KR800001547B1 - Process for preparing thiazoyl cinnamic acid nitriles - Google Patents

Abstract

Title compds. (I; X = monosubstituted-aromatic hydrocarbon, hydrocarbon which is substituted by halogen, alkyl, alkoxy, CF3, NO2), useful as insecticide, were prepd. by reaction of III and III. Thus, 2-chlorobenzoylchloride was added to 2-cyanomethyl-4-phenylthiazole and heated to 140-150≰C. The reactant was cooled to 60≰C and EtOH was added to give 2'-chloro-3-hydroxy-2-(4-phenyl-2-thiazolyl)-cinnamic nitrile.

Description

Manufacturing method of thiazolyl cinnamic acid nitriles

The present invention relates to a process for preparing a compound of formula (I) which is effective as an insecticide.

In the above structural formula,

X represents an unsubstituted aromatic hydrocarbon group or an aromatic hydrocarbon group substituted with one or more substituents selected from halogen atoms, alkyl groups, alkoxy groups, trifluoromethyl groups or nitro groups.

The same or different when the aromatic hydrocarbon group represented by X is a substituent substituted with two or more.

Commercial insecticides having the same action, namely phosphoric acid esters (German Patent No. 814,152), chlorinated hydrocarbons (German Patent No. 1,105,797) and carbamate (US Patent No. 2,903,478) always exhibit satisfactory pesticidal effects. Could not.

The present invention is the result of efforts to make a new pesticide having an excellent pesticidal effect compared to commercial insecticides.

The compound of the present invention has excellent and long-term residual effects when compared to commercial insecticides having the same effect, it can be seen that the toxicity is very low for warm-blooded animals.

Several economically severe pests can be controlled using the active compounds of the present invention while protecting the insects.

Larvae Coleoptera, for example, S. itophilus granarius, Epipilna varivestis and Leptinotarsa decemlineata, Lepidoptera ), For example plutella maculipennis and hemitera, for example Dysdercus Cingulatus, can be successfully controlled.

The active compounds have excellent effects at concentrations ranging from 0.01 to 5.0%, preferably from 0.05 to 0.5% and have a lasting effect on various pests. When two or more types of compounds of formula (I) are used, of course, the total amount of these compounds is used.

The invention also relates to an insecticidal composition wherein the compound of formula (I) is mixed with a suitable carrier. This formulation may, of course, contain one or more types of compounds of formula (I).

The invention also relates to a method for protecting a plant from pests, characterized by treating the plant with a compound of formula (I). The present invention also relates to a method of protecting the plantation from pests by treating the compound (I) with the crop cultivation.

The invention also relates to a pack characterized by containing a compound of formula (I) for use as a pesticide.

The compounds of the present invention can be used as such or in admixture with a carrier or other pesticide. If desired, other plant protection or pesticides such as acaricides or fungicides may be added depending on the desired effect.

The synergistic effect can be achieved by adding additives that enhance the effect, such as organic solvents, wetting agents and oils. Therefore, such additives may be added to the active compound as necessary.

The active compounds of formula (I) and mixtures thereof are prepared in the form of a compatibilizer, for example powders, dispersants, granules, solutions, emulsions or suspensions or by adding liquid and / or solid carriers or diluents or as necessary surfactants. For example, it may be used in the form of adding a humectant, an additive, an emulsifier and / or a dispersant.

Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons, and cyclohexanone, isophorone, dimethylsulfoxide, dimethylformamide, and light fractions.

Suitable solid carriers include, for example, terrestrial such as tonsil, silica gel, talc, kaolin, etaclay, limestone and silicic acid, and vegetable products such as flour.

Examples of the surfactant include calcium lignin sulfonate, polyoxyethylene alkylphenyl ether, naphthalene sulfonic acid and salts thereof, formaldehyde condensates, fatty alcohol supporton and substituted benzene sulfonic acids and salts thereof.

The total amount of active compound in the various formulations can vary over a wide range. For example, the formulation may contain approximately 10-80% by weight of the active compound, approximately 90-20% by weight of a liquid or solid carrier and, if desired, up to 20% by weight of surfactant.

The active compounds may employ conventional methods, for example about 100 to 300 liters of spray solution per hectare using water as a carrier. The active compounds can also be used in so-called "low dose" and "ultra low dose" methods and can be used in the form of so-called microparticles.

These formulations can be prepared by conventional methods of mixing or grinding. If desired, the individual components can be simply mixed before use, for example as in the so-called tank mixing method.

The compound of the present invention is a halogen atom, a nitro group, an alkyl group containing 1 to 4 carbon atoms, an alkoxy group containing 1 to 3 carbon atoms or a trifluoromethyl group in X position 2 in the above formula (I) Compounds representing phenyl groups substituted with have particularly good pesticidal effects.

2'-Chloro-3-hydroxy-2- (4-phenyl-2-thiazolyl) -cinnamic acid nitrile and 3-hydroxy-2'-trifluoromethyl-2- (4) in the compounds according to the invention -Phenyl-2-thiazolyl) -cinnamic acid nitrile and the like have excellent effects.

Compounds of formula (I) may be prepared by the process of the invention, for example as defined below.

According to the invention a compound of formula (I) is obtained by reacting 4-phenylthiazole-2-acetonitrile of formula (II) or an alkali salt thereof with aryl-carbonyl chloride of formula (III).

In the above structural formula,

X is as described above.

This reaction is preferably carried out by heating the mixture of reactants at 100 to 160 ° C., preferably at 130 to 159 ° C., without solvent or in an organic solvent, for example o-dichlorobenzene.

In the case of a comparatively large amount of reaction mixture, it is preferable to dropwise add arylcarbonyl chloride to the 4-phenylthiazole-2-acetonitrile solution at a temperature of 130 to 150 ° C.

Alkali salts of 4-phenylthiazole-2-acetonitrile, for example sodium or potassium salts, when reacted with arylcarbonyl chlorides, are reacted at 20 to 100 ° C. in a solvent such as dimethylformamide, preferably at room temperature. It is good to do.

Starting materials are known or can be prepared according to known processes.

The measuring compounds of the present invention are listed in the following table.

[table]

The compounds of the present invention are particularly insoluble in water and benzine, slightly soluble in acetone and methylene chloride, and well soluble in dimethylformamide and dimethyl sulfoxide.

Irradiation with a spectrophotometer shows that the compounds of the present invention are in the form of an enol, as can be seen in the above formula (I).

The following examples illustrate the invention. Examples 1 and 2 illustrate the preparation of the compound of formula (I), and examples 3 to 7 illustrate the superior effect of the method of using the compound of formula (I) and the known control compound.

Example 1

[2'-Chloro-3-hydroxy-2- (4-phenyl-2-thiazolyl) -cinnamic acid nitrile]

17.5 g (0.1 mol) of 2-chlorobenzoyl chloride is added to 20 g (0.1 mol) of 2-cyanomethyl-4-phenylthiazole and heated slowly to 140-150 ° C. The reaction mixture is held at this temperature for 10-15 minutes. After cooling to 60 ° C., 100 ml of ethanol are added. The resulting precipitate is removed by suction filtration and washed with alcohol and water.

Example 2

[3-hydroxy-2'-nitro-2- (4-phenyl-2-thiazolyl) -cinnamic acid nitrile

10 g (0.05 mol) of 2-cyanomethyl-4-phenyl-thiazole dissolved in 25 ml of dimethylformamide was added dropwise to a suspension of 1.2 g (0.5 mol) of sodium hydride dissolved in 25 ml of dimethylformamide at 30 ° C. do. After stirring for 15 minutes, a solution of 9.28 g (0.05 mol) of 2-nitrobenzoyl chloride dissolved in 25 ml of dimethylformamide is added dropwise. After standing overnight, 750 ml of water was added to the reaction mixture and the whole was thoroughly stirred. Hydrochloric acid is added to make the mixture slightly acidic and extracted with chloroform. The chloroform layer is washed twice with water and dehydrated with magnesium sulfate. The solvent is removed in vacuo and the residue is taken up in a small amount of methylene chloride and filtered off with suction.

Other compounds listed in the table above may be prepared by the methods described in Examples 1 or 2.

Example 3

In a series of experiments, the compounds of the invention listed in the table below were each used in the form of a suspension of the desired concentration. Dilute with water and use in the form of a suspension or emulsion, diluted with water, to the control formulation.

The lower surface of the petri dish is sprayed with a preparation of the active compound (4 mg of spray solution / cm 2). After standing in the air for 10, 17 and 28 days, respectively, approximately 100 grain weevil (Sitophilus granarius) adults per test ingredient are exposed for 4 days in a closed petri dish. The criterion for evaluating the effect is expressed as percentage mortality of weevil after 4 days of exposure. The results obtained are shown in Table 1 below.

TABLE 1

Example 4

In a series of tests, the compounds of the present invention listed in the table below were each used in the form of a suspension at the desired concentration. Diluted with water as a control formulation, it was used in the form of a suspension or emulsion to each desired concentration.

A small amount of coliflower in a plastic petri dish was sprayed with an amount of the active compound formulation (4 mg spray / cm 2). After spraying the sprayed liquid on the leaves, 10 larvae of plutella maculipennis were placed in a petri dish and exposed to a feed treated for 3 days in a closed petri dish.

Criteria for evaluating the effect were expressed as percent mortality after 3 days. The obtained results are shown in Table 2 below.

TABLE 2

Example 5

In a series of tests, the compounds of the invention listed in the table below were each used in the form of a water suspension of the desired concentration. A control formulation was used in the form of a water suspension of the desired concentration.

Soybean plants (Phaseolus Vulgaris) in the early leafy stage are moistened until moistened with the preparation of the active compound. In each case, 5 weeks of plants were sprayed with active compounds to cut the second leaves and roots, and then left for 11 days in a glass container filled with water. In each case, Epilapa Varivestis larvae ( L III) Five are placed in a glass cylinder.

The criterion to evaluate the effect was expressed as% mortality of larvae after 7 days. The obtained results are shown in Table 3 below.

TABLE 3

Example 6

In the work test, Leptinotarsa decemlineata larvae are placed in a test pot with potato plants and left for 1, 3 and 7 days. The effect of the active compounds was evaluated according to the Schneider-Orelli chart.

The application amount of the active compound according to the present invention is 200 g per hectare (active substance), the control formulation is 225 g per hectare (active compound), and in each case 600 liters of water per hectare are used.

The obtained results are shown in Table 4.

TABLE 4

Example 7

In a series of tests, the compounds of the invention listed in the table below were each used in the form of a water suspension of the desired concentration.

A small amount of the preparation of the active compound was sprayed in a small amount (4 mg of spray solution / cm 2) in a small couliflower in a plastic petri dish. After spraying the sprayed solution, 10 larvae of Plutella maculipennis were placed in a petri dish and exposed to a feed treated for 2 days in a closed petri dish.

The criterion for evaluating the effect was expressed as% mortality of larvae after 2 days. The obtained results are shown in Table 5 below.

TABLE 5

Claims (1)

As described above in the text, the 4-phenylthiazole-2-acetonitrile of the following formula (II) or an alkali salt thereof is reacted with the aryl-carbonyl chloride of the following formula (III) to give the compound of the following formula (I) How to manufacture.

In the above formula, X represents an aromatic hydrocarbon group substituted with an unsubstituted aromatic hydrocarbon group or one or more substituents selected from halogen atoms, alkyl groups, alkoxy groups, trifluoromethyl groups and nitro groups.