JPS58219167A - Substituted phenylhydantoin derivative, its preparation, and herbicide comprising it as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (X is Cl, or Br; R<1> is lower alkyl, 3-4C alkenyl, or 3-4C alkynyl; R<2> is lower alkyl; with the proviso that R<1> is 3-4C alkenyl or 3-4C alkynyl when X is Cl). EXAMPLE:3-[4-Chloro-2-fluoro-5-(2-propionyloxy)phenyl]-1-isopropylimid azolidine- 2,4-dione. USE:A herbicide. Showing strong herbicidal effect on broadleaf weeds such as Pharbitis purpurea Voigt, gramineous weeds such as barnyard grass, etc. in plowed fields by soil treatment and foliar treatment, on perennial weeds such as bulrush, etc., annual weeds such as Echinochloa oryzicola Vasing, etc. in paddy fields by treatment before germination or during growth period, having low phytotoxicity to soybean, cotton, etc. PROCESS:A substituted phenylisocyanate derivative shown by the formula II is reacted with an aminoacetonitrile derivative shown by the formula III to give a urea derivative shown by the formula IV, which is subjected to ring formation in the presence of a mineral acid to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (I) (wherein,
~4 alkynyl group, and R2 represents a lower alkyl group. However, when X is a chlorine atom, R represents an alda=lL4 group having 8 to 4 carbon atoms or a furkynyl group having 8 to 4 carbon atoms. ) The present invention relates to a substituted phenylhydantoin derivative represented by the following, a method for producing the same, and a herbicide containing the same as an active ingredient.

It is already known that phenylhydantoin derivatives are useful as active ingredients in herbicides.

? , :,! :,t,8-(4-chlorophenyl')
-1-methylhydantoin, 8-(4-chloro-2-fluorophenyl)-1-methylhydantoin, etc. are disclosed in U.S. Patent No. 8184668 and JP-A-57-5
Although these compounds are not always sufficient as active ingredients in herbicides, the compounds of the present invention have superior herbicidal efficacy compared to these known compounds.

The compounds of the present invention can be used against a wide range of weeds in upland fields, such as broad-leaved weeds such as morning glory, commonweed, datura, American goldenrod, blue-leaved weed, black-and-white weed, black-and-white weed, and grass weeds such as barnyard grass, oat, hackberry, and Seiban sorghum. On the other hand, it has a strong herbicidal effect in soil treatment and foliage treatment, and has little phytotoxicity on crops such as soybeans and cotton.

In addition, the compounds of the present invention have a strong herbicidal effect on perennial weeds such as bulrush and pineweed in paddy fields, as well as on annual weeds such as Japanese millet, Aspergillus japonica, Azena, and Kikashigusa, when treated before germination and during the growing season.

The compound of the present invention can be produced according to the following reaction formula.

(tV) (1) (In the formula, R, R and px are as described above.) In the general formula equivalent to the substituted phenyl isocyanate derivative represented by the general formula (II)) The substituted aminoacetonitrile spinner is mixed with an inert solvent such as benzene,
Toluene, xylene, ligroin, hexane, etc. are used, and if necessary, the reaction is carried out by heating. Without isolating the intermediate, add an aqueous solution of an inorganic acid, preferably hydrochloric acid, to the reactant, heat if necessary, and allow the reaction to occur. After the reaction is completed, the reaction solution is cooled and purified by extraction and, if necessary, column chromatography.

The substituted phenyl isocyanate derivative represented by the general formula (6) as a raw material can be obtained by reacting a substituted aniline derivative obtained by 4-fluorophenolation and reduction with phosgene.

Next, production examples of the compounds of the present invention will be shown.

Production Example 1 (Production of Compound (2) of the Present Invention) A solution of 5f of 4-chloro-2-fluoro-6-(2-propy, nyloxy) phenyl isocyanate and 1.96f of N-isopropylaminoacetonitrile dissolved in 80% of toluene. was added dropwise at 60 to 60°C and heated to reflux.

After refluxing for 8 hours, cool to room temperature and add 10% hydrochloric acid 20-
was added and refluxed for 6 hours. After cooling to room temperature, the toluene layer was separated, and the aqueous layer was extracted with toluene. The extract was combined with the toluene layer, washed with water, dried over anhydrous magnesium sulfate, concentrated, and the residue was purified by silica gel or ram chromatography to give 8-[4-chloro-2-
Fluoro-5-(2-propynyloxy)phenyl]-
1-isopropylimidazolidine-2,4-dione 5t
I got it. mp 1B9-148°C Some of the compounds of the present invention produced by such a production method are shown in Table 1.

Table 1 100 Derivatives When the compound of the present invention is applied as a herbicide, it may be applied as it is, but it is generally mixed with a solid carrier, liquid carrier, or other formulation auxiliary to form a powder, It is formulated into granules, wettable powders, emulsions, etc. and applied.

The content of the compound of the present invention as an active ingredient in a formulation is usually 8 to 80%, but it can also be formulated to less than 8% or more than 80%. Examples of solid carriers include talc, bentonite, clay, kaolin, diatomaceous earth, vermiculite, white carbon, and slaked lime. Examples of liquid carriers include water, benzene, alcohols, acetone, xylene, methylnaphthalene, and depending on the geothermal They are emulsifiers, suspending agents, spreading agents, and stabilizers.

Formulation Example 1 Compound of the present invention (2) 80 parts by weight, alkyl sulfate 8 parts by weight, lignin sulfonate 2, [.

Part by weight and 15 parts by weight of white crab bon are thoroughly ground and mixed to obtain a wettable powder.

Formulation Example 2 20 parts by weight of the compound of the present invention (1), emulsifier Tsurupol 2
680 (registered trademark of Toho Chemical), 50 parts by weight of cyclohexanone, and 20 parts by weight of xylene were thoroughly mixed to obtain an emulsion.

Formulation Example 8 5 parts by weight of the compound (8) of the present invention, 1 part by weight of white carbon, 85 parts by weight of bentonite and 59 parts by weight of clay were thoroughly ground and mixed, water was added and the mixture was thoroughly kneaded, followed by granulation and drying to form granules. get.

Formulation Example 4 8 parts by weight of the compound (4) of the present invention, 0.0 parts by weight of isopropyl phosphate.
8 parts by weight, 66.7 parts by weight of clay, and 80 parts by weight of talc are thoroughly ground and mixed to obtain a powder.

In addition, the compound of the present invention can be used in combination with other herbicides in order to improve its effectiveness as a herbicide, and in some cases a synergistic effect can be expected. It is also possible to use it in combination with

When the compound of the invention is used as an active ingredient in a herbicide, the application rate can vary within a fairly wide range and is generally from 0.1 f to 50 t, preferably from 0.2 f to 80 t per are.

Next, a test example will be shown, in which the chemical damage to crops and the herbicidal efficacy against weeds were expressed as numerical evaluation values from 0 to 5 according to the criteria described below. In other words, we measured the fresh weight of the above-ground parts of the plants that remained withered at the time of the survey, calculated the ratio (%) when compared with the fresh weight of the plants in the untreated area, and calculated the weight of the plants and weeds as shown in Table 2. The chemical damage and herbicidal efficacy were evaluated on a scale of 0 to 5 based on the following criteria. An evaluation value of 0 or 1 for crops or an evaluation value of 5 or 4 for weeds is generally considered to be a reasonable crop retention effect or weed control effect.

In addition, only in the case of the paddy rice test, depending on the i dry weight of the plant,
Evaluation values were calculated.

Table 2 In addition, the compounds shown in Table 8 were used as control compounds.Table 8 Test Example 1 Upland pre-germination soil treatment test A cylindrical plastic beaker with a diameter of 10 m and a height of 1OL: m was filled with upland soil, Weed seeds of oat, morning glory, and yamweed were sown. After covering with soil, a predetermined amount of the test compound formulated into an emulsion according to Formulation Example 2 was diluted with water and subjected to ±ill treatment with a hand shaker. Thereafter, the plants were grown in a greenhouse, and the herbicidal efficacy was observed 20 years after treatment, and the results are shown in Table 4.

Table 4 Test Example 2 Paddy field early growth stage treatment test Fill a 500cc volume plastic potsu with paddy soil containing various weed seeds, add water to a depth of 4 cm, and then plant rice at the two-leaf stage. Seedlings and overwintered buds of Pinus vulgaris were transplanted and grown in a greenhouse for 5 days. A predetermined amount of the test compound formulated into an emulsion according to Formulation Example 2 was dispersed in water, and the solution was irrigated into a pot at a rate of 10 liters per are. After growing in a greenhouse for a further 8 weeks, phytotoxicity and herbicidal efficacy were investigated.

The soil was mixed with seeds of Japanese millet, firefly, and broad-leaved weeds (Japanese aspen, Japanese azalea, Kikashigusa, etc.).

The results are shown in Table 5.

Table 6 Test Example 3 Post-germination foliage treatment test in upland field A cylindrical plastic beaker with a diameter of 10 cm and a height of 1 OcrR was filled with upland soil, and weed seeds of barnyard grass, oat, field mustard, and Japanese grass were sown. After covering with soil and growing in a greenhouse for two weeks, a predetermined amount of the test compound formulated into an emulsion according to Formulation Example 2 was dispersed in water containing a spreading agent.
The entire stem and leaves were treated from the top of the plant using a hand sprayer at a rate of 5 liters per are. After growing indoors for another 8 weeks, the herbicidal efficacy was investigated and the results are shown in Table 6.

Table 6 Test Example 4 Field soil surface treatment test before germination Fresh 85an
Filled with field soil in a 41m plastic tray with a width of 25 lines and a height of 15 meters, sowing weeds such as mulva morning glory, Japanese crocodile, golden deer, butterfly weed, sagebrush, blueberry, Seiban sorghum and foxtail weed, as well as cotton and diver crops. Shitko.

A predetermined amount of the test compound formulated into a wettable powder according to Formulation Example 1 was dispersed in water, and the entire surface of the soil was sprayed with a small sprayer from above a tray at a rate of 5 liters per are.

After treatment, the plants were placed in a greenhouse for 20 days and their phytotoxicity and herbicidal efficacy were investigated.

The results are shown in Table 7.

Claims (4)

[Claims] (1) General formula (wherein, X is a chlorine atom or a bromine atom, R1 is a lower alkyl group, an alkenyl group having 8-4 carbon atoms, or
~4 alkynyl group, and R2 represents a lower alkyl group. However, when X is a chlorine atom, R represents an alkenyl group having 8 to 4 carbon atoms or an alkynyl group having 8 to 4 carbon atoms. (2) General formula (wherein, X is a chlorine atom or a bromine atom, R1 is a lower alkyl group, an alkenyl group having 8 to 4 carbon atoms, or
~4 alkynyl group, and R2 represents a lower alkyl group. However, when X is a chlorine atom, R1 represents an alkenyl group having 8 to 4 carbon atoms or an alkynyl group having 8 to 4 carbon atoms. ) of a substituted phenylhydantoin derivative represented by the general formula (wherein, !, R' and R2 are as described above), which is characterized by subjecting a urea derivative represented by the formula to a cyclization reaction in the presence of a mineral acid. Manufacturing method. (3) General formula (wherein, X is a chlorine atom or a bromine atom, R is a lower y
R4 represents a fulkenyl group having 8 to 4 carbon atoms or an alkynyl group having 8 to 4 carbon atoms, and R2 represents a lower alkyl group. However, when X is a chlorine atom, R1 has 8 to 4 carbon atoms.
represents an alkenyl group or an alkynyl group having 8 to 4 carbon atoms. ) A substituted phenyl isocyanate derivative represented by the general formula % is reacted with an aminoacetonitrile derivative represented by the general formula % (in the formula, R2 represents a lower alkyl group).
A general formula characterized by obtaining a urea derivative represented by , :, 1 tod (in the formula, X, R1 and R2 are as described above), and then subjecting the compound to a cyclization reaction in the presence of a mineral acid. (In the formula, X, R1 and R2 are as described above.) A method for producing a substituted phenylhydantoin derivative represented by the following. (4) General formula (wherein, represents a chlorine atom.However, when X is a chlorine atom, R1 has 8 carbon atoms.
-4 alkenyl group or an alkynyl group having 8 to 4 carbon atoms. ) A herbicide characterized by containing a substituted phenylhydantoin derivative represented by the following as an active ingredient.