JPS5927864A - Benzoylurea derivative, its preparation and insecticidal and miticidal agent - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (X is H or halogen; Y is halogen; R<1> is halogen or nitro; R<2> is halogen or trifluoromethyl; Z is CH or N). EXAMPLE:N-( 2,6-Difluorobenzoyl )-N'-[4-( 2-nitro-4-trifluoromethylanilino )phenyl] urea. USE:Insecticidal and miticidal agent exhibiting excellent activity especially against lepidopterous vermin such as night crawler, diamondback moth, green caterpillar, etc. PROCESS:The compound of formula I can be prepared by reacting the benzoylisocyanate derivative of formula II with the aniline derivative of formula III in a solvent such as benzene, chloroform, etc. preferably in the presence of a base such as triethylamine. pyridine, etc., at a temperature between room temperature and the boiling point of the solvent.

Description

[Detailed description of the invention] The present invention is based on the general formula (wherein, X is a hydrogen atom or) a 10 gen atom.

Y represents a halogen atom, R1 represents a halogen atom or a nitro group, R2 represents a halogen atom or a trifluoromethyl group, and 2 represents CH or a nitrogen atom. This invention relates to benzoyl urea derivatives represented by the following formulas, their production methods, and insecticides and acaricides containing them as active ingredients.

Agricultural crops are seriously damaged by various pests.

In particular, the damage caused by armyworms, diamondback moths, green caterpillars, spider mites, and spider mites is significant (and a large amount of cost is spent on controlling these pests every year).

On the other hand, in recent years, insect pests that are resistant to existing drugs have appeared,
In addition, environmental pollution caused by chemicals has become a problem, and there is a strong demand for new chemicals that have high efficacy, can effectively control pests with a low dosage, and are free from environmental pollution. The inventors.

In view of the request of υ・karu, as a result of intensive research, the general formula (Il
The present invention has been completed by discovering that the compound of the present invention shown in (1) solves the above-mentioned problems.

Up to now, benzoyl urea-based compounds have been commercially available as insecticides with the structural formula of Demirin, but the compound of the present invention represented by the general formula (Il) is more effective than this drug for insecticides that target insects such as Spodoptera spp., diamondback moths, and green caterpillars. It has particularly excellent insecticidal effects against pests.

The compounds of the present invention represented by the general formula (Il) are exemplified in Table 1. The compound numbers will be referred to in the following description.

Table 1 shows that the compounds of the present invention are highly safe insecticides and acaricides that have low toxicity and do not cause chemical harm to crops.

Next, one of the manufacturing methods of the present invention is as follows.

General Formula [In the formula, X and Y have the same meanings as above. ] and the benzoyl isocyanate derivative represented by the general formula (II
I) 1 [In the formula, R1, B2 and 2 have the same meanings as above.

] It consists of reacting with the aniline derivative represented by these.

This reaction is carried out in an inert organic solvent such as benzene, toluene, xylene, acetone, chloroform, dimethylacetamide, dimethylformamide, etc., but the reaction can be made easier by using an organic capping group catalyst such as triethylamine or pyridine. As it progresses, it becomes -. The reaction is carried out in the temperature range from room temperature to the boiling point of the solvent, and the reaction time varies depending on the reaction temperature, the solvent used, and the type of raw materials, but if carried out instantly to 10 hours, the desired product can be obtained in good yield.

Moreover, the second method of the production method of the present invention is based on the general formula (IV
)! [In the formula, X and Y have the same meanings as above. ] and the general formula M [wherein R1,
R2 and 2 have the same meanings as above. ] It consists of reacting with a phenyl isocyanate derivative represented by these.

This reaction, like the first reaction, uses benzene.

Toluene, xylene, acetone, chloroform.

Although the reaction is carried out in an inert organic solvent such as dimethylacetamide or dimethylformamide, the reaction can be made to proceed more easily by using an organic filler group such as triethylamine or pyridine as a catalyst. The reaction ranges from room temperature to the boiling point of the solvent, which varies depending on the type of solvent raw material, but if it is carried out instantly to 10 hours, the desired product can be obtained in good yield.

The aniline derivative represented by the general formula (LID), which is the starting material for the compound of the present invention, is synthesized according to the following method. Then, by reduction to a nitro amine group, 4
-Synthesize substituted aniline derivatives. Furthermore, the phenyl isocyanate derivative represented by the general formula M can be synthesized by reacting the corresponding aniline derivative with phosgene.

Next, the present invention will be explained in detail with reference to Examples.

Example I CN -<2.6-difluoropenzoyl)-N'-(4-(2-nitro-4-trifluoromethylanilino)phenyl] Preparation of urea (compound 4)] 4-(2-nitro -4-trifluoromethyla 50mt
3.0% solution of 2,6-difluorobenyl isocyanate in toluene with stirring at room temperature.
When p (0,008 mol) was added dropwise, crystals precipitated immediately. After the addition was complete, the mixture was stirred for an additional hour.

When the precipitate is collected and washed with n-hexane, the melting point is 24.
3.2 N-(2,o-difluoropenzoyl)-N'-[4-(2-nitro-4-trifluoromethylanilino)phenyl]urea as an orange powder at 2-244°C.
A yield of 84.2%) was obtained.

Example 2 (N-(2-chlorobenzoyl) -N'-(
Preparation of 4((3,5-dichloro-pyridin-2-yl)amino)phenyl]urea (compound 7)]]2-chlorobenzubumide 3-1 f (0,02 mo#) and 4(
(3,5-dichloropyridin-2-yl)amino)phenyl isocyanate 5.6. P (0.02 mol) was rubbed with xylene at 60° C. and heated and stirred at 100 to 120° C. for 8 hours. Thereafter, the precipitate was collected and washed with toluene to obtain the target product N-12-chlorobenzoyl) -N'-(4
-((3,5-dichloro-pyridin-2-yl)amino)phenylurea was obtained as white crystals with a melting point of 226-227°C at 7.57 (yield: 86, 2%). Compounds 1 to 6, Compound 5. Compound 6. Compound 8 can also be synthesized according to the production method of Example 1 or Example 2.

Next, the insecticide and acaricide of the present invention contains the compound of the present invention as an active ingredient, and is formed by blending the compound of the present invention alone or with various auxiliaries such as diluents, solvents, surfactants, etc. . Preparation forms include emulsions, aqueous preparations, powders, etc., and can be applied as is, or after dilution.

Examples of diluents include clay, talc, bentonite,
Examples include diatomaceous earth and white carbon. Examples of solvents include xylene, toluene, methyl ethyl ketone, isopropanol, dimethylnaphthalene, dimethylformamide, and the like. Examples of surfactants include alkylbenzene sulfonic acids/metal salts, polyoxyethylene alkyl allyl ethers, sodium alkyl sulfates,
Examples include sodium alkylnaphthalene sulfonate and sodium likunin sulfonate.

Harmful insects and mites that can be effectively controlled by the insecticide and acaricide of the present invention include the following.

Paddy rice pests: Japanese armyworm, brown borer moth, rice beetle Upland crop pests: Japanese armyworm, fall armyworm, Japanese caterpillar, Japanese green tea pest: Tea leafhopper: tea leaf beetle, chaff one fruit tree pest: Korikumon no maki, peach beetle.

Red spider mites: Mikanno 1 mite, Namino 1 mite, false red spider mite, Kanzawa spider mite, apple soda sanitary pests: House fly, Shikiji Next, examples of formulations of the insecticide and acaricide of the present invention will be explained at ℃・It goes without saying that the types and blending ratios are not limited to these, and can be varied within a wide range. In addition, in the following formulation examples, all parts are by weight.

Formulation example 1 (milk) 1.40 parts of compound, dimethylformamide.

50 parts and 10 parts of Tsurupol SNX (registered trademark of Toho Chemical Industries, Ltd.) were uniformly dissolved to form an emulsion.

Formulation Example 2 (Aqueous phase agent) 3.20 parts of compound, 35 parts of diatomaceous earth, 35 parts of clay,
5 parts of White Carbon, 3 parts of Ninicol 564 (registered trademark name of Nippon Nyukazai Co., Ltd.), and Zan Extract P252
(Registered trademark name of Kurup Co., Ltd.) 2 parts are mixed and ground to make a wettable powder.

Next, the effects of the compounds of the present invention will be explained using test examples.

Test Example 1 ()・Insecticidal test against Spodoptera trifoliata) The aqueous phase agent of the present compound prepared according to Formulation Example 2 at 10°C was mixed with water for 10 min.
The solution was diluted to 0.20 and 4 ppm, and citrus leaves were immersed in it, air-dried, and then placed in a 60CC vinyl chloride cup. Five 3rd instar Spodoptera larvae were released into this, stored in a constant temperature room at 25°C, and the number of deaths was counted after 5 days to determine the mortality rate. The test was conducted with 3 repetitions per section. The test results are shown in Table 2.

Table 2 Test Example 2 (Insecticidal test against diamondback moth) A hydrating powder of the compound f of the present invention prepared according to Formulation Example 2 was mixed with water at 1001) I.
'm diluted, dipped the Cilantro leaves in it, and air-dried it for 60 minutes.
It was placed in a cc vinyl chloride cup. The third instar larvae of the diamondback moth were released into this, stored in a constant temperature room at 25°C, and after 14 days, the number of adults emerging was measured to determine the inhibition rate of adultization. The exam is.

The test was carried out in two repetitions per section, and 20 animals were used.

Table 3 shows the results of evaluation according to the following formula.

Table 6 Test Example 6 (Insecticidal test against green caterpillars) The aqueous phase agent of the compound of the present invention prepared according to Formulation Example 2 was mixed with water for 20. and 4 ppm K'8, diluted with 4 ppm K'8, immersed Cilantro leaves in it, air-dried it, and placed it in a 60 cc vinyl chloride cup. Five 3rd instar green caterpillar larvae were released into these, stored in a constant temperature room at 25°C, and the number of deaths was determined after 5 days. The test was conducted three times per section, and 15 animals were tested. The test results are shown in Table 4.

Continued from page 1 ■Inventor Tadahiko Inoue 16-18 Shinminami Araya, Fujieda City ■Applicant Ihara Chemical Industry Co., Ltd. 1-4-26 Ikenohata, Taito-ku, Tokyo

Claims (1)

[Claims] (1) General formula [wherein, X is a hydrogen atom or a halogen atom, Y is a halogen atom, nl is a halogen atom or a nitro group, R
2 represents a halogen atom or a trifluoromethyl group, and %2 represents a CH or nitrogen atom. ] A benzoyl urea derivative represented by. (2) General formula [wherein, X represents a hydrogen atom or a halogen atom, and Y represents a halogen atom]. ] A benzoyl isocyanate derivative represented by the general formula [wherein R1 is a halogen atom or a nitro group, R2 is a halogen atom or a trifluoromethyl group, and 2 is a CB
Or nitrogen atom 7 is shown. [In the formula, X, Y, Z, R', and R2 have the same meanings as above.] ] A method for producing a benzoyl urea derivative represented by Y [wherein, X represents a hydrogen atom or a halogen atom, and Y represents a halogen atom]. ] A benzoic acid amide derivative represented by the general formula [wherein R1
represents a halogen atom or a nitro group, R2 represents a halogen atom or a trifluoromethyl group, and 2 represents a CH or a nitrogen atom. [In the formula, X, Y, Z, R', and R'' have the same meaning as above.] (4) General formula [in the formula, x6-z hydrogen atom or) / rogen atom]
is a halogen atom, Bl is a /''-halogen atom or a nitro group, R1 is a halogen atom or a trifluoromethyl group, and 2 is a CH or a nitrogen atom. Contains a benzoyl urea derivative represented by the following as an active ingredient. An insecticide and acaricide characterized by: