CA1340326C - Pyrazolesulfonylurea derivative, preparation therof, herbicide containing said derivative as active ingredient and herbicidal method by use thereof - Google Patents

Abstract

Disclosed is a novel pyrazolesulfonylurea derivative represented by the formula (I), preparation thereof, a herbicide containing said derivative as an active ingredient and a herbicidal method by use thereof.

Description

f' 1340326 Pyrazolesulfonylurea derivative, preparation thereof, herbicide containing said derivative as active ingredient and herbicidal method by use thereof This invention relates to a novel pyrazolesulfonylurea derivative represented by the formula (I), preparation thereof, a herbicide containing said derivative as an active ingredient and a herbicidal method by use thereof.
B

IN ~ X

A ~ SO2NHC~ Z (I) C D N ~
y wherein A represents a hydrogen atom, a Cl-C8 alkyl group or a phenyl group which may be substituted with Cl-C8 alkyl groups, halogen atoms or nitro groups; B
and C represent independently hydrogen atoms, halogen atoms, nitro groups, Cl-C8 alkyl groups, arylalkyl groups, Cl-C~ alkox~ groups, haloalkyl groups, -C02R
(where R is a hydrogen atom, a Cl-C8 alkyl group, an allyl group or a propargyl group), -CONRlR~ lwhere R
is a hydrogen atom, a Cl-C8 alkyl group or a phenyl group, R2 is a hydrogen atom or a Cl-C8 alkyl group, or Rl and R2 taken together may represent -(CH2)m- (_ is 4, 5 or 6), -CH2CH2OCH2CH2- or -CH2CH2N(CH3)CH2CH2-], -S(O)nR3( where R3 is a Cl-C8 alkyl group, a phenyl 1~ ~

, 13~032~

group or an arylalkyl group and n is 0, 1 or 2), -SO2NR4R5 [where R4 is a Cl-C8 alkyl group, R5 is a hydrogen atom or a Cl-C8 alkyl group, or R4 and R5 taken together may represent -(CH2)p- (p is 4, 5 or 6), CH OCH C~2- or -cH2cH2N(cH3)cH2cH2 group which may be substituted with Cl-C8 alkyl groups, halogen atoms or nitro groups; D represents a hydrogen atom or a Cl-C8 ~lkyl group; X and Y represent independently hydrogen atoms, halogen atoms, Cl-C8 alkyl groups, Cl-C8 alkoxy groups, Cl-C8 a~ko~xyalkyl groups, -CF3 groups, Cl-C8 h'aloàlkoxy groups, alkylamino groups, dialkylamino groups, -OCHC02R~ (where R6 and R7 each represent hydrogen ~ atoms or Cl-C8 alkyl groups) or either X or Y may form a five-membered ring containing an oxygen atom together with Z; and Z represents a nitrogen atom or C-R8 (where R8 represents a hydrogen atom, a haloalkyl group or may form a five-membered ring containing an oxygen atom together with X or Y).

The compounds of this invention are novel compounds not disclosed in literature and have excellent herbicidal activities.

Japanese Unexamined Patent Publication Nos.102577/1980 and 139466/1981 disclose pyridinesulfonylurea derivatives and Japanese Unexamined Patent Publication No.169688/1981 discloses pyrolesulfonylurea derivatives, respectively, as useful herbicides.
Heretofore, in using herbicides, it has been pointed out that the economical cost involved in the use of a herbicide depends on the application amount of the active ingredient per unit area. For this reason, studies have been continued for many years to obtain ~;r 1~40326 compounds which can exhibit high herbicidal effects at lower application rate.

In the prior art, as pyrazole derivatives, there have been known a large number of compounds, as disclosed in Japanese Patent Publication No.36648/1979 and Japanese Unexamined Patent Publication Nos.41872/1979, 2276/1982, 58670/1982 and 133265/1976.

The present inventors have made various investigations for many years and consequently found that the compounds of this invention have markedly high herbicidal effects as compared with the above pyrazole derivatives known in the art and are practically - useful. On the other hand, as sulfonylurea derivatives containing a nitrogen-containing heterocyclic ring, the aforementioned pyrolesulfonylurea and pyridinesulfonyl-urea are known. As compared with these known compounds, the compounds of this invention have been found to exhibit markedly higher herbicidal effects.
The present invention has been accomplished on the basis of these findings.

That is, the compounds of this invention may be said to be epoch-making herbicides capable of decreasing markedly the amount of the active ingredient applied per unit area as compared with these compounds known in the art, having a very great economical effect as compared with the herbicides of the prior art, and also capable of alleviating markedly the environmental pollution which may be caused by application of a large amount of pesticides.

Typical examples of the derivatives represented by the above formula (I) suitable for use as herbicides may include those as shown in Table 1, Table 2 and Table 3 set forth below.

13gO326 The Compounds Nos. in these Tables are referred to in the following description.

Table 1 O N

C

Comp. A B C ~ Y Z
No .

CH3 CH3 CH3 ~ CH3 O CH3 N

6 ~ CH3 CH3 CH3 H CH

7 (~ CH3 CH3 CH3 CH3 CH

8 ~ CH3 CH3 CH3 O CH3 CH

9 ~ CH3 CH, O CH3 OCH3 CH

1 0 ~ CH3 CH~ CHI OCH3 N

l340326 -No. A B C X Y Z
1 1 ~ CH3 CH3 OCH3 OCH8 N

1 2 CH3 ~ CH3 CH3 CH3 ~H

13 CH3 ~ CTH3 CH3 o CH3 CH

1 4 CH3 ~ CH3 OCH3 0 CH3 CH

1 5 CH3 ~ CH3 CH3 OC~3 N

1 6 CH3 ~ CH3 ~CH3 OC-~3 N

1 7 CH3 ~ CH3 CH3 CHs N

18 CH3 ~ CH3 C ~3 C ~ CH

1 9 C .~ s ~) C L~ 3 C ~ 8 C ~ C (C~2C~

CH3 <~ C7~3 CH3 -OCH2C'~3 C

21 CH3 ~ CH3 C~ N (CH3)2! N

22 CH3 ~> C7L~3 ~CH3N (CH3)2 N

2 3 CH3 ~>- CH3 CHS CH, CH3 CH

2 4 CHt ~ C~3 Cr~3 . CH; O CH3 CH

CH3 ~CH3 CH3 CH3 ~5H3 N

13~0~26 Comp. A B C ~r, y Z

2 6 CH3 ~C~Hs CH3 CH3 0C-~3 CH

2 7 5H3 ~C2Hs CH3 C 'd ~ O CH3 N

28 CH3 ~ CH3 CH3 CH3 CH

2 9 C-~3 _~ H3 5-;~ CH3 .O CH3 CH

3 0 CH3 ~ C-dt ~3 O CH3 -N

31 C'~3 ~) C-~3 CH3 C~9 CH

32 CH~ CH3 CH3 3C-~3 CH
C~3 3 3 CHs ~ CH~ CH3 ~ Cld3 3 4 CHt 4~C~ crdt C~d3 ~ C-dy C H

3 5 CH:~ ~Cf~ CH3 C~3 OCH3 N

3 6 CH C ~~ CH3 C-L~3 OCH3 CH

3 7 CH~ C ~ CH3 CE~3 O CH~ N

3 8 CH3 ~NO2 CH3 C-.~3 3 Cd3 CH

3 9 CH3 ~NO2 CH3 C~3 OC~I3 1340~26 Comp. A B C ~ Y Z

4 o CH3 ~ H CH3 CH3 CH
41 CH3 ~ ~ CH3 O CEI3 CTrl 4 2 CH3 ~) H CH3 O ''H~ N
4 3 CH3 CH3 (~ CH3 CH3 - C H
4 4 CH3 cr~3 ~ c-~3 O CH3 CH
4 5 CH3 CH3 ~ OCH3 OCH3 CH
4 6 CH3 CH3 ~ CH3 ~ CH3 N
4 7 CH~ CH3 ~ O CH3 O CH3 N
4 8 H ~> -CH3 CH3 CH3 CH
4 9 T~ CH3 C-~3 O ~H3 CH

5 0 H ~> CH3 CH3 OCH~, N
5 1 -CH3 CH3 ~ CH3 CHl 5H3 CH

5 2 -CH2 CH3 ~ CH3 CH3 O CH3 CH
53 -CH2 CH3 ~> CH3 CH3 OCH3 N
54 -CH,CH2CH3 ~ CH3 CH3 CH3 CE~
-CH~,CEI2CH3 ~> CH9 Cl~3 OCH3 CH

.

Comp. A B C ~: Y Z
No .
5 6- CH~ CH2 CH3 ~ CH3 c-~3 O CH3 N

5 7 <~ ~ CH3 CH9 ;CH~ CH

5 8 ~ ~ CH3 CH3 OCH3 CH

59 ~ ~ CH3 CH3 ~ CH3 6 0 CH3 ~ <~ CH3 CH3 ~ CH

61 CH5 ~ ~> CH3 ~ CTc~3 CH

6 2 CH3 ~ ~> CH8 ~ C;~3 N

6 3 H ~ ~ C~J9 CH3 CH

64 E~ O ~ . Ci~3 OCH3 C

H ~ ~ CH3 OCH3 N

6 6 CH5 ~ (~CH3 c~-~3 CH3 CH

6 7 CH3 ~ (3 CH3 CH3 ~ CH 3 CH

68 CH.J ~ OCH3 OCH3 OCH3 CH

- 6 9 CH3 (~ OCH3 OCH2CH3 OCH2CH3 CH

7 0 CH3 ~ O C~d3 CH3 O CH3 71 CH3 ~ OCTl-I3OCHa OCH3 N

134032fi Comp.A B C X Y Z
7 2C H3 ~ O CHJ CH3 CH3 N

7 3CH5 ~> O CH3 CH3 C~ C (CH2)~

7 4CH3 ~ oCH3 CEI3 -OCH2 CEl3C -75 CH3 <~) OCH3 OCH3 N(CH3)3 N

76 CH3 ~CH~ OCH~ CH3 CH3 CH

7 7CH3 _~CH3 ~ CH3 CH3 O CH3 CH

7 8C H5 ~CH3 ~ CH3 CH3 O CH3 N

7 9CH3 _~C~ o CH3 CH3 CH3 CH

8 oCH3 ~C~ OC-H3 CH3 OCH3 CH

81 CH3 ~C~ OCH3 CH3 OCH3 N

8 2CH3 _~N 3 O CH3 CEI3 CH3 CH

8 3C~3 _~5N~3 o CH3 CH3 ~ ~H3 CH

8 4CH3 _~NO2 OCH3 CH3 OCH~ ~

8 5CH3 CH3 C~ CH, CH3 CH

8 6CH3 CH3 'C~ CH~ o CH3 CH

134032~

Comp. A B C X Y Z
8 7 CH3 CH3 C~ o CHa ~ CEI3 CH
88 CH3 CH3 C~ CH3 OCH5 8 9 CH3 CHg C~ O CH3 O CH3 N

9 o CH3 CH3 C~ CH3 C'~ID N
9 1 C~3 CH3 C~ CH3 C~C(CH2)~C~
. .
9 2 C-H3 CH3 c,e: c-~3-OCH 2 CHa C -9 3 C~3 CH3 C~ OCH3 N(CH3)2 N

9 4 CE~3 CH3 .C~ CH2C~13 OCH3 CH

9 5 CE~3 CTn3 C~ CH3 CH2OCH3 CH

9 6 CH3 ~H3 C~ CH3OCH3CO.~CH3 CH

9 7 CH3 ~ C~ CH3 CH3 C'~

9 8 C~3 ~ C~ C H3 O CH3 CH

9 9 CH3 ~ O CH3 O CH3 CH

1 00 CH3 ~ C~ CH3 OCH3 N
__ 1 01 CH3 (~ CC oCE~3 OCH3 N

10 2 C H3 ~H3l CH, CH3 CH

- ll 13~0326 Col~p.
No. A B C ~r~ y I Z
1 0 3 CH3 ~ CH3 C~ CH3 _ _ 1 04 CH3 ~ CH3 C~ CH5 OCHs N

10 5 CT~3 CH3 Br CH3 CH3 CH

1 0 6 CH3 Cr~3 Br CE~3 ~ CH3 , CH

1 0 7 CH3 CH3 Br O CH3 O CH3 CH

10 8 cr~3 CH" Br c-~3 O CH3 N

10 9 CH3 CHy Br OCH3 OCH3 N

1 1 ~ CH3 H C4~ CH3 CH3 I CH

1 1 1 CH3 H C~ cr-~3 OCH3 CH

1 1 2 CH3 H C~ O CH3 OCHg CH

1 1 3 CH3 H C~ crd3 OCH3 N

1 1 4 CH3 H C~ OCH~ OCH~ N
. _ _ 1 1 5 CH~CH~ CH3 C~ CH3 ICH3 Crd 1 1 6 cr-~CH 2 CH3 C~ c-n3 OCH3 lCH

1 1 7 CHsCH2 CH3 C~ CHs OCH3 N

1 18 CH3CrlaCH2CHg C~ CH3 CH3 CH
-. . _ 134032~

NoP A B C X Y Z

1 1 9CH3 CH2CH3CH3 CC CHg OCH3 CH

1 2 ~cr~3 CH2 CH2cH3 C~ CH3 ~ CH3 CH

12 1 CE3 CH (CH3)2 C~ CH3 CE~3 CH

1 2 2CT.~,3CH (CH3) 2 C~ CH3 O CH3 CII

1 23 CH3 CH (CH3)2 C~ C-~3 OCH3 CH

12 4 H CH3 C~ CH3 CH3 CH

1 2 5 ~ CH3 C~ C~3 O CEI3 CH

12 6 H CH3 C~ C-~3 OCH3 N

12 7 ~3 CE33 , C~ CH3 CE~3 5H

1 28 ~) CH3 i-~ CH3 OCH8 CH

129 ~ CH3 C~ CH3 OCH3 N

1 3 0~-~3 CH3 -~> CH3 CH3 I CH3 CH

131 c-~3 CHz ~ CH3 CH3 OCH3 CE~

1 32 CHl CHz ~ CH3 OCH3 oc~3 cTd 1 3 3C~3 CH ~ ~ CH3 CH3 1OCld8 N

13 4 C-~3 CH2 -~ CH3 OCH3 OC.-~I" N

134032fi Comp .
No A B C X Y Z

135 CH3 CH3 CH2~ CH3 CH3 CH

136 CH5 CH3 CH ~ CH3 OCH3 CH

139 C~3 CF3 C~d3 CH3 OCH3 CH

140 Cld3CF3 CH3 OCH3 OCH3 CH

144 CH3 CF" CH3 CH3 C~ N

145 C.~3CF3 C H3 CH3 C~ C(CH2)2C~

147 CH3 CF3 C~d3 C~ N(CH3)2 N

148 CH3 CF3 CH3 OCH3 N(CH3)2 N

149 C'd3CF3 CH3 OCH~CHa NHCH3 150 CH3 CF3 ' CH3 CH3 , C~ CH
._ ,_ , Comp. A B C I ~ Y

1 5 1 CH8 CF3 CHs CC C~ CH

1 52 H CF3 CH3 CH8 C~-d3 CH

153 H CF3 CH3 CHt OCH3 CH

1 5 4 H C~3 C-~3 C~3 OCH3 N

1 55 O CF3 CTd3 Cf~3 CH3 CH

15 6 ~ CF3 CH3 CTL~3 OCH3 CH

1 5 7 ~ CF~ crd3 c--~3 OCH3 N

. 1 58 CH3C02 CH~ CH3 CH3 CH3 CH

1 59 CLI3CO2 C~IJ crd3 CH3 OCH3 CH

1 6 0 CH3CO2 CH3 CHa OCH3 OCH3 CH

1 61 CH3CO~ CH" CH3 CH3 OCH3 N

1 62 CH3C02 CH3 CH,sOC-~3 OCH3 N

1 6 4 CH3CO2 C~3 C~3 CH3 C~ N

16 5 CH3CO~ CH3 CT.~3CH3 C~ C(CH2)2C~

16 6 CH3CO~ CH3 CH3 CH3 -OCHy C H2C-, No. A B C X Y ' Z
1 6 7 CH3 CO~ CH3 CH3 C~ N(CTd3)~ ~J
1 6 8 CH3 C~2 CH3 CH3 0 CH3 N(CH3) 2 N
1 6 9 CH3 CO2 CH3 CH3 C~ CH3 5H
1 70 CH3 CO2 CH, CH3 CH3 OCH2 CH3 CH
1 71 CH3 C~2 CH3 CH3 lCH3 OCH2CH3 N
1 72 CH3 C02 CE~3 CH3 Cd3 NHCH3 N
17 3 CH3 CO, CH 3 CE~3 CH3 H CH
1 74 CH3 CO2 CH 3 CH3 H H ~ CH
1 75 CE~ C02 CEI~ CH3 C~ C~ . CH
1 76 CH3 C;32CH2CH3 CH3 CH3 CHd ' CH
1 77 CH3 CO25E32CTd3 CT~3 CH3 OCH3 CH
1 78 CH3 CO2C-d2CH3 CH3 OCEI3 OCE~3 : CH
17 ~ CH3 CO2C-d2CH3 ! CH3 CH3 ,O CH3 1 81 CH3 CO2CH2CH3 CH, CH3 CH3 ~, N
182 CH3 CO2C~H, -~ CH3 I CH3 CH, CH

13~0326 ._ .

Comp. A B I C ~ Y Z
No.
183 c-~3 c03C3Hr~~ CH3 CHa OCH3 CH

184 CTd~ C02 C3H7-ll CH3 OCH3 O CH3 CH

185 CH3 CO~ C3H7-n CH3 CH~ OCH3 N

186 CH3 CO, C3H7 -n CH8 o r~-~3 OC--~3 N

187 CH3 CO2 C3H7-i CH8 C-~3 CH3 CH

188 CH3 CO, C3H8-i CH3 c-~3 OCH3 CH

189 CH3 CO3 C3H7-i CH8 OC;~3 OCH3 CH

190 CH3 CO2 C3H7-i CH3 CH3 OCH3 N

191 C-d3 CO2 C3H7-i CH3 O''H3 OCH3 N

192 CH3 COiCH2CH=CH2 CH8 CH3 CH3 CH

193 CH8 CO2 CH2 CH=CH3 CH3 CH3 O CH3 C H

194 CE~ CO.~CH2CE~CH2 CH3 O CHl OCH3 CH

195 ~ CH3 CO2CH2CH=CH2 C-d3 CH3 OCH3 N

196 CH3 C4CHaCH=CH2 CH3 OCH3 OCH3 N

197 CH, CO,CH2 C--CH C-d3 ! CH

198 CH" CO2CH2C-- CH CH3 CH3 CH3 CH

- 17 - 1340~26 Comp. A ~ C g Y~;
No .
1 9 9 CH3 CO;~CH2C--CH CH3 CH3 OCH3 N

2 00 c-~3 C32H CH3 CH3 CH3 CH

2 0 2 CH3 CO2H CH3 O CH3 .O CH3 CH

2 03 CH3 CO2H CH3 CH3 OCH3 '~-20 5 H CO2 CH3 C-~3 CH3 CH3 CH

2 0 6 H CO2 CH3 CH3 CT.~3 OCH3 CH

2 0 8 H CO2 CH3 CH" CH3 ~ CH3 N

20 9 H CO~ CH3 CHl OCH3 OCH3 N

2 10CHa CH3 C~2 CH3 C-H, c-~3 CH3 CH

21 1CH2 CH3 CO2 CH3 C-.I3 CH3 OCH3 CH

212 CH2 CH3 CO~ CH3 CH3 CH3 OCH3 N

213CH2CH2CH3 C~2 CH3 C~3 CH3 CH3 CH

214CH2CH2CH3 CO2 CH3 I CH~s CH3 OCH3 CH

1340~2fi Comp. A ~ C ~ Y Z

215 CH2CH~ CH3 CO1CH3 CH3 CH3 OC~3 N
216 CH(CH3 )aC02C-'~3 C~3 CH3 C~3 C~

217 CH(CH8 )~CO2CH3 CH3 C.I3 OCHS CT

218 CH(CH3 )2 CO~5H3 CH3 CH3 OCH3 N

219 ~CO2CH3 Cr~3 ''CH3 CH3 C~

220 ~i CO2CH3 CH3 ' CE3 OCH3 CH

221 ~ C32CH3 CH3 , OCH3 OCH3 CE

222 ~, CO2CH3 CH3 CH3 OCH3 N

223 ~CO,CH3 CE3 OCE3 OCH3 N

225 CH3CO2CE3 H CE~ OCH3 CH

226 CH3CO2 CH3 H . CH3 O CH3 N

227 CH3C ~2 CH3 CH,CH3 CH3 I CH3 CH

230 ~ CH3I CO~CH3 CH(CH3)1 CH3 CH3 CH
-No. A B C ~ y z 231 CH3 Coa CH3 CH(CH3)2 CH3OCH3 CH
232 C~3 C02 CH3 CH(CH3)2 OCH3OCH3 CH
233 c~3 C~8 CH3 CH(CH3)2 CH3OCH3 N
234 CH3 COq CH3 CH(CH3)2 OCH3OCH3 N
235 CH,~ C02 CH3 C(CH3)3 CH3 CH8 CH
236 CH3 Coa CH3 C(CH3)3 C~3OCH3 CH
237 CH3 CO, CH3 C(CH3)3 CH3,OCH3 N
238 CH3 CoN(cH3)2 c-~3 CH3; CH3 CH
239 CH3 CoN(cH3)2 CH3 C-~3OCH3 "Çl 240 CH3 CON(CH3)2 CH3 OCH3OCH3 CH
241C1-~3 CON(CH3)2 CE~3 5T,~3OCH3 N
242C .I3 CO N( CH~)2CT~3 O CH3O CH3 N
243C-.I3 CON(C2H5)2 c-~3 CT,~3CH3 CH
244 CH3 CO~(C3H6)2 CH3 CH3OCH2 CH
245 CH~ CON(C2r'~5), CH3OCH3 OCH3 CH
246 CH~ CON(C.Hl)2CH,, CH3OCH3 N

- 134û326 Comp. A ' B C ~ y Z
No.
247 CH3 CON(C2H6)a C33OCEI3 OCEI3 N

248 CH3 CON ~CH~ CH3 CH3 CH3 CH

249 CH3 CON ~ CH3 CH3 C-d3 OCH3 CH

250 CH3 CON C~3 CH3 CH3 OCH3 N

251 CH3 CONHCH3 C~3 C~3 CH3 CH

252 CH3 CONE~CH3 CH3 CEI3 OCH3 CH

254 CH3 CONHC2H,, ~ CH~ CH9 .CH3 CH

255 CHg CONHC2H5 CH3 CH3 OCH3 CH

256 C~3 CONH C2 H5 C-~3 5rd3 OCH3 N

257 CH3 CON~ 3 CH3 CH3 CH3 CH

258 CH3 CON~ CHi3 CH3 OCH3 ~ CH

25 ~ CH3 CON~ CH3 CH3 OCH3, N

260 I CH3 C O~ CH3 ! CH3 CH3 CH

134032~

_No . _ _ __ _ _ ._ __ 261 CH3 C02 CH3 ~ CH3 OCH3 C~

262 CH3 COy CH3 ~ OCHa OCH3 CH

263 CH3 COy CH3 ~ CHg OCH3 N

264 cr~3 CO~ CH3 ~ OCH3 OCH3 265 CHI COz CH3 ~CH3 CH3 OCH3 CH

266 CH3 CO, CH3 ~CH3 5H3 OCH3 N

267 C-da COz CH3 ~-C2H6, CH3 OCH3 CH

268 CH3 C02 CH3 ~CzH6 CH3 OCH3 N

269 CH3 C~2 CH3 ~) CH3 OCH3 CH

270 C-13 CO, CH3 C~ CH3 OCEI3 :~

271 "H3 C03 C~3 ~ C~ Cr~3 C H3 CH

272 CH3 C~3 CH~ ~ C~ CH3 OCH3 CH

273 CX3 C~a CH3 ~-c,e,CEI3 ,05H3 N
. _....................... C~
274 CH3 C02 CH3 _~ CX3 ,C H3 CH

Comp- A B C X Y Z
_No . -C~.~
2 75 CH3 COaCH3 C~ CH3 OCH3 CH

2 7 6 CH3 CO~ C~,~) CH3 0 C~3 N
NOa 2 7 7 CE3 CO3 CH3 ~ CH3 CH3 "H

2 7 8 CH3 CO2 CH3~5N(~ CH3 ~ CH3 CH
NO.~
27 9 CH3 CO2CH3 ~ CH3 OCH3 280 H CO2CH3 ~ CH3 CH3 CH

2 81 H CO2CH3 ~ CH3 OCE~3 CH

282 H CO2CH3 <~) CH3 O_E~3 N

28 4 CH3 CO2CH3OCE33 CT~3 OCH3 CH

286 C~L~3 CO2CH3OC;I3 CH3 OCH3 287 CH3 CO2CH3OCH~ OCH3 OCH3 N

288 C~3 CO2CH3OCHaCH3 CH, CH3 CE

289 C~3 CO,CH3OCH2CH3 CH3 OCH3 CH

- 23 - 1340~26 Comp. A B C ~ Y
No . __ 2 9 0 CH3CO2CH3OCHa CH3 CH3 o c-~3 N

2 93 C'H3 CH3 OCE~3 OCH3 OCH3 CH

295 c~3 CH3 OCr~3 OC-~3 05H3 N

29 6 Cr.~3CH3 OCH3 CH3 CH3 N

297 CH3 cr~i3 OCH3 OCH3 N(CH3)2 N

29 8 Cr~3 CH3 ~C-~3 CH3 c~3 CH

30 0 CH3 Cr~3 OCH3 OCH305H2 C~3 N

302 CH3 CH3 OCH2 CH3 CH3 o5H3 CE~

303 C~3 CH3 O''H2CH3 CH3 OCH3 N

3 0 4 CH3 CH3 H CH3 C'~3 CH

3 0 5 CH3 CH3 ! H CH3 OCrc~3 CH

-Comp. A B C ~ Y Z

307 CH3 CH3 H CH3 ~CH3 309 CH3 CH3 H Crd3CH a N

311 CH3CH~CH3 H CH3OCH~ Cd 312 CH3CH2CH3 H C~3OCH3 313 C~3C~d ( CH3)2 H CH3C r~3 CH

314 C~3CH( Cr~I3)2 H C~3O~H3 C~

315 CH3CH(CHa)2 H CHa ~CH3 316 , E~ CH3 CH3 C~d3CH 3 Cd 317 H CH3 CH3 CH3O CH3 CT~

318 rd CH3 CH3 ~CH3 ~~H3 CH

319 H C ~d3 C1d3 CH3OCH3 N

320 H CH3 CH3 ~CH5 ~CH3 321 i H CH2 CH3 CH2 CH3 CH3CH 3 CH

- 25 - 1340~26 No. A B C X Y l Z

322 H CH2 CH3 CH~ CH3 CH3 OCH3 CH

332 CH3 H CH~ CH3 CH3 OCH3 N

333 CH3 H CH(CH3)2 ', CH3 CH3 CH

334 CH3 H CH( CH3)2 , CH3 O CH3 CH

335 CH3 H CH( CH3)2 CH3 OCH3 N
336 CH3 H C ( CH3)3 CH3 CH3 CH

337 CH3 H IC ( CH3)3 ,CH3 O CH3 CH ' _ Comp. A B C X Y Z
No .
338 CH3 H C (CHa)3 CH3 ~ CH3 N

339 H CH~ CH3 O CH3 CH3 CHJ CE~

341 H CH~ CH3 OCH3 CH3 OCH3 N

342 HCH(CH3)2 O CH3 CH3 CH3 CH

343 HCH(CH3)2 OCH3 CH3 OCH3 CH

344 HCH(CH3)2 OCH3 CH3 OCH3 N

345 H ~ O CH3 CH3 CH3 CH

346 ~ O CH3 CH3 1 O CH3 CH

347 H ~ OCH3 CH3 OCH3 N

349 CH3CH2 CH3 O CH3 CH3 ~ CH3 CH

351 CH3CH2 CH3 o CH3 CH3 ~ CH3 N

352 CH3CH2 CH3 OCH3 OCH3 OCH3 ! N

353 CH3! CH2CH2 CH3 OCH, , CH3 ' CH3 CH

-Comp. A B C X Y Z

356 CH3CH (CH3)2 O CH3 CH3 CH3 CH
357 CH3CH (CH3)~ O CH3 CH3 O CH3 CH
358 CH3CH(CH3)2 OCH3 OCH3 OCH3 CH
359 CH3CH(CH3)2 OCH3 CEl3 OCH3 N
360 CH3CH(CH3)2 OCH3 OCH3 OCH3 N
361 CH3CH(CHs)~ OCH3 CH3 -Cf~- CH
362 CH3CH(CH3)2 OCH3 OCH3CH2C.~20CH9 CH
363 CH3CH(CH3)2 OCH3 CH3CH!2(t3-~H3 N
364 CH3C ( CH3) 3 O CH3 CH3 CH2 CH
365 CH3C ( CH3)3 O CH3 CHa O CH2 CH
366 CH3C (CH3)~ OCH3 Cd3 OCH:! N
367 CH3S CH3 CH3 CTd3 CH3 CH

369 CH3S CH3 CH3 !CH3 O CH3 ' N

-~3~0326 Comp. A B C X Y Z

370 CH3S (O) CH~ CH3 CH3 CH3 CH

371 CH3S (O)CH3 CH3 CH3 OCH3 CH

372 CH3S (O) CH3 CH3 CH3 O CH3 N

374 CH3S ~2 CH3 CH3 CH3 ~ CH3 CH

376 CH3SO2CH2 CH3 CH3 CH3 CH3 ~ CH

378 CH3SO2 CH2 CH3 CH~ CH3 ~ CH3 N

379 CH3SO2 C~ H,-n CH3 CH3 CH 3 CH

380 CH3SO2C3 H,-~ CH3 CH3 OCH3 CH

381 CH3SO2C~H,-n CH3 OCH3 OCH3 CH

382 CH3SO2 C3 H,-n CH3 CH~ o CH3 N

383 CH3SO2C3 H,-n CH3 OCH3 OCH3 N

385 ; CH, CH8 ~cO2 CH3CH~ IO CH3 CH

- 1340~2fi Comp. A B C X y z No.

3 8 9 CH3 CH3 C 02 CH3 C~3 CH3 N

3 9 0 CH3 CH3 CO2CH3 CP.3 C~ C(CH2) 3 91 CH3 CH3CO2CH3 CHt ~ OCH2 CH2C -3 9 2 CH3 CH3CO2CH3 CH3 C~ CH

393 CH3 CH3CO2CH3 c~3 OCH2CH3 . CH

3 9 4 CP,3CH3CO3 CH3 CH3 H CH

3 9 8 CH3 CH3CO2 CH3 C'r.3OCH2C02CH3 CH

3 9 9 CH3 CH3CO2CH3 C~ c~ CH

4 0 0 CH3 CH3CO2 CH3 Br Br CH

40 1 CH3 CH3CO,CH3 CH3 C~ N
-~ 30 - 134032~

Comp. A B C X Y Z
No .
402 CH~ CH3 CO~ CH3 C~N(CH3)2 N

403 CH3 CH3 CO2 CH3 OCH3N(CH3)2 N

404 CH3 CH3 CO2 CH3 CH~OCH2CH3 N

40 5 CH3 CH3 CO2 CH3 CH,,NHCH2CH3 N

408 CH3 ~ CH3 CO2CH2 CH3 CH~ CH3 CH

409 CH3 CH8 CO2CH2 CH3 CH3o CH3 CH

413 CH3 CH3 I CO2CH2CH3 CH3C~ C(CH2)2C~

415 CH3 CH3 CO2C3Hr-n CH3CH3 I CH

416 CH3 CH3 CO2C8H7-n CH3OCH3 CH

417 CH3 CH3 C02 C3H7-n ~ OCH3 OCH3 CH

- 31- 1340~2~

Comp. A B C ! X I Y Z
4 1 8 CH3 CH9 COO CgH~ -~1 CH3 O CH3 N
41 9 CH3 CHt COoC3H7 ~1 OCH3 OCH3 N
4 2 0 CH3 CH3 CO2 C3 H~ -n CH3 CH 3 CH
421 CH3 CH3 COaC3H, -n CH3 OCH3 CH
4 2 2 CH3 CH3 CO2 C3H, ~1 OC H 9 0 CH3 CH
4 2 3 CH3 CH3 CO2 C5 H~ ~1CH3 O CH3 N
4 2 4 CH3 CH~ CO2 C3 H7 -~1OCH 3 O CH3 N
4 2 5 CH3 CH3 Coa CH~ CHCHa CH3 CH3 CH
42 6 CH3 CH3 CO2CH2C~-CE~ CH3 OCH3 CH
427 CH3 CH3 CO2CH2CH--CE~OCH3 OCH3 CH
428 CH3 CH3 CO2 CY2CH--CHaCH3 . OCH3 N
42 9 CHt CH3 CO2CE~aCH=CHa~ OCH3 OCH3 N
4 3 0 CH3 CH3 CO2 CE~2C-CEICH3 CH3 CH
4 31 CH~ CH3 CO2CH C --CH CH3 OCH3 CH
4 32 CH3 CH3 CO2CHC _CH OCH3 OCH3 CH
433 I CH3 CH3 CO2CHC_CH CH3 OCHt N

_ 1340~26 Comp. A B C X Y . Z

434 CH3 CH3CCLCHCsCH O CH3 0 CH3 N

436 CH3 CH~C O2H CH3 0 CH, CH

441 CHgCH3 CH~CO2 CH3 CH3 , CH3 CH

442 CH2CH3 CH,CO2 CH3 CH3 OCH3 CH

443 CH2CH3 CH3COg CH3 OCH3 OCH3 ~ CH

444 CH,CH3 CH3CO2 CH3 CH3 OCH3 N

445 CH2CH3 CH3C~a CH3 OCH3 OCH3 N

447CH2CH,CH3 CH3CO2 CH3 CH3 OCH3 CH

448CHaCH2CH, CH3CO2 CH3 CH3 OCH3 N

449CH(CE~)2 CH~C 4 CH, CH3 CH3 CH

Comp..... A B C X Y I Z
No .
450 CH (CH3)2 CH3 CO2CH3 CH3 OCH3 CH

451 CH(CH3)2 CHt - CO2CH3 CH3 OCH3 N

452 ~ CH3 CO3CH3 CH3 CH3 CH

453 ~ CH3 CO2CH3 CH3 OCH3 CH

454 ~ CH3 C O2 CH3CCH3 O CH3 CH

455 (~ CH3 CO2CH3 CH3 OCH3 N

456 ~ CH3 C O, CH3OCH3 O CH5 N

457 CH3 H 'C03 CH3CH3 CH3 CH

458 CH3 H CO2CH~ CH3 OCH3 CH

459 CH3 H C ~2 CH3 CH3 O CH3 CH

460 CH3 H CO~CH3 CH3 OCH3 N

462 CH3 CH2CH3 CO~CH3 CH3 CH3 CH

463 CHt CH2CH3 CO2CH3 CH3 OCH3 CH

464 CH3 CH2CHt CO2 CH3OCH3 O CH3 CH

Comp. A B C ~ Y

467 CH3 CH2 CH.lCH3 C02CH9 CH3 CH3 CH
468 CH3 Cd2CH2CH3 CO,CH3 CH3 OCH3 CH
469 CH3 CH2 CH2CH3 COaCH3 O CH3O CH3 CH
470 CH3 CH2CH,CH3 C02CH3 CH3 OCH3 N
471 CH3 CH2 CH,CH3 CO, CH3 O CH3O CH3 N
472 CH3 CH(CH3)~ CO2CH3 c~3 CH3 CH
473 CH3 CH(CH3)2 C02CH3 cH3 OCH3 CH
474 CH3 CH(CH3)2 CO"CH~ OCH3 OCH8 CH
475 CH3 CH(CH3)2 CO,CH3 CH3 OCH3 N
476 CH3 CH(CH3)2 C02CH3 OCH3 OCH3 477 CH3 iC (CH3 )3 CC2CH3 CH3 CH3 CH
478 CH3 C (CH3)3 CO2CH3 CH3 OCH3 CH
479 CH3 C (CH3)3 co2CH3 CH3I OCH, N
480 CH3 CH9 CON(CE~ )2 CH3 CH3 CH
CH8 CH3 ! CON(CH3)2 l CH3 o CH3 I CH

13~0326 -~ 35 --No. B C ~ Y

482 CH3 CH3CON(CH3)2 OCH3 OCH3 CH

483 CH3 CH3CON(CH3)2 CH3 OCH3 N

484 CH3 CH3CON(CH~)a OCH3 OCH3 N

485 CH3 CH3CON(C2H5)2 CH3 CH3 .CE~, 486 CH3 CH~cON(C2H5)2 CH3 OCH3 ,CH

487 CH3 CH3CON(C2H5)2 OCH3 OCH3 CH

488 CH3 CH3CON(C2H5)2 CH3 OCH3 , N

489 CH3.CH3CON(C8H5)2 OCH3 OCH3 N

490 CH3 CH3 'C2H5 CH~ CH3 CH

491 CH3 CH CoN~CH3 CH3 O CH3 CH

492 CH3 CH3CON~c H CH3 OCH3 N

494 CH3 CH3CO NH CH3 CH3 ~ CH3 CH

495 CH" CH3CONHCH3 CH3 OCH3 N

496 CHl CH5CONH C2H5 CH3 CH3 CH
-. .

- 36 - 1340~25 ! Comp. A B C ~ Y Z

498 CH3 c~3 CONHC2H5 CH3 OCH3 N

4 9 9 CH3 CH CoN,CH3 CH CH3 CH

5 0 0 CH3 CH3 CON ~ CH3 O CH3 CH

5 01 CH3 CH3 CON~ CH3 OCH3 N

5 0 2 CH3 j~ CO2 CH3 CH 3 CH3 CH

503 CH3 ~ CO3 CH3 CH3 OCH3 CH

5 o 4 CH3 ~ CO2 CH3 OCH3 OCH3 CH

50 5 CH3 ~ CO2 CH2 c~3 OCH3 N

5 0 6 CH3 ~ C~a CH3 OCH3 OCH3 N

5 o 7 CH3 O CO2 CH3 CH3 CH3 N

508 C~3 ~ CO2 CH3 CH3-OCH2CH2C-509 CH3 (~ CO2 CH3 CH3C~ C(CH2) 51 0 CH3 ~ C~2 CH3 OCH3N(CH3)3 N

51 1 CH3 ~CH3 C02 CH3 CH3 CH3 CH

1340~26 NoP A B C ~ Y Z

51 2 CH3~CH3 C03 CH3 CH3OCH3 CH

51 3 CH3~CH3 C~2C~3 CH3OCH3 N

514 CH~ ~ C O~ CH3 CH3 CH3 CH

5 1 5 CH3 ~ CO,CH3 CH3OCH3 CH
~CH3 516 CH3 C CO,CP.3 CH3OCH3 N

51 7 CH3 H~ CO2CE;3 CH3 CH3 CH

518 CH3 CH~ CO2C~3 CH3OCH3 CH

51 9 CH3 ~ CO,CH3 CH9OCH3 N

5 2 0 CH3 ~C~ CO2CH3 CH3 CH3 CH

5 2 1 CH3~- C~ C O~ CEl3 CH3O CH3 CH

5 2 2 CH3~ C~ CO, CH3 CH3O CH3 N

52 3 CH3 ~> CO2CH3 CH3 CH3 CH

5 2 4 CH" C~ C02 CH3 CH3~ CH3 CH

525 CH~ ~ CO2CH, CH3OCH3 N

13~0326 Comp. A I B C ' X y No .
526 CH3 ~ CO2 CH3 CH8 CH3 CH

527 CH3 ~ CO~ CH3 CH8 O CH3 CH

528 CH3 ~ CO3 CH3 CH3 OCH3 N

531 CH3oCH3 C02 CH3 O CH3 . OCH3 : CH

532 CH3OCH3 CO, CH3 CH3 OCH3 N

535 CH3OCH2CH3 CO2 CH3 CH3 . CH3 CH

536 CH3OCH2CH~CO2 CH3 . CH3 O CH3 CH

539 C H~ CH3 S CH3 CH3 OC H3 CH

540 ~ CH3 S CH3 O CH3 OGH3 CH -omp. A B C X Y Z
No .

543 CH9 CH9SO~CH9 CH9 CH9 CH

544 CH9 CH9S ~2 CH9 CH9 O CH9CH

545 CH9 CH9SO~CH9 OCH9 OCH3 CH

546 CH3 CH9S O, CH 9 CH9 O CH3 N

551 CH3 CHtSO2CH2CH3OCH9 OCH9 CH

554 CH9 CH9SC9H7-n CH9 CH9 CH

555 CH~ CH9SC9H7-n CH9 OCH9 CH

556 CHt CH9 S C~ H, -n I O CH9 O CH9 CH

_ 40 _ 1340~2fi Comp. A B C X Y Z
No .
557 CH3 CH8 SC3H7-n CH3 OCH3 N

5 5 8 CH3 CH3 S C3H, -n O CH3 O CH3 N

55 9 CH3 CH3 SC3H7 -n CH3 CH3 N

5 6 0 CH3 CH3 ,S(O)C3H7-n CH3 CH3 CH

561 CH3 CH~ S(O)C3H7-n CH3 OCH3 CH

56 2 CH3 CHS S(O)C3H7~n OCH3 O CH3 CH

5 6 3 CH3 CH8 S(O)C3H7 -n CH3 OCH3 N

56 4 CH3 CH3 S(O)C3H7-n OCH3 OCY3 N

565 CH3 CH3 S03 CSHT-~ CH3 CH3 CH

56 6 CH3 CH3 S~a C3HT -n CH3 OCH3 CH

567 CH3 CH~ SO2 C3HT -n OCH3 OCH3 CH

568 CH3 CH3 SO2 C3 Hr -n CH3 OCH3 N

569 CH3 CH3 SO, C3H7 -n OCH3 OCH3 N

570 CH3 CH3 SO, C3H7 -n CH3 CH3 N

571 CH3 CH, S~2 C3H7 -n CH3 CH3 C(CH3)~

572 CH3 CH3SO, C8H, -n CH3 -OCH 2 CH25-- ' 134032fi Comp. A B C X Y Z
No .
5 73 CHs CH3SO"C~H7-n CH3 C~ CH

5 7 4 CH3 CH3SO3C3H7-n CH3OCH2CH3 CH

5 7 5 CH3 CH3SOaC3Hr-n CH3 H CH

5 7 6 CH8 CH3SO2 C3H7-n H H CH

5 7 7 C~3 CH3S O2 C3H, -n CH3CH2OCH3 CH

578 CH3 CH3SO3C3H7-n CH3OCH2CO2CH3 CH

5 7 9 CH3 CH3SO2C3H7 -n CH3 . CQ N

580 CH3 CH3SO2C3H7-n C~ N(CH3)2 N

581 CH3 CH3SO2C~H7-n OCH3 N(CH3)2 N

582 CH3 CH3SO2C3H7-n CH3 OCH2CH3 N

5 8 3 CH3 CH3S O~ C3H7 - nCH 3 NHCH3 N

5 8 4 CH~ CH3S O2 C3H7 -n CH3 OCH2CF3 N

5 8 5 CH3 CH3S O2 C3Hr -n CH3 CH3 N

5 8 6 CH3 CH3SO2c3H7-i CH3 CH3 CH

587 CH3 CH3So2c~H7-l CH3 CH3_ CH

588 CH3 CH,So2c3H7-i OCH" CH3 ! CH

- 42 - 1 3~0 3 2 6 NoP A B C X , Y , Z
5 8 9CH3 CH3SO2C3H, -i CH3 ~ CH3 N
59a CH3 CH3SO2C3H7-i OCH3 OCH3 N
5 91 CH3 CH3SO~C3H7 -i CH3 CH3 N
5 9 2CH3 CH3SO2C3H7 -i CH3 - OCH3CH2C -5 93 CH3 CH3SO8C3HT -1 CH3 C~ C(CH2)2 59 4 CH~ CH3S03C3H7 -i OCH3 N(CH~)2 N
595 CH3 CH3SO2N(CH3)l CH3 CH3 CH
596 CH3 CX3SO2N(CH3)2 CH3: OCH3 ' CH
5 9 7CH3 CH3SOs,N( CH3)2OCH3, O CH3 CH
5 9 8CH3 CH3So2N( CH,), CH3 o CH3 N

599 CH3 CH3SO~N(CH3)2 OCH3 OCH3 N
6 0 0CH3 CH3SO2N( CH3)2 CH3 .? CH3 N
60 1 CH3 CH3SO2N(CH3)2 CH3 -aCH2CH2C-6 0 ZCH3 CH3SO2N(CHa)2 JCH3 C~ 1 C(CH2)2C~
603 CH3 CHsSO~N(CH3)2 OCH8 N(CH,)2 N

60 4 CH3 ¦ CH3SO3N(C2H5), CH3 CH3 CH

1340~2fi Comp. A B C X Y , Z
No .

6 0 5 CH3 CH3 SO2N (C2H5)2CH3 OCH3 CH

606 CH3 CH3 SO2N(C2H5)2OCH3 OCH3 CH

6 ~ 7 CH3 CH3 SO2N (C2H5) 2 CH3 o CH3 N

6 0 8 CH3 CH~ SO2N (C2H5)2O CH3 O CHt N

6 ~ 9 CH8 CH3 SO2N(C2H5)2 CH8 CH3 N

610 CH3 CHt SO2N~ CH3 CH3 CH

6 1 ~ CH3 CH3 . SO2N~C H CH3 OCH3 CH

61 2 CH3 CH SO N,CH3 OCH3 OCH3 CH

613 CH3 CH3 SO2'N~C H CH3 OCH3 N

6 1 4 CH3 CH3 SO2N OCH, OCH3 N

615 C~3 CH3 SO3N~C H CH3 CH3 N

61 6 . CH3 CEI.3 SO2NHCH3 CH3 CH3 CH

61 7 CH3 CH3 SO2NHCE~3 CH3 OCH3 CH

6 1 8 CH3 CH3 SOaNHCH3 CHt OCH3 N

61 9 ¦ CH3 CH3 SO~NHC2H~ CH3 ICH3 CH

~- 134q~2~

Comp. A B C X Y Z

6 2 0CH3 CH3S 02NHC3H6 CH, O CH3 C

6 21 CH3 CH3So2NHc2H6 CH3 OCH3 N

6 2 2CH3 CH3SO2NHC3H7-n CH3 CH3 CH

6 23 CH3 CH3SO2NHC3H7-n CH3 OC H3 CH

624 CH3 CH3SO2NHC 3H7-n CH3 OCH3 N

6 2 7CH3 HS(O)CH3 CH3 C~3 CH

628 CH,~ HS(O)CH3 CH3 OCH~ CH

6 2 9CHt HS (O) CH3 CH3 ~ CH3 N

63 1 CH3 HSO2CH3 CH3 OCHa ¦CH

6 3 3CH3 HS O~ CH3 CH3 ~ CH3 N

6 3 4CH3 HS02CH3 O CH3 O CH~ N

6 3 5CH" HS 02 C2H6 CH3 CH3 CH

-- 45 - 1340-32~

Comp. A B C ~ Y Z
No .

637 CH 3 H S ~2 Ca H~ CH3 O CH3 N

638 CH 8 H S ~2 C3H,-~ CH3 CH3 CH

639 CH 3 H SO2C3H7-~ CH3 O CH3 CH

640 CH3 H SO~C3H7-~ OCH3 OCH3 CH

641 CH8 H SO2C3H7-~ CH3 OCH3 642 CH3 H S O, C3HT-~O CH3 o CH3 N

643 CH3 H S O ~ C3H7-~CH3 CH3 N

644 CH3 H SO2C3Hr-~ CH3 -OCH 2CH2C-645 CH3 H SO2C3H,-n CH3 C~ C(CH2)2C~

646 CH3 H S ~2 C3H7-~ O CH3N (CH3) 2 N

647 CH3 H SO2C3H,-i CH3 CH3 CH

648 CH3 H S O2 C3H, -iCH3 O CH3 CH

649 CH3 H SO2C3H,-i OCH3 OCH3 CH

650 CH~ H SO3 C3H7 -iCH3 ~ CH3 N

651 C~3 H SO2C3H7-i OCH~ OCH3 N

1340~2fi Comp. A B C X Y Z

652 CH3 HS02C3H7-l CH3 CH8 N
6 53 CH8 HSO2C H9-n CH3 CH3 N

654 CH3 HSO2C~H9-n CH3 OCH3 CH

6 55 CH3 H SOaC H~, -n CH3 OCH3 N

6 5 6 CH3 HSO,N (CH3) ~ CH3 CH3 CH

657 CH5 HSO2N(CH~)2 CH~ OCH3 CH

658 CH3 H SO~N(CH3)s OCH3 OCH~ CH

6 5 9 CH~ HS O,N (CH3)2 CH3 ~ CH3 N

6 6 0 CH3 HS 03N (CH3), 0 CH3 0 CH, N

6 61 CHt HSO2N (CH3)2 CH3 CH3 N

6 6 2 CH~ HSO2N(C3H5)2 CH3 CH3 CH

6 6 3 CH~ HS 02N (C~Hs)2 CH3 0 CH3 CH

6 6 4 CH3 HS O,N (CqH5)2 0 CH3 0 CH3 CH

6 6 5 CH3 HS 02N (C2H5)2 CH3 0 CH3 N

6 6 6 CH3 H SO,N(CqH5), OCH3 OCH~ N

- 47 - 13~0~2 Comp. A B C X Y Z
No.

672 CH3 HS02NHCoH5 CH3OCH3 N

673 H CH3 SCH3 CHt CH3 CH

679 H CH3So2c2H5 CH3CH3 CH

680 H CH~S03 C2Hs CH3OCH3 CH

681 H CH,SO2C2H5 CH~OCH3 N

682 H CH~SOaC3H7-~ CH3CH3 CH

683 H CH3 SO3C3H,-~ CH~OCH3 CH

- 48 - 13~0~2~

Comp.- A B C X Y Z
No.
684 H CH3 S02 C3H~ -nOCH3 .OCH3 CH

685 H CH8 SOaC3H7 -n CH3 OCH3 N

686 H CHt SO2C3H7 -nOCH3 OCH3 N

687 H CH3 S02N(CH3)2 CH3 CH3 CH

688 H CH3 S02N (CH3)2CH3 O CEI3 CH

689 H CH3 S02N(CH3)2 CH3 OCH3 N

690 H CH3 S02N(C2Hs)2CH3 - CH3 - CH

691 H CH3 S03N(C2H5)2CH3 OCH3 CH

692 H CH3 S~2N(C2~s)~ CH3 OCH3 N

694 H H SO2CH3 CH3 .OCH3 CH

695 H H SO,CH3 CH3 OCH3 N

696 H H S ~2 C3H7 -n CH~ CH3 CH

697 H H S02C3Hr~ll CH3 OCH3 CH

698 H H SO2C3H~-n CH3 OCH3 N

699 H H SO~N(CH3)2CH3 CH3 CH
--~ 49 ~ 1340326 Comp. A B C

700 H H S02N(CH3)a CH3OCH3 CH
7 0 1 H H S02N(CH3 )2 CH3 OCH3 N
7 0 2 H H So2N(c2Hs)3 CH~ CH3 CH
703 H H S02N(C2Hs)2 CH3 OCH3 CH
7 0 4 H H S02N(C2H~)2 CH3 o CH3 N
705 ~ CH3 SO2CH3 CH3 CH3 CH
7 0 6 (~ CH3 S 02 CH3CH3 ~ CH3 CH
707 (~ CH3 SO2CH3 CH~OCH3 N
7 0 8 ~ CH3 SO2C~H7 ~~ CH3 CH3 CH
7 0 9 ~) CH3 SO2C3H7 ~~ CH3 OCHs CH
710 ~ CH3 SO2C3H7-n CH3OCH3 N
71~ ~ CH3 SO2N(CH3)2 CH~ CH3 CH
712 ~ CH3 SO2N(CH3)2 CH3 OCH3 CH
71 3 ~ CH3 SO2N(CH3)2 CH3 OCH3 N
71 4 ~ CH3 SO2N(C2H~)2 CH3 CH3 CH
71 5 ~ CH3 SO2N(C,H~)2 CH~ OCH3 CH

~ 50 - 1340326 C omp ~ A ~ C X I Y Z

71 6 ~ CH3SO~N(C2H5)3 CH3 OCH3 N

7 2 1 C~3 H H O CH3 O CH3 N

7 2 5 H H H CH3 OC~I3 N

-~ - 51 - 1340~2~

Comp.
N A B C X Y Z

727CH2CH3 C~2CH3 CH3 3 3 CH

728CH2CH3 C~2CH3 CH3 3H3 N

729CH3 CO2CH2CH3 ~ ~ CH3CH3 CH

730CH3 CO2CH2CH3 ~ CH3OCH3 CH

731CH3 CO2CH2CH3 ~ OCH3OCH3 CH

732CH3 -~2CH2cH3 ~ CH3OCH3 N

733CH3 -~2CH2cH3 ~ OCH3OCH3 N

734CH3 CH3 02C3 7 i CH3CH3 CH

735CH3 CH3 ~2C3H7 i CH3OCH3 CH

736CH3 CH3 CO2C3H7-i ~ 3C 3 CH

737CH3 CH3 CO2C3 7 i CH3OCH3 N

740 CH3 H H CH3 CQ C(CH2)2 . 3 H H 3 3 N

-- 52 - 1 3q n ~2 Comp ~ A B C X Y Z

747 CH3 CH3 S ~ 3 3 CH

748 CH3 CH3 S ~ CH3OCH3 CH

749 CH3 CH3 S ~ CH3OCH3 N

750 CH3 CH3SCH2 ~ CH3 C 3 CH

751 CH3 CH3SCH2 ~ CH3OCH3 CH

752 CH3 CH3C 2 ~ C 3 3 CH

753 CH3 CH3SCH2 ~ CH3OCH3 754 CH3 CH3SCH2 ~ OC 3 3 N

755 CH3 CO ~ CH3 CH3OCH3 CH

756 CH3 CO ~ CH3 CH3OCH3 N

3 CON ~ CH3 CH3 OCH3 CH

758 CH3 CON ~ CH3 CH3OCH3 N

~ _ 53 _ 1340~26 Comp ~ A B CX Y Z

759 CH3CON ) CH3 CH3 OCH3 CH

760 CH3CON~ CH3 CH3 OCH3 N

761 CH3CON~_~NCH3 CH3 CH3 OCH3 CH

762 CH3CH3 CON~ 3 3 CH

763 CH3CH3 CON~CH3 OCH3 CH

764 CH3CH3 CON~ 3 OCH3 CH

765 CH3CH3 CO ~CH3 OCH3 N

766 CH3CH3 CO~ ~ C 3 OCH3 N

767 CH3CH3 CO ~ 3 C 3 N

768 CH3CH3 CO ~ CQ CQ N

769 CH3CH3 CON ~ CH3 OCH3 CH

770 CH3CH3 CO ~ CH3 OCH3 N

771 CH3CH3 CON ~ CH3 OCH3 CH

772 CH3CH3 CON ~ CH3 OCH3 N

3CH3 CO ~ CH3 CH3 OCH3 CH

774 CH3CH3 ~_~ 3 3 3 N

1340~2fi Table 2 ~ O ~
~N ~ S02NHCNH~i ~Z
I N=<
A Y

Comp. A B C X Y Z

~ 781 CH3 CH3 CH3 CH3 OCH3 CH

783 ~ CH3 H CH3 OCH3 CH

784 ~ CH3 H CH OCH N

785 ~ H H CH3 OCH3 CH

786 ~ H H CH3 OCH3 N

787 CH3 3 ~ CH3 OCH3 CH

788 CH3 3 ~ CH3 OCH3 N

C~3 CQ C 3 C 3 CH

-_ 1340326 Co~;p. A B C X Y Z

796 CH3 H . CQOC 3 ~ 3 CH

798 CH3 H CQOC 3 ~ 3 N

3 H N~2 C 3 O 3 CH

- 1~4032fi C~o~.p. A B C X Y Z

807 CH3 CH3 Br CH3 OCH3 CH

808 CH3 CH3 Br CH3 OCH3 N

809 CH3 CH3 Br OCH3 OCH3 N

812 CH3 CH3 C~2C 3 OC 3 OC 3 CH

813 ~H3 CH3 C~2C 3 CH3 OCH3 N

817 CH3 H CO2C 3 OC 3 ~ 3 CH

819 CH3 . H CO2C 3 OC 3 3 N

820 CH3 H C~2CH3 CH3 CH3 N

821 CH3 H CO2C 3 CH3 C(CH2)2C

822 C 3 C~2CH3 CH3 C CH

_ 57 _ 1340326 Comp B C ~ y z 823 CH3 H C~2CH3 CH3~C2H5 CH

826 CH3 H C~2CH3 OCH3N(CH3)2 N

827 C 3 H C~2CH3 CHOjCHCO2H N

832 CH3 CH3 CO2C2H5 oCH3 OCH3 N

833 CH3 H C~2C2H5 CH3 CH3 CH

834 CH3 H C~2C2H5 CH3 OCH3 CH

835 CH3 CH3 CO2C2H5 oCH3 OCH3CH

836 CH3 H C~2C2H5 CH3 OCH3 N

837 CH3 H C~2C2H5 OCH3 OCH3 N

-- ~8 - 1340326 CN~om.P A B C X y z 840 H CH3 C~2CH3 CH3 OCH3 N

841 H H C~2CH3 CH3 OCH3 CH

852 ~ C 2C 3 CH3 OCH3 CH

853 ~ 2C 3 CH3 OCH3 N

854 CH2 H CO2C3H7-n CH3 OCH3 CH

139û326 Comp.
A B C X Y Z

855 CH3 H CO2C3H7-n OCH3 OCH3 CH

856 CH3 H CO2C3H7-n CH3 OCH3 N

857 CH3 H CO2C3H7-n CH3 OCH3 CH

858 CH3 H CO2C3H7-n OCH3 OCH3 CH

859 CH3 H CO2C3H7-n CH3 OCH3 N

86~ CH3 H CO2CH2CH=CH2 CH3 CH3 CH

861 CH3 H CO2CH2CH=CH2 CH3 OCH3 CH

862 CH3 H CO2CH2CH=CH2 CH3 OCH3 N

864 CH3 H CO2CH2C_CH CH3 OCH3 CH

865 CH3 H CO2C4Hg CH3 OCH3 CH

866 CH3 H C~2C4 9 CH3 OCH3 N

868 C2H5 H C~2CH3 CH3 OCH3 CH

869 C2H~ H C~2CH3 CH3 OCH3 N

.

~ - 60 - 134D32~

Comp. A B C X y z 873 CH3 C2H5 C~2C 3 CH3 OCH3 CH

874 CH3 C2H5 C~2C 3 CH3 OCH3 N

875 CH3 CH3 CON(CH3)2 CH3 CH3 CH

876 CH3 CH3 CON(CH3)2 CH3 OCH3 CH

877 CH3 CH3 CON(CH3)2 CH3 OCH3 N

878 CH3 CH3 CON(CH3)2 OCH3 OCH3 N

879 CH3 CH3 SO2N(CH3)2 CH3 CH3 CH

880 CH3 CH3 SO2N(CH3)2 CH3 OCH3 CH

881 CH3 CH3 S~2N(CH3)2 OCH3 OCH3 CH

882 CH3 CH3 SO2N(CH3)2 CH3 OCH3 N

883 CH3 CH3 SO2N(CH3)2 OCH3 OCH3 N

884 CH3 CH3 SO_N(CH3)_ CH3 CH3 N

885 CH3 H SO2N(CH3)2 CH3 CH3 CH

886 CH3 H SO2N(CH3)2 CH3 OCH3 CH

- 61- 1~40326 CNoOm,p. A B C X Y Z

887 CH3 H SO2N(CH3)2 CH3 OCH3 N

888 CH3 CH3SO2N(C2H5)2 CH3 OCH3 CH

889 CH3 CH3SO2N(C2H5)2 CH3 OCH3 N

890 CH3 ~ CH3 OCH3 CH

891 CH3 CH3 2 ~--~ CH3 OCH3 N

892 CH3 CH3 S~2NO CH3 OCH3 CH

893 CH3 CH3 02N~ CH3 OCH3 N

894 CH3 CH3 S~2N ~ CH3 OCH3 CH
895 CH3 CH3 S02N NCH~ CH3 OCH3 CH

899 3 OE~ H CH3 OCH3 CH

900 CH3 ~ H OCH3 OCH3 CH

901 C 3 ~ H CP.3 OCH3 N

902 CH3 H ~ CH3 OCH3 CH

Co~.~
~o. R, C X Y Z

903 C~3 H ~ 3 3 ~H

S04 3 ~C~i3 OCH3 N

905 ~ H CQ CH3OCH3 CH
906 ~ H CQ ~ 3 C 3 CH

907 ~ H CQ CH3OCH3 N

908 ~CQ H C~2CH3 CH3OCH3 CH

909 ~ H C~2CH3 CH3OCH3 N

910 ~ H3 H C~2C2H5 CH3OCH3 CH

911 ~ H3 H C~2C2H5 CH3OCH3 N

91 C~3 ~ 3 C~2C 3 C~I3OCH3 CH

91 CH3 ~ 3 co2CIi3 3 3 CH

914 CH3 ~ CH3 C~2C 3 CH3OCH3 N

NO2 ~ 2 3 C~I3OCH3 CH

NO2 ~ 2 3 CH3OCH3 N

~ - 63 - 134032fi .

Comp. A B C X Y Z

917NO2 ~ C~3 C~2CH3 CH3OC 3 CH

918NO2 ~ CH3 C~2CH3 CH3OCH3 N

919CH3 ~ H NO2 CH3OCH3 CH
CH
9203~ H NO2 CH3OCH3 N

921 ~ H CO2H CH3 OCH3 CH

922 ~ H CO2H CH3 OCH3 N

923 ~ H N~2 CH3 OCH3 CH

924 ~ H NO2 CH3 OCH3 N

3 CH3 N~2 CH3 CH3 N

932C~3 CH3 SO2N(CH3)2 CH3 CQ CH

13~0~2~

CN~om.P A B C X y z 933 CH3 CH3S02N (CH3) 2 CH3 -OCH2CH2C-934 CH3 CH3S02N(CH3)2 CQ N(CH3)2 N

~ - 65 - 134032~ ' Table 3 C~S02NHCNH~
B

Conl~
;-' A B C ~ yz 939 CH3 H H OCH3 OC~3 N

943 CH3 H H ( H3)2 N

944 CH3 H H CH3 O~HCO2H N

- 66 - 134032~

Comp ' A B C X Y Z

948 CH3 CH3 H CH3 OCY.3 N

953 ~ H H CH3 OCH3 CH

954 @ H 3C 3 CH

955 @ H H CH3 OCH3 N

961 CH3 Br H CH3 OCH3 CH

962 CH3 Br O 3 3 CH

~ - 67 - 1340326 Comp ' A B C X Y Z

963 CH3 Br H CH3OCH3 N

966 CH3 N~2 3 3 CH

968 CH3 N~2 3 3 N

970 CH3C~2C 3 H CH3 OCH3 CH

978 CH3C~2C2H5 3 3 N

- 68 - 13~032~

Comp.
A B C X Y Z

982 CH3 a~2CH2CH=CH2 H CH3OCH3 CH

983 CH3 (!~2CH2CH=CH2 H C 3OCH3 CH

984 CH3 C~2CH2CH=CH2 H CH3OCH3 N

985 CE~3 C~2CH3 CH3 CH3OCH3 CH

986 CH3 C~2CH3 CH3 C 3OCH3 CH

989 CH3 CON(CH3)2 H CH3OCH3 CH

990 CH3 CON(CH3)2 3 3 CH

991 CH3 CON(CH3)2 H CH3OCH3 N

992 CH3 SO2N(CH3)2 H CH3OCH3 CH

993 CH3 SO2N(CH3)2 3 3 CH

994 CH3 SO2N(CH3)2 H CH3OCH3 N

995 CH3 SO2N(C2H5)2 H CH3OCH3 CH

- 69 - 13~0326 Comp. A B C X Y Z

996 CH3 S~2N(C2H5)2 3 3 CH

997 CH3 SO2N(C2H5)2 CH3 OCH3 N
998 CH3 S~2CH3 H CH3 OCH3 CH

.1000 CH3 S~2CH3 H CH3 OCH3 N

-13~032~

The compounds of this invention represented by the above formula (I) can readily be produced by selecting suitably the following reaction scheme 1, 2 or 3.

Reaction scheme 1 N ~ S02NCO + HN

(IV) (V) /N ~ S02NHC-N ~ z A C D N

(I) wherein A, B, C, D, X, Y and Z have the same meanings as defined above.

That is, a pyrazolesulfonylisocyanate derivative (IV) is dissolved in an inert solvent such as sufficiently dried dioxane, acetonitrile, etc., and to the resultant solution is added pyrimidine or a triazine derivative (V). By stirring the mixture, the reaction proceeds generally rapidly to give the compound (I) of this invention. In case when the reaction proceeds difficultly, a minute amount of a suitable base such as lS triethylamine, triethylenediamine, pyridine, sodium ethoxide, sodium hydride, etc. may be added to the reaction mixture, whereby the reaction can proceed easily.

13~0326 Reaction scheme 2:
X

D NJ
B NH~/ Z
I=L NC( Cl CO 2 R g N ~ O ( V ) Y
N~S02NH2 ~ A \ S02NHCORg A C C

(VI) (VII) B X
N I O N~
~ . il~/ \\
~N~ 'S02NHC-N--~ Z
A C D N=~
Y
(I) wherein A, B, C, D, X, Y and Z have the same meanings as defined above, and Rg represents an alkyl group or a phenyl group.

That is, a pyrazolesulfonamide derivative (VI) is allowed to react with a chlorocarbonate in a solvent such as acetone or methyl ethyl ketone in the presence of a base such as potassium carbonate, followed by acid precipitation with hydrochloric acid, etc., to give a compound (VII). This compound is then heated in a solvent such as toluene with a compound (V) to give the compound (I) of this inventions.

Reaction scheme 3 13~032~
G
N¦
O=C=N~ Z
B N ~\ B G
N ~ (X) E N ~ O N ~
N ~ S02NH2 ~ / ~ S02NHCONH ~ Z

(VI) (VIII) B G
R10~Na N ~ ~ I N
S02NHC-NH~

ORlo (IX) wherein A, B, C and Z have the same meanings as defined above, E represents a halogen atom, G
represents H, Cl, Br, Cl-C4 alkyl, CF3, methoxymethyl or methoxy ethyl, and Rlo represents a lower alkyl group.

By referring to Japanese Une~Arined Patent Publication No.154471/1981, a pyrazolesulfonamide derivative (VI) can be allowed to react with pyrimidine or a triazine isocyanate (X) to synthesize a compound ~VIII), which is a part of the compound of this invention, followed by reaction with a sodium alcoholate, to further synthesize a compound (IX), which is also a part of the compounds of this invention.

The other reactant aminopyrimidine can be synthesized by referring to ~ The Chemistry of HeterocycliC
Compounds (Interscience Publishers Inc., New York) Vol.
16, The pyrimidines n.

13~0326 Aminotriazine can be synthesized according to the method disclosed in " Journal of Organic Chemistry, Vol. 28, pp.l812-1821 (1963) ".

2-Amino-4-methyl-5,6-dihydrofura[2,3-d]pyrimidine and 2-amino-4-chloro-5 -chloroethyl-6-methylpyrimidine can be synthesized accordng to the method disclosed in "
Journal of Organic Chemistry, Vol.16, pp.ll53 (1951).

Most of the pyrazolesulfonamide (VI) or the pyrazolesulfonyl isocyanate derivative (IV) used as the starting material in the reaction scheme 1, 2 or 3 are novel compounds, and they can be synthesized by selecting suitably the following reaction scheme 4, 5 or 6 .

Reaction scheme 4 CQ5~3H A- ~ ~ 1) 9~CQ2 A- ~ S~2NH2 n-B~CO~
(VI) B O B
N=h ll COCQ2 N~
A-~ S02NHCl!l~u-n C

,.

3~0326 Reaction scheme 5 N=h \ OH
A-N~
C \p2S5 B B B

C Q H2S,Na A-~-SH ~ 40H, A-N =~--SNH2 NaSCH2~) CQ2/CH3C02H ~. n-BuNCO
\3. COCQ2 B CQ2/cH3cooH ~ 2. n-BV a~ A_N~S02NC~

2 (IV) Reaction scheme 6 B B
Nl\ 1) NaN02 ~ H IN~\ 1. NEI40H
A-N ~NH2 ~A-N SO CQ
C>~ 2) S02-Cu salts C . 2 2 nBuNCO

N~
A~'~ S02NCO

(IV) .

Most of the pyrazolesulfonyl isocyanate derivatives obtained hereinabove ar~ unstable in the air, and should preferably be stored in a cold and dark place under a nitrogen atmosphere when they are to be stored, but alternatively they can be used as such without purification in many cases in the subsequent reaction step.

Most of the intermediates pyrazolesulfonamides (VI) to be used in this invention are novel compounds, and synthetic examples thereof are shown below as Reference examples.

Reference example 1 Synthesis of 1,3-dimethyl-5-methoxypyrazole-4-sulfon-amide:

13~032~

Into 70 ml of chlorosulfonic acid was added dropwise under cooling at 5 ~C or lower 12.6 g (0.1 mol) of 1,3-dimethyl-5-methoxypyrazole. After the addition, the mixture was stirred at 100 ~C for 8 hours. Then, the reaction mixture was cooled to 80 ~C, followed by dropwise addition of 11.9 g (o.l mol) of thionyl chloride over 30 minutes. After the dropwise addition, the mixture was stirred at 100 ~C for 2 hours. The reaction mixture was cooled and poured carefully into ice-water, whereby crude 1,3-dimethyl-5-methoxy-pyrazole-4-sulfonylchloride was formed as crystals.
The crystals were separated by filtration, dissolved in 20 ml of tetrahydrofuran and the resultant solution was added dropwise into 100 ml of aqueous ammonia (28%) at 10 ~C or lower. After the addition, the mixture was stirred at room temperature for 30 minutes. The reaction mixture was evaporated under reduced pressure to remove low boiling components, whereby crystals were - precipitated. The crystals were filtered, washed with water and dried to give 11.5 g of 1,3-dimethyl-5-methoxypyrazole-4-sulfonamide melting at 144 - 146 ~C .

Reference example 2 Synthesis of 1,5-dimethyl-3-trifluoromethylpyrazole-4-sulfonamide:

Into 100 ml of an ethanolic solution of 25 g (0.16 mol) of trifluoroacetylacetone, there was added dropwise 7.4 g (0.16 mol) of methylhydrazine. After stirring at room temperature for 3 hours, the mixture was left to stand overnight and the solvent was evaporated to give 19.2 g of 1,5-dimethyl-3-trifluoromethylpyrazole as an oil. Following then the procedures as Reference example 1, this product was allowed to react with chlorosulfonic acid and then with thionyl chloride to obtain 29 g of 1,5-dimethyl- 3-trifluoromethylpyrazole-4-sulfonyl-chloride, which was in turn reacted with aqueous ammonia (28%) in tetrahydrofuran to give 21.5 g of 1,5-dimethyl-3-trifluoromethylpyrazole-4-sulfonamide melting at 204 - 206 ~C.

Reference example 3 Synthesis of 1,3-dimehyl-5-methoxycarbonylpyrazole-4-sulfonamide:

Into 200 ml of chlorosulfonic acid, there was added dropwise 50.4 g (0.3 mol) of Ethyl 1,3-dimethyl-5-pyrazole carboxylate under cooling at 5 ~C or lower.
After heating at 120 ~C under stirring for 10 hours, the reaction mixture was poured into ice-water and extracted with ether. After washing with water and drying, evaporation of the solvent gave 49 g of crude 1,3-dimethyl-4-chlorosulfonyl-5-pyrazole carboxylic acid as a solid.

23.9 g (0.1 mol) of this product was dissolved in 60 ml of tetrahydrofuran and the resultant solution was added dropwise into 150 ml of aqueous ammonia(28%) at 10 ~C
or lower. The mixture was stirred at room temperature for 4 hours and concentrated to dryness under reduced pressure. Then, 300 ml of dry methanol was added to the mixture, and the mixture was refluxed for 3 hours while passing gaseous hydrogen chloride thereinto.
After the reaction, methanol was evaporated and ice-water was added to the residue, followed by extraction with ethyl acetate. After washing with water and drying, the solvent was evaporated and the crude crystals obtained were recrystallized from methanol to give 9.0 g of 1,3-dimethyl-5-methoxycarbonylpyrazole-4-sulfonamide melting at 174 oC .

Reference example 4 Synthesis of 1,3-dimethyl-5-n-propylsulfonylpyrazole-4-sulfonamide:

With the use of 1,3-dimethyl-5-chloropyrazole as the starting material, following the procedure in the above Reference examples, there was obtained 5-chloro-1,3-dimethylpyrazole-4-sulfonamide melting at 173 ~C. Into a mixture of 14.1 g (0.067 mol) of the above sulfonamide, 10.7 g (0.268 mol) of sodium hydroxide and 120 ml of DMF, 6.6 g (0.087 mol) of n-propylmercaptan was added dropwise at room temperature. After the addition, the mixture was heated at 80 to 90 ~C for 3 hours. After completion of the reaction, DMF was evaporated under reduced pressure, and the residue was diluted with water, adjusted to pH 4 with conc.
hydrochloric acid and the precipitated crystals were collected by filtration. After drying, there was obtained 14.3 g of 1,3-dimethyl-5-n- propylthio-pyrazole-4-sulfonamide melting at 105 - 106~C.

As the next step, this intermediate was dissolved in 80 ml of acetic acid and 23 g of 30 % aqueous hydrogen peroxide was added dropwise into the resultant solution under ice-cooling. After stirring at room temperature for 4 hours, the reaction mixture was poured into water. The precipitated crystals were collected by filtration to obtain 14 g of 1,3-dimethyl-5-n-propylsulfonylpyrazole-4-sulfonamide melting at 127 -129 ~C.

Following the procedures as described in Reference examples 1 to 4, there were synthesized the substituted pyrazolesulfoamides (IV) shown below~

-~ 79 ~ 134032~
Reference example 5:

Synthesis of 1,5-dimethyl-3-phenylpyrazole-4-sulfon-amide:

Obtained, following the above Reference examples, from 1,5-dimethyl-3-phenylpyrazole. m.p. 144-148 ~C

Reference example 6:

Synthesis of 5-chloro-1-methylpyrazole-4-sulfonamide:

Obtained from 5-chloro-1-methylpyrazole. m.p.159-152 ~C

Reference example 7:

Synthesis of 1,5-dimethyl-3-methoxycarbonylpyrazole-4-sulfonamide:

Obtained from 1,5-dimethyl-3-methoxycarbonylpyrazole.
m.p. 183-185 ~C

Reference example 8:

Synthesis of 1,5-dimethyl-3-ethoxycarbonylpyrazole-4-sulfonamide:

Obtained from 1,5-dimethyl-3-ethoxycarbonylpyrazole.
m.p. 159-161 ~C

Reference example 9:

Synthesis of 1,3-di-methylpyrazole-4-sulfonamide:

Obtained from 1,3-dimethylpyrazole. m.p.114-115 ~C

', 1340~26 Reference example 10:

Synthesis of 3,5-dimethylpyrazole-4-sulfonamide:

Obtained from 3,5-dimethylpyrazole. m.p.215-223 ~C

Reference example ll:

Synthesis of 1,5-dimethylpyrazole-4-sulfonamide:

Obtained from 1,5-dimethylpyrazole. m.p.l65-166 ~C

Reference example 12:

Synthesis of 5-methoxy-1-methyl-3-i-propylpyrazole-4-sulfonamide:

Obtained from 5-methoxy-1-methyl-3-i-propylpyrazole.
m.p.114-115 ~C

Reference example 13:

Synthesis of 1,3-dimethyl-5-ethoxycarbonylpyrazole-4-sulfonamide:

Obtained from 1,3-dimethyl-5-ethoxycarbonylpyrazole.
m.p.150-154 ~C

Reference example 14:

Synthesis of 3,5-dimethyl-1-phenylpyrazole-4-sulfon-amide:

Obtained from 3,5-dimethyl-1-phenylpyrazole.
m.p.178-180 ~C

134032~

Reference example 15:

Synthesis of 3-ethoxycarbonyl-1-methyl-5-phenyl-pyrazole-4-sulfonamide:

A solution of 7.5 ml of chlorosulfonic acid and 15 ml of dry chloroform was cooled to 0 ~C, and a solution of 11.5 g (0.05 mol) of 3-ethoxycarbonyl-1-methyl-5-phenylpyrazole in 25 ml of dry chloroform was added dropwise thereinto. Then, the mixture was stirred at room temperature for one hour and under reflux for 3 hours. After the reaction, by evaporation of chloroform, there was obtained oily 3-ethoxycarbonyl-l-methyl-5-phenylpyrazole-4-sulfonic acid. As the next step, at room temperature 20.9 g of phosphorus pentachloride was-added portionwise, followed by stirring at 90 to 100 ~C for one hour. The reaction mixture was added into ice-water and extracted with ether to obtain 14.7 g of 3-ethoxycarbonyl-1-methyl-5-phenylpyrazole-4-sulfonylchloride. Then, the resultant sulfonylchloride was dissolved in 20 ml of acetone and 4.48 g of KHCO3 was added to the solution.
After a solution of 2.7 g of aqueous ammonia (28 %) and 6.5 ml of acetone was added dropwise thereinto at room temperature, the mixture was heated at 50 to 60 ~C for 30 minutes. After evaporation of acetone, water was added to the residue, whereby 12.9 g of the title compound was precipitated as a solid.
Recrystallization from benzene gave 8.4 g of the product. m.p. 141-144 ~C

Following the procedures as described above, there were synthesized the substituted pyrazolesulfon-amides shown below.

Reference example 16:
Synthesis of 5-chloro-1,3-dimethylpyrazole-4-sulfon-amide:

- 82 - 134032~
Obtained from 5-chloro-1-3-dimethylpyrazole. m.p. 173~C

Reference example 17:

Synthesis of l-ethyl-5-methyl-3-methoxycarbonyl-pyrazole-4-sulfonamide:
Obtained from l-ethyl-5-methyl-3-methoxycarbonyl-pyrazole. m.p. 165-168 ~C

Reference example 18:

Synthesis of 5-ethyl-1-methyl-3-methoxycarbonyl-pyrazole-4-sulfonamide:
Obtained from 5-ethyl-1-methyl-3-methoxycarbonyl-pyrazole. m.p. 188 - 191 ~C

Reference example 19:

Synthesis of l-ethyl-3-methyl-5-methoxycarbonyl-pyrazole-4-sulfonamide:
Obtained from l-ethyl-3-methyl-5-methoxycarbonyl-pyrazole. m.p. 130-133 ~C

Reference example 20 Synthesis of 3-ethyl-1-methyl-5-methoxycarbonyl-pyrazole-4-sulfonamide:
Obtained from 3-ethyl-1-methyl-5-methoxycarbonyl-pyrazole. m.p. 162 - 165 ~C

Reference example 21:

Synthesis of 1,3-dimethyl-5-dimethylcarbamoylpyrazole-4-sulfonamide:
Obtained from 1,3-dimethyl-5-dimethylcarbamoylpyrazole.
m.p. 150 - 152 ~C

- 134032~

Reference example 22:

Synthesis of l-methylpyrazole-4-sulfonamide:
Obtained from l-methylpyrazole. m.p. 122-123 ~C

Reference example 23:

Synthesis of 1,3-dimethyl-5-i-propoxycarbonylpyrazole-4-sulfonamide:
Obtained by heating 1,3-dimethyl-5-carboxylpyrazole-4-sulfonamide btained in Reference example 3 in i-propyl alcohol in the co-presence of hydrogen chloride. m.p. 105-108 ~C

Reference example 24:

Synthesis of 1,3-dimethyl-5-(N,N-tetramethylene-carbamoyl)-4-sulfonamide:
Obtained from 1,3-dimethyl-5-(N,N-tetramethylene-carbamoyl)pyrazole. m.p. 92-95 ~C.

Reference example 25:

Synthesis of 4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide:

(1) Synthesis of ethyl-5-hydroxy-1-methyl-4-pyrazolecarboxylate To a solution of 216 g (1 mol) of diethylethoxy-methylenemalonate in 216 g of ethanol, there was added 46 g (1 mol) of methylhydrazine at 10 ~C. Then, at room temperature, the mixture was stirred and further refluxed for one hour, and thereafter the reaction mixture was left to stand. The precipitated crystals were filtered and dried to obtain 148 g of the title compound melting at 134-135 ~C.
-1340~2~

(2) Synthesis of ethyl 5-chloro-1-methyl-4-pyrazole carboxylate:

A mixture of 10 g of ethyl 5-hydroxy-1-methyl-4-pyrazole carboxylate and 50 ml of phosphorus oxychloride was stirred at 90 to 100 ~C for 65 hours.
Excessive phosphorus oxychloride was evaporated under reduced pressure, and the residue was poured into ice-water. The precipitated crystals were filtered and dried to obtain 4.5 g of 5-chloro-1-methyl-4-pyrazole carboxylic acid. The filtrate was neutralized with aqueous ammonia (28%) and extracted with ether. After drying of the extract, evaporation of the solvent gave 4.0 g of ethyl 5-chloro-1-methyl-4-pyrazole carboxylate. To 5-chloro-1-methyl-4-pyrazole carboxylic acid were added 30 ml of thionyl chloride and 0.2 ml of dimethylformamide, and the mixture was refluxed for 5 hours. Then, excessive thionyl chloride was evaporated and the residue was added to dry ethanol. After stirring at room temperature for 3 hours, the solvent was evaporated and ether was added to the residue. After washing with water, drying and evaporation of the solvent, there was obtained 4.5 g of ethyl 5-chloro-1-methyl-4-pyrazole carboxylate as an oil. Total of the title compound: 8.5 g.

(3) Synthesis of ethyl 5-mercapto-1-methyl-4-pyrazole carboxylate:

After 2.2 g (0.094 mol) of sodium was dissolved in 35 ml of ethanol, 50 ml of dimethylformamide was added to the resultant solution, and most of ethanol was removed. Then, under cooling, hydrogen sulfide was passed into the mixture to saturation, followed by addition of 7.4 g (0.039 ml) of ethyl 5-chloro-l-methyl-4-pyrazole carboxylate. After stirring at 70 - 13~032fi to 80 ~C for 3.5 hours, the reaction mixture was concentrated under reduced pressure. Ice-water was added to the reside, and insolubles were filtered off.
The filtrate was made acidic, extracted with chloroform and dried, followed by evaporation of the solvent, to give 6.8 g of the title compound as an oil.

(4) Synthesis of 4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide:

To 100 ml of a 28 % aqueous ammonia, there was added 20 ml of aqueous solution containing 7.1 g of ethyl-5-mercapto-1-ethyl-4-pyrazole carboxylate and 1.6 g of sodium hydroxide. To this reaction mixtur was added 61 g of 6 % aqueous NaOCl solution at 5 - 10 ~C.
The precipitated crystals were filtered and washed with water. The resultant moist sulfenamide (5.6g) was suspended in water and an aqueous saturated solution of 5.5 g of potassium permanganate was added to the suspension at room temperature. After stirring vigorously at room temperature, the mixture was filtered. The filtrate was made acidic and extracted with ethyl acetate. After drying, the solvent was evaporated to obtain 1.8 g of the title compound. m.p.
102 - 104 ~C

(5) Synthesis of 4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide (alternative method):

A solution of 3.0 g of ethyl 5-mercapto-1-methyl-4-pyrazole carboxylate in 50 ml acetic acid was stirred while passing chlorine at 15 to 20 ~C. Then, after nitrogen was passed into the mixture, the reaction mixture was poured into ice-water and the crystals precipitated were separated by filtration.

134032~

The sulfonyl chloride as prepared above was dissolved in 20 ml of tetrahydrofuran, and added under ice-cooling to 50 ml of 28 % aqueous ammonia. After stirring at room temperature for 2 hours, the reaction mixture was concentrated under reduced presure. The precipitated crystals were filtered, washed with water and further washed with n-hexane. After drying, 1.3 g of the title compound was obtained. m.p. 102-104 ~C

Reference example 26 Synthesis of 4-methoxycarbonyl-1-methylpyrazole-5-sulfonamide:

Synthesized similarly as in Reference example 25.
m.p. 127-128 ~C

The respective intermediates have the following physical properties.

Methyl 5-hydroxy-1-methyl-4-pyrazole carboxylate:
m.p. 111-113 ~C

Methyl 5-chloro-1-methyl-4-pyrazole carboxylate:
m.p. 70-71 ~C

Methyl 5-mercapto-1-methyl-4-pyrazole carboxylate:
m.p. 64-66 ~C

Reference example 27:

Synthesis of 1,3-dimethylpyrazole-5-sulfonamide and 4-chloro-1,3-dimethylpyrazole-5-sulfonamide (1) Synthesis of 1,3-dimethyl-5-mercaptopyrazole To a solution of 84 g (0.75 mol) of 1,3-dimethyl-- 5-hydroxypyrazole in 630 ml of xylene was added portionwise 65.3 g (0.294 mol) of phosphorus penlasulfide at 110 to 120~C. After heating under reflux for 1.5 hours, the hot reaction mixture was filtered. The filtrate was concentrated to give 21.4 g of the title compound. m.p. 130 - 132~C.

(2) Synthesis of 4-chloro-1.3-dimethylpyrazole-5-sulfonamide Into a solution of 12 g (0.094 ml) of the mercaptopyrazole obtained above in a mixture of acetic acid (100 ml) and water (15 ml), chlorine was passed at 10~C for 2 hours. After completion of the reaction, the mixture was poured into ice-water and extracted with ether. The organic extracts were washed with water, dried and evaporated to give 19.5 g of crude 4-chloro-1,3-dimethylpyrazole-5-sulfonyl chloride as an oll .

Then, into 130 ml of aqueous ammonia (28 %) was added dropwise the sulfonyl chloride obtained above in 50 ml of THF at 10~C or lower. After the addition, the reaction mixture was stirred at room temperature for 3 hours and then concentrated under reduced pressure to form precipitates.

The preipitated solids were filtered, washed with water and dried to give 10.8 g of the title compound. m.p.
135 - 138~C.

Further, the filtrate obtained above was extracted with benzene several times and the aqueous layer was concentrated under reduced pressure to dryness. The residual product was extracted with 100 ml of ethyl acetate. After evaporation of the solvent there was also obtained 4.0 g of 1,3-dimethylpyrazole-5-sulfonamide. m.p. 63 - 66~C.
-, ~ - 88 - 134032~
Reference example 28:

Synthesis of 1,3-dimethyl-4-nitropyrazole-5-sulfonamide (1) Synthesis of 5-chloro-1,3-dimethyl-4-nitropyrazole Concentrated H2S04 (35 g) was added to 10 ml of 90%
HNO3 and at 75 - 85~C, 13 g (0.1 mol) of 5-chloro-1,3-dimethylpyrazole was added dropwise with stirring to maintain the temperature at 85~C. After completion of the addition, the mixture was heated at 75 - 85~C for 1.5 hr. The nitration mixture was cooled and poured into ice. The suspention was filtered and the solid was washed with water and dried to give 14.5 g of the title compound. m.p. 70~C.

(2) Synthesis of 5-benzylthio-1,3-dimethyl-4-nitropyrazole Benzylmercaptan (50.8 g) (0.41 mol) was added to 21 g of sodium methoxide in 480 ml of DMF under ice-cooling and then 65.2 g (0.37 ml) of 5-chloro-2,3-dimethyl-4-nitropyrazole was added. After stirring at room temperature for 3 hr., DMF was evaporated under reduced pressure, and the residue ws diluted with ice-water.
The precipitated solids were filtered, washed with water and further with n-hexane and dried to give 82.4 g of the title compound. m.p. 82 - 83~C.

(3) Synthesis of 1,3-dimethyl-4-nitropyrazole-5-sulfonamide Into a solution of 40 g (0.152 mol) of 5-benzylthio-1,3-dimethyl-4-nitropyrazole in 300 ml of acetic aid and 30 ml of water chlorine was passed at 3 to 8~C for 1.5 hr. After completion of the reaction, the mixture was poured into ice-water and extracted with ether to give crude l,3-dimethyl-4-nitropyrazole-5-sulfonylchloride as an oil.

134~32~

The sulfonylchloride obtained above in 50 ml of THF was added into 150 ml of aqueous ammonia (28~) under ice-cooling. After stirrig at room temperature for 5 hrs, the reaction mixture was evaporated under reduced pressure. The precipitated solids were filtered, washed with water and further with n-hexane and dried to give 19.6 g of the title compound. m.p. 138 -140~C.

Reference example 29:

Synthesis of 1,3-dimethyl-4-dimethylsulfamoylpyrazole-5-sulfonamide:

(1) Syntheisis of N,N-dimethyl-(5-chloro-1,3-dimethyl-pyrazole)-4-sulfonamide Into 150 ml of chlorosulfonic acid was added dropwise under cooling at 5~C or lower, 30 g (0.23 ml) of 5-chloro-1,3-dimethylpyrazole. After the addtion, the mixture was stirred at 100~C for 8 hours. Then, the reaction mixture was cooled to 80~C, followed by dropwise addition of 36 g of thionyl chloride over 30 minutes. After the addition, the mixture was stirred at 100~C for an additional 2 hours. The rection mixture was cooled on ice and poured carefully ino ice-water, whereby crude 5-chlro-1,3-dimethylpyrazole-4-sulfonylchloride (50 g) was formed as crystals.
Subsequently, into a solution of 40 g of dimethylamine in 250 ml of THF, the above compound was added under cooling and the reaction mixture was stirred at room temperature for 3 hours. After the reaction, THF was evaporated under reduced pressure and into the residue was added ether and washed with water. After drying and evaporating the etherial solution, there was obtained 47 g of the title compound. m.p. 53 - 55~C.

134~32fi (2) Synthesis of N,N-dimethyl-(5-benzylthio-1,3-dimethylpyrazole)-4-sulfonamid Obtained, following the above Reference example 28-(2), from N,N-dimethyl-(5-chlro-1,3-dimethylpyrazole)-4-sulfonamide. m.p. 108 - 109~C.

(3) Synthesis of 1,3-dimethyl4-dimethylsulfamoyl-pyrazole-5-sulfonamide Obtained, following the above Reference example 28-(3), from N,N-dimethyl-(5-benzylthio-1,3-dimethylpyrazole)-4-sulfoamide. m.p. 209 - 210~C.

Reference example 30:

Synthesis of l-methylpyrazole-3-sulfonamide:

To a solution of 32 g (0.33 mol) of l-methyl-3-aminopyrazole in a mixture of conc.
hydrochloric acid (120 ml) and acetic acid (40 ml) was added a solution of 34.1 g (0.494 mol) of sodium nitrite in water (80 ml at -10~ to 0~C. The solution was stirred at -5~C for 30 minutes and then added, in several portions, into a sulfur dioxide saturated solution of acetic aid (440 ml) containig 6.7 g of cuprous chlride at -10~ to -5~C. The resultig solution was strred at 0~ to 5~C for 4 hours and then poured into ice-water and extracted with ether. The extracts were washed with water and saturated aqueous sodium bicarbonate, dried and evaporated to give 20.8 g of crude sulfonylchloride as an oil. The sulfonyl-chloride obtained bove was dissolved in 50 ml of THF
and added to 150 ml of aqueous ammonia (28%) at 10~C or - 134032~

lower. After stirring at room temperature for 3 hours, the reaction mixture was concentrated under reduced pressure to form precipitates. The precipitated solids were filtered, washed with water and further with n-hexane and dried to give 24. g of the title compound.
m.p. 156 - 158~C.

Specific synthetic examples of the compounds according to this invention are illustrated below by using the substituted pyrazolesulfonamides (VI) obtained in -~
Reference examples, but this invention is not limited thereto.

Example 1 Synthesis of N-[(4-methoxy-6-methylpyrimidin-2-yl)-aminocarbonyll-1,3-dimethyl-5-methoxypyrazole-4-sulfon-amide (Compound No. 292):

.~

1340'32~
-To a mixture of 10.25 g (0.05 mol) of the sulfonamide obtained in Reference example 1, 8.29 g (0.06 mol) of dry potassium carbonate and 50 ml of dry acetone was added 4.95 g (0.05 mol) of n-butyl isocyanate at room temperature, and the mixture was stirred for 4 hours.
Then, the reaction mixture was refluxed for one hour.
After the reaction, acetone was evaporated under reduced pressure and the residue was dissolved in 200 ml of water. After separation of a trace of water insolubles, the filtrate was made acidic with hydrochloric acid and the crystals formed were filtered, washed with water and dried to give 9.2 g of N-(butylcarbamoyl)-1,3-dimethyl-5-methoxypyrazole-4-sulfonamide melting at 135 - 142 ~C.

Into a mixture of 100 ml of dry benzene and 9.12 g (0.03 mol) of N-(n-butylcarbamoyl)-1,3-dimethyl-5-methoxypyrazole-4-sulfonamide, under reflux, 8.9 g (0.09 mol) of phosgene was passed over 1.5 hours.
Then, the reaction mixture was further refluxed for 30 minutes. After completion of the reaction, evaporation of benzene under reduced pressure gave crude 1,3-dimethyl-5-methoxypyrazole-4-sulfonyl isocyanate as an oil.

The crude isocyanate was taken out in an amount of 1.39 g (0.006 mol), dissolved in 20 ml of dry acetonitrile and 0.695 g (0.005 mol) of 4-methoxy-6-methyl-2-amino-pyrimidine was added to the resultant solution. The mixture was stirred at room temperature for one hour, then refluxed for 30 minutes, followed by cooling.

The crystals formed were filtered, washed and dried to obtain 1.09 g of N-[(4-methoxy-6-methylpyrimidin-2-yl)-aminocarbonyl]-1,3-dimethyl-5-methoxypyrazole-4-sulfonamide melting at 183-184 ~C.

13~032~

Example 2 Synthesis of N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino-carbonyl]-1,3-dimethyl-5-methoxycarbonyl-pyrazole-4-sulfonamide (Compound No. 387):

With the use of 6.8 g of the sulfonamide obtained in Reference example 3, following the procedure as in Example 1, there was obtained 8.6 g (0.026 mol) of N-(n-butylcarbamoyl)-1,3-dimethyl-5-methoxy-carbonylpyrazole-4-sulfonamide. The compound obtained was mixed into 200 ml of xylene and under reflux 7.7 g (0.078 mol) of phosgene was passed into the mixture over 1.5 hours. The reaction mixture was refluxed for 30 minutes, followed by evaporation of xylene, to obtain crude 1,3-dimethyl-5-methoxycarbonylpyrazole-4-sulfonyl isocyanate as an oil.

The crude isocyanate was taken out in an amount of 0.90 g (0.0035 mol) and dissolved in 20 ml of dry acetonitrile and 0.35 g of (0.0025 mol) of 2-amino-4-methoxy-6-methyl-5-triazine was added to the solution. After the mixture was stirred at room temperature for 2 hours, the reaction mixture was refluxed for 30 minutes and cooled. The crystals formed were filtered, washed and dried to obtain N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-1,3-dimethyl-5-methoxycarbonyl-pyrazole-4-sulfonamide melting at 195-198 ~C.

Example 3 Synthesis of N-[(4,6-dimethylpyrimidin-2-yl)amino-carbonyl]-1,3-dimethyl-5-propenyloxycarbonylpyrazole-4-sulfonamide (Compound No. 425):

134032~

Into a mixture of 17.4 ml of methanol and 8.7 g of 10 %
aqeous sodium hydroxide was added 3.3 g (0.00864 mol) of N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-1,3-dimethyl-5-methoxycarbonylpyrazole-4-sulfonamide (Compound No. 384), and the resultant mixture was refluxed for 45 minutes. After the reaction, the reaction mixture was made acidic with conc.
hydrochloric acid to obtain 2.3 g of a hydrolyzed compound (Compound No. 435). The above compound was taken out in an amount of 1.5 g (0.00408 mol), dissolved in 8 ml of THF and 0.416 g of triethylamine was added to the resultant solution. After stirring for 10 minutes, a solution of 0.493 g of allyl bromide in 8 ml of THF was added and the mixture was refluxed for 3 hours. The precipitated salt was filtered off and the filtrate was evaporated to obtain 0.5 g of the crystals of the title comound. m.p. 180-183 ~C

Example 4 Synthesis of N-[(4.6-dimethoxy-1,3,5-triazin-2-yl)-aminocarbonyl]-1,3-dimethyl-5-dimethylcarbamoylpyrazole-4-sulfonamide (Compound No. 484):

In 15 ml of dry acetonitrile, there were added 1.97 g (0.008 mol) of the sulfonamide obtained in Reference example 21 and 1.68 g (0.0088 mol) of dichloro-S-triazinyl isocyanate, and the mixture was refluxed for one hour. The reaction mixture was then left to stand at room temperature to give 2.2 g of crystals of N-[( 4,6-dichloro-1,3,5-triazin-2-yl)aminocarbonyl]-1,3-dimethyl-5-dimethylcarbamoylpyrazole-4-sulfonamide.
m.p.182-185 ~C

Then, the above compound was taken out in an amount of 1.3 g (0.00297 mol) and added into 12 ml of methanol.
Into this mixture, there were added portonwise sodium 134032~
.~

methoxide prepared from 0.205 g of sodium and 5 ml of methanol. After the reaction, the mixture was filtered and methanol was evaporated. The residue was dissolved in ice-water and made acidic with hydrochlorice acid, whereby 0.8 g of the crystals of the title compound was obtained. m.p. 170-175 ~C

Example 5 Synthesis of N-[(4-methoxy-6-methylpyrimidin-2-yl)-aminocarbonyl]-1,3-dimethyl-5-dimethylsulfamoyl-pyrazole-4-sulfonamide (Compound No. 596):

With the use of 39 g (0.186 mol) of the sulfonamide obtained in Reference example 16, following the procedure as in Example 1, there was prepared 57.6 g N-(n-butylcarbamoyl)-1,3-dimethyl-5-chloropyrazole-4-sulfonamide. m.p. 188 ~C

As the next step, 4.7 g of 55 % sodium hydride was added to 100 ml of dimethylformamide and 9.1 g (0.074 mol) of benzylmercaptan was added to the mixture, followed by portionwise addition of 15 g (0.049 g) of the sulfonamide as prepared above. After stirring at room temperature for several hours, the reaction mixture was further stirred at 70 to 80 ~C for 5 hours.
After evaporation of the solvent, the residue was added into ice-water and the insolubles were filtered off. The filtrate was made acidic with hydro- chloric acid to precipitate 19 g of N-(n-butyl-carbamoyl)-1,3-dimethyl-5-benzylthiopyrazole-4-sulfonamide. Then, into a solution of 19 g (0.0479 mol) of the above compound dissolved in 100 ml of acetic acid, chlorine was passed at 10 to 20 ~C for 1.5 hours. After the reaction, the reaction mixture was poured into ice-water to precipitate N-(n-butylcarbamoyl)-1,3-~ 134032~

dimethyl-5-chlorosulfonyl-4-sulfonamide. Subsequently, into a solution of 8.6 g of dimethylamine in 50 ml of THF, the above compound was added and the mixture was stirred at room temperature for 3 hours. After the reaction, THF was evaporated, and the residue was dissolved in an aqueous potassium carbonate solution.
After removal of the insolubles, the residual solution was made acidic with hydrochoric acid to precipitate 10.0 g (0.026 mol) of N-(n-butylcarbamoyl)-1,3-dimethyl-5-dimethylsulfamoyl-4-sulfonamide. m.p.
163-164 ~C

From the compound as prepared above, following the procedures of Examples 1 and 2, there was synthesized 1,3-dimethyl-5-dimethylsulfamoylpyrazole-4-sulfonyl isocyanate, which was in turn allowed to react with 2-amino-4-methoxy-6-methylpyrimidine to obtain the title compound. m.p. 215-217 ~C

Example 6 Synthesis of N-[(4,6-dimethylpyrimidin-2-yl)amino-carbonyl]-1,3-dimethyl-5-ethylthiopyrazole-4-sulfon-amide: (Compound No.742) Into 10 ml of dimethylformamide, there were added 1.5 g (0.0042 mol) of N-[(4,6-dimethylpyrimidin-2-yl)amino-carbonyl]-1,3-dimethyl-5-chloropyrazole-4-sulfonamide (Compound No. 85), 0.4 g of ethylmercaptan and 0.67 g of sodium hydroxide, and the resultant mixture was stirred at 60 to 70 ~C for 4 hours. After the reaction, the solvent was evaported, and the residue was added into ice-water, followed by acidification with hydrochloric acid, to precipitate 1.2 g of the crystals of the title compound. m.p. 189-190 ~C
-13~03~fi Example 7 Synthesis of N-[(4,6-dimethoxypyrimidin-2-yl)amino-carbonyl]-4-ethoxycarbonyl-1-methylpyrazole-5-sulfon-amide (Compound No. 835):

To a mixture of 5.0 g of4-ethoxycarbonyl-l-methylpyrazole-5-sulfonamide(Reference example 25), 4.45 g of dry potassium carbonate and 50 ml of acetone was added 2.13 g of n-butyl isocyanate at room temperature, and the mixture was stirred under reflux for 3 hours. After the reaction, acetone was evaporated under reduced pressure, and ice-water was added to the residue, followed by filtration of the insolubles. The filtrate was made acidic with hydrochloric acid and the crystals precipitated were filtered, washed with water and dried to give 5.1 g of N-(n-butylcarbamoyl)-4-ethoxycarbonyl-1-methyl-pyrazole-5-sulfonamide melting at 117-119 ~C. Then, this product was added into 120 ml of dry toluene, and 9.1 g of phosgene was passed into the mixture under reflux, followed further by refluxing for 1.5 hours.
After completion of the reaction, the reaction mixture was concentated under reduced pressure to obtain crude sulfonyl isocyanate.

The above crude sulfonyl isocyanate (0.98 g) was added to a solution of 0.4 g of 2-amino-4,6-dimethoxy pyrimidine in 20 ml of dry acetonitrile and the mixture was stirred at room temperature. The crystals formed were filtered, washed and dried to obtain 0.8 g of the title compound melting at 170-172 ~C.

Example 8 Synthesis of N-[(4-methoxy-6-methylpyrimidin-2-yl)-aminocarbonyl]-4-methoxycarbonyl-1-methylpyrazole-5-sulfonamide(Compound No. 816):

With the use of the sulfonamide obtained in Reference example 26, following the procedure of Example 7, there was obtained N-(n-butylcarbamoyl)-4-methoxycarbonyl-l-methylpyrazole-5-sulfonamide. m.p. 88-90 ~C

Further, following the procedure of Example 7, there was synthesized a sulfonyl isocyanate, which was further allowed to react with 2-amino-4-methoxy-6-methylpyrimidine to obtain the title compound melting at 183-184 ~C.

Example 9 Synthesis of N-[(4,6-dimethylpyrimdine-2-yl)-aminocarbonyl]-4-chloro-1,3-dimethylpyrazole-5-sulfonamide (Compound No. 789):

(1) Synthesis of N-(ethoxycarbonyl)-4-chloro-1,3-dimethylpyrazole-5-sulfonamide A mixture of 2.1 g (0.01 mol) of the sulfonamide obtained in Reference example 27, 1.41 g (0.013 mol) of ethyl chloroformate and 1.73 g (0.0125 mol) of potassium carbonate in 30 ml of dry acetone was stirred at room temperature for 18 hours. After the reaction, acetone was evaporated under reduced pressure and the residue was dissolved in water. The resultant solution was made acidic with conc. hydrochloric acid and extracted with ether. After evaporation of ether, the precipitated solids were recrystallized from a mixture 134û32~

of benzene and n-hexane to obtain 2.0 g of the title compound. m.p. 106 - 109~C.

(2) Synthesis of N-t(4,6-dimethylpyrimidine-2-yl)-aminocarbonyl]-4-chloro-1,3-dimethylpyrazole-5-sulfonamide Into 1.41 g (0.005 ml) of the compound obtained above in 10 ml of xylene was added 0.74 g (0.006 ml) of 2-amino-4,6-dimethylpyrimidine and the reaction mixture was refluxed for 2 hours. The resultant mixture was left to stand at room temperature to give 1.2 g of the title compound. m.p. 191-194~C.

Example 10 Synthesis of t(4-methoxy-6-methylpyrimidine-2-yl)aminocarbonyl]-l-methylpyrazole-3-sulfonamide (Compound No. 936) With the use of the sulfonamide obtained in Reference example 30, following the procedure of Example 7, there was obtained N-(n-butylcarbamoyl)-l-methylpyrazole-3-sulfonamide. m.p. 168 - 169~C.

Further, following the procedure of Example 7, there was synthesized a sulfonyl isocyanate, which was further allowed to react with 2-amino-4-methoxy-6-methylpyrimidin to btain the title compound. m.p.
185 - 186~C.

Next, similarly as in the above Examples, specific compounds were prepared and they are shown together with the compounds synthesized in Examples 1 to 10 in Table 4.

134032~
-Table 4 Comp. No. m. p. ( ~C) Status 2 1 1 ~ 2 1 4 ~ite crystal 2 2 0 1 ~ 2 0 3 /~
3 1 7 1 ~ 1 7 2 /' 4 1 8 0 ~ 1 8 1 //
1 7 3 ~ 1 7 4 a 6 . 1 1 5 ~ 1 2 0 /' 7 1 7 1 ~ 1 7 5 //
8 1 7 7 ~ 1 7 9 /r 9 1 7 4 ~ 1 7 6 /~
1 0 1 6 3 ~ 1 6 6 /' 1 1 1 8 7 ~ 1 9 0 r' 1 2 1 83 ~ 1 84 1 3 2 1 9 ~ 2 2 0 //
1 4 2 1 0 ~ 2 1 1 /' 1 5 1 8 1 ~ 1 8 3 1 6 2 0 2 ~ 2 0 3 ~7 1 7 1 8 0 ~ 1 82 1 8 1 8 0 ~ 1 8 2 ,r 9 2 0 2 ~ 2 0 3 2 0 2 1 3 ~ 2 1 4 D t 134032fi Comp. No. m. p. ( ~C) Status 2 1 2 2 2 --- 2 2 4 ~ite crystal 8 5 2 1 2 ~ 2 1 7 8 6 1 9 2 ~ 1 9 6 8 7 1 8 4 ~ 1 88 8 8 1 4 8 ~ 1 5 2 8 9 1 53 ~ 1 5 7 a 1 1 a 1 9 9 ~ 2 0 2 /7 1 1 1 1 78 ~ 1 8 1 1 1 2 1 8 3 ~ 1 8 6 /~

3 2 2 0 ~ 2 2 7 r 1 1 4 1 6 4 ~ 1 6 S
1 3 8 2 4 2 ~ 2 4 4 1 3 9 2 3 2 ~ 2 3 4 4 0 2 1 0 ~ 2 1 4 4 1 1 9 0 ~ 1 9 3 1 4 2 1 9 a ~ 1 9 5 /~
1 4 6 2 4 2 ~ 2 4 4 4 7 2 1, 6 ~ 2 1 8 4 8 2 2 1 ~ 2 2 3 1 5 0 2 4 2 ~ 2 4 5 1 5 9 1 6 3 ~ 1 6 6 /7 1 6 0 1 9 8 ~ 2 0 0 /~
1 6 1 2 0 1 ~ 203 n 6 2 1 2 0 8 ~ 2 1 0 ~ , .

..

Comp. No. m. p. ( ~C) Status 165 212 ~ 215~ite c~stal 166 219 ~ 220r/
177 197 ~ 199//
178 207 ~ 209//
179 191 ~ 193//

291 189 ~ 192//
292 183 ~ 184//
293 148 ~ 149 o 294- 158 ~ 161/7 295 174 ~ 175 a 304 230 ~ 232 a 305 206 ~ 208/~
306 202 ~ 204 a 307 185 ~ 195 a 308 185 ~ 188//

316 203 ~ 205 317 220 ~ 225 320 194 ~ 196 a 324 202 ~ 203//
325 187 ~ 188 a 327 191 ~ 194//
328 184 ~ 186 356 182 ~ 183 357 163 ~ 164 358 ! 176 ~ 178//

, 13~032~

Comp. No. m. p. ( ~C) Status 359 158 ~ 165 ~ite c~stal 360 167 ~ 169 //
361 169 ~ 171 384 195 ~ 198 /' 385 187 ~ 190 386 182 ~ 183 //
387 195 ~ 198 /' 388 173 ~ 176 391 209 ~ 211 403 185 ~ 188 "

409 186 "
410 180 ~ 183 /' 411 175 ~ 180 565 179 ~ 180 D
566 178 ~ 179 567 182 ~ 183 /7 568 145 ~ 147 - R
569 132 ~ 133 /' 570 170 ~ 171 571 2a4 ~ 206 572 183 ~ 184 573 163 ~ 165 580 185 ~ 186 581 178 ~ 179 Comp . No . m . p . ( ~ C )Status 210 182 ~ 185, White crystal 211 177 ~ 178 "
228 195 ~ 199 "
389 194 ~ 195 "
390 192 ~ 193 "
392 198 ~ 201 "
394 205 ~ 207 "
396 142 ~ 146 "
399 178 ~ 181 "
425 180 ~ 183 "
435 189 ~ 192 "
441 196 ~ 199 442 182 ~ 184 "
443 178 ~ 180 "
444 183 ~ 185 "
445 175 ~ 178 "
463 162 ~ 164 "
465 166 ~ 169 "
484 170 ~ 175 "
545 185 ~ 187 "

13~0~26 Comp. No. m.p. (~C) Status 546 166 ~ 169 White crystal 595 227 ~ 230 "
596 215 ~ 217 "
- 597 203 ~ 205 "
598 209 ~ 211 "
599 189 ~ 191 "
600 221 ~ 223 "
601 229 ~ 230 "
602 252 ~ 254 "
717 216 ~ 219 "
718 205 ~ 208 "
719 202 ~ 205 "
720 188 ~ 190 "
721 192 ~ 194 "
727 174 ~ 177 "
728 194 ~ 197 "
729 199 ~ 201 "
730 174 ~ 177 "
731 192 ~ 195 "
733 180 ~ 183 "
734 179 ~ 181 735 198 ~ 200 737 140 ~ 142 "

3~32fi Comp . No . m. p . ( ~C) Status 739 195 ~ 198 White crystal 740 216 ~ 219 "
7 ~1 199 ~ 203 "
742 189 ~ 190 "
750 173 ~ 176 "
766 190 ~ 193 "
768 167 ~ 170 "
775 184 ~ 187 ll 776 160 ~ 162 "
778 162 ~ 165 "
789 191 ~ 194 "
790 165 ~ 168 . "
791 176 ~ 178 . "
792 158 ~ 160 . "
793 180 ~ 183 "
799 194 ~ 195 "
800 212 ~ 213 "
801 166 ~ 168 "
802 170 ~ 171 "
803 198 ~ 200 "
815 196 ~ 198 "
~ 816 183 ~ 184 i 817 1 110 ~ 113 i 13~0326 Comp. No . m. p . ( ~C) Status 818 171 ~ 172 White crystal 819 163 ~ 165 "
833 163 ~ 165 "
834 152 ~ 154 "
835 170 ~ 172 "
836 138 ~ 139 "
837 142 ~ 144 "
879 212 ~ 215 "
880 , 206 ~ 209 "
881 . 169 ~ 172 "
882 175 ~ 177 "
883 190 ~ 193 "
884 193 ~ 195 ; "
925 178 ~ 180 "
926 . 173 ~ 176 "
927 200 ~ 201 "
928 156 ~ 158 ~ 929 218 ~ 220 ~ "
930 ~ 220 ~ 222 "
931 189 ~ 191 "
932 - 205 ~ 207 "
933 218 ~ 220 "
934 213 ~ 216 "
.

Comp. No. m.p. (~C) Status 935 212 ~ 215 White crystal 936 185 ~ 186 "
937 182 ~ 183 "
938 176 ~ 180 "
939 181 ~ 184 "
940 182 ~ 184 "
941 -195 ~ 197 "
942 -211 ~ 213 "
943 197 ~ 200 "

~ 134032~

In application of the compounds of this invention as herbicides, they can be applied by mixing with solid carriers, including for example clay, talc, bentonite, diatomaceous earth and others or liquid carriers, including for example water, alcohols (methanol, ethanol and the like), aromatic hydrocarbons (benzene, toluene, xylene and the like), chlorinated hydrocarbons, ethers, ketones, esters (ethyl acetate, etc.), acid amides and others. They can be provided for practical use with addition of any desired additive selected from a emulsifier,a dispersing agent,a suspending agent, a wetting agent, a spreader and a stablizer and in any desired form such as a soluble concentrate, an emulsifiable concentrate, a wettable powder, a dust, a granule, a suspension concentrate, etc.

In the following, there are shown examples of formulations of herbicides containing the compounds of this invention as active ingredients, but they are not limitaive of this invention. In the exemplary formulations shown below, "parts" mean "parts by weight".

Exemplary formulation 1: Wettable powder Compound No.2 of this invention 50 parts Ziegleit A 46 parts (kaolin type clay:produced by Ziegleit Kogyo Co.,) Ltd.) Solpol 5039 2 parts (mixture of nonionic surfactant and anionic surfactant; trade name; produced by Toho Kagaku Co., Ltd.) Carplex (anticaking agent) 2 parts (white carbon; trade name, produced by Shionogi Seiyaku Co., Ltd.) - 13~0326 All of the above components are mixed and pulverized homogeneously to prepare a wettable powder. In use, the above wettable powder is diluted with water to 50 to 50,000 times, and sprayed in an amount of the active ingredient of 0.0005 kg to 10 kg per hectare.

Exemplary formulation 2: Wettable powder Compound No.86 of this invention 75 parts Ziegleit A 19 parts (kaolin type clay:produced by Ziegleit Kogyo Co.,) Ltd.) Solpol 5039 2 parts (mixture of nonionic surfactant and anionic surfactant; trade name; produced by Toho Kagaku Co., Ltd.) Carplex (anticaking agent) 4 parts (white carbon; trade name, produced by Shionogi Seiyaku Co., Ltd.) The above components are mixed and pulverized homogeneously to prepare a wettable powder.

Exemplary formulation 3: Wettable powder Compound No.140 of this invention 50 parts Ziegleit A 46 parts (kaolin type clay:produced by Ziegleit Kogyo Co.,) Ltd.) Solpol 5039 2 parts (mixture of nonionic surfactant and anionic surfactant; trade name; produced by Toho Kagaku Co., Ltd.) Carplex (anticaking agnet) 2 parts (white carbon; trade name, produced by Shionogi Seiyaku Co., Ltd.) ~ 134032~

The above components are mixed and pulverized homogeneously to prepare a wettable powder.

Exemplary formulation 4: Wettable powder Compound No.159 of this invention 50 parts Ziegleit A 46 parts (kaolin type clay:produced by Ziegleit Kogyo Co.,) Ltd.) Solpol 5039 2 parts (mixture of nonionic surfactant and anionic surfactant; trade name; produced by Toho Kagaku Co., Ltd.) Carplex (anticaking agent) 2 parts (white carbon; trade name, produced by Shionogi Seiyaku Co., Ltd.) The above components are mixed and pulverized homogeneously to prepare a wettable powder.

Exemplary formulation 5: Wettable powder Compound No.292 of this invention 25 parts Ziegleit A 71 parts (kaolin type clay:produced by Ziegleit Rogyo Co.,) Ltd.) Solpol 5039 2 parts (mixture of nonionic surfactant and anionic surfactant; trade name; produced by Toho Kagaku Co., Ltd.) Carplex (anticaking agent) 2 parts (white carbon; trade name, produced by Shionogi Seiyaku Co., Ltd.) The above components are mixed and pulverized homogeneously to prepare a wettable powder.

.
-Exemplary formulation 6: Wettable powder Compound No.384 of this invention 50 parts Ziegleit A 44 parts (kaolin type clay:produced by Ziegleit Kogyo Co.,) Ltd.) Solpol 5039 4 parts (mixture of nonionic surfactant and anionic surfactant; trade name; produced by Toho Kagaku Co., Ltd.) Carplex (anticaking agnet) 2 parts ~white carbon; trade name, produced by Shionogi Seiyaku Co., Ltd.) The above components are mixed and pulverizedhomogeneously to prepare a wettable powder.

Exemplary formulation 7: Wettable powder Compound No.387 of this invention 45 parts ziegleit A 51 parts (kaolin type clay:produced by Ziegleit Kogyo Co.,) Ltd.) Solpol 5039 2 parts (mixture of nonionic surfactant and anionic surfactant; trade name; produced by Toho Kagaku Co., Ltd.) Carplex (anticaking agent) 2 parts (white carbon; trade name, produced by Shionogi Seiyaku Co., Ltd.) The above components are mixed and pulverized homogeneously to prepare a wettable powder.

Exemplary formulation 8: Emulsifiable concentrate 134032~

Compound No.817 of this invention2 parts Xylene 78 parts Dimethylformamide 15 parts Solpol 2680 5 parts (mixture of nonionic surfactant and anionic surfactant; trade name; produced by Toho Kagaku Co., Ltd.) The above components are homogeneously mixed to prepare an emulsifiable concentrate. In use, the above emulsifiable concentrate is diluted to 10 to 10,000 times and sprayed in an amount of the active ingredient of 0.0005 to 10 kg per hectare.

Exemplary formulation 9: Suspension concentrate Compound No.387 of this invention 25 parts Agrisol S-710 10 parts (nonionic surfactant;trade name; produced by Kao-Atlas Co., Ltd.) Runox 1000 C 0.5 part (anionic surfactant; trade name; produced by Toho Kagaku Co., Ltd.) 1 % Rodopol water 20 parts (thickener; trade name; produced by Rohne Poulainc) The above components are mixed to provide a suspnsion concentrate preparation.

Exemplary formulation 10: Granule Compound No. 816 of this inention0.1 prts Bentonite 55 parts Talc 44.9 parts All of the above components are mixed and pulverized homogeneously, then a little amount of water is added 134032~

and the whole is stirred, kneaded and granulated by excluding granulator, then dried to prepare a granule.

Exemplary formulation 11: Granule Compound No. 817 of this invention 0.25 parts Bentonite 55 parts Talc 44.57 parts All of the above components are mixed and pulverized homogenerously, then a little amount of water is added and the whole is stirred, kneaded and granulated by excluding granulator, then dried to prepare a granule.

Exemplary formulation 12: Granule Compound No. 834 of this invention 0.5 parts Bentonite 55 parts Talc 44.5 parts All of the above components are mixed and pulverized homogenerously, hen a little amount of water is added and the whole is stirred, kneaded and granulated by excluding granulator, then dried to prepre a granule.

Exemplary formulation 13: Granule Compound No. 835 of this invention 1 part Bentonite 55 parts Talc 44 parts All of the above components are mixed and pulverized homogeneously, then a little amount of water is added and the whole is stirred, kneaded and granulated by excluding granulator, then dried to prepare a granule.
-134~32~

If desired, the compound of this invention can be applied as a mixture with other kinds of herbicides, various insecticides, sterilizers or adjuvants during preparation or spraying.

As the other kinds of herbicides as mentioned above, there may be included those as described in Farm Chemicals Handbook, 69 th edition (1983).

The compounds of this invention can also be applied, in addition to the agricultural and horticultural fields such as farm fields, paddy fields, fruit gardens and the like, to athletic grounds, vacant lands, belts along the railroads and others. The amounts of the pesticide to be applied, which may differ depending on the scenes to be applied, the time of application, the application method, the kinds of the objective grasses and the crops harvested, may generally range suitably from 0.005 to 10 kg per hectare.

The following test examples are set forth for illustration of the utility of the compounds of this invention as herbicides.

Test example 1: Herbicidal effect test by soil treat-ment In a plastic box of 15 cm length, 22 cm width and 6 cm depth, there was placed a deluvium soil, seeds of (A) rice (Oryza sativa), ~B) barnyardgrass (Echinochloa crusgalli), (C) large crabgrass (Digitaria adscendens), , ,_ 13~032~

(D) annual sedge (Cyperus microiria), (E) lambsquarters (Chenopodium ficifolium), (F) common purslane (Portulaca oleracea), (G) hairly galinosoga (Galinosoga ciliata), and (H) yellow cress (Rorippa atrovirens) were sown mixedly. After covering soil to about 1.5 cm over the seeds, herbicides were sprayed evenly on the soil surface to predetermined proportions of the active ingredient. In spraying, the wettable powder as shown in the foregoing exemplary formulations was diluted with water and sprayed over the entire surface by means of a small sprayer. Four weeks after spraying, the herbicidal effect on rice and the various weeds were examined according to the judgement criteria shown below. The results are shown in Table 5.

Judgement criteria:

5... Growth control rates of more than 90% (almost completely withered) 4Growth control rates of 70 to 90%
3............. .. 40 to 70 %
2............. n 20 to 40 %
1............. " 5 to 20 %
0............. " less than 5 %
(substantially no effect) The above growth control rates are determined by measuring the top fresh weights of the treated plants and those of the non-treated plants, and calculated from the following formula:

Growth Top fresh weight of the controle = 1 - treated plants x 100 rate(%) Top fresh weight of the non-treated plants ~ 134032~

Table 5 Amount or Comp. active ingredient(A) (B) (C) (D) (.E) (F) (G) (H) No. (~g/ha) 0.1 6 5 5 5 5 5 5 5 5 0.08 5 5 5 5 5 5 5 5 0.1 6 5 5 5 5 5 5 5 5 0.08 5 5 5 5 5 5 5 4 0.1 6 5 5 5 5 5 5 5 5 0.08 5 5 5 5 5 5 5 4 0.16 5 5 5 5 5 5 5 5 0.08 5 5 5 5 5 5 5 5 0.1 6 5 5 5 5 5 1 5 5 5 0.08 5 5 5 5 5 5 5 5 0.1 6 5 5 5 5 5 5 5 5 0.08 5 5 5 5 5 5 5 5 88 al6 5 1 5 5 5 5 5 5 5 0.08 5 5 5 5 5 5 5 5 0.1 6 5 5 5 5 5 5 5 5 0.08 5 5 5 5 5 5 5 5 0.1 6 5 5 5 5 5 5 5 5 139 0.08 5 5 5 5 5 5 5 5 ao4 5 5 5 5 5 5 5 5 - 118 - ~ 134032~

- Amount of Comp. active ingredient ~A) (B) (C) (D) (E) (F) (G) (H) No. applied 0.1 6 5 5 5 5 5 5 5 5 1 400.0 8 5 5 5 5 5 5 5 5 0.04 5 5 5 5 5 5 5 5 0.16 5 5 ~ 5 5 5 5 5 5 141 0.08 5 5 5 5 5 5 5 5 0.04 5 5 5 5 5 5 5 5 0.08 5 5 5 5 5 5 5 5 1 5 9~-~ 4 5 5 5 5 5 5 5 5 0.02 5 5 5 5 5 5 5 5 0.16 5 5 5 5 5 5 5 5 0.08 S 5 5 5 5 5 5 5 0.1 6 5 5 5 5 5 5 5 5 0.08 5 5 5 5 5 5 5 3 0.1 6 5 5 5 5 5 5 5 2 0.08 5 5 5 5 5 5 5 0.08 5 , 5 5 5 5 5 5 5 384 0-04 5 ' 5 5 5 5 5 5 5 0.02 5 i 5 5 5 5 5 5 5 0.08 5 ~ 5 5 5 5 5 5 5 385 ~-~ 4 5 5 5 5 5 5 5 5 0.02 5 5 5 5 5 5 5 5 0.08 5 5 5 5 5 5 5 5 0.02 5 5 5 5 5 5 5 5 0.08 5 5 5 5 5 5 5 5 ' 387 0-04 5 5 5 5 5 5 5 5 0.02 5 5 5 5 5 5 5 5 - 119 - - 13~0326 r . Amount of CQ~ 1ngredient(A? (B) (C) (D) (E) (F) (G) (H) No. appl ed 0.08 5 5 5 5 5 5 5 5 388 0.04 5 5 5 5 5 5 5 5 0.02 5 5 5 5 5 5 5 5 0.08 5 ~t 5 5 5 5 5 5 5 4 09 0.04 5 5 5 5 5 5 5 5 0.02 5 5 5 5 5 5 5 5 0.08 5 5 5 5 5 5 5 5 41 0 ~-~ 4 5 5 5 5 5 5 5 5 0.02 5 5 5 5 5 5 5 5 0.08 5 5 5 5 5 5 5 5 0.04 5 5 5 5 S 5 5 5 392 0.16 5 5 5 5 5 5 5 5 ~ 0.08 S 5 5 5 5 5 5 5 394 0.16 5 5 5 5 5 5 5 5 0.16 5 5 5 5 5 5 5 5 0.08 5 5 5 5 5 5 5 5 0.165 5 5 55 5 5 5 0.08 4 5 5 5 5 5 5 5 442 0.16 5 5 5 5 5 5 5 5 0.08 4 5 5 5 5 5 5 5 443 0.16 5 5 5 5 5 5 5 5 0.08 5 5 5 5 5 5 5 5 444 0.16 5 5 555555 0.08 5 5 5 5 5 5 5 5 445 0.16 5 5 5 5 5 2 5 5 0.08 5 5 5 5 5 4 5 5 ~
- 120 - 13~0326 AIT~unt of Comp. active mgredient (A) (B) (C) (D) (E) (F) (G) (H) No . ~I pl i etl (kg/ha) 0.16 5 5 5 5 5 5 5 5 463 0.08 5 5 5 5 5 5 5 5 0.04 5 5 5 5 5 5 5 5 0.16 5 5 5 5 5 5 5 5 465 0.08 5 5 5 5 5 5 5 5 0.04 5 5 5 5 5 5 5 5 546 0.16 5 5 5 5 5 5 5 5 595 0.16 5 5 5 5 5 5 5 5 596 0.16 5 5 5 5 5 5 5 5 597 0.16 5 5 5 5 5 5 5 5 598 0.16 5 5 5 5 5 5 5 5 599 0.16 5 5 5 5 5 5 5 5 600 0.16 5 5 5 5 5 5 5 5 601 0.16 5 5 5 5 5 5 5 5 0.l6 5 5 5 5 5 5 5 5 734 0.08 5 5 5 5 5 5 5 5 0.0~ 5 5 5 5 5 5 5 5 0.16 5 5 5 5 5 5 5 5 735 0.08 5 5 5 5 5 5 5 5 0.04 5 5 5 5 5 5 5 5 0.16 5 5 5 5 5 5 5 5 737 0.08 5 5 5 5 5 5 5 5 0.04 5 5 5 5 5 5 5 5 13~0326 Amount of Comp. active ingredient (A) (B) (C) (D) (E) (F) (G) No. applied (kg/ha) 815 0.16 5 5 5 5 5 5 5 5 0.08 4 4 4 5 4 4 4 4 816 0.16 5 5 5 5 5 5 5 5 0.08 5 5 5 5 5 5 5 5 817 0.16 5 5 5 5 5 5 5 5 0.08 5 5 5 5 5 5 5 5 818 0.16 5 5 5 1 5 5 5 5 5 0.08 5 5 4 5 5 5 5 5 819 0.16 5 5 5 5 5 4 5 4 0.08 5 4 5 5 4 4 5 4 833 0.16 5 5 5 5 5 5 5 5 0.08 4 4 4 5 4 4 4 4 834 0.16 5 5 5 5 5 5 5 5 0.08 5 5 5 5 5 5 5 5 835 0.16 5 5 5 5 5 5 5 5 0.08 5 5 5 5 5 5 5 5 836 0.16 5 5 5 5 5 5 5 5 0.08 5 4 4 5 4 5 5 5 0.16 5 5 5 5 5 4 5 5 0.08 5 4 5 5 4 3 4 4 Control 0.16 3 2 2 4 3 2 2 3 Compound A 0.08 2 0 1 4 1 1 1 3 Control 0.16 4 4 3 3 4 3 4 4 Compound B 0.08 3 3 3 1 3 2 3 3 Control 0.16 3 2 2 4 3 2 2 3 Compound C 0.08 2 1 1 2 1 1 1 2 Control 0.16 5 4 4 4 3 3 3 4 Compound D 0.08 4 3 4 3 Control Compounds in the above Table 5 are as follows:

Control Comp. A (disclosed in Japanese Unexamined Publn. No. 169688/1981):

~ S 03 NHCNH
- H

Control Comp. B (disclosed in Japanese Unexamined Publn. No. 169688/1981):

~ SO~NHC~H ~ ~

Control Comp. C (disclosed in Japanese Unexamined Publn. No. 169688/1981):

CH3O2C ~ SO NHCNH ~/ ~

Control Comp. D (disclosed in Japanese Unexamined Publn. No. 102577/1980):

8 N~ocH3 ~ SO2~HCNH ~ ~

13~032~

Test example 2: Herbicidal effect test by stem-leaf treatment In a plastic box of 15 cm length, 22 cm width and 6 cm depth, there was placed a deluvium soil, seeds of ~A) rice (Oryza sativa), (C) large crabgrass (Digitaria adscendens), (D) annual sedge (Cyperus microiria), (E) lambsquarters (Chenopodium ficifolium), (G) hairly galinosoga (Galinosoga ciliata), (H) yellow cress (Rorippa atrovirens), (I) corn (zea mays), (J) soybean (Glysine max), (K) wheat (Triticum vulgare), and (L) tomato (Lycopersicum esculentum) were sown in shapes of spots, respectively, followed by covering of soil to about 1.5 cm over the seeds. After respective plants have grown to the second and the third leaf stage, herbicides were sprayed evenly onto the stem-leaf portion at predetermined proportions of the active ingredient.

In spraying, the wettable powder as shown in the foregoing exemplary formulations was diluted with water and sprayed over the entire surface of the stem-leaf portions of various weeds by means of a small sprayer.

Four weeks after spraying, the herbicidal effect on rice and the various plants were examined according to the judgement criteria as shown in Test example 1. The results are shown in Table 6.

Some of the compounds of this invention have selectivities on some kinds of crops.

In the following Table 6, the Control Compounds A, B
and D are the same as those in the foregoing Test example 1.

134032~
-- 1~4 --Table 6 Amount of Camp ingredient ~A) (C ) (D ) ~E ) (G ) (;~ ) (I ) (J ) (K ) (L ) (~g/ha) 0.16 5 5 5 5 5 5 5 3 4 2 0.0 8 5 5 5 5 5 5 5 2 3 0.1 6 4 5 5 5 4 5 5 5 5 5 0.08 4 5 5 5 4 5 4 4 4 5 0.1 6 5 5 5 5 5 5 5 5 5 4 0.08 5 5 5 5 5 5 5 5 4 4 0.1 6 5 5 5 5 5 5 5 5 5 5 o.n8 5 4 4 5 4 5 5 5 5 3 86 0.08 5 5 5 5 5 5 5 5 5 0 0.1 6 5 5 5 5 5 5 5 5 5 5 87 0.08 5 5 5 5 5 5 5 5 5 5 0.1 6 5 5 5 5 5 5 5 5 5 5 0.08 5 5 5 5 5 4 5 5 $ 5 - 0.16 5 5 5 5 5 5 5 5 5 4 ' 0.08 5 5 5 4 4 5 4 4 4 3 0.1 6 5 5 5 5 5 5 5 5 5 5 1 59 0.~8 5 5 5 5 5 5 5 5 4 4 0.04 5 5 5 5 5 5 5 5 4 3 .

Ccmp ~nont of No ingredient (A) (C) (D) (E) (G) (H) ~ J) (K) (L) (kg/ha) 0.08 5 5 5 5 5 5 5 5 4 5 0.1 6 5 5 5 5 5 5 5 5 5 4 0.08 5 5 5 5 5 4 4 4 4 3 0.1 6 5 5 5 5 5 5 5 5 5 - 5 384 0.08 5 5 5 5 5 5 5 5 5 5 0.04 5 5 5 5 ~5 5 1 5 5 5 5 0.1 6 5 5 5 5 5 5 5 5 5 385 0.08 5 5 5 5 5 5 5 5 5 o 0.04 5 5 5 5 5 5 5 5 5 0 0.1 6 5 ~ 5 5 5 5 5 5 5 5 5 0.1 6 5 5 5 5 5 5 5 5 5 5 387 0.08 5 5 5 5 5 5 5 5 5 5 0.04 5 5 5 5 5 5 5 5 5 5 0.1 6 5 5 5 5 5 5 5 5 5 5 388 0.08 5 5 5 5 5 5 5 5 5 5 0.04 5 5 5 5 5 ' 5 5 5 5 5 0.1 6 5 5 5 5 5 5 5 5 5 409 0.08 5 5 5 5 5 5 5 5 5 o 0.04 5 5 5 5 5 5 5 5 5 0 0.16 5 5 5 5 5 5 5 5 5 z 41 0 0.08 5 5 5 5 5 5 5 5 5 0.04 5 5 5 5 5 5 5 5 5 0 0.1 6 5 5 5 5 5 5 5 5 5 ~ 5 41 1 0.08 5 5 5 5 5 5 5 5 5 5 0.04 5, 5 5 5 5 5, 5 5 5 5 1340~2~

P~nount of C~p. active No. ingredient (A) (C) (D) (E) (G) (H) (I) (J) (K) (L) applied (kg/ha) 392 0.16 4 5 5 5 5 3 4 o 4 5 394 0.16 5 4 5 5 5 5 5 5 5 5 396 0.16 5 5 5 5 5 5 5 5 5 5 425 0.16 5 4 5 5 5 5555 5 442 0.16 5 5 555 5 5 5 5 o 0.08 4 5 5 5 5 4 55 4 ~
443 0.16 4 5 5 55 5 5 5 5 5 0.08 4 4 5 5 55 5 5 5 5 444 0.16 5 5 5 5 5 5 5 5 5 5 0.08 5 5 5 5 4 5 5 5 5 5 445 0.16 5 5 5 5 5 5 5 5 5 5 0.08 5 5 5 5 5 4 5 5 5 5 0.16 5 5 5 5 5 5 5 5 5 5 463 0.08 5 5 5 5 5 5 5 5 5 5 0.04 5 5 5 5 5 5 5 5 5 5 0.16 5 5 5 5 5 5 5 5 5 5 465 0.08 5 5 5 5 5 5 5 5 5 5 0.04 5 5 5 5 5 5 5 5 5 5 546 0.16 5 5 5 5 5 5 5 5 5 5 595 0.16 5 5 5 5 5 5 5 5 5 5 596 0.16 5 5 5 5 5 5 5 5 5 3 597 0.16 5 5 5 5 5 5 5 5 5 5 598 0.16 5 5 5 5 5 5 5 5 5 5 599 0.16 55 5 5 555 5 55 600 0.16 5 4 5 55 5 5 5 5 5 ~ - 134032~
.

a'lp actlve ingr~dient (A) (C) (D) (E) (G) (H) (I) (J) (K) (L) ~ ~pl; e~l (kg/ha) 601 0.16 5 5 4 5 5 5 5 5 5 5 0.16 5 5 5 5 5 5 5 5 5 5 734 0 . 08 5 4 5 4 5 4 4 5 5 5 0.16 5 5 5 5 5 5 5 5 5 735 0. 08 - 4 5 5 4 5 4 5 5 5 0 0.16 5 5 5 5 5 5 5 5 5 ~
737 0 . 08 5 5 5 4 5 4 5 5 5 0 0.16 5 5 5 5 5 5 5 5 2 5 815 0 . 08 5 4 5 5 5 5 5 5 1 4 0.16 5 5 5 5 5 5 5 5 4 5 816 0. 08 5 4 5 5 5 5 5 5 3 5 0.16 5 5 5 5 5 5 5 5 2 5 817 0. 08 4 4 5 5 5 5 5 5 1 4 0.16 5 4 5 5 5 5 5 5 2 3 818 0 . 08 4 3 5 5 5 5 5 5 0 0.16 5 5 5 5 5 5 5 5 3 5 819 0.08 4 4 5 5 5 4 4 5 2 4 0.16 5 4 5 5 5 5 5 5 2 5 833 0. 08 5 3 5 5 5 5 5 5 1 4 0.16 5 5 5 5 5 5 5 5 3 5 834 0.08 5 4 5 5 5 5 5 5 2 3 ~_ 13~032~

~nount of No ingredient (A) (C) (D~ (E) (G) (H) (I) (J) (K) (L) ~ ~3~?1 i ~
(kg/ha) 0.16 5 4 5 5 5 5 5 5 2 4 835 0.08 4 3 5 5 5 5 5 5 1 2 0.16 4 3 5 5 5 5 5 5 2 3 836 0.08 3 2 5 4 5 4 4 4 0 0.16 5 3 5 5 5 5 5 5 2 5 837 0.08 4 3 5 4 5 4 4 4 1 4 Control 0.16 4 4 4 4 4 4 4 4 4 2 0.08 3 4 4 4 4 4 4 4 3 2 Control 0.16 3 3 3 3 3 3 3 4 2 2 ~olm(l O.08 3 2 2 3 3 2 3 3 1 2 Control 0.16 3 4 3 3 4 3 3 3 2 2 ~DP 0.08 3 3 3 3 3 3 3 2 2 2 _ 1340326 -Test example 3: Herbicidal effect test under paddy condtion In a Wagner pot of 1/50 m2, there was placed an alluvial soil, water was put thereinto, soil and water were mingled and a paddy condition of 2 cm depth of the water was made. Seeds of (B) barnyardgrass (Echinochloa crus-galli), (M) ducksalad (Monochoria vaginalis), (N) false pimpernel (Lindernia procumbens), (O) toothcup (Rotala indica) and (P) bulrush (Scirpus hotarui) were sown mixedly therein and tuberns of (Q) arrowhead (Sagittaria pygmaea) and (R) perennial flat sedge (Cyperus serotinus) were placed thereon. Then, young rice plants of the 2.5 leaf stage were transplanted.

On the next day, the diluted solution containing the compound of this invention was dropped on the water surface in predetermined proportions of the active ingradient.

Three weeks after application, the herbicidal effect on rice and the various weeds were examined according to the judgement criteria as shown in Test Example 1. The results are shown in Table 7.

.

-- 130 _ Table 7 Amount of Compoundactive No.ingredient (A) (B) (M) (N) (O) (P) (Q) (R) applied (kg/ha) 0.04 0 5555555 816 0.02 0 5555555 0.01 0 4 5 55555 0.04 0 5555555 817 0.02 0 555 5 5 55 0.01 0 4 55555 5 0.04 0 5 5 5 5 5 5 5 834 0.02 0 5 5 5 5 5 5 5 0.01 0 4 5 5 5 5 5 5 0.04 0 5 5 5 5 5 5 5 835 0.02 0 5 5 5 5 5 5 5 0.01 0 4 5 5 5 5 5 5

Claims (19)

1. A compound represented by the formula (I) wherein:
A represents a hydrogen atom, a C1-C8 alkyl group or a phenyl group which may be substituted with C1-C8 alkyl groups, halogen atoms or nitro groups;
B and C independently represent hydrogen atoms, halogen atoms, nitro groups, C1-C8 alkyl groups, arylalkyl groups, C1-C8 alkoxy groups, haloalkyl groups, -CO2R (where R is a hydrogen atom, a C1-C8 alkyl group, an allyl group or a propargyl group), -CONR1R2 [where R1 is a hydrogen atom, a C1-C8 alkyl group or a phenyl group, R2 is a hydrogen atom or a C1-C8 alkyl group, or R1 and R2 taken together may represent -(CH2)m- (m is 4, 5 or 6), -CH2CH2OCH2CH2- or -CH2CH2N(CH3)CH2CH2-], -S(O)n R3 (where R3 is a C1-C8 alkyl group, a phenyl group or an arylalkyl group and n is 0, 1 or 2), -SO2NR4R5 [where R4 is a C1-C8 alkyl group, R5 is a hydrogen atom or a C1-C8 alkyl group, or R4 and R5 taken together may represent -(CH2)p-(p is 4, 5 or 6), -CH2CH2OCH2CH2- or -CH2CH2N(CH3)CH2CH2-] or a phenyl group which may be substituted with C1-C8 alkyl groups, halogen atoms or nitro groups;
D represents a hydrogen atom or a C1-C8 alkyl group;
X and Y independently represent hydrogen atoms, halogen atoms, C1-C8 alkyl groups, C1-C8 alkoxy groups, C1-C8 alkoxyalkyl groups, -CF3 groups, C1-C8 haloalkoxy groups, alkylamino groups, dialkylamino groups, (where R6 and R7 each represent hydrogen atoms or C1-C8 alkyl groups), or either X or Y may form a five-membered ring containing an oxygen atom together with Z; and Z represents a nitrogen atom or C-R8 (where R8 represents a hydrogen atom, a haloalkyl group or may form a five-membered ring containing an oxygen atom together with X or Y).

2. A compound according to Claim 1, wherein:
A is a C1-C4 alkyl group, a hydrogen atom or a phenyl group;
B and C are independently selected from the group consisting of hydrogen atom, halogen atoms, C1-C4 alkyl groups, -COOR (where R is allyl or a C1-C4 alkyl group), -CF3, SO2-C1-C4-alkyl group, -SO2N(CH3)2, -OCH3, -CONHC1-C4-alkyl, -CON(C1-C4- alkyl)2, -CON(CH2)p (p is 4, 5 or 6) and phenyl group;
D is a hydrogen atom;
X and Y are independently selected from the group consisting of hydrogen atom, halogen atoms, C1-C4 alkyl groups, C1-C4 alkoxy groups, C1-C4 alkoxyalkyl groups, -CF3 and C1-C4 haloalkoxy groups; and Z is N or CH.

3. A compound according to Claim 1, which is represented by the formula (II) wherein:
Alk represents methyl, ethyl, n-propyl or i-propyl; and X and Y are independently selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, n-propoxy and i-propoxy; and Z is N or CH.

4. A compound according to Claim 1, which is represented by the formula (III) wherein:
Alk is methyl or ethyl;
X and Y are independently selected from the group consisting of methyl and methoxy; and Z is N or CH.

5. A compound according to Claim 4, wherein Y is methoxy and Z is CH.

6. A compound according to Claim 1, which is N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-1, 3-dimethyl-5-methoxy-carbonylpyrazole-4-sulfonamide.

7. A compound according to Claim 1, which is N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-1,3-dimethyl-5-methoxy-carbonylpyrazole-4-sulfonamide.

8. A compound according to Claim 1, which is N-[(4-chloro-6-methylpyrimidin-2-yl)aminocarbonyl]-1,3-dimethyl-5-methoxy-carbonylpyrazole-4-sulfonamide.

9. N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide.

10. A compound of the formula wherein A is H or CH3; each of B and D is H, lower alkyl, F, Cl, Br or lower alkoxycarbonyl; each of X and Y is CH3, or OCH3; and Z is CH or N, provided that when A is H, D is H, Cl or CH3.

11. A compound of the formula

12. A compound of the formula wherein A is H or CH3; each of B and D is H, lower alkyl, F, Cl, Br or lower alkoxycarbonyl; each of X and Y is CH3 or OCH3; and Z is CH or N, with the provisions that, (i) when either B or D is lower alkoxycarbonyl, then the other is H, Cl or CH3;
(ii) when B is H or lower alkyl, then D is other than H, lower alkyl, F, Cl or Br.

13. A compound of the formula wherein A is H or CH3; B is H or lower alkyl, F, Cl or Br;
D is H, lower alkyl, F, Cl or Br; each of X and Y is CH3 or OCH3; and Z is CH or N.

14. A process for synthesizing a compound of the formula I

wherein:
A represents a hydrogen atom, a C1-C8 alkyl group or a phenyl group which may be substituted with C1-C8 alkyl groups, halogen atoms or nitro groups;
B and C independently represent hydrogen atoms, halogen atoms, nitro groups, C1-C8 alkyl groups, arylalkyl groups, C1-C8 alkoxy groups, haloalkyl groups, -CO2R (where R is a hydrogen atom, a C1-C8 alkyl group, an allyl group or a propargyl group), -CONR1R2 [where R1 is a hydrogen atom, a C1-C8 alkyl group or a phenyl group, R2 is a hydrogen atom or a C1-C8 alkyl group, or R1 and R2 taken together may represent -(CH2)m- (m is 4, 5 or 6), -CH2CH2OCH2CH2- or -CH2CH2N(CH3)CH2CH2-], -S(O)n R3 (where R3 is a C1-C8 alkyl group, a phenyl group or an arylalkyl group and n is 0, 1 or 2), -SO2NR4R5 [where R4 is a C1-C8 alkyl group, R5 is a hydrogen atom or a C1-C8 alkyl group, or R4 and R5 taken together may represent -(CH2)p- (p is 4, 5 or 6), -CH2CH2OCH2CH2- or -CH2CH2N(CH3)CH2CH2-] or a phenyl group which may be substituted with C1-C8 alkyl groups, halogen atoms or nitro groups;
D represents a hydrogen atom or a C1-C8 alkyl group;
X and Y independently represent hydrogen atoms, halogen atoms, C1-C8 alkyl groups, C1-C8 alkoxy groups, C1-C8 alkoxyalkyl groups, -CF3 groups, C1-C8 alkoxy groups, -CH3 groups, C1-C8 haloalkoxy groups, alkyl-amino groups, dialkylamino groups, (where R6 and R7 each represent hydrogen atoms or C1-C8 alkyl groups) or either X
or Y may form a five-membered ring containing an oxygen atom together with Z; and Z represents a nitrogen atom or C-R8 (where R8 represents a hydrogen atom, a haloalkyl group or may form a five-membered ring containing an oxygen atom together with X or Y), which process comprises:
(a) allowing a compound represented by the formula (IV) where A, B and C are the same as defined above, to react with a compound represented by the formula (V) where D, X, Y and Z are the same as defined above;
(b) allowing a compound represented by the formula (VII) wherein A, B and C are the same as defined above and R9 represents an alkyl group or a phenyl group, to react with a compound represented by the formula (V) wherein D, X, Y and Z are the same as defined above, or (c) allowing a compound represented by the formula (VI) to react with a compound represented by the formula (X) wherein E, G and Z are the same as defined above.

15. A process for synthesizing a compound of the formula (I) wherein;

A represents a hydrogen atom, a C1-C8 alkyl group or a phenyl group which may be substituted with C1-C8 alkyl groups, halogen atoms or nitro groups;
B and C independently represent hydrogen atoms, halogen atoms, nitro groups, C1-C8 alkyl groups, arylalkyl groups, C1-C8 alkoxy groups, haloalkyl groups, -CO2R (where R is a hydrogen atom, a C1-C8 alkyl group, an allyl group or a propargyl group), -CONR1R2 [where R1 is a hydrogen atom, a C1-C8 alkyl group or a phenyl group, R2 is a hydrogen atom or a C1-C8 alkyl group, or R1 and R2 taken together may represent -(CH2)m- (m is 4, 5 or 6), -CH2CH2OCH2CH2- or -CH2CH2N(CH3)CH2CH2-], -S(O)nR3 (where R3 is a C1-C8 alkyl group, a phenyl group or an arylalkyl group and n is 0, 1 or 2), -SO2NR4R5 [where R4 is a C1-C8 alkyl group, R5 is a hydrogen atom or a C1-C8 alkyl group, or R4 and R5 taken together may represent -(CH2)p- (p is 4, 5 or 6), -CH2CH2OCH2CH2- or -CH2CH2N(CH3)CH2CH2-] or a phenyl group which may be substituted with C1-C8 alkyl groups, halogen atoms or nitro groups;
D represents a hydrogen atom or a C1-C8 alkyl group;
X and Y independently represent hydrogen atoms, halogen atoms, C1-C8 alkyl groups, C1-C8 alkoxy groups, C1-C8 alkoxyalkyl groups, -CF3 groups, C1-C8 haloalkoxy groups, alkylamino groups, dialkylamino groups, where R6 and R7 each represent hydrogen atoms or C1-C8 alkyl groups) or either X or Y may form a five-membered ring containing an oxygen atom together with Z;
and Z represents a nitrogen atom or C-R8 (where R8 represents a hydrogen atom, a haloalkyl group or may form a five-membered ring containing an oxygen atom together with X or Y), which process comprises allowing a compound represented by the formula (IV) wherein A, B and C are the same as defined above, to react with a compound represented by the formula (V) wherein D, X, Y and Z are the same as defined above.

16. A process for synthesizing a compound of the formula (I) wherein:
A represents a hydrogen atom, a C1-C8 alkyl group or a phenyl group which may be substituted with C1-C8 alkyl groups, halogen atoms or nitro groups;
B and C independently represent hydrogen atoms, halogen atoms, nitro groups, C1-C8 alkyl groups, arylalkyl groups, C1-C8 alkoxy groups, haloalkyl groups, -CO2R (where R is a hydrogen atom, a C1-C8 alkyl group, an allyl group or a propargyl group), -CONR1R2 [where R1 is a hydrogen atom, a C1-C8 alkyl group or a phenyl group, R2 is a hydrogen atom or a C1-C8 alkyl group, or R1 and R2 taken together may represent -(CH2)m- (m is 4, 5 or 6), -CH2CH2OCH2CH2- or -CH2CH2N(CH3)CH2CH2-], -S(O)nR3 (where R3 is a C1-C8 alkyl group, a phenyl group or an arylalkyl group and n is 0, 1 or 2), -SO2NR4R5 [where R4 is a C1-C8 alkyl group, R5 is a hydrogen atom or a C1-C8 alkyl group, or R4 and R5 taken together may represent -(CH2)p- (p is 4, 5 or 6), -CH2CH2OCH2CH2- or -CH2CH2N(CH3)CH2CH2-] or a phenyl group which may be substituted with C1-C8 alkyl groups, halogen atoms or nitro groups;
D represents a hydrogen atom or a C1-C8 alkyl group;
X and Y independently represent hydrogen atoms, halogen atoms, C1-C8 alkyl groups, C1-C8 alkoxy groups, C1-C8 alkoxyalkyl groups, -CF3 groups, C1-C8 haloalkoxy groups, alkylamino groups, dialkylamino groups or (where R6 and R7 each represent hydrogen atoms or C1-C8 alkyl groups) or either X
or Y may form a five-membered ring containing an oxygen atom together with Z; and Z represents a nitrogen atom or C-R8 (where R8 represents a hydrogen atom, a haloalkyl group or may form a five-membered ring containing an oxygen atom together with X or Y), which process comprises allowing a compound represented by the formula (VII) wherein A, B and C are the same as defined above and R9 represents an alkyl group or a phenyl group, to react with a compound represented by the formula (V) wherein D, X, Y and Z are the same as defined above.

17. A process for synthesizing a compound of the formula (IX) wherein:
A represents a hydrogen atom, a C1-C8 alkyl group or a phenyl group which may be substituted with C1-C8 alkyl groups, halogen atoms or nitro groups;
B and C independently represent hydrogen atoms, halogen atoms, nitro groups, C1-C8 alkyl groups, arylalkyl groups, C1-C8 alkoxy groups, haloalkyl groups, -CO2R (where R is a hydrogen atom, a C1-C8 alkyl group, an allyl group or a propargyl group), -CONR1R2 [where R1 is a hydrogen atom, a C1-C8 alkyl group or a phenyl group, R2 is a hydrogen atom or a C1-C8 alkyl group, or R1 and R2 taken together may represent -(CH2)m- (m is 4, 5 or 6), -CH2CH2OCH2CH2- or -CH2CH2N(CH3)CH2CH2-], -S(O)n R3 (where R3 is a C1-C8 alkyl group, a phenyl group or an arylalkyl group and n is 0, 1 or 2), -SO2NR4R5 [where R4 is a C1-C8 alkyl group, R5 is a hydrogen atom or a C1-C8 alkyl group, or R4 and R5 taken together may represent -(CH2)p- (p is 4, 5 or 6), -CH2CH2OCH2CH2- or -CH2CH2N(CH3)CH2CH2-] or a phenyl group which may be substituted with C1-C8 alkyl groups, E represents a halogen atoms;
G represents a hydrogen atom, chlorine, bromine, C1-C4 alkyl, CF3, methoxymethyl or methoxyethyl; and Z represents a nitrogen atom or C-R8 (where R8 represents a hydrogen atom or a haloalkyl group), which process comprises allowing a compound represented by the formula (VI) to react with a compound represented by the formula (X) wherein E, G and Z are the same as defined above.

18. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound as defined in any one of claims 1 to 13.

19. A herbicidal composition comprising a compound as defined in any one of claims 1 to 13, and a herbicidal carrier.