JPH05301861A - New pyrimidine derivative and herbicide containing the derivative as active component - Google Patents

Abstract

PURPOSE:To provide a new compound having broad herbicidal spectrum and excellent herbicidal activity and useful as a herbicide having high safety to crops. CONSTITUTION:The compound of formula I [X is halogen or lower alkoxy; R is lower alkyl or lower alkoxy; Y is lower alkoxy, OH or NR1R2 (R1 and R2 are H or lower alkyl); n is 0 or 1], e.g. 1,2,3,4-tetrahydro-1-ethoxycarbonyl-1- fluoro-2-(4,6-dimethoxypyrimidin-2-yloxy)-naphthalene. The compound of formula I can be produced by reacting a compound of formula II with a substituted pyrimidine of formula III in the presence of a base (e.g. sodium hydride) without using a solvent or in a solvent (e.g. toluene) at -78 deg.C to the boiling temperature of the solvent. Excellent herbicidal effect can be attained by the foliar treatment in the growing stage of weeds of the soil treatment before the germination of weeds.

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 In Japanese Patent Application Laid-Open No. 3-128362, a cycloalkanecarboxylic acid moiety and a pyrimidine ring moiety having a specific substituent bonded to the 4- and 6-positions are bonded via an oxygen atom or a sulfur atom. Cycloalkanecarboxylic acid derivatives having a structure and herbicides containing the same are described.

[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 broad herbicidal spectrum, a high herbicidal effect, and excellent safety against crops. As a result, a pyrimidine derivative represented by the following general formula (I) is novel. Therefore, it has been found that this compound has a high herbicidal activity against not only annual but also perennial weeds and has excellent safety against crops, and has completed the present invention.

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

[0006]

[Chemical 3]

[Wherein, X represents a halogen atom or a lower alkoxy group, R represents a lower alkyl group or a lower alkoxy group, Y represents a lower alkoxy group, a hydroxyl group or a group: -NR ₁ R ₂ is shown. Here, R ₁ and R ₂ each independently represent a hydrogen atom or a lower alkyl group. n represents 0 or 1. ] The present invention provides a novel pyrimidine derivative and a herbicide containing the same as an active ingredient.

[0008]

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

[0009]

[Chemical 4]

[Wherein X represents a halogen atom or a lower alkoxy group, R represents a lower alkyl group or a lower alkoxy group, Y represents a lower alkoxy group, a hydroxyl group or a group: -NR ₁ R ₂ is shown. Here, R ₁ and R ₂ each independently represent a hydrogen atom or a lower alkyl group. n represents 0 or 1. ] It is a novel pyrimidine derivative represented by.

Specific examples of the above general formula (I) are shown below.

Lower alkoxy group ; for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, sec-butoxy, and lower alkoxy group having 4 or less carbon atoms; for example, methyl group, ethyl group. Group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, secondary butyl group, tertiary butyl group, alkyl group having a carbon number of 4 or less; halogen atom ; for example, chlorine, fluorine, bromine, and Y being a hydroxy group In the case of “agronomically acceptable
That salts "such as sodium, potassium, ammonium, isopropyl ammonium or such, such as triethylammonium, and alkali metal, ammonium or lower alkyl ammonium, n represents the case of 2.0 indicating 0 or 1, and represents a bond ..

Of course, it should be understood that the optically active isomers of the compounds represented by the above general formula (I) are within the scope of the present invention.

The compounds of the present invention represented by the general formula (I) are shown in Table 1.

In Table 1, "Me" means a methyl group "E".
t "means an ethyl group.

Further, the compound represented by the above general formula (I) of the present invention has stereoisomers on the saturated ring.
A compound in which a pyrimidyloxy group has a cis configuration based on the COY group of the general formula (I) is a cis isomer, and a 1-position CO
A compound in which the 2-position substituent has a trans configuration based on the Y group is referred to as a trans form.

[0017]

[Table 1]

[0018]

[Table 2]

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

[0020]

[Chemical 5]

[In the formula, X, Y, R and n 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 formula, the compound represented by the formula (I) is
A derivative of formula (II) above, in the presence of a suitable base, in the presence of no solvent or a suitable solvent, in the temperature range of −78 ° C. to the boiling point of the solvent, with a substituted pyrimidine of the above formula (III); It can be produced by reacting for a time.

When a solvent is used in this reaction, examples thereof include hydrocarbon solvents such as benzene, toluene or xylene; halogenated hydrocarbon solvents such as dichloromethane or chloroform; diethyl ether, diisopropyl ether, tetrahydrofuran. Or an ether solvent such as 1,4-dioxane; a ketone solvent such as acetone or methyl ethyl ketone; an ester solvent such as methyl acetate or ethyl acetate; an aprotic polar solvent such as dimethylformamide, dimethylsulfoxide or dimethylacetamide; acetonitrile or Water etc. can be mentioned.

As the base, carbonates such as sodium carbonate or potassium carbonate; metal hydroxides such as sodium hydroxide or potassium hydroxide; metal alcoholates such as sodium methylate or sodium ethylate; sodium hydride or Alkyl metal hydrides such as potassium hydride; lithium amides such as lithium diethylamide, lithium diisopropylamide or lithium bistrimethylsilylamide.

Next, synthetic examples of the compounds belonging to the above formula (I) of the present invention will be explained with reference to Examples.

[0025]

【Example】

(Example 1) 1,2,3,4-tetrahydro-1-
Ethoxycarbonyl-1-fluoro-2- (4,6-di
Methoxypyrimidin-2-yloxy) -naphthalene 1) 1,2,3,4-tetrahydro-1-ethoxycarba
Synthesis of Rubonyl-2-oxonaphthalene 2- tetralone (5 g) and pyrrolidine (3.6 g) were added to toluene (1).
It was dissolved in 00 ml. After stirring for 1.5 hours under reflux, the solvent was distilled off and the residue was recrystallized from hexane. The obtained crystals were dissolved in 20 ml of dioxane, and 9 ml of ethyl chloroformate was added dropwise thereto. After stirring for 5 hours under reflux, the reaction solution was returned to room temperature, 20 ml of dilute hydrochloric acid was added, and the mixture was stirred for 30 minutes.
The reaction solution was extracted with ether, and the ether layer was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the concentrated residue was purified by silica gel chromatography to obtain 1.2 g of the title compound.

2) 1,2,3,4-tetrahydro-1
-Ethoxycarbonyl-1-fluoro-2-oxonaphth
Synthesis of Talen 0.22 g of sodium hydride was dissolved in 20 ml of tetrahydrofuran under ice cooling, and 1,2,3,4-tetrahydro-dissolved in 10 ml of tetrahydrofuran.
1-ethoxycarbonyl-2-oxonaphthalene 1.2
g was added dropwise. After completion of the dropping, N-fluoro-
2,4,6-Trimethylpyridinium triflate 1.
9 g was added and the mixture was stirred at room temperature for 3 hours. After ethyl acetate was added to the reaction solution, it was washed with diluted hydrochloric acid, saturated aqueous sodium hydrogen carbonate and saturated saline, and the organic layer was dried over anhydrous sodium sulfate. Under reduced pressure,
The solvent was distilled off and the concentrated residue was purified by silica gel chromatography to obtain 1 g of the title compound.

¹ H-NMR (CDCl ₃ / TMS) δpp
m: 1.20 (t, 3H), 2.2 to 3.6 (m, 4)
H), 4.17 (q, 2H), 6.9 to 7.7 (m, 4)
H). 3) 1,2,3,4-tetrahydro-1-ethoxyca
Synthesis of Rubonyl-1-fluoro-2-oxonaphthalene 1 g of 1,2,3,4-tetrahydro-1-ethoxycarbonyl-1 -fluoro-2-oxonaphthalene was dissolved in 30 ml of ethanol, and sodium borohydride was added thereto. 40 mg was added and stirred for 1 hour. The reaction solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography,
0.56 g of the title compound was obtained.

¹ H-NMR (CDCl ₃ / TMS) δpp
m: 1.27 (t, 3H), 1.7 to 3.2 (m, 4)
H), 3.8 to 4.6 (m, 3H), 7.0 to 7.6.
(M, 4H).

4) 1,2,3,4-tetrahydro-1
-Ethoxycarbonyl-1-fluoro-2- (4,6-
Dimethoxypyrimidin-2-yloxy) -naphthalene
Synthesis of 1,2,3,4-tetrahydro-1-ethoxycarbonyl-1-fluoro-2-oxonaphthalene 0.56
g, potassium carbonate 0.63 g, tetrabutylammonium bromide 0.15 g and 2-methyl-4,6-dimethoxypyrimidine 0.51 g, and acetonitrile 10 ml.
And was heated to reflux for 3.5 hours. After allowing to cool, water was added to the reaction solution and extracted with ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and the residue was purified by silica gel chromatography to obtain 0.6 g of the title compound.

¹ H-NMR (CDCl ₃ / TMS) δpp
m: 1.0-1.4 (m, 3H), 2.0-3.3
(M, 4H), 3.87 (s, 6H), 4.25 (q,
2H), 5.5-6.2 (m, 2H), 7.0-7.6.
(M, 4H).

Example 2 1,2,3,4-tetraha
Idro-1-carboxy-1-fluoro-2- (4,6
-Dimethoxypyrimidin-2-yloxy) -naphthale
Emissions 1,2,3,4-tetrahydro-1-ethoxycarbonyl-1-fluoro-2- (4,6-dimethoxypyrimidin-2-yloxy) - naphthalene 0.3g was dissolved in dioxane 5 ml, water to 0.13 g of potassium hydroxide dissolved in 6 ml was added, and the mixture was stirred at room temperature for 1 hour. The reaction solution was made acidic with concentrated hydrochloric acid and then extracted with ether. The solvent was distilled off under reduced pressure to obtain 0.25 g of the title compound.

¹ H-NMR (CDCl ₃ / TMS) δpp
m: 1.5 to 3.1 (m, 4H), 3.67 (s, 6)
H), 5.1 to 5.9 (m, 2H), 6.8 to 7.2.
(M, 4H).

The physical property data of the compound of the present invention obtained by the same method are shown in Table 2. In addition, NMR represents a nuclear magnetic resonance spectrum, and the unit is ppm.

[0034]

[Table 3]

The herbicidal composition of the present invention containing the compound of the general formula (1) as an active ingredient exhibits an excellent herbicidal effect by foliar treatment during the growing season of weeds or soil treatment before weed germination.

The herbicide of the present invention contains the compound of the general formula (I) as an active ingredient.

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 to prepare a formulation form usually used as an agricultural chemical, for example, a powder or granules. It is prepared and used as an agent, a wettable powder, an emulsion, an aqueous solvent, a flowable agent and the like. 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.

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, polygloskite group and the like, more specifically, pyrophyllite, attapulgite, sepiolite, kaolinite, bentonite, vermiculite, mica. , Talc, etc .; gypsum, calcium carbonate, dolomite, diatomaceous earth,
Other inorganic substances such as magnesium lime, apatite, zeolite, silicic acid anhydride, synthetic calcium silicate; soy flour, tobacco flour, walnut flour, wheat flour, wood flour, starch, crystalline cellulose and other plant organic substances; 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 dumbrum gum; and 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, monochlorobenzene, ortho. Chlorinated hydrocarbons such as chlorotoluene; 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, maleic acid Esters such as dibutyl and diethyl succinate; methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, benzyl alcohol Alcohols such Lumpur, 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 to be used may be nonionic, anionic, cationic and zwitterionic, but are usually nonionic and / or anionic. Stuff 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 surface active agents include, for example, alkyl sulphate salts such as sodium lauryl sulphate, oleyl alcohol sulphate amine salt, etc., alkyl succinate dioctyl ester sodium, sodium 2-ethylhexene sulphonate 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. Molecular compounds and other auxiliary agents can also be used in combination.

The above-mentioned carrier and various auxiliary agents are appropriately used alone or in combination depending on the purpose in consideration of the dosage form 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 contained in an amount of 25 to 90% by weight, the balance being a solid carrier and a dispersion wetting agent, and if necessary, a protective colloid agent, a defoaming agent and the like are added. Be done.

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, a surfactant and the like. 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 an emulsion, for example, the active ingredient compound is usually contained in an amount of 5 to 30% by weight, and about 5 to 20% by weight is contained therein.
A weight% emulsifier is contained, and the balance 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, and 3 to 10% by weight of a dispersant wetting agent is contained therein, and the balance is water, and if necessary, it is protected. Colloidal agents, preservatives, antifoaming agents and the like are added.

The compound of the general formula (I) of the present invention can be used as a herbicide as the compound itself or in any of the above-mentioned preparation forms.

The composition of the present invention can be applied to various weeds from the pre-emergence stage to the growing season, which grow in paddy fields, cultivated lands such as upland fields, 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 the weed, the growth stage, the place of application, the weather and the like.

Next, several embodiments of formulation examples using the compound of the present invention will be shown. In addition, "part" in the following formulation examples is based on weight.

Formulation Example 1 (Granule) Compound No. 1a 5 parts Bentonite 40 parts Talc 52 parts Sodium lignin sulfonate 2 parts Polyoxyethylene alkylaryl ether 1 part After thoroughly mixing the above, add an appropriate amount of water and knead. Then, it was granulated using a granulator to obtain 100 parts of granules.

Formulation Example 2 (wettable powder) Compound No. 2a 20 parts Diatomaceous earth 60 parts White carbon 15 parts Sodium lignin sulfonate 3 parts Sodium dialkylnaphthalene sulfonate 2 parts The above components are mixed and uniformly mixed and pulverized with a jet mill. To obtain 100 parts of wettable powder.

Formulation Example 3 (Emulsion) Compound No. 1a 30 parts Xylene 55 parts Cyclohexanone 10 parts Calcium dodecylbenzene sulfonate 3 parts Polyoxyethylene alkylaryl ether 2 parts The above components were uniformly mixed and dissolved to obtain 100 parts of an emulsion.

Formulation Example 4 (Flowable Agent ) Compound No. 2a 10 parts Sulfosuccinic acid di-2-ethylhexyl ester sodium salt 2 parts Polyoxyethylene nonyl phenyl ether 2 parts Defoamer 0.1 part Water 85.9 parts Wet the above Uniformly pulverized and mixed with a ball mill to obtain 100 parts of a flowable agent.

Drugs using the compound of the present invention were each prepared according to the above-mentioned preparation examples.

[0059]

The novel pyrimidine derivative represented by the general formula (I) of the present invention is a novel compound described in the end of the literature.

The compound and the herbicide of the present invention can be applied to annual weeds such as Nobie, Kodaira, Oyster grass, Oyster grass, Periwinkle, Azena and Abnomome, which occur in paddy fields, before the occurrence of perennial weeds such as Heraomodaka, Urikawa, Mizugaya-tsui, Shizui and Kurogwai. It exhibits a very high herbicidal effect in a wide range over the growing season and, at the same time, has high safety against paddy rice. In addition, various weeds that are problematic in the field as well, for example, annual and perennial grass weeds such as Nobie, Enocorogusa, Messiah grass, Sparrowgrass, Wild Oat, Johnsongrass, Aobiyu, Shiroza, citrus,
Broad-leaved weeds such as Ona fir and Japanese horse mackerel
It shows a high herbicidal effect on annual and perennial cyperaceae such as Himekugu and Kogomeya Cyper, and at the same time shows high safety against field crops such as corn, soybean, cotton, wheat and sugar beet.

Next, the herbicidal effect will be described with reference to test examples.

Test Example 1 (Treatment of Upland Field and Leaves) A square pot (16 × 20 × 5 cm) was filled with upland soil,
A constant amount of each weed seed shown in Table 3 was sown and grown in a greenhouse until each weed reached the 1.5 to 2 leaf stage. The compounds of the present invention shown in Table 3 were prepared into wettable powders according to Preparation Example 2,
The water diluted solution is shown in Table 3 with the amount of active ingredient and the amount of sprayed water 500
The weeds were sprayed evenly on the foliage of each weed at an equivalent of L / ha. Twenty-one days after the chemical spraying, the herbicidal effect on various weeds was discriminated according to the following criteria. The results are shown in Table 3.

[0063]

[Table 4]

Test Example 2 (Soil Treatment Before Germination of Upland Field) A square pot (16 × 20 × 5 cm) was filled with upland soil,
A constant amount of each weed seed shown in Table 4 was sown. On the next day, the compounds of the present invention shown in Table 4 were prepared as wettable powders according to Formulation Example 2, and the diluted solution was evenly sprayed on the soil surface at an amount of the active ingredient of 500 g / 10a and a sprayed water amount of 500 L / ha.
Twenty-one days after the chemical spraying, the herbicidal effect on various weeds was discriminated according to the criteria of Test Example 1. The results are shown in Table 4.

Test Example 3 (Stem and Leaf Treatment of Paddy Field ) A square pot (16 × 20 × 5 cm) was filled with paddy soil, and after weeding, various weed seeds shown in Table 5 were sown in fixed amounts, and then the two-leaf stage. Transplanted rice. 1.5-2 for each plant
The compound of the present invention shown in Table 5 was prepared into a wettable powder according to Formulation Example 2 until it reached the leaf stage, and the water-diluted solution was spray-dried so that the amount of active ingredient was 100 g / 10a. .. Twenty-one days after chemical spraying, the herbicidal effect on various weeds and the degree of phytotoxicity of rice were determined according to the criteria of Test Example 1. The results are shown in Table 5.

Test Example 4 (Soil Treatment Before Germination of Paddy Field ) A square pot (16 × 20 × 5 cm) was filled with paddy field soil, and after weeding, various weed seeds shown in Table 6 were sown in fixed amounts and then 2 Leaf stage rice was transplanted. On the next day, the compounds of the present invention shown in Table 6 were prepared as wettable powders according to Formulation Example 2, and the diluted solution was sprayed dropwise so that the amount of the active ingredient was 100 g / 10a. Twenty-one days after the chemical spraying, the herbicidal effect on various weeds and the degree of phytotoxicity of rice were determined according to the criteria of Test Example 1. The results are shown in Table 6.

[0067]

[Table 5]

[0068]

[Table 6]

[0069]

[Table 7]

[0070]

[Table 8]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mitsuru Hikido 8-3-1 Chuo, Ami-machi, Inashiki-gun, Ibaraki Sanryo Petrochemical Co., Ltd. Tsukuba Research Institute (72) Inventor, Kumiko Tamura, Ami-cho, Inashiki-gun, Ibaraki Chuo 8-3-1 Sanritsu Yuka Co., Ltd. Tsukuba Research Institute

Claims (2)

[Claims] 1. A compound represented by the general formula (I): [In the formula, X represents a halogen atom or a lower alkoxy group, R represents a lower alkyl group or a lower alkoxy group, and Y represents a lower alkoxy group, a hydroxyl group, or
Group: represents -NR ₁ R ₂ . Here, R ₁ and R ₂ each independently represent a hydrogen atom or a lower alkyl group. n represents 0 or 1. ] The novel pyrimidine derivative represented by these, and its agronomically acceptable salt. 2. A compound represented by the general formula (I): [In the formula, X represents a halogen atom or a lower alkoxy group, R represents a lower alkyl group or a lower alkoxy group, and Y represents a lower alkoxy group, a hydroxyl group, or
Group: represents -NR ₁ R ₂ . Here, R ₁ and R ₂ each independently represent a hydrogen atom or a lower alkyl group. n represents 0 or 1. ] The herbicide which contains the novel pyrimidine derivative represented by these, and its agronomically acceptable salt as an active ingredient.