DE2901334A1 - 1-Phenyl-3-benzoyl-urea derivs. - useful as insecticides - Google Patents

Abstract

Urea derivs. of formula (I) are new: (A is naphthylthio, tolylthio, or X,Y-substd.naphthyloxy, where X and Y are each H, Cl or Br; Z is H or Cl; Z1 is Cl or F; Z2 is H, Cl or F). Cpds. (I) are insecticides esp. active against mosquitoes, caterpillars, beetles and bettle larvae.

Description

New urea derivatives

The subject matter of the invention is characterized in the claims.

The new active ingredients are characterized by a strong insecticidal effect, especially against pests in caterpillars or.

Larval stage, with good plant tolerance.

Methods known per se can be used to prepare the new active ingredients; see the following reaction scheme: Step (a) is known, step (b) is analogous to Tetrahedron Letters 1968, pages 5071-5074.

In order to achieve the greatest possible implementation of component III, becomes the connection H - Ar used in significant excess (at least the double molar narrow) and also serves as a solvent. However, you can solvents which are also inert under the reaction conditions, e.g.

chlorinated aliphatic hydrocarbons' are added.

For stage c) reducing agents are used which carry out the reduction of the nitro group without otherwise changing the molecule. Are suitable especially base metals such as iron and tin and acids, e.g. hydrochloric acid, glacial acetic acid. Also catalytic reduction with hydrogen and catalysts, such as those used for aniline production serve, comes into consideration. The reaction takes place at temperatures between room temperature and the boiling temperature of the reaction mixture.

The amino compound obtained is reacted in a customary manner with phosgene (stage d), preferably with an excess of phosgene, in an inert Solvent such as an aromatic hydrocarbon such as toluene in an ether such as dioxane or a chlorinated hydrocarbon such as carbon tetrachloride or Chloroform1 at temperatures between room temperature and the boiling point of Reaction mixture converted into the isocyanate of the formula VI.

The compounds according to the invention are obtained by the reaction a compound VI with a benzamide of the formula VII (step e) in the usual manner. For this purpose, it is expedient to use the two components at temperatures between room temperature and the boiling point of the reaction mixture in an inert solvent (e.g. a aromatic hydrocarbon such as toluene or xylene or an ether such as dioxane, Tetrahydrofuran) optionally in the presence of a tertiary aromatic base (e.g.

Triethylamine, pvridine) as a catalyst. It is beneficial to the Catalyst in amounts up to about 30 wt. - To use the isocyanate.

Instead of isocyanate VI, 2,6-benzoyl isocyanate can also be used (stage f) VIII react with an amine of the formula V analogously to step e).

The superior action of the compounds according to the invention is shown, for example, in the comparison of the commercial product of the formula (Difluobenzuron) with the compounds according to the invention according to Example 1 (B) and Example 2 (C); Greenhouse trial; 0.5 percent solution of the active ingredients in acetone, diluted with water to 5 ppm (experiment 1) or 2 ppm (experiment 2): 1. Prodenia caterpillars,% activity in control after 3 days: A 64% B 100, '2 Epilachna larvae,% activity on control after 6 days: A 67% C 96% For use, the active ingredients according to the invention are processed with customary auxiliaries and / or carriers to form customary formulations, for example emulsion concentrates, suspension powders, dusts. It is used in spray liquors and dusts with active ingredient concentrations between about 0.0025 and 2%, in the form of ULV formulations also with higher active ingredient concentrations (up to about 90%). The application rate per hectare is between about 0.05 and 0.5 kg, depending on the active ingredient and crop.

Formulation example: suspension powder (data in wt. -5 ') 25 % Active ingredient according to the invention 55% kaolin 10% colloidal silica 9% lignin sulfonate (Dispersant) 1% sodium tetrapropylene benzene sulfonate (wetting agent) The ingredients are processed as usual to a suspension powder (particle size: <4 / G1). For the application, a spray mixture is prepared with water, which is about 0.0025 contains up to 0.025% by weight of active ingredient.

Example 1 N- (4-Naphthylmercapto-phenyl) -N '- (2,6-dichlorobenzoyl) -urea a) -Nitrobenzenesulfenyl chloride To the slurry of 30.8 g (0.10 ol) di (4-nitrophenyl) disulfide in 200 ml of chloroform, with stirring at an internal temperature of 25-30 ° C., chlorine is added for so long initiated until a clear solution is obtained and no more chlorine is absorbed. The mixture is then stirred at 40-45 ° C. for a further 3 hours. Then distilled the solvent is removed in vacuo at a maximum bath temperature of 500C. Oily 4-nitrobenzenesulfenyl chloride remains behind.

b) 4-Nitrophenyl-naphthyl-thioether The crude 4-Nitrobenzenesulfenylchlorid (38 g of product from the previous stage) becomes 200 g of molten naphthalene at 80 ° C. given. Then a further 0.5 g of Fe (III) chloride are added. After that, will Heated with stirring to such an extent that hydrogen chloride is clearly released (in this Fall to 950C). After the evolution of gas has subsided, 1 - 2 hours at about 105 0C stirred.

The excess naphthalene is then distilled in a water jet vacuum away. The distillation residue is dissolved in 300 ml of ethylene chloride and this solution shaken twice with water. The organic phase is after the addition of 0.5 1 distilled water in vacuo until the distillate remains clear. The residue is redissolved in 300 ml of ethylene chloride; the remaining water is separated. The solvent is then distilled off in vacuo. Then the residue with 1000 ml of gasoline (Boiling range: 40-800C) boiled with stirring. Then undissolved solid constituents are filtered off and twice more Treated with 1000 ml of petrol each. Ultimately, what remains is a by-product Di- (4-nitrophenyl) disulfide undissolved, which is isolated by filtration. The filtrates are combined and concentrated to a residue. What remains is the oily product.

Yield: 31.3 g (0.111 mol) of 4-nitrophenyl-naphthylthio ether, correspondingly 55.5% of theory Regarding the di- (4-nitrophenyl) disulfide used in stage a) recovered: 12.5 g (0.040 mol) of di- (4-nitrophenyl) disulfide, corresponding to ~ 40% of that in stage a) amount used.

c) 4-NaphthylmercaEto-aniline To the mixture of 31.0 g (0.11 mol) 4-Nitrophenylnaphthylthioether (product of the previous stage), 500 ml of water and 2 ml of acetic acid are added to 34 g of iron powder with stirring. Then will the mixture obtained in this way was stirred well for 5 hours at 95 ° -1000 ° C. It colors it turns black-brown.

The reaction mixture is then allowed to cool to 60.degree. If those Temperature is reached, are 200 ml of ethylene chloride and 10 g of kieselguhr. Afterward The resulting mixture is stirred very intensively for 5 minutes. Then you suck the solid components off. The filtrate is divided into 2 phases. The organic Phase is separated off, extracted once with 50 ml of water and then in vacuo concentrated to residue. The oily product remains.

Yield: 25.7 g (0.102 mol) of 4-napthylmercapto-aniline, correspondingly 93% of the total based on the used nitro compound.

d) N- (4-Naphthylmercapto-phenyl) -N '- (2,6-dichlorobenzoyl) -urea To the solution of 2.51 g (10 mmol) of N- (4-naphthylmercapto) aniline in 20 ml of toluene at room temperature the solution of 2.4 g (11 1 mmol of 2,6-dichlorobenzoyl isocyanate in Given 10 ml of toluene. The reaction mixture warms up to -30 ° C. It stays then stand at about room temperature for 15 hours. During this time it crystallizes Part of the product. The product which has crystallized out is filtered off with suction and dried. The filtrate is concentrated to a residue in vacuo.

Yield of product crystallized out: 3.3 g, 71% of theory) melting point 207.- 2090C.

According to the results of the elemental analysis and the NMR recording lies the desired product in pure form (or as a mixture of isomers of α- and ß-naphthyl compounds).

1.2 g of residue (crude product) are obtained from the mother liquor; M.p. 166-1700C.

According to elemental analysis and NMR recording, this substance also exists mainly from the desired product.

As an alternative to d), the following reaction steps are possible: e) N-4-naphthylmercapto-phenyl-isocyanate into the solution of 25.1 g (0.10 mol) of 4-itaphthylmercaptoaniline (Product of the previous stage) in 200 ml of dioxane is stirred at room temperature so long hydrogen chloride introduced until no more hydrochloride precipitates. Afterward are in the resulting mixture after cooling to 5 - 100C under intensive Stirring 15 g of phosgene initiated. After the end of the introduction, it is warmed up Reaction mixture to about 250C and then stirred for 3 hours at this temperature. During this time a clear solution emerges.

This is 1 hour at 50 ° C and then another 1 hour at 95 - Stirred at 1000C. Thereafter, excess phosgene at s 950C by introducing Stripped off nitrogen. The solvent is then distilled off in vacuo. The oily product remains.

Yield: 27.5 g (0.993 mol) of 4-naphth; l-mercapto-phenyl isocyanate, practical quantitative yield.

f) N- (4-naphthylmercapto-phenyl) -N '- (2,6-dichlorobenzoyl) urea To the solution of 11.0 g (40 mmol) of isocyanate (product of the previous stage) in 100 ml of dioxane are 7.6 g (40 mmol) of 2,6-dichlorobenzoylamide and 2 ml of trieth: '1-amine admitted. The resulting mixture is refluxed for 15 hours with stirring cooked. The solvent is then distilled off in vacuo and the residue dissolved in a mixture of 100 ml of ethylene chloride and 100 ml of water. The watery one Phase is then separated off and the organic phase is added twice with 100 ml of water each time shaken out. It is then dried with magnesium sulfate. After that, will the Solvent distilled off in vacuo. The initially oily residue becomes crystalline after rubbing with water. The crystals are suctioned off and im Vacuum desiccator over conc. Dried sulfuric acid.

Yield: 17.8 g (38.2 mmol) of N- (4-naphthylmercaptophenyl) -N '- (2,6-dichlorobenzoyl) urea, corresponding to 95% of the theory, based on Isocyanate.

M.p .: 188-10000C.

Example 2: N- (4-tolylmercapto-phenyl -N1 - (2. 6-dichlorobenzoyl ) urea a) 4-nitrophenyl tolyl thioether crude p-nitrobenzenesulfenyl chloride (38 g) is dissolved in 200 ml of toluene. The solution is after the addition of 0.5 g of iron (III) chloride heated with stirring so high that hydrogen chloride is clearly released (in this Fall to »70 - 800C). After the evolution of gas has subsided, another 1 - 2 hours stirred for a long time at a temperature about 10 ° C higher. The solution is then left Cool to 300C and shake it out three times with 100 ml of water each time. Then it will be the organic phase concentrated in vacuo to a residue. This arrears will with 500 ml petrol (boiling range: 40 - 800C) boiled up. Thereafter unresolved, Solid components are filtered off and treated twice with 500 ml of gasoline each time. Di- (4-nitrophenyl) disulfide formed as a by-product remains undissolved. The filtrates are combined and concentrated to a residue. The oily product remains.

Yield: 25.0 g (0.102 mol) of 4-nitrophen; 1-tolyl thioether; recovered: 13 g (0.042 mole) di (4-nitrophen1) disulfide.

b) 4-Tolzlmercaqtoanilin approach: 24.5 g (0.10 mol) of p-nitrophenyl-tolyl-thioether (Product of the previous stage) Procedure as for lc).

Yield: 20.4 g (0.095 mol) of 4-tolylmercapto-aniline, correspondingly 95% of theory (based on the nitro compound used).

c) N- (4-tolylmercapto-phenyl) -N '- (2,6-dichlorobenzoyl) -urea approach: 2.15 (10 mmol) 4-tolylmercapto-aniline (product of the previous stage) procedure as with 1 d).

Yield of crystallized product: 2.13 g (4.9 mmol; 49% of theory) M.p. 189-2030C.

According to the results of the elemental analysis and the NMR recording lies pure mixture of isomers (position of the methyl group of the tolyl radical uncertain).

Yield of crude product from the mother liquor 2.0 g.

M.p. 148-152 ° C.

This product is also according to the results of the elemental analysis and the NMR recording largely pure mixture of isomers.

The compounds of the following tables can be obtained analogously to the above examples: Table I Formula Example Z Ar Fp. Or consistency CH3 3H for 3 m.p. 144-1470C CH3 4 H% »QCH3 m.p. 138-141 ° C CH3 5 H <0- (CH2) 3-CH3 m.p. 138-1400C 6 H t C 5 - m.p. 123-1250C 7 H to CH (CH3) 2 m.p. 142-1480C For example Z Ar. or consistency 8 H 4ffi-CH2-CH (CH3) 2 resin 9 H 4 O-C2H5 m.p. 155-158 ° C 10 H t OC3H, 1st crystallate 0C2H5 169-170 C 2, crystals CH3 m.p. 153-1550C 11 C1 DJ CH3 Pp. 192 - 1950C Tanelle II formula Example Z Ar Fp. CH3 12 H 170-1'70 " 13 H <-C2H5 138-141 ° C 3 14 Cl <CH3 186-1890C 15 Cl ¼ 227-2300C 16 | Cl to CH3 165-1680C CH3 17 C1 zuy½C2H5 178-1820C CH3 Table III formula Example Z Ar Fp. 18 H HÜ CH3 186-188 ° C 19 8 H ¼ 213-215 0C 20 H yÜ 0-C 2H5 163-1650C 3 21 Cl 4ÜCH3 197-1990C 22 C1 ¼ 236-239 0C Table IV Formula Example Z Ar Fp. 23 H CHS 138-1390c 24 H .CH3 24 H 4 CHs cH 142-1580C CH, 25 H ¼ 197 - 1980C 26 H 4t 0-C2H5 156-1600C 27 H v 0-C2H5 166-1690C 28 C1 CH3 3 201-2040C 29 Cl CH3 157-1600C 1Ej7 - 3 Example ZZ Ar 24Ci - 2470C 30 C1 <245 - 247 ° C 31 C1 t 0-C2H5 185-1880C 32 Cl 4½ o-c2Hci 203-2050C 3 All of the compounds mentioned in Tables I-IV are characterized by elemental analyzes and NMR recordings.

The nitro compounds of the formula used as starting materials are compiled in the following table: No. R1 R2 Position of Fp. Or consistency R1 and R2 of the raw products to each other 1 * -H -CH3 - Ö1 2 * -H -C2H5 oil 3 CH3 CH3 m oil 4 -CH3 -CH3 p Ö1 5 * -H -CH (CH3) 2 - Ö1 6 * -H-0-C2H5 86-880C 7 * -CH3 -OC2H5 m 79-81 ° C 8 * -H -CH (CH3) -C2H5 - Ö1 9 * -H -CH2-CH (CH3) 2 - Ö1 10 * -CH = CH-CH = CH- o Ö1 11 * -H -O- (CH2) 3-CH3 - 73-75 ° C 12 * -CH3 -O- (CH2) 3-CH3 m 57-59 ° 13 * -CH3 -OCH3 m 57-590C * Is a mixture of mers with regard to the position of R1 / R2 in relation to S Starting materials of the formula No. R1 R2 Position of Fp. Or consistency R1 and R2 the crude product to each other 1 * -H -CH3 - Ö1 CH3 2 * -H -CH - m.p. 60-63 ° C CH3 3 -CH3 -CH3 m m.p. 116-1180C 4 -CH3 -CH3 m.p. 130-132 ° C 5 * -CHZ3 -OCH3 m.p. 103-106 ° C 6 * -CH3 -O-C2H5 m.p. 102-105 ° C 7 -H-O-C2H5 m.p. 98-1000C 8 * -H -O- (CH2) 3-CH3 - m.p. 69-72 ° C 9 * -CH = CH-CH = CH- o mp 81-83 ° C 10 * -CH3 -O- (CH2) 3-CH3 m.p. 71-73 ° C * Is a mixture of mers with regard to the position of R1 / R2 in relation to S

Claims (5)

Claims (1.) Connections of the formula in the Ar: naphthyl or Is hydrogen, fluorine or chlorine, fluorine or chlorine, Z: hydrogen or chlorine, R1: hydrogen or C1-C4-alkyl, R2: C1-C4-alkyl or Cl-C4-alkoxy. 2. Insecticides, characterized in that they contain one or more Connections according to claim 1. 3. Use of compounds according to claim 1 for the use of Insects. 4. Process for the production of insecticides, characterized in that that one or more compounds according to claim 1 with customary auxiliary and / or Carriers for common formulations, especially emulsion concentrates, Suspension powders, dusts, Granules or spray liquors processed. 5. A process for the preparation of compounds according to claim 1, characterized in that using customary methods a) an isocyanate of the formula with a benzamide of the formula or b) a benzoyl isocyanate of the formula with an amine of the formula implements.