JPH051043A - Uracil derivative and herbicide - Google Patents

Abstract

PURPOSE:To provide a new uracil derivative having an excellent herbicidal effect on various kinds of weeds including perennial weeds at a low dosage while showing selectivity to important crops and useful as a herbicide capable of not only soil drench but foliage application. CONSTITUTION:Compounds of formula I (R<1> is H, 1-4C alkyl or 1-4C haloalkyl; R<2> is 1-6C alkyl; R<4> is H or halogen; R<5> is halogen or NO2; D<26> is 1-4C alkyl or 1-3C haloalkyl), e.g. 3-(4-chloro-5-ethanesulfonylamino2-fluorophenyl)-6- methyl-2,4(1H,3H)-pyrimidinedione. The compounds can be produced by reacting a compound of formula V (G<1> is 1-4C alkyl) with a compound of formulae VI-VII (G<2> is 1-4C alkyl or phenyl) and alkylating 1 position of the uracil ring of the resultant compound of formula I', as necessary. In addition, the above-mentioned compounds show a fast-acting effect by spraying a remarkably low dosage (0.0001-10kg per 1ha) thereof and also have a suitable residual effect.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel uracil derivative and a selective herbicide containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art Conventionally, many herbicides have been put into practical use in order to protect important crops such as rice, soybean, wheat, corn, cotton and beet from weeds and to improve the productivity of these important crops. . These agents can be broadly classified into three categories, upland action, paddy field, and non-arable land, depending on the application scene. Furthermore, in each case, it can be classified into a soil admixture treatment type, a pre-emergence soil treatment type, a post-emergence treatment (stem and leaf treatment) type and the like depending on the application method of the drug.

It is clear that productivity of important crops affects the food economy of each country as the population of the world increases in recent years. With these changes, it is inevitable that the traditional agricultural form will change toward the 21st century. Actually, there is an increasing need for farmers to develop herbicides that can kill or control economically and efficiently weeds that interfere with crop cultivation.

As such a herbicide, the development of a drug having the following conditions has been earnestly desired. Those that have a high herbicidal effect at low doses (especially it is necessary to kill weeds by spraying as low a dose as possible from the viewpoint of environmental protection), those that have an appropriate residual effect (in recent years, soil residue It has been a problem that long drugs damage the succeeding crops, and it is important to show appropriate residual effect after spraying.) Those that kill weeds immediately after spraying (after chemical treatment) , The next crop can be sown and transplanted in a short period of time.), The number of times of chemical treatment is small (it is important for farmers to minimize the number of complicated weed control work), weeds. A broad range of control targets (for broad-leaved weeds, gramineous weeds, perennial weeds, and other weed species with different properties, it is desirable to use a single agent to control these). Combines treatment effects and foliage treatment effects By doing so, a stronger herbicidal effect can be obtained.) Those that do not show harmful chemical damage to crops (those that can selectively kill only weeds in arable land where crops and weeds are mixed) Preferred) is preferred. However, existing herbicides do not meet all of these requirements.

On the other hand, it is known that a specific compound of the uracil derivative exhibits herbicidal activity, for example, The Pesticide Manual No. 8
Edition, p. 89, The British Crop Protection Council
Bromacil is described as one of the herbicides having a uracil skeleton in the Council) (1987) and the like.

[0006]

In view of such a situation, the present inventors show selectivity for important crops and have excellent herbicidal effect against many weeds with a low dose. As a result of continued research to develop a herbicide having both soil treatment and foliar treatment effect, formula (I)

[0007]

[Chemical 4]

[In the formula, R ¹ is a hydrogen atom or a carbon atom number 1 to
4 represents an alkyl group having 4 to 4 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms, R ² represents an alkyl group having 1 to 6 carbon atoms, R ⁴ represents a hydrogen atom or a halogen atom, and R ⁵
Represents a halogen atom or a nitro group, and D ²⁶ represents an alkyl group having 1 to 4 carbon atoms or a haloalkyl group having 1 to 3 carbon atoms. ] The uracil derivative represented by the following (hereinafter, referred to as the compound of the present invention) was found.

The structural characteristics of the compound of the present invention are that it has an alkyl group at the 6-position of the uracil ring, and has R ⁴ , R ⁵ and NHSO ₂ as substituents on the benzene ring at the 3-position of the uracil ring.
It has a unique combination of D ²⁶ . Therefore, the compound of the present invention has systemic migration and extremely high herbicidal activity. As a result, the compound of the present invention can be applied to various kinds of weeds including perennial weeds in any method of soil treatment and foliage treatment, as compared with conventional herbicides, and has an immediate effect in spite of application of an extremely low dose. It has a great feature that it exerts a highly effective effect and also has an appropriate residual effect.

The compound of the present invention is used as a herbicide for upland fields, paddy fields, and non-cultivated lands, regardless of whether it is a soil treatment or a foliar treatment.
American stag deer, Malva morning glory, Inuyuyu, Aobiyu, Onami fir, Ragweed, Sunflower, Toothbrush,
Thistle, thistle, syringa, himejeon, pupa, nuptera, thorns, staghorn, buckwheat,
Broad-leaved, white, black-necked, broom, chickweed, barnyardgrass, communis, quercus chinensis, myrtle, corngrass, red-crowned hornbill, broad-leaved grasses such as yamgra, madder, violet, corngrass, corngrass, corngrass, oleaceae, weeds, weeds , Weedgrass, oat grass, ohoshiba, green foxtail, perennial grass weeds, cyperaceae weeds such as scutellaria, Heraomodaka, Omodaka, Urikakawa, Tamagaya periwinkle, Mizunogiwana, Higurashi swordweed, Aquilegus vulgaris, Spodoptera chinensis, Azuna napus It has high herbicidal activity with low dosage in weeds. Further, it can be safely used for important crops such as wheat, corn, barley, soybean and rice.

Further, the compound of the present invention is a defoliant.
Is also useful as The compound of the present invention can be synthesized, for example, by the method shown in Schemes 1 to 8 (Schemes 1 to 8).
R ⁴ , R ⁵ and D ²⁶ have the same meanings as described above, and G
¹ represents an alkyl group having 1 to 4 carbon atoms, G ² represents an alkyl group having 1 to 4 carbon atoms or a phenyl group,
R'represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and Hal represents a halogen atom. ).

[0012]

[Chemical 5]

(1) In Scheme 1, as the first step, β-aminoacrylic acid ester (V) is added to phenyl isocyanate.
(VI) is reacted to give a uracil derivative (I '), and after the isolation of (I') or without isolation, as a second step, the uracil ring 1-position is alkylated to produce a uracil derivative (I). Represents how to do. Reaction of the first step (VI) 0.5 to 1.5 equivalents (VI) relative to (V), preferably 0.1.
Use 8 to 1.2 equivalents.

The reaction proceeds even without solvent, but it is usually promoted by using a solvent. Hexane as a solvent, heptane, ligroin, aliphatic hydrocarbons such as petroleum ether, benzene, toluene, xylene, aromatic hydrocarbons such as chlorobenzene, chloroform, halogenated hydrocarbons such as methylene chloride, diethyl ether, dioxane, Ethers such as tetrahydrofuran, acetone, ketones such as methyl ethyl ketone, acetonitrile, nitriles such as isobutyronitrile, pyridine, N,
Tertiary amines such as N-diethylaniline, N, N-dimethylacetamide, N, N-dimethylformamide, N-
Examples include acid amides such as methylpyrrolidone, dimethyl sulfoxide, sulfur-containing compounds such as sulfolane, water and mixtures thereof, preferably the above aliphatic hydrocarbons,
Examples thereof include aromatic hydrocarbons, acid amides, sulfur-containing compounds and mixtures thereof.

The reaction proceeds without a base, but usually
0.5 to 10 equivalents, preferably 1.0 to 3.0 equivalents, are used with respect to (V). Pyridine, triethylamine, N, as base
N-dimethylaniline, N, N-diethylaniline, 4- (N, N
-Dimethylamino) pyridine, 1,4-diazabicyclo
[2.2.2] Nitrogen-containing organic bases such as octane, inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, potassium te
Examples thereof include metal alcoholates such as rt-butoxide, preferably sodium hydride, sodium hydroxide and potassium hydroxide.

The reaction temperature is usually -70 to 200 ° C, preferably -30 ° C to the reflux temperature of the reaction mixture. The reaction time is usually 5 minutes to 72 hours, preferably 10 minutes to 12 hours. After completion of the reaction, (I ′) can be isolated by acidifying with a mineral acid such as hydrochloric acid or an organic acid such as acetic acid, trifluoroacetic acid or p-toluenesulfonic acid.

0.5 to 10 equivalents of alkylating agent, preferably 2nd stage (I ′),
Use 0.8 to 5.0 equivalents. Examples of the alkylating agent include dialkyl sulfates such as dimethyl sulfate and diethyl sulfate, halogenated alkyls such as ethyl bromide, chlorodifluoromethane, methyl chloride, methyl bromide and methyl iodide, and diazomethane.

The reaction proceeds even without solvent, but it is usually promoted by using a solvent. Hexane as a solvent, heptane, ligroin, aliphatic hydrocarbons such as petroleum ether, benzene, toluene, xylene, aromatic hydrocarbons such as chlorobenzene, chloroform, halogenated hydrocarbons such as methylene chloride, diethyl ether, dioxane, Ethers such as tetrahydrofuran, acetone, ketones such as methyl ethyl ketone, acetonitrile, nitriles such as isobutyronitrile, pyridine, N,
Tertiary amines such as N-diethylaniline, N, N-dimethylacetamide, N, N-dimethylformamide, N-
Examples include acid amides such as methylpyrrolidone, dimethyl sulfoxide, sulfur-containing compounds such as sulfolane, water and mixtures thereof, preferably the above aliphatic hydrocarbons,
Examples thereof include aromatic hydrocarbons, ethers, ketones, nitriles, acid amides, sulfur-containing compounds and mixtures thereof.

Usually, 0.5 to 10 equivalents, preferably 0.8 to 3.0 equivalents of base are used with respect to (I '). Nitrogen-containing organic bases such as pyridine, triethylamine, N, N-dimethylaniline, N, N-diethylaniline, 4- (N, N-dimethylamino) pyridine, 1,4-diazabicyclo [2.2.2] octane as a base, Examples thereof include inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like, and preferable examples include inorganic bases such as sodium hydride and potassium carbonate.

The reaction temperature is usually from -30 to 150 ° C, preferably from -10 ° C to the reflux temperature of the reaction mixture. The reaction time is usually 10 minutes to 96 hours, preferably 30 minutes to 48 hours.

[0021]

[Chemical 6]

(2) In Scheme 2, as a first step, β-aminoacrylic acid ester (V) is reacted with N-phenylcarbamate (VII) to give a uracil derivative (I '), and (I') is isolated. The following is a method for producing a uracil derivative (I) by alkylating the 1-position of the uracil ring as the second step after or without isolation. First step reaction Usually, 0.5 to 1.5 equivalents of (VII) with respect to (V), preferably 0.1.
Use 8 to 1.2 equivalents.

The reaction usually requires a solvent, and as the solvent, aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, chloroform, methylene chloride and the like are used. Halogenated hydrocarbons, diethyl ether,
Dioxane, ethers such as tetrahydrofuran, acetone, ketones such as methyl ethyl ketone, acetonitrile, nitriles such as isobutyronitrile, pyridine, N,
Tertiary amines such as N-diethylaniline, N, N-dimethylacetamide, N, N-dimethylformamide, N-
Acid amides such as methylpyrrolidone, dimethyl sulfoxide, sulfur-containing compounds such as sulfolane, alcohols such as methanol, ethanol, propanol, butanol, water and mixtures thereof, and the like, preferably the above-mentioned aliphatic hydrocarbons, aromatic Examples thereof include group hydrocarbons, acid amides, sulfur-containing compounds and mixtures thereof.

Usually, 0.5 to 1.0 equivalent of the base is used, preferably 1.0 to 3.0 equivalent to the amount of (V). Nitrogen-containing organic bases such as pyridine, triethylamine, N, N-dimethylaniline, N, N-diethylaniline, 4- (N, N-dimethylamino) pyridine, 1,4-diazabicyclo [2.2.2] octane as a base, Inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc., metal alcoholates such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium methyl mercaptide, sodium Examples thereof include metal alkylmercaptides such as ethyl mercaptide, preferably inorganic bases such as sodium hydride, and metal alcoholates such as sodium methoxide.

The reaction temperature is generally 0 to 200 ° C., preferably room temperature to the reflux temperature of the reaction mixture. The reaction time is usually 10 minutes to 72 hours, preferably 30 minutes to 24 hours. After completion of the reaction, (I ′) can be isolated by acidifying with a mineral acid such as hydrochloric acid or an organic acid such as acetic acid, trifluoroacetic acid or p-toluenesulfonic acid.

Second Step The alkylation can be carried out under the same reaction conditions as in the second step of Scheme 1.

[0027]

[Chemical 7]

(3) Scheme 3 represents a method for producing a uracil derivative (I) by reacting N-alkyl-β-aminoacrylic acid ester (VIII) with phenylisocyanate (VI) in one step. It can be carried out under the same reaction conditions as.

[0029]

[Chemical 8]

(4) Scheme 4 represents a method for producing a uracil derivative (I) by reacting N-alkyl-β-aminoacrylic acid ester (VIII) with N-phenylcarbamate (VII) in one step. The reaction can be performed under the same reaction conditions as in Scheme 2.

[0031]

[Chemical 9]

(5) Scheme 5 represents a method for producing the uracil derivative (I) by reacting the amino derivative (IX) with a sulfonyl halide (Xa) or a sulfonic anhydride (Xb) as the first step. Normally (IX) to (Xa) or (Xb) 0.3 to 10
Equivalents, preferably 0.5-2.0 equivalents, are used.

The reaction proceeds even without solvent, but it is usually promoted by using a solvent. Hexane as a solvent, heptane, ligroin, aliphatic hydrocarbons such as petroleum ether, benzene, toluene, xylene, aromatic hydrocarbons such as chlorobenzene, chloroform, halogenated hydrocarbons such as methylene chloride, diethyl ether, dioxane, Ethers such as tetrahydrofuran, acetone, ketones such as methyl ethyl ketone, acetonitrile, nitriles such as isobutyronitrile, pyridine, N,
Tertiary amines such as N-diethylaniline, N, N-dimethylacetamide, N, N-dimethylformamide, N-
Examples thereof include acid amides such as methylpyrrolidone, sulfur-containing compounds such as dimethyl sulfoxide and sulfolane, and a mixture thereof.

The reaction proceeds without a base, but usually (I
Use 0.3 to 10 equivalents relative to X). Moreover, you may use it as a solvent in large excess. Nitrogen-containing organic bases such as pyridine, triethylamine, N, N-dimethylaniline, N, N-diethylaniline, 4- (N, N-dimethylamino) pyridine, 1,4-diazabicyclo [2.2.2] octane as a base, Inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide,
Examples thereof include metal alcoholates such as potassium tert-butoxide, and preferably the above-mentioned nitrogen-containing organic bases and inorganic bases.

The reaction temperature is usually -30 to 160 ° C, preferably -10 to 130 ° C. Reaction time is usually 10 minutes to 48
It takes about 30 minutes to 24 hours.

[0036]

[Chemical 10]

(6) In Scheme 6, as the first step, the amino compound (IX) is reacted with an acylating agent to obtain an acylamino compound (IX-a).
After isolation of (IX-a) or without isolation, the second step is sulfonylation of (IX-a) to give the N-acylsulfamoyl derivative (IX-b), (IX-b ) Is isolated or is not isolated, and is continuously followed by a third step of deacylating (IX-b) to produce a uracil derivative (I).

First Step Reaction Usually, the acylating agent is used in an amount of 0.5 to 5.0 equivalents, preferably 0.8 to 2.0 equivalents, relative to (IX). Examples of the acylating agent include acetyl chloride, benzoyl chloride, acetic anhydride and formic acid, and acetic anhydride is preferable. The reaction proceeds even without solvent, but it is usually promoted by using a solvent. Hexane, heptane, ligroin, petroleum ether and other aliphatic hydrocarbons, benzene, toluene, xylene, chlorobenzene and other aromatic hydrocarbons, chloroform, methylene chloride and other halogenated hydrocarbons, pyridine, N, N -Tertiary amines such as diethylaniline, N, N-dimethylacetamide, N, N-dimethylformamide, acid amides such as N-methylpyrrolidone, sulfur-containing compounds such as dimethyl sulfoxide and sulfolane, formic acid, acetic acid, butyric acid And the like, and mixtures thereof, and preferably the above-mentioned aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and organic acids.

The reaction proceeds without a base, but usually (I
X) is used in 0.5 to 5.0 equivalents, preferably 0.8 to 2.0 equivalents. Pyridine, triethylamine, N, as base
N-dimethylaniline, N, N-diethylaniline, 4- (N, N
-Dimethylamino) pyridine, 1,4-diazabicyclo
[2.2.2] Nitrogen-containing organic bases such as octane, inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, and acetates such as sodium acetate and potassium acetate. To be

The reaction temperature is usually -30 to 200 ° C, preferably 0 to 130 ° C. The reaction time is usually 10 minutes to 24 hours, preferably 30 minutes to 6 hours. Sulfonyl halide (Xa) or sulfonic anhydride (Xb) 0.5 to 5.0 equivalents, preferably 0.8 to 2.0 relative to the second step (IX-a)
Use equivalents.

The reaction proceeds even without solvent, but it is usually promoted by using a solvent. Hexane as a solvent, heptane, ligroin, aliphatic hydrocarbons such as petroleum ether, benzene, toluene, xylene, aromatic hydrocarbons such as chlorobenzene, chloroform, halogenated hydrocarbons such as methylene chloride, diethyl ether, dioxane, Ethers such as tetrahydrofuran, acetone, ketones such as methyl ethyl ketone, acetonitrile, nitriles such as isobutyronitrile, pyridine, N,
Tertiary amines such as N-diethylaniline, N, N-dimethylacetamide, N, N-dimethylformamide, N-
Examples thereof include acid amides such as methylpyrrolidone, sulfur-containing compounds such as dimethyl sulfoxide and sulfolane, and a mixture thereof.

Usually, 0.5 to 5.0 equivalents of base, preferably 0.8 to 2.0 equivalents, relative to (IX-a) are used. Pyridine, triethylamine, N, N-dimethylaniline, N, as a base
Nitrogen-containing organic bases such as N-diethylaniline, 4- (N, N-dimethylamino) pyridine, 1,4-diazabicyclo [2.2.2] octane, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide Inorganic bases such as sodium carbonate and potassium carbonate, metal alcoholates such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, and the like, and the above nitrogen-containing organic bases and inorganic bases are preferred.

The reaction temperature is usually -30 to 160 ° C, preferably -10 to 130 ° C. The reaction time is usually 30 minutes to 48 hours, preferably 1 to 12 hours. 3rd stage Normal (IX-b) with water and alkali or acid 0.5-3.0
The equivalent is used, preferably 0.8 to 2.0 equivalent. Examples of the alkali include inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, and preferably. Are the above-mentioned inorganic bases. Examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid and trifluoroacetic acid.

The reaction proceeds even without solvent, but it is usually promoted by using a solvent. Hexane, heptane, ligroin, petroleum ether and other aliphatic hydrocarbons, benzene, toluene, xylene, chlorobenzene and other aromatic hydrocarbons, chloroform, methylene chloride and other halogenated hydrocarbons, methanol, ethanol, etc. Alcohols, ethers such as diethyl ether, dioxane and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and isobutyronitrile, pyridine, triethylamine, N, N-dimethylaniline, N, N-diethylaniline Such as tertiary amines, N, N-dimethylacetamide, N, N-
Dimethylformamide, acid amides such as N-methylpyrrolidone, organic acids such as formic acid, acetic acid and butyric acid, water and mixtures thereof are preferable, and the above alcohols, ethers, ketones and tertiary amines are preferable. , Acid amides, organic acids and water.

The reaction temperature is usually -30 to 130 ° C, preferably -10 to 100 ° C. The reaction time is usually 10 minutes to 48 hours, preferably 30 minutes to 24 hours.

[0046]

[Chemical 11]

(7) In Scheme 7, as the first step, the amino compound (IX) is sulfonylated to give a disulfonylamino compound (IX-
c), and after or without isolation of (IX-c),
As a second step, (IX-c) is hydrolyzed to give a uracil derivative.
It represents a method for producing (I). First stage 1.0 to 20 equivalents of sulfonyl halide (Xa) or sulfonic anhydride (Xb), preferably 2.0 to 5.0, relative to normal (IX).
Use equivalents.

The reaction proceeds even without solvent, but it is usually promoted by using a solvent. Hexane as a solvent, heptane, ligroin, aliphatic hydrocarbons such as petroleum ether, benzene, toluene, xylene, aromatic hydrocarbons such as chlorobenzene, chloroform, halogenated hydrocarbons such as methylene chloride, diethyl ether, dioxane, Ethers such as tetrahydrofuran, acetone, ketones such as methyl ethyl ketone, acetonitrile, nitriles such as isobutyronitrile, pyridine, N,
Tertiary amines such as N-diethylaniline, N, N-dimethylacetamide, N, N-dimethylformamide, N-
Examples thereof include acid amides such as methylpyrrolidone, sulfur-containing compounds such as dimethyl sulfoxide and sulfolane, and a mixture thereof.

The reaction proceeds without a base, but usually (I
X) is used in 1.0 to 10 equivalents, preferably 2.0 to 3.0 equivalents. Moreover, you may use it as a solvent in large excess. Nitrogen-containing organic bases such as pyridine, triethylamine, N, N-dimethylaniline, N, N-diethylaniline, 4- (N, N-dimethylamino) pyridine, 1,4-diazabicyclo [2.2.2] octane as a base, Inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like, metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide and the like, and preferably the above And nitrogen-containing organic bases and inorganic bases.

The reaction temperature is usually -30 to 160 ° C, preferably -10 to 130 ° C. Reaction time is usually 30 minutes to 60
It takes 1 to 30 hours. 0.5 to 3.0 equivalents of water, alkali or acid are used, preferably 0.8 to 2.0 equivalents, relative to the second step (IX-c). Examples of the alkali include inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, and preferably. Are the above-mentioned inorganic bases. Examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid and trifluoroacetic acid.

The reaction proceeds even without solvent, but it is usually promoted by using a solvent. Hexane, heptane, ligroin, petroleum ether and other aliphatic hydrocarbons, benzene, toluene, xylene, chlorobenzene and other aromatic hydrocarbons, chloroform, methylene chloride and other halogenated hydrocarbons, methanol, ethanol, etc. Alcohols, ethers such as diethyl ether, dioxane and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and isobutyronitrile, pyridine, triethylamine, N, N-dimethylaniline, N, N-diethylaniline ,Four-
(N, N-Dimethylamino) pyridine, tertiary amines such as 1,4-diazabicyclo [2.2.2] octane, N, N-dimethylacetamide, N, N-dimethylformamide, N-
Examples include acid amides such as methylpyrrolidone, organic acids such as formic acid, acetic acid, butyric acid, water and mixtures thereof, preferably the above alcohols, ethers, ketones, tertiary amines, acid amides, Examples include organic acids and water.

The reaction temperature is usually -30 to 160 ° C, preferably -10 to 130 ° C. The reaction time is usually 5 minutes to 48 hours, preferably 30 minutes to 24 hours.

[0053]

[Chemical 12]

(8) In Scheme 8, the sulfonamide derivative (I ′) is sulfonylated as the first step to give the disulfonylamino derivative (I ″), and the second step is alkylation of (I ″) (IX-c). To manufacture. Furthermore, as a third step, a method of hydrolyzing (IX-c) to produce a uracil derivative (I) is shown. First step 0.5 to 5 equivalents, preferably 0.8 to 2.0 equivalents of sulfonyl halide (Xa) or sulfonic anhydride (Xb) are used with respect to the usual (I ').

The reaction proceeds even without solvent, but it is usually promoted by using a solvent. Hexane as a solvent, heptane, ligroin, aliphatic hydrocarbons such as petroleum ether, benzene, toluene, xylene, aromatic hydrocarbons such as chlorobenzene, chloroform, halogenated hydrocarbons such as methylene chloride, diethyl ether, dioxane, Ethers such as tetrahydrofuran, acetone, ketones such as methyl ethyl ketone, acetonitrile, nitriles such as isobutyronitrile, pyridine, N,
Tertiary amines such as N-diethylaniline, N, N-dimethylacetamide, N, N-dimethylformamide, N-
Examples thereof include acid amides such as methylpyrrolidone, sulfur-containing compounds such as dimethyl sulfoxide and sulfolane, and a mixture thereof.

In the reaction, usually 0.5 to 10 equivalents, preferably 1.0 to 3.0 equivalents of the base are used with respect to (I '). Also,
You may use it as a solvent in large excess. Pyridine, triethylamine, N, N-dimethylaniline, N, N as base
-Diethylaniline, 4- (N, N-dimethylamino) pyridine, nitrogen-containing organic bases such as 1,4-diazabicyclo [2.2.2] octane, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, Examples thereof include inorganic bases such as sodium carbonate and potassium carbonate, metal alcoholates such as sodium methoxide, sodium ethoxide and potassium Tert-butoxide, and preferably the above-mentioned nitrogen-containing organic bases and inorganic bases.

The reaction temperature is usually -30 to 160 ° C, preferably -10 to 130 ° C. Reaction time is usually 5 minutes to 60
The time is preferably 10 minutes to 10 hours. Second stage The alkylation can be carried out under the same reaction conditions as in the second stage of Scheme 1. Third stage Hydrolysis can be carried out under the same reaction conditions as in the second stage of Scheme 7.

The synthesis examples of the compound of the present invention and the intermediate will be specifically described below as Examples, but the present invention is not limited thereto. [Example 1] 3- (4-chloro-5-ethanesulfonylamino-2-
Fluorophenyl) -6-methyl-2,4 (1H, 3
H) -Synthesis of pyrimidinediones

[0059]

[Chemical 13]

0.78 g of methyl 3-amino-crotonate was added to N,
It was dissolved in 10 ml of N-dimethylformamide, and 0.59 g of 60% sodium hydride was added. After 10 minutes, cool below 5 ° C,
After adding 2.00 g of ethyl N- (4-chloro-5-ethylsulfonylamino-2-fluorophenyl) carbamate, the mixture was heated and reacted at 130 ° C for 2 hours. After the reaction, N, N
-Dimethylformamide was distilled off, dissolved by adding water, washed twice with diethyl ether, acidified by adding dilute hydrochloric acid, and extracted with ethyl acetate. The extract was washed with water and saturated saline and then dried over anhydrous sodium sulfate. By distilling off ethyl acetate, 1.82 g of the target compound was obtained as pale yellow crystals.

Melting point 231-232 ° C. ¹ H-NMR (d ₆ -DMSO) δ (ppm): 1.40 (3H, t, J = 7H
z), 2.20 (3H, s), 3.11 (2H, q, J = 7Hz), 5.56 (1H, s),
7.35 (1H, d, J = 9Hz), 7.59 (1H, d, J = 7Hz), 8.61 (1H, br
s), 11.29 (1H, br s) [Example 2] 3- [4-chloro-5-bis (ethanesulfonyl) amino-2-fluorophenyl] -6-methyl-2,4 (1
Synthesis of (H, 3H) -pyrimidinedione (intermediate)

[0062]

[Chemical 14]

3- (4-chloro-5-ethylsulfonylamino-2-fluorophenyl) -6-methyl-2,4
To a mixture of 1.00 g of (1H, 3H) -pyrimidinedione, 0.28 g of triethylamine and 20 ml of dichloromethane, 0.36 g of ethanesulfonyl chloride was added at 5 ° C or lower, and the mixture was stirred for 1 hour. The reaction solution was washed twice with water, then with saturated saline, and dried over anhydrous sodium sulfate. By distilling off dichloromethane, 1.00 g of the objective compound was obtained as pale yellow crystals.

Melting point 231-232 ° C. ¹ H-NMR (CDCl ₃ ) δ (ppm): 1.45 (6H, t, J = 7Hz),
2.05 (3H, s), 3.60 (4H, q, J = 7Hz), 5.54 (1H, s), 7.26
(1H, d, J = 9Hz), 7.38 (1H, d, J = 7Hz), 9.91 (1H, br s) [Example 3] 3- [4-chloro-5-bis (ethanesulfonyl) amino-2 -Fluorophenyl] -1,6-dimethyl-2,
Synthesis of 4 (1H, 3H) -pyrimidinedione (intermediate)

[0065]

[Chemical 15]

0.83 g of 3- [4-chloro-5-bis (ethanesulfonyl) amino-2-fluorophenyl] -6-methyl-2,4 (1H, 3H) -pyrimidinedione was added to N,
It was dissolved in 10 ml of N-dimethylformamide, 0.13 g of anhydrous potassium carbonate and 0.27 g of methyl iodide were added, and the mixture was stirred overnight at room temperature. After distilling off N, N-dimethylformamide,
It was dissolved in ethyl acetate and washed with water and saturated brine. After drying over anhydrous sodium sulfate, ethyl acetate was distilled off to obtain 0.58 g of the objective compound as pale yellow crystals.

Melting point 237-238 ° C. ¹ H-NMR (CDCl ₃ ) δ (ppm): 1.49 (6H, t, J = 7Hz),
2.31 (3H, s), 3.43 (3H, s), 3.67 (4H, q, J = 7Hz), 5.71 (1
H, s), 7.35 (1H, d, J = 9Hz), 7.45 (1H, d, J = 8Hz) [Example 4] 3- (4-chloro-5-ethanesulfonylamino-2-
Fluorophenyl) -1,6-dimethyl-2,4 (1
Synthesis of (H, 3H) -pyrimidinedione

[0068]

[Chemical 16]

3- [4-chloro-5-bis (ethanesulfonyl) amino-2-fluorophenyl] -1,6-dimethyl-2,4 (1H, 3H) -pyrimidinedione 0.46
g was dissolved in 5 ml of dioxane, and 1 ml of 2.5 M aqueous sodium hydroxide solution was added. After reacting for 4 hours at room temperature, dilute hydrochloric acid was added to acidify the mixture, and the mixture was extracted with ethyl acetate. water,
The extract was washed with saturated saline and dried over anhydrous sodium sulfate. By distilling off the ethyl acetate, the target compound, 0.
30 g was obtained as yellow crystals.

Melting point 74-76 ° C. ¹ H-NMR (CDCl ₃ ) δ (ppm): 1.38 (3 H, t, J = 7 Hz),
2.31 (3H, s), 3.11 (2H, d, J = 7Hz), 3.42 (3H, s), 5.72
(1H, s), 7.02 (1H, br s), 7.31 (1H, d, J = 9Hz), 7.68 (1
H, d, J = 7 Hz) [Example 5] 3- (4-chloro-5-ethanesulfonylamino-2-
Fluorophenyl) -6-ethyl-2,4 (1H, 3
H) -Synthesis of pyrimidinediones

[0071]

[Chemical 17]

Synthesis was carried out according to Example 1. Viscous oily compound ¹ H-NMR (CDCl ₃ ) δ (ppm): 1.24 (3H, t, J = 7Hz),
1.32 (3H, t, J = 7Hz), 2.43 (2H, q, J = 7Hz), 3.18 (2H, q,
J = 7Hz), 5.68 (1H, s), 6.74 (1H, br s), 7.03 ~ 7.69 (2
H, m), 8.15 (1H, br s) [Example 6] 3- [4-chloro-5-bis (ethanesulfonyl) amino-2-fluorophenyl] -6-ethyl-2,4 (1
Synthesis of (H, 3H) -pyrimidinedione (intermediate)

[0073]

[Chemical 18]

Synthesis was carried out according to Example 2. Melting point 278-279 ° C ¹ H-NMR (d ₆ -DMSO) δ (ppm): 1.22 (3H, t, J = 7H
z), 1.46 (6H, t, J = 7Hz) 2.48 (2H, q, J = 7Hz), 3.69 (4H,
q, J = 7Hz), 5.57 (1H, s), 7.59 (1H, d, J = 6Hz), 7.72 (1
H, d, J = 4 Hz) [Example 7] 3- [4-chloro-5-bis (ethanesulfonyl) amino-2-fluorophenyl] -6-ethyl-1-methyl-2,4 (1H, 3H ) -Pyrimidinedione (intermediate)
Synthesis of

[0075]

[Chemical 19]

Synthesis was carried out according to Example 3. Melting point 63 to 64 ° C. ¹ H-NMR (CDCl ₃ ) δ (ppm): 1.28 (3H, t, J = 7Hz),
1.48 (6H, t, J = 7Hz), 2.59 (2H, q, J = 7Hz), 3.43 (3H,
s), 3.67 (4H, q, J = 7Hz), 5.72 (1H, s), 7.28 ~ 7.56 (2
H, m) [Example 8] 3- (4-chloro-5-ethanesulfonylamino-2-
Fluorophenyl) -6-ethyl-1-methyl-2,4
Synthesis of (1H, 3H) -pyrimidinedione

[0077]

[Chemical 20]

Synthesis was carried out according to Example 4. Glassy ¹ H-NMR (CDCl ₃ ) δ (ppm): 1.28 (3H, t, J = 7Hz),
1.32 (3H, t, J = 7Hz), 2.58 (2H, q, J = 7Hz), 3.07 (2H, q,
J = 7Hz), 3.39 (3H, s), 5.65 (1H, s), 6.96 (1H, br s),
7.18 (1H, d, J = 8Hz), 7.51 (1H, d, J = 7Hz) Table 1 shows the structural formulas of the synthesized compounds of the present invention including the above-mentioned Examples.

[0079]

[Table 1]

[0080]

[Table 2]

The compounds of the present invention synthesized according to the above schemes or Examples are shown in Table 3 including the compounds synthesized in the above Examples, but the present invention is not limited thereto.

[0082]

[Chemical 21]

[0083]

[Table 3]

[0084]

[Table 4]

[0085]

[Table 5]

When the compound of the present invention is applied as a herbicide, generally, a suitable carrier, for example, solid carrier such as clay, talc, bentonite, diatomaceous earth, white carbon or the like, water, alcohols (isopropanol, butanol, benzyl alcohol, flue alcohol) Furyl alcohol etc.), aromatic hydrocarbons (toluene, xylene etc.), ethers (anisole etc.), ketones (cyclohexanone, isophorone etc.), esters (butyl acetate etc.), acid amides (N-methylpyrrolidone etc.) ) Or halogenated hydrocarbons (chlorobenzene etc.) and other liquid carriers can be mixed and applied, and if desired, surfactants, emulsifiers, dispersants, penetrants, spreading agents, thickeners, antifreeze. Agents, anti-caking agents, stabilizers, etc., liquids, emulsions, wettable powders,
It can be put into practical use in any dosage form such as a dry flowable agent, a flowable agent, a powder agent, and a granule agent.

If desired, the compound of the present invention may be mixed and applied with other kinds of herbicides, various insecticides, fungicides, plant growth regulators, synergists and the like during formulation or spraying. In particular,
By applying it in combination with other herbicides, it is expected that the cost will be reduced by reducing the amount of the applied drug, the herbicidal spectrum will be expanded by the synergistic action of the mixed agents, and a higher herbicidal effect will be expected. At this time, it is possible to combine a plurality of known herbicides at the same time. Examples of the type of herbicide used in combination with the compound of the present invention include, for example, Farm Chemicals Handbook (F
arm Chemicals Handbook) 1990 compound.

In particular, when the compound of the present invention is applied to soybean, preferred agents to be mixed with the compound of the present invention include trifluralin, pendimethalin, alachlor and metolachor. , Metribuzin, linuron, chlorimur-ethyl
on ethyl), imazaquin, imazethapyr (i
mazethapyr), dinoceb (dinoseb), bifenox (b
ifenox), clomazone, etc.

The application amount of the compound of the present invention varies depending on the application scene, application time, application method, cultivated crop, etc., but generally 0.0001 to 10 per hectare (ha) as an active ingredient amount.
About kg, preferably about 0.001 to 5 kg is suitable. Next, specific examples of formulation of the preparation when the compound of the present invention is used are shown. However, the compounding examples of the present invention are not limited to these. In the following formulation examples, "part" means part by weight.

[Wettable powder] Compound of the present invention ─────── 5 to 80 parts Solid carrier ─────── 10 to 85 parts Surfactant ─────── 1-10 parts Other ─────── 1-5 parts Other examples include anti-caking agents.

[Emulsion] Compound of the present invention ─────── 1 to 30 parts Liquid carrier ─────── 30 to 95 parts Surfactant ─────── 5 to 15 parts [Flowable] Agent] Compound of the present invention ─────── 5-70 parts Liquid carrier ─────── 15-65 parts Surfactant ─────── 5-12 parts Others ────── -Other than 5 to 30 parts, for example, antifreezing agents, thickeners and the like can be mentioned.

[Granular wettable powder (dry flowable agent)] Compound of the present invention ─────── 20-90 parts Solid carrier ─────── 10-60 parts Surfactant ─────── 1-20 parts [Granule] Compound of the present invention ─────── 0.1-10 parts Solid carrier ─────── 90〜99.99 parts Other ─────── 1-5 parts [Formulation Example 1] Wettable powder Inventive compound No. 4 ────────── 50 parts Sieglite PFP ───────── 43 copies (Kaolin clay: product name of Siglite Industrial Co., Ltd.) Solpol 5050 ───────── Part 2 (Anionic surfactant: Toho Chemical Industry Co., Ltd. trade name) Lunox 1000 C ──────── Part 3 (Anionic surfactant: Toho Chemical Industry Co., Ltd. trade name) Carplex # 80 (anti-caking agent)-2 parts (White carbon: Shionogi Pharmaceutical Co., Ltd. product name) The above is uniformly mixed and pulverized to obtain a wettable powder.

[Formulation Example 2] Emulsion Compound No. 4 of the present invention ────────── 3 parts xylene ──────── 76 parts Isophorone ───────── 15 parts SOLPOL 3005X ──────── 6 parts (mixture of nonionic surfactant and anionic surfactant: trade name of Toho Chemical Industry Co., Ltd.) The above ingredients are uniformly mixed to form an emulsion.

[Formulation Example 3] Flowable agent Inventive compound No. 4 ────────── 35 parts Agrisol S-711 ──────── 8 parts (Nonionic surfactant: Kao Corporation trade name) Lunox 1000 C ──────── 0.5 part (Anionic surfactant: Toho Chemical Industry Co., Ltd. trade name) 1% Rhodopol water ──────── 20 copies (Thickener: Loan Poulin's trade name) Ethylene glycol (antifreeze) ── 8 parts Water ──────── 28.5 copies The above is uniformly mixed to obtain a flowable agent.

[Formulation Example 4] Granular wettable powder (dry flowable agent) Compound of the present invention No. 4 ─────────── 75 parts Isoban No. 1 ───────── 10 parts ( Anionic surfactant: Kuraray Isoprene Chemical Co., Ltd. product name Vanillex N ───────── 5 parts (Anionic surfactant: Sanyo Kokusaku Pulp Co., Ltd. product name) Carplex # 80 ─── ────── 10 parts (White carbon: Shionogi Seiyaku Co., Ltd. trade name) The above is uniformly mixed and pulverized to obtain a dry flowable agent.

[Formulation Example 5] Granules Compound of the present invention No. 4 ───────── 0.1 parts Bentonite ─────── 55.0 parts Talc ─────── 44.9 parts or more uniform After mixing and pulverizing, a small amount of water was added, and the mixture was kneaded with stirring, granulated by an extrusion granulator, and dried to give granules.

In use, the wettable powder, emulsion, flowable powder and granular wettable powder are diluted 50 to 1000 times with water and sprayed so that the active ingredient is 0.0001 to 10 kg per hectare (ha). .

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hiroshi Kita             1 Nissan Chemical, 722, Tsuboi-cho, Funabashi, Chiba             Central Research Institute (72) Inventor Yasuo Kawamura             1 Nissan Chemical, 722, Tsuboi-cho, Funabashi, Chiba             Central Research Institute (72) Inventor Koichi Suzuki             1470 Shiraoka, Shirooka-cho, Minami-Saitama-gun, Saitama             Gaku Kogyo Co., Ltd. Biological Science Laboratory (72) Inventor Tsutomu Namaki             1470 Shiraoka, Shirooka-cho, Minami-Saitama-gun, Saitama             Gaku Kogyo Co., Ltd. Biological Science Laboratory (72) Inventor Shigenomi Watanabe             1470 Shiraoka, Shirooka-cho, Minami-Saitama-gun, Saitama             Gaku Kogyo Co., Ltd. Biological Science Laboratory

Claims (4)

[Claims] 1. Formula (I): [In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms, and R 1
² represents an alkyl group having 1 to 6 carbon atoms, R ⁴ represents a hydrogen atom or a halogen atom, R ⁵ represents a halogen atom or a nitro group, D ²⁶ represents an alkyl group having 1 to 4 carbon atoms, carbon It represents a haloalkyl group having 1 to 3 atoms. ] The uracil derivative represented by these. 2. Formula (I): [In the formula, R ¹ and R ² represent the above meanings, R ⁴ represents a hydrogen atom, a fluorine atom or a chlorine atom, and R ⁵ represents a chlorine atom. ] The uracil derivative of Claim 1 represented by these. 3. Formula (I): [In the formula, R ¹ and R ² represent the above meanings, R ⁴ represents a hydrogen atom, a fluorine atom or a chlorine atom, and R ⁵ represents a bromine atom. ] The uracil derivative of Claim 1 represented by these. 4. A herbicide containing the uracil derivative according to claim 1.