JPH06329690A - Pyrimidine derivative and herbicide containing it as an active ingredient - Google Patents

Abstract

(57) [Summary] (Revised) [Purpose] Wide herbicidal spectrum, high herbicidal effect,
Provided are compounds with excellent crop safety. [Structure] A pyrimidine derivative represented by the following formula [eg, 2-
(4,6-dimethoxy-pyrimidinyl-2-oxy)-
2-Dimethylphosphonoacetic acid methyl ester] and a herbicide containing the same as an active ingredient. [In the formula, R ¹ and R ² each independently represent a lower alkyl group, a lower alkoxy group or a hydroxyl group,
R ³ represents a lower alkyl group or a hydrogen atom. ]

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel pyrimidine derivative which has not been described in the literature, its salt, and a herbicide containing the same as an active ingredient.

[0002]

2. Description of the Related Art JP-A-3-31266 describes an alkanoic acid containing a pyrimidine ring and a herbicide containing the same.

[0003]

However, the compounds described in the above-mentioned documents have many points to be improved in terms of spectrum, dosage amount, selectivity and the like. The present invention aims to develop a novel compound having a broad herbicidal spectrum, a high herbicidal effect, and excellent safety for crops.

[0004]

DISCLOSURE OF THE INVENTION As a result of intensive studies conducted by the present inventors to solve the above problems, the pyrimidine derivative and its salt of the present invention are novel, and this compound has a herbicidal action. They have found that they have high safety against various crops and have completed the present invention. That is, the present invention has the following general formula (I):

[0005]

[Chemical 3]

[In the formula, R ¹ and R ² each independently represent a lower alkyl group, a lower alkoxy group or a hydroxyl group, and R ³ represents a lower alkyl group or a hydrogen atom. ] The pyrimidine derivative represented by this and its salt, and the herbicide containing it as an active ingredient are provided.

[0007]

DETAILED DESCRIPTION OF THE INVENTION In the definitions of the substituents, R ¹ , R ² and R ^{3 in} the general formula (I), specific examples of each group are shown below. Lower alkyl group : for example, methyl, ethyl, propyl,
Examples thereof include lower alkyl groups having 4 or less carbon atoms such as isopropyl, butyl, sec-butyl and tert-butyl groups. Lower alkoxy group : Examples thereof include lower alkoxy groups having 4 or less carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, secondary butoxy, tertiary butoxy groups and the like.

In the novel pyrimidine derivative represented by the above general formula (I) of the present invention, when R ¹ , R ² or R ³ is a hydroxyl group, the salt is, for example, an inorganic substance such as sodium, potassium or calcium. Salts, and ammonium, methylammonium, propylammonium,
Isopropyl ammonium, butyl ammonium and its isomers, pentyl ammonium and its isomers,
Hexyl ammonium and its isomers, heptyl ammonium and its isomers, octyl ammonium and its isomers, nonyl ammonium and its isomers,
Decyl ammonium and its isomers, organic amine salts such as triethyl ammonium and the like can be mentioned. Of course, it should be understood that the stereoisomers (diastereomers and enantiomers) of the compounds represented by the above general formula (I) are within the scope of the present invention. In the above general formula (I) of the present invention, R ¹ or R ² is preferably a methyl group or a methoxy group, and R ³ is preferably a methyl group or a hydroxyl group. Representative examples of the compound of the present invention represented by the above general formula (I) are shown in Table 1.

[0009]

[Table 1]

[0010]

[Table 2]

The compound of the present invention can be produced, for example, by the following method (method A, method B).

[0012]

[Chemical 4]

[In the formula, R ¹ , R ² and R ³ have the same meanings as described above. X represents a halogen atom or a lower alkylsulfonyl group. In the reaction formula of the above Method A, the compound represented by the above formula (I) is obtained by using the glycolic acid derivative represented by the above formula (II) without a solvent or in the presence of a suitable solvent, and using a suitable base. It can be produced by reacting with the pyrimidine derivative represented by the above formula (III) in the temperature range of 78 ° C. to the boiling point of the solvent for 1 to 24 hours. When a solvent is used in this reaction, for example, a hydrocarbon solvent such as benzene, toluene, xylene; a halogenated hydrocarbon solvent such as dichloromethane, chloroform; diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, etc. Ether-based solvents; ketone-based solvents such as acetone and methyl ethyl ketone; ester-based solvents such as methyl acetate and ethyl acetate;
Aprotic polar solvents such as dimethylformamide, dimethylsulfoxide and dimethylacetamide; acetonitrile, water and the like can be mentioned.

Examples of the base include carbonates such as sodium carbonate and potassium carbonate; sodium hydroxide,
Metal hydroxides such as potassium hydroxide; Metal alcoholates such as sodium methylate and sodium ethylate; Alkyl metal hydrides such as sodium hydride and potassium hydride; Lithium diethylamide, lithium diisopropylamide, lithium bistrimethylsilylamide, etc. Lithium amides; organic bases such as pyridine, triethylamine and diazabicycloundecene. Further, the lower alkylsulfonyl group in the definition of X is a lower alkylsulfonyl group having 4 or less carbon atoms such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, sec-butylsulfonyl, and tert-butylsulfonyl group. Is mentioned. The ratio of the compound of the formula (III) to the compound of the formula (II) is not particularly limited, but it is generally preferably 1 to 5 mol, particularly 1 to 2 mol per 1 mol of the compound of the formula (II). . The amount of the base used is not limited, but it is generally 1 to 5 mol, preferably 1 to 2 mol per mol of the compound of the formula (II). After completion of the reaction, the reaction solution is subjected to usual post-treatments such as organic solvent extraction and concentration, and if necessary, purified by operations such as chromatography and recrystallization,
The desired compound of the present invention can be produced.

Among the compounds represented by the above general formula (I), especially when carboxylic acid is synthesized, the following method B can be applied.

[0016]

[Chemical 5]

[In the formula, R ¹ and R ² have the same meanings as described above, and R ³ represents a lower alkyl group. In the above reaction scheme, the compound represented by the formula (Ia) is the carboxylic acid ester represented by the formula (Ib) in the presence of a suitable solvent with a suitable acid or base at −78 ° C. to the boiling point of the solvent. It can be manufactured by reacting in the temperature range of 1 to 24 hours. When a solvent is used in this reaction, for example, a hydrocarbon solvent such as benzene, toluene, xylene; a halogenated hydrocarbon solvent such as dichloromethane, chloroform; diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, etc. Ether-based solvents; ketone-based solvents such as acetone and methyl ethyl ketone; ester-based solvents such as methyl acetate and ethyl acetate; dimethylformamide, dimethyl sulfoxide,
An aprotic polar solvent such as dimethylacetamide; a mixed solvent composed of acetonitrile, water, or an appropriate combination thereof, and the like can be mentioned.

As the base, carbonates such as sodium carbonate and potassium carbonate; metal hydroxides such as sodium hydroxide and potassium hydroxide; metal alcoholates such as sodium methylate and sodium ethylate; sodium hydride. Alkyl metal hydrides such as potassium hydride; lithium amides such as lithium diethylamide, lithium diisopropylamide and lithium bistrimethylsilylamide; organic bases such as pyridine, triethylamine and diazabicycloundecene, and the like. Examples thereof include mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and trifluoroacetic acid. The amount of these bases or acids used is not strictly limited,
Generally, it is preferably used in the range of 1 to 5 mol, particularly 1 to 2 mol, per 1 mol of the compound of the formula (Ib). After completion of the reaction, the reaction solution is subjected to usual post-treatments such as neutralization, extraction with an organic solvent and concentration, and if necessary, purified by operations such as chromatography and recrystallization to give the desired compound of the present invention. It can be manufactured.

The novel compounds of the general formula (I) have remarkable herbicidal activity. When the compound of the present invention is used as a herbicide, it is mixed with a carrier or a diluent, an additive, an auxiliary agent and the like by a known method, and a formulation form usually used as an agricultural chemical, for example, powder, granule, water. Japanese medicine,
It is used by preparing it as an emulsion, water solvent, flowable agent, etc.
Further, it can be used in combination or in combination with other agricultural chemicals such as fungicides, insecticides, acaricides, herbicides, plant growth regulators, fertilizers and soil conditioners. In particular, when used in combination with other herbicides, not only can the amount of the drug used be reduced and labor saving can be achieved, but the synergistic action of both drugs can be expected to broaden the herbicidal spectrum and achieve higher effects. .

The carriers or diluents used in the preparation include solid or liquid carriers generally used. Examples of the solid carrier include clays represented by kaolinite group, montmorillonite group, illite group, polygoskite group and the like, specifically, pyrophyllite, attapulgite, sepiolite, kaolinite, bentonite, vermiculite, mica, talc and other inorganic substances. Substances: gypsum, calcium carbonate, dolomite, diatomaceous earth, magnesium lime, apatite, zeolite,
Other inorganic substances such as anhydrous silicic acid and synthetic calcium silicate; vegetable organic substances such as soybean flour, tobacco flour, walnut flour, wheat flour, wood flour, starch, crystalline cellulose; coumarone resin, petroleum resin, alkyd resin, polychlorination Examples thereof include synthetic or natural polymer compounds such as vinyl, polyalkylene glycols, ketone resins, ester gums, cobal gums, dammal gums; waxes such as carnauba wax and beeswax and urea.

Suitable liquid carriers include, for example, paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil and white oil; aromatic hydrocarbons such as xylene, ethylbenzene, cumene and methylnaphthalene; trichloroethylene, Chlorinated hydrocarbons such as monochlorobenzene and orthochlorotoluene; ethers such as dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, isophorone; ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol Esters such as acetate, dibutyl maleate, diethyl succinate; methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, Alcohols such as emissions benzyl alcohol, ethylene glycol ethyl ether, ether alcohols such as diethylene glycol butyl ether; dimethylformamide, polar solvents or water such as dimethyl sulfoxide.

In addition, emulsification, dispersion, wetting, spreading, spreading, binding, regulation of disintegration, stabilization of active ingredient of the compound of the present invention,
Surfactants and other auxiliary agents can be used for the purpose of improving fluidity, preventing rust, and preventing freezing. Examples of the surfactant used include nonionic, anionic, cationic and zwitterionic, but usually nonionic and (or) anionic ones are used. used.
Suitable nonionic surfactants include, for example, compounds obtained by polymerizing and adding ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol, and oleyl alcohol; and polymerizing and adding ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol. Compounds; compounds obtained by polymerizing addition of ethylene oxide to higher fatty acids such as palmitic acid, stearic acid and oleic acid; higher fatty acid esters of polyhydric alcohols such as sorbitan and compounds obtained by polymerizing addition of ethylene oxide. Suitable anionic surfactants include, for example, sodium lauryl sulfate, alkyl sulfate salts such as oleyl alcohol sulfate amine salt, sulfosuccinic acid dioctyl ester sodium,
Examples thereof include alkyl sulfonates such as sodium 2-ethylhexene sulfonate, sodium isopropyl naphthalene sulfonate, sodium methylene bisnaphthalene sulfonate, sodium lignin sulfonate, and aryl sulfonates such as sodium dodecylbenzene sulfonate.

Further, the herbicide of the present invention has a high content of casein, gelatin, albumin, glue, sodium alginate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, etc. for the purpose of improving the properties of the preparation and enhancing the effect. A molecular compound and other auxiliary agents can also be used in combination. The above carriers and various auxiliary agents are appropriately used alone or in combination depending on the purpose, taking into consideration the formulation system of the preparation, the application scene and the like.

The content of the active ingredient of the compound of the present invention in the various dosage forms thus obtained varies depending on the dosage form, but is usually 0.1 to 99% by weight, preferably 1 to 99% by weight. 80% by weight is most suitable. In the case of a wettable powder, for example, the active ingredient compound is usually 25 to 90%.
The rest is a solid carrier and a dispersion wetting agent, and a protective colloid agent, a defoaming agent and the like are added if necessary. In the case of granules, for example, the active ingredient compound is usually 1 to 35% by weight.
The balance is solid carrier and surfactant. The active ingredient compound is uniformly mixed with the solid carrier, or is uniformly fixed or adsorbed on the surface of the solid carrier, and the particle diameter is about 0.2 to 1.5 mm. In the case of an emulsion, for example, the active ingredient compound is usually contained in an amount of 5 to 30% by weight, which contains about 5 to 20% by weight of an emulsifier, and the balance is a liquid carrier. Anti-corrosion agent is added. In the case of a flowable agent, for example, the active ingredient compound is usually contained in an amount of 5 to 50% by weight, and this contains a dispersion wetting agent in an amount of 3 to 10% by weight, the balance being water, and a protective colloid agent if necessary. Preservatives, defoamers and the like are added.

The compound of the general formula (I) of the present invention can be used as a herbicide as it is or in any of the above-mentioned preparation forms. INDUSTRIAL APPLICABILITY The composition of the present invention can be applied to various weeds from the pre-emergence period to the growing season, which grow in paddy fields, agricultural lands such as upland fields, and non-agricultural lands. The application rate is 0.1 to 10 per 1 ha as the active ingredient amount,
It is about 000 g, preferably about 1 to 5,000 g. The application rate can be appropriately selected and changed depending on the type of weed, the growth stage, the place of application, the weather and the like.

[0026]

EXAMPLES Next, the present invention will be described more specifically with reference to examples. Example 1 2- (4,6-dimethoxy-pyrimidinyl-2-oxy
Si) -2-dimethylphosphonoacetic acid methyl ester (compound
Manufacture of product No. 2) First, 2- dimethyl phosphite and glyoxylic acid methyl ester were prepared according to the method described in Tetrahedron Letters, Vol. 25, page 3529 (1984).
Hydroxy-2-dimethylphosphonoacetic acid methyl ester was synthesized. Next, 1 g (5.1 mmol) of this ester and 2
1.1 g (5.1 mmol) of -methylsulfonyl-4,6-dimethoxypyrimidine was dissolved in 20 ml of acetonitrile, and 0.7 g (5.1 mmol) of anhydrous potassium carbonate was added.
The mixture was stirred at 0 ° C for 5 hours. Acetonitrile was distilled off under reduced pressure, 10 ml of water was added to the residue, and the mixture was extracted with ethyl acetate.
The ethyl acetate layer was dried over anhydrous sodium sulfate and the solvent was distilled off to obtain a crude product, which was subjected to silica gel column chromatography (developing solvent: hexane / ethyl acetate = 1/1).
The desired 2- (4,6-dimethoxy-pyrimidinyl-2-oxy) -2-dimethylphosphonoacetic acid methyl ester (Compound No. 2) (0.97 g, yield: 56.
5%) was obtained. ¹ H-NMR (δ, CDCl ₃ ): 3.8 (3H, s), 3.87 (6H,
s), 3.90 (6H, d, J = 11Hz), 5.64 (1H, d, J = 17Hz), 5.70 (1
H, s) ppm

Example 2 2- (4,6-dimethoxy-pyrimidinyl-2-oxy)
Si) -2-dimethylphosphonoacetic acid (Compound No. 1)
Additionally ester 0.30g synthesized in Production Example 1 (0.9 mmol) in 2.5% aqueous potassium hydroxide 3 ml, and 15 minutes at room temperature. The solution was acidified with dilute hydrochloric acid, the aqueous layer was removed by filtration, and the desired 2- (4,6-dimethoxy-pyrimidinyl-2-oxy) -2-dimethylphosphonoacetic acid (Compound No. 1) (0.1 g, yield) Rate 34.8%). ¹ H-NMR (δ, CDCl ₃ ): 3.89 (3 H, d, J = 11 Hz),
3.91 (3H, d, J = 11Hz), 3.86 (6H, s), 5.70 (1H, s), 5.70 (1
H, d, J = 17Hz) ppm

Next, several modes of formulation examples using the compound of the present invention will be shown. The "parts" in the following preparations are based on weight. Formulation Example 1 (emulsion) Compound No. 2 20 parts xylene 50 parts cyclohexanone 20 parts calcium dodecylbenzene sulfonate 5 parts polyoxyethylene styryl phenyl ether 5 parts The above components were uniformly mixed and dissolved to obtain 100 parts of an emulsion.

Formulation Example 2 (Wettable powder) Compound No. 2 20 parts Clay 70 parts Calcium lignin sulfonate 7 parts Alkylnaphthalene sulfonate formalin condensate 3 parts The above components were mixed and pulverized with a jet mill to obtain 100 parts of a wettable powder.

Formulation Example 3 (Flowable Agent) Compound No. 2 20 parts Sulfosuccinic acid di-2-ethylhexyl ester sodium salt 2 parts Polyoxyethylene nonylphenyl ether 2 parts Defoamer 0.5 parts Propylene glycol 5 parts Water 70.5 parts The above are uniformly pulverized and mixed by a wet ball mill, 100 parts of a flowable agent was obtained. Herbicides containing the compound of the present invention can be prepared according to the above-mentioned preparation examples.

Next, the herbicidal effect of the compound of the present invention will be described with reference to test examples. Test Example 1 (paddy soil treatment) A 130 cm ² plastic pot was filled with paddy soil,
A proper amount of water and chemical fertilizer were added and kneaded to form a paddy field. Rice seedlings (cultivar: Koshihikari), which had been grown in a greenhouse so that the number of leaves was 2 in advance, were transplanted to each plant as 1 strain per pot, and further, various plants such as Nobie, Konagi, Azena and Firefly were planted. A certain amount of pups were sowed and submerged at a depth of 3 cm. The next day, a wettable powder was prepared according to Formulation Example 2 and the active ingredient was added for 1 h.
It was diluted with an appropriate amount of water so that the amount per a was 1 kg, and the solution was dropped with a pipette. 21 days after drug treatment,
The herbicidal effect on each weed and the degree of chemical damage to paddy rice were determined according to the following criteria. The results are shown in Table 2.

[0032]

[Table 3]

[0033]

[Table 4]

Test Example 4 (Treatment of upland field foliage) A 130 cm ² plastic pot was filled with upland field soil,
Novier, crabgrass, green foxtail, velvetleaf, ona fir,
A certain amount of each seed of the Japanese horse mackerel and the Japanese morning glory was sown in a fixed amount and then covered with 1 cm of soil. After seeding, the pot was placed in a glass greenhouse, and after each plant was grown to the 2-4 leaf stage, a wettable powder was prepared according to Formulation Example 2, and an appropriate amount of water was added so that the active ingredient was 1 kg per ha. It was diluted with and sprayed evenly on the surface of foliage. 21 after drug spraying
After a day, the herbicidal effect on each weed was determined according to the criteria of Test Example 1. The results are shown in Table 3.

[0035]

[Table 5]

[0036]

Industrial Applicability The compound represented by the general formula (I) of the present invention is used in the paddy field, such as the fly, the pearl oyster, the corn,
It exhibits an excellent herbicidal effect with an extremely low dose over a wide range from the germination to the growing season of annual weeds such as yellow sedge, azena, and abnotum, and perennial weeds such as firefly, matsubai, herring mold, cyperus edulis, etc. It has a high level of safety against direct-seeded paddy rice and dry-seeded rice. In addition, various weeds that are problematic in the field as well, such as broad-leaved weeds such as Polygonum japonicum, Aubiyu, and white azalea, perennial and annual perennial Cyperaceae weeds, such as pearl nutsedges, yellow hemlocks, Himekugu, cyperaceae, Kogomegayasuri, weegrass, echinacea, echinocora, chinensis, chinensis. , Weeds such as Johnson grass, Wide oat, Amberjack, etc. show high herbicidal effect by soil treatment or foliar treatment, and at the same time, for soybean, cotton, sugar beet, rapeseed, sunflower, corn, upland rice, wheat, etc. Has a feature of showing high safety.
Furthermore, it can be used not only in paddy fields and upland fields but also in orchards, mulberry fields, lawns, and non-agricultural fields. In addition, when the compound of the present invention is used in combination with a known herbicide, each compound alone shows a complete herbicidal effect against weeds difficult to control, and a synergistic herbicidal effect makes it difficult to control a single agent. Effectively control various weeds in terms of amount, and show high safety against rice, soybean, cotton, sugar beet, rapeseed, sunflower, corn, upland rice, wheat, etc., and a very useful herbicide for agriculture. Can be provided.

Claims (2)

[Claims] 1. The following general formula (I): [Wherein R ¹ and R ² each independently represent a lower alkyl group, a lower alkoxy group or a hydroxyl group, and
³ represents a lower alkyl group or a hydrogen atom. ] The pyrimidine derivative represented by this and its salt. 2. The following general formula (I): [Wherein R ¹ and R ² each independently represent a lower alkyl group, a lower alkoxy group or a hydroxyl group, and
³ represents a lower alkyl group or a hydrogen atom. ] The herbicide which contains the pyrimidine derivative and its salt represented by these as an active ingredient.