JPH0723355B2 - Substituted phenoxyurea, process and herbicide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel substituted phenoxyurea and a herbicide containing the same as an active ingredient.

[Problems to be solved by conventional techniques and inventions]

Many herbicides have been used in order to secure the yield of crops, but conventional herbicides have various problems such as narrowing of a suitable treatment period or phytotoxicity of crops. It was In particular, urea compounds, for example, DCMU, which is widely used as a herbicide for upland fields, have a drawback that they cannot be used in paddy fields due to strong phytotoxicity.

The US patent (US 3,332,975) describes that m-chlorophenoxyurea, which is relatively similar to the substance of the present invention, can be used for pharmaceutical use. However, as will be described later, this compound does not exert a herbicidal effect even when used in the same manner as the compound of the present invention.

[Means for solving problems]

From the pre-emergence of weeds, having a wide use period over the growing season, and for the purpose of creating a highly safe herbicide for crops, earnestly researched, and the present invention solves the above-mentioned problems That is, the present invention has been completed.

[Outline of Invention]

The present invention has the general formula [I] [In the formula, A represents a chlorine atom or a trifluoromethyl group, X, Y and Z may be the same or different and each represents a hydrogen atom, a chlorine atom or a trifluoromethyl group, and R ¹ Represents a lower alkoxyl group, a lower alkoxyl-substituted lower alkyl group or a cyclo lower alkyl group-substituted lower alkyl group, and R ² represents a hydrogen atom or a lower alkyl group. ] The substituted phenoxyurea represented by the following is a substance invention, and the method for producing the substituted phenoxyurea, No. 1 to No. 3 is an invention of the production method, and the herbicide containing the substituted phenoxyurea as an active ingredient is a use invention. is there.

[Material invention]

The substituted phenoxyurea according to the present invention is represented by the general formula [I]. In the formula, the lower alkoxy group of R ¹ or the lower alkoxy group of the lower alkoxy group-substituted lower alkyl group is a C ₁ to C ₄ group, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group,
A butoxy group, etc., preferably a methoxy group,
The alkyl group in the latter is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or the like, and preferably an ethyl group. The latter is preferably 2-
It is a methoxyethyl group. Further, as the cyclo lower alkyl group of the cyclo lower alkyl group-substituted lower alkyl group of R ¹ ,
The lower alkyl group of C _{3 to} C ₅ may be the same as those exemplified for the lower alkoxyl-substituted lower alkyl group, and the methyl group is preferable. Further, the lower alkyl group for R ² may be the same as mentioned above, and is preferably a methyl group, an ethyl group or an n-propyl group.

Examples of the aryl group moiety of the general formula [I] include a 3-chlorophenyl group, a 2,3-dichlorophenyl group,
3,5-dichlorophenyl group, 2,5-dichlorophenyl group,
2,3,5-trichlorophenyl group, 2,3,6-trichlorophenyl group, 23,5,6-tetrachlorophenyl group, 3-trifluoromethylphenyl group, 3,5-di (trifluoro Methyl) phenyl group, 2,3-di (trifluoromethyl (phenyl group, 2,5-di (trifluoromethyl) phenyl group,
2-chloro-3-trifluoromethylphenyl group, 3-
Chloro-2-trifluoromethylphenyl group, 2-chloro-5-trifluoromethylphenyl group, 5-chloro-
2-trifluoromethylphenyl group, 3-chloro-5-
A trifluoromethyl phenyl group etc. can be mentioned. Among these, preferred are 3-trifluoromethylphenyl group, 2,5-dichlorophenyl group,
Mention may be made of the 3,5-dichlorophenyl group.

Further, the substance of the present invention may be in a free state or in a salt form, for example, an acid addition salt form. Similarly, such a salt can be used as a herbicide. Examples of the acid that constitutes the acid addition salt include mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, and organic acids such as acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, maleic acid and citric acid.

Among the substituted phenoxyureas according to the present invention, preferred specific examples include those listed in Table 1.

[Production Method 1] Among the substituted phenoxyureas according to the present invention, those in which R ² is a lower alkyl group instead of a hydrogen atom, that is, general formula [I-2] [In the formula, A, X, Y, Z, and R ¹ are the same as above. R ^2-1 represents a lower alkyl group. Substituted phenoxyurea represented by the general formula [II] and [III] (A, X, Y, Z, R ¹ and R ^2-1 in each formula are the same as above.)
It can be produced by reacting a compound represented by As the phenoxyamines of the formula [II],
Those having an aryl group moiety as listed in [Material Invention] can be used. In addition, R ¹ and R in the formula [III]
Each group represented by ^2-1 may be the same as those listed in [Material Invention].

Examples of the base used in the reaction include pyridine bases such as pyridine, picoline, lutidine and collidine, triethylamine, tertiary amines such as 1,8-diazabicyclo [5.4.0] undecene-7 and N, N-dimethylaniline. , N
Inorganic bases such as aHCO ₃ , KHCO ₃ , Na ₂ CO ₃ , K ₂ CO ₃ and the like can be mentioned, with pyridine being preferred. The amount of base used is 0.5 in terms of molar ratio to carbamic acid chloride [III].
It is from 20 to 20, preferably from 1 to 10.

A reaction solvent may not be used, but a solvent inert to the reaction, for example, aromatic hydrocarbon such as benzene, toluene, xylene, chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene. Halogenated hydrocarbons such as, tetrahydrofuran, ethyl acetate, dimethylformamide and the like may be used.

In the reaction, carbamic acid chloride is usually used in an amount of 0.8 to 3 times mol, preferably 1 to 2 times mol with respect to the phenoxyamines, and both of them and the base are mixed in a solvent-free state or in the above solution, and then the temperature is adjusted to 0. Stir for 0.5 to 30 hours at -100 to 100 ° C, preferably 0 to 60 ° C.

After the reaction, the desired product can be obtained by a conventional method as shown in Examples below.

[Production Method 2] Among the substituted phenoxyureas according to the present invention, those in which R ² is a hydrogen atom, that is, the general formula [I-3] [In the formula, A, X, Y, Z, and R ¹ are the same as above. The substituted phenoxyurea represented by the formula] is an isocyanate represented by the general formula [II] and a phenoxyamine represented by the general formula [IV] R ¹ -NCO [IV] (wherein R ¹ is the same as the above). It can be produced by reacting with. Specific examples of the phenoxyamines [II] in this case include [Production Method 1]
The same as those used in can be mentioned. The same applies to specific examples of the alkyl group represented by R ^{1 in} the formula [IV].

The reaction uses 0.1 to 10 mol% of a Lewis acid such as AlCl ₃ and ZnCl _{2 in} addition to a tertiary amine such as triethylamine in the reaction solvent listed in [Production Method 1], relative to the phenoxyamines [II]. The target compound can be obtained by the same method as in [Production Method 1] except that the isocyanate ester [IV] is used in a molar ratio of 0.8 to 2 with respect to the phenoxyamines [II].

[Production Method 3] Among the substituted phenoxyureas according to the present invention, those in which R ² is a hydrogen atom, that is, the general formula [I-3] [In the formula, A, X, Y, Z, and R ¹ are the same as above. The substituted phenoxyurea represented by the above formula can also be produced by reacting a phenoxycarbamic acid ester represented by the following general formula [V] with an amine represented by the following general formula [VI]. .

(In the formula, A, X, Y and Z are the same as the above. Ar is an aryl group.) R ¹ NH ₂ [VI] (R ¹ is the same as the above) Of the compound represented by the general formula [V] As for the part of,
Examples thereof include a phenyl group, a chlorophenyl group and a tolyl group. The phenoxycarbamic acid esters [V] are phenoxyamines [II] and ArOCOCl.
Can be produced using the base and the solvent described in [Production Method 1].

Further, as the alkyl group of R ₁ of the amine [VI], the same as those listed in [Material Invention] can be mentioned.

The reaction can be carried out by using the amine [VI] in an amount of 0.8 to 5 times the molar amount of the phenoxycarbamic acid ester [V], at a temperature of 0 to 100 ° C, preferably 0 to 80 ° C, and a reaction time of 0.5 to 5 hours. it can. At that time, the same solvent as in [Production Method 1] can be used.

[Substances of the present application and production examples thereof]

Example 1 3- (2,5-Dichlorophenoxy) -1-methoxy-1-methylurea (Compound No. 1) 4.5 g of 2,5-dichlorophenoxyamine in 10 ml of pyridine (2
5 mmol) was dissolved, 5.6 g (38 mmol) of methoxymethylcarbamoyl chloride was added, and the mixture was stirred at 25 to 30 ° C for 12 hours.
150 ml of water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off, and the obtained crystals were recrystallized from ethyl acetate-hexane to obtain 4.8 g of the desired product (yield 72%).

White powder Melting point 119-120 ° C (decomposition) Mass spectrum (FD method) m / Z264 (Molecular ion peak) IR spectrum (KBr tablet, cm ^-1 ) 3200 (ν _NH ), 1685 (ν _{C = 0} ) ¹ H- NMR spectrum (CDCl ₃ solution, ppm) 3.18 (3H, s), 3.76 (3H, s), 6.84 (1H, dd, J = 2,8H
z), 7.16 to 7.36 (2H, m), 8.76 (1H, br, s). Example 2 3- (2,5-dichlorophenoxy) -1-
(2-Methoxyethyl) urea (Compound No. 2) 4.5 g of 2,5-dichlorophenoxyamine in 30 ml of toluene (2
(5 mmol) is dissolved and 2-methoxyethyl isocyanate is dissolved.
Add a solution of 3.8 g (38 mmol) in 70 ml of ethyl acetate, and add 20-30 ° C.
The mixture was stirred for 12 hours. After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography (developing solution; ethyl acetate / hexane = 1/4) and recrystallized from ethyl acetate-hexane to obtain 3.2 g of the desired product (yield 48%). It was

Light yellow powder Melting point 116-118 ° C (decomposition) IR spectrum (KBr tablet, cm ^-1 ) 3360 (ν _NH ), 3160 (ν _NH ), 1670 (ν _{C = 0} ) Examples 3-10 The method of Example 1 According to the above, compounds 3 to 10 described in Table 1
Was synthesized and the results are shown in Table 2.

[Invention of Use as Herbicide] Next, the herbicide of the present invention comprises the compound of the present invention as an active ingredient. To use the compound of the present invention as a herbicide, the compound of the present invention may be used as it is, but granules, wettable powders,
Even better results can be obtained by processing into any of the formulation forms such as emulsions, powders, fine granules and the like. Herbicides having these formulation forms include talc,
Bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, solid carriers such as urea, alcohol, dioxane, acetone,
Liquid carriers such as cyclohexanone, methylnaphthalene, dimethylformamide, and dimethylsulfoxide, salts of alkyl sulfuric acid esters, alkylaryl sulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene sorbitan monoalkylate And the like, and various auxiliary agents such as carboxymethyl cellulose and gum arabic are appropriately used for the production. The blending ratio of the active ingredient can be adjusted as necessary, but in the case of granules, it is 0.
5 to 20% (weight) is suitable, and 5 to 70% (weight) is suitable when it is used as an emulsion or wettable powder.

The herbicide of the present invention is applied as it is, or in the form of being appropriately diluted or suspended with water or the like, in an amount effective for controlling the weeds. The amount of the compound of the present invention used as a herbicide cannot be unconditionally specified due to differences in soil conditions, formulation form, time of use, method of use, type of cultivated crop or target weed, etc., but is 10 g to 5 kg per hectare. It is effective to apply as follows.

If desired, the herbicide of the present invention can be used in combination with other pesticides, fertilizers or the like.

The formulation of the herbicide of the present invention will be described below. In addition,% in formulation examples means percentage by weight.

Formulation Example 1 (granules) 10% of the compound of the present invention, 2% of sodium salt of lauryl alcohol sulfate, sodium ligninsulfonate 5
%, Carboxymethylcellulose 2% and clay 81% are uniformly mixed and ground.

20 parts of water is added to 80 parts of this mixture, and the mixture is kneaded, processed into granules of 14 to 32 mesh with an extrusion type granulator, and dried to obtain granules.

Formulation Example 2 (granules) Lauryl alcohol sulfate sodium salt 2%,
Sodium lignin sulfonate 5%, carboxymethyl cellulose 2% and clay montmorillonite mixture 91%
Are uniformly mixed and pulverized. 22 parts of water is added to 78 parts of this mixture, and the mixture is kneaded, processed into granules of 14 to 32 mesh by an extrusion-type granulator, and then dried to obtain an adsorption base. 20 parts of a mixture of 20% of the compound of the present invention and 80% of polyethylene glycol dissolved in 80 parts of this base material is uniformly adsorbed to obtain a granule.

Formulation Example 3 (hydrate) 10% of the compound of the present invention, diatomaceous earth 85%, sodium dinaphthylmethanedisulfonate 2% and sodium ligninsulfonate 3% are uniformly mixed and pulverized to obtain a wettable powder.

Formulation Example 4 (emulsion) 30% of the present compound, 20% cyclohexane, 11% polyoxyethylene alkylaryl ether, 4% calcium alkylbenzene sulfonate and 35% methylnaphthalene
Are uniformly dissolved to form an emulsion.

Formulation Example 5 (Dust) 4% of the compound of the present invention, 5% of diatomaceous earth and 91% of clay are uniformly mixed and pulverized to obtain a dust.

〔The invention's effect〕

The substituted phenoxyureas of the present invention are novel and useful as herbicides.

According to each production method of the present invention, the substituted phenoxyurea as described above can be efficiently produced.

The herbicide of the present invention is, as compared to commercially available herbicides, Nobie, which occurs in paddy fields, Magnolia japonicus, Conidia, Scutellaria, Azena,
It exerts an excellent herbicidal effect by applying not only annual weeds such as Abenome, but also perennial weeds such as firefly, pine nutrack, hemlock vine, and herring mold, at the time of germination and growing season, while it is a useful drug for useful crops, especially paddy rice. It has an extremely high selectivity without causing phytotoxicity. Further, the herbicide of the present invention is a variety of weeds that are problematic in upland fields, for example, weeds such as millet, crabgrass, green locusts, Poa annua, and Spodoptera chinensis, and weeds such as Kogomeka citrus, broad-leaved weeds such as Aobiyu and Shiroza. Against soil treatment or foliage treatment shows a high herbicidal effect on rice, wheat, corn, soybean,
It has the feature of showing high safety against major crops such as cotton. Further, the herbicide of the present invention can be used as a herbicide for orchards, lawns and non-agricultural lands.

Next, the effect of the herbicide of the present invention will be described with reference to test examples.

Test Example 1 (Weeding test by paddy field soil treatment) Paddy field soil was packed in a porcelain pot with a diameter of 10 cm, and after scratching, seeds of Taenia japonicus, Pleurotus cornucopia, Leek, Firefly were sown and submerged at a depth of 3 cm. The next day, a wettable powder prepared according to Formulation Example 3 was diluted with water and treated dropwise on the water surface (application rate: 4 kg per hectare as an active ingredient). After that, the plants were grown indoors, and 30 days after the treatment, the herbicidal activity was investigated according to the criteria shown in Table 3 below. The results are shown in Table 4.

Test Example 2 (Selective weeding test between rice and millet) 1 / 5,000a Wagner pots were filled with paddy soil, and after scratching, seeds of Tainubie were sown and grown in a greenhouse up to the 2-leaf stage.
The number of Tainubie at the 2-leaf stage was adjusted to 15 per pot, and rice at the 2-leaf stage was further transplanted into the same pot. The day after transplantation, the test compound was used as a wettable powder according to Formulation Example 3, and a predetermined amount of the compound was diluted with water and added dropwise to the water surface. After treatment, the plants were grown in a greenhouse for 30 days, and herbicidal activity and phytotoxicity were investigated according to the criteria shown in Table 3. The results are shown in Table 5.

Test Example 3 (Weeding test by treatment of upland soil) A field soil was filled in a 600 cm ² plastic stick, and seeds of millet, crabgrass, green locust, Aobiyu, Kogomeka citrus, soybean, cotton, and sugar beet were sown and covered with soil. A test compound was made into a wettable powder according to Formulation Example 3, a predetermined amount thereof was diluted with water, and sprayed uniformly on the soil surface with a small sprayer at a spraying rate of 1000 per hectare. After the treatment, the plants were grown in a greenhouse for 20 days, and the herbicidal effect and phytotoxicity were investigated according to the criteria shown in Table 3. The results are shown in Table 6.

Test Example 4 (Herbalization test by foliage treatment in upland field) 120 cm ² plastic pots were filled with upland field soil, ground fly,
Sowing the seeds of crabgrass, Aoyu, and Kogomeka vine,
Flies were grown in the greenhouse until the three-leaf stage. In the three-leaf stage of the fly, the test compound was made into a wettable powder according to Formulation Example 3, 4 kg per hectare of the active ingredient was diluted with water, and sprayed at a spraying rate of 1000 per hectare. From the foliage. After spraying, grow in the greenhouse for 20 days
The herbicidal activity was investigated according to the criteria in the table. The results are shown in Table 7.

Front page continuation (72) Inventor Takeshige Miyazawa 1809 Kamo, Kikugawa-cho, Ogasa-gun, Shizuoka Prefecture (72) Inventor Yasuo Nakamura 1809 Kamo, Kikugawa-cho, Ogasa-gun, Shizuoka Prefecture (56) References JP 608243 (JP, JP A)

Claims (5)

[Claims] 1. A general formula [I] [In the formula, A represents a chlorine atom or a trifluoromethyl group, X, Y and Z represent a hydrogen atom, a chlorine atom or a trifluoromethyl group, and R ¹ is a lower alkoxyl group or a lower alkoxyl group-substituted lower alkyl group. Or a cyclo lower alkyl group-substituted lower alkyl group, and R ² represents a hydrogen atom or a lower alkyl group. ] The substituted phenoxy urea represented by these. 2. General formula [II] [In the formula, A represents a chlorine atom or a trifluoromethyl group, and X, Y and Z represent a hydrogen atom, a chlorine atom or a trifluoromethyl group. ] And a phenoxyamine represented by the general formula [III] [In the formula, R ¹ represents a lower alkoxyl group, a lower alkoxyl group-substituted lower alkyl group or a cyclo lower alkyl group-substituted lower alkyl group, and R ^2-1 represents a lower alkyl group. ] The general formula [I-2] characterized by reacting with a carbamic acid chloride represented by [In the formula, A, X, Y, Z, R ¹ and R ^2-1 are the same as defined above. ] The manufacturing method of the substituted phenoxy urea represented by these. 3. General formula [II] [In the formula, A represents a chlorine atom or a trifluoromethyl group, and X, Y and Z represent a hydrogen atom, a chlorine atom or a trifluoromethyl group. And a phenoxyamine represented by the general formula [IV] R ¹ -NCO [IV] [in the formula, R ¹ represents a lower alkoxyl group, a lower alkoxyl group-substituted lower alkyl group or a cyclo lower alkyl group-substituted lower alkyl group] . ] Isocyanic acid ester represented by the following general formula [I-3] characterized by reacting [In the formula, A, X, Y, Z, and R ¹ are the same as above. ] The manufacturing method of the substituted phenoxy urea represented by these. 4. A general formula [V] [In the formula, A represents a chlorine atom or a trifluoromethyl group, X, Y and Z represent a hydrogen atom, a chlorine atom or a trifluoromethyl group, and Ar represents an aryl group. And a phenoxycarbamic acid ester represented by the general formula [VI] R ¹ NH ₂ [VI] [wherein R ¹ is a lower alkoxyl group, a lower alkoxyl group-substituted lower alkyl group or a cyclo lower alkyl group-substituted lower alkyl group] Indicates. ] The general formula [I-3] characterized by reacting with an amine represented by [In the formula, A, X, Y, Z, and R ¹ are the same as above. ] The manufacturing method of the substituted phenoxy urea represented by these. 5. A general formula [I] [In the formula, A represents a chlorine atom or a trifluoromethyl group, X, Y and Z represent a hydrogen atom, a chlorine atom or a trifluoromethyl group, and R ¹ is a lower alkoxyl group or a lower alkoxyl group-substituted lower alkyl group. Or a cyclo lower alkyl group-substituted lower alkyl group, and R ² represents a hydrogen atom or a lower alkyl group. ] A herbicide containing a substituted phenoxyurea represented by the following as an active ingredient.