CS252839B2 - Method of new substituted 1-phenyl-3-benzoyl (thio) ureas production - Google Patents

Description

The present invention relates to a process for the production of novel substituted 1-phenyl-3-benzoyl (thio) ureas which have insecticidal and acaricidal effects and can therefore be used as active ingredients of insecticidal and acaricidal compositions in combating insects and mites.

It has already been known that certain benzoylureas have insecticidal properties (cf., for example, European Patent Specification No. 0 057 888).

It has now been found that the novel substituted 1-phenyl-3-benzoyl (thio) ureas of Formula I

(I) in which

X represents a sulfur atom or an oxygen atom,

R 5 represents a hydrogen atom, a halogen atom, a nitro group or a radical selected from the group consisting of C 1 -C 6 alkyl and C 1 -C 6 alkylthio, r ² , r ⁴ and r ⁵ are the same or different from each other, and means a hydrogen atom or a halogen atom,

R represents a hydrogen atom, a halogen atom or a nitro group,

7

R and R are the same or different from each other and are hydrogen, halogen or C 1 -C 6 alkyl,

9 o t

R and R are the same or different and represent a hydrogen atom or a halogen atom and

R ¹⁰ is C 1 -C 4 haloalkylthio or C 1 -C 4 haloalkoxy, C 1 -C 4 halo, preferably chlorodifluoromethylthio, trifluoromethylthio, chlorodifluoromethoxy or trifluoromethoxy, wherein (1) when X is oxygen and

3 4 5 6 7

R, R, R, R, R, and R are hydrogen and

R is hydrogen or halogen; and are both halogen or (b) r 1! is halogen, nitro or (C1-C6) -alkyl and r5 is hydrogen, in which case rIG is in each case C1-C4-haloalkylthio and wherein (2) when X is oxygen or sulfur and

R 6 is chloro and o

R is hydrogen or chloro and

R is hydrogen and

R @ ¹ represents halogenoalkylthio having 1 to 4 carbon atoms or halogenoalkoxy having 1 to 4 carbon atoms and

3 (a) R and R are halogen and

R ² , R ⁴ and R ⁵ represent hydrogen or

3 (b) R 1 and R 2 are halogen and r 1, R ² and R ⁴ are hydrogen or (c) R ¹ and R ⁴ are halogen and

3 3

R, R and R are hydrogen or

5 (d) R and R are halogen and

4

R, R and R are hydrogen, then a residue in these cases

R is in each case hydrogen or alkyl having 1 to 6 carbon atoms and has strong biological, in particular insecticidal and acaricidal properties, which make them suitable for use as active ingredients of insecticidal and acaricidal compositions.

SUMMARY OF THE INVENTION The present invention provides a process for the preparation of the novel substituted 1-phenyl-3-benzoyl (thio) ureas of the above-defined and defined general formula (I), wherein the substituted phenyl-iso (thio) cyanates of the formula

R ⁶

R 'in which

X, R ^, R R, R ^ and rIG are as defined above, reacting with benzoic amides of formula V

in which

2 3 4 5

R, R, R, R and R are as defined above, optionally in the presence of a catalyst and optionally in the presence of a diluent.

7

The alkyl groups R, R and R and the alkylthio groups R ¹ contain in the alkyl part a straight or branched alkyl group having 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms.

Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methylthio, ethylthio, n-propylthio, isopropyl thio, n-butylthio , isobutylthio, sec-butylthio and tert-butylthio.

The haloalkylthio and haloalkoxy radicals R @ ¹¹ each contain in the alkyl part a straight or branched alkyl group having 1 to 4 carbon atoms, in particular 1 to 2 carbon atoms and preferably 1 to 4 halogen atoms, the halogen atoms being the same or different and suitable halogen atoms are preferably fluorine, chlorine or bromine atoms, in particular fluorine.

Examples include trifluoromethylthio, chlorodifluoromethylthio, trifluoroethylthio, chlorotrifluoroethylthio, tetrafluoroethylthio, trifluoromethoxy, difluoromethoxy, tetrafluoroethoxy, chlorotrifluoroethoxy and bromotrifluoroethoxy.

Halogen means, unless otherwise indicated, a fluorine, chlorine, bromine and iodine atom, preferably a fluorine, chlorine and bromine atom.

X is preferably oxygen.

The process according to the invention advantageously produces compounds of formula I in which:

X is oxygen or sulfur; means hydrogen, fluorine, chlorine, bromine, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methylthio, ethylthio, n-propylthio , isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio,

4 5

R, R and R are the same or different and are hydrogen, fluoro, chloro or bromo

R is hydrogen, fluoro, chloro, bromo or nitro;

R 0 and R 2 are the same or different and are hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl ,

9

R and R are the same or different and are hydrogen, fluorine, chlorine or bromine;

R ^{8 9 10} represents trifluoromethylthio or trifluoromethoxy, wherein (1) when X is oxygen and

9 4 fi fi 9

R, R, R, R, R and R are hydrogen and r 7 is hydrogen, fluorine, chlorine or bromine and (a) a is both fluorine, chlorine and / or bromine or (b) R 6 is fluorine, chlorine, bromine , nitro or the above alkyl groups; and

R ⁵ is hydrogen, in which case it is in each case trifluoromethylthio and in which case (2) when X is kyric or sulfur and is chlorine and

O

R is hydrogen or chloro and

Q

R is hydrogen and

R ¹⁰ is trifluoromethylthio or trifluoromethoxy; and R ³ is fluoro, chloro or bromo and

4 5

R, R and R are hydrogen or

3 (b) R and R are fluoro, chloro or bromo;

4

R, R and R are hydrogen or (c) r 1 is hydrogen; and R 6 is fluoro, chloro or bromo and

3 5

R, R and R are hydrogen or

(D) R and R are fluoro, chloro or bromo;

4

R, R and R are hydrogen, then a residue in these cases

R is in each case hydrogen or the above-mentioned alkyl group.

Particularly preferably, the process of the present invention provides compounds of formula (I) wherein:

X is oxygen,

R ³ is hydrogen, fluoro, chloro, bromo, nitro, methyl or methylthio,

4 5

R, R and R are hydrogen, fluoro, chloro or bromo,

R is hydrogen, fluoro, chloro or nitro,

R ^ and R? are the same or different and are hydrogen, chlorine or methyl,

9 _z

R and R are the same or different and are hydrogen, fluorine or chlorine, and R10 is tri fluoromethylthio or tri fluoromethyl,

3 4 6 8 9 (1) if R, R, R, R, R and R are hydrogen and

R is hydrogen or chloro and

5 (a) R 1 and R 2 are both fluoro, chloro and / or bromo or (b) r 5; is fluorine, chlorine, bromine, nitro or methyl and when ^j is hydrogen, then in these cases the residue is always trifluoromethylthio and wherein (2) when R is chlorine and g

R stands for hydrogen or chlorine and '

R is hydrogen and

R ¹⁰ is trifluoromethylthio or trifluoromethoxy and

3 (a) R and R are fluoro, chloro and / or bromo and

4 5

R, R and R are hydrogen or

(B) R 1 and R 2 are fluorine, chlorine and / or bromine and R 1, R 2 and R 2 are hydrogen or

4 (c) R and R are fluoro, chloro and / or bromo and

3 5

R, R and R are hydrogen or

5 (d) R and R are fluorine, chlorine and / or bromine and r 1, r 3 and are hydrogen, then in these cases the residue

R? is hydrogen or methyl.

If 4- (2-chloro-4-trifluoromethoxyphenoxy) -3-methylphenylthioisocyanate and 2,6-difluorobenzamide are used as starting materials in the process of the invention, the reaction scheme can be illustrated as follows:

The substituted phenyl-iso (thio) cyanates of the formula IV which are used as starting materials in the process according to the invention can be obtained by conversion of the amino group in the substituted anilines of the formula II

R (II)

Η, Ν

in which

7 8 9 10

R, R, R, R and R are as defined above, per isocyanate group or isothiocyanate group, for example by reaction with phosgene or thiophosgene.

The substituted anilines of the general formula (II) which are used as starting materials are known and / or can be prepared by processes and methods known from the literature (cf. DE-OS 32 17 619, DE-OS 32 17 620 and European patent specification). No. 00 57 588).

Examples of compounds of formula IV include the corresponding isocyanates or isothiocyanates of the substituted anilines of formula II shown in Table 1 below.

Table 1

r, 6 _7 '8 9 '10 R R R R R H H H H ^0CF 3 Cl H H H ^0CF 3 Cl Cl H H ^0CF 3 H Cl Cl H ^0CF 3 H H Cl Cl ocf ₃ Cl H H Cl ocf ₃ H H Cl. H OCE 3 H H II Cl ^0CF 3 Cl Cl Cl H ocf ₃ Cl Cl H Cl ° cf ₃ Cl H Cl Cl OCF ₃ Cl Cl Cl Cl ocf ₃

continuation of Table 1 R ⁶ 'R ⁷ R ⁸ ch ₃ H H ^CH 3 Cl H ^CH 3 H Cl ^CH 3 ÍI H ck ₃ H Cl ^CH 3 Cl Cl ch ₃ Cl H ^CH 3 Cl Cl ^CH 3 ^Objective 3 H ^CH 3 ^CH 3 Cl ^CH 3 ch ₃ H ch ₃ ^CH 3 Cl H H H Cl H H Cl Cl H H Cl Cl H H Cl Cl H H Cl H Cl H H Cl H H H Cl Cl Cl Cl Cl H Cl H Cl Cl Cl Cl CH ₃ H

Ή

Η

Η

NO. 1

NO. 1

Η

NO. 1

NO. 1

Η

Η

NO. 1

NO. 1

Η

Η

Η

Η

NO. 1

NO. 1

Η

Η

NO. 1

Η

NO. 1

NO. 1

NO. 1

Η

^R10 ocp ₃ ^0CF 3 OCF ₃ OCF ₃ ^0CF 3

OCF ₃

OCF ₃ ° _C f ₃

OCFj ocf ₃ ocf ₃ ocf ₃

SCF ₃

SCF ₃ scf ₃

₃ SCF ₃ scf scf scf _{3 3}

SCF ₃

SCFj ₃ ^SCF 3 scf scf scf _{3 3} SCF ₃ sequel Table 1

'6 8 _9 '10 R R R R R ch ₃ Cl H H ^SCF 3 ^CH 3 H Cl H ^SCF 3 ^CH 3 H H Cl scf ₃ ^CH 3 H Cl Cl scf ₃ ch ₃ Cl Cl H SCF ₃ ch ₃ Cl H Cl scf ₃ ^CH 3 Cl Cl Cl scf ₃ ch ₃ ^CH 3 H H scf ₃ ^{C [I} 3 ^CH 3 Cl H SCF ₃ ^CH 3 ^CH 3 H Cl scf ₃ ^CH 3 ch ₃ Cl Cl ^SCF 3

Examples of compounds of formula IV include: 2-fluoro-, 2-chloro-, 2-bromo-, 2-nitro-, 2-methyl-, 2-methylthio-, 2,6-difluoro-, 2,6- dichloro, 2-chloro-6-fluoro-, 2-chloro-4-nitro-, 3,4-difluoro-, 3,4-dichloro, 2,3,6-trichloro, 4-fluoro-, 4 -chloro-, 4-bromo- and 4-nitrobenzamide.

The compounds of formula (V) are known compounds.

Suitable diluents for the process according to the invention are virtually all inert organic solvents. These include in particular aliphatic and aromatic optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl ether and dibutyl ether, glycol dimethyl ethers and diglycol dimethyl ethers, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methylisopropyl ketone and methyl isobutyl ketone, esters such as methyl acetate and ethyl acetate, nitriles such as acetonitrile and propionitrile;

Tertiary amines such as triethylamine and 1,4-diazabicyclo [2.2.2] octane as well as organic tin compounds such as dibutyltin dilaurate may be used as catalysts for the process according to the invention.

The reaction temperature can be varied within a wide range. In general, the process according to the invention is carried out at temperatures between 20 and 200 ° C, preferably between 60 and 190 ° C.

The process according to the invention is generally carried out at atmospheric pressure.

In carrying out the process of the invention, the starting materials are usually used in approximately equimolar amounts. Excess of one or the other reactant does not bring any significant advantages.

The reaction products are worked up by conventional methods, for example by filtering off the precipitated products or by dissolving undesired by-products from the reaction mixture.

The melting point is used to characterize the reaction products.

The following Examples illustrate the preparation of the compounds of formula (I).

Example 1

To a solution of 3.32 g (0.01 mol) of 3,5-dimethyl-4- (3-chloro-4-trifluoromethoxyphenoxy) aniline in 50 ml of absolute toluene is added 2.42 g (0.01) at 60 ° C. mol) of 2-bromobenzoyl isothiocyanate in 10 ml of toluene. The mixture was then stirred at 80 ° C for 30 minutes and then concentrated to a volume of about 20 mL. The precipitate was filtered off and dried.

5.1 g (89% of theory) of 1- (2-bromobenzoyl) -3- [3,5-dimethyl-4- (3-chloro-4-trifluoromethoxyphenoxy) phenyl] urea, m.p.

Example 2

In an analogous manner to that described in Example 1, 1- (2,6-difluorobenzoyl) -3- [3,5-dichloro-4- (4-trifluoromethoxyphenoxy) phenyl] urea of the formula:

-OCF

Melting point: 194 ° C.

The compounds of the formula I n ² R ¹ Q 1 - co-nh-cx-

^nh ~ (c ^ ^o-r1 )

R R R (I)

Table 2

Example number R ¹ R ² R ³

R ⁴ R ⁵ R ⁶ R ⁷ R ⁸ R ⁹ R ¹⁰

Melting point (° C)

Cl H

Cl H

Η H Cl Cl H

H F Cl Cl H

194

193 continued Table 2 .10

Example number R ¹ R ² R ³

Melting point

Br H Cl H

F H

Cl H

Cl H

F H

Cl H

Cl H

F H

Br H

Cl H ^NO 2 ^H sch ₃ H

Η H

Cl H

H Cl

Br H ^CH 3 ^H

Cl H and ₃ H

Br H

Cl H

Cl H

F H

Cl H

F H

Η H

Η H

Η H

Η H

Η H

Η H

Η H

Η H

Η H

Η H

Η H

Η H

Η H

Cl H no ₂ H

Cl H

Η H

Η H

Η H

Η H

Η H

Η H

Η H

Η H

Η H

Η H

H

H

F

Cl

F

F

F

H

F

H

F

H

H

H

H

H

H

H

Cl

H

H

Cl

F

F

Cl

F

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

II H

Η H

Η H

Η H

Η H

Η H

Η H

Cl H

Cl H

Cl H

Cl H

Cl H

Cl H

Cl H

Cl H

Cl H

Cl H

Cl H

Cl H

Cl H

Cl H

Η H

Η H

Η H

Η H

Η H

Η H

Η H scf ₃ 0 scf ₃ O scf ₃ O scf ₃ O scf ₃ O ocf ₃ O

OCF ₃ o

OCF ₃ o

OCF ₃ p

OCF ₃ p

OCF ₃ with ocf ₃ o

OCF ₃ o

OCF ₃ o

OCF ₃ o

OCF ₃ o

OCF ₃ o ocf ₃ o

OCF ₃ o

OCF ₃ o ocf ₃ o ocf ₃ sec

OCF ₃ p

OCF ₃ p

OCF ₃ p

OCF ₃ p

199 198

215

226

226

167

154

178

170

151

182

202

181

232

230

128

171

188

203

206

200

194

152

145

154

139 continued Table 2

Example Melting point

number R ¹ R ² R ³ R ⁴ R ^S R ⁶ R ⁷ R ⁸ R ⁹ R ¹⁰ X (° CI 31 Cl H H H F Cl H H H OCF ₃ with 121 32 Cl H H H H H H Cl H ocf ₃ 0 154 33 F H H H F H H Cl H OCF ₃ 0 162 34 Br H H H H H H Cl H ocf ₃ 0 167 35 Cl H H H Cl H H Cl H ^0CF 3 with 156 36 Cl H H H F H H Cl H ° cf ₃ with 148 37 Cl H H H H Cl H Cl H ^ocf 3 0 151 38 F H H H F Cl H Cl H ocf ₃ 0 156 39 Cl H H H Cl Cl H Cl H ^0CF 3 with 143 40 Cl H H H Cl Cl H Cl H ^0CF 3 0 188 41 Cl H H H H Cl Cl H Cl ^0CF 3 0 200 42 Cl H H H H Cl Cl Cl H scf ₃ 0 207 43 F H H H F Cl Cl Cl H ^SCF 3 0 216 44 F H H H F Cl Cl H Cl ^0CF 3 0 196 45 Cl H H H F Cl Cl Cl H SCF ₃ with 166 46 CH ₃ H H H H Cl Cl Cl H scf ₃ 0 207 47 Cl H H H F Cl Cl H Cl ^0CF 3 with 161 48 Br H H H H Cl Cl H Cl ° cf ₃ with 154 49 Br H H H H Cl Cl Cl H scf ₃ 0 204 50 Br. H H H H Cl Cl H Cl OCF ₃ 0 180 51 ^CH 3 H H H H Cl Cl H Cl ^0CF 3 0 207 52 Cl H H H Cl Cl Cl Cl H scf ₃ 0 205 53 Cl H H H Cl Cl Cl Cl H ° cf ₃ 0 220 54 Cl H H H Cl ^CH 3 ^CH 3 H Cl OCF ₃ 0 191-192 55 Cl H H H H CH ₃ CH ₃ H Cl «° CF ₃ 0 174-175 56 Cl H H H F CH ₃ CH ₃ H Cl ocf ₃ 0 172-173

continuation of Table 2

Example number R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ R ⁷ R ⁸ R ⁹ R ¹⁰ X Melting point <° C) 57 F H H H F ^CH 3 ^CH 3 H Cl ° CF ₃ 0 182-183 58 Cl H H H H ^CH 3 ^CH 3 Cl H ocf ₃ 0 200-206 59 Cl H H H H CH ₃ ch ₃ H H scf ₃ 0 201 60 Cl H H H F ^CH 3 ^CH 3 Cl H ° cf ₃ 0 151 61 F H H H F ^CH 3 ck ₃ H H. scf ₃ 0 200 62 F F F F F Cl Cl Cl H ° CF ₃ 0 196 63 F H H H F ^CH 3 ^CH 3 ' Cl H ° CF ₃ 0 149 64 Cl H H H F cb ₃ ^CH 3 Cl H ocf ₃ with 155 65 F H H H F ch ₃ ^CH 3 Cl H ocf ₃ with 133

OBJECT OF THE INVENTION

Claims (4)

A process for the preparation of the novel substituted 1-phenyl-3-benzoyl (thio) ureas of general formula (I) in which: X represents a sulfur atom or an oxygen atom, i R represents a hydrogen atom, a halogen atom, a nitro group or a radical from the group consisting of a C1-C6 alkyl group and a C1-C6 alkylthio group, R ^2, R ⁴ and R ⁵ are identical or different and represent hydrogen or halogen, R represents a hydrogen atom, a halogen atom or a nitro group, R ⁶ and R ⁷ are the same or different from each other and are hydrogen, halogen or C 1 -C 6 alkyl, 8 9 R and R are the same or different from each other and are hydrogen or halogen, and R 10 is C 1 -C 4 haloalkylthio or C 1 -C 4 haloalkoxy, wherein (1) when X is oxygen and R ² , R ³ , R ⁴ , R ⁶ , R ⁸ and R ⁹ are hydrogen and R is hydrogen or halogen; and 15, (a) R and R are both halogen or (b> r 1 is halogen, nitro or C 1 -C 6 alkyl and r 5 is hydrogen, then in these cases the radical R 7 is ^-8 in each case a haloalkylthio group having 1 to 4 carbon atoms and wherein (2) when X is oxygen or sulfur and r6 is chloro and R is hydrogen or chloro and q R is hydrogen and R ³⁸ is C 1 -C 4 haloalkylthio or C 1 -C 4 haloalkoxy and (a) R and R are halogen and 2 4 5 R, R and R are hydrogen or (B) R and R are halogen and R ³ , R ² and R ⁴ are hydrogen or (c) R ³ and R ⁴ are halogen and 2 3 5 R, R and R are hydrogen or (D) R and R are halogen and R ^1, R ³ and R represent hydrogen, in these cases, radical (IV) R is in each case hydrogen or (C1-C6) -alkyl, characterized in that the substituted phenyliso (thio) cyanates of the formula IV &apos; XCIM 10 R ⁷ R ⁸ R ^{8 9} in which 6 7 8 9 X, R, R, R, R and R are as defined above, in reaction with benzoic acid amides of formula V wherein R 1, R 1, R ³ , R ⁴ and R ⁵ are as defined above, optionally in the presence of a catalyst and optionally in the presence of a diluent. 2. A process according to claim 1, wherein the corresponding compounds of the general formulas (IV) and (V) are used as starting materials to produce compounds of the general formula (I) in which: X is oxygen or sulfur; means hydrogen, fluorine, chlorine, bromine, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-isobutyl, sec-butyl, tert-butyl, methylthio, ethylthio, n- propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, 2 4 5 R, R and R are the same or different and are hydrogen, fluoro, chloro or bromo, □ R is hydrogen, fluoro, chloro, bromo or nitro, 6 7 R and R are the same or different and are hydrogen, fluorine, chlorine, bromine or methyl. ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, 8 9 R and R are the same or different and are hydrogen, fluorine, chlorine or bromine; R @ ¹ = ^O is trifluoromethylthio or trifluoromethoxy, wherein (1) when X is oxygen and 2 3 4 5 6 7 R, R, R, R, R, and R are hydrogen and R? is hydrogen, fluoro, chloro or bromo and (A) R 1 and R 2 are both fluoro, chloro and / or bromo, or (b) R 1 'is fluoro, chloro, bromo, nitro or the above alkyl groups; and R ⁵ is hydrogen, then in these cases the radical r 10 is always trifluoromethylthio and wherein (A) when X is oxygen or sulfur and R 6 is chloro and O R is hydrogen or chloro and R is hydrogen and R @ 1 is trifluoromethylthio or trifluoromethoxy (A) R and R are fluoro, chloro or bromo; 2 4 5 R, R and R are hydrogen or (B) R and R are fluoro, chloro or bromo; 12 4 R, R and R are hydrogen or (C) R and R are fluoro, chloro or bromo; 2 3 5 R, R and R are hydrogen or (D) R and R are fluoro, chloro or bromo; 13 4 R, R and R are hydrogen, then a residue in these cases R is in each case hydrogen or the above-mentioned alkyl groups. 3. Process according to claim 1 or 2, characterized in that the corresponding compounds of the general formulas (IV) and (V) are used as starting materials to give compounds of the general formula (I) in which X is oxygen and the other substituents have the meanings given in 1. 2. 4. A process according to claim 1, wherein the corresponding compounds of the formulas IV and V are used as starting materials to form compounds of the formula I in which: X is oxygen, R ³ is hydrogen, fluoro, chloro, bromo, nitro, methyl or methylthio, 2 4 5 R, R and R are hydrogen, fluoro, chloro or bromo, R ³ represents hydrogen, fluorine, chlorine or nitro, R ⁷ and R ⁷ are the same or different and are hydrogen, chlorine or methyl, O Q R and R are the same or different and are hydrogen, fluoro or chloro and R ¹⁰ is trifluoromethylthio or trifluoromethoxy, wherein (1) when R ⁴ , R ⁴ , R ⁴ , R ⁸ , R ⁸ and R 6 are hydrogen and R 6 is hydrogen; is hydrogen or chlorine and (a) R 1 and R ⁵ are both fluoro, chloro and / or bromo or (b) R ¹ is fluoro, chloro, bromo, nitro or methyl and is hydrogen, in which case the radical r 10 is is in each case trifluoromethylthio and wherein (2) when R 1 is chloro and R ⁸ is hydrogen or chlorine; R is hydrogen and R ¹⁰ is trifluoromethylthio or trifluoromethoxy; and (a) R ⁸ and R ⁸ are fluoro, chloro and / or bromo, and 2 4 5 R, R and R are hydrogen or r 3 (b) R and R are fluorine, chlorine and / or bromine and 12 4 R, R and R are hydrogen or (O) R ¹ and R ⁴ signify fluorine, chlorine or / a bromine and R ² , R ³ and R ⁵ signify hydrogen or (d) R ² and R ⁵ signify fluorine, chlorine or / a bromine and R ¹ , - R ³ and R ⁴ is hydrogen, then in these cases the rest R is in each case hydrogen or methyl.