DE2417839A1 - DICARBOXIMIDES, METHOD FOR MANUFACTURING AND USING them - Google Patents

Description

ClB

Dr. F. Zumstein Sr. - Dr, E. Assmann Dr. R. Koenigsborger - Dipl. Phyo. R- timber builder

Dr. F. Zumciein jun. Patent attorneys

8 Munich 2, Bräuhausstrasse 4/111

Case 5-8731 / 1 + 2 / =
Germany

"Dicarboximides, process for their preparation and their

Use"

The present invention relates to dicarboximides, processes for their preparation and their use for Control of insects.

The dicarboximides have the formula

N-E

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CiBA-GEIGYAG - 2 -

wherein R one to three times, identically or differently by fluorine, chlorine, bromine, iodine, trifluoromethyl, nitro, cyano, - C-. -C, -alkyl, methoxy, methylthio or phenyl which is monosubstituted by a methylenedioxy group, and Z- and Z _{2 are} each hydrogen or, together with the carbon atoms to which they are bonded, a carbon-carbon bond.

_{The C 1} -C -alkyl groups which are suitable as substituents of the phenyl group can be branched or unbranched and are preferably the methyl or ethyl group.

The compounds of the formula I are preferred because of their action,

where R one to three times, identically or differently, by fluorine, chlorine, bromine, iodine, trifluoromethyl, Methyl, ethyl, methoxy, methylthio, nitro, cyano or simply by a methylenedioxy group substituted phenyl and

Z ₁ and Ζ «each represent hydrogen or, together with the carbon atoms to which they are bonded, a carbon-carbon bond.

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CIBA-GEIGYAG - 3 -

Particularly preferred are the compounds of the formula I in which R is one to three times, identical or different by fluorine, chlorine, bromine, iodine, trifluoromethyl, ethyl, methylthio, nitro, cyano or phenyl simply substituted by a methylenedioxy group and

Ζ-, and Z "together with the carbon atoms to which they are bound, a carbon-carbon bond mean.

The compounds of the formula I can according to methods known per se, for example by reacting a compound the formula

(II)

with a compound of the formula

wherein R, Z, and Z_ have the meaning given for the formula I. have to be produced.

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The reaction is conducted at normal pressure, a temperature of 60-150 ⁰ C, preferably at 80-120 ⁰ C and carried out in a high boiling solvent such as glacial acetic acid, benzene, toluene or xylene.

The starting materials of the formula II are known and can be used analogously to the Ber. 86 ^ 1528-39 (1953) Method.

■ The compounds of the formula I are suitable for combating of insects. Particularly noteworthy is their good effect against lepidoptera.

U.S. Patents 2,462,835 and 2,545,283 Dicarboximides described as synergists. Reference is made to their insecticidal effect, among other things. US Pat. No. 3,654,302 describes the insecticidal, herbicidal and fungicidal action of dicarboximides.

Compared to those described in the above patents Compounds, the dicarboximides of the formula I have an unexpectedly better larvicidal effect, in particular in larvae of lepidoptera.

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The insecticidal effect can be significantly broadened by adding other insecticides and adapted to the specified circumstances.
Suitable additives are, for example:

organic phosphorus compounds,

Nitrophenols and derivatives,

Formamidine,

Carbamates and

chlorinated hydrocarbons.

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G - 6 -

The compounds of the formula I can be used alone or together with suitable carriers and / or additives can be used. Suitable carriers and additives can be solid or liquid and correspond to those in the Substances commonly used in formulation technology such as natural or regenerated substances, solvents, dispersants, wetting agents, Adhesives, thickeners, binders and / or fertilizers. For application, the compounds of the formula I can be used Dusts, emulsion concentrates, granules, dispersions, sprays, to solutions or slurries in the usual way Formulation used in application technology for General knowledge should be processed. Furthermore, "cattle dips", i.e. cattle baths, and "spray races", i.e. Mention should be made of spray courses in which aqueous preparations are used.

The compositions according to the invention are produced in a manner known per se by intimate mixing and / or Milling of active ingredients of the formula I with the suitable carriers, optionally with the addition of opposite dispersants or solvents that are inert to the active ingredients. The active ingredients can be used in the following working-up forms are available and applied;

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CIBA-GEIGYAG 7

Fixed ...

Forms of processing: dust, grit,

Granulates, enveloping granulates, Impregnation granules and homogeneous granules

Liquid

Forms of processing:

a) dispersible in water
Active ingredient concentrates: wettable powders

Pastes, emulsions;

b) Solutions

The content of active ingredient in the agents described above is between 0.1 and 95%.

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CIBA-GEIGYAG - 8 -

The active ingredients of the formula I can, for example, be formulated as follows:

Dust: The following substances are used to produce a) 5% and b) 2% dust:

a) 5 parts of active ingredient
95 parts of talc;

b) 2 parts of active ingredient

1 part of highly disperse silica, 97 parts of talc

'The active ingredients are mixed with the carriers and marry.

Granules: The following substances are used to produce 5% granules:

5 parts of active ingredient

0.25 part of epichlorohydrin, 0.25 part of cetyl polyglycol ether, 3.50 parts of polyethylene glycol

91 parts of kaolin (grain size 0.3-0.8 mm). The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol is added and cetyl polyglycol ether added. The solution obtained in this way is sprayed onto kaolin and then the

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CIBA-GEIGY AG - 9 ~

Acetone evaporated in vacuo.

Wettable powders: weight To prepare an a) 40%, b) and c) 25% d) 107 _o wettable powder following constituents are used:

a) 40 parts of active ingredient

5 parts of lignin sulfonic acid sodium salt,

1 part of dibuty inaphthalenesulfonic acid sodium salt,

Parts of silica;

b) 25 parts of active ingredient

4.5 parts calcium ligin sulfonate,

1.9 parts of champagne chalk / hydroxyethyl cellulose mixture (1: 1),

1.5 parts of sodium dibutyl naphthalene sulfonate, 19.5 parts of silica, 19.5 parts of Champagne chalk, 28.1 parts of kaolin;

c) 25 parts of active ingredient

2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts of champagne chalk / Eydroxyäthylcellulose-

Mixture (1: 1), 8.3 parts of sodium aluminum silicate,

16.5 parts of kieselguhr, parts of kaolin;

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CIBA-GEIGYAG - 10 -

d) 10 parts of active ingredient

3 parts mixture of the sodium salts of saturated

Fatty alcohol sulfates,
5 parts of naphthalenesulfonic acid / formaldehyde condensers

sat,

• 82 parts of kaolin. '

The active ingredients are mixed with the additives in suitable mixers intimately mixed and ground on appropriate mills and rollers. One receives wettable powder that can be diluted with water to form suspensions of any desired concentration.

Emulsifiable concentrates: To produce a) 10% and b) 25% emulsifiable concentrate x ^ the following substances are used:

a) IO parts active ingredient

3.4 parts epoxidized vegetable oil,

13.4 parts of a combination emulsifier, consisting of fatty alcohol polyglycol ether and alkylarylsulfonate calcium salt,

40 parts of dimethylformamide,

43.2 parts of xylene;

b) 25 parts of active ingredient

2.5 parts epoxidized vegetable oil,

10 parts of an alkylarylsulfonate / fatty alcohol polygllycol ether -Mixture,

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5 parts of dimethylformamide, -

57.5 parts of xylene. "

Emulsions of any desired concentration can be prepared from such concentrates by dilution with water will.

Spray: The following ingredients are used to produce a 5% spray:

5 parts active ingredient,

1 part epichlorohydrin, 94 parts gasoline (boiling point 160 - 190 ⁰ C)

40 9845/1073

example 1

\ a) Preparation of N- (4'-nitrophenyl) -tricyclo- [4.2.2. 0

O /

* 3-non-8-en-o, 7-dicarboximide

250 g of tricyclo- [4.2.2.0 ² '^] - non-8-en-6,7-dicarboxylic anhydride (prepared from cycloheptatriene and maleic anhydride, K. Aider, Ber. 86., 1528-39 (1953)) and 200 g 4-nitroaniline are refluxed for 3 hours in 1500 ml of glacial acetic acid. The reaction mixture, cooled to 60 ^° C., is poured onto 2000 ml of hot water, whereupon the crude product precipitates. After cooling, the crude product is filtered off, dried and recrystallized from ethyl acetate.
M.p. 210-212 ° C.

b) Preparation of N- (3 ', 5'-dichlorophenyl) -tricyclo- [4.2.2.0'] -nonane-6,7-dicarboximide

19.2 g of tricyclo- [4.2.2.0] -nonane-6,7-dicarboxylic acid anhydride (prepared from the cycloheptatriene / maleic anhydride adduct (see example la) by cat. Hydrogenation, K. Aider, Ber. 86, 1528-39 (1953) and 19.4 g of 3,5-dichloro '. 16 hours aniline are refluxed in 1000 ml toluene, the water formed in the reaction abgetrennt_wird with a water separator. After cooling, the toluene is removed by suction in a vacuum and the residue recrystallized from Essigester, mp. 145 - 153 ⁰ C.

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CIBA-GEIQY AQ

The following connections are also established in the same way:

Acc / '

R = M.p. ⁰ C 3,4-dichlorophenyl 204-2O6 ° C 4-bromophenyl 206-2O7 ° C 4-fluorophenyl 184 ° C 4-chlorophenyl 2O3 ° C 3-trifluoromethyl-phenyl 2O6 ° C 3-methylthio-phenyl 186-188 ° C 3,5-dichlorophenyl 167-169 ° C 2,4,5-trichlorophenyl 168-170 ° C 2,5-dibrotophenyl 191-192 ° C 2,5-dichlorophenyl 195-196 ° C 3-chlorophenyl 182-183 ° C 3-nitropheny1 204-2O6 ° C 3,5-bis-trifluoromethyl-phenyl 100-101 ^° C 2-chloro-5-trifluoromethyl-phenyl 126-127 ° C 2-ethyl-phenyl 152-154 ° C 4-cyano-phenyl 190-191 ° C 2-methyl-4-chlorophenyl 179 to 180 ⁰ C

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CIBA-GEIGY AG

NO

R = M.p. ⁰ C 2-methyl-5-chlorophenyl 184 to 190 ⁰ C 3-trifluoromethyl-4- ^i- chloro-phenyl 189 to 190 ⁰ C 2-methyl-5-nitro-phenyl 189-190 ° C 2-nitrophenyl 168-170 ° C 4-methoxyphenyl 198-200 ° C 2-fluorophenyl 148 to 149 ⁰ C 3-fluoropheny1 152-154 ° C 2-iodophenyl 149 to 151 ⁰ C 4-iodophenyl 216-218 ° C 2-chloro-4-bromophenyl 208 to 210 ⁰ C 2,5-dimethoxy-4-chlorophenyl 196-198 ° C 4-methylthio-phenyl 186-188 ° C 3,5-dinitro-phenyl 178 to 180 ⁰ C 2-nitro-4-methyl-phenyl 202-204 ° C 2,4-dichloro-phenyl 162-164 ° C 2-trifluoromethyl-phenyl 128 ° C 2-methyl-3-chlorophenyl 157 ° C 3,4-methylenedioxy-phenyl 217 ° C 4-trifluoromethyl phenyl 218 ° C

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CIBA-GEIGY AG

R = M.p. ⁰ C 2-methoxy-4-chlorophenyl 170 ⁰ C 2,4-dibromophenyl 2O7 ° C 2,4-difluorophenyl 135 ° C 2,5-difluorophenyl 135 ⁰ C 2- methyl-4-bromophenyl 198 ° C 3-fluoro-4-methyl-phenyl 2O2 ° C 3-Bromo-5-trifluoromethyl-pheny1 141 ° C 3,4,5-trichlorophenyl 186 to 187 ⁰ C 2-methyl 1-3-nitro-phenyl 210 ° C

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CIBA-QEIQY AG

ι
R = M.p. ⁰ C 4-bromo-phenyl
2-chloro-5-trifluoromethyl-phenyl
2,4-dichloro-phenyl 230-240 ⁰ C.
157 ° C
175 ⁰ C

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CIBA-GEIGY AG ~ ZT -

Example 2

Insecticidal activity against Spodoptera littoralis 15 era high cotton plants were sprayed with 25 ml of a solution containing 0.2% active substance (acetone / water 1: 1). After drying, 5 Spödoptera caterpillars (3rd stage) were set on per plant. A plastic cylinder was placed over the plant and closed with a copper gauze lid. The mortality was determined after 2 days. The compounds according to Example 1 showed a good action against Spodoptera littoralis in this test.

Example 3

Insecticidal activity against Leptinotarsa decetnlineata 15 cm high potato plants were sprayed with 25 ml of a solution containing 0.1% active substance (acetone / water 1: 1). After drying, 10 Leptinotarsa larvae (3rd stage) were placed on each plant. A plastic cylinder was placed over the plant and closed with a copper gauze lid. The mortality was determined after 2 days.

The compounds according to Example 1 showed a good action against Leptinotarsa decemlineata in this test.

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Claims (1)

CiBA-GEIGY AG Claims Compounds of the formula where R Z-. and one to three times by identical or different fluorine, chlorine, bromine, iodine, trifluoromethyl, nitro, cyano, C -, - C, alkyl, methoxy, methylthio or monosubstituted by a methylenedioxy phenyl and j are each hydrogen or together with the Kohleri The substance atoms to which they are bound represent a carbon-carbon bond. 409845/1073 2. Compounds according to claim 1, where R one to three times, identical or different by fluorine, chlorine, bromine, iodine, trifluoromethyl, Methyl, ethyl, methoxy, methylthio, nitro, cyano or simply by a methylenedioxy group substituted phenyl and Z-, and Z "each hydrogen or together with the carbon atoms, to which they are bound represent a carbon-carbon bond. 3. Compounds according to claim 2, where R one to three times, identically or differently, by fluorine, chlorine, bromine, iodine, trifluoromethyl, Methyl, ethyl, methylthio, nitro, cyano or simply by a methylenedioxy group substituted phenyl and Z- * and Z _? together with the carbon atoms to which they are attached represent a carbon-carbon bond. 409845/1073 CIBA-GEIGY AG 4. A compound according to claim 3 of the formula 5. A compound according to claim 3 of the formula Ii A compound according to claim 3 of the formula Il Cl 409845/1073 CtBA-GEIGY AG 7. A compound according to claim 3 of the formula Il 0 8. A compound according to claim 3 of the formula A compound according to claim 3 of the formula C ^Br Α09845 / Ί073 CIBA-GEIGY AG 10. A compound according to claim 3 of the formula 11. Compound according to claim 3 of the formula 12. Process for the preparation of compounds of the formula Z, 409845/1073 CIBA-GEIGY AG "where R one to three times, identically or differently due to fluorine, chlorine, bromine, iodine, trifluoromethyl, nitro, cyano, C-, -C, -alkyl, methoxy, methylthio. or phenyl which is simply substituted by a methylenedioxy group and each is hydrogen or together with the J- in Carbon atoms to which they are attached, a carbon-carbon bond mean, characterized in that one is a compound of the formula and with a compound of the formula converts, in which R, Z. and have meaning. specified in claim 1 409845/1073 CIBA-GEIGY AG '- 24 - 13. Insecticidal agents which, as the active component, are a compound according to claims 1 to 11 and suitable Contain carriers and / or other additives. 14. Use of compounds according to claims 1 to 11 for combating insects. 15. Use according to claim 14 for combating lepidoptera. FO 3.35 / JA / sl 409845/1073