CS244950B2 - Production method of new n-arylsulphonyl-n-pyrimidinyl-ureas - Google Patents

Description

New N-arylsulfonyl-N'- _: pyrimidinylureas corresponding to formula I have been found

of.

II c

v i

ti

in which

X represents a group of formula (T)

Y represents a C 1 -C 3 alkyl group, a C 1 -C 3 haloalkyl group, a C 1 -C 3 alkoxy group, a C 1 -C 3 haloalkoxy group, a C 1 -C 3 alkylthio group, a halogen or a C 1 -C 3 dialkylamino group 4 carbon atoms in alkyl radicals,

Z is oxygen or sulfur,

R 1 is hydrogen, halogen, nitro, C 1 -C 4 haloalkyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkoxy, or -SO 2 R 9,

R2 is hydrogen, fluoro, chloro, nitro, methyl, methoxy or (C1 -C4) alkylthio,

R3 is hydrogen, fluoro, chloro, amino, nitro or methoxy,

R 5 is halogen,

R 6 is C 3 -C 5 alkenyloxy, C 3 -C 5 alkynyloxy or optionally C 1 -C 3 halogen or C 1 -C 3 alkoxy substituted by C 1 -C 5 alkoxy,

R 7 is hydrogen, C 1 -C 4 alkyl or -CO-R 12,

R 5 is hydrogen or C 1 -C 4 alkyl,

R 9 is -O-R 13 or a (C 1 -C 4) dialkylamino group;

R12 is C1-C4alkyl,

R 13 is optionally 1 to 3 halogen atoms substituted with 1 to 4 carbon atoms, and m is 0 or 2, and salts thereof which have herbicidal activity and further have the ability to control plant growth.

Urea derivatives, triazine derivatives, and pyrimidine derivatives having a herbicidal action are generally known. Arylsulfamoylheterocyclylaminocarbamoyl derivatives having herbicidal activity and the ability to control plant growth are briefly described, for example, in European Patent Publication Nos. 9,419 or 30,141.

In the definition of the above symbols, alkyl means straight or branched alkyl such as methyl, ethyl, n-propyl, isopropyl or the four isomers of butyl.

Alkoxy refers to methoxy, ethoxy groups, n-propyloxy, isopropyloxy, four isomers of butyloxy, in particular methoxy, ethoxy or isopropoyloxy.

Examples of alkylthio groups include methylthio, ethylthio, n-propylthio, isopropylthio, in particular all methylthio and ethylthio,

Examples of alkenyl groups include vinyl, allyl, isopropenyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-isobutenyl, 2-isobutenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl and 4-pentenyl, in particular vinyl, allyl and 4-pentenyl.

Examples of the alkylsulfonyl group include methylsulfonyl, ethylsulfonyl or n-propylsulfonyl, in particular methylsulfonyl and ethylsulfonyl.

Halogen means, alone or as part of a haloalkoxy group, fluorine, chlorine and bromine, preferably fluorine and chlorine.

Alkynyl radicals as defined above generally mean propargyl, 2-butynyl, 3-hutinyl and isomers of pentinyl radicals, but preferably alkynyl radicals are propargyl or 2- or 3-butynyl radicals.

The invention also includes salts which can form compounds of formula I with alkali metal amines or their compounds and with alkaline earth metal bases or quaternary ammonium bases.

Alkali or alkaline earth metal hydroxides as salt-forming components are understood to be lithium, sodium, but sodium or potassium hydroxides.

Examples of amines suitable for salt formation include primary, secondary and tertiary aliphatic and aromatic amines such as methylamine, ethylamine, propylamine, isopropylamine, the four isomers of butylamine, dimethylamine, diethylamine, diethanolamine, dipropylamine, diisopropylamine, di-n-butylamine, pyrrolidine piperidine, morpholine, trlmethylamine, triethylamine, tripropylamine, quinuclidine, pyridine, quinoline and isoquinoline, in particular all ethylamine, propylamine, diethylamine or triethylamine, in particular isopropylamine and diethanolamine.

Examples of quaternary ammonium bases are, in general, cations of halogenammonium salts, for example tetramethylammonium cation, trimethylbenzylammonium cation, triethylbenzylammonium cation, tetraethylammonium cation, trimethylethylammonium cation, but also ammonium cation.

Among the compounds of formula (I), those corresponding to formula (Ia) are preferred

From OCHF, il N

X - 5o f NH - C - NH - X '

N in which

X represents a group of the formula

Y represents a methyl group, an ethyl group, an ethoxy group, a methoxy group, a difluoromethoxy group, a dimethylamino group or an ethylmethylamino group,

Z is oxygen or sulfur,

R 1 represents hydrogen, fluoro, chloro, bromo, iodo, nitro, trifluoromethyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, -CO-Re, -NR 7 R 8, -S (O) _m - (C 1 -C 4) -alkyl or -SO 2 -R 9;

R2 is hydrogen, fluoro, chloro, nitro, methyl, methoxy or (C1 -C3) alkylthio,

R3 is hydrogen, fluoro, chloro, nitro or methoxy,

R 5 is halogen,

R 6 is C 3 -C 5 alkenyloxy, C 3 -C 5 alkynyloxy, or optionally C 1 -C 5 halogen substituted C 1 -C 5 alkoxy,

R 7 is hydrogen, C 1 -C 4 alkyl or -CO-R 12,

R 5 is hydrogen or C 1 -C 4 alkyl,

R12 is C1-C4alkyl,

R 13 is C 1 -C 4 alkyl, phenyl or benzyl and m is 0 or 2, as well as salts thereof.

Among the compounds of formulas I and Ia, which are preferably prepared according to the process of the invention, those in which

a) X is an optionally substituted phenyl moiety of the formula

in which

R1, R2 and R3 have the above meanings, bj Y is a radical having at most 2 carbon atoms,

c) Z is oxygen and dj R 3 and R 1 are hydrogen.

Combining some preferred features, the following additional preferred groups of compounds of Formula I and Ia are then available in which

X is an optionally substituted phenyl radical of formula

R1 in which

R1, R2 and Ro are as defined above,

Y represents a residue of at most 2 carbon atoms,

Z is oxygen and R3 is hydrogen.

Within this group, further preferred are those compounds wherein R 2 is hydrogen.

A particularly preferred subgroup of compounds of formula I are those wherein X is optionally substituted phenyl core of the formula

in which

R1, R2 and R3 are as defined above, Y is a residue of up to 2 carbon atoms, Z is oxygen, wherein R1 is hydrogen, halogen, nitro, C1-C4haloalkyl, C1-C4alkoxy, alkyl (C 1 -C 4) -S (O) _{m (} C 1 -C 4) alkyl, -SO 2 -N (CH 3) 2 ', -SO 2 -OOH 2 CF 3, or -CO-R 6,

R 2 is hydrogen, fluoro, chloro, nitro, methyl, methoxy or C 1 -C 4 alkylthio, R 6 is C 3 -C 5 alkenyloxy, C 3 -C 5 alkynyloxy, or optionally 1 to 3 halogen or alkoxy (C 1 -C 3) -substituted C 1 -C 5 -alkoxy; and m is 0 or 2.

Preferred individual compounds include:

N- (2-chlorophenylsulfonyl) -N- (4-difluoromethoxy-6-methylpyrimidin-2-yl) urea,

N- (2-methoxycarbonylphenylsulfonyl) -N-N- (4-difluoromethoxy-6-methoxypyrimidin-2-yl) urea,

N- (2-nitro-phenylsulfonyl) -N- (4-difluoromethoxy-6-methylpyrimidin-2-yl) urea,

N- (2-methoxycarbonylphenylsulfonyl) -N- [4,6-bis- (difluoromethoxy) pyrimidin-2-yl] urea; and

N- (2-methoxycarbonylphenylsulfonyl) -N '- (4-difluoromethoxy-6-methylpyrimidin-2-yl) urea.

According to the invention, the compounds of the formula I are prepared by reacting an arylsulfonamide of the formula II

X — SO2 — NHz (Π) in which

X is as defined in formula I, at a temperature between -20 ° C and +120 ° C in the presence of a base with an isocyanate or isothiocyanate of formula VI

OO \

W - i

2 ·· ON '* \ ¹ (VI) in which

Y and Z are as defined in Formula I.

The ureas of the formula I obtained can optionally be converted into addition salts by treatment with amines, alkali metal hydroxides or alkaline earth metal hydroxides or with quaternary ammonium bases. This is done, for example, by reaction with an equimolar amount of the base and evaporation of the solvent.

The reaction to give the compounds of formula I is preferably carried out in aprotic, inert, organic solvents such as methylene chloride, tetrahydrofuran, acetonitrile, dioxane, toluene.

The reaction temperatures are preferably between -20 ° C and +120 ° C. The reaction generally proceeds slightly exothermally and can be carried out at room temperature. Suitably, the reaction mixture is heated to the boiling point of the reaction mixture for a short time in order to shorten the reaction time or also to initiate the reaction. The reaction times can also be shortened by adding a few drops of base or isocyanate as reaction catalyst.

As bases, both organic bases such as amines such as triethylamine, quinuclidine, pyridine, etc., as well as inorganic bases such as hydrides such as sodium hydride or calcium hydride, hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as carbonate sodium and potassium carbonate or bicarbonates such as potassium and sodium bicarbonate.

The reaction products may be isolated by concentration and / or evaporation of the solvent and purified by recrystallization or trituration of a solid residue in solvents in which these compounds do not dissolve well, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.

The compounds of formula I are stable compounds. Handling of these substances does not require any safety measures.

The starting materials of the formula II are known or can be prepared analogously to known processes.

Some of the starting materials of the formula (VI) are known or are prepared analogously to known processes.

The following examples illustrate the invention but do not limit it in any way.

Example 1

N- (2-chlorophenylsulfonyl) -N‘- (4,6-bis-difluoromethoxy-pyrimidin-2-yl) urea and J 4,6-bis- (difluoromethoxy) -2-isocyanatopyrimidine

A mixture of 4.55 g of 2-amino-4,6-bis- (difluoromethoxy p-pyrimidine), 3.8 g of oxalyl chloride and 40 ml of ethylene glycol dimethyl ether was heated at reflux for 15 hours to give a clear solution. 4.0 g of 4,6-bis- (difluoromethoxy) -2-isocyanatopyrimidine are obtained in the form of a colorless oil, b.p. 130 DEG-140 ^DEG C./1600 Pa.

bj A mixture of 2.53 g of 4,6-bis- (difluoromethoxy) -2-isocyanatopyrimidine, 1.92 g of 2-chlorophenylsulfonamide, 1.55 g of 1,8-diazabicyclo (5.4.0-iodec-7-ene) and 30 ml. The mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate, evaporation of the organic phase and crystallization of the residue from a mixture of acetone and ether gave 2.9 g of N- (2-). chlorophenylsulfenyl) -N '- (4,6-bis-difluoromethoxypyrimidin-2-yl) urea, m.p. 181-182 ° C (compound 1.7.

The compounds listed in the following tables are also obtained in an analogous manner:

TABLE 1

N \ ochf,

example number Ri R2 Y of (temperature mp ° C 1.1 —COOCH3 H CH3 O 163-164 1.2 —COOCH3 H —OCHF2 O. 186—188 1.3 —COOCH3 H C2H5 0 170—171 1.4 —COOCHi H OCH3 0 177—178 1.5 Cl H CH3 0 169—170 1.6 Cl H C2H5 0 1.7 Cl H —OCHFz 0 181—182 1.8 CH3 H CH3 0 168—171 1.9 CH3 H —OCHFz 0 1.10 OCH3 H CH3 0 164—165 1.11 OCH3 H —OCHF2 0 183—184 1.12 OCH3 H OCH.3 0 173—174 1.13 CF3 H —OCHFz 0 1.14 CF3 H CH3 0 203—204 (decomposition) 1.15 Br H —OCHFz 0 1.16 Br H CH3 0 170—171 1.17 Br H C2H5 0 1.18 NO2 H CH3 0 194—195 (decomposition) 1.19 NOz H —OCHF2 0 173—174 1.20 NOz H OCH3 0 182—184 1.21 OCHs 5-OCHs CH3 0 177—178 1,22 OCH3 5-OCH3 —OCHFz 0 1.23 —CO — SCH3 H —OCHF2 0 1.24 —CO — SCH3 H CH3 0 1.25 —CO — N (CH3) 2 H CH3 0 1.26 —CO — N (CH3) 2 H —OCHFz 0 1.27 —CO — N (CH3) 2 H —N (CH3) 2 0 1.28 —CO — N (CH3) OCH3 H CH3 0 1.29 —CO — N (CH3) OCH3 H —OCHFz 0 1.30 —CHO H CH3 0 1.31 —CHO H —OCHF2 0 1.32 —CHO H C2H5 0 1.33 —SO2 - (CH2) z —CH3 H CH3 0 169—170 1.34. —SO2 - (CH2) z —CH3 H —OCHF2 0 1.35 —SO2 — CH (CH3) 2 H CH3 0 1.36 —SO2 —CH (CH3) 2 H —OCHFz 0 1.37 - SO 2 - CH ('CH 3) 2 H OCH3 0 1.38 —SO2 — CH (CH3) 2 H -N (CH ₃₎ 2 0 1.41 —COOCH3 H —N (CH3) C2 H5 0 1.42 Cl H - N (CH 3) 2 0 185—187 1.43 NO2 H -N (CH ₃₎ from 0 198—199 1.44 OCH3 H -N (CH ₃₎ from 0 1.45 CF3 H —N (CH3) 2 0 1.46 OCH3 5-OCH3 —N (CH3) 2 0 1.47 —CO — CH3 H -N (CH ₃₎ from 0 1.48 NH2 H -N (CH 3) 2 0 1.49 —COOCH.3 5-F CH3 0 1.50 —COOCH3 5-F —OCHFz 0 1.51 —COOCHs 5-F —N (CH3) 2 0 1.52 -CODCH3 6-F CH3 0

example number Rl R2 y OF melting point ° C 1.53 —COOCH3 6-F —0CHF2 O 1.54 —COOCH3 6-F —N (CH3) 2 O 1.55 OCHs 6-C1 CH3 O 163—164 1.56 OCHs 6-C1 —0CHF2 O 1.57 OCHs 6-C1 -N (CH ₃ ) 2 O 1.58 —COOCHs 5-C1 CH3 O 1.59 —COOCH3 5-C1 —0CHF2 O 1.60 —COOCHs 5-C1 C2H5 O 1.61 NO2 H CH3 with 1.62 NO2 H —OCHF2 with 1.63 —SO2 —N (CH3) 2 H CH3 with 1.64 —SO2 —N (CH3) 2 H —OCHF2 with 1.65 —CO — CH3 H CH3 with 1.66 —CO — CH3 H —OCHFZ with 1.67 —COOCH (CH3) 2 H CH3 O 169—170 1.68 —COOCH (CH3) 2 H —OCHF2 O 170—172 1.69 —COOCH (CH3) 2 H OCH3 O 178—180 1.70 —COOCH2 — CH = CH2 H CH3 O 138—140 1.71 —COOCH2 — CH = CH2; H —OCHF2 O 1.72 —COOCH2 — CH = CH2 H C2H5 O 1.73 —C00CH2 — CFS H CH3 O 1.74 —COOCHa — CF3 H —OCHF2 O 1.75 —COOCH2 ¹ —OCH3 H CH3 O 1.76 —COOCH2 — OCH3 H —OCHF2 O 1.77 —COOCHs H —OCH2 — CH3 O 158—159 1.78 —COOCH3 H —N (CH3) 2 O 229—230 1.79 NHz H CH3 O 222—225 (decomposition) 1.80 —NH — CO — CH3 H CH3 O 171—172 1.81 NH2 H —OCHFZ O 1.82 —NH — CO — CH3 H —OCHF2 O 1.83 sch ₃ H CH3 O 168—169 1.84 SCH3 H —OCHF2 O 187—188 1.85 —SO2 — CH3 H CH3 O 208 (decomposition) 1.86 —SO2 — CH3 H —OCHF2 O 1.90 —CO — CH3 H CH3 O 1.91 —CO — CH3 H —OCHF2 O 1.92 —CO — CH3 H OCH3 O 1.93 -SO 2 - N (CH 3) 2 H CH3 O 196—198 1.94 —SO2 —N (CH3) 2 H —OCHF2 O 170—172 1.95 F H CH3 O 158—159 1.96 F H —OCHF2 O 200—201 1.97 Cl H —OCHF2 with 157—159 1.98 Cl H CH3 with 167 (decomposition) 1.99 —COOCH3 H CHF2 O 1.100 —COOCHs H CH2F O 164—165 1.101 —COOCHs H CF3 O 165—166 1.102 —COOCHs H Cl O 171—172 1.103 —COOCHs H —OCH2 — CH2F O 1.104 —COOCH3 H —OCH2 — CF3 O 1.105 —COOCH3 H —NH — CH3 O 1.106 —COOCH3 H Br O 1.107 —COOCH3 H CH2Cl O 1.108 —COOCH3 H F O 1.109 NO2 H Cl O 190—191 1.110 NO2 H CF3 O 175—176 1.111 NO2 H CH2F O 1.112 NO2 H CH2Cl O 1.113 OCHs H Cl O 142—144 1.114 OCH3 H CF3 O 153—154 1.115 OCH3 H CHzF O 1.116 NHz H OCH3 O 1.117 NH2 H Cl O 1.118 Br H CH2F O 1.119 Br H OCHs O

example number Rl Ra Y of mp ° C 1.120 Br H -N (CH ₃ ) 2 O 1.121 Br H Cl O 1.122 —C00CH3 3-C1 CHs O 1.123 —COOCH3 3-C1 OCH3 O 1.124 —C00CH3 3-C1 —OCHF2 O 1.125 —COOCH3 3-C1 —N (CH3) 2 O 1.126 —COOCH3 3-F CHs O 1.127 —COOCHs 3-F OCH3 O 1.128 —COOCH3 3-F —OCHF2 O 1.129 —COOCH3 3-F - N (CH 3) 2 O 1.130 CH3 6-C1 CH3 O 173—176 1.131 CH3 6-C1 OCH3 O 1.132 CH3 6-C1 OCHF2 O 1.133 CH3 6-C1 —N (CH3) 2 O 1.134 NO2 3-C1 CH3 O 1.135 CH3 6-CH3 CH3 O 1.136 CH3 6-CH3 OCH3 O 1.137 —COOCH3 6-CH3 CH3 O 140 (decomposition) 1.138 —OOOCH3 3-CH3 CH3 O 173—175 (decomposition) 1.139 OCH3 H C2H5 O 1.140 OCH3 5-F CHS O 173—175 (decomposition) 1.141 OCH3 5-F OCHF2 O 1.142 OCH3 5-F OCH3 O 1.143 OCH3 5-F —N (CH3) 2 O 1.144 OCH3 5-C1 CH3 O 176—177 (decomposition) 1.145 OCH3 5-C1 OCH3 O 1.146 J H CH3 O 164—166 1.147 OCH3 H C2H5 O 170—171 1.148 H H CHs O 176—177 1.149 Cl H OCH3 O 172—173 1.150 CH3 5-NO2 CH3 O 189—190 1.151 CH3 5-NH2 CH3 O 133—135 1.152 CH3 H Cl O 1,153 CH3 H OCH3 O 1.154 CH3 H —N (CH3) 2 O 1.155 —NH — CO — CH3 H OCH3 O 1.156 OCH3 5-OCH3 OCH3 O 1.157 —CO — SCH3 H OCH3 O 1.158 —CO — SCH3 H —N (CH3) O 1.159 —CO — SCH3 H Cl O 1.160 —CO — N (CH3) 2 H OCH3 O 1.161 —CO — N [CH3] 2 H Cl O 1.162 —SO2 — C3H7-n H OCH3 O 1.163 —SO2 — C3H7-11 H —N (CH3) 2 O 1.164 —SOa — C3H7-11 H Cl O 1.165 —SO2 — C3H7-11 H Cl O 1.166 —SO2 — C2H5 H CH3 O 1.167 —SO2 — C2H5 H -OCHF2 O 1.168 —SO2 — C2H5 H OCH3 O 1.169 —SO2 — C2H5 H -N (CH ₃₎ 2 O 1.170 —SO2 — C2H5 H Cl O 1.171 - SO 2 - CH 3 H OCH3 O 1.172 —SO2-CH3 H -N (CH 3) 2 O 1.173 —SO2 — CH3 H Cl O 1.174 Cl H Cl O 1.175 OCH3 5-OCH3 Cl O 1.176 SCH3 H OCH3 O 181—182 1.177 SCH3 H Cl O 1.178 SCH3 H —N (CH3) 2 O 1.179 —SO2 — N (CH3) 2 H OCH3 O 1.180 -SO 2 -N (CH ₃ ) 2 H Cl O

2449 S O

example number Ri Ra Y of temperature mp ° C 1.181 —SO2 — N (CH5) 2 H —N (CH3) 2 0 1.182 —COOCH3 6-F OCH3 0 1.183 —CO — CH3 H Cl 0 1.184 —COOCH3 6-F Cl 0 1.185 OCH3 6-C1 OCH3 0 1.186 OCH3 6-C1 Cl 0 1.187 —COOCH3 5-C1 OCH3 0 1.188 —COOCH3 5-C1 Cl 0 1.190 F H OCH3 0 198—199 1.191 F H -N (CH 3) 2 0 1.192 F H Cl 0 1.193 J H OCHF3 0 174—176 (decomposition) 1.194 J H OCH3 0 134—136 (decomposition) 1.195 J H - N (CH 3) 2 0 234 (decomposition) 1.196 H H —OCHF2 0 1.197 H H OCH3 0 1.198 H H -N (CH 3) 2 0 1.199 H H -N (CH 3) 2 0 1.200 NO? 5-F CH3 0 1.201 NO2 5-C1 CH3 0 1.202 OCH3 6-SCH3 CH3 0 140-143 1.203 OCH3 6-SCH3 OCH3 0 1.204 OCH3 6-SCH3 OCHF2 0 1.205 —S — C3H7-I H CH3 0 1.206 —S — C3H7-1 H OCH3 0 1.207 -S-C 3 H 7 -I H OCHF2 0 1.208 —O — C2H5 H CH3 0 188—189 1.209 —O — C2H5 H OCH3 0 172—173 1.210 —O — C2H5 H OCHF2 0 165—166 1.211 —O — C2H5 H -N (CH 3) 2 0 195—196 1.212 —O — C2H5 H Cl 0 1.213 —O — C3H7-I H CH3 0 166—167 1.214 —O — C3H7-1 H OCH3 0 168—170 1.215 —O — C3H7-1 H OCHF2 0 147—148 1.216 —O — C3H7-I H - N (CH ₃ ) 2 0 1.217 —O — C3H7-1 H Cl 0 1.218 —O — C3H7-n H CH3 0 1.219 C2H5 H CH3 0 1.220 C2H5 H OCH3 0 1.221 C2H5 H OCHF2 0 1.222 C2H5 H —N (CH3) 2 0 1.223 C2H5 H Cl 0 1.224 C2H5 H CH2F 0 1.225 C2H5 H CF3 0 1.226 —COOCH3 H —O — C3H7-1 0 1.227 NO2 H —O — C3H7-I 0 1.228 NO2 H —O — C2H5 0 128—129 1.229 NO2 H —0 — CH2 — CF3 0 1.230 —COOCH3 H —O — CH2 — CF3 0 1.231 —COOCHs H SCH3 0 187—189 1.232 NO2 H SCH3 0 1.233 CF3 H SCH3 0 1.234 —SO2 —N (CH3) 2 H SCH3 0 1.235 OCH3 H SCHj 0 1.240 —CH2 — CH2 — CF3 H CH3 0 164—165 1.241 —CH2 —CH2 —CF3 H OCH3 0 1.242 —CH2 —CH2 — CFs H OCHF2 0 1.243 —CH2 — CH2 — CF3 H Cl 0 1.244 —CH2 — CH2 — CF3 H —N '(CH3) 2 0 1.245 CF3 H OCH3 0

example number Rl Ra Y OF melting point ° C 1.246 CFs H Cl O 1.247 CF3 H —OC2H5 O 1.248 nh ₂ H OCHs O 1.249 NHž H Cl O 1.250 -N (CH 3) 2 H CH3 O 1.251 —N (CH3) 2 H OCH3 O 1.252 —N (CH3) 2 H OCHF2 O 1.253 - N (CH 2) 2 H —N (CH3) 2 O 1.254 - N (CH 2) 2 H Cl O 1.255 Nose H OCH3 with 1.256 —CO — NH — CH3 H CHs O 1.257 —CO — NH — CH3 H OCH3 O 1.258 —CO — NH — CH3 H OCHF2 O 1.259 _-CO-NH2 H CHs O 1.260 —CO — NH2 H OCH3 O 1.261 —CO — NH2 H OCHF2 O 1.262 CHO H OCH3 O 1.263 CHO H —N (CH3) 2 O 1.264 - CO — CFs H CHs O 1.265 —CO — CF3 H OCHs O 1.266 —CO — CFs H OCHFz O 1.267 -SO — CH3 H CHs O 1.268 —SO — CH3 H OCH3 O 1.269 —SO — CH3 H OCHF2 O 1.270 OCHs H —OC2H5 O 1.271 —OC3H7-11 H OCHs O 1.272 —OC3H7-I1 H OCHF2 O 1.273 —OCsHz-n H - N (CH 3) 2 O 1.274 —OC3H7-I1 H Cl O 1.275 -OClHg-n H CH3 O 1.276 —OClHg-n H OCHs O 1.277 —OC1H9-11 H OCHF2 O 1.278 —COO — CiHg-s H CH3 O 168—169 1.279 —COO — C1H9-S H OCH3 O 164—166 1.280 —COO — C1H9-S H OCHF2 O 167—169 1.281 —COO — CH (CH3) CH2 —OCH3 H CHs O 1.282 —COO — CH (CH3) CH2 —OCH3 H OCHs Ď 125—130 1.283 —COO — CH (CH3) CH2 —OCH3 H OCHFz O 167—168 1.284 —COO — CiHg-i H CH3 O 164—165 1.285 —COO — CiHg-i H OCHs O 1.286 —COO — CiHg-i H OCHF2 O 1.287 —COO — CsHn-n H CH3 O 1.288 —COO — CsHn-n H OCH3 O 1.289 —COO — CsHn-n H OCHF2 O 1.290 -COO — CH2 — CH = CH2 H OCH3 O 1.291 -COO — CH2 — CF3 H OCH3 O 1.292 —COO — CH2 — C6H5 H CHs O 144—146 1.293 -COO — CH2 — C6H5 H OCH3 O 1.294 —COO — CH2 — C6H5 H OCHF2 O 1.295 —COO — CH2 — C = CH H CH3 O 1.296 —COO — CH2 — C = CH H OCHs O 1.297 —COO — CH3 —C ^CH H OCHF2 O 164—166 1.298 —COO — CHs H CHs with 1.299 —COO — CHs H OCHs with 1.300 —COO — CHs H OCHF2 with 1.301 —COO — CHs H -N (CH ₃₎ 2 with 1.302 —COO — CHs H —CH2.C1 O 1.303 —COO — CHs 6-C1 CH3 O 1.304 —COO — CHs 6-C1 OCH3 O 1.305 —COO — CHs 6-C1 OCHF2 O 1.306 —COO — CHs 6-C1 —N (CH3) 2 O 1.307 —COO — CH3 6-C1 Cl O 1.308 —COO — CHs 6-C1 CHsF O

example number Rl Ra Y OF melting point ° C 1.309 —COO — CHs 6-C1 —OC2H5 0 1.310 —COO — C2H5 H CH3 0 150—152 1.311 —COO — C2H5 H OCH3 0 1.312 —COO — C2H5 H OCHF2 0 1.313 —COO — C2H5 H —N (CH3) 2 0 1.314 —COO — C2H5 H Cl 0 1.315 —COO — C2H5 H CHaF 0 1.316 —COO — C3H7-1 H —N (CH3) 2 0 1.317 —COO — CH2CH2 — OCH3 H CH3 0 150—152 1.318 —COO — CH2CH2 — OCH3 H OCH3 0 1.319 —COO — CH2CH2 — OCH3 H OCHFa 0 1.320 —COO — CH2CH2 — OCH3 H - N (CH 3) 2 0 1.321 —COO — CH2CH2 — OCH3 H Cl 0 1.322 —COO — CH2CH2 — Cl H CH3 0 177—179 1.323 —COO — CH2CH2 — Cl H 0CH3 0 1.324 —COO — CH2 — CH2 — Cl H OCHFZ 0 1.325 —COO — CH2 — CH2 — Cl H - N (CI-13) 2 0 1.326 —COO — CH2-CH2 — Cl H Cl 0 1.327 C3H7-I1 I-1 CH3 0 147—148 (decomposition) 1.328 C3H7-n H OCH3 0 1.329 C3H7-11 H OCHF2 0 1.330 C 7 H 7 -n H -N (CH 3) 2 0 1.331 C3H7-11 H Cl 0 1.332 C3H7-I1 H CH2F 0 1.333 H 3-NOa CH3 0 190—193 1.334 H 3-NOa OCH3 0 1.335 H 3-NOa OCHF2 0 1.336 CH 2 Cl H CH3 0 153—156 1.337 CH2Cl H OCH3 0 1.338 CH2Cl H OCHF2 0 1.339 CH2Cl H -N (CH 3) 2 0 1.340 CH2Cl2 H Cl 0 1.341 CH 2 Cl H CH2F 0 1.342 —SO2 - O — CH2CF3 H CHs 0 176—179 1.343 —SO2 —O — CH2 — CF3 H OCH3 0 1.344 —SO2 —O — CH2 — CF3 H OCHF2 0 1.345 —SO2 —O — CH2 — CF3 H -N (CH 3) 2 0 1.346 —SO2 —O — CH2 — CF3 H Cl 0 1.347 —SOa — O — CH2 — CF3 H CHzF 0 1.352 OCH3 4-NO2 CHs 0 164—167 1.353 OCH3 4-NO2 OCH3 0 1.354 OCH3 4-NOa OCHF2 0 1.355 OCH3 4-NO2 - N (CH 3) 2 0 1.356 OCH3 4-NOa Cl 0 1.357 OCH3 4-NH2 CH3 0 1.357 OCH3 4-NH2 OCH3 0 1.358 OCH3 4-NH2 OCH? 0 1.359 OCH3 4-NH2 OCHFa 0 1.360 OCH3 4-NH2 N (CH 3) 2 0 1.361 OCH3 4-NHa Cl 0 1.362 NH2 ¹ 6-OCH 3 CH3 0 1.363 NHz 6-OCH 3 OCH3 0 1.364 NH2 6-OCH 3 OCHF2 0 1.365 NH2 6-OCH 3 —N (CH3) 2 0 1.366 NH2 6-OCH 3 Cl 0 1.367 OCH3 6-OCH 3 CH3 0 1.368 OCH3 6-OCH 3 OCH3 0 1.369 OCH3 6-OCH 3 OCHF2 0 1.370 OCH3 6-OCH 3 —N (CH3) 2 0 1.371 OCH3 6-OCH 3 Cl 0 1.372 OCH3 3-OCH5 CH3 0 1.373 OCH3 3-OCH3 OCH3 0 1.374 OCH3 3-OCH3 OCHF2 0 1.375 Cl 6-C1 CH3 0 170—172

example. number Ri R2 Y OF temperature mp ° C 1.376 Cl 6-C1 OCH3 O 1.377 Cl 6-C1 OCHFz O 1.378 Cl 6-C1 —N (CH3) Z O 1.379 Cl 6-C1 Cl O 1.380 Cl 6-C1 CHzF O 1.381 NOz 6-C1 CH3 O 180 (decomposition) 1.382 NO2 6-C1 OCHs O 157 (decomposition) 1.383 NO? 6-C1 OCHFz O 175—177 (decomposition) 1.384 NOz 6-C1 - N (CH 3) 2 O 185—188 (decomposition) 1.385 NO? 6-C1. Cl O 1.386 NOz 6-C1 CHzF O 1.387 Cl 5-C1 CH3 O 207—209 1.388 Cl 5-C1 OCH3 O 1.389 Cl 5-C1 OCHFz O 1.390 OCH3 5-CH 2 CH3 O 164—167 1.391 OCHs 5-CH 2 OCH3 O 1.392 OCH3 5-CH 2 OCHF2 O 1.393 OCH3 5-CH3 —NfCHsJz O 1.394 OCH3 5-CH3 Cl O 1.395 Cl 3-C1 CH3 O 182—184 1.396 Cl 3-C1 OCH3 O 1.397 Cl 3-C1 OCHFz O 1.398 Cl 3-C1 —N (CH3) 2 O 1.399 Cl 3-C1 WHOSE O 1.400 Cl 3-C1 CHzF O 1.401 CH3 5-NO2 CHs O 189—190 1.402 CH3 5-NO2 OCH3 O 1.403 CHS 5-NOž OCHFz O 1.404 CHs 5-NO2 -N (CH 3) 2 0 1.405 CH3 5-NO2 Cl O 1.406 CHs 5-NHz CH3 O 133—135 1.407 CH3 5-NH2 OCH3 O 1.408 CH3 5-NHz OCHF3 O 1.409 CHS 5-NHz - N (CH 3) 2 O 1.410 CH3 5-NHz WHOSE O 1.411 NO2 6-OCH 3 CH3 O 1.412 NOz 6-OCH 3 C2H5 O 1.413 NO2 6-OCH 3 CHzF O 1.414 NOz 6-OCH 3 CF3 O 1.415 NOz 6-OCHs OCHs O 1.416 NOz 6-OCH 3 OC2H5 O 1.417 NOz 6-OCH 3 OCHFz O 1.418 NO2 6-OCH 3 Cl O 1.419 NOz 6-OCH 3 - N (CH 3) 2 O 1.420 NOz 6-OCH 3 CH3 with 1.421 NH2 6-C1 CHs O 123 (decomposition) 1.422 NHz 6-C1 C2H5 O 1.423 NH2 6-C1 CHzF O 1.424 NHz 6-C1 CF3 O 1.425 NHz 6-C1 OCH3 O 1.426 NHz 6-C1 OC2H5 O 1.427 NHz 6-C1 OCHFz O 1.428 NHz 6-C1 Cl O 1.429 NH2 6-C1 ~ N (CH3) 2 O 1.430 F 6-C1 CH3 O 1.431 F 6-C1 CHzF O 1.432 F 6-C1 CF3 O 1.433 F 6-C1 OCHs O 1.434 F 6-C1 OCHFz O 1.435 F 6-C1 Cl O 1.436 F 6-C1 N (CH 3) 2 O 1.437 F 6-C1 CH3 with 1.438 F 6-C1 OCH3 with

example number Rl R2 Y of ° C (temp 1.439 F 6-C1 OCHF2 with 1.440 F 6-C1 -N (CH _3] 2 with 1.441 Br 6-C1 CH3 O 150—152 (decomposition) 1.442 Br 6-C1 CHZF O 1.443 Br 6-C1 CFs O 1.444 Br 6-C1 OCH3 O 1.445 Br 6-C1 OCHF2 O 1.446 Br 6-C1 Cl O 1.447 Br 6-C1 —N (CH3) 2 O 1.448 J 6-C1 CH3 O 129—131 (decomposition) 1.449 and 6-C1 CH2F O 1.450 J 6-C1 CF3 O 1.451 and 6-C1 OCHs O 1.452 Ϊ 6-C1 OCHF2 O 138 (decomposition) 1.453 J 6 Cl —N (CH3) 2 O 1.454 J 6-C1 CHs with 1.455 Br 6-C1 CH3 with 1.456 —COOCHs 6-CH 2 C2H5 O 1.457 —COOCHs 6-CH3 CH ₂ F O 1.458 —COOCHs 6-CH3 CFs O 1.459 —COOCH3 6-CH3 OCH3 O 1.460 —COOCH3 6-CH3 OCHF2 O 1.461 —COOCHs 6-CH3 Cl O 1.462 —COOCHs 6-CH 2 OC2H5 O 1.463 —COOCHs 6-CH3 —N (CH3) 2 O 1.464 —COO — C2H5 6-CH 2 CH3 O 1.465 —COO — C2H5 6-CH3 OCH3 O 1.466 —COO — C2H5 6-CH3 OCHF2 O 1.467 —COO — C2H5 6-CH 2 —N (CH3) z O 1.468 —COO — C3H7-I 6-CH 2 CH3 O 1.469 —COO — C3H7-1 6-CH3 OCH3 O 1.470 —COO — C3H7-I 6-CH3 OCHF2 O 1.471 —COO — C3H7-I 6-CH 2 —N (CH3) 2 O 1.472 —COOCHs 6-CH 2 CH3 with 1.473 —COOCHs 6-CH3 OCH3 with 1.474 —COOCHs 6-CH 2 OCHFz with 1.475 —COOCH3 6-CH 2 - N (CH 2) 2 with 1.476 —COO — C3H7-I 6-CH 2 CHs with 1.477 —COO — C3H7-1 6-CH 2 OCH3 with 1.478 —COO — C3H7-I 6-CH3 OCHF2 with 1.479 —COO — C3H7-I 6-CH3 - N (CH 3) 2 with 1.480 —COOCH3 4-NO2 CH3 O 186—187 1.481 —COOCHs 4-NO2 OCH3 O 1.482 —COOCHs 4-NO2 OCHFz O 1.483 —COOCHs 4-NO2 —N (CH3) 2 O 1.484 —COOCHs 4-NH2 CHs O 1.485 —COOCHs 4-NH2 OCH3 O 1.486 —COOCHs 4-NH2 OCHF2 O 1.487 —COOCHs 4-NH2 —N (CH3) 2 O 1.488 Cl H OCH3 with 165—166 1.489 Cl H —N (CH3) 2 with 191 (decomposition) 1.490 —COO — C3H7-I H Cl O 163—166 1.491 —COO — C4H9-S H Cl O 165—167

TABLE 2

SO _? ~ NH-C “NN ~ < ^z _ ^x > N

OCHF _q

example number Rs Y OF 2.4 Cl CH.3 0 2.5 Cl —OCHF2 0 2.6 Cl OCH3 0 2.7 Cl C2H5 0 2.18 Cl - N (CH 3) 2 0 TABLE 3

OF

N ^ /

() - SO _from NH - C - N 1 - (-) -

melting point ° C

173—174

QC // R

Y

example number Ri R2 R3 Y OF melting point ° C 5.1 OCHs 3-C1 5-C1 CH3 0 152—155 5.2 OCH3 3-C1 5-Cl OCH3 0 5.3 OCH3 3-C1 5-C1 OCHF2 0 5.4 OCH3 3-C1 5-C1 Cl 0 5.5 OCH3 3-C1 5-C1 -N (CH ₃₎ from 0 5.6 CH3 3-CH3 5-NO2 CH3 0 201 (decomposition) 5.7 CH3 3-CH3 5-NO? OCH3 0 5.8 CH3 3-CI13 5-NO2 OCHF2 0 5.9 CH3 3-CH3 5-NO2 - N (CH 3) 2 0 5.10 OCH3 3-C1 5-C1 CH3 with 5.11 CH3 3-CH3 5-NO2 OCH3 with

SUBJECT OF THE INVENTION

A process for the preparation of the novel N-arylsulfonyl-N‘-pyrimidinyl ureas of the general formula I

OCHR // 'A

Ν '

III v nemz

X represents a group of the formula

Y represents a C 1 -C 3 alkyl group, a C 1 -C 3 haloalkyl group, a C 1 -C 3 alkoxy group, a C 1 -C 3 haloalkoxy group, a C 1 -C 3 alkylthio group, a halogen or a C 1 -C 3 dialkylamino group 4 carbon atoms in alkyl radicals,

Z is oxygen or sulfur,

R 1 is hydrogen, halogen, nitro, C 1 -C 4 haloalkyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy,

-CO-Re, -NR7R8, -S (O) _m alkyl of 1 to 4 carbon atoms, or -SO2R9,

R2 is hydrogen, fluoro, chloro, nitro, methyl, methoxy or (C1 -C4) alkylthio,

R3 is hydrogen, fluoro, chloro, amino, nitro or methoxy,

R 5 is halogen,

R 6 is C 3 -C 5 alkenyloxy, C 3 -C 5 alkynyloxy or optionally C 1 -C 3 halogen or C 1 -C 3 alkoxy substituted by C 1 -C 5 alkoxy,

R 7 is hydrogen, C 1 -C 4 alkyl or -CO-R 12,

R 5 is hydrogen or C 1 -C 4 alkyl,

R 8 is -O-R 13 or a (C 1 -C 4) dialkylamino group;

R12 is C1-C4alkyl,

R 13 is optionally 1 to 3 halogen atoms substituted with 1 to 4 carbon atoms, m is 0 or 2, and salts thereof, characterized in that the arylsulfonamide of formula II - X - SO 2 - NH 2 (Π) is reacted ) in which

X is as defined in Formula I, at a temperature between -20 ° C and +120 T in the presence of a base with an isocyanate or isothiocyanate of Formula VI

Z. - C in which

Y and Z are as defined in formula I, whereupon the sulfonylureas of formula I obtained are optionally converted into salts by treatment with an amine, an alkali metal hydroxide or an alkaline earth metal hydroxide or a quaternary ammonium base.

2. A process according to claim 1, wherein the corresponding compounds of formula (II) and (VI) are used as starting materials to form compounds of formula (I) in which:

X is a group

Claims (10)

Y represents a methyl group, an ethyl group, an ethoxy group, a methoxy group, a difluoromethoxy group, a dimethylamino group or an ethylmethylamino group, Z is oxygen or sulfur, R 1 represents hydrogen, fluoro, chloro, thunder, iodo, nitro, trifluoromethyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, -CO-R 5, -NR 7 R 8, -S (O) _m - alkyl of 1 to 4 carbon atoms or -SO 2 — R9, R2 is hydrogen, fluoro, chloro, nitro, methyl, methoxy or (C1 -C3) alkylthio, R3 is hydrogen, fluoro, chloro, nitro or methoxy, R 5 is halogen, R 6 is C 3 -C 5 alkenyloxy, C 3 -C 5 alkynyloxy, or optionally C 1 -C 5 halogen substituted C 1 -C 5 alkoxy, R 7 is hydrogen, C 1 -C 4 alkyl or -CO-R 12, R 5 is hydrogen or C 1 -C 4 alkyl, R 12 is C 1 -C 4 alkyl, R 13 is C 1 -C 4 alkyl, Ifenyl, or benzyl, and m is 0 or 2. 3. The process of claim 1 wherein the corresponding compounds of formula (II) and (VI) are used as starting materials to form compounds of formula (I) wherein X is an optionally substituted phenyl group of formula And the other symbols have the meaning given in point 1, 4. A process according to claim 1, wherein the corresponding compounds of formula (II) and (VI) are used as starting materials to form compounds of formula (I) wherein Y is a radical having at most 2 carbon atoms and the other symbols have the meaning given in 1. 5. Process according to claim 1, characterized in that the corresponding compounds of the general formula IIa are used as starting materials VI to form compounds of formula I wherein Z is oxygen and the other symbols are as defined in 1. 6. The process of claim 1 wherein the corresponding compounds of formula (II) and (VI) are used as starting materials to form compounds of formula (I) wherein R @ 3 and R @ 4 are hydrogen and the other symbols are as defined in point 1. 7. A process according to claim 1, wherein the corresponding compounds of formula (II) and (VI) are used as starting materials to form compounds of formula (I) wherein X is an optionally substituted phenyl group of formula Y represents a radical of up to 2 carbon atoms, Z represents oxygen and R 3 represents hydrogen and the other symbols have the meaning given in point 1. 8. The process of claim 1 wherein the corresponding compounds of formula (II) and (VI) are used as starting materials to form compounds of formula (I) wherein X, Y and Z are as defined in point 7 and R2 is hydrogen. 9. A process as claimed in claim 1, wherein the corresponding compounds of the formulas II and VI are used as starting materials to give compounds of the formula I wherein X is an optionally substituted phenyl group of the formula Y represents a radical of not more than 2 carbon atoms, Z represents oxygen, wherein R 1 represents hydrogen, halogen, nitro, haloalkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkyl of 1 to 4 carbon atoms, - S (O) _m- C 1 -C 4 -alkyl, -SO 2 -N ('CH 3) 2, -SO 2 -OCH 2 CF 3 or -CO-R 6, R 2 is hydrogen, fluoro, chloro, nitro, methyl, R 6 is C 3 -C 5 alkenyloxy, C 3 -C 5 alkynyloxy or optionally C 1 -C 3 halogen or C 1 -C 3 alkoxy substituted by C 1 -C 5 alkoxy and m is 0 or 2. 10. A process according to claim 1, wherein the corresponding compounds of the formulas II and VI are used as starting materials to form compounds of the formula I selected from the group consisting of: N- (2-chlorophenylsulfonyl) -N- (4-difluoromethoxy-6-methylpyrimidin-2-yl) urea, N- (2-methoxycarbonylphenylsulphonyl) -N‘- [4,6-bis- (difluoromethoxy) pyrimidin-2-yl] urea, N- (2-methoxycarbonylphenylsulfonyl) -N‘- (4-difluoromethoxy-6-methylpyrimidin-2-yl) urea, N- (2-methoxycarbonylphenylsulfonyl) -N- (4-difluoromethoxy-6-methoxypyrimidin-2-yl) urea; and N- (2-nitrophenylsulfonyl) -N- (4-difluoromethoxy-6-methylpyrimidin-2-yl) urea.