JP2730022B2 - 3-Alkoxybutylyl imidazole derivatives, their production and herbicides - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a herbicide containing a novel 3-alkoxybutylyl imidazole derivative as an active ingredient.

[0002]

2. Description of the Prior Art Many herbicides have been developed so far in order to save labor in agricultural work and improve productivity of agricultural products. However, conventional herbicides cannot be said to have a sufficient selective herbicidal effect on crops such as cotton, and it cannot be said that they sufficiently satisfactorily satisfy the problem of safety for living organisms. Therefore, development of a new herbicide that solves these problems is desired. The 3-alkoxybutylylimidazole derivative of the present invention is a novel compound, and its herbicidal effect has not been known.

[0003]

The object of the present invention is to provide a novel 3-
An object of the present invention is to provide an alkoxybutylimidazole derivative, a method for producing the same, and a herbicide containing the same as an active ingredient.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a novel 3-alkoxybutylylimidazole derivative has been found to be an annual grassy weed and an annual broadleaf weed. The present inventors have found a production method which shows an excellent herbicidal effect on, for example, cotton, a selective herbicidal effect on crops such as cotton, and which can be obtained in a high yield, thereby completing the present invention. That is, the present invention is as follows. The first invention has the following formula:

[0005]

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Wherein R ¹ represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a halo lower alkyl group or a cyano lower alkyl group; R ² represents a hydrogen atom or a lower alkyl group; Or a sulfur atom;
Z represents CH or N. The present invention relates to a 3-alkoxybutylyl imidazole derivative represented by the following formula: The second invention has the following formula:

[0007]

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Wherein R ¹ , R ² , X and Z have the same meanings as described above, and N, N′-carbonyldiimidazole is reacted. The present invention relates to a method for producing a 3-alkoxybutylimidazole derivative represented by the formula (I). The third invention relates to a herbicide containing a 3-alkoxybutylylimidazole derivative represented by the above formula (I) as an active ingredient.

Hereinafter, the present invention will be described in detail. R ¹ , R ² , X ³ and Z in the compound (I), the novel 3-alkoxybutylyl imidazole derivative (I), which is the target compound, and the compound (II), which is a raw material for producing the same, are as follows.

Examples of R ¹ include a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a halo-lower alkyl group, a cyano-lower alkyl group, etc .; A chain or branched one is preferred, preferably one to four, more preferably one to three (eg, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, etc.). The lower alkenyl group is preferably a linear or branched one having 2 to 6 carbon atoms, preferably 2 to 5, more preferably 2 to 3 (for example, propenyl group and the like); The lower alkynyl group is preferably a straight or branched one having 2 to 6 carbon atoms, preferably 2 to 5, more preferably 2 to 3 (for example, propynyl). The halo-lower alkyl group is preferably a straight or branched one having 1 to 6 carbon atoms (halogen atoms include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom). And preferably a chlorine atom.), Preferably 1 to 5
And more preferably 1 to 3 (eg, chloroethyl group, chloropropyl group, etc.);
The cyano lower alkyl group is preferably a linear or branched one having 1 to 6 carbon atoms, preferably 1 to 5 and more preferably 1 to 3 (for example, a cyanoethyl group or the like). Is good.

Examples of R ² include a hydrogen atom and a lower alkyl group. The lower alkyl group is preferably a linear or branched one having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. But more preferably 1 to 3
(Eg, a methyl group, an ethyl group, etc.) are preferred.

X includes an oxygen atom, a sulfur atom and the like.

Examples of Z include CN and N.

The novel 3-alkoxybutyrylimidazole derivative (I) as the target compound also includes optical isomers based on asymmetric carbon atoms. Compound (I) can be produced, for example, by the following production method. (Manufacturing method)

[0015]

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(Wherein R ¹ , R ² , X and Z have the same meanings as described above.) The compound (I) is usually prepared by reacting the starting compound (II) with N, N′-carbonyldiimidazole. It can be produced by reacting in a solvent.
Compound (II) is, for example, as described in Japanese Patent Application No. 2-279328, a 2-hydroxyalkanoic acid or 2-mercaptoalkanoic acid and a 2-methylsulfonylpyridine or 2-chlorotriazine, It can be easily produced by reacting as described below.

[0017]

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(Wherein R ¹ , R ² , X and Z have the same meanings as described above; Y represents a chlorine atom or CH ₃ SO ₂ —). As the compound (II), for example, Table 1 Compounds consisting of the types of substituents corresponding to Compound Nos. 1 to 38 shown in Compounds 1 to 38 [Compounds (II) ₁ to (II), respectively]
_{No. 38} . [For example, compound (II) corresponding to compound No. ₁ is referred to as compound (II) ₁ . Compound (II) ₁ is compound (I)
In I), R ¹ represents CH ₃ , R ² represents H, R ³ represents a lower alkyl group, X represents O, and Z represents CH. ].

The solvent is not particularly limited as long as it does not directly participate in the reaction, and examples thereof include water; ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane; acetone. Methyl ethyl ketone. Ketones such as methyl isobutyl ketone; nitriles such as acetonitrile; N, N-dimethylformamide, N, N-
Examples thereof include dipolar aprotic solvents such as dimethyl-2-imidazolidinone and dimethyl sulfoxide; halogenated alkyl solvents such as chloroform and methylene chloride; and mixtures of the above solvents.

The method for producing the compound (I) has a reaction concentration of 5 to 5.
80%. In the production method, the ratio between the starting compound (II) and N, N′-carbonyldiimidazole is 0.5 to 2 mol of N, N′-carbonyldiimidazole per 1 mol of the starting compound (II). , But preferably 1 to 1.5
A mole is good. The reaction temperature is not particularly limited as long as the reaction is carried out at a temperature equal to or lower than the boiling point of the solvent to be used, but it can be usually carried out at 0 to 50 ° C, preferably 5 to 15 ° C. The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be carried out for 0.5 to 10 hours.

As the compound (I), for example, Tables 1 to 5
Each compound consisting of the types of the substituents corresponding to the compound numbers 1 to 38 shown therein [referred to as compounds 1 to 38. [For example, Compound (I) corresponding to Compound No. 1 is referred to as Compound 1. Compound 1 means that R ¹ in compound (I) is CH ₃ , R ² is H, X is O, and Z is CH. ].

Herbicides containing compound (I) as an active ingredient include:
It has high selectivity to cotton and the like and shows an excellent herbicidal effect. That is, the herbicide of the present invention exhibits an excellent herbicidal effect on annual weeds and perennial weeds that occur in paddy fields, fields, etc., and the herbicidal effect is particularly high for annual grasses (for example, Mehishiba, Nobie, Enokorogosa),
It is remarkable in annual broadleaf weeds (for example, morning glory, shiroza, dogwood, and strawberry) and perennial weeds (for example, Johnsongrass, firefly, and sedge).
Further, the herbicide of the present invention exhibits an excellent herbicidal effect on the above-mentioned weeds, but does not show phytotoxicity to field crops (for example, cotton and the like) at such a treatment concentration. The herbicide of the present invention contains at least one compound (I) as an active ingredient. The compound (I) can be used alone, but it is usually compounded with a carrier, a surfactant, a dispersant, an auxiliary agent and the like (for example, powders, emulsions, fine granules, granules, hydrates). , An oily suspension, aerosol, etc.).

Examples of the carrier include talc, mica, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, dolomite, zeolite, slaked lime, silica sand, silicic anhydride, ammonium sulfate, urea, wood powder,
Solid carriers such as starch and cellulose; hydrocarbons (kerosene, mineral oil, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform,
Carbon tetrachloride, etc., ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol) ,
Liquid carriers such as ethylene glycol), polar solvents (dimethylformamide, dimethyl sulfoxide, etc.), water; and gas carriers such as air, nitrogen, carbon dioxide, and freon (in this case, mixed injection can be performed). I can do it.

Surfactants that can be used to improve the performance of this agent, such as adhesion to plants, improvement in absorption, dispersion, emulsification, and spreading of drugs, include nonionic, anionic, and cationic surfactants. And amphoteric surfactants (eg, alcohol sulfates, alkyl sulfonates, lignin sulfonates, polyoxyethylene glycol ethers, etc.). In order to improve the properties of the preparation, carboxymethylcellulose, polyethylene glycol, gum arabic and the like can be used as adjuvants. In the manufacture of this agent, other than the above-mentioned carriers, surfactants, dispersants, adjuvants, etc., other pesticides (bactericides, insecticides, etc.), fertilizers, soil conditioners and the like according to their respective purposes, Each can be used alone or in an appropriate combination.

When the compound (I) of the present invention is formulated, the concentration of the active ingredient is usually 1 to 50% by weight for emulsions, usually 0.3 to 25% by weight for powders, and usually 1 to 90% by weight for wettable powders. % For granules, usually 0.5 to 5% by weight for oils, usually 0.5 to 5% by weight for oils, and 0.1 to 5% by weight for aerosols. These preparations can be diluted to an appropriate concentration and applied to various uses by spraying them on plant foliage, soil, or the water surface of paddy fields, or directly applying them, depending on the purpose.

[0026]

The present invention will be described below by way of examples. In addition,
These examples do not limit the scope of the invention. Example 1 (1) 1- [3-ethoxy-2- (4,6-dimethoxypyrimidin-2-yl) oxy-3-methylbutyryl]
Synthesis of imidazole (Compound 12) N, N′-carbonyldiimidazole (19.4 g,
0.12 mol) was dissolved in methylene chloride (100 ml) and kept at 5 ° C., and 3-ethoxy-2- (4,6-dimethoxypyrimidin-2-yl) oxy-3-methylbutanoic acid (30.0 g, 0 .1 mol) dissolved in N, N '
-Dimethylformamide (DMF) solution (100 ml)
After dropwise addition, the mixture was stirred at room temperature for 0.5 hour. After completion of the stirring, methylene chloride was washed with water, dried over sodium sulfate,
The crystals obtained by distilling off methylene chloride under reduced pressure are washed with n-hexane to give the target compound as white crystals in 2 ml.
9.8 g (yield: 85%) was obtained.

(2) 1- [2- (4,6-dimethoxy-
2-yl) thio-3-methoxy-3-methylbutyryl]] imidazole (Compound 7) Synthesis of N, N′-carbonyldiimidazole (19.4 g,
0.12 mol) was dissolved in methylene chloride (150 ml) and kept at 5 ° C, and 2- (4,6-dimethoxy-2-yl) thio-3-methoxy-3-methylbutanoic acid (30.
2 g, 0.1 mol) in a DMF solution (100 m
After l) was added dropwise, the mixture was stirred at 5 ° C for 1 hour. After completion of the stirring, water (100 ml) was added to the reaction solution, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with brine, dried over sodium sulfate, and evaporated to remove ethyl acetate under reduced pressure. The crystals were washed with n-hexane to obtain 30.0 g (yield: 85%) of the target compound as white crystals.

(3) Other compounds (I) in Tables 1 to 5
According to any one of the synthesis methods (1) and (2),
The target compound (I) as shown in 5 was obtained. Example 2

(1) [Preparation of granules] 8 parts by weight of compound 5, 30 parts by weight of bentonite, 59 parts by weight of talc, 1 part by weight of neoperex powder (trade name, manufactured by Kao Corporation) and sodium ligninsulfonate 2 The parts by weight were uniformly mixed and then kneaded by adding a small amount of water, and then granulated and dried to obtain granules.

(2) [Preparation of wettable powder] 50 parts by weight of compound 7, 46 parts by weight of kaolin, 2 parts by weight of Neoperex powder (trade name, manufactured by Kao Corporation) and Demol N
(Product name; manufactured by Kao Corporation) 2 parts by weight are mixed uniformly,
Then, it was pulverized to obtain a wettable powder.

(3) [Preparation of emulsion] 30 parts by weight of compound 12, 60 parts by weight of xylene, 5 parts by weight of dimethylformamide and 5 parts by weight of Solpol 3005X (trade name; manufactured by Toho Chemical Industry Co., Ltd.) were added and mixed uniformly. And dissolved to obtain an emulsion.

(4) [Preparation of dust] A powder was obtained by uniformly mixing 5 parts by weight of compound 24, 50 parts by weight of talc and 45 parts by weight of clay. Example 3

(1) Paddy field weeding test A 1/5000 arel Wagner pot is filled with Ube soil (alluvial clay loam), and seeds or tubers of weeds (Nobie, firefly, serrata) are planted, and water is added thereto to add water. It was flooded by 3 cm. The wettable powder of the target compound (I) shown in Tables 1 to 5 prepared according to Example 2 was diluted with water, and the effective concentration of the compound (I) in each of these drug solutions was increased at the time of the 1st leaf of Nobie. 20
g / a was dropped using a pipette. And after controlling for 3 weeks in a glass room with an average temperature of 25 ° C., their herbicidal effect was investigated. Evaluation of drug effect
Compared to the untreated area, 6 stages [0: harmless (normal growth), 1: slight harm, 2: small harm, 3: moderate harm, 4: major harm,
5: complete withering). Table 6 shows the results.

(2) [Upland soil treatment test] 1/5000
Earl's Wagner pot was filled with Ube soil (alluvial clay loam), and seeds of cotton, crabgrass, nobie, ibis, shiroza and morning glory were sowed and covered. The wettable powder of the target compound (I) shown in Tables 1 to 5 prepared according to Example 2 was diluted with water so that the effective concentration of the compound (I) in each of these chemical solutions was 20 g / a. Was sprayed uniformly on the surface layer of each soil. And after controlling for 3 weeks in a glass room with an average temperature of 25 ° C., their herbicidal effect was investigated. Table 7 shows the evaluation results of the drug effects by the evaluation method described in the paddy field herbicidal effect test (I).

(3) [Field foliage treatment test] 1/5000
Earl's Wagner pot was filled with volcanic ash soil, and seeds of Nobie, Mehishiba, Ichibi, Shiroza, Inubeyu and Asagao were sown, covered with soil, and grown for two weeks. A wettable powder of the target compound (I) shown in Tables 1 to 5 prepared according to Example 2 was used as a spreading agent neoesterin (manufactured by Kumiai Chemical Co., Ltd.).
(500 ppm) diluted to 2000 ppm with water containing
Each of the above plants was sprayed uniformly. And average temperature 2
After three weeks of management in a glass room at 5 ° C., their herbicidal effect was investigated. Table 8 shows the evaluation results of the drug effect by the evaluation method described in the paddy field herbicidal effect test (1).

[0036]

Industrial Applicability The novel 3-alkoxybutylylimidazole derivative of the present invention has an excellent herbicidal effect on annual grasses, annual broadleaf weeds, etc., and is excellent in selection against cotton and the like. Has the property.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

Continued on the front page (72) Inventor Takashi Hayama Examiner, Ube Laboratory, Ube Research Institute, Ube Research Institute, 1978 Kogushi, Ube City, Ube City, Yamaguchi Prefecture Tamotsu Tominaga

Claims (3)

(57) [Claims] (1) The following formula: (Wherein, R ¹ represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a halo lower alkyl group or a cyano lower alkyl group; R ² represents a hydrogen atom or a lower alkyl group; X represents an oxygen atom or a sulfur atom Z represents CH or N.) 3-alkoxybutylyl imidazole derivative. 2. The following formula: (Wherein, R ¹ , R ² , X and Z have the same meanings as in claim 1) and N, N′-carbonyldiimidazole is reacted.
A method for producing a 3-alkoxybutylyl imidazole derivative represented by the above formula (I). 3. The compound represented by the formula (I) according to claim 1,
A herbicide containing an alkoxybutylyl imidazole derivative as an active ingredient.