Sulfamoyltriazole derivatives of fungicidal composition containing same as effective component thereof

FIELD OF INVENTION
The present invention relates to a novel sulfamoyltriazole derivatives and a novel fungicidal composition same as an effective component thereof.
PREVIOUS ART
Japanese Patent Application Laid-Open No. 63-255269 discloses that sulfamoyltriazole derivatives having a specific structure can be used as an effective component of an antifungal agent.
However, the fungicidal activity of the foregoing conventional compounds has been unsatisfactory.
DISCLOSURE OF THE INVENTION
The inventors of the present invention have earnestly studied a variety of substituted sulfamoyltriazole type compounds to develop an agricultural fungicide having high fungicidal activity and excellent safety. As a result, it was found that sulfamoyltriazole derivatives having a triazole ring including a third carbon atom which is substituted by a specific aryl sulfonic group or an aryl oxysulfonic group are novel fungicides which do not damage field and garden plants and which exhibits excellent effects of preventing and curing various disease injury at very small dosages.
(SUMMARY OF THE INVENTION)
According to the present invention, there is provided a sulfamoyltriazole derivative and a fungicide containing same as an effective component thereof, the sulfamoyltriazole derivative being expressed by general formula (I): ##STR2## in which R.sup.1 and R.sup.2 are the same or different lower alkyl groups or an alkylene chain formed by integrating R.sup.1 and R.sup.2 and having 3 to 6 carbon atoms which may be substituted by a lower alkyl group; is an integer 0 or 1; and A is expressed by any one of the following substances: ##STR3## in which X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkenyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group, a lower alkylcarbonyl group, a phenyl group, a phenoxy group, a benzyl group, a benzyloxy group, a formyl group, a lower alkoxycarbonyl group, a nitro group, a cyano group or an acetylamino group; m Is an integer 1, 2, 3, 4 or 5, Y is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkenyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group, a lower alkylcarbonyl group, a formyl group, a lower alkoxycarbonyl group, a nitro group, a cyano group or an acetylamino group; n is an integer 1, 2, 3, 4 or 5; R.sup.3 and R.sup.4 are the same or different hydrogen atoms or lower alkyl groups; and p is an integer 1, 2, 3 or 4.
(CONCRETE DESCRIPTION OF THE INVENTION)
[I] Sulfamoyl Triazole Derivative
The sulfamoyltriazole derivatives according to the present invention and expressed by general formula (I) are described in detail below.
Atoms and groups of the compounds expressed in the general formula (I) expressed by R.sup.1, R.sup.2, R.sup.3, R.sup.4, X and Y defined as described above are exemplified as follows:
Lower Alkyl Group
A lower alkyl group having one to four carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a secondary butyl group, etc.
Halogen Atom
For example, fluorine, chlorine or bromine.
Lower Alkenyl Group
A lower alkenyl group having two to four carbon atoms such as an allyl group, a 2-methyl-2-propenyl group, a 2-butenyl group, a 3-butenyl group, etc.
Lower Alkoxy Group
A lower alkoxy group having one to four carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a secondary butoxy group, a tert-butoxy group, etc.
Lower Haloalkyl Group
A lower haloalkyl group having one to three carbon atoms such as a dichloromethyl group, a trichloromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2-chloroethyl group, a 2-fluoroethyl group, etc.
Lower Haloalkoxy Group
A lower haloalkoxy group having one to three carbon atoms such as a difluoromethoxy group, a trifluoromethoxy group, a 2-chloroethoxy group, 2-2-dichloroethoxy group, a 2,2,2-trichloroethoxy group, a 2-fluoroethoxy group, a 3-bromopropoxy group, etc.
Lower Alkyl Carbonyl Group
A lower alkylcarbonyl group having two to four carbon atoms such as a methylcarbonyl group, an ethylcarbonyl group, an n-propylcarbonyl group, an isopropylcarbonyl group, etc.
Lower Alkoxy Carbonyl Group
A lower alkoxycarbonyl group having two to four carbon atoms such as a methoxycarbonyl group, an ethoxy carbonyl group, an n-propoxycarbonyl group, an isopropoxy carbonyl group, etc.
Groups that are not exemplified above may be selected from the foregoing atoms and groups as to be combined arbitrarily or selected according to generally known common sense.
The lower alkyl groups denoted by R.sup.1 and R.sup.2 in general formula (I) are preferably methyl groups, ethyl groups, n-propyl groups or isopropyl groups.
The lower alkyl groups denoted by R.sup.3 and R.sup.4 are preferably methyl groups, ethyl groups or n-propyl groups.
It is preferable that the halogen atoms denoted by X and Y be fluorine atoms or chlorine atoms, the lower alkyl group be a methyl group, an ethyl group, an n-propyl group or an isopropyl group, the lower haloalkyl group be a trichloromethyl group or a trifluoromethyl group, and the lower haloalkoxy group be a difluoromethoxy group, a trifluoroethoxy group or a tetrafluoroethoxy group. It is preferable that m be 1, 2, 3 or 4, n be 1, 2 or 3 and p be 1, 2 or 3.
It Is preferable that A be the phenyl group substituted by the foregoing substituent, such as a 2,4-dichloro-3-methylphenyl group, a 4-trifluoromethylphenyl group, a 3-chlorophenyl group, a 2,3-dichlorophenyl group, a 2-chloro-4-trifluoromethylphenyl group, a 4-chlorophenyl group and a 3-trifluoromethylphenyl group.
The specific structure of the compounds according to the present invention and expressed by general formula (I) will now be exemplified.
(1) If l in general formula (I) is 1:
(i) General formula (I-1) ##STR4## in which R.sup.1, R.sup.2, X and m are the same as in general formula (I).
(ii) General Formula (I-2) ##STR5## in which, R.sup.1, R.sup.2, Y and n are the same as in general formula (I).
(iii) General formula (I-3) ##STR6## in which R.sup.1, R.sup.2, Y and n are the same as in general formula (I).
(iv) General formula (I-4) ##STR7## in which R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are the same as in general formula (I).
(v) General formula (I-5) ##STR8## in which R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are the same as in general formula (I).
(2) If l in general formula (I) is 0:
(vi) General formula (I-6) ##STR9## In which R.sup.1, R.sup.2, X and m are the same as in general formula (I).
(vii) General formula (I-7) ##STR10## in which R.sup.1, R.sup.2, Y and n are the same as in general formula (I).
(viii) General formula (I-8) ##STR11## in which R.sup.1, R.sup.2, Y and n are the same as in general formula (I).
(ix) General formula (I-9) ##STR12## in which R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are the same as In general formula (I).
(x) General formula (I-10) ##STR13## in which R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are the same as in general formula (I).
(xi) General formula (I-11) ##STR14## in which X, R.sup.1, R.sup.2 and p are the same as in general formula (I).
Examples of the compounds expressed by formula (I-1) according to the present invention are shown in Table 1, examples of the compounds expressed by formula (I-2) are shown in Table 2, examples of the compounds expressed by formula (I-3) are shown in Table 3, examples of the compounds expressed by formula (I-4) are shown in Table 4, examples of the compounds expressed by formula (I-5) are shown in Table 5, examples of the compounds expressed by formula (I-6) are shown in Table 6, examples of the compounds expressed by formula (I-7) are shown in Table 7, examples of the compounds expressed by formula (I-8) are shown in Table 8, examples of the compounds expressed by formula (I-9) are shown in Table 9, examples of the compounds expressed by formula (I-10) are shown in Table 10 and examples of the compounds expressed by formula (I-11) are shown in Table 11.
The abbreviations in Tables 1 to 11 respectively denote the following:
Me denotes a methyl group, Et denotes an ethyl group, nPr denotes an n-propyl group, iPr denotes an isopropyl group and tBu denotes a t-butyl group.
TABLE 1__________________________________________________________________________CompoundNo. R.sup.1 R.sup.2 X.sub.m__________________________________________________________________________ 1 Me Me H 2 Me Et H 3 Et Et H 4 Et nPr H 5 Et iPr H 6 nPr nPr H 7 CH(Me)-(CH.sub.2).sub.3 CH.sub.2 H 8 CH(Me)-(CH.sub.2).sub.3 CH(Me)- H 9 CH(Et)-(CH.sub.2).sub.3 CH.sub.2 H 10 Me Me 2-Me 11 Et Et 2-Me 12 Me Me 3-Me 13 Et Et 3-Me 14 Me Me 4-Me 15 Et Et 4-Me 16 CH(Me)-(CH.sub.2).sub.3 CH.sub.2 4-Me 17 Me Me 2-Et 18 Et Et 2-Et 19 Me Me 3-Et 20 Et Et 3-Et 21 Me Me 4-Et 22 Et Et 4-Et 23 Me Me 2-iPr 24 Et Et 2-iPr 25 Me Me 3-iPr 26 Et Et 3-iPr 27 Me Me 4-iPr 28 Et Et 4-iPr 29 Me Me 4-tBu 30 Et Et 4-tBu 31 Me Me 2-F 32 Et Et 2-F 33 Me Me 3-F 34 Et Et 3-F 35 Me Me 4-F 36 Et Et 4-F 37 Me Me 2-Cl 38 Et Et 2-Cl 39 Me Me 3-Cl 40 Et Et 3-Cl 41 Me Me 4-Cl 42 Et Et 4-Cl 43 Me Me 2-Br 44 Et Et 2-Br 45 Me Me 2-CH.sub.2 CHCH.sub.2 46 Et Et 2-CH.sub.2 CHCH.sub.2 47 Me Me 2-OMe 48 Et Et 2-OMe 49 Me Me 3-OMe 50 Et Et 3-OMe 51 Me Me 4-OMe 52 Et Et 4-OMe 53 Me Me 3-OEt 54 Et Et 3-OEt 55 Me Me 4-OEt 56 Et Et 4-OEt 57 Me Me 2-CF.sub.3 58 Et Et 2-CF.sub.3 59 Me Me 3-CF.sub.3 60 Et Et 3-CF.sub.3 61 Me Me 4-CF.sub.3 62 Et Et 4-CF.sub.3 63 Me Me 2-OCHF.sub.2 64 Et Et 2-OCHF.sub.2 65 Me Me 4-OCHF.sub.2 66 Et Et 4-OCHF.sub.2 67 Me Me 2-OCH.sub.2 CF.sub.3 68 Et Et 2-OCH.sub.2 CF.sub.3 69 Me Me 4-OCH.sub.2 CF.sub.3 70 Et Et 4-OCH.sub.2 CF.sub.3 71 Me Me 2-OCF.sub.2 CFClH 72 Et Et 2-OCF.sub.2 CFClH 73 Me Me 2-C.sub.6 H.sub.5 74 Et Et 2-C.sub.6 H.sub.5 75 Me Me 2-CH.sub.2 C.sub.6 H.sub.5 76 Et Et 2-CH.sub.2 C.sub.6 H.sub.5 77 Me Me 2-OCH.sub.2 C.sub.6 H.sub.5 78 Et Et 2-OCH.sub.2 C.sub.6 H.sub.5 79 Me Me 2-COCH.sub.3 80 Et Et 2-COCH.sub.3 81 Me Me 2-COOMe 82 Et Et 2-COOMe 83 Me Me 4-COOMe 84 Et Et 4-COOMe 85 Me Me 2-CHO 86 Et Et 2-CHO 87 Me Me 2-NO.sub.2 88 Et Et 2-NO.sub.2 89 Me Me 4-NO.sub.2 90 Et Et 4-NO.sub.2 91 Me Me 2-CN 92 Et Et 2-CN 93 Me Me 3-CN 94 Et Et 3-CN 95 Me Me 4-CN 96 Et Et 4-CN 97 Me Me 2-NHCOCH.sub.3 98 Et Et 2-NHCOCH.sub.3 99 Me Me 4-NHCOCH.sub.3100 Et Et 4-NHCOCH.sub.3101 Me Me 2,6-(Me).sub.2102 Me Et 2,6-(Me).sub.2103 Et Et 2,6-(Me).sub.2104 Et nPr 2,6-(Me).sub.2105 Et iPr 2,6-(Me).sub.2106 nPr nPr 2,6-(Me).sub.2107 CH(Me)-(CH.sub.2).sub.3 CH.sub.2 2,6-(Me).sub.2108 Me Me 2,4-(Me).sub.2109 Et Et 2,4-(Me).sub.2110 Me Me 3,4-(Me).sub.2111 Et Et 3,4-(Me).sub.2112 Me Me 3,5-(Me).sub.2113 Et Et 3,5-(Me).sub.2114 Me Me 2,3-(Me).sub.2115 Et Et 2,3-(Me).sub.2116 Me Me 2,6-(Et).sub.2117 Et Et 2,6-(Et).sub.2118 Me Me 2-Me-6-Et119 Et Et 2-Me-6-Et120 Me Me 2-Me-5-iPr121 Et Et 2-Me-5-iPr122 Me Me 2-iPr-5-Me123 Et Et 2-iPr-5-Me124 Me Me 2-Me-4-Cl125 Et Et 2-Me-4-Cl126 Me Me 2-Me-6-Cl127 Et Et 2-Me-6-Cl128 Me Me 3-Me-4-Cl129 Et Et 3-Me-4-Cl130 Me Me 2-Me-4-F131 Et Et 2-Me-4-F132 Me Mer 2,4-F.sub.2133 Et Etr 2,4-F.sub. 2134 Me Me 2,6-F.sub.2135 Et Et 2,6-F.sub.2136 Me Me 2,3-Cl.sub.2137 Et Et 2,3-Cl.sub.2138 Me Me 2,4-Cl.sub.2139 Et Et 2,4-Cl.sub.2140 Me Me 2,5-Cl.sub.2141 Et Et 2,5-Cl.sub.2142 Me Me 2,6-Cl.sub.2143 Et Et 2,6-Cl.sub.2144 Me Me 2-Cl-4-F145 Et Et 2-Cl-4-F146 Me Me 2-Cl-6-F147 Et Et 2-Cl-6-F148 Me Me 4-Cl-2-F139 Et Et 4-Cl-2-F150 Me Me 2-OMe-4-Me151 Et Et 2-OMe-4-Me152 Me Me 2,6-(OMe).sub.2153 Et Et 2,6-(OMe).sub.2154 Me Me 2-F-6-OMe155 Et Et 2-F-6-OMe156 Me Me 3-Cl-5-OMe157 Et Et 3-Cl-5-OMe158 Me Me 2-OMe-4-CHCHCH.sub.3159 Et Et 2-OMe-4-CHCHCH.sub.3160 Me m 2-OMe-4-CH.sub.2 CHCH.sub.2161 Et Et 2-OMe-4-CH.sub.2 CHCH.sub.2162 Me Me 3,5-(CF.sub.3).sub.2163 Et Et 3,5-(CF.sub.3).sub.2164 Me Me 2-Cl-4-CF.sub.3165 Et Et 2-Cl-4-CF.sub.3166 Me Me 2-Cl-5-CF.sub.3167 Et Et 2-Cl-5-CF.sub.3168 Me Me 2-Me-6-COOMe169 Et Et 2-Me-6-COOMe170 Me Me 2-OMe-6-COOMe171 Et Et 2-OMe-6-COOMe172 Me Me 2-Cl-6-COOMe173 Et Et 2-Cl-6-COOMe174 Me Me 2-NO.sub.2 -3-Me175 Et Et 2-NO.sub.2 -3-Me176 Me Me 2-CN-4-F177 Et Et 2-CN-4-F178 Me Me 2-CN-4-Cl179 Et Et 2-CN-4-Cl180 Me Me 2-CN-4-Br181 Et Et 2-CN-4-Br182 Me Me 4-CN-2-F183 Et Et 4-CN-2-F184 Me Me 4-CN-2-Cl185 Et Et 4-CN-2-Cl186 Me Me 4-CN-2-Br187 Et Et 4-CN-2-Br188 Me Me 2,3,5-(Me).sub.3189 Et Et 2,3,5-(Me).sub.3190 Me Me 2,3,6-(Me).sub.3191 Et Et 2,3,6-(Me).sub.3192 Me Me 2,4,6-(Me).sub.3193 Me Et 2,4,6-(Me).sub.3194 Et Et 2,4,6-(Me).sub.3195 Et nPr 2,4,6-(Me).sub.3196 Et iPr 2,4,6-(Me).sub.3197 nPr nPr 2,4,6-(Me).sub.3198 Me Me 2,4-(Me).sub.2 -6-Cl199 Et Et 2,4-(Me).sub.2 -6-Cl200 Me Me 2,6-(Me).sub.2 -4-Cl201 Et Et 2,6-(Me).sub.2 -4-Cl202 Me Me 2,4-Cl.sub.2 -6-Me203 Et Et 2,4-Cl.sub.2 -6-Me204 Me Me 2,6-Cl.sub.2 -4-Me205 Et Et 2,6-Cl.sub.2 -4-Me206 Me Me 2,4-Cl.sub.2 -3-Me207 Et Et 2,4-Cl.sub.2 -3-Me208 Me Me 2,6-Cl.sub.2 -4-CF.sub.3209 Et Et 2,6-Cl.sub.2 -4-CF.sub.3210 Me Me 2,3,4-Cl.sub.3211 Et Et 2,3,4-Cl.sub.3212 Me Me 2,3,6-Cl.sub.3213 Et Et 2,3,6-Cl.sub.3214 Me Me 2,4,5-Cl.sub.3215 Et Et 2,4,5-Cl.sub.3216 Me Me 2,4,6-Cl.sub.3217 Me Et 2,4,6-Cl.sub.3218 Et Et 2,4,6-Cl.sub.3219 Et nPr 2,4,6-Cl.sub.3220 Et iPr 2,4,6-Cl.sub.3221 nPr nPr 2,4,6-Cl.sub.3222 Me Me 3,4,5-(OMe).sub.3223 Et Et 3,4,5-(OMe).sub.3224 Me Me 2,4-Cl.sub.2 -6-COOMe225 Et Et 2,4-Cl.sub.2 -6-COOMe226 Me Me 2-NO.sub.2 -3,5-(Me).sub.2227 Et Et 2-NO.sub.2 -3,5-(Me).sub.2228 Me Me 2,3,5,6-F.sub.4229 Et Et 2,3,5,6-F.sub.4230 Me Me 2,3,4,5,6-F.sub.5231 Et Et 2,3,4,5,6-F.sub.5232 Me Me 2,3,4,5,6-Cl.sub.5233 Et Et 2,3,4,5,6-Cl.sub.5234 Me Me 2,3,4,5,6-(Me).sub.5235 Et Et 2,3,4,5,6-(Me).sub.5__________________________________________________________________________
TABLE 2______________________________________CompoundNo. R.sup.1 R.sup.2 Y.sub.n______________________________________236 Me Me H237 Et Et H238 Me Me 4-Cl239 Et Et 4-Cl240 Me Me 2-Me241 Et Et 2-Me242 Me Me 2-OMe243 Et Et 2-OMe244 Me Me 4-CF.sub.3245 Et Et 4-CF.sub.3246 Me Me 2-OCH.sub.2 CF.sub.3247 Et Et 2-OCH.sub.2 CF.sub.3248 Me Me 2-COCH.sub.3249 Et Et 2-COCH.sub.3250 Me Me 2-CHO251 Et Et 2-CHO252 Me Me 2-COOMe253 Et Et 2-COOMe254 Me Me 2-NO.sub.2255 Et Et 2-NO.sub.2256 Me Me 4-NHCOCH.sub.3257 Et Et 4-NHCOCH.sub.3______________________________________
TABLE 3______________________________________CompoundNo. R.sup.1 R.sup.2 Y.sub.n______________________________________258 Me Me H259 Et Et H260 Me Me 1-Br261 Et Et 1-Br262 Me Me 1-Me263 Et Et 1-Me264 Me Me 1-OMe265 Et Et 1-OMe266 Me Me 1-CF.sub.3267 Et Et 1-CF.sub.3268 Me Me 1-OCH.sub.2 CF.sub.3269 Et Et 1-OCH.sub.2 CF.sub.3270 Me Me 1-COCH.sub.3271 Et Et 1-COCH.sub.3272 Me Me 1-CHO273 Et Et 1-CHO274 Me Me 3-COOMe275 Et Et 3-COOMe276 Me Me 1-NO.sub.2277 Et Et 1-NO.sub.2278 Me Me 3-NHCOCH.sub.3279 Et Et 3-NHCOCH.sub.3______________________________________
TABLE 4______________________________________CompoundNo. R.sup.1 R.sup.2 R.sup.3 R.sup.4______________________________________280 Me Me H H281 Et Et H H282 Me Me Me H283 Et Et Me H284 Me Me Me Me285 Me Et Me Me286 Et Et Me Me287 Et nPr Me Me288 Et iPr Me Me289 nPr nPr Me Me______________________________________
TABLE 5______________________________________CompoundNo. R.sup.1 R.sup.2 R.sup.3 R.sup.4______________________________________290 Me Me H H291 Et Et H H292 Me Me Me H293 Et Et Me H294 Me Me Me Me295 Me Et Me Me296 Et Et Me Me297 Et nPr Me Me298 Et iPr Me Me299 nPr nPr Me Me______________________________________
TABLE 6__________________________________________________________________________CompoundNo. R.sup.1 R.sup.2 X.sub.m__________________________________________________________________________301 Me Me H302 Me Et H303 Et Et H304 Et nPr H305 Et iPr H306 nPr nPr H307 CH(Me)-(CH.sub.2).sub.3 CH.sub.2 H308 CH(Me)-(CH.sub.2).sub.3 CH(Me)- H309 CH(Et)-(CH.sub.2).sub.3 CH.sub.2 H310 Me Me 2-Me311 Et Et 2-Me312 Me Me 3-Me313 Et Et 3-Me314 Me Me 4-Me315 Et Et 4-Me316 CH(Me)-(CH.sub.2).sub.3 CH.sub.2 4-Me317 Me Me 2-Et318 Et Et 2-Et319 Me Me 3-Et320 Et Et 3-Et321 Me Me 4-Et322 Et Et 4-Et323 Me Me 2-iPr324 Et Et 2-iPr325 Me Me 3-iPr326 Et Et 3-iPr327 Me Me 4-iPr328 Et Et 4-iPr329 Me Me 4-tBu330 Et Et 4-tBu331 Me Me 2-F332 Et Et 2-F333 Me Me 3-F334 Et Et 3-F335 Me Me 4-F336 Et Et 4-F337 Me Me 2-Cl338 Et Et 2-Cl339 Me Me 3-Cl340 Et Et 3-Cl341 Me Me 4-Cl342 Et Et 4-Cl343 Me Me 2-Br344 Et Et 2-Br345 Me Me 2-CH.sub.2 CHCH.sub.2346 Et Et 2-CH.sub.2 CHCH.sub.2347 Me Me 2-OMe348 Et Et 2-OMe349 Me Me 3-OMe350 Et Et 3-OMe351 Me Me 4-OMe352 Et Et 4-OMe353 Me Me 3-OEt354 Et Et 3-OEt355 Me Me 4-OEt356 Et Et 4-OEt357 Me Me 2-CF358 Et Et 2-CF.sub.3359 Me Me 3-CF.sub.3360 Et Et 3-CF.sub.3361 Me Me 4-CF.sub.3362 Et Et 4-CF.sub.3363 Me Me 2-OCHF.sub.2364 Et Et 2-OCHF.sub.2365 Me Me 4-OCHF.sub.2366 Et Et 4-OCHF.sub.2367 Me Me 2-OCH.sub.2 CF.sub.3368 Et Et 2-OCH.sub.2 CF.sub.3369 Me Me 4-OCH.sub.2 CF.sub.3370 Et Et 4-OCH.sub.2 CF.sub.3371 Me Me 2-OCF.sub.2 CFClH372 Et Et 2-OCF.sub.2 CFClH373 Me Me 2-C.sub.6 H.sub.5374 Et Et 2-C.sub.6 H.sub. 5375 Me Me 2-CH.sub.2 C.sub.6 H.sub.5376 Et Et 2-CH.sub.2 C.sub.6 H.sub.5377 Me Me 2-OCH.sub.2 C.sub.6 H.sub.5378 Et Et 2-OCH.sub.2 C.sub.6 H.sub.5379 Me Me 2-COCH.sub.3380 Et Et 2-COCH.sub.3381 Me Me 2-COOMe382 Et Et 2-COOMe383 Me Me 4-COOMe384 Et Et 4-COOMe385 Me Me 2-CHO386 Et Et 2-CHO387 Me Me 2-NO.sub.2388 Et Et 2-NO.sub.2389 Me Me 4-NO.sub.2390 Et Et 4-NO.sub.2391 Me Me 2-CN392 Et Et 2-CN393 Me Me 3-CN394 Et Et 3-CN395 Me Me 4-CN396 Et Et 4-CN397 Me Me 2-NHCOCH.sub.3398 Et Et 2-NHCOCH.sub.3399 Me Me 4-NHCOCH.sub.3400 Et Et 4-NHCOCH.sub.3401 Me Me 2,6-(Me).sub.2402 Me Et 2,6-(Me).sub.2403 Et Et 2,6-(Me).sub.2404 Et nPr 2,6-(Me).sub.2405 Et iPr 2,6-(Me).sub.2406 nPr nPr 2,6-(Me).sub.2407 CH(Me)-(CH.sub.2).sub.3 CH.sub.2 2,6-(Me).sub.2408 Me Me 2,4-(Me).sub.2409 Et Et 2,4-(Me).sub.2410 Me Me 3,4-(Me).sub.2411 Et Et 4-(Me).sub.2412 Me Me 3,5-(Me).sub.2413 Et Et 3,5-(Me).sub.2414 Me Me 2,3-(Me).sub.2415 Et Et 2,3-(Me).sub.2416 Me Me 2,6-(Et).sub.2417 Et Et 2,6-(Et).sub.2418 Me Me 2-Me-6-Et419 Et Et 2-Me-6-Et420 Me Me 2-Me-5-iPr421 Et Et 2-Me-5-iPr422 Me Me 2-iPr-5-Me423 Et Et 2-iPr-5-Me424 Me Me 2-Me-4-Cl425 Et Et 2-Me-4-Cl426 Me Me 2-Me-6-Cl427 Et Et 2-Me-6-Cl428 Me Me 3-Me-4-Cl429 Et Et 3-Me-4-Cl430 Me Me 2-Me-4-F431 Et Et 2-Me-4-F432 Me Me 2,4-F.sub.2433 Et Etr 2,4-F.sub.2434 Me Me 2,6-F.sub.2435 Et Et 2,6-F.sub.2436 Me Me 2,3-Cl.sub.2437 Et Et 2,3-Cl.sub.2438 Me Me 2,4-Cl.sub.2439 Et Et 2,4-Cl.sub.2440 Me Me 2,5-Cl.sub.2441 Et Et 2,5-Cl.sub.2442 Me Me 2,6-Cl.sub.2443 Et Et 2,6-Cl.sub.2444 Me Me 2-Cl-4-F445 Et Et 2-Cl-4-F446 Me Me 2-Cl-6-F447 Et Et 2-Cl-6-F448 Me Me 4-Cl-2-F449 Et Et 4-Cl-2-F450 Me Me 2-OMe-4-Me451 Et Et 2-OMe-4-Me452 Me Me 2,6-(OMe).sub.2453 Et Et 2,6-(OMe).sub.2454 Me Me 2-F-6-OMe455 Et Et 2-F-6-OMe456 Me Me 3-Cl-5-OMe457 Et Et 3-Cl-5-OMe458 Me Me 2-OMe-4-CHCHCH.sub.3459 Et Et 2-OMe-4-CHCHCH.sub.3460 Me Me 2-OMe-4-CH.sub.2 CHCH.sub.2461 Et Et 2-OMe-4-CH.sub.2 CHCH.sub.2462 Me Me 3,5-(CF.sub.3).sub.2463 Et Et 3,5-(CF.sub.3).sub.2464 Me Me 2-Cl-4-CF.sub.3465 Et Et 2-Cl-4-CF.sub.3466 Me Me 2-Cl-5-CF.sub.3467 Et Et 2-Cl-5-CF.sub.3468 Me Me 2-Me-6-COOMe469 Et Et 2-Me-6-COOMe470 Me Me 2-OMe-6-COOMe471 Et Et 2-OMe-6-COOMe472 Me Me 2-Cl-6-COOMe473 Et Et 2-Cl-6-COOMe474 Me Me 2-NO.sub.2 -3-Me475 Et Et 2-NO.sub.2 -3-Me476 Me Me 2-CN-4-F477 Et Et 2-CN-4-F478 Me Me 2-CN-4-Cl479 Et Et 2-CN-4-Cl480 Me Me 2-CN-4-Br481 Et Et 2-CN-4-Br482 Me Me 4-CN-2-F483 Et Et 4-CN-2-F484 Me Me 4-CN-2-Cl485 Et Et 4-CN-2-Cl486 Me Me 4-CN-2-Br487 Et Et 4-CN-2-Br488 Me Me 2,3,5-(Me).sub.3489 Et Et 2,3,5-(Me).sub.3490 Me Me 2,3,6-(Me).sub.3491 Et Et 2,3,6-(Me).sub.3492 Me Me 2,4,6-(Me).sub.3493 Me Et 2,4,6-(Me).sub.3494 Et Et 2,4,6-(Me).sub.3495 Et nPr 2,4,6-(Me).sub.3496 Et iPr 2,4,6-(Me).sub.3497 nPr nPr 2,4,6-(Me).sub.3498 Me Me 2,4-(Me).sub.2 -6-Cl499 Et Et 2,4-(Me).sub.2 -6-Cl500 Me Me 2,6-(Me).sub.2 -4-Cl501 Et Et 2,6-(Me).sub.2 -4-Cl502 Me Me 2,4-Cl.sub.2 -6-Me503 Et Et 2,4-Cl.sub.2 -6-Me504 Me Me 2,6-Cl.sub.2 -4-Me505 Et Et 2,6-Cl.sub.2 -4-Me506 Me Me 2,4-Cl.sub.2 -3-Me507 Et Et 2,4-Cl.sub.2 -3-Me508 Me Me 2,6-Cl.sub.2 -4-CF.sub.3509 Et Et 2,6-Cl.sub.2 -4-CF.sub.3510 Me Me 2,3,4-Cl.sub.3511 Et Et 2,3,4-Cl.sub.3512 Me Me 2,3,6-Cl.sub.3513 Et Et 2,3,6-Cl.sub.3514 Me Me 2,4,5-Cl.sub.3515 Et Et 2,4,5-Cl.sub.3516 Me Me 2,4,6-Cl.sub.3517 Me Et 2,4,6-Cl.sub.3518 Et Et 2,4,6-Cl.sub.3519 Et nPr 2,4,6-Cl.sub.3520 Et iPr 2,4,6-Cl.sub.3521 nPr nPr 2,4,6-Cl.sub.3522 Me Me 3,4,5-(OMe).sub.3523 Et Et 3,4,5-(OMe).sub.3524 Me Me 2,4-Cl.sub.2 -6-COOMe525 Et Et 2,4-Cl.sub.2 -6-COOMe526 Me Me 2-NO.sub.2 -3,5-(Me).sub.2527 Et Et 2-NO.sub.2 -3,5-(Me).sub.2528 Me Me 2,3,5,6-F.sub.4529 Et Et 2,3,5,6-F.sub.4530 Me Me 2,3,4,5,6-F.sub.5531 Et Et 2,3,4,5,6-F.sub.5532 Me Me 2,3,4,5,6-Cl.sub.5533 Et Et 2,3,4,5,6-Cl.sub.5534 Me Me 2,3,4,5,6-(Me).sub.5535 Et Et 2,3,4,5,6-(Me).sub.5__________________________________________________________________________
TABLE 7______________________________________CompoundNo. R.sup.1 R.sup.2 Y.sub.n______________________________________536 Me Me H537 Et Et H538 Me Me 4-Cl539 Et Et 4-Cl540 Me Me 2-Me541 Et Et 2-Me542 Me Me 2-OMe543 Et Et 2-OMe544 Me Me 4-CF.sub.3545 Et Et 4-CF.sub.3546 Me Me 2-OCH.sub.2 CF.sub.3547 Et Et 2-OCH.sub.2 CF.sub.3548 Me Me 2-COCH.sub.3549 Et Et 2-COCH.sub.3550 Me Me 2-CHO551 Et Et 2-CHO552 Me Me 2-COOMe553 Et Et 2-COOMe554 Me Me 2-NO.sub.2555 Et Et 2-NO.sub.2556 Me Me 4-NHCOCH.sub.3557 Et Et 4-NHCOCH.sub.3______________________________________
TABLE 8______________________________________CompoundNo. R.sup.1 R.sup.2 Y.sub.n______________________________________558 Me Me H559 Et Et H560 Me Me 1-Br561 Et Et 1-Br562 Me Me 1-Me563 Et Et 1-Me564 Me Me 1-OMe565 Et Et 1-OMe566 Me Me 1-CF.sub.3567 Et Et 1-CF.sub.3568 Me Me 1-OCH.sub.2 CF.sub.3569 Et Et 1-OCH.sub.2 CF.sub.3570 Me Me 1-COCH.sub.3571 Et Et 1-COCH.sub.3572 Me Me 1-CHO573 Et Et 1-CHO574 Me Me 3-COOMe575 Et Et 3-COOMe576 Me Me 1-NO.sub.2577 Et Et 1-NO.sub.2578 Me Me 3-NHCOCH.sub.3579 Et Et 3-NHCOCH.sub.3______________________________________
TABLE 9______________________________________CompoundNo. R.sup.1 R.sup.2 R.sup.3 R.sup.4______________________________________580 Me Me H H581 Et Et H H582 Me Me Me H583 Et Et Me H584 Me Me Me Me585 Me Et Me Me586 Et Et Me Me587 Et nPr Me Me588 Et iPr Me Me589 nPr nPr Me Me______________________________________
TABLE 10______________________________________CompoundNo. R.sup.1 R.sup.2 R.sup.3 R.sup.4______________________________________590 Me Me H H591 Et Et H H592 Me Me Me H593 Et Et Me H594 Me Me Me Me595 Me Et Me Me596 Et Et Me Me597 Et nPr Me Me598 Et iPr Me Me599 nPr nPr Me Me______________________________________
TABLE 11______________________________________CompoundsNo. R.sup.1 R.sup.2 X.sub.p______________________________________600 Me Me 3-CF.sub.3601 Et Et 3-CF.sub.3602 Me Me 4-CF.sub.3603 Et Et 4-CF.sub.3604 Me Me 5-CF.sub.3605 Et Et 5-CF.sub.3606 Me Me 6-CF.sub.3607 Et Et 6-CF.sub.3608 Me Me 3-Cl-4-CF.sub.3609 Et Et 3-Cl-4-CF.sub.3610 Me Me 3-Cl-5-CF.sub.3611 Et Et 3-Cl-5-CF.sub.3612 Me Me 3-Cl-6-CF.sub.3613 Et Et 3-Cl-6-CF.sub.3______________________________________
A method of manufacturing the compound according to the present invention and expressed by general formula (I) will now be described. However, the compounds according to the present invention is not limited to those manufactured by the following methods. ##STR15## in which Z is a halogen atom, and A, l, R.sup.1 and R.sup.2 are the same as in general formula (I).
The compounds according to the present invention and expressed by general formula (I) can be obtained by causing a triazole derivatives expressed by general formula (II) and sulfamoylhalide expressed by general formula (III) to react with each other, preferably in a solvent, in the presence of a base. Although the quantities of the materials are not particularly limited, it is preferable that sulfamoylhalide (III) be 1 to 1.5 equivalents and the base be 1 to 5 equivalents with respect to 1 equivalent of triazole derivative (II).
The reaction temperature may be arbitrarily determined so far as it ranges from the temperature realized by ice cooling to the boiling point of the solvent.
Although the reaction time varies depending upon the conditions, the reactions can usually be completed in 10 minutes to 24 hours.
The solvent may be any one of the following materials selected from the group consisting of aliphatic hydrocarbons such as hexane, heptane, ligroin or petroleum ether; aromatic hydrocarbons such as benzene, toluene or xylene; halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene or dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone or cyclohexanone; nitro compounds such as nitroethane or nitrobenzene; nitriles such as acetonitrile or isobutylonitrile; tertiary amines such as pyridine, triethylamine, N,N-diethylaniline, tributylamine or N-methylmorpholine; acid amides such as N,N-dimethylformamide; and sulfur compounds such as dimethyl sulfoxide or sulforan; and their mixtures.
Examples of a base include organic bases such as pyridine, triethylamine or N,N-dietylaniline; inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium hydride; and alkali metal alkoxides such as sodium methoxide or sodium ethoxide.
Water is added to the solution, in which the reactions have been allowed to take place, and then subjected to normal post-processes such as extraction of the organic solvent, immersion, and the like. If necessary, the products may be purified by recrystallization, silica gel column chromatography or medium-pressure liquid chromatography.
The triazole derivatives expressed by general formula (II) can be manufactured by the following method (1) or (2). However, the triazole derivatives are not limited to that manufactured by the following methods.
(1) If l of the foregoing general formula is 1, ##STR16## in which Z is a halogen atom and A is the same as in general formula (I).
The compounds expressed by general formula (II-1) can be obtained by causing the compounds expressed by general formula (IV) and the compounds expressed by general formula (V) to react with each other in an adequate solvent in the presence of a basic substance. Although the quantities of the materials are not particularly limited, the compound (V) Is preferably 1 to 1.2 equivalents with respect to 1 equivalent of the compound (IV).
The reaction temperature may be arbitrarily determined so far as it ranges from a level realized by ice-cooling to the boiling point of the solvent.
Although the reaction time varies depending upon the conditions, the reactions can usually be completed in 1 hour to 24 hours.
The solvent may be any of the following materials selected from a group consisting of aliphatic hydrocarbons such as hexane, heptane, ligroin or petroleum ether; aromatic hydrocarbons such as benzene, toluene or xylene; halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene or dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methylisobutyl ketone, isophorone or cyclohexanone; nitro compounds such as nitroethane or nitrobenzene; nitriles such as acetonitrile or isobutylonitrile; tertiary amines such as pyridine, triethylamine, N,N-diethylaniline, tributyl amine or N-methylmorpholine; acid amides such as N,N-dimethylformamide; and sulfur compounds such as dimethyl sulfoxide or sulforan; and their mixtures.
Examples of a base include organic bases such as pyridine, triethylamine or N,N-dietylanitine; inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium hydride; and alkali metal alkoxides such as sodium methoxide or sodium ethoxide.
The products (II-1) can be isolated from the mixture of reactants by a usual method and can easily be purified by recrystallization or column chromatography.
(2) If l of the foregoing general formula is 0, the triazole derivatives expressed by general formula (II-2) can be manufactured by the following method A or B. ##STR17## in which A is the same as in general formula (I).
The compounds expressed by general formula (VII) can be obtained by causing the compounds expressed by general formula (VI) and 3-mercapto-1,2,4-triazole to react with each other in an adequate solvent in the presence of a basic substance. Although the quantities of the materials are not particularly limited, 3-mercapto-1,2,4-triazole Is preferably 1 to 1.2 equivalents with respect to 1 equivalent of the compound (VI).
The reaction temperature may be arbitrarily determined so far as it ranges from -20.degree. C. to 100.degree. C.
Although the reaction time varies depending upon the conditions, the reactions can usually be completed in 1 hour to 24 hours.
The basic material may be an inorganic material such as alkaline carbonate or caustic alkali. Although the quantity of the basic material is not particularly limited, the basic material is preferably 1 to 1.5 equivalents with respect to 1 equivalent of the compound (VI).
The products (VII) can be isolated from the mixture of reactants by a usual method and can easily be purified by recrystallization or column chromatography.
The compounds expressed by general formula (II-2) can be obtained by causing the compounds expressed by general formula (VII) to react in an adequate solvent in the presence of an oxidant. Although the quantities of the materials are not particularly limited, the oxidant is preferably 2 to 5 equivalent with respect to 1 equivalent of the compound (VII).
The reaction temperature may be arbitrarily determined so far as it ranges from room temperature to 100.degree. C. Although the reaction time varies depending upon the conditions, the reactions can usually be completed in 30 minutes to 24 hours.
Examples of solvent include: ketones such as acetone; ethers such as tetrahydrofuran, dioxane and diethyl ether; esters such as ethyl acetate; halogenated hydrocarbons such as dichloromethane; aromatic hydrocarbons such as chlorobenzene; or polar solvents such as N,N-dimethylformamide or acetic acid or their mixtures. Further, a mixture system of water and the foregoing solvent may be employed.
Although the quantity of the solvent is not particularly limited, normally the solvent is 5 to 20 times, by wt %, that of the compound (VII) is appropriate.
Examples of oxidant include aromatic peracids such as methachloroperbenzoic acid; aliphatic peracids such as acetyl hydroperoxide; or pertrifluoroacetate and hydrogen peroxide.
The products (II-2) can be isolated from the mixture of reactants by a usual method and can easily be purified by recrystallization or column chromatography. ##STR18## in which W is a halogen atom and A is the same as in general formula (I).
The compounds expressed by general formula (VII) can be obtained by causing the compounds expressed by general formula (VIII) and 3-mercapto-1,2,4-triazole to react with each other in an adequate solvent in the presence of a basic substance. Although the quantities of the materials are not particularly limited, 3-mercapto-1,2,4-triazole is preferably 1 to 1.2 equivalents with respect to 1 equivalent of the compound (VIII).
The reaction temperature may be arbitrarily determined so far as It ranges from a level realized by ice-cooling to the boiling point of the solvent. Although the reaction time varies depending upon the conditions, the reactions can usually be completed in 1 hour to 24 hours.
Examples of solvent may include: ketones such as acetone; ethers such as tetrahydrofuran, dioxane and diethyl ether; esters such as ethyl acetate; halogenated hydrocarbons such as dichloromethane; aromatic hydrocarbons such as chlorobenzene; or polar solvents such as N,N-dimethylformamide or acetic acid or their mixtures. Although the quantity of the solvent is not particularly limited, the quantity of the solvent is preferably 1.05 to 20 times, by wt %, the quantity of the compound (VIII).
Examples of basic materials include: inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium hydride; organic bases such as pyridine, triethylamine or N,N-diethyl aniline; and alkali metal alkoxides such as sodium methoxide or sodium ethoxide.
The products (VII) can be isolated from the mixture of reactants by a usual method and can easily be purified by recrystallization or column chromatography.
The compounds expressed by general formula (II-2) can be manufactured from the compounds expressed by general formula (VII) by a method similar to method A.
[II] FUNGICIDE
The fungicidal compositions according to the present invention contains a sulfamoyltriazole derivative expressed by general formula (I) as an effective component thereof.
When the compounds expressed by general formula (I) is used as the fungicide, they are mixed with a carrier, a diluent or an additive and an adjuvant by a known method while being formed into a formulation which is usually employed as agricultural chemicals, for example, powder material, granules, water-dispersible powder, emulsion, water soluble powder or flowable material. The compound may be mixed or used together with other agricultural chemicals, for example, fungicities, insecticides, miticides, herbicides, plant growth regulators, fertilizers and soil conditioners.
In particular, the mixed use with other fungicides can reduce the dosage of the compound, and therefore save labor. Further, the cooperative operation of the chemicals enlarges the fungicidal spectrum. In addition, the synergetic operation enables an ever greater effect to be obtained.
The carrier and the diluent may be normal solid or liquid carriers.
The solid carrier is exemplified by clay represented by the kaolinite group, montmorillonite group, illite group and polygorskite group. Specifically, it is exemplified by inorganic substances such as pyrophillite, attapulgite, sepeorite, kaolinite, bentonite, vermiculite, mica or talc; other inorganic substances such as gypsum, calcium carbonate, dolomite, diatomaceous earth, magnesium lime, apatite, zeolite, silicic anhydride or synthetic calcium silicate; vegetable organic substances such as soybean meal, tobacco flour, walnut flour, wheat flour, wood flour, starch or crystalline cellulose; synthetic or natural polymers such as coumarone resin, petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol, ketone resin, ester gum, covar gum or dam mar gum; waxes such as carnauba wax or beeswax; and urea.
Examples of adequate liquid carriers include pararline- or naphthene-hydrocarbons such as kerosene, mineral oil, spindle oil or white oil: aromatic hydrocarbons such as xylene, ethyl benzene, cumene or methyl naphthalene; chlorinated hydrocarbons such as trichloroethylene, monochlorobenzene or ortho chlorotoluene; ethers such as dioxane or tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone or isophorone; esters such as ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate or diethyl succinate; alcohols such as methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol or benzyl alcohol; ether alcohols such as ethylene glycol ethyl ether or diethylene glycol butyl ether; polar solvents such as dimethyl formamide or dimethyl sulfoxide; and water.
Further, a surface active agent and another adjuvant may be added to emulsificate, disperse, wet, spread, develop, bond, regulate degradation, stabilize the effective components, improve the fluidity, prevent corrosion and prevent freezing.
The surface active agent may be a nonionic compound, an anion compound, a cation compound or a dipolar compound. A nonionic and/or cation compound is usually employed.
Appropriate nonionic surface active agents include; compounds prepared by polymerizing and adding ethylene oxide to a higher alcohol, such as lauryl alcohol, stearyl alcohol or oleyl alcohol: compounds prepared by polymerizing and adding ethylene oxide to alkyl naphthol such as butyl naphthol or octyl naphthol; compounds prepared by polymerizing and adding ethylene oxide to a higher fatty acid such as palmitic acid, stearic acid or oleic acid; higher fatty acid esters of a polyatomic alcohol such as sorbitan; compounds prepared by polymerizing and adding ethylene oxide to the foregoing higher fatty acid ester; and compounds prepared by block-polymerizing ethylene oxide and propylene oxide.
The preferred cation surface active agents include: alkyl sulfonic ester salts such as sodium lauryl sulfate or oleyl alcohol sulfuric ester amine salt; alkyl sulfonates such as sulfone succinate dioctyl sodium ester or 2-ethyl hexene sodium sulfonate; and aryl sulfonates such as isopropyl naphthalene sodium sulfonate, methylene bisnapthalene sodium sulfonate, lignosulfonic sodium or dodecylbenzene sodium sulfonate.
In order to improve the characteristics of the fungicide and to enhance the effect thereof, polymers or other adjuvants such as casein, gelatin, albumin, glue, alginic soda, carboxylic methyl cellulose, methyl cellulose, hydroxyethyl cellulose or polyvinyl alcohol may be used.
The foregoing carriers and the various adjuvants may be arbitrarily used alone or in the form of a mixture to meet the desired object considering the system of formulation and the specific use.
Although the content of the compound according to the present invention in each of the foregoing prepared chemicals as an effective compound varies depending upon the formulation of the prepared chemicals, the preferred content is usually 0.1 wt % to 99 wt %, more preferably 1 wt % to 80 wt %.
In a water-dispersible powder according to the present invention, the compound serving as an effective component usually comprises 5% to 90% of the mixture with the solid carrier and dispersed wetting agent as a balance. If necessary, a protection colloid agent, an antifoaming agent and the like may be added.
In granule form according to the invention, the compound serving as an effective component usually comprises, for example, 1 wt % to 35 wt % of the mixture with the solid carrier and surface active agent as a balance. The compound serving as the effective component is uniformly mixed with the solid carrier or uniformly secured to or adsorbed in the surface of the solid carrier. The grain size is about 0.2 mm to 1.5 mm.
In an emulsion according to the invention, the compound serving as an effective component usually comprises, for example, 5 wt % to 30 wt % of the mixture with the emulsifier comprise about 5 wt % to 20 wt % and the balance composed of a liquid carrier. If necessary, a spreading agent and rust preventives may be added.
In a flowable material according to the invention, the compound serving as an effective component usually comprises, for example, 5 wt % to 50 wt % of the mixture with the disperse wetting agent comprise 3 wt % to 10 wt % and the balance composed of water. If necessary a protective collide agent, rust preventives and antifoaming agent may be added.
The sulfamoyltriazole derivative according to the present invention can be used as a fungicide in the form of the compound expressed by general formula (I) or in the form of any one of the foregoing formulations.
Although the concentration of the compound according to the present invention cannot be generalized because it varies depending upon the kind of plants to be used on, the application method, the formulation, and the application rate, the compound expressed by general formula (I) may be added by 0.1 ppm to 10,000 ppm to serve as the effective component when the compound is used in foliage treatment, preferably 1 ppm to 500 ppm. In soil treatment use, it may be contained by 10 g/ha to 100,000 g/ha, preferably 200 g/ha to 20,000 g/ha.

[EXAMPLES]
The present invention will now be described by providing examples.
(1) Synthesis of Precursor
Reference Example 1
Preparation of 3-(2,4,6-trimethylphenoxysulfonyl)-1,2,4-triazole
4.1 g of 2,4,6-trimethylphenol was dissolved in 15 ml of dichloromethane, and 4.2 ml of triethylamine was added while stirring the solution. Further, 4.6 g of 3-chlorosulfonyl-1,2,4-triazole was gradually added while being cooled with ice and stirred. Then, the solution was stirred at room temperature for 14 hours. After that, 2N hydrochloric acid was added to separate the components. The organic layer was washed with water, and then it was dried with magnesium sulfate. Then, the solvent was removed by distillation, so that coarse crystals were obtained. The coarse crystals were recrystallized from n-hexane/ethyl acetate, so that 3.0 g of the titled compound was obtained.
Reference Example 2
Preparation of 3-(3,3-dimethyl-2,3-dihydrobenzofuran-5-yl-oxysulfonyl)-1,2,4-triazole
5.4 g of 3,3-dimethyl-5-hydroxy-2,3-dihydrobenzofuran was dissolved in 30 ml of tetrahydrofuran, and then 4.6 ml of triethylamine was added while stirring the solution. Then, 5.0 g of 3-chlorosulfonyl-1,2,4-triazole was gradually added while cooling with ice and stirring the solution. Then, this was stirred for 14 hours. Tetrahydrofuran was evaporated, and 2N hydrochloric acid was added and extracted with ethyl acetate. The organic layer was washed with brine, dried with magnesium sulfate, and the solvent was removed, so that coarse crystals were obtained. This was then recrystallized from n-hexane/ethyl acetate, so that 2.7 g of the titled compound was obtained.
Reference Example 3
Preparation of 3-(2,4-dichloro-3-methylphenoxysulfonyl)-1,2,4-triazole
2.33 g of 2.4-dichloro-3-methylphenol was dissolved in 15 ml of tetrahydrofuran, and 1.84 ml of triethylamine was added while stirring the solution. Then, 2.0 g of 3-chlorosulfonyl-1,2,4-triazole was gradually added while cooling with ice and stirring the solution. Then, the solution was stirred at room temperature for 14 hours. Tetrahydrofuran was removed by distillation at reduced pressure, 2N hydrochloric acid was added, and extracted with ethyl acetate. The organic layer was washed with brine, and dried with magnesium sulfate. Then, the solvent was removed by distillation, so that coarse crystals were obtained. The coarse crystals were recrystallized from n-hexane/ethyl acetate, so that 2.25 g of the titled compound was obtained.
Reference Example 4
Preparation of 3-[4-(trifluoromethyl)phenylthiol-1,2,4-triazole
(A) 62.4 ml of concentrated hydrochloric acid was dissolved in 45 ml of water, and 60 g of p-aminobenzotrifluoride was added. Then, 28.2 g of sodium nitrite dissolved in 60 ml of water was slowly dropped in at 5.degree. C., and the solution was stirred for 30 minutes.
(B) 25.1 g of potassium hydroxide was dissolved in 100 ml of water, and 41.4 g of 3-mercapto-1,2,4-triazole was added.
The solution obtained in the process (B) was heated to 55.degree. C., and the solution obtained in the process (A) was gradually added. Then, the resulting solution was stirred for 40 minutes. Chloroform was added to the reactant solution, and this was stirred for 20 minutes. Then, impurities were removed by filtration, and the chloroform layer was washed with water and brine. The organic layer was dried with magnesium sulfate, evaporated and a residue was purified by silica gel column chromatography. As a result, 47.2 g (yield was 52%) of the titled compound was obtained.
Reference Example 5
Preparation of 3-(4-nitrophenylthio)-1,2,4-triazole
5 g of 3-mercapto-1,2,4-triazole was dissolved in 40 ml of N,N-dimethylformamide, and 2.17 g of sodium hydride (60% in mineral oil) was added at 0.degree. C.. The solution was stirred at the same temperature for one hour, and then 7.78 g of 1-chloro-4-nitrobenzene was added. The solution was stirred at room temperature for one hour, and refluxed for 2 hours. Then, 10% hydrochloric acid was added to the reactant solution, it was extracted with ethyl acetate. The organic layer was washed with brine, dried with magnesium sulfate, and the solvent was evaporated, so that coarse crystals were obtained. The coarse crystals were recrystallized from n-hexane/ethyl acetate, so that 7.72 g of the titled compound was obtained (at a yield of 66%).
Reference Example 6
Preparation of 3-[4-(trifluoromethyl)phenylsulfonyl]-1,2,4-triazole
76.4 g of 3-[4-(trifluoromethyl)phenylthio]-1,2,4-triazole synthesized by a method similar to that employed to prepare the precursor according to Reference Example 4 was dissolved in 400 ml of acetic acid, and 140 g of 30% hydrogen peroxide solution was added. Then, the temperature was gradually raised, and the solution was stirred at 100.degree. C. for three hours. Then, the reactant solution was cooled to room temperature, and a water solution of sodium thiosulfate was added. Then, precipitate was filtered, so that 66.4 g of the titled compound was obtained (at a yield of 77%).
(2) Preparation of Sulfamoyl Triazole Derivative
Example 1
Preparation of 1-dimethylsulfamoyl-3-(3-trifluoromethylphenoxysulfonyl)-1,2,4-triazole (Compound No. 59)
1.0 g of 3-(3-trifluoromethylphenoxysulfonyl)-1,2,4-triazole synthesized by a method similar to that employed to prepare the precursor according to Reference Example 1 was dissolved in 10 ml of acetonitrile. Then, 0.57 g of potassium carbonate was added, and 0.59 g of dimethylsulfamoylchloride was gradually added at room temperature while stirring them. Then, they were refluxed for one hour, and the reactant solution was poured into water and extracted with ethyl acetate. The organic layer was washed with brine and dried with magnesium sulfate, and then the solvent was removed by distillation and the residue was purified by silica gel chromatography. As a result, 1.33 g of the titled compound was obtained.
Example 2
Preparation of 1-dimethylsulfamoyl-3-(4-trifluoromethylphenoxysulfonyl)-1,2,4-triazole (Compound No. 61).
1.0 g of 3-(4-trifluoromethylphenoxysulfonyl)-1,2,4-triazole synthesized by a method similar to that employed to prepare the precursor according to Reference Example 3 was dissolved in 10 ml of acetonitrile. Then, 0.57 g of potassium carbonate anhydride was added, and 0.59 g of dimethylsulfamoyl chloride was gradually added at room temperature while stirring the solution. The solution was then refluxed for one hour, and the reactant solution was poured into water and extracted with ethyl acetate. The organic layer was washed with brine and dried with magnesium sulfate, and then the solvent was removed by distillation and the residue was purified by silica gel chromatography. As a result, 1.18 g of the titled compound was obtained.
Example 3
Preparation of 1-dimethylsulfamoyl-3-(4-chloro-2-methylphenoxysulfonyl)-1,2,4-triazole (Compound No. 124)
0.57 g of 3-(4-chloro-2-methylphenoxysulfonyl)-1,2,4-triazole synthesized by a method similar to that employed to prepare the precursor according to Reference Example 1 was dissolved in 10 ml of acetonitrile, and 0.35 g of potassium carbonate was added, and 0.36 g of dimethylsulfamoylchloride was gradually added at room temperature while stirring the solution. The solution was then refluxed for one hour, and the reactant solution was poured into water and extracted with ethyl acetate. The organic layer was washed with brine and dried with magnesium sulfate. The solvent was removed by distillation, so that coarse crystals were obtained. This was recrystallized from n-hexane/ethyl acetate, so that 0.65 g of the titled compound was obtained.
Example 4
Preparation of 1-dimethylsulfamoyl-3-(2,4,6-trimethylphenoxysulfonyl)-1,2,4-triazole (Compound No. 192)
24.2 g of 3-(2,4,6-trimethylphenoxysulfonyl)-1,2,4-triazole was dissolved in 200 ml of acetonitrile, and 15.0 g of potassium carbonate was added, and 15.6 g of dimethylsulfamoylchloride was gradually added at room temperature while being stirred. Then, the solution was refluxed for one hour, and the reactant solution was poured into water and extracted with ethyl acetate. The organic layer was washed with brine and dried with magnesium sulfate. Then, the solvent was removed by distillation, so that coarse crystals were obtained. The coarse crystals were recrystallized from n-hexane/ethyl acetate, so that 30.94 g of the titled compound was obtained.
Example 5
Preparation of 1-dimethylsulfamoyl-3-(2,4,-dichloro-3-methylphenoxysulfonyl)-1,2,4-triazole (Compound No. 206)
1.0 g of 3-(2,4-dichloro-3-methylphenoxysulfonyl)-1,2,4-triazole synthesized by a method similar to that employed to prepare the precursor according to Reference Example 3 was dissolved in 15 ml of acetonitrile. Then, 0.54 g of potassium carbonate was added, and 0.56 g of dimethylsulfamoylchloride was gradually added at room temperature while being stirred. The solution was then refluxed for one hour, and the reactant solution was added and extracted with ethyl acetate. The organic layer was washed with brine and dried with magnesium sulfate. Then, the solvent was removed by distillation, so that coarse crystals were obtained. The coarse crystals were recrystallized from n-hexane/ethyl acetate, so that 1.05 g of the titled compound was obtained.
Example 6
Preparation of 1-dimethylsulfamoyl-3-(3,3-dimethyl-2,3-dihydrobenzofuran-5-yl-oxysulfonyl)-1,2,4-triazole (Compound No. 294)
1.00 g of 3-(3,3-dimethyl-2,3-dihydrobenzofuran-5-yl-oxysulfonyl)-1,2,4-triazole synthesized by a method similar to that employed to prepare the precursor according to Reference Example 2 was dissolved in 10 ml of acetonitrile. Then, 0.56 g of potassium carbonate was added, and 0.58 g of dimethylsulfamoylchloride was gradually added at room temperature while being stirred. The solution was then refluxed for one hour, and the reactant solution was poured into water and extracted with ethyl acetate. The organic layer was washed with brine and dried with magnesium sulfate, and then the solvent was removed by distillation, so that coarse crystals were obtained. The coarse crystals were recrystallized from n-hexane/ethyl acetate, so that 1.13 g of the titled compound was obtained.
Example 7
Preparation of 1-dimethylsulfamoyl-3-[4-(trifluoromethyl)phenylsulfonyl]-1,2,4-triazole (Compound No. 361)
66.4 g of 3-[4-(trifluoromethyl)phenylsulfonyl]-1,2,4-triazole synthesized by a method similar to that for preparing the precursor according to the Reference Example 6 was dissolved in 500 ml of acetonitrile. Then, 75.0 g of potassium carbonate was added, and 50.6 g of dimethylsulfamoylchloride was gradually added at room temperature while being stirred. The solution was then refluxed for two hours, and the reactant solution was poured into water and extracted with ethyl acetate. The organic layer was washed with brine and dried with magnesium sulfate, and then the solvent was evaporated, so that coarse crystals were obtained. The coarse crystals were recrystallized from n-hexane/ethyl acetate, so that 42.7 g of the titled compound was obtained (the yield was 47%).
The .sup.1 H-NMR peak values and the melting points of the substances according to the Examples and Reference Examples are shown in Table 12.
TABLE 12______________________________________Compound MeltingNo. NMR .delta. (ppm) Solvent CDCl.sub.3 point (.degree.C.)______________________________________ 1 2.99(s, 6H), 7.1.about.7.4(m, 3H) 117.0.about.118.4 23 1.18(s, 3H), 1.20(s, 3H), 3.05(s, 6H) 77.4.about.80.6 3.32(sep, 1H), 7.1.about.7.4(m, 4H), 8.71(s, 1H) 37 3.05(s, 6H), 7.2.about.7.6(m, 4H), 8.69(s, 117.8.about.119.6 1H) 39 3.03(s, 6H), 7.1.about.7.4(m, 4H), 8.65(s, 101.1.about.102.9 1H), 8.01(d, 2H), 8.75(s, 1H) 41 3.03(s, 6H), 7.1.about.7.5(m, 4H), 8.63(s, 139.6.about.141.6 1H) 47 3.02(s, 6H), 3.67(s, 3H), 6.7.about.7.5(m, 148.5.about.151.0 4H), 8.77(s, 1H) 49 2.99(s, 6H), 3.74(s, 3H), 6.6.about.7.1(m, 74.5.about.76.1 4H), 8.59(s, 1H) 59 3.01(s, 6H), 7.3.about.7.6(m, 4H), 8.59(s, Oil 1H) 61 3.01(s, 6H), 7.38, 7.61(ABq, 1H), 8.63 125.8.about.127.5 (s, 1H) 81 3.04(s, 6H), 3.85(s, 3H), 7.26.about.7.96(m, 131.3.about.132.8 4H), 8.67(s, 1H) 83 3.00(s, 66H), 3.87(s, 3H), 7.27, 7.99 127.7.about.130.0 (ABq, 4H), 8.60(s, 1H) 89 3.06(s, 6H), 7.47, 8.20(ABq, 4H), 8.63 139.4.about.141.7 (s, 1H) 91 3.11(s, 6H), 7.44.about.7.79(m, 4H), 8.63(s, 135.2.about.137.6 1H) 93 3.08(s, 6H), 7.50.about.7.68(m, 4H), 8.72(s, 136.9.about.139.6 1H) 95 3.07(s, 6H), 7.43, 7.72(ABq, 4H), 8.70 184.9.about.188.3 (s, 1H)101 2.25(s, 6H), 3.05(s, 6H), 7.03(s, 3H), 100.1.about.101.4 8.63(s, 1H)124 2.23(s, 3H), 3.00(s, 6H), 7.12(s, 2H) 96.0.about.97.3 8.55(s, 1H)136 3.02(s, 6H), 7.1.about.7.6(m, 3H), 8.63(s, 116.7.about.119.3 1H)140 3.06(s, 6H), 7.2.about.7.6(m, 3H), 8.65(s, 128.5.about.130.8 1H)152 3.03(s, 6H), 3.67(s, 6H), 6.3.about.7.2(m, 156.2.about.159.5 3H), 8.61(s, 1H)164 3.07(s, 6H), 7.5.about.7.8(m, 3H), 8.71(s, 109.3.about.110.8 1H)166 3.08(s, 6H), 7.5.about.7.65(m, 2H), 7.80(s, 117.6.about.120.0 1H), 8.72(s, 1H)192 2.22(s, 6H), 2.26(s, 3H), 3.08(s, 6H), 113.4.about.115.7 6.86(bs, 2H), 8.68(s, 1H)198 2.24(s, 3H), 2.34(s, 3H), 3.04(s, 6H), 131.5.about.133.5 8.59(s, 1H)206 2.44(s, 3H), 3.05(s, 6H), 7.28(s, 2H), 149.2.about.151.6 8.63(s, 1H)210 3.06(s, 6H), 7.42(s, 2H), 8.66(s, 1H) 153.6.about.156.4212 3.06(s, 6H), 7.28(s, 2H), 8.64(s, 1H) 140.5.about.142.8216 3.03(s, 6H), 7.33(s, 2H), 8.62(s, 1H) 149.3.about.151.2284 1.34(s, 6H), 3.00(s, 2H), 3.03(s, 6H), 136.7.about.138.7 6.5.about.7.2(m, 3H), 8.59(s, 1H)294 1.27(s, 6H), 3.00(s, 6H), 4.19(s, 2H), 108.4.about.111.0 6.5.about.7.2(m, 3H), 8.58(s, 1H)301 3.05(s, 6H), 7.55.about.7.75(m, 3H), 126.1.about.128.5 8.09.about.8.17(m, 2H), 8.58(s, 1H)310 2.68(s, 3H), 3.07(s, 6H), 7.34(d, 1H), 113.6.about.114.0 7.44(t, 1H), 7.58(dt, 1H), 8.25(dd, 1H), 8.60(s, 1H)312 2.45(s, 3H), 3.05(s, 6H), 7.42.about.7.55(m, 102.1.about.102.4 2H), 7.88.about.7.98(m, 2H), 8.58(s, 1H)314 2.46(s, 3H),3.06(s, 6H), 7.39(d, 2H), 137.6.about.139.6 7.88.about.7.98(m, 2H), 8.58(s, 1H)337 3.04(s, 6H), 7.48.about.7.70(m, 3H), 8.38 133.0.about.134.8 (dd, 1H), 8.62(s, 1H)339 3.07(s, 6H), 7.54(t, 1H), 7.61.about.7.70(m, 1H), 7.97.about.8.06(m, 1H), 8.07.about.8.15 (m, 1H), 8.61(s, 1H)341 3.05(s, 6H), 7.57(d, 2H), 8.06(d, 2H), 122.5.about.124.2 8.60(s, 1H)357 3.03(s, 6H), 7.82.about.7.97(m, 3H), 122.8.about.124.9 8.55.about.8.64(m, 1H), 8.56(s, 1H)359 3.07(s, 6H), 7.77(t, 1H), 7.96(d, 1H), 122.5.about.123.7 8.34(d, 1H), 8.40(s, 1H), 8.61(s, 1H)361 3.07(s, 6H), 7.87(d, 2H), 8.28(d, 2H), 153.6.about.155.6 8.61(s, 1H)363 3.04(s, 6H), 6.50(t, 1H), 7.13.about.7.90(m, 105.8.about.108.0 3H), 8.25(dd, 1H), 8.56(s, 1H)389 2.95(s, 6H), 8.31(d, 2H), 8.48(d, 2H), 189.5.about.192.0 9.46(s, 1H) Solvent DMSO492 2.28(s, 3H), 2.68(s, 6H), 3.02(s, 6H), 181.0.about.185.7 6.90(s, 2H), 8.47(s, 1H)506 2.51(s, 3H), 3.05(s, 6H), 7.50(d, 1H), 148.0.about.152.5 8.11(d, 1H), 8.53(s, 1H)540 3.06(s, 6H), 8.07.about.8.53(m, 2H), 8.55(s, 139.4.about.142.7 1H), 8.88(bs, 1H)610 3.05(s, 6H), 8.09(bs, 1H), 8.57(bs, 1H), 137.5.about.139.5 8.61(s, 1H)______________________________________
Formulation examples of chemicals using the compounds according to the present invention will now be described. The "parts" used below means parts by weight.
Example Chemical 1 (Emulsion)
______________________________________Compound No. 192 10Xylene 45Dodecylbenzenesulfonic acid calcium 7Polyoxy ethylene styrylphenyl ether 13dimethylformamide 25______________________________________
The foregoing materials were uniformly mixed and dissolved, so that 100 parts of emulsion were obtained.
Example Chemical 2 (Water-Dispersible-Powder)
______________________________________Compound No. 361 20Diatomaceous earth 70Lignosulfonic acid calcium 5Naphthalenesulfonic acid formalin condensate 5______________________________________
The foregoing materials were mixed and crushed, so that 100 parts of water-dispersible-powder were obtained.
Example Chemical 3 (Granules)
______________________________________Compound No. 192 5Bentonite 50Talc 42Lignosulfonic acid soda 2Polyoxyethylenealkylaryl ether 1______________________________________
The foregoing materials were mixed sufficiently, and water is added in an adequate quantity as to be kneaded. Then, an extruding granulator was used, so that 100 parts of granule were obtained.
Example Chemical 4 (Flowable Agent)
______________________________________Compound No. 361 30Sulfosuccinate di-2-ethylhexylester sodium salt 2Polyoxyethylenenonylphenylether 3Antifoaming agent 1Propylene glycol 5Water 59______________________________________
The foregoing materials were crushed and uniformly mixed by using a wet-type ball mill, so that 100 parts of flowable agent were obtained.
[Efficiency Test Examples of The Fungicide]
Effects of preventing and curing crop damage obtainable from the fungicide according to the present invention will now be specifically described.
The compound according to the present invention and the fungicide containing same have excellent effects in preventing and curing the following various crop diseases caused from Oomycetes: grape downy mildew (Plasmopara viticola), gourd downy mildew (Pseudoperonospora cubensis), damping-off type disease (Phytophthora melonis), phytophora blight (Phytophthora capsici), late blight (Phytophthora infestans), rape vegetable downy mildew (Peronospora brassicae), Welsh onion downy mildew (Peronospora destructor), spinach downy mildew (Peronospor spinaciae), soybean downy mildew (Peronospora manshurica), broad bean downy mildew (Peronospora viciae), tobacco disease (Phytophthora nicotiana var. nicotiana), potato disease (Phytophthora infestaris), hop disease (Pseudoperonospora humuli), pineapple disease (Phytophthora cinnamomi), green pepper disease (Phytophthora capsici), strawberry root rot (Phytophthora fragarie) and various damping-off type diseases (caused from Pythium group germs).
The results of the following tests were evaluated in such a manner that the degree of crop damages were examined in accordance with the following reference seven days after the inoculation of disease-causing germs and the severity and the preventive value were obtained by the following equations.
______________________________________Evaluation Degree of Disease______________________________________Excellent No disease foundGood Lesion area was less than 1/3Allowable Lesion area was 1/3 to less than 2/3No Good Disease area was 2/3 or more______________________________________ ##STR19##- where
n.sup.0 : No of leaves in which the degree of disease was Excellent
n.sup.1 : No of leaves in which the degree of disease was Good.
n.sup.2 : No of leaves in which the degree of disease was Allowable
n.sup.3 : No of leaves in which the degree of disease was No Good.
N: n.sup.0 +n.sup.1 +n.sup.2 +n.sup.3 ##EQU1##
The test results were evaluated in accordance with the following criteria.
______________________________________Criteria______________________________________A: Preventive value was 95% or higherB: Preventive value was 80% to lower than 95%C: Preventive value was 50% to lower than 80%D: Preventive value was lower than 50%______________________________________
Test Example 1
Test to evaluate the effect of preventing cucumber downy mildew
Five seeds of cucumber (variety: Sagami Hanshiro) were seeded in vinyl chloride pots each having a diameter of 9 cm and cultivated in a greenhouse for seven days. The water-dispersible powder according to Example Chemical 2 was diluted with water to obtain a concentration of effective component of 200 ppm, 10 ml of this was sprayed on each seedling of cucumbers having spread cotyledons. One day after spraying, a globule suspension of cucumber downy mildew (Pseudoperonospora cubensis) was inoculated by atomization. The seedlings were allowed to stand in a wet room at 20.degree. C. for one day. Then, the seedlings were transferred and Brown in a greenhouse so as to observe the degree of disease. The results of the evaluations are shown in Table 13.
TABLE 13______________________________________Compound No. Grade Compound No. Grade______________________________________ 1 A 301 A 37 A 310 A 41 B 312 A 49 A 314 A 59 A 337 A 61 A 339 A 83 B 341 A 89 B 357 A101 A 359 A124 A 361 A192 A 363 B206 A 389 D216 A 492 C284 B 502 D294 A 610 B______________________________________
Test Example 2
Test to evaluate the effect of preventing potato disease
The water-dispersible powder according to Example Chemical 2 was diluted with water to obtain a concentration of effective component of 200 ppm and 10 ml of this was sprayed on each leaf of the potatoes (variety: Meikuin). One day after spraying, a globule suspension of potato disease (Phytophthora infestans) was inoculated by atomization. The seedlings were allowed to stand in a wet room at 17.degree. C. for one day. Then, the seedlings were transferred and grown in a greenhouse so as to observe the degree of disease. The results of the evaluations are shown in Table 14.
TABLE 14______________________________________Compounds No. Evaluation______________________________________ 61 A206 A______________________________________
(Effect of the Invention)
The compound expressed by general formula (I) is characterized by a structure in which the specific aryl group is bonded to the 1-sulfamoyl-1,2,4-triazole ring while interposing the sulfonyl group. The characterized structure is considered to cause the sulfamoyltriazole derivative to exhibit the excellent fungicidal performance.

Sulfamoyltriazole derivatives of fungicidal composition containing same as effective component thereof

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