JPH06321911A - Novel pyrimidine derivative and herbicide containing the same as active ingredient - Google Patents

Abstract

PURPOSE:To obtain a novel pyrimidine derivative exhibiting high herbicidal activities not only against annual weeds but also against pernnial weeds, having high safety for some kinds of crops, and useful as a herbicide. CONSTITUTION:A pyridine derivative of formula I (X is H, halogen, lower alkyl, lower alkoxy; R<1>, R<2> are halogen, lower alkyl, lower alkoxy), e.g. 2- chloro-6-(2,6-dimethoxypyrimidin-2-yloxy)benzyl azide. the compound of formula I is obtained by reacting a 2-azidomethylphonol derivative of formula Ii with a compound of formula III (R<3> is halogen, lower alkylsulfonyl, arylalkylsulfonyl) in the presence of a suitable base in a solvent-free state or in a suitable solvent at -78 deg.C to the boiling point of the solvent.

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 not described in the literature and a herbicide containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art JP-A-4-221372 describes a compound having a phenoxy group or a pyridyloxy group at the 2-position of a pyrimidine ring and a herbicide containing the compound.

[0003]

However, the compounds described in the above-mentioned documents have many points to be improved in terms of herbicidal spectrum, dosage amount, selectivity and the like. The present inventors have conducted extensive studies to develop a compound having a wide herbicidal spectrum, a high herbicidal effect, and excellent safety against crops. As a result, the pyrimidine derivative represented by the following general formula (I) is novel. The present inventors have found that the compounds have high herbicidal activity against perennial weeds as well as annual weeds, and have high safety against certain crops, and completed the present invention.

That is, the present invention has the general formula (I)

[0005]

[Chemical 3]

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

[0007]

The compound of the present invention has the following general formula (I):

[0008]

[Chemical 4]

[In the formula, X represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, and R ¹ and R ² each independently represent a halogen atom, a lower alkyl group or a lower alkoxy group. ] It is a pyrimidine derivative represented by.

In the present specification, the term "lower" means that the group or compound to which this group is attached has 6 or less carbon atoms, preferably 4 to 1. The “halogen atom” includes four kinds of fluorine, chlorine, bromine and iodine. The "lower alkyl group" may be linear or branched and is, for example, methyl, ethyl, n-propyl,
Examples thereof include isopropyl, n-butyl, sec-butyl and tert-butyl groups. The "lower alkoxy group" is a lower alkyl-O- group in which the lower alkyl group moiety has the above-mentioned meaning, for example, methoxy, ethoxy, n-propoxy,
Examples thereof include isopropoxy, n-butoxy, isobutoxy, secondary butoxy and tertiary butoxy groups.

The groups not specifically mentioned in the above groups are selected from the above atoms and groups in any combination or in accordance with generally known common sense. Preferred compounds represented by the general formula (I) include compounds in which X is a hydrogen atom, a methyl group or a chlorine atom, and R ¹ and R ² are simultaneously a methoxy group.

Specific examples of the compound of the present invention represented by the general formula (I) are shown in Table 1. In Table 1, "M
e "is a methyl group," Et "is an ethyl group, and" n-P "
“R” means a normal propyl group and “i-Pr” means an isopropyl group.

[0013]

[Table 1]

[0014]

[0015]

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

The compound of the present invention can be produced, for example, by the method shown below.

[0027]

[Chemical 5]

[In the formula, R ¹ and R ² have the same meanings as described above, and R ³ represents a halogen atom, a lower alkylsulfonyl group or an arylalkylsulfonyl group. ]

In the above reaction scheme, the compound represented by the formula (I) is obtained by reacting the 2-azidomethylphenol derivative represented by the formula (II) with a suitable base in the presence of no solvent or a suitable solvent. It can be produced by reacting with the compound 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 or xylene; a halogenated hydrocarbon solvent such as dichloromethane or chloroform; diethyl ether, diisopropyl ether, tetrahydrofuran or 1,4- Ether solvents such as dioxane; ketone solvents such as acetone or methyl ethyl ketone; ester solvents such as methyl acetate or ethyl acetate; aprotic polar solvents such as dimethylformamide, dimethyl sulfoxide or dimethylacetamide; acetonitrile or water You can

Examples of the base used in the reaction include carbonates such as sodium carbonate and potassium carbonate;
Metal hydroxides such as sodium hydroxide or potassium hydroxide; Metal alcoholates such as sodium methylate or sodium ethylate; Alkyl metal hydrides such as sodium hydride or potassium hydride; Lithium diethylamide, lithium diisopropylamide or lithium Examples thereof include lithium amides such as bistrimethylsilylamide.

In addition, a compound of formula (I
The proportion of the compound of the formula (II) used is not strictly limited, but it is convenient to use the compound of the formula (III) in the range of usually 1 to 5 equivalents, particularly 1 to 2 equivalents per equivalent of the compound of the formula (II). is there. 2 represented by the general formula (II) as a raw material
-Azidomethylphenol derivatives are, for example, tetrahedron letters (Tetrahedron Lett)
ers), 30 , 1939, (1989).

The compound represented by the general formula (III) can be isolated according to the method described in JP-A-63-23870, for example. After completion of the reaction, the reaction solution is subjected to usual post-treatments such as organic solvent extraction and concentration,
If necessary, the desired compound of the present invention can be produced by purifying by operations such as chromatography and recrystallization.

Next, the present invention will be described more specifically with reference to examples.

[0035]

EXAMPLES Example 1 2-chloro-6- (2,6-dimethoxypyrimidine-2
-Yloxy) benzyl azide (Compound No. 3)
Manufacturing of Tetrahedron Letters (Tetrahedron)
(Letters), 30 , 1939, (1989), and prepared according to the method described in (1989) 3-chloro-2-azidomethylphenol 0.4 g and potassium carbonate 0.4 g and 2.
0.5 g of -methyl-4,6-dimethoxypyrimidine was added to 10 ml of dimethylformamide, and the mixture was stirred at room temperature for 6 hours. The reaction solution was diluted with ethyl acetate, washed with saturated saline three times, and then dried over anhydrous magnesium sulfate.
The solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography (developing solvent: ethyl acetate / hexane = 1/3) to obtain 70 mg of the title compound.

The compounds shown in Table 1 above were synthesized by the same method. Table 2 shows the NMR and melting point data of these compounds.

[0037]

[Table 2]Table 2 Compound number NMR (CDCl ₃ δ ppm) and melting point 1 3.77 (s, 6H), 4.30 (s, 2H), 5.70 (s, 1H)_,6.8-7.5 (m, 4H) 51 to 53 ℃ 3 3.82 (s, 6H), 4.50 (s, 2H), 5.75 (s, 1H)_,6.8-7.4 (m, 3H) 116〜120 ℃ 10 3.77 (s, 6H), 3.87 (s, 3H), 4.33 (s, 2H)_,5.70 (s, 1H), 6.5-7.5 (m, 3H) 107-110 ℃

The compound of the present invention represented by the above general formula (I) has activity as a herbicide. 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, a powder, a granule,
It is prepared and used as a wettable powder, an emulsion, a water solvent, a 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 the amount of the drug used is reduced and labor is saved, but also the synergistic action of the two drugs broadens the herbicidal spectrum and further increases the synergistic effect. Can be expected. As the carrier or diluent used in the preparation, generally used solid or liquid carriers can be mentioned.

Examples of the solid carrier include clays represented by kaolinite group, montmorillonite group, illite group, polygoskite group and the like, more specifically, pyroflight, attapulgite, sepiolite, kaolinite, bentonite, vermiculite, mica, talc. Etc; plaster, calcium carbonate, dolomite, diatomaceous earth,
Other inorganic substances such as magnesium lime, apatite, zeolite, silicic acid anhydride, and synthetic calcium silicate; vegetable organic substances such as soybean flour, tobacco flour, walnut flour, wheat flour, wood flour, starch and crystalline cellulose; coumarone resin Examples thereof include synthetic or natural polymer compounds such as petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol, ketone resin, ester gum, cobal gum, and d'umal gum; 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 and monochloro. Chlorinated hydrocarbons such as benzene 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 acetate , Esters such as dibutyl maleate and 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, disintegration control, 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, preventing freezing and the like. As the surfactant to be used, for example, any of nonionic, anionic, cationic and zwitterionic may be used, but usually nonionic and / or anionic ones are used. To be done.

Suitable nonionic surfactants include, for example, compounds obtained by polymerizing addition of ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol and oleyl alcohol; ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol. Polymerized compounds; compounds obtained by polymerizing addition of ethylene oxide to higher fatty acids such as palmitic acid, stearic acid, 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, alkyl sulphate salts such as sodium lauryl sulphate, oleyl alcohol sulphate amine salt, etc., alkyl succinate dioctyl ester sodium, 2-ethylhexene sulphonate sodium and the like. Examples thereof include aryl sulfonates such as sulfonates, sodium isopropylnaphthalene sulfonate, sodium methylenebisnaphthalene sulfonate, sodium lignin sulfonate, and 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 and the like 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 compound of the present invention (active ingredient) 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 80%. A range of weight% is 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 contained in an amount of 1 to 35% by weight, and the balance is a solid carrier and a surfactant. The active ingredient compound is either 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 emulsions, for example, the active ingredient compound is usually 5
-30% by weight, which contains about 5 to 20% by weight of an emulsifier, and the rest is a liquid carrier, and a spreading agent, a rust preventive agent and the like are added if necessary.

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, the dispersion wetting agent is contained in an amount of 3 to 10% by weight, and the balance is water. A protective colloid agent, an antiseptic agent, an antifoaming agent and the like are added. The compound represented by the above 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.

The herbicide of the present invention can be applied to various weeds from the pre-emergence period to the growing season, which grow in paddy fields, cultivated lands such as upland and non-cultivated lands. The application rate is 1 as the active ingredient amount.
It is about 0.1 to 10,000 g, preferably about 1 to 5,000 g per ha. 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.

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. 3 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. 3 20 parts Clay 70 parts Calcium lignin sulfonate 7 parts Alkylnaphthalene sulfonic acid 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. 3 20 parts Sulfosuccinic acid di-2-ethylhexyl ester sodium salt 2 parts Polyoxyethylene nonyl phenyl ether 2 parts Defoamer 0.5 part 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 using the compound of the present invention can be prepared according to the above-mentioned preparation examples.

[0055]

Industrial Applicability The compounds represented by the above general formula (I) of the present invention are:
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 also problematic in fields, such as, for example, broad-leaved weeds such as Polygonum japonicum, Aubiyu, white azalea, perennial and annual perennial Cyperaceae weeds, such as Rhus japonicus, Yellow hemlock, Himekugu, Cyperaceae, Kogomegayasuri, weeds, Japanese herb, Enochogusa, For grass weeds such as Aedes chinensis, Johnson grass, wide oat, and Aedes aegypti, it shows a high herbicidal effect by soil treatment or foliage treatment, and at the same time soybean, cotton, sugar beet, rapeseed, sunflower, corn, upland rice,
It has the feature of showing high safety against wheat and the like.

Further, it can be used not only in paddy fields and upland fields but also in orchards, mulberry fields, lawns and non-agricultural fields.
When the compound of the present invention is used as a mixture with a commonly used herbicide known per se, each compound alone shows a complete herbicidal effect against weeds difficult to control,
Due to the synergistic herbicidal effect, it is possible to effectively control various weeds even at a dose which is difficult to control by each compound alone.

Next, the effects of the compound of the present invention and the herbicide 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, diluted with an appropriate amount of water so that the dose of the active ingredient shown in Table 3 was obtained, and the solution was added dropwise 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 3.

[0058]

[Table 3]

[0059]

[Table 4]

Test Example 2 (paddy foliage 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. After growing Nobie in the greenhouse until the 1.5 leaf stage, a wettable powder was prepared according to Formulation Example 2 and diluted with an appropriate amount of water to give the active ingredient dose shown in Table 4. Then, it was dropped by a pipette. Twenty-one days after the chemical treatment, the herbicidal effect on each weed and the degree of chemical damage to paddy rice were determined according to the criteria of Test Example 1. The results are shown in Table 4.

[0061]

[Table 5]

Test Example 3 (Treatment of Upland Soil) A 130 cm ² plastic pot was filled with upland 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. The day after sowing, a wettable powder was prepared according to Formulation Example 2, diluted with an appropriate amount of water so that the dose of the active ingredient shown in Table 5 was obtained, and sprayed evenly on the soil surface. Twenty-one days after spraying the chemicals, the herbicidal effect on each weed was determined according to the criteria of Test Example 1. The results are shown in Table 5.

[0063]

[Table 6]

Test Example 4 (Treatment of Upland Field and Leaves) 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 so that the active ingredient doses shown in Table 6 were obtained. Was diluted with an appropriate amount of water and sprayed evenly on the leaf surface of the plant. 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 6.

[0065]

[Table 7]

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Mitsuru Hikido 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Mitsubishi Petrochemical Co., Ltd. Tsukuba Research Institute (72) Inventor Rika Higure Chuo, Ami-cho, Inashiki-gun, Ibaraki 8-3-1 Mitsubishi Petrochemical Co., Ltd. Tsukuba Research Institute (72) Inventor Kumiko Tamura 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Mitsubishi Petrochemical Co., Ltd. Tsukuba Research Institute

Claims (2)

[Claims] 1. A compound represented by the general formula (I): [In the formula, X represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, and R ¹ and R ² each independently represent a halogen atom, a lower alkyl group or a lower alkoxy group. ] The pyrimidine derivative represented by these. 2. A compound represented by the general formula (I): [In the formula, X represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, and R ¹ and R ² each independently represent a halogen atom, a lower alkyl group or a lower alkoxy group. ] The herbicide which contains the pyrimidine derivative represented by these as an active ingredient.