is an integer of 1-5, provided that when j is 2 or more, R.sup.2 may optionally be same or different combination), m is an integer of 2-5 and Y may optionally be same or different combination}, and insecticides and acaricides containing the derivative as an active ingredient and methods thereof.
In this specification, the alkyl group means a straight or branched-chain alkyl group having a carbon number of 1-30 and 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-methyltetradecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group and the like.
The 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 each alkyl portion has the same meaning as mentioned above. The alkylthioalkyl group, alkylsulfinylalkyl group and alkylsulfonyl group are (alkyl)-S-(alkyl)-group, (alkyl)-SO-(alkyl)-group and (alkyl)-SO.sub.2 -(alkyl)-group, in which each alkyl portion has the same meaning as mentioned above. The halogen atom includes fluorine, chlorine, bromine and iodine.
The alkenyl group means a straight or branched-chain alkenyl group having a carbon number of 2-20 and 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 alkynyl group means a straight or branched-chain alkynyl group having a carbon number of 2-20 and 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-1hexynyl 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 cycloalkyl group means a cycloalkyl group having a carbon number of 3-12 and includes, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like. The cycloalkylalkyl group means a cycloalkylalkyl group having a carbon number of 6-12 and includes, for example, cyclopentylmethyl group, cyclohexylmethyl group, cyclopentylethyl group, cyclohexylethyl group, cyclopentylpropyl group, cyclohexylpropyl group, cyclohexylpentyl group and the like.
The cycloalkylalkoxy group means (cycloalkylalkyl)-O-group in which the cycloalkylalkyl portion has the same meaning as mentioned above. The cycloalkylalkenyl group means a cycloalkylalkenyl group having a carbon number of 5-12 and 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 cycloalkylalkynyl group means a cycloalkylalkynyl group having a carbon number of 5-12 and includes, for example, cyclopentylethynyl group, cyclohexylethynyl group, 3-cyclopentyl-1-propynyl group, 3-cyclohexyl-1-propynyl group and the like.
The haloalkyl group means an alkyl group substituted with a halogen atom and includes, for example, trifluoromethyl group, pentafluoroethyl group and the like. The haloalkoxy group is (haloalkyl)-O-group in which the haloalkyl portion has the same meaning as described above.
The trialkylsilylalkyl group is, for example, trimethylsilylmethyl group, dimethylethylsilylmethyl group, butyldimethylsilylmethyl group or the like. The trialkylsilylalkoxy group is (trialkylsilylalkyl)-O-group in which the trialkylsilylalkyl portion has the same meaning as described above.
The lower alkylene group includes, for example, methylene group, ethylene group, methylmethylene group, trimethylene group, 1-methylethylene group, dimethylmethylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group and the like. The lower alkyleneoxy group is -(lower alkylene)-O-group in which the lower alkylene portion has the same meaning as described above. The oxy lower alkylene group is --O-(lower alkylene)-group in which the lower alkylene portion has the same meaning as described above.
The lower alkyleneoxy lower alkylene group is -(lower alkylene)-O-(lower alkylene)-group in which the lower alkylene portion has the same meaning as described above. The lower alkylenethio group is -(lower alkylene)-S-group in which the lower alkylene portion has the same meaning as described above. The thio lower alkylene group is -S-(lower alkylene)-group in which the lower alkylene portion has the same meaning as described above.
As a preferable compound group in the general formula �I!, mention may be made of compounds in which 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 a trifluoromethyl group, n is an integer of 1-3 provided that when n is 2 or 3, X may optionally be same or different combination, Y is a halogen atom, a nitro group, a straight or branched-chain alkyl group having a carbon number of 1-20, a straight or branched-chain alkoxy group having a carbon number of 1-20, a cycloalkyl group having a carbon number of 3-12, a cycloalkylalkyl group having a carbon number of 6-12, a cycloalkylalkoxy group having a carbon number of 3-12, a straight or branched-chain alkylthio group having a carbon number of 1-20, an alkylsulfinyl group, an alkylsulfonyl group, a straight or branched-chain alkynyl group having a carbon number of 3-16, a cycloalkylalkynyl group having a carbon number of 5-12, tri(alkyl)silylalkyl group, tri(alkyl)silylalkoxy group or a group represented by the formula: ##STR4## (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 alkyleneoxy lower alkylene group, k is 0 or 1, Q is methine group or a nitrogen atom, R.sup.2 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a trifluoromethyl group or a trifluoromethoxy group, j is an integer of 1-5 provided that when j is 2 or more, R.sup.2 may optionally be same or different combination), m is an integer of 2-5 and Y may optionally be same or different combination.
The compounds of the general formula �I! according to the invention are exemplified in Tables 1-2. Moreover, compound number is referred in subsequent description.
TABLE 1__________________________________________________________________________ ##STR5## Melting point (.degree.C.)Compound or refractiveNo R.sup.1 Xn Ym index (n.sub.D.sup.20)__________________________________________________________________________1 CH.sub.3 2-Cl 2-Cl, 3-NO.sub.2 124.0-125.02 CH.sub.3 2 Cl, 6-F 2-Cl, 3-NO.sub.2 112.0-114.03 CH.sub.3 2-Cl 2-Cl, 4-NO.sub.24 CH.sub.3 2-Cl, 6-F 2-Cl, 4-NO.sub.2 144.0-148.05 CH.sub.3 2-Cl 2-Cl, 5-NO.sub.2 129.0-130.06 CH.sub.3 2-Cl, 6-F 2-Cl, 5-NO.sub.2 121.0-124.07 CH.sub.3 2-Cl 3-NO.sub.2, 4-Cl8 CH.sub.3 2-Cl, 6-F 3-NO.sub.2, 4-Cl 124.0-126.59 CH.sub.3 2-Cl 2,6-Cl.sub.2, 3-NO.sub.2 155.0-156.010 CH.sub.3 2-Cl, 6-F 2,6-Cl.sub.2, 3-NO.sub.2 108.0-109.011 CH.sub.3 2-Cl 2,6-Cl.sub.2, 4-NO.sub.212 CH.sub.3 2-Cl, 6-F 2,6-Cl.sub.2, 4-NO.sub.2 158.0-162.013 CH.sub.3 2-Cl 2,4-Cl.sub.2, 3,5-(NO.sub.2).sub.214 CH.sub.3 2-Cl, 6-F 2,4-Cl.sub.2, 3,5-(NO.sub.2).sub.215 CH.sub.3 2-Cl 2-Cl, 4-C.sub.2 H.sub.5 75.5-77.516 CH.sub.3 2-Cl, 6-F 2-Cl, 4-C.sub.2 H.sub.5 1.593017 CH.sub.3 2-Cl, 6-F 3-Cl, 4-C.sub.2 H.sub.518 CH.sub.3 2-Cl 2-Cl, 4-C.sub.3 H.sub.7 70.0-72.019 CH.sub.3 2-Cl, 6-F 2-Cl, 4-C.sub.3 H.sub.7 1.586820 C.sub.2 H.sub.5 2-Cl 2-Cl, 4-C.sub.3 H.sub.721 C.sub.2 H.sub.5 2-Cl, 6-F 2-Cl, 4-C.sub.3 H.sub.722 C.sub.3 H.sub.7 -i 2-Cl 2-Cl, 4-C.sub.3 H.sub.723 C.sub.3 H.sub.7 -i 2-Cl, 6-F 2-Cl, 4-C.sub.3 H.sub.724 CH.sub.3 2-Cl 2-Cl, 4-C.sub.3 H.sub.7 -i 90.0-92.025 CH.sub.3 2-Cl, 6-F 2-Cl, 4-C.sub.3 H.sub.7 -i26 CH.sub.3 2-Cl 2,4,6-(C.sub.3 H.sub.7 -i).sub.327 CH.sub.3 2-Cl, 6-F 2,4,6-(C.sub.3 H.sub.7 -i).sub.328 CH.sub.3 2-Cl 2-Cl, 4-C.sub.4 H.sub.9 1.596229 CH.sub.3 2-Cl, 6-F 2-Cl, 4-C.sub.4 H.sub.9 1.566730 CH.sub.3 H 2-Cl, 5-C.sub.4 H.sub.9 -t31 CH.sub.3 2-Cl 2-Cl, 5-C.sub.4 H.sub.9 -t 1.593132 CH.sub.3 2-Cl, 6-F 2-Cl, 5-C.sub.4 H.sub.9 -t 1.594333 CH.sub.3 2,6-F.sub.2 2-OC.sub.2 H.sub.5, 4-C.sub.4 H.sub.9 -t 146.0-148.034 CH.sub.3 2-Cl 2-OC.sub.2 H.sub.5, 4-C.sub.4 H.sub.9 -t 1.581835 CH.sub.3 2-Cl, 6-F 2-OC.sub.2 H.sub.5, 4-C.sub.4 H.sub.9 -t 108.0-111.036 CH.sub.3 2,6-F.sub.2 2-Cl, 4-C.sub.5 H.sub.11 1.562937 CH.sub.3 2-Cl 2-Cl, 4-C.sub.5 H.sub.11 1.584938 CH.sub.3 2-Cl, 6-F 2-Cl, 4-C.sub.5 H.sub.11 1.571039 CH.sub.3 2,6-F.sub.2 2-Cl, 4-C.sub.6 H.sub.13 1.559140 CH.sub.3 2-Cl 2-Cl, 4-C.sub.6 H.sub.13 1.583041 CH.sub.3 2-Cl, 6-F 2-Cl, 4-C.sub.6 H.sub.13 1.563842 CH.sub.3 2-Cl 2-F, 5-C.sub.6 H.sub.13 1.577943 CH.sub.3 2-Cl, 6-F 2-F, 5-C.sub.6 H.sub.13 1.560844 CH.sub.3 2-Cl 2-Cl, 4-C.sub.7 H.sub.15 1.582445 CH.sub.3 2-Cl, 6-F 2-Cl, 4-C.sub.7 H.sub.1546 CH.sub.3 2,6-F.sub.2 2-F, 5-C.sub.11 H.sub.23 70.0-73.047 CH.sub.3 2-Cl 2-F, 5-C.sub.11 H.sub.23 35.0-37.048 CH.sub.3 2-Cl, 6-F 2-F, 5-C.sub.11 H.sub.23 1.541949 CH.sub.3 2,6-F.sub.2 2-Cl, 4-C.sub.12 H.sub.2550 CH.sub.3 2-Cl 2-Cl, 4-C.sub.12 H.sub.25 76.0-77.051 CH.sub.3 2-Cl, 6-F 2-Cl, 4-C.sub.12 H.sub.25 1.549052 CH.sub.3 2-Cl, 6-F 3-Cl, 4-C.sub.15 H.sub.3153 CH.sub.3 H 3,5-(OC.sub.2 H.sub.5).sub.254 CH.sub.3 2-CH.sub.3 3,5-(OC.sub.2 H.sub.5).sub.255 CH.sub.3 2-OCH.sub.3 3,5-(OC.sub.2 H.sub.5).sub.256 CH.sub.3 2-SCH.sub.3 3,5-(OC.sub.2 H.sub.5).sub.257 CH.sub.3 2-NO.sub.2 3,5-(OC.sub.2 H.sub.5).sub.258 CH.sub.3 2-CN 3,5-(OC.sub.2 H.sub.5).sub.259 CH.sub.3 2-CF.sub.3 3,5-(OC.sub.2 H.sub.5).sub.260 CH.sub.3 2-Cl 2-OC.sub.2 H.sub.5, 4,5-Cl.sub.261 CH.sub.3 2-Cl, 6-F 2-OC.sub.2 H.sub.5, 4,5-Cl.sub.2 115.0-117.062 CH.sub.3 2-Cl 2-OC.sub.2 H.sub.5, 4,5-F.sub.263 CH.sub.3 2-Cl, 6-F 2-OC.sub.2 H.sub.5, 4,5-F.sub.2 1.559064 CH.sub.3 2-Cl 2-Cl, 4-OC.sub.4 H.sub.9 60.0-62.065 CH.sub.3 2-Cl, 6-F 2-Cl, 4-OC.sub.4 H.sub.9 1.563166 CH.sub.3 2-Cl 2-Cl, 4-OC.sub.5 H.sub.11 71.0-73.067 CH.sub.3 2-Cl, 6-F 2-Cl, 4-OC.sub.5 H.sub.1168 CH.sub.3 2-Cl, 6-F 3-OC.sub.5 H.sub.11, 4-Cl not measurable69 CH.sub.3 2-Cl, 6-F 3-OC.sub.5 H.sub.11, 4-Cl70 CH.sub.3 2-Cl 3,5-(OC.sub.5 H.sub.11).sub.271 CH.sub.3 2-Cl, 6-F 3,5-(OC.sub.5 H.sub.11).sub.272 CH.sub.3 2,6-Cl.sub.2 2-Cl, 4-OC.sub.8 H.sub.17 1.572873 CH.sub.3 2-Cl 2-Cl, 4-OC.sub.8 H.sub.17 51.0-54.074 CH.sub.3 2-Cl, 6-F 2-Cl, 4-OC.sub.8 H.sub.17 1.564175 CH.sub.3 2-Cl 3-Cl, 4-OC.sub.8 H.sub.17 47.0-49.076 CH.sub.3 2-Cl, 6-F 3-Cl, 4-OC.sub.8 H.sub.17 1.565877 CH.sub.3 2-Cl 3-OC.sub.8 H.sub.17, 4-Cl not measurable78 CH.sub.3 2-Cl, 6-F 3-OC.sub.8 H.sub.17, 4-Cl 1.565879 CH.sub.3 2-Cl 3,5-(OC.sub.8 H.sub.17).sub.280 CH.sub.3 2-Cl, 6-F 3,5-(OC.sub.8 H.sub.17).sub.281 CH.sub.3 2-NO.sub.2 3-Cl, 4-OC.sub.12 H.sub.2582 CH.sub.3 2-SCH.sub.3 3-Cl, 4-OC.sub.12 H.sub.2583 CH.sub.3 2-Cl 3-Cl, 4-OC.sub.15 H.sub.3184 CH.sub.3 2-Cl, 6-F 3-Cl, 4-OC.sub.15 H.sub.3185 CH.sub.3 2-Cl, 6-F 3-Cl, 4-CH.sub.2 OCH.sub.386 CH.sub.3 2-Cl, 6-F 3-Cl, 4-(CH.sub.2).sub.3 OC.sub.3 H.sub.787 CH.sub.3 2-Cl 2-Cl, 4-OC.sub.2 H.sub.4 OCH.sub.3 1.594688 CH.sub.3 2-Cl, 6-F 2-Cl, 4-OC.sub.2 H.sub.4 OCH.sub.389 CH.sub.3 2-Cl, 6-F 3-SCH.sub.3, 4-Cl90 CH.sub.3 2-Cl, 6-F 3-SC.sub.3 H.sub.7, 4-Cl91 CH.sub.3 2-Cl, 6-F 3-SC.sub.6 H.sub.13, 4-Cl92 CH.sub.3 2-Cl, 6-F 3-SOCH.sub.3, 4-Cl93 CH.sub.3 2-Cl, 6-F 3-SOC.sub.3 H.sub.7, 4-Cl94 CH.sub.3 2-Cl, 6-F 3-SOC.sub.6 H.sub.13, 4-Cl95 CH.sub.3 2-Cl, 6-F 3-SO.sub.2 CH.sub.3, 4-Cl96 CH.sub.3 2-Cl, 6-F 3-SO.sub.2 C.sub.3 H.sub.7, 4-Cl97 CH.sub.3 2-Cl, 6-F 3-SO.sub.2 C.sub.6 H.sub.13, 4-Cl98 CH.sub.3 2-Cl, 6-F 3-CH.sub.2 SCH.sub.3, 4-C.sub.2 H.sub.599 CH.sub.3 2-Cl, 6-F 3-CH.sub.2 SC.sub.3 H.sub.7, 4-C.sub.2 H.sub.5100 CH.sub.3 2-Cl 3-Br, 4-CH.sub.2 SC.sub.5 H.sub.11101 CH.sub.3 2-Cl, 6-F 3-Br, 4-CH.sub.2 SC.sub.5 H.sub.11102 CH.sub.3 2-Cl, 6-F 3-CH.sub.2 SC.sub.6 H.sub.13, 4-C.sub.2 H.sub.5103 CH.sub.3 2-Cl, 6-F 3-CH.sub.2 SOCH.sub.3, 4-C.sub.2 H.sub.5104 CH.sub.3 2-Cl, 6-F 3-CH.sub.2 SOC.sub.3 H.sub.7, 4-C.sub.2 H.sub.5105 CH.sub.3 2-Cl 3-Br, 4-CH.sub.2 SOC.sub.5 H.sub.11106 CH.sub.3 2-Cl, 6-F 3-Br, 4-CH.sub.2 SOC.sub.5 H.sub.11107 CH.sub.3 2-Cl, 6-F 3-CH.sub.2 SOC.sub.6 H.sub.13, 4-C.sub.2 H.sub.5108 CH.sub.3 2-Cl 3-Br, 4-CH.sub.2 SO.sub.2 C.sub.5 H.sub.11109 CH.sub.3 2-Cl, 6-F 3-Br, 4-CH.sub.2 SO.sub.2 C.sub.5 H.sub.11110 CH.sub.3 2-Cl, 6-F 3-CH.sub.2 SO.sub.2 CH.sub.3, 4-C.sub.2 H.sub.5111 CH.sub.3 2-Cl, 6-F 3-CH.sub.2 SO.sub.2 C.sub.3 H.sub.7, 4-C.sub.2 H.sub.5112 CH.sub.3 2-Cl, 6-F 3-CH.sub.2 SO.sub.2 C.sub.6 H.sub.13, 4-C.sub.2 H.sub.5113 CH.sub.3 2-Cl 2-Cl, 5-C.sub.2 F.sub.5114 CH.sub.3 2-Cl, 6-F 2-Cl, 5-C.sub.2 F.sub.5115 CH.sub.3 2-Cl 2-Cl, 5-C.sub.4 F.sub.9116 CH.sub.3 2-Cl, 6-F 2-Cl, 5-C.sub.4 F.sub.9 1.5110117 CH.sub.3 2-Cl 3-C.sub.4 F.sub.9, 4-Cl118 CH.sub.3 2-Cl, 6-F 3-C.sub.4 F.sub.9, 4-Cl 1.5392119 CH.sub.3 2-Cl 2-Cl, 5-C.sub.6 F.sub.13 70.0-76.0120 CH.sub.3 2-Cl, 6-F 2-Cl, 5-C.sub.6 F.sub.13 78.0-82.0121 CH.sub.3 2-Cl, 6-F 2-F, 5-C.sub.4 H.sub.9 1.5090122 CH.sub.3 2-Cl 3, 5-Cl.sub.2, 5-C.sub.8 H.sub.17123 CH.sub.3 2-Cl, 6-F 3, 5-Cl.sub.2, 5-O(CF.sub.2).sub.2 H 96.0-101.0124 CH.sub.3 2-Cl, 6-F 3-Cl, 4-(CH.sub.2).sub.2 C.sub.4 F.sub.9125 CH.sub.3 2-Cl 2-Cl, 5-OC.sub.2 F.sub.5126 CH.sub.3 2-Cl, 6-F 2-Cl, 5-OC.sub.2 F.sub.5127 CH.sub.3 2-Cl 3-Cl, 4-O(CH.sub.2).sub.2 C.sub.4 F.sub.9128 CH.sub.3 2-Cl, 6-F 3-Cl, 4-O(CH.sub.2).sub.2 C.sub.4 F.sub.9129 CH.sub.3 2-Cl 3-Br, 4-CH.sub.2 Si(CH.sub.3).sub.3130 CH.sub.3 2-Cl, 6-F 3-Br, 4-CH.sub.2 Si(CH.sub.3).sub.3131 CH.sub.3 2-Cl 3-Br, 4-OCH.sub.2 Si(CH.sub.3).sub.3132 CH.sub.3 2-Cl, 6-F 3-Br, 4-OCH.sub.2 Si(CH.sub.3).sub.3133 CH.sub.3 2-Cl, 6-F 3-CHCH.sub.2, 4-Cl134 CH.sub.3 2-Cl 3-Br, 4-CHCHCH.sub.3135 CH.sub.3 2-Cl, 6-F 3-Br, 4-CHCHCH.sub.3136 CH.sub.3 2-Cl, 6-F 3-CH.sub.2 CHCHC.sub.3 H.sub.7, 4-Cl137 CH.sub.3 2-Cl, 6-F 3-OCHCH.sub.2, 4-Cl138 CH.sub.3 2-Cl 2-Cl, 4-OCHCH.sub.2 1.6083139 CH.sub.3 2-Cl, 6-F 2-Cl, 4-OCHCH.sub.2140 CH.sub.3 2-Cl, 6-F 3-OCH.sub.2 CHCHC.sub.3 H.sub.7, 4-Cl141 CH.sub.3 2-Cl, 6-F 3-Cl, 4-C CH142 CH.sub.3 2-Cl, 6-F 3-Cl, 4-C CC.sub.4 H.sub.9143 CH.sub.3 2-Cl, 6-F 3-Cl, 4-OC CH144 CH.sub.3 2-Cl, 6-F 3-Cl, 4-OC CC.sub.4 H.sub.9145 CH.sub.3 2-Cl 2-Cl, 4-OCH.sub.2 C CH 103.5-105.0146 CH.sub.3 2-Cl, 6-F 2-Cl, 4-OCH.sub.2 C CH147 CH.sub.3 2-Cl ##STR6##148 CH.sub.3 2-Cl, 6-F ##STR7##149 CH.sub.3 2-Cl ##STR8##150 CH.sub.3 2-Cl, 6-F ##STR9##151 CH.sub.3 2-Cl ##STR10##152 CH.sub.3 2-Cl, 6-F ##STR11##153 CH.sub.3 2-Cl ##STR12##154 CH.sub.3 2-Cl, 6-F ##STR13##__________________________________________________________________________
TABLE 2__________________________________________________________________________ ##STR14## Melting point (.degree.C.)Compound or refractiveNo. R.sup.1 Xn R.sup.4 index (n.sub.D.sup.20)__________________________________________________________________________155 CH.sub.3 2-Cl ##STR15##156 CH.sub.3 2-Cl, 6-F ##STR16##157 CH.sub.3 2-Cl, 6-F ##STR17## 117.0-119.0158 CH.sub.3 2-Cl, 6-F ##STR18## 1.5925159 CH.sub.3 2-Cl, 6-F ##STR19##160 CH.sub.3 2-Cl, 6-F ##STR20##161 CH.sub.3 2-Cl, 6-F ##STR21## 179.0-185.0162 CH.sub.3 2-Cl, 6-F ##STR22##163 CH.sub.3 2,6-F.sub.2 ##STR23##164 CH.sub.3 2-Cl, 6-F ##STR24##165 CH.sub.3 2,6-F.sub.2 ##STR25##166 CH.sub.3 2-Cl, 6-F ##STR26##167 CH.sub.3 2,6-F.sub.2 ##STR27##168 CH.sub.3 2-Cl, 6-F ##STR28##169 CH.sub.3 2,6-F.sub.2 ##STR29##170 CH.sub.3 2-Cl, 6-F ##STR30##171 CH.sub.3 2,6-F.sub.2 ##STR31##172 CH.sub.3 2-Cl, 6-F ##STR32##173 CH.sub.3 2,6-F.sub.2 ##STR33##174 CH.sub.3 2-Cl, 6-F ##STR34##175 CH.sub.3 2,6-F.sub.2 ##STR35##176 CH.sub.3 2-Cl, 6-F ##STR36##177 CH.sub.3 2,6-F.sub.2 ##STR37##178 CH.sub.3 2-Cl, 6-F ##STR38##179 CH.sub.3 2,6-F.sub.2 ##STR39##180 CH.sub.3 2-Cl, 6-F ##STR40##181 CH.sub.3 2,6-F.sub.2 ##STR41##182 CH.sub.3 2-Cl, 6-F ##STR42##183 CH.sub.3 2,6-F.sub.2 ##STR43##184 CH.sub.3 2-Cl, 6-F ##STR44##185 CH.sub.3 2,6-F.sub.2 ##STR45##186 CH.sub.3 2-Cl, 6-F ##STR46##187 CH.sub.3 2,6-F.sub.2 ##STR47##188 CH.sub.3 2-Cl, 6-F ##STR48##189 CH.sub.3 2,6-F.sub.2 ##STR49##190 CH.sub.3 2-Cl, 6-F ##STR50##191 CH.sub.3 2-Cl ##STR51##192 CH.sub.3 2-Cl, 6-F ##STR52##193 CH.sub.3 2,6-F.sub.2 ##STR53##194 CH.sub.3 2-Cl, 6-F ##STR54##195 CH.sub.3 2,6-F.sub.2 ##STR55##196 CH.sub.3 2-Cl, 6-F ##STR56## 113.0-114.0197 CH.sub.3 2-Cl, 6-F ##STR57## 1.6010198 CH.sub.3 2,6-F.sub.2 ##STR58##199 CH.sub.3 2-Cl, 6-F ##STR59## 1.5961200 CH.sub.3 2,6-F.sub.2 ##STR60##201 CH.sub.3 2-Cl, 6-F ##STR61## 1.5701202 CH.sub.3 2-Cl, 6-F ##STR62##203 CH.sub.3 2,6-F.sub.2 ##STR63##204 CH.sub.3 2-Cl, 6-F ##STR64##205 CH.sub.3 2,6-F.sub.2 ##STR65##206 CH.sub.3 2-Cl, 6-F ##STR66##207 CH.sub.3 2,6-F.sub.2 ##STR67##208 CH.sub.3 2-Cl, 6-F ##STR68##209 CH.sub.3 2,6-F.sub.2 ##STR69##210 CH.sub.3 2-Cl, 6-F ##STR70##211 CH.sub.3 2-Cl, 6-F ##STR71##212 CH.sub.3 2,6-F.sub.2 ##STR72##213 CH.sub.3 2-Cl, 6-F ##STR73##214 CH.sub.3 2,6-F.sub.2 ##STR74##215 CH.sub.3 2-Cl, 6-F ##STR75##216 CH.sub.3 2,6-F.sub.2 ##STR76##217 CH.sub.3 2-Cl, 6-F ##STR77##218 CH.sub.3 2,6-F.sub.2 ##STR78##219 CH.sub.3 2-Cl, 6-F ##STR79##220 CH.sub.3 2,6-F.sub.2 ##STR80##221 CH.sub.3 2-Cl, 6-F ##STR81##222 CH.sub.3 2,6-F.sub.2 ##STR82##223 CH.sub.3 2-Cl, 6-F ##STR83##224 CH.sub.3 2,6-F.sub.2 ##STR84##225 CH.sub.3 2-Cl, 6-F ##STR85##226 CH.sub.3 2,6-F.sub.2 ##STR86##227 CH.sub.3 2-Cl, 6-F ##STR87##228 CH.sub.3 2,6-F.sub.2 ##STR88##229 CH.sub.3 2-Cl, 6-F ##STR89##230 CH.sub.3 2,6-F.sub.2 ##STR90##231 CH.sub.3 2-Cl, 6-F ##STR91##232 CH.sub.3 2,6-F.sub.2 ##STR92##233 CH.sub.3 2-Cl, 6-F ##STR93##234 CH.sub.3 2,6-F.sub.2 ##STR94##235 CH.sub.3 2-Cl, 6-F ##STR95##236 CH.sub.3 2,6-F.sub.2 ##STR96##237 CH.sub.3 2-Cl, 6-F ##STR97##238 CH.sub.3 2-Cl, 6-F ##STR98##239 CH.sub.3 2,6-F.sub.2 ##STR99##240 CH.sub.3 2-Cl, 6-F ##STR100##241 CH.sub.3 2-Cl, 6-F ##STR101## 135.0-140.0242 CH.sub.3 2,6-F.sub.2 ##STR102##243 CH.sub.3 2-Cl, 6-F ##STR103##244 CH.sub.3 2,6-F.sub.2 ##STR104##245 CH.sub.3 2-Cl, 6-F ##STR105##246 CH.sub.3 2,6-F.sub.2 ##STR106##247 CH.sub.3 2-Cl, 6-F ##STR107##248 CH.sub.3 2,6-F.sub.2 ##STR108##249 CH.sub.3 2-Cl, 6-F ##STR109##250 CH.sub.3 2,6-F.sub.2 ##STR110##251 CH.sub.3 2-Cl, 6-F ##STR111##252 CH.sub.3 2,6-F.sub.2 ##STR112##253 CH.sub.3 2-Cl, 6-F ##STR113##254 CH.sub.3 2,6-F.sub.2 ##STR114##255 CH.sub.3 2-Cl, 6-F ##STR115##256 CH.sub.3 2,6-F.sub.2 ##STR116##257 CH.sub.3 2-Cl, 6-F ##STR117##258 CH.sub.3 2,6-F.sub.2 ##STR118##259 CH.sub.3 2-Cl, 6-F ##STR119## 67.0-72.0260 CH.sub.3 2,6-F.sub.2 ##STR120##261 CH.sub.3 2-Cl, 6-F ##STR121##262 CH.sub.3 2,6-F.sub.2 ##STR122##263 CH.sub.3 2-Cl, 6-F ##STR123##264 CH.sub.3 2,6-F.sub.2 ##STR124##265 CH.sub.3 2-Cl, 6-F ##STR125##266 CH.sub.3 2-Cl, 6-F ##STR126##267 CH.sub.3 2-Cl, 6-F ##STR127## 101.0-107.0268 CH.sub.3 2-Cl, 6-F ##STR128## 115.0-120.0269 CH.sub.3 2-Cl, 6-F ##STR129## 74.0-77.0270 CH.sub.3 2-Cl ##STR130##271 CH.sub.3 2-Cl, 6-F ##STR131##272 CH.sub.3 2-Cl, 6-F ##STR132##273 CH.sub.3 2-Cl, 6-F ##STR133## 156.0-159.0274 CH.sub.3 2-Cl, 6-F ##STR134## 109.0-111.0275 CH.sub.3 2-Cl, 6-F ##STR135## 43.0-47.0276 CH.sub.3 2,6-F.sub.2 ##STR136## 171.0-177.0277 CH.sub.3 2-Cl, 6-F ##STR137## 1.5680278 CH.sub.3 2,6-F.sub.2 ##STR138## 132.0-136.0279 CH.sub.3 2-Cl, 6-F ##STR139##280 CH.sub.3 2-Cl ##STR140##281 CH.sub.3 2-Cl, 6-F ##STR141##282 CH.sub.3 2-Cl ##STR142##283 CH.sub.3 2-Cl, 6-F ##STR143##284 CH.sub.3 2-Cl ##STR144##285 CH.sub.3 2-Cl, 6-F ##STR145##286 CH.sub.3 2,6-F.sub.2 ##STR146##287 CH.sub.3 2-Cl, 6-F ##STR147##288 CH.sub.3 2,6-F.sub.2 ##STR148##289 CH.sub.3 2-Cl, 6-F ##STR149##290 CH.sub.3 2,6-F.sub.2 ##STR150##291 CH.sub.3 2-Cl, 6-F ##STR151##292 CH.sub.3 2,6-F.sub.2 ##STR152##293 CH.sub.3 2-Cl, 6-F ##STR153##294 CH.sub.3 2,6-F.sub.2 ##STR154##295 CH.sub.3 2-Cl, 6-F ##STR155##296 CH.sub.3 2-Cl ##STR156##297 CH.sub.3 2-Cl, 6-F ##STR157##298 CH.sub.3 2,6-F.sub.2 ##STR158##299 CH.sub.3 2-Cl, 6-F ##STR159##300 CH.sub.3 2,6-F.sub.2 ##STR160##301 CH.sub.3 2-Cl, 6-F ##STR161##302 CH.sub.3 2,6-F.sub.2 ##STR162##303 CH.sub.3 2-Cl, 6-F ##STR163##304 CH.sub.3 2,6-F.sub.2 ##STR164##305 CH.sub.3 2-Cl, 6-F ##STR165##306 CH.sub.3 2,6-F.sub.2 ##STR166##307 CH.sub.3 2-Cl, 6-F ##STR167##308 CH.sub.3 2,6-F.sub.2 ##STR168##309 CH.sub.3 2-Cl, 6-F ##STR169##310 CH.sub.3 2,6-F.sub.2 ##STR170##311 CH.sub.3 2-Cl, 6-F ##STR171## 135.0-139.0312 CH.sub.3 2,6-F.sub.2 ##STR172##313 CH.sub.3 2-Cl, 6-F ##STR173## 109.0-112.0314 CH.sub.3 2,6-F.sub.2 ##STR174##315 CH.sub.3 2-Cl, 6-F ##STR175##316 CH.sub.3 2,6-F.sub.2 ##STR176##317 CH.sub.3 2-Cl, 6-F ##STR177## not measurable318 CH.sub.3 2,6-F.sub.2 ##STR178##319 CH.sub.3 2-Cl, 6-F ##STR179## 1.5698320 CH.sub.3 2-Cl, 6-F ##STR180## 123.5-126.0321 CH.sub.3 2-Cl, 6-F ##STR181## 1.5638322 CH.sub.3 2-Cl, 6-F ##STR182## 137.0-141.0323 CH.sub.3 2,6-F.sub.2 ##STR183##324 CH.sub.3 2-Cl, 6-F ##STR184##325 CH.sub.3 2,6-F.sub.2 ##STR185##326 CH.sub.3 2-Cl, 6-F ##STR186##327 CH.sub.3 2-Cl, 6-F ##STR187##328 CH.sub.3 2,6-F.sub.2 ##STR188##329 CH.sub.3 2-Cl, 6-F ##STR189##330 CH.sub.3 2-Cl, 6-F ##STR190## 153.0-155.0331 CH.sub.3 2,6-F.sub.2 ##STR191##332 CH.sub.3 2-Cl, 6-F ##STR192## 47.0-49.0333 CH.sub.3 2,6-F.sub.2 ##STR193##334 CH.sub.3 2-Cl, 6-F ##STR194## 1.5879335 CH.sub.3 2,6-F.sub.2 ##STR195##336 CH.sub.3 2-Cl, 6-F ##STR196##337 CH.sub.3 2,6-F.sub.2 ##STR197##338 CH.sub.3 2-Cl, 6-F ##STR198## 88.0-90.0339 CH.sub.3 2,6-F.sub.2 ##STR199##340 CH.sub.3 2-Cl, 6-F ##STR200##341 CH.sub.3 2-Cl ##STR201##342 CH.sub.3 2-Cl, 6-F ##STR202##343 CH.sub.3 2-Cl ##STR203##344 CH.sub.3 2-Cl, 6-F ##STR204##345 CH.sub.3 2-Cl, 6-F ##STR205## 109.5-112.0346 CH.sub.3 2-Cl, 6-F ##STR206##347 CH.sub.3 2,6-F.sub.2 ##STR207##348 CH.sub.3 2-Cl, 6-F ##STR208##349 CH.sub.3 2,6-F.sub.2 ##STR209##350 CH.sub.3 2-Cl, 6-F ##STR210##351 CH.sub.3 2-Cl ##STR211##352 CH.sub.3 2-Cl, 6-F ##STR212##353 CH.sub.3 2,6-F.sub.2 ##STR213##354 CH.sub.3 2-Cl, 6-F ##STR214##355 CH.sub.3 2,6-F.sub.2 ##STR215##356 CH.sub.3 2-Cl, 6-F ##STR216##357 CH.sub.3 2,6-F.sub.2 ##STR217##358 CH.sub.3 2-Cl, 6-F ##STR218##359 CH.sub.3 2,6-F.sub.2 ##STR219##360 CH.sub.3 2-Cl, 6-F ##STR220##361 CH.sub.3 2,6-F.sub.2 ##STR221##362 CH.sub.3 2-Cl, 6-F ##STR222##363 CH.sub.3 2,6-F.sub.2 ##STR223##364 CH.sub.3 2-Cl, 6-F ##STR224##365 CH.sub.3 2,6-F.sub.2 ##STR225##366 CH.sub.3 2-Cl, 6-F ##STR226##367 CH.sub.3 2,6-F.sub.2 ##STR227##368 CH.sub.3 2-Cl, 6-F ##STR228##369 CH.sub.3 2,6-F.sub.2 ##STR229##370 CH.sub.3 2-Cl, 6-F ##STR230##371 CH.sub.3 2,6-F.sub.2 ##STR231##372 CH.sub.3 2-Cl, 6-F ##STR232##373 CH.sub.3 2-Cl, 6-F ##STR233## 1.5391374 CH.sub.3 2-Cl, 6-F ##STR234## 108.0-111.0375 CH.sub.3 2,6-F.sub.2 ##STR235##376 CH.sub.3 2-Cl, 6-F ##STR236## 58.0-62.0377 CH.sub.3 2,6-F.sub.2 ##STR237## not measurable378 CH.sub.3 2-Cl, 6-F ##STR238## not measurable379 CH.sub.3 2,6-F.sub.2 ##STR239##380 CH.sub.3 2-Cl, 6-F ##STR240##381 CH.sub.3 2,6-F.sub.2 ##STR241##382 CH.sub.3 2-Cl, 6-F ##STR242##383 CH.sub.3 2,6-F.sub.2 ##STR243##384 CH.sub.3 2-Cl, 6-F ##STR244##385 CH.sub.3 2,6-F.sub.2 ##STR245##386 CH.sub.3 2-Cl, 6-F ##STR246##387 CH.sub.3 2,6-F.sub.2 ##STR247##388 CH.sub.3 2-Cl, 6-F ##STR248##389 CH.sub.3 2-Cl ##STR249## 104.0-108.0390 CH.sub.3 2-Cl, 6-F ##STR250## 139.0-141.0391 CH.sub.3 2-Cl, 6-F ##STR251## 110.0-112.0392 CH.sub.3 2,6-F.sub.2 ##STR252##393 CH.sub.3 2-Cl, 6-F ##STR253##394 CH.sub.3 2,6-F.sub.2 ##STR254##395 CH.sub.3 2-Cl, 6-F ##STR255## 127.0-132.0396 CH.sub.3 2,6-F.sub.2 ##STR256##397 CH.sub.3 2-Cl, 6-F ##STR257##398 CH.sub.3 2,6-F.sub.2 ##STR258##399 CH.sub.3 2-Cl, 6-F ##STR259##400 CH.sub.3 2,6-F.sub.2 ##STR260## 129.0-130.0401 CH.sub.3 2-Cl, 6-F ##STR261## not measurable402 CH.sub.3 2,6-F.sub.2 ##STR262##403 CH.sub.3 2-Cl ##STR263## 150.0-152.0404 CH.sub.3 2-Cl, 6-F ##STR264## 149.0-151.5405 CH.sub.3 2,6-F.sub.2 ##STR265##406 CH.sub.3 2-Cl, 6-F ##STR266## 140.0-144.0407 CH.sub.2 2,6-F.sub.2 ##STR267##408 CH.sub.3 2-Cl, 6-F ##STR268##409 CH.sub.3 2,6-F.sub.2 ##STR269## not measurable410 CH.sub.3 2-Cl, 6-F ##STR270## not measurable411 CH.sub.3 2,3,4,5,6-F.sub.5 ##STR271##412 CH.sub.3 2,6-F.sub.2 ##STR272## not measurable413 CH.sub.3 2-Cl, 6-F ##STR273## 116.0-117.0414 CH.sub.3 2,6-F.sub.2 ##STR274##415 CH.sub.3 2-Cl, 6-F ##STR275##416 CH.sub.3 2,6-F.sub.2 ##STR276##417 CH.sub.3 2-Cl, 6-F ##STR277##418 CH.sub.3 2,6-F.sub.2 ##STR278##419 CH.sub.3 2-Cl, 6-F ##STR279## 120.0-123.0420 CH.sub.3 2-Cl ##STR280##421 CH.sub.3 2-Cl, 6-F ##STR281##422 CH.sub.3 2-Cl ##STR282##423 CH.sub.3 2-Cl, 6-F ##STR283##424 CH.sub.3 2-Cl ##STR284##425 CH.sub.3 2-Cl, 6-F ##STR285##426 CH.sub.3 2-Cl, 6-F ##STR286##427 CH.sub.3 2-Cl, 6-F ##STR287##428 CH.sub.3 2-Cl, 6-F ##STR288##429 CH.sub.3 2-Cl, 6-F ##STR289##430 CH.sub.3 2,6-F.sub.2 ##STR290##431 CH.sub.3 2-Cl, 6-F ##STR291##432 CH.sub.3 2,6-F.sub.2 ##STR292##433 CH.sub.3 2-Cl, 6-F ##STR293##434 CH.sub.3 2,6-F.sub.2 ##STR294##435 CH.sub.3 2-Cl, 6-F ##STR295##436 CH.sub.3 2,6-F.sub.2 ##STR296##437 CH.sub.3 2-Cl, 6-F ##STR297##438 CH.sub.3 2,6-F.sub.2 ##STR298##439 CH.sub.3 2-Cl, 6-F ##STR299##440 CH.sub.3 2,6-F.sub.2 ##STR300##441 CH.sub.3 2-Cl, 6-F ##STR301##442 CH.sub.3 2,6-F.sub.2 ##STR302##443 CH.sub.3 2-Cl, 6-F ##STR303##444 CH.sub.3 2,6-F.sub.2 ##STR304##445 CH.sub.3 2-Cl, 6-F ##STR305##446 CH.sub.3 2,6-F.sub.2 ##STR306##447 CH.sub.3 2-Cl, 6-F ##STR307##448 CH.sub.3 2,6-F.sub.2 ##STR308##449 CH.sub.3 2-Cl, 6-F ##STR309##450 CH.sub.3 2,6-F.sub.2 ##STR310##451 CH.sub.3 2-Cl, 6-F ##STR311## 123.0-127.0452 CH.sub.3 2,6-F.sub.2 ##STR312##453 CH.sub.3 2-Cl, 6-F ##STR313## 1.5020454 CH.sub.3 2,6-F.sub.2 ##STR314##455 CH.sub.3 2-Cl, 6-F ##STR315##456 CH.sub.3 2-Cl, 6-F ##STR316## 78.0-83.0457 CH.sub.3 2-Cl, 6-F ##STR317## 117.0-122.0458 CH.sub.3 2-Cl, 6-F ##STR318##459 CH.sub.3 2,6-F.sub.2 ##STR319##460 CH.sub.3 2-Cl, 6-F ##STR320##461 CH.sub.3 2,6-F.sub.2 ##STR321##462 CH.sub.3 2-Cl, 6-F ##STR322##463 CH.sub.3 2,6-F.sub.2 ##STR323##464 CH.sub.3 2-Cl, 6-F ##STR324##465 CH.sub.3 2,6-F.sub.2 ##STR325##466 CH.sub.3 2-Cl, 6-F ##STR326##467 CH.sub.3 2,6-F.sub.2 ##STR327##468 CH.sub.3 2-Cl, 6-F ##STR328##469 CH.sub.3 2,6-F.sub.2 ##STR329##470 CH.sub.3 2-Cl, 6-F ##STR330##471 CH.sub.3 2,6-F.sub.2 ##STR331##472 CH.sub.3 2-Cl, 6-F ##STR332##473 CH.sub.3 2,6-F.sub.2 ##STR333##474 CH.sub.3 2-Cl, 6-F ##STR334##475 CH.sub.3 2,6-F.sub.2 ##STR335##476 CH.sub.3 2-Cl, 6-F ##STR336##477 CH.sub.3 2,6-F.sub.2 ##STR337##478 CH.sub.3 2-Cl, 6-F ##STR338##479 CH.sub.3 2-Cl ##STR339##480 CH.sub.3 2-Cl, 6-F ##STR340## 116.0-119.0481 CH.sub.3 2,6-F.sub.2 ##STR341##482 CH.sub.3 2-Cl, 6-F ##STR342##483 CH.sub.3 2,6-F.sub.2 ##STR343##484 CH.sub.3 2-Cl, 6-F ##STR344##485 CH.sub.3 2,6-F.sub.2 ##STR345##486 CH.sub.3 2-Cl, 6-F ##STR346##487 CH.sub.3 2,6-F.sub.2 ##STR347##488 CH.sub.3 2-Cl, 6-F ##STR348##489 CH.sub.3 2-Cl, 6-F ##STR349## 129.0-131.0490 CH.sub.3 2,6-F.sub.2 ##STR350##491 CH.sub.3 2-Cl, 6-F ##STR351##492 CH.sub.3 2,6-F.sub.2 ##STR352##493 CH.sub.3 2-Cl, 6-F ##STR353##494 CH.sub.3 2-Cl ##STR354##495 CH.sub.3 2-Cl, 6-F ##STR355##496 CH.sub.3 2-Cl, 6-F ##STR356## 97.0-102.0497 CH.sub.3 2-Cl, 6-F ##STR357## 74.0-79.0498 CH.sub.3 2-Cl, 6-F ##STR358## 129.0-134.0499 CH.sub.3 2-Cl ##STR359##500 CH.sub.3 2-Cl, 6-F ##STR360##501 CH.sub.3 2-Cl ##STR361##502 CH.sub.3 2-Cl, 6-F ##STR362##503 CH.sub.3 2-Cl, 6-F ##STR363##504 CH.sub.3 2-Cl, 6-F ##STR364##505 CH.sub.3 2,6-F.sub.2 ##STR365##506 CH.sub.3 2-Cl ##STR366##507 CH.sub.3 2-Cl ##STR367##508 CH.sub.3 2-Cl, 6-F ##STR368## 142.0-144.0509 CH.sub.3 2-Cl ##STR369## not measurable510 CH.sub.3 2-Cl, 6-F ##STR370## not measurable511 CH.sub.3 2-Cl, 6-F ##STR371## 1.6087512 CH.sub.3 2-Cl ##STR372##513 CH.sub.3 2,6-F.sub.2 ##STR373## 105.0-109.0514 CH.sub.3 2-Cl, 6-F ##STR374## 155.0-157.0515 CH.sub.3 2-Cl ##STR375##516 CH.sub.3 2-Cl, 6-F ##STR376## not measurable517 CH.sub.3 2,6-F.sub.2 ##STR377## not measurable518 CH.sub.3 2,6-F.sub.2 ##STR378##519 CH.sub.3 2-Cl, 6-F ##STR379##520 CH.sub.3 2,6-F.sub.2 ##STR380##521 CH.sub.3 2-Cl, 6-F ##STR381##522 CH.sub.3 2,6-F.sub.2 ##STR382## 140.0-143.0523 CH.sub.3 2-Cl, 6-F ##STR383## not measurable524 CH.sub.3 2-Cl, 6-F ##STR384## not measurable525 CH.sub.3 2,6-F.sub.2 ##STR385##526 CH.sub.3 2-Cl, 6-F ##STR386## not measurable527 CH.sub.3 2,6-F.sub.2 ##STR387##528 CH.sub.3 2-Cl, 6-F ##STR388##529 CH.sub.3 2,6-F.sub.2 ##STR389##530 CH.sub.3 2-Cl, 6-F ##STR390##531 CH.sub.3 2-Cl, 6-F ##STR391## 102.0-104.0532 CH.sub.3 2,6-F.sub.2 ##STR392##533 CH.sub.3 2-Cl, 6-F ##STR393##534 CH.sub.3 2,6-F.sub.2 ##STR394##535 CH.sub.3 2-Cl, 6-F ##STR395##__________________________________________________________________________
The compounds according to the invention can be produced according to the following methods.
Production Method 1-1 ##STR396## (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, Y and m are the same as mentioned above).
That is, the compound according to the invention represented by the general formula �I! can be obtained by reacting an N-acylimidate derivative or N-acylthioimidate derivative represented by a general formula �II! with a hydrazine derivative represented by a general formula �III! in an inert solvent.
As the solvent, any solvents not obstructing the reaction can be used, which include, for example, alcohols such as methanol, ethanol and so on; ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme and so on; aromatic hydrocarbons such as benzene, toluene, chlorobenzene, dichlorobenzene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on; nitriles such as acetonitrile and so on; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and so on; water and a mixed solvent comprised of a combination of solvents selected from the above. Furthermore, the amount of the starting material used is usually 1.0-5.0 moles of the compound shown by the general formula �III! per 1 mole of the compound shown by the general formula �II!.
The reaction temperature is within a range of from 0.degree. C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 1 hour-72 hours. A concrete example of this reaction is described, for example, in Synthesis, page 483 (1983).
The starting compound shown by the general formula �II! can be produced by the following method.
Production Method 1-2 ##STR397## (wherein Z is a halogen atom, and L, W, X, n, Y and m are the same as mentioned above).
That is, the compound shown by the general formula �II! can be obtained by reacting a compound of a general formula �IV! with a compound of a general formula �V! in the presence of a base in an inert solvent. The compound of the general formula �IV! may be an acid addition salt such as a salt with boron tetrafluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide or the like.
As the base, use may be made of inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like; and organic bases such as diethylamine, triethylamine, pyridine, 4-(N,N-dimethylamino) pyridine and the like.
As the solvent, use may be made of ketones such as acetone, methyl ethyl ketone and so on; ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme and so on; aromatic hydrocarbons such as benzene, toluene, chlorobenzene, dichlorobenzene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on; nitriles such as acetonitrile and so on; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and so on; and a mixed solvent comprised of a combination of solvents selected from the above.
The amount of the reactant used is usually 0.8-1.3 moles of the compound shown by the general formula �V! per 1 mole of the compound shown by the general formula �IV!. The amount of the base used is 1.0-2.0 moles per 1 mole of the compound shown by the general formula �IV!. The reaction temperature is within a range of from 0.degree. C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 1 hour-24 hours.
Production Method 2 ##STR398## (wherein R.sup.1, X, n, Y and m are the same as mentioned above, and R.sup.3 is a phenyl group, which may be substituted with an alkyl group having a carbon number of 1-4, or an alkyl group having a carbon number of 1-4).
That is, the compound of the general formula �I! according to the invention can be obtained by reacting a benzohydrazonoyl chloride derivative represented by a general formula �VI! with a benzonitrile derivative represented by a general formula �VII! in the presence of a Lewis acid in an inert solvent.
As the solvent, any solvents not obstructing the reaction can be used, which include, for example, ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme, 1,2-dimethoxyethane and so on; aromatic hydrocarbons such as benzene, toluene, chlorobenzene, dichlorobenzene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on; aprotic polar solvents such as nitrobenzene, dimethylformamide, dimethylacetamide, dimethylsulfoxide and so on; a mixed solvent comprised of a combination of solvents selected from the above.
As the Lewis acid, use may be made of aluminum bromide, aluminum chloride, iron (III) chloride, boron trifluoride, titanium tetrachloride and so on. Furthermore, the amounts of the starting material and the like used are usually 1.0-2.0 moles of the compound shown by the general formula �VII! and 1.0-2.0 moles of the Lewis acid per 1 mole of the compound shown by the general formula �VI!. The reaction temperature is within a range of from 0.degree. C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object Tan usually be attained for 30 minutes-5 hours. A concrete example of this reaction is described, for example, in Bulltein of the Chemical Society of Japan (Bull. Chem. Soc. Jpn), vol. 56, page 545 (1983).
Production Method 3-1 ##STR399## (wherein R.sup.1, R.sup.3, X, n, Y, m and Z are the same as mentioned above).
That is, the compound of the general formula �I! according to the invention can be obtained by reacting a benzamidrazone derivative of a general formula �VIII! with a benzoylhalide derivative of a general formula �V! in the absence of a solvent or in an inert solvent.
As the solvent, any solvents not obstructing the reaction can be used, which include, for example, ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme and so on; aromatic hydrocarbons such as benzene, toluene, chlorobenzene, dichlorobenzene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, 1-methyl-2-pyrolidinone and so on; and a mixed solvent comprised of a combination of solvents selected from the above.
The amount of the starting material used is usually 1.0-2.0 moles of the compound shown by the general formula �V! per 1 mole of the compound shown by the general formula �VIII!. The reaction temperature is within a range of from 0.degree. C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 30 minutes-5 hours. A concrete example of this reaction is described, for example, in Bulltein of the Chemical Society of Japan (Bull. Chem. Soc. Jpn), vol. 56, page 545 (1983).
Moreover, the compound of the general formula �VIII! as a starting material can be produced by the following method.
Production Method 3-2 ##STR400## (wherein R.sup.1, R.sup.3, X and n are the same as mentioned above).
The compound of the general formula �VIII! can be obtained by reacting a compound of a general formula �VI! with an ammonia gas in an inert solvent.
As the solvent, any solvents not obstructing the reaction can be used, which include, for example, ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme and so on; aromatic hydrocarbons such as benzene, toluene, chlorobenzene, dichlorobenzene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and so on; and a mixed solvent comprised of a combination of solvents selected from the above.
The amount of the starting material used is usually 5.0-10.0 moles of ammonia per 1 mole of the compound shown by the general formula �VI!. The reaction temperature is within a range of from 0.degree. C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 1 hour-24 hours. A concrete example of this reaction is described, for example, in Bulltein of the Chemical Society of Japan (Bull. Chem. Soc. Jpn), vol. 56, page 545 (1983).
Production Method 4-1 ##STR401## (wherein X, R.sup.1, Y', n and m' are the same as mentioned above).
A compound of a general formula �X! can be obtained by reacting a compound of a general formula �IX! in the presence of a Lewis acid in an inert solvent.
As the Lewis acid, use may be made of aluminum bromide, aluminum chloride, iron (III) chloride, boron trifluoride, titanium tetrachloride and so on.
As the solvent, any solvents not obstructing the reaction can be used, which include, for example, ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme and so on; aromatic hydrocarbons such as benzene, toluene, chlorobenzene, dichlorobenzene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on; aprotic polar solvents such as nitrobenzene, dimethylformamide, dimethylacetamide, dimethylsulfoxide and so on; and a mixed solvent comprised of a combination of solvents selected from the above.
The amount of the reactant used is usually 1.0-5.0 moles of the Lewis acid per 1 mole of the compound shown by the general formula �IX!. The reaction temperature is within a range of from -20.degree. C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 1 hour-24 hours.
Production Method 4-2 ##STR402## �wherein B is a halogen atom, R.sup.4 --SO.sub.2 -group or R.sup.4 --SO.sub.3 -group (R.sup.4 is an alkyl group having a carbon number of 1-4 or a phenyl group which may be substituted), k is 0 or 1, and X, Y', R.sup.1, R.sup.2, Q, j, m' and n are the same as mentioned above).
The compound of a general formula �XII! according to the invention can be obtained by reacting a compound of a general formula �X! with a compound of a general formula �XI! in the presence of a base in an inert solvent.
As the base, use may be made of inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like; metal hydrides such as sodium hydride, poptassium hydride and the like; and organic bases such as triethylamine, pyridine and the like.
As the solvent, use may be made of ketones such as acetone, methyl ethyl ketone and the like; ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme and so on; aromatic hydrocarbons such as benzene, toluene, chlorobenzene, dichlorobenzene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on; nitriles such as acetonitrile and the like; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and so on; and a mixed solvent comprised of a combination of solvents selected from the above.
The amount of the reactant used is usually 1.0-2.0 moles of the compound shown by the general formula �XI! per 1 mole of the compound shown by the general formula �X!. The amount of the base used is 1.0-2.0 moles per 1 mole of the compound shown by the general formula �X!. The reaction temperature is within a range of from -20.degree. C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 1-24 hours.
Production Method 5-1 ##STR403## (wherein X, R.sup.1, Z, Y', n and m' are the same as mentioned above).
A compound of a general formula �XIV! can be obtained from a triazole derivative of a general formula �XIII! with a halogenating agent. This compound can be reacted with an acetoxylating agent to obtain a compound of a general formula �XV!. Then, the compound of the general formula �XV! can be reacted with an acid or alkali to obtain a compound of a general formula �XVI!.
As the halogenating agent used in the step A, use may be made of, for example, N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide and so on.
As the solvent used, mention may be made of aromatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on. Furthermore, it is required to use a catalytic amount of benzoyl peroxide, azobisisobutyronitrile or the like as a radical initiator in this reaction.
The amount of the halogenating agent used is usually 0.8-1.5 moles per 1 mole of the compound shown by the general formula �XIII!. The reaction temperature is within a range of from 0.degree. C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 30 minutes-12 hours.
As the acetoxylating agent used in the step B, use may be made of lithium acetate, sodium acetate, potassium acetate, calcium acetate and so on.
As the solvent, use may be made of ketones such as acetone, methyl ethyl ketone and so on; ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme and so on; aromatic hydrocarbons such as benzene, toluene, chlorobenzene, dichlorobenzene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on; nitriles such as acetonitrile and so on; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and so on; and a mixed solvent comprised of a combination of solvents selected from the above.
The amount of the acetoxylating agent used is usually 1.0-4.0 moles per 1 mole of the compound shown by the general formula �XIV!. The reaction temperature is within a range of from 0.degree. C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 1-24 hours.
As the acid used in the step C, use may be made of mineral acids such as hydrochloric acid, sulfuric acid and so on; and Lewis acids such as aluminum bromide, aluminum chloride and so on. In this case, as the solvent, use may be made of carboxylic acids such as acetic acid, formic acid and so on; ketones such as acetone, methyl ethyl ketone and so on; ethers such as diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane and so on; aromatic hydrocarbons such as benzene, toluene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, carbon tetrachloride and so on; water and a mixed solvent comprised of a combination of solvents selected from the above.
The amount of the acid used is usually a catalytic amount--4.0 moles per 1 mole of the compound shown by the general formula �XV!. The reaction temperature is within a range of from 0.degree. C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 30 minutes-24 hours.
As the alkali used in the step C, use may be made of aqueous solutions of sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and so on. In this case, as the solvent, use may be made of alcohols such as methanol, ethanol, ethylene glycol and so on; ketones such as acetone, methyl ethyl ketone and so on; ethers such as tetrahydrofuran, dioxane, 1,2-dimethoxyethane and so on; water and a mixed solvent comprised of a combination of solvents selected from the above.
The amount of the alkali used is usually 0.5-4.0 moles per 1 mole of the compound shown by the general formula �XV!. The reaction temperature is within a range of from 0.degree. C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 30 minutes-24 hours.
Production Method 5-2 ##STR404## (wherein X, Y', B, Q, R.sup.1, R.sup.2, j, k, m' and n are the same as mentioned above).
The compound shown by the general formula �XVII! according to the invention can be obtained by reacting a compound of a general formula �XVI! with a compound of a general formula �XI! in the presence of a base in an inert solvent.
As the base, use may be made of inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like; metal hydrides such as sodium hydride, potassium hydride and the like; and organic bases such as triethylamine, pyridine and the like.
As the solvent, use may be made of ketones such as acetone, methyl ethyl ketone and so on; ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme and so on; aromatic hydrocarbons such as benzene, toluene, chlorobenzene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on; nitriles such as acetonitrile and so on; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and so on; and a mixed solvent comprised of a combination of solvents selected from the above.
The amount of the reactant used is usually 1.0-2.0 moles of the compound shown by the general formula �XI! per 1 mole of the compound shown by the general formula �XVI!. The amount of the base used is 1.0-2.0 moles per 1 mole of the compound shown by the general formula �XVI!. The reaction temperature is within a range of from -20.degree. C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 1-24 hours.
Production Method 5-3 ##STR405## (wherein X, Y', Q, R.sup.1, R.sup.2, Z, j, k, m' and n are the same as mentioned above).
The compound shown by the general formula �XVII! according to the invention can be obtained by reacting a compound of the general formula �XIV! with a compound of the general formula �XVIII! in the presence of a base in an inert solvent.
As the base, use may be made of inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like; metal hydrides such as sodium hydride, potassium hydride and the like; and organic bases such as triethylamine, pyridine and the like.
As the solvent, use may be made of ketones such as acetone, methyl ethyl ketone and so on; ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme and so on; aromatic hydrocarbons such as benzene, toluene, chlorobenzene and so on; aliphatic hydrocarbons such as pentane, hexane, petroleum ether and so on; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and so on; nitriles such as acetonitrile and so on; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and so on; and a mixed solvent comprised of a combination of solvents selected from the above.
The amount of the reactant used is usually 1.0-2.0 moles of the compound shown by the general formula �XVIII! per 1 mole of the compound shown by the general formula �XIV!. The amount of the base used is 1.0-2.0 moles per 1 mole of the compound shown by the general formula �XIV!. The reaction temperature is within a range of from -20.degree. C. to a boiling point of the solvent. The reaction time is different in accordance with the compound, but the object can usually be attained for 1-24 hours.
�BEST MODE FOR CARRYING OUT THE INVENTION!

The preparation method of the compounds according to the invention, formulation method and applications will concretely be described with reference to the following examples.
EXAMPLE 1
Preparation of 3-(2-chlorophenyl)-5-(2-chloro-3-nitrophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 1)
A mixture of N-methyl-N-(benzenesulfonyl)-2-chlorobenzohydrazonoyl chloride (1.72 g), 2-chloro-3-nitrobenzonitrile (1.00 g), anhydrous aluminum chloride (0.70 g) and o-dichlorobenzene (20 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.12 g of desired compound (melting point: 124.0.degree.-125.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 3.83 (3H, s) 7.16-8.10 (7H, m)______________________________________
EXAMPLE 2
Preparation of 3-(2-chloro-6-fluorophenyl)-5-(2-chloro-3-nitrophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 2)
A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.90 g), 2-chloro-3-nitrobenzonitrile (1.19 g), anhydrous aluminum chloride (0.70 g) and o-dichlorobenzene (20 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.19 g of desired compound (melting point: 112.0.degree.-114.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 3.90 (3H, s) 6.90-8.10 (6H, m)______________________________________
EXAMPLE 3
Preparation of 3-(2-chloro-6-fluorophenyl)-5-(2-chloro-4-nitrophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 4)
A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.90 g), 2-chloro-4-nitrobenzonitrile (1.80 g), anhydrous iron (III) chloride (1.60 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 1 hour. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 2.20 g of desired compound (melting point: 144.0.degree.-148.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 3.88 (3H, s) 6.90-8.46 (6H, m)______________________________________
EXAMPLE 4
Preparation of 5-(2-chloro-4-ethylphenyl)-3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 15)
Ethyl 2-chlorobenzimidate (2.75 g) and triethylamine (1.60 g) are dissolved in toluene (30 ml) and 2-chloro-4-ethylbenzoyl chloride (2.64 g) is added dropwise thereto within a range of 5.degree. C.-15.degree. C. with stirring, which is stirred at room temperature for 1 hour and further heated under reflux for 3 hours. After cooling to room temperature, the reaction mixture is added with toluene (200 ml) and washed with dilute hydrochloric acid and saline, and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (1.00 g) and stirred at room temperature for 16 hours. On completion of the reaction, the reaction mixture is washed with dilute hydrochloric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 2.10 g of desired compound (melting point: 75.5.degree.-77.5.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 1.27 (3H, t) 2.70 (2H, q) 3.83 (3H, s) 7.10-7.60 (6H, m) 7.90-8.10 (1H, m)______________________________________
EXAMPLE 5
Preparation of 5-(2-chloro-4-ethylphenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 16)
Ethyl 2-chloro-6-fluorobenzimidate (3.02 g) and triethylamine (1.60 g) are dissolved in toluene (30 ml) and 2-chloro-4-ethylbenzoyl chloride (2.64 g) is added dropwise thereto within a range of 5.degree. C.-15.degree. C. with stirring, which is stirred at room temperature for 1 hour and further heated under reflux for 3 hours. After cooling to room temperature, the reaction solution is added with toluene (200 ml) and washed with dilute hydrochloric acid and saline, and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (2.00 g) and heated under reflux for 2 hours. On completion of the reaction, the reaction mixture is washed with dilute hydrochloric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 2.63 g of desired compound (refractive index: 1.5930).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 1.26 (3H, t) 2.69 (2H, q) 3.83 (3H, s) 6.90-7.50 (6H, m)______________________________________
EXAMPLE 6
Preparation of 3-(2-chlorophenyl)-5-(2-chloro-4-propylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 18)
Ethyl 2-chlorobenzimidate (2.75 g) and triethylamine (1.80 g) are dissolved in toluene (30 ml) and 2-chloro-4-propylbenzoyl chloride (3.30 g) is added dropwise thereto within a range of 5.degree. C.-15.degree. C. with stirring, which is stirred at room temperature for 1 hour and further heated under reflux for 1 hour. After cooling to room temperature, the reaction solution is added with toluene (200 ml) and washed with dilute hydrochloric acid and saline, and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (0.80 g) and stirred at room temperature for 18 hours. On completion of the reaction, the reaction mixture is washed with dilute hydrochloric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 2.78 g of desired compound (melting point: 70.0.degree.-72.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 0.95 (3H, t) 1.66 (2H, m) 2.63 (2H, t) 3.83 (3H, s) 6.90-7.10 (1H, m) 7.10-7.50 (6H, m)______________________________________
EXAMPLE 7
Preparation of 3-(2-chloro-6-fluorophenyl)-5-(2-chloro-4-propylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 19)
Ethyl 2-chloro-6-fluorobenzimidate (3.02 g) and triethylamine (1.80 g) are dissolved in toluene (30 ml) and 2-chloro-4-propylbenzoyl chloride (3.30 g) is added dropwise thereto within a range of 5.degree. C.-15.degree. C. with stirring, which is stirred at room temperature for 1 hour and further heated under reflux for 1 hour. After cooling to room temperature, the reaction solution is added with toluene (200 ml) and washed with dilute hydrochloric acid and saline, and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (1.80 g) and heated under reflux for 4 hours. On completion of the reaction, the reaction mixture is washed with dilute hydrochloric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 0.41 g of desired compound (refractive index: 1.5868).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 0.95 (3H, t) 1.65 (2H, m) 2.62 (2H, t) 3.83 (3H, s) 6.80-7.50 (6H, m)______________________________________
EXAMPLE 8
Preparation of 5-(4-butyl-2-chlorophenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 29)
N-methyl-N-(phenylsulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.10 g), 4-butyl-2-chlorobenzonitrile (0.60 g) and anhydrous aluminum chloride (0.50 g) are added to o-dichlorobenzene (10 ml) and stirred at 120.degree. C. for 1 hour. On completion of the reaction, chloroform (100 ml) is added and washed with dilute hydrochloric acid. After washing with water, the organic layer is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 0.70 g of compound (refractive index: 1.5667).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 0.75-1.12 (3H, m) 1.15-2.00 (4H, m) 2.65 (2H, t) 3.85 (3H, s) 6.83-7.60 (6H, m)______________________________________
EXAMPLE 9
Preparation of 5-(4-t-butyl-2-ethoxyphenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 35)
A mixture of N-methyl-N-(benzenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.60 g), 4-t-butyl-2-ethoxybenzonitrile (1.00 g), anhydrous aluminum chloride (0.60 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.20 g of desired compound (melting point: 108.0.degree.-111.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 1.15 (9H, s) 1.36 (3H, t) 3.87 (3H, s) 4.10 (2H, q) 6.83-7.58 (6H, m)______________________________________
EXAMPLE 10
Preparation of 3-(2-chlorophenyl)-5-(2-fluoro-5-hexylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 42)
A mixture of N-methyl-N-(benzenesulfonyl)-2-chlorobenzohydrazonoyl chloride (2.06 g), 2-fluoro-5-hexylbenzonitrile (1.23 g), anhydrous aluminum chloride (0.88 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (200 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.60 g of desired compound (refractive index: 1.5779).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 0.87 (3H, t) 1.00-1.90 (8H, m) 2.62 (2H, t) 3.87 (3H, d) 6.90-8.00 (7H, m)______________________________________
EXAMPLE 11
Preparation of 3-(2-chloro-6-fluorophenyl)-5-(2-fluoro-5-hexylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 43)
A mixture of N-methyl-N-(benzenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (2.17 g), 2-fluoro-5-hexylbenzonitrile (1.23 4), anhydrous aluminum chloride (0.88 g) and o-dichlorobenzene (10 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (200 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.11 g of desired compound (refractive index: 1.5608).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 0.87 (3H, t) 1.00-1.80 (8H, m) 2.61 (2H, t) 3.89 (3H, d) 6.80-7.40 (6H, m)______________________________________
EXAMPLE 12
Preparation of 3-(2,6-difluorophenyl)-5-(2-fluoro-5-undecylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 46)
A mixture of N-methyl-N-(benzenesulfonyl)-2,6-difluorobenzohydrazonoyl chloride (1.28 g), 2-fluoro-5-undecylbenzonitrile (1.09 g), anhydrous aluminum chloride (0.55 g) and o-dichlorobenzene (10 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (200 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.08 g of desired compound (melting point: 70.0.degree.-73.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 0.88 (3H, t) 1.10-1.80 (18H, m) 2.63 (2H, t) 3.93 (3H, d) 6.90-7.60 (6H, m)______________________________________
EXAMPLE 13
Preparation of 3-(2-chlorophenyl)-5-(2-fluoro-5-undecylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 47)
A mixture of N-methyl-N-(benzenesulfonyl)-2-chlorobenzohydrazonoyl chloride (1.27 g), 2-fluoro-5-undecylbenzonitrile (1.09 g), anhydrous aluminum chloride (0.55 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (200 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.85 g of desired compound (melting point: 35.0.degree.-37.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 0.88 (3H, t) 1.10-1.70 (18H, m) 2.66 (2H, t) 3.93 (3H, d) 6.90-7.60 (6H, m) 7.90-8.00 (1H, m)______________________________________
EXAMPLE 14
Preparation of 3-(2-chloro-6-fluorophenyl)-5-(2-fluoro-5-undecylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 48)
A mixture of N-methyl-N-(benzenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.34 g), 2-fluoro-5-undecylbenzonitrile (1.09 g), anhydrous aluminum chloride (0.55 g) and o-dichlorobenzene (10 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (200 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.04 g of desired compound (refractive index: 1.5419).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 0.87 (3H, t) 1.10-1.80 (18H, m) 2.63 (2H, t) 3.94 (3H, d) 6.90-7.60 (6H, m)______________________________________
EXAMPLE 15
Preparation of 3-(2-chloro-6-fluorophenyl)-5-(2-chloro-4-dodecylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 51)
A mixture of N-methyl-N-(benzenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.50 g), 2-chloro-4-dodecylbenzonitrile (1.20 g), anhydrous aluminum chloride (0.60 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.80 g of desired compound (refractive index: 1.5490).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 0.50-2.03 (23H, m) 2.65 (2H, t) 3.83 (3H, s) 6.82-7.52 (6H, m)______________________________________
EXAMPLE 16
Preparation of 5-(4-butoxy-2-chlorophenyl)-3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 64)
Ethyl 2-chlorobenzimidate (2.40 g) and triethylamine (1.20 g) are dissolved in toluene (100 ml) and 4-butoxy-2-chlorobenzoyl chloride (2.60 g) is added drop-wise thereto below 10.degree. C. with stirring. It is stirred at room temperature for 2 hours and further heated under reflux for 2 hours. On completion of the reaction, the reaction solution is washed with saline, further washed with water and the organic layer is dried over anhydrous magnesium sulfate. The toluene layer is added with monomethyl hydrazine (1.50 g) and reacted at room temperature for 24 hours. On completion of the reaction, it is washed with dilute hydrochloric acid, further washed with water and the organic layer is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.00 g of desired compound (melting point: 60.0.degree.-62.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 0.80-1.16 (3H, m) 1.20-2.10 (4H, m) 3.84 (3H, s) 4.02 (2H, t) 6.76-7.95 (6H, m) 7.83-8.12 (1H, m)______________________________________
EXAMPLE 17
Preparation of 3-(2-chloro-6-fluorophenyl)-5-(4-chloro-3-pentyloxyphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 68)
A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.10 g), 4-chloro-3-pentyloxybenzonitrile (0.70 g), anhydrous iron (III) chloride (0.60 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.50 g of desired compound.
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 0.72-2.16 (9H, m) 4.06 (3H, s) 4.10 (2H, t) 6.85-7.60 (6H, m)______________________________________
EXAMPLE 18
Preparation of 5-(4-chloro-3-octyloxyphenyl)-3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 77)
A mixture of N-methyl-N-(benzenesulfonyl)-2-chlorobenzohydrazonoyl chloride (1.50 g), 4-chloro-3-octyloxybenzonitrile (1.30 g), anhydrous iron (III) chloride (0.80 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.80 g of desired compound.
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 0.65-2.13 (15H, m) 4.07 (3H, s) 4.13 (2H, t) 6.92-7.66 (7H, m)______________________________________
EXAMPLE 19
Preparation of 3-(2-chlorophenyl)-5-(2-chloro-4-methoxyethoxyphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 87)
Ethyl 2-chlorobenzimidate (4.00 g) and triethylamine (2.60 g) are dissolved in toluene (20 ml) and 2-chloro-4-methoxyethoxybenzoyl chloride (4.20 g) is added dropwise thereto within a range of 5.degree. C.-10.degree. C. with stirring. It is stirred at room temperature for 1 hour and further heated under reflux for 30 minutes. After cooling to room temperature, the reaction solution is added with toluene (20 ml) and washed with dilute sulfuric acid and saline and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (2.00 g) and stirred at room temperature for 4 hours. On completion of the reaction, the reaction mixture is washed with dilute sulfuric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.70 g of desired compound (refractive index: 1.5946).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 3.45 (3H, s) 3.60-3.97 (4H, m) 4.00 (3H, s) 6.83-8.13 (7H, m)______________________________________
EXAMPLE 20
Preparation of 3-(2-chloro-6-fluorophenyl)-5-(2-chloro-5-perfluorobutylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 116)
A mixture of N-methyl-N-(benzenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.70 g), 2-chloro-5-perfluorobutylbenzonitrile (1.75 g), anhydrous iron (III) chloride (0.73 g) and o-dichlorobenzene (10 ml) is stirred at an oil bath temperature of 130.degree. C. for 2 hours. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.68 g of desired compound (refractive index: 1.5110).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 3.87 (3H, s) 6.80-7.97 (6H, m)______________________________________
EXAMPLE 21
Preparation of 3-(2-chlorophenyl)-5-(2-chloro-5-perfluorohexylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 119)
A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chlorobenzohydrazonoyl chloride (0.51 g), 2-chloro-5-perfluorohexylbenzonitrile (0.70 g), anhydrous aluminum chloride (0.20 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 1 hour. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.15 g of desired compound (melting point: 70.0.degree.-76.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 3.85 (3H, s) 7.13-8.06 (7H, m)______________________________________
EXAMPLE 22
Preparation of 3-(2-chloro-6-fluorophenyl)-5-(2-chloro-5-perfluorohexylphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 120)
A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (0.73 g), 2-chloro-5-perfluorohexylbenzonitrile (1.00 g), anhydrous iron (III) chloride (0.36 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 1 hour. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.15 g of desired compound (melting point: 78.0.degree.-82.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 3.86 (3H, s) 6.86-7.86 (6H, m)______________________________________
EXAMPLE 23
Preparation of 3-(2-chlorophenyl)-5-(2-chloro-4-allyloxyphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 138).
Ethyl 2-chlorobenzimidate (2.60 g) and triethylamine (1.10 g) are dissolved in toluene (20 ml) and 2-chloro-4-allyloxybenzoyl chloride (2.20 g) is added dropwise thereto within a range of 5.degree. C.-10.degree. C. with stirring. It is stirred at room temperature for 1 hour and further heated under reflux for 30 minutes. After cooling to room temperature, the reaction solution is added with toluene (20 ml) and washed with dilute sulfuric acid and saline and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (2.00 g) and stirred at room temperature for 5 hours. On completion of the reaction, the reaction mixture is washed with dilute sulfuric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.60 g of desired compound (refractive index: 1.6083).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 3.85 (3H, s) 4.50-4.80 (2H, m) 5.25-5.62 (2H, m) 5.77-6.40 (1H, m) 6.82-8.16 (7H, m)______________________________________
EXAMPLE 24
Preparation of 3-(2-chlorophenyl)-5-(2-chloro-4-propargyroxyphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 145)
Ethyl 2-chlorobenzimidate (3.00 g) and triethylamine (1.50 g) are dissolved in toluene (20 ml) and 2-chloro-4-propargyroxybenzoyl chloride (2.30 g) is added dropwise thereto within a range of 5.degree. C.-10.degree. C. with stirring. It is stirred at room temperature for 1 hour and further heated under reflux for 30 minutes. After cooling to room temperature, the reaction solution is added with toluene (20 ml) and washed with dilute sulfuric acid and saline and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (2.00 g) and stirred at room temperature for 4 hours. On completion of the reaction, the reaction mixture is washed with dilute sulfuric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.60 g of desired compound (melting point: 103.0-105.0).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 2.47-2.71 (1H, m) 3.83 (3H, s) 4.75 (2H, d) 6.83-8.20 (7H, m)______________________________________
EXAMPLE 25
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�4-fluoro-3-(4-trifluoromethoxyphenyl)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 157)
A mixture of N-methyl-N-(methanesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.50 g), 4-fluoro-3-(4-trifluoromethoxyphenyl)benzonitrile (1.43 g), anhydrous iron (III) chloride (0.90 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, the reaction mixture is dissolved in ethylacetate (200 ml), washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.90 g of desired compound (melting point: 117.0.degree.-119.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.10 (3H, s) 6.80-7.90 (10H, m)______________________________________
EXAMPLE 26
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�2-chloro-4-(4-trifluoromethoxyphenyl)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 158)
A mixture of N-methyl-N-(methanesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.50 g), 4-(4-trifluoromethoxyphenyl)benzonitrile (1.56 g), anhydrous iron (III) chloride (0.90 g) and chlorobenzene (20 ml) is stirred at an oil bath temperature of 140.degree. C. for 1 hour. After cooling, the reaction mixture is dissolved in chloroform (300 ml), washed with dilute hydrochrolic acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.80 g of desired compound (refractive index: 1.5925).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 3.90 (3H, s) 6.90-7.70 (10H, m)______________________________________
EXAMPLE 27
Preparation of 5-�3-chloro-4-(3,4-dichlorobenzyl)phenyl!-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 161)
A mixture of N-methyl-N-(benzenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.00 g), 3-chloro-4-(3,4-dichlorobenzyl)benzonitrile (0.93 g), anhydrous iron (III) chloride (0.50 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 1 hour. After cooling, the reaction mixture is dissolved in chloroform (300 ml), washed with dilute hydrochrolic acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.64 g of desired compound (melting point: 179.0.degree.-185.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.03 (3H, s) 4.23 (2H, s) 6.67-7.86 (9H, m)______________________________________
EXAMPLE 28
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�3-chloro-4-(2-chloro-4-trifluoromethylphenoxymethyl)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 196)
To 30 ml of N,N-dimethylformamide are added 2-chloro-4-trifluoromethyl phenol (0.29 g) and potassium carbonate (0.25 g) and 5-(4-bromomethyl-3-chlorophenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (0.60 g) is added thereto at room temperature with stirring, which is stirred at 120.degree. C. for 1 hour. On completion of the reaction, the reaction solution is cooled to room temperature, poured into water and extracted with toluene. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 0.61 g of desired compound (melting point: 113.0.degree.-114.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.10 (3H, s) 5.30 (2H, s) 6.87-8.10 (9H, m)______________________________________
EXAMPLE 29
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�3-chloro-4-(2-fluoro-4-trifluoromethylphenoxymethyl)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 197)
To 100 ml of N,N-dimethylformamide are added 5-(3-chloro-4-chloromethylphenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (1.60 g) and potassium carbonate (0.60 g) and 2-fluoro-4-trifluoromethyl phenol (0.80 g) is added thereto at room temperature with stirring, which is stirred at 70.degree. C. for 3 hours. On completion of the reaction, the reaction solution is cooled to room temperature, poured into water and extracted with ethyl acetate. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 1.62 g of desired compound (refractive index: 1.6010).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.10 (3H, s) 5.31 (2H, s) 6.75-8.00 (9H, m)______________________________________
EXAMPLE 30
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�3-chloro-4-(4-trifluoromethylphenoxymethyl)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 199)
To 30 ml of N,N-dimethylformamide are added 4-trifluoromethyl phenol (0.77 g) and potassium carbonate (0.72 g) and 5-(4-bromomethyl-3-chlorophenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (1.60 g) is added thereto at room temperature with stirring, which is stirred at 120.degree. C. for 1 hour. On completion of the reaction, the reaction solution is cooled to room temperature, poured into water and extracted with toluene. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 1.50 g of desired compound (refractive index: 1.5961).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.08 (3H, s) 5.23 (2H, s) 6.87-7.47 (7H, m) 7.65 (2H, s) 7.83 (1H, s)______________________________________
EXAMPLE 31
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�3-chloro-4-(4-trifluoromethoxyphenoxymethyl)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 201)
To 30 ml of N,N-dimethylformamide are added 4-trifluoromethoxy phenol (0.33 g) and potassium carbonate (0.25 g) and 5-(4-bromomethyl-3-chlorophenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (0.70 g) is added thereto at room temperature with stirring, which is stirred at 120.degree. C. for 1 hour. On completion of the reaction, the reaction solution is cooled to room temperature, poured into water and extracted with toluene. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 0.83 g of desired compound (refractive index: 1.5701).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.08 (3H, s) 5.19 (2H, s) 6.70-7.40 (7H, m) 7.65 (1H, s)______________________________________
EXAMPLE 32
Preparation of 3-(2-chloro-6-fluorophenyl)-5-(2-chloro-4-phenoxyphenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 241)
A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (3.30 g), 2-chloro-4-phenoxybenzonitrile (2.30 g), anhydrous iron (III) chloride (1.60 g) and o-dichlorobenzene (10 ml) is stirred at an oil bath temperature of 140.degree. C. for 1 hour. After cooling, the reaction mixture is dissolved in chloroform (100 ml), washed with dilute hydrochrolic acid, dilute aqueous solution of sodium hydroxide and saline in this order, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.15 g of desired compound (melting point: 135.0.degree.-140.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 3.91 (3H, s) 6.90-8.06 (11H, m)______________________________________
EXAMPLE 33
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�3-chloro-4-(2,6-dichloro-4-trifluoromethylphenoxy)-phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 259)
Ethyl 2-chloro-6-fluorobenzimidate (1.80 g) and triethylamine (1.20 g) are dissolved in toluene (50 ml) and 3-chloro-4-(2,6-dichloro-4-trifluoromethylphenoxy)benzoyl chloride (3.70 g) is added dropwise thereto at room temperature with stirring, which is stirred at 100.degree. C. for 3 hours. After cooling to room temperature, the reaction solution is added with toluene (50 ml) and washed with dilute hydrochloric acid and saline and the organic layer is dried over anhydrous magnesium sulfate. The reaction solution is added with monomethyl hydrazine (0.80 g) and stirred at 100.degree. C. for 3 hours. On completion of the reaction, the reaction mixture is washed with dilute hydrochloric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 1.50 g of desired compound (melting point: 67.0-72.0).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.05 (3H, s) 6.40-7.95 (8H, m)______________________________________
EXAMPLE 34
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�3-chloro-4-(2-chloro-4-trifluoromethylbenzyloxy)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 273)
To 20 ml of N,N-dimethylformamide are added 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-hydroxyphenyl)-1-methyl-1H-1,2,4-triazole (0.70 g) and potassium carbonate (0.31 g) and 2-chloro-4-trifluoromethylbenzyl chloride (0.50 g) is added thereto at room temperature with stirring, which is stirred at 120.degree. C. for 5 hours. On completion of the reaction, the reaction solution is cooled to room temperature, poured into water and extracted with ethyl acetate. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 0.80 g of desired compound (melting point: 156.0.degree.-159.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.05 (3H, s) 5.30 (2H, s) 6.80-7.95 (9H, m)______________________________________
EXAMPLE 35
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�3-chloro-4-(2-fluoro-4-trifluoromethylbenzyloxy)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 274)
To 20 ml of N,N-dimethylformamide are added 3-(2-chloro-6-fluorophenyl)-5-�3-chloro-4-hydroxyphenyl)-1-methyl-1H-1,2,4-triazole (0.90 g) and potassium carbonate (0.40 g) and 2-fluoro-4-trifluoromethylbenzyl chloride (0.50 g) is added thereto at room temperature with stirring, which is stirred at 120.degree. C. for 5 hours. On completion of the reaction, the reaction solution is cooled to room temperature, poured into water and extracted with ethyl acetate. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 0.60 g of desired compound (melting point: 109.0.degree.-111.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.00 (3H, s) 5.25 (2H, s) 6.80-7.90 (9H, m)______________________________________
EXAMPLE 36
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�3-chloro-4-(4-trifluoromethylbenxyloxy)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 275)
Ethyl 2-chloro-6-fluorobenzimidate (2.40 g) and triethylamine (1.20 g) are dissolved in toluene (50 ml) and 3-chloro-4-(4-trifluoromethylbenzyloxy)benzoyl chloride (3.50 g) is added dropwise thereto at room temperature with stirring, which is stirred at 100.degree. C. for 3 hours. After cooling to room temperature, the reaction solution is added with toluene (50 ml) and washed with dilute hydrochloric acid and saline and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (0.90 g) and stirred at 100.degree. C. for 3 hours. On completion of the reaction, the reaction mixture is washed with dilute hydrochloric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 2.20 g of desired compound (melting point: 43.0.degree.-47.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.05 (3H, s) 5.25 (2H, s) 6.90-7.95 (10H, m)______________________________________
EXAMPLE 37
Preparation of 5-�3-chloro-4-(4-trifluoromethylbenzyloxy)phenyl!-3-(2,6-difluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 276)
Ethyl 2,6-difluorobenzimidate (2.20 g) and triethylamine (1.20 g) are dissolved in toluene (50 ml) and 3-chloro-4-(4-trifluoromethylbenzyloxy)benzoyl chloride (3.50 g) is added dropwise thereto at room temperature with stirring, which is stirred at 100.degree. C. for 3 hours. After cooling to room temperature, the reaction solution is added with toluene (50 ml) and washed with dilute hydrochloric acid and saline and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (0.90 g) and stirred at 100.degree. C. for 3 hours. On completion of the reaction, the reaction mixture is washed with dilute hydrochloric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 2.00 g of desired compound (melting point: 171.0.degree.-177.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.00 (3H, s) 5.20 (2H, s) 6.65-7.90 (10H, m)______________________________________
EXAMPLE 38
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�3-chloro-4-(4-trifluoromethoxybenzyloxy)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 277)
Ethyl 2-chloro-6-fluorobenzimidate (2.40 g) and triethylamine (1.20 g) are dissolved in toluene (50 ml) and 3-chloro-4-(4-trifluoromethoxybenzyloxy)benzoyl chloride (3.70 g) is added dropwise thereto at room temperature with stirring, which is stirred at 100.degree. C. for 3 hours. After cooling to room temperature, the reaction solution is added with toluene (50 ml) and washed with dilute hydrochloric acid and saline and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (0.90 g) and stirred at 100.degree. C. for 3 hours. On completion of the reaction, the reaction mixture is washed with dilute hydrochloric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 2.50 g of desired compound (refractive index: 1.5680).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.00 (3H, s) 5.10 (2H, s) 6.85-7.90 (10H, m)______________________________________
EXAMPLE 39
Preparation of 5-�3-chloro-4-(4-trifluoromethoxybenzyloxy)phenyl!-3-(2,6-difluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 278)
Ethyl 2,6-difluorobenzimidate (2.20 g) and triethylamine (1.20 g) are dissolved in toluene (50 ml) and 3-chloro-4-(4-trifluoromethoxybenzyloxy)benzoyl chloride (3.70 g) is added dropwise thereto at room temperature with stirring, which is stirred at 100.degree. C. for 3 hours. After cooling to room temperature, the reaction solution is added with toluene (50 ml) and washed with dilute hydrochloric acid and saline and the organic layer is dried over anhydrous magnesium sulfate. The organic layer is added with monomethyl hydrazine (0.90 g) and stirred at 100.degree. C. for 3 hours. On completion of the reaction, the reaction mixture is washed with dilute hydrochloric acid and saline, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 2.50 g of desired compound (melting point: 132.0.degree.-136.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.00 (3H, s) 5.10 (2H, s) 6.70-8.20 (10H, m)______________________________________
EXAMPLE 40
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�2-chloro-4-(3-chloro-5-trifluoromethylpyridine-2-yloxymethyl)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 317)
3-(2-chloro-6-fluorophenyl)-5-(2-chloro-4-hydroxymethylphenyl)-1-methyl-1H-1,2,4-triazole (0.50 g) is dissolved in 1,2-dimethoxyethane (20 ml) and cooled to 0.degree. C., to which is added sodium hydride (60%, 0.07 g) and the reaction mixture is stirred for 15 minutes. Then, a solution of 2,3-dichloro-5-trifluoromethyl pyridine (0.34 g) in 1,2-dimethoxyethane (10 ml) is added dropwise and stirred for 3 hours. On completion of the reaction, the reaction solution is warmed to room temperature and poured into water and extracted with ether. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 0.62 g of desired compound.
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 3.83 (3H, s) 5.50 (2H, s) 6.83-8.37 (8H, m)______________________________________
EXAMPLE 41
Preparation of 5-�3-chloro-4-(3,5-dichloropyridine-2-yloxymethyl)phenyl!-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 330)
Sodium hydride (60%, 0.12 g) is added to 1,2-dimethoxyethane (50 ml) and a solution of 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-hydroxymethylphenyl)-1-methyl-1H-1,2,4-triazole (1.00 g) in 1,2-dimethoxyethane (20 ml) is added dropwise thereto at -5.degree. C. and stirred for 20 minutes. The reaction solution is added dropwise with a solution of 2,3,5-trichloropyridine (0.60 g) in 1,2-dimethoxyethane (20 ml) at -5.degree. C. for 10 minutes with stirring. The reaction mixture is warmed to room temperature, poured into water and extracted with ethyl acetate. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 0.40 g of desired compound (melting point: 153.0.degree.-155.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.06 (3H, s) 5.48 (2H, s) 6.75-7.30 (3H, m) 7.50-8.00 (5H, m)______________________________________
EXAMPLE 42
Preparation of 5-�3-chloro-4-(3-chloro-5-trifluoromethylpyridine-2-yloxymethyl)phenyl!-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 332)
Sodium hydride (60%, 0.16 g) is added to 1,2-dimethoxyethane (50 ml) and a solution of 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-hydroxymethylphenyl)-1-methyl-1H-1,2,4-triazole (1.20 g) in 1,2-dimethoxyethane (20 ml) is added dropwise thereto at -5.degree. C. with stirring. To the reaction solution is added dropwise a solution of 2,3-dichloro-5-trifluoromethyl pyridine (0.80 g) in 1,2-dimethoxyethane (20 ml) at -5.degree. C. for 10 minutes, which is further stirred for 15 minutes. On completion of the reaction, the reaction solution is warmed to room temperature, poured into water and extracted with ethyl acetate. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 1.10 g of desired compound (melting point: 47.0.degree.-49.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.06 (3H, s) 5.57 (2H, s) 6.84-7.50 (3H, m) 7.60-7.75 (4H, m) 8.30 (1H, s)______________________________________
EXAMPLE 43
Preparation of 5-�3-chloro-4-(5-trifluoromethylpyridine-2-yloxymethyl)phenyl!-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 334)
Sodium hydride (60%, 0.12 g) is added to 1,2-dimethoxyethane (50 ml) and a solution of 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-hydroxymethylphenyl)-1-methyl-1H-1,2,4-triazole (1.00 g) in 1,2-dimethoxyethane (20 ml) is added dropwise thereto at -5.degree. C., which is stirred for 15 minutes. To the reaction solution is added dropwise a solution of 2-chloro-5-trifluoromethyl pyridine (0.60 g) in 1,2-dimethoxyethane (20 ml) at -5.degree. C., which is stirred for 15 minutes. The reaction mixture is warmed to room temperature, poured into water and extracted with ethyl acetate. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 0.80 g of desired compound (refractive index: 1.5879).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.06 (3H, s) 5.57 (2H, s) 6.75-8.42 (9H, m)______________________________________
EXAMPLE 44
Preparation of 5-�4-chloro-3-(5-trifluoromethylpyridine-2-yloxy)phenyl!-3-(2,6-difluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 377)
A mixture of N-methyl-N-(benzenesulfonyl)-2,6-difluorobenzohydrazonoyl chloride (0.90 g), 4-chloro-3-(5-trifluoromethylpyridine-2-yloxy)benzonitrile (0.90 g), anhydrous iron (III) chloride (0.50 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.30 g of desired compound.
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.02 (3H, s) 6.64-7.98 (8H, m) 8.20-8.38 (1H, m)______________________________________
EXAMPLE 45
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�4-chloro-3-(5-trifluoromethylpyridine-2-yloxy)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 378)
A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.00 g), 4-chloro-3-(5-trifluoromethylpyridine-2-yloxy)benzonitrile (0.90 g), anhydrous iron (III) chloride (0.50 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.40 g of desired compound.
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.12 (3H, s) 6.92-8.11 (8H, m) 8.33-8.50 (1H, m)______________________________________
EXAMPLE 46
Preparation of 3-(2-chlorophenyl)-5-�2-chloro-4-(5-trifluoromethylpyridine-2-yloxy)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 389)
A mixture of N-methyl-N-(benzenesulfonyl)-2-chlorobenzohydrazonoyl chloride (2.05 g), 2-chloro-4-(5-trifluoromethylpyridine-2-yloxy)benzonitrile (1.88 g), anhydrous iron (III) chloride (1.07 g) and o-dichlorobenzene (10 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, it is dissolved in chloroform (300 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.87 g of desired compound (melting point: 104.0.degree.-108.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 3.88 (3H, s) 6.90-8.40 (10H, m)______________________________________
EXAMPLE 47
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�2-chloro-4-(5-trifluoromethylpyridine-2-yloxy)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 390)
A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (2.25 g), 2-chloro-4-(5-trifluoromethylpyridine-2-yloxy)benzonitrile (1.88 g), anhydrous iron (III) chloride (1.07 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, it is dissolved in chloroform (300 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 1.54 g of desired compound (melting point: 139.0.degree.-141.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 3.90 (3H, s) 6.90-8.40 (9H, m)______________________________________
EXAMPLE 48
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�3,5-dichloro-4-(3-chloro-5-trifluoromethylpyridine-2-yloxy)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 401)
A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.00 g), 3,5-dichloro-4-(3-chloro-5-trifluoromethylpyridine-2-yloxy)benzonitrile (1.00 g), anhydrous iron (III) chloride (0.50 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.60 g of desired compound.
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.10 (3H, s) 6.73-7.52 (3H, m) 7.80 (2H, s) 7.97-8.10 (1H, m) 8.12-8.26 (1H, m)______________________________________
EXAMPLE 49
Preparation of 5-�3-chloro-4-(3-chloro-5-trifluoromethylpyridine-2-yloxy)phenyl!-3-(2,6-difluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 409)
A mixture of N-methyl-N-(benzenesulfonyl)-2,6-difluorobenzohydrazonoyl chloride (0.90 g), 3-chloro-4-(3-chloro-5-trifluoromethylpyridine-2-yloxy)benzonitrile (0.90 g), anhydrous iron (III) chloride (0.50 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.70 g of desired compound.
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.10 (3H, s) 6.72-8.06 (7H, m) 8.14-8.30 (1H, m)______________________________________
EXAMPLE 50
Preparation of 5-�3-chloro-4-(3-chloro-5-trifluoromethylpyridine-2-yloxy)phenyl!-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 410)
A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (0.90 g), 3-chloro-4-(3-chloro-5-trifluoromethylpyridine-2-yloxy)benzonitrile (0.80 g), anhydrous iron (III) chloride (0.40 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.60 g of desired compound.
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.16 (3H, s) 6.92-8.16 (7H, m) 8.24-8.40 (1H, m)______________________________________
EXAMPLE 51
Preparation of 5-�3-chloro-4-(5-trifluoromethylpyridine-2-yloxy)phenyl!-3-(2,6-difluorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 412)
A mixture of N-methyl-N-(benzenesulfonyl)-2,6-difluorobenzohydrazonoyl chloride (1.72 g), 3-chloro-4-(5-trifluoromethylpyridine-2-yloxy)benzonitrile (1.50 g), anhydrous iron (III) chloride (0.85 g) and o-dichlorobenzene (10 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, it is dissolved in chloroform (200 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent and washed with hexane to give 1.25 g of desired compound.
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 3.11 (3H, s) 6.80-8.40 (9H, m)______________________________________
EXAMPLE 52
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�3-chloro-4-(5-trifluoromethylpyridine-2-yloxy)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 413)
To N,N-dimethylformamide (50 ml) are added 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-hydroxyphenyl)-1-methyl-1H-1,2,4-triazole (3.04 g), 2-chloro-5-trifluoromethyl pyridine (1.70 g) and potassium carbonate (1.40 g), which is heated at 120.degree. C. for 2 hours with stirring. After cooling to room temperature, the reaction solution is poured into water and extracted with ethyl acetate, and the layer is washed with water and dried over anhydrous magnesium sulfate. After the concentration under reduced pressure, the crude solid is purified by silica gel column chromatography using mixed solution of hexane-ethyl acetate as eluent to give 3.30 g of desired compound (melting point: 116.0.degree.-117.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.10 (3H, s) 6.90-8.30 (9H, m)______________________________________
EXAMPLE 53
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�3-perfluorobutyl-4-(3-chloro-5-trifluoromethylpyridine-2-yloxymethyl)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 451)
3-(2-chloro-6-fluorophenyl)-1-methyl-5-(3-perfluorobutyl-4-hydroxymethylphenyl)-1H-1,2,4-triazole (1.00 g) is dissolved in 1,2-dimethoxyethane (20 ml) and cooled to 0.degree. C. It is added with sodium hydride (60%, 0.08 g) and stirred for 30 minutes. A solution of 2,3-dichloro-5-trifluoromethyl pyridine (0.44 g) in 1,2-dimethoxyethane (10 ml) is added dropwise thereto and stirred for 3 hours. On completion of the reaction, the reaction solution is warmed to room temperature, poured into water and extracted with ether. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 1.00 g of desired compound (melting point: 123.0.degree.-127.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.08 (3H, s) 5.73 (2H, s) 6.85-7.40 (4H, m) 7.75-8.27 (4H, m)______________________________________
EXAMPLE 54
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�3-perfluorobutyl-4-(5-trifluoromethylpyridine-2-yloxymethyl)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 453)
3-(2-chloro-6-fluorophenyl)-1-methyl-5-(3-perfluorobutyl-4-hydroxymethylphenyl)-1H-1,2,4-triazole (1.00 g) is dissolved in 1,2-dimethoxyethane (20 ml) and cooled to 0.degree. C. It is added with sodium hydride (60%, 0.08 g) and stirred for 30 minutes. A solution of 2-chloro-5-trifluoromethyl pyridine (0.36 g) in 1,2-dimethoxyethane (10 ml) is added dropwise thereto and stirred for 5 hours. On completion of the reaction, the reaction solution is warmed to room temperature, poured into water and extracted with ether. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography to give 0.70 g of desired compound (refractive index: 1.5020).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.12 (3H, s) 5.70 (2H, s) 6.80-8.53 (9H, m)______________________________________
EXAMPLE 55
Preparation of 3-(2-chloro-6-fluorophenyl)-1-methyl-5-�3-methyl-4-(4-trifluoromethoxyphenyl)phenyl!-1H-1,2,4-triazole (Compound No. 457)
A mixture of N-methyl-N-(methanesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.50 g), 3-methyl-4-(4-trifluoromethoxyphenyl)benzonitrile (1.42 g), anhydrous iron (III) chloride (0.90 g) and chlorobenzene (10 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, it is dissolved in chloroform (300 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent and washed with hexane to give 1.64 g of desired compound (melting point: 117.0.degree.-122.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 2.23 (3H, s) 4.10 (3H, s) 6.90-7.70 (10H, m)______________________________________
EXAMPLE 56
Preparation of 3-(2-chlorophenyl)-1-methyl-5-�4-methyl-3-(5-trifluoromethylpyridine-2-yloxy)phenyl!-1H-1,2,4-triazole (Compound No. 509)
A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-benzohydrazonoyl chloride (1.1 g), 4-methyl-3-(5-trifluoromethylpyridine-2-yloxy)benzonitrile (1.00 g), anhydrous iron (III) chloride (0.60 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.50 g of desired compound.
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 2.26 (3H, s) 4.07 (3H, s) 6.95-8.16 (9H, m) 8.36-8.52 (1H, m)______________________________________
EXAMPLE 57
Preparation of 3-(2-chloro-6-fluorophenyl)-1-methyl-5-�4-methyl-3-(5-trifluoromethylpyridine-2-yloxy)phenyl!-1H-1,2,4-triazole (Compound No. 510)
A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.10 g), 4-methyl-3-(5-trifluoromethylpyridine-2-yloxy)benzonitrile (0.90 g), anhydrous iron (III) chloride (0.60 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.60 g of desired compound.
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 2.24 (3H, s) 4.12 (3H, s) 6.85-8.07 (8H, m) 8.36-8.52 (1H, m)______________________________________
EXAMPLE 58
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�4-methoxy-3-(5-trifluoromethylpyridine-2-yloxy)phenyl!-1H-1,2,4-triazole (Compound No. 516)
A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (1.00 g), 4-methoxy-3-(5-trifluoromethylpyridine-2-yloxy)benzonitrile (0.90 g), anhydrous iron (III) chloride (0.50 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.50 g of desired compound.
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 3.85 (3H, s) 4.14 (3H, s) 6.92-8.08 (8H, m) 8.35-8.52 (1H, m)______________________________________
EXAMPLE 59
Preparation of 3-(2,6-difluorophenyl)-5-�4-methoxy-3-(5-trifluoromethylpyridine-2-yloxy)phenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 517)
A mixture of N-methyl-N-(benzenesulfonyl)-2,6-difluorobenzohydrazonoyl chloride (0.70 g), 4-methoxy-3-(5-trifluoromethylpyridine-2-yloxy)benzonitrile (0.80 g), anhydrous iron (III) chloride (0.50 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.30 g of desired compound.
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 3.84 (3H, s) 4.10 (3H, s) 6.75-8.10 (8H, m) 8.30-8.47 (1H, m)______________________________________
EXAMPLE 60
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�3-(3-chloro-5-trifluoromethylpyridine-2-yloxy)-5-methoxyphenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 523)
A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (0.90 g), 3-(3-chloro-5-trifluoromethylpyridine-2-yloxy)-5-methoxybenzonitrile (0.80 g), anhydrous iron (III) chloride (0.80 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.60 g of desired compound.
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 3.92 (3H, s) 4.12 (3H, s) 6.85-7.53 (6H, m) 7.96-8.06 (1H, m) 8.23-8.40 (1H, m)______________________________________
EXAMPLE 61
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�3-methoxy-4-(5-trifluoromethylpyridine-2-yloxy)phenyl!-1-methyl-1-1,2,4-triazole (Compound No. 524)
A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (3.75 g), 3-methoxy-4-(5-trifluoromethylpyridine-2-yloxy)benzonitrile (3.03 g), anhydrous iron (III) chloride (1.70 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, it is dissolved in chloroform (300 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent and washed with hexane to give 2.80 g of desired compound.
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 2.97 (3H, s) 3.07 (3H, s) 6.90-8.30 (9H, m)______________________________________
EXAMPLE 62
Preparation of 3-(2-chloro-6-fluorophenyl)-5-�4-(3-chloro-5-trifluoromethylpyridine-2-yloxy)-3-methoxyphenyl!-1-methyl-1H-1,2,4-triazole (Compound No. 526)
A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (0.90 g), 4-(3-chloro-5-trifluoromethylpyridine-2-yloxy)-3-methoxybenzonitrile (0.90 g), anhydrous iron (III) chloride (0.50 g) and o-dichlorobenzene (5 ml) is stirred at an oil bath temperature of 140.degree. C. for 30 minutes. After cooling, it is dissolved in chloroform (100 ml) and washed with dilute hydrochloric acid, dilute aqueous solution of sodium hydroxide and saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.60 g of desired compound.
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 3.81 (3H, s) Z 4.13 (3H, s) 6.90-7.60 (6H, m) 7.93-8.06 (1H, m) 8.16-8.30 (1H, m)______________________________________
EXAMPLE 63
Preparation of 5-(2-chloro-4-hexylphenyl)-3-(2-chlorophenyl)-1-methyl-1H-1,2,4-triazole (Compound No. 40)
A mixture of N-methyl-N-phenylsulfonyl-2-chlorobenzamidrazone (3.24 g) and 2-chloro-4-hexylbenzoyl chloride (3.37 g) is stirred at an oil bath temperature of 170.degree.-180.degree. C. for 4 hours. After cooling to room temperature, it is added with ethyl acetate and the organic layer is washed with water. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 0.85 g of desired compound (refractive index: 1.5830).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 0.90 (3H, t) 1.00-1.90 (8H, m) 2.67 (2H, t) 3.87 (3H, s) 7.10-7.60 (6H, m) 7.90-8.05 (1H, m)______________________________________
Reference Example 1
Preparation of N-methyl-N-(benzenesulfonyl)-2-chlorobenzamidorazone
N-methyl-N-(benzenesulfonyl)-2-chlorobenzhydrazonoyl chloride (17.2 g) is dissolved in N,N-dimethylformamide (100 ml) and stirred at 60.degree.-70.degree. C. for 3 hours while introducing ammonia gas thereinto. After cooling, it is dissolved in 500 ml of ethyl acetate and washed with water. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure and the crude solid is washed with hexane to give 15.4 g of desired compound (melting point: 94.0.degree.-96.0.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 2.75 (3H, s) 5.80 (2H, s) 7.10-8.00 (9H, m)______________________________________
Reference Example 2
Preparation of 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-methylphenyl)-1-methyl-1H-1,2,4-triazole
A mixture of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (7.50 g), 3-chloro-4-methylbenzonitrile (3.33 g), anhydrous aluminum chloride (3.00 g) and o-dichlorobenzene (20 ml) is stirred at an oil bath temperature of 140.degree. C. for 1 hour. After cooling, it is washed with saline. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 3.70 g of desired compound.
Reference Example 3
Preparation of 5-(4-bromomethyl-3-chlorophenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1,2,4-triazole
To carbon tetrachloride (50 ml) are added 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-methylphenyl)-1-methyl-1H-1,2,4-triazole (3.37 g), N-bromosuccinicimide (2.14 g) and azobisisobutyronitrile (30 mg), which are heated under reflux for 1 hour with stirring. After cooling of the reaction mixture, insoluble matter is filtered off, and the filtrate is concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 2.51 g of desired compound (melting point 124.0.degree.-126.0.degree. C.).
Reference Example 4
Preparation of 5-(4-acetoxymethyl-3-chlorophenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole
To N,N-dimethylformamide (200 ml) are added 5-(4-bromomethyl-3-chlorophenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (24.3 g) and potassium acetate (29.0 g), which are stirred at 130.degree. C. for 3 hours. The reaction mixture is cooled to room temperature, poured into water and extracted with ethyl acetate. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography using mixed solvent of hexane-ethyl acetate as eluent to give 11.8 g of desired compound.
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 2.13 (3H, s) 4.07 (3H, s) 5.24 (2H, s) 6.90-7.85 (6H, m)______________________________________
Reference Example 5
Preparation of 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-hydroxymethylphenyl)-1-methyl-1H-1,2,4-triazole
5-(4-acetoxymethyl-3-chlorophenyl)-3-(2-chloro-6-fluorophenyl)-1-methyl-1H-1,2,4-triazole (11.1 g) is dissolved in a mixed solvent of ethanol (50 ml) and water (20 ml), added with sodium hydroxide (2.3 g) and heated under reflux for 1 hour with stirring. After cooling to room temperature, the reaction mixture is added with ethyl acetate and washed with water. Then, it is dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain crude solid. The crude solid is washed with mixed solvent of hexane-ethanol to give 6.7 g of desired compound (melting point: 111.degree.-113.degree. C.).
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 3.50 (1H, t) 4.05 (3H, s) 4.75 (2H, d) 6.95-7.70 (6H, m)______________________________________
Reference Example 6
Preparation of 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-hydroxyphenyl)-1-methyl-1H-1,2,4-triazole
To o-dichlorobenzene (200 ml) are added 3-chloro-4-methoxybenzonitrile (40.3 g) and anhydrous iron (III) chloride (42.2 g), which are heated at 120.degree. C. with stirring. To this mixture is added dropwise a solution of N-methyl-N-(p-toluenesulfonyl)-2-chloro-6-fluorobenzohydrazonoyl chloride (62.2 g) in o-dichlorobenzene (300 ml) at 120.degree. C. for 30 minutes with stirring, which are further stirred at 120.degree. C. for 3 hours. After cooling to room temperature, the reaction mixture is poured into a large amount of water and extracted with chloroform. The organic layer is added with aqueous solution of 10% NaOH (200 ml) and aqueous solution of 25% ammonia (200 ml) and stirred at 50.degree. C. for 1 hour. After cooling to room temperature, the organic layer is washed with water, dried over anhydrous magnesium sulfate, concentrated under reduced pressure to give 70.5 g of a crude product of 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-methoxyphenyl)-1-methyl-1H-1,2,4-triazole.
To benzene (300 ml) are added the crude product of 3-(2-chloro-6-fluorophenyl)-5-(3-chloro-4-methoxyphenyl)-1-methyl-1H-1,2,4-triazole (70.5 g) and anhydrous aluminum chloride (80.0 g), which are heated under reflux for 3 hours with stirring. After cooling to room temperature, the reaction mixture is poured into ice water and extracted with toluene. The organic layer is washed with water, extracted with aqueous solution of 20% NaOH, and the aqueous layer is acidified by adding a concentrated sulfuric acid little by little while cooling with ice and extracted with ethyl acetate. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 64.2 g of desired compound.
NMR data (60 MHz, CDCl.sub.3 solvent, .delta. value: ppm)
______________________________________ 4.10 (3H, s) 7.00-7.90 (6H, m) 10.85 (1H, s)______________________________________
The insecticide and acaricide according to the invention contain the triazole derivative shown by the general formula �I! as an active ingredient.
When the compounds according to the invention are used in the insecticide and acaricide, these compounds themselves may be used alone, or may be compounded with a carrier, a surfactant, a dispersing agent, an adjuvant or the like, which is usually used in the formulation, to form dust, wettable powder, emulsion, fine powder, granulate 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 dinaphthylmethane disulfonic acid, a salt of 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 carboxymethyl cellulose, polyethylene glycol, gum arabic and the like. In use, the active ingredient is sprayed by diluting to a proper concentration or directly applied.
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. The compounding ratio of the active ingredient may properly be selected, if necessary, but in case of the dust or granulate, it may properly be selected from a range of 0.05-20% (by weight), preferably 0.1%-10% (by weight). In case of the emulsion or wettable powder, it is suitable within a range of 0.5-80% (by weight). Preferably, it may properly be selected within a range of 1-60% (by weight).
The amount of the insecticide or acaricide according to the invention applied is dependent upon the kind of the compound used, injurious insect to be controlled, tendency and degree of insect injury, environmental condition, kind of formulation used and the like. When it is directly used as dust or granulate, the amount of the active ingredient is properly selected within a range of 0.05 g-5 kg, preferably 0.1 g-1 kg per 10 are. Furthermore, when it is used in form of a liquid as emulsion or wettable powder, the amount is properly selected within a range of 0.1-5,000 ppm, preferably 1-1,000 ppm. And also, the insecticide and acaricide according to the invention may be used by mixing with other insecticide, fungicide, fertilizer and plant growth regulator.
Then, 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 is prepared by uniformly dissolving 30% of the compound (41), 20% of cyclohexanone, 11% of polyoxyethylene alkylaryl ether, 4% of calcium alkylbenzene sulfonate and 35% of methylnaphthaline.
Formulation Example 2
Wettable powder
A wettable powder is prepared by uniformly mixing and pulverizing 40% of the compound (389), 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 is prepared by uniformly mixing and pulverizing 2% of the compound (116), 5% of diatomaceous earth and 93% of clay.
Formulation Example 4
Granulate
5% of the compound (41), 2% of sodium salt of lauryl alcohol sulfuric acid ester, 5% of sodium lignin sulfonate, 2% of carboxymethyl cellulose and 86% of clay are mixed and pulverized uniformly. Then, 100 parts by weight of this mixture is added and kneaded with 20 parts by weight of water and shaped into granulates of 14-32 mesh through an extrusion type granulating machine and dried to prepare granulates.
�EFFECT OF THE INVENTION!
The triazole derivatives according to the invention are effective for the control of 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 scales, e.g. mulberry scale or the like and bugs, e.g. corbett rice bug or the like; lepidopteran injurious insects such as diamond-back moth, beet armyworm, common cutworm and the like; dipteran injurious insects such as house fly, mosquito and the like; elytron injurious insects such as rice plant weevil, azuki bean weevil, cucurbit leaf beetle and the like; orthopteran injurious insects such as American cockroach, German cockroach and the like; and mites such as two-spotted spider mite, Kanzawa spider mite, citrus red mite and the like. Especially, they have a very excellent controlling effect against mites such as two-spotted spider mite, Kanzawa spider mite, citrus red mite and the like; and aphids such as cotton aphid, green peach aphid, cabbage aphid and the like.
The effect of the compound according to the invention will be described with respect to the following test examples. Moreover, compounds shown by chemical formula 3 in JP-A-56-154464 as comparative chemicals a-b and compounds shown in Technical Report RD278004 as comparative chemicals c-d are used in the same formulation as in the test compounds.
Comparative chemical a: 3,5-bis(2-chlorophenyl)-1-methyl-1H-1,2,4-triazole
Comparative chemical b: 3-(2-chlorophenyl)-1-methyl-5-(3-methylphenyl)-1H-1,2,4-triazole
Comparative chemical c: 3-(2-chlorophenyl)-1-methyl-5-(3-chloro-2-methylphenyl)-1H-1,2,4-triazole
Comparative chemical d: 3-(2-chloro-6-fluorophenyl)-1-methyl-5-(2,4-dichlorophenyl)-1H-1,2,4-triazole
Test Example 1
Acaricidal test for two-spotted spider mite
The wettable powder prepared according to Formulation Example 2 is diluted with water so that the concentration of the active ingredient is 500 ppm. In the resulting diluted wettable powder are immersed soy bean seedlings previously inoculated with adults of two-spotted spider mite and then dried in air. After the treatment, the soy bean seedlings are placed in a thermostatic chamber of 25.degree. C. for 14 days and then the number of living adults is counted to calculate the percentage of control efficiency according to a calculation formula (1). The control efficiency is evaluated according to a standard of Table 3. The results are shown in Table 4. Moreover, the test is carried out by double series. ##EQU1##
TABLE 3______________________________________Control efficiency Evaluation______________________________________control efficiency of not less than 90% Acontrol efficiency of not less than 70% Bbut less than 90%control efficiency of not less than 50% Cbut less than 70%control efficiency of less than 50% D______________________________________
TABLE 4______________________________________ Compound No. Evaluation______________________________________ 1 A 2 A 5 A 6 A 15 A 16 B 18 B 19 B 24 B 28 B 29 A 34 B 40 A 41 A 44 A 47 A 48 A 50 A 65 B 66 A 68 B 72 B 73 B 74 A 76 A 77 A 78 A 87 A 118 A 119 A 120 A 121 B 123 A 138 A 145 A 157 A 158 A 161 A 196 A 197 A 199 A 201 A 241 A 267 A 268 A 269 A 273 A 274 A 275 A 276 A 277 A 278 A 313 B 317 A 319 A 320 A 321 A 322 A 330 A 332 A 334 A 338 A 345 B 373 A 374 A 376 A 377 A 378 A 389 A 390 B 391 A 395 A 400 A 401 A 403 A 404 A 406 A 409 A 410 A 412 A 413 A 419 A 451 B 453 B 456 A 457 A 489 A 496 A 497 A 498 A 508 A 509 A 510 A 511 A 516 A 517 A 522 A 523 A 524 A 526 A 531 B Comparative D chemical b Comparative D chemical c Comparative D chemical d______________________________________
Test Example 2
Insecticidal test for diamond-back moth
The wettable powder prepared according to Formulation Example 2 is diluted with water so that the concentration of the active ingredient is 500 ppm. Cabbage leaves are immersed in the resulting diluted solution, dried in air and then placed in a vinyl chloride cup. Ten larvae of diamond-back moth are released in the cup and thereafter a cover is placed thereon. Then, the cup is placed in a thermostatic chamber of 25.degree. C. for 6 days, and the number of larvae died is counted to calculate the percentage of mortality according to a calculation formula (2). The mortality is evaluated according to a standard of Table 5. The results are shown in Table 6. Moreover, the test is carried out by double series. ##EQU2##
TABLE 4______________________________________Mortality Evaluation______________________________________mortality of not less than 90% Amortality of not less than 70% Bbut less than 90%mortality of not less than 50% Cbut less than 70%mortality of less than 50% D______________________________________
TABLE 6______________________________________ Compound No. Evaluation______________________________________ 51 A 78 A 116 A 118 A 157 A 158 A 161 A 196 A 197 A 199 A 276 A 317 A 319 A 320 A 321 A 322 A 330 A 332 A 334 A 338 A 376 A 391 A 409 A 413 A 419 A 456 A 457 A 496 A 497 A 498 A 514 A 524 A 526 A Comparative D chemical a Comparative D chemical c Comparative D chemical d______________________________________
Test Example 3
Insecticidal test for brown planthopper
The wettable powder prepared according to Formulation Example 2 is diluted with water so that the concentration of the active ingredient is 500 ppm. In the resulting diluted wettable powder are immersed rice stems and leaves, which are then dried in air and placed in a test tube. In the test tube are released 10 larvae of brown planthopper and then the opening of the test tube is plugged with absorbent wadding. Thereafter, the test tube is placed in a thermostatic chamber of 25.degree. C. for 6 days and then the number of larvae died is counted to calculate the percentage of mortality according to the calculation formula (2). The mortality is evaluated according to a standard of Table 5. The results are shown in Table 7. Moreover, the test is carried out by double series.
TABLE 7______________________________________ Compound No. Evaluation______________________________________ 2 A 78 B 116 A 311 B 378 B 395 B 517 A 524 A Comparative D chemical a Comparative C chemical b Comparative D chemical d______________________________________
Test Example 4
Insecticidal test for cotton aphid
The wettable powder prepared according to Formulation Example 2 is diluted with water so that the concentration of the active ingredient is 100 ppm. In the resulting diluted wettable powder are immersed cucumber seedlings previously inoculated with larvae of cotton aphid and then dried in air. After the treatment, the cucumber seedlings are placed in a thermostatic chamber of 25.degree. C. for 3 days and then the number of larvae died is counted to calculate the percentage of mortality according to the calculation formula (2). The mortality is evaluated according to a standard of Table 5. The results are shown in Table 8. Moreover, the test is carried out by double series.
TABLE 8______________________________________ Compound No. Evaluation______________________________________ 1 B 2 A 4 A 8 B 15 A 16 A 18 A 19 A 24 A 28 A 29 A 36 A 37 A 38 A 40 A 41 A 42 A 43 A 44 A 51 A 63 B 64 A 65 A 66 A 68 A 72 A 74 A 76 A 77 A 78 A 87 A 118 A 121 A 123 A 138 A 145 A 157 A 158 A 161 A 201 A 267 A 274 B 277 A 313 A 317 A 319 A 320 A 321 A 322 A 332 A 334 A 338 A 374 A 376 A 377 A 378 A 389 A 390 A 391 A 395 A 404 B 412 A 413 A 419 A 456 A 457 A 480 A 496 A 497 A 509 A 510 A 511 A 513 A 516 A 517 A 524 A 526 A 531 A______________________________________

Number	Name	Date
4151169	Sale et al.	Apr 1979
4414221	Parsons et al.	Nov 1983
4778210	Luthy et al.	Oct 1988
4788210	Luthy et al.	Nov 1988
5318959	Ozaki et al.	Jun 1994

Number	Date	Country
0572142	Dec 1993	EPX
5310712	Nov 1993	JPX

Triazole derivatives, insecticide, acaricide and methods thereof

Information

Patent Number

Date Filed

Date Issued

Inventors

Original Assignees

Examiners

Agents

CPC

US Classifications

Field of Search

US

International Classifications

Abstract

Description

Claims

Priority Claims (1)

Parent Case Info

US Referenced Citations (5)

Foreign Referenced Citations (2)

Non-Patent Literature Citations (3)

Divisions (1)

Entry
Research Disclosure, "New 1-methyl-1H-1,2,4-Triazoles", 278, pp. 356-357, Jun. 1987.
Cram & Hammond "Organic Chemistry" McGraw-Hill Book Co NY (1964), 2nd Ed. pp. 565-567, 1964.
Chemical Abstracts vol. 80, No. 15, 15 Apr. 1974, #82270b.