HU176496B - Insecticides and acaricides containing substituted 1-phenyl-3-penyl-2-trichloromethyl-imidazolidines and process for prenaring the active materials thereof - Google Patents

Abstract

Compounds of the formula II are prepared <IMAGE> in which R1, R2, R3 and R4, which are identical or different, denote hydrogen, halogen, lower alkyl or lower alkoxy or the nitro group, the substituents R1 to R4 being in the 3-, 4- or 5-position and the phenyl radicals A and B being substituted by different substituents, by reacting corresponding N,N'-diphenyl-substituted ethylenediamines with chloral. The compounds of the formula II, which are distinguished by an outstanding insecticidal and acaricidal activity, in particular a highly selective insecticidal and acaricidal activity, are used for controlling insects and acarids.

Description

FIELD OF THE INVENTION The present invention relates to insecticides and acaricides containing substituted 1-phenyl-3-phenyl-2-trichloromethylimidazolidines as active ingredients and their preparation.

German Patent Publication No. 2,263,239 discloses imidazolidine derivatives of formula I wherein R 1 and R ₂ are independently hydrogen, halogen, nitro, lower alkyl or alkoxy, and the substituents are 3-, They are in 4 or 5 positions. The compounds of the formula I are active insecticides and acaricides.

In the formula I, the substituents on the A and B ring rings are the same.

It has now been found that the imidazolidine derivatives of formula II, wherein R 1 and R _{2 are} as defined above, and R ₃ and R ₄ are independently selected from the group consisting of hydrogen, halogen, lower alkyl and alkoxy, and the substituents are , 4 or 5, but the phenyl rings A and B are substituted in different ways - they have a particularly beneficial effect.

Compounds of Formula II may be prepared by chloral condensation of Ν, Ν'-diphenyl-substituted ethylenediamine of Formula III, wherein R _p R ₂ , R ₃ and R _{4 are} as defined above, by HW Wanzlick and E. Schikora, Chem. 94, 2839 (1961)].

AIII starting compound can be prepared by reacting a compound of the general formula IV - wherein, R _and R ₂ are as defined above, and

X is an easily cleavable group, preferably a chlorine or bromine atom, with an aniline of formula V, wherein R ₃ and R _{4 are} as defined above, during the cleavage of a compound of formula HX. Compounds of formula AIV can be prepared by various methods, for example, an aniline of formula VI, wherein R 1 and R _{2 are} as defined above, with ethylene oxide [Houben-Weyl, Methoden derorganchen Chemie, XI / 1. Volume 313 (1957) or with ethylene chloro or ethylene bromohydrin, and the hydroxyl group is replaced by a known group X, preferably chlorine or bromine, in known manner.

Compounds of formula IV may be prepared in part from compounds of formula VII, wherein R 1, R ₂ and X are as defined above, by reduction with NaAlH ₂ (OCH ₂ CH ₂ - OCH ₃ ) ₂ (Tetrahedron Letters 1968, 3303). ).

According to the invention, the imidazolidine ring can be sealed, for example, in glacial acetic acid or glacial acetic acid and hydrochloric acid at room temperature or under heating. It is often advantageous to carry out the hydrolysis by azeotropic distillation in a water immiscible solvent. For example, benzene, toluene or xylene are preferred and the reaction can be accelerated by the addition of a catalyst such as p-toluenesulfonic acid. By this procedure, the unsubstituted or? -Substituted diamines can be obtained in better yield in pure form.

Surprisingly, the compounds of formula IIII are very good against various pests. For example, even with low levels of active ingredient (e.g.

Musca domestica), cockroaches (eg Phyllodroma germanica), spider mites (eg Tetranychus urticae), aphids (eg Aphis fabae), caterpillars (eg Plutella maculipennis) and beetles (eg Epilachna varivestis) are killed.

Because of the selective insecticidal and acaricidal activity of the active compounds according to the invention, they are particularly suitable for targeted plant protection. The active ingredients are virtually harmless to warmbloods. In particular, it should be noted that the active compounds are rapidly degraded to harmless compounds during chloroform depletion and thus do not harm the environment.

For controlling pests, the active compounds are known in the form of emulsion concentrates, suspension powders, powders, granules or colloids, etc. with the usual excipients and carriers. It can be used.

The concentrates may optionally be mixed with water to give a spray liquid having an active ingredient content of from about 0.02 to about 5% by weight. The concentrates may contain up to about 80% active ingredient content,

The following examples illustrate the compositions of the invention.

1. Suspension powder

Ingredients:

sr. 1- (4-chlorophenyl) -3-phenyl-2-trichloromethylimidazolidine, m.p. sodium lignin sulfonate, sr. sodium naphthalenesulfonate, sr. kaolin, sr. Diatomaceous.

manufacture:

The components are mixed and ground in a rolling mill. The particle size is about 2-6 μ. The active ingredient content can be increased at the expense of the carriers and can be up to about 80%. For use with water, a spray can be prepared with the desired concentration of active ingredient, usually in the range of 0.02 to 5%.

2. Composition of dusting agents:

1.5 sr. l- (3-chlorophenyl) -3- (4-methylphenyl-2-trichloromethyl

imidazolidine,

98.0 sr. talc,

0.5 sr. aluminum stearate.

manufacture:

The active ingredient is ground on a roll mill and mixed with the other components.

3. Colloidal preparation

Ingredients:

20.0 sr. l- (3-chlorophenyl) -3- (4-methylphenyl) -2-trichloromethyl-imidazolidine,

2.5 sr. ethoxylated isotridecanol polyglycol ether (wetting agent, emulsifier),

2.5 sr. ethoxylated coconut fat polyglycol glycol ether (wetting agent, emulsifier),

1.5 sr. alkiifenolpoliglikoléter,

73.5 sr. liquid n-paraffin.

manufacture:

The ingredients are first dispersed and then ground in a glass bead mill. The particle size is below 2 μ and 20% is below 1.1 μ.

4. Spray

0.5 sr. l- (4-chlorophenyl) -3-phenyl-2-trichloromethyl-imidazolidine,

35.0 sr. talc,

0.5 sr. zinc stearate,

0.5 sr. hexadecilalkohol,

63.5 sr. propellant (Frigene).

Propylene butane, nitrogen, carbon dioxide or air can be used as propellants in addition to Frigene.

5. Suspension powder

Composition:

sr. 1- (4-methylphenyl) -3- (4-ethylphenyl) -2-trichloromethylimidazoline, m.p. sodium lignin sulfonate, sr. sodium naphthalenesulfonate, sr. kaolin, sr. Diatomaceous.

The ingredients are mixed and ground to a particle size of 2-6 μιη.

The effects of the compounds against house flies (Musca domestica) (A) and mosquito larvae (B) were investigated by treatment with different concentrations of spray. The results are shown in the following table (50% and 95% killing agent concentration, ppm).

Λ Example number of active substance (THE) (B) LDjq ppm LD95 pPM LD 100 ppm pPM First 16 60 0.11 0.35 Third 30 70 0.21 0.62 4th 78 380 3.3 7.5 5 35 85 0.062 0.11 6th 15 68 0.13 0.7 7th 9 20 4.8 9 8th 21 85 0.08 0.18 9th 19 62 0.45 0.75 10th 30 130 0.1 0.37 12th 54 140 0.21 0.68

The following example illustrates the preparation of the active ingredient.

Example 1 1- (3-Chlorophenyl) -3- (4-methylphenyl) -2-trichloromethylimidazolidine

To 12.2 g of N- (3-chlorophenyl) -N '- (4-methylphenyl) ethylenediamine, 9 g of chloral and 100 ml of toluene are added 1.2 g of p-toluenesulphonic acid and refluxed after 45 minutes. After cooling, the oily product is triturated with a little glacial acetic acid, filtered off, washed with a little cold methanol and recrystallized from ethanol, 6.5 g, m.p. 84-86 ° C.

In a similar manner, the compounds of formula II listed in the following table can be prepared.

examples da Ri rj rj R < Melting point, ° C Second H H 3 — CH ₃ 5-CH ₃ 130 Third H H 4 — CH ₃ H 80 4th H H 4 OCHq H 120-122 5th H H 4-Cl H 141-144 6th 3-Cl H 4-Cl H 138 7th 4 — CH ₃ H 4 — OCH ₃ H 111-113 8th 4 — CH ₃ H 4-Cl H 124-125 9th 4 — CH ₃ H 4-C ₂ H ₅ H 98-100 10th 3 — CH ₃ H 3-Cl H oil 11th 3-Cl 5-Cl 3 — CH ₃ 5-CH ₃ 163 12th 3 — CH ₃ 5-CH ₃ 4-Cl H 112 13th 4-CH ₃ H 3-Cl 5-Cl 117

The following examples illustrate the preparation of starting materials.

N- (3-Chlorophenyl) -N '- (4-methylphenyl) ethylenediamine

a) N- (2-Hydroxyethyl) -3-chloroaniline

50.8 g of 3-chloroaniline, 36 g of ethylene chlorohydrin and 50 g of anhydrous sodium carbonate are heated under reflux for 4 hours. It is then filtered off with suction and the filter residue is washed with ethyl acetate. The filtrate was distilled under reduced pressure to give the desired product at 14 Torr and 182 ° C.

b) N- (2-Bromomethyl) -3-chloroaniline hydrobromide 50 g of 50% hydrogen bromide are slowly added dropwise with stirring to the product obtained in a). A Vigreux column was placed on the flask and heated to about 124 ° C. After 3 hours, approximately 35 ml of liquid was distilled off. The residue solidified on cooling and washed with cold acetone for purification. Yield 22 g. 148 ° C.

c) N- (3-Chlorophenyl) -N '- (4-methylphenyl) ethylenediamine

15.8 g of N- (2-bromomethyl) -3-chloroaniline hydrobromide and

10.7 g of 4-methylaniline in 50 ml of toluene are heated under reflux for 8 hours in the presence of 15 g of anhydrous sodium carbonate. It is filtered and the residue is washed with ethyl acetate. The filtrate was evaporated in vacuo. 10 g of an oil are obtained which can be used without further purification.

N-phenyl-N '- (3,5-dimethylphenyl) -ethylenediamine

a) [N- (3,5-Dimethylphenyl) glycine] anilide g chloroacetanilide and 20 g 3,5-dimethylaniline are added in an oil bath at 5 185 ° C for 6 hours, after addition of 25 g sodium carbonate. Water was added and the organic phase was dissolved in ethyl acetate. It was dried over sodium sulfate and concentrated in vacuo to give a light brown oil. It solidifies completely. Yield 20g.

IQ b) To a solution of N-Phenyl-N '- (3,5-dimethylphenyl) ethylenediamine g sodium bis (2-methoxyethoxy) dihydroaluminate in 100 ml benzene is added dropwise

A solution of the product obtained in (a) in 35 ml of benzene. The mixture warms up and hydrogen is evolved. After refluxing for a further 15 hours, 200 ml of 20% sulfuric acid are added dropwise after cooling. The benzene is evaporated off with water vapor, the aqueous residue is made basic with concentrated ammonia solution and diluted to 2 liters with water. The mixture was extracted with ethyl acetate, dried over sodium sulfate and concentrated in vacuo to give the title compound as an oil which was used without further purification.

The other starting compounds of formula III can be prepared as described above.

Claims (2)

Patent claims An insecticide and acaricide, characterized in that it contains from 0.02% to 85% by weight of the active ingredient 1-phenyl-3-phenyl-2-trichloromethylimidazolidine II - in which R _{b is} R ₂ , R 1 and R ₄ each independently represents a hydrogen or halogen atom, a lower alkyl or alkoxy group having 3, 4 or 6 carbon atoms; They may be in the 5-position and the phenyl rings A and B may be substituted in various ways; 40 with one or more. 2. A process for the preparation of 1-phenyl-3-phenyl-2-trichloromethylimidazolidines of formula II: wherein R 1, R ₂ , R 8 and R _{4 are} as defined in claim 1. 45, characterized in that a compound of formula III, in which R ₁ , R ₂ , R ₃ and R _{4 have} the meanings given above, is chlorinated, optionally in a water immiscible solvent and optionally in the presence of a catalyst, preferably p-toluenesulfonic acid, in the presence of 50.