JPH05255316A - Triazole derivative and herbicide - Google Patents

Abstract

PURPOSE:To provide a new triazole derivative free from phytotoxicity to crops and exhibiting excellent herbicidal effect on weeds of paddy field, especially echinochloa which is a harmful paddy field weed at a low rate of application. CONSTITUTION:The compound of formula I (A is cyclohexyl, phenyl, furan-2-yl or thiophen-2-yl; R1 and R2 are H or lower alkyl; R3 and R4 are lower alkyl), e.g. 1-diethylcarbamoyl-3-(3-cyclohexyl-5-methyl-1-pyrazolyl) sulfonyl-1,2,4-triazole. The compound can be produced by reacting a triazole derivative of formula II (X is halogen) with a pyrazole derivative of formula III at 0-150 deg.C, preferably 20-70 deg.C.

Description

Detailed Description of the Invention

[0001]

[Object of the Invention]

FIELD OF THE INVENTION The present invention relates to a novel triazole derivative and a herbicide containing the derivative as an active ingredient.

Accordingly, the present invention is useful in the chemical industry as well as agriculture, especially in the agrochemical manufacturing industry.

[0003]

2. Description of the Related Art The compounds similar to the triazole derivative of the present invention include the following compounds, all of which are known to have herbicidal activity.

JP-A-48-77030

[Chemical 3]Where R ₁And R ₂Are the same or different and
R represents a kill group, etc. ₃And R _FourTogether with the nitrogen atom form a ring
None, morpholino group, pyrrolidino group, piperidino group, etc.
Shows the heterocyclic ring of.

JP-A-63-22083

[Chemical 4]Where R ₁Indicates an alkylaminocarbonyl group, etc.
And R ₂Is a hydrogen atom or the like, R ₃Is replaced or non-
Represents a substituted phenyl group, heterocyclic group or aralkyl group, R
_FourIs a hydrogen atom, a lower alkyl group, a lower alkenyl group,
A lower alkynyl group is shown.

Japanese Unexamined Patent Publication No. 1-106883

[Chemical 5]Where R ₁, R ₂Are the same or different and are lower alkyl
A group, X and Y are the same or different and are CH or
Or a nitrogen atom, Z is the same or different and is halo.
Gen atom, trifluoromethyl group or lower alkyl group
, M is 0, 1 or 2, and n is 0, 1 or 2.
Or 2 is shown.

[0007]

However, the compounds described in these documents (1) to (4) have insufficient herbicidal efficacy or cause phytotoxicity to crops, as shown in the test examples described below. It's hard to say that we should be satisfied. Therefore, development of a herbicide with few such defects is desired.

Accordingly, the present invention is to provide, in place of these compounds, a novel compound having excellent herbicidal activity and safety, and a herbicide for paddy rice and field crops containing the same.

[0009]

[Means for Solving the Problems] The inventors of the present invention have synthesized a number of triazole derivatives in order to achieve the above object, and have made earnest studies on their usefulness. as a result,
The novel triazole derivative represented by the following general formula (1) does not cause phytotoxicity to crops, and weeds in paddy fields,
In particular, it was found that the application of a low dose to Tainubie, which is a weed that is highly damaging to paddy fields, exhibits an excellent herbicidal effect.

Therefore, the gist of the first aspect of the present invention lies in the general formula (1)

[0011]

[Chemical 6] [In the formula, A represents a cyclohexyl group, a phenyl group, a furan-2-yl group or a thiophen-2-yl group,
R ₁ and R ₂ represent the same or different hydrogen atoms or lower alkyl groups, and R ₃ and R ₄ represent the same or different lower alkyl groups. ] It exists in the triazole derivative shown by these.

In the compound represented by the general formula (1),
In the formula, the lower alkyl group in the definition of R _{1 to} R ₄ has 1 to 6 carbon atoms and may be linear or branched, and examples thereof include a methyl group, an ethyl group and an n-propyl group. , Isopropyl group, n-butyl group, isobutyl group, s
Examples thereof include an ec-butyl group and a t-butyl group.

The gist of the second aspect of the present invention is a herbicide containing the compound of formula (1) as an active ingredient.

Next, Table 1 shows typical examples of the compound of the general formula (1) of the present invention.

Compound No. Is also referred to in the following examples and test examples.

[0016]

[Chemical 7]

[Table 1]

[0017]

[0018]

The compound of the general formula (1) of the present invention is a novel compound. The compound of the general formula (1) is
Acts as an active ingredient for controlling various weeds in upland fields.

[0019]

EXAMPLES (Method for Producing the Compound of the Present Invention) Next, the method for producing the compound of the present invention will be described in detail. That is, the general formula (2) is used as a starting material.

[Chemical 8](In the formula, R ₃, R _FourRepresents the above meaning, and X represents a halogen
Represents an atom. ) And a triazole derivative represented by
General formula (3)

[Chemical 9] (In the formula, A, R ₁ and R ₂ have the same meanings as described above.)
By reacting with a pyrazole derivative represented by the general formula (1)

[Chemical 10](In the formula, A, R ₁, R ₂, R ₃And R_FourIs the same meaning as above
Represents the taste. The compound of the present invention represented by

In the step of reacting the compound of formula (2) with the compound of formula (3), 1 equivalent or more, preferably 1 to 1.2 equivalents of the compound of formula (3) is reacted with the compound of formula (2).
The reaction temperature in this case is 0 to 150 ° C., preferably 2
0 to 70 ° C.

As the dehydrohalogenating agent, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydrogen carbonate, and organic bases such as triethylamine, pyridine and N, N-diethylaniline can be used. ..

Examples of the solvent include hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chloroform, dichloromethane and chlorobenzene, ethers such as diethyl ether, tetrahydrofuran and dioxane, and ketones such as acetone and methyl ethyl ketone. , Acetonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide, pyridine, water or a suitable mixed solvent thereof can be used.

After completion of the reaction, the reaction solution is added with water, extracted with an organic solvent, subjected to usual post-treatments such as concentration, and if necessary, purified by operations such as chromatography and recrystallization. it can.

Examples of production by this method are shown in Examples 1 and 2.

The compound represented by the general formula (3), which is a starting material, can be easily synthesized by a known method or a known method. Reference Production Example 1 shows a production example of the compound of the general formula (2).

[0026]

【Example】

Example 1 1-Diethylcarbamoyl-3- (3-cyclohexyl-5-methyl-1-pyrazolyl) sulfonyl-1,2,
Preparation of 4-triazole (Compound No. 2) 3-cyclohexyl-5-methylpyrazole 3.3 g, anhydrous potassium carbonate 3.3 g, acetonitrile 70 ml In a mixture of 1-diethylcarbamoyl-1,2,4-triazole-3- Sulfonyl chloride (5.3 g) was added, and the temperature was 50 ° C.
The mixture was stirred for 1 hour. Then, the reaction solution was concentrated under reduced pressure, 100 ml of toluene was added, and the mixture was washed with water. After drying this over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel chromatography (eluent, toluene:
Purification with ethyl acetate = 15: 1), melting point 89-9
6.1 g (yield 77%) of the title compound at 1 ° C. was obtained as colorless crystals.

Example 2 1-Diethylcarbamoyl-3- [3- (thiophene-
Preparation of 2-yl) -5-methyl-1-pyrazolyl] -sulfonyl-1,2,4-triazole (Compound No. 13) 3- (thiophen-2-yl) -5-methylpyrazole 3.3 g, anhydrous 5.3 g of 1-diethylcarbamoyl-1,2,4-triazole-3-sulfonyl chloride was added to a mixture of 3.3 g of sodium carbonate and 40 ml of dimethylformamide, and the mixture was stirred at room temperature for 1 hour. After that, the reaction solution was concentrated under reduced pressure and chloroform was added to the residue.
60 ml was added and washed with water. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 7.3 g of light brown crude crystals. When this was recrystallized from a mixed solvent of isopropyl ether and n-hexane, the title compound having a melting point of 128 to 130 ° C was obtained as colorless crystals.
6 g (yield 71%) was obtained.

Reference Production Example 1 Production of 1-diethylcarbamoyl-1,2,4-triazole-3-sulfonyl chloride 3-mercapto-1,2,4 in 150 ml of methanol
-51 g of triazole was dissolved, 100 g of sodium methylate methanol solution (28%) was added thereto, and the mixture was stirred at 20 ° C for 30 minutes, and then benzyl chloride 6
6 g was added dropwise at 15 ° C. After dropping, the mixture was stirred at 30 ° C. for 1 hour, and the precipitated inorganic salt was filtered off. When the filtrate is concentrated,
90 g (yield 93%, melting point 81-82 ° C) of 3-benzylthio-1,2,4-triazole was obtained as white crystals.

The resulting 3-benzylthio-1,2,4-
Dissolve 90 g of triazole in 400 ml of acetone,
68.5 g of potassium carbonate was added, and then 67.0 g of diethylcarbamoyl chloride was added. After this 55
After stirring at ℃ for 1 hour, it was cooled and the inorganic salt was filtered off. The filtrate was concentrated to give 1-diethylcarbamoyl-3-benzylthio-1,2,4-triazole as white crystals,
120 g (88% yield, melting point 77-78 ° C) were obtained.

80 g of this 1-diethylcarbamoyl-3-benzylthio-1,2,4-triazole was added to 60 g of acetic acid.
It was dissolved in 0 ml and 150 ml of water, and 69 g of chlorine gas was blown thereinto for 30 minutes while cooling to -5 ° C. 30 minutes after that,
Stir at 5 ° C. Then add 600 ml of water and mix at 5 ° C for 3
After stirring for 0 minutes, the precipitated white crystals were filtered and washed with water. After air drying overnight, the title compound was obtained as white crystals, 62.5
g (yield 85%, melting point 60-61 ° C.) was obtained.

Example (Method for formulating a herbicide) When the compound of the present invention is used as an active ingredient of a herbicide,
Usually, it is mixed with solid carrier, liquid carrier, surfactant, and other auxiliaries for preparations, and emulsions, wettable powders, liquids, flowable (sols), powders, driftless agents, granules, and fine particles are prepared by a conventional formulation. It can be prepared in an appropriate form such as an agent or a tablet.

The carrier used here may be either solid or liquid as long as it is commonly used for agricultural and horticultural chemicals, and is not limited to a particular one. ,
For example, these carriers include mineral powders (kaolin,
Bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, apatite, white carbon, slaked lime, silica sand, ammonium sulfate, urea, etc., vegetable powder (soybean flour, wheat flour, wood flour,
Tobacco powder, starch, crystalline cellulose, etc., polymer compounds (petroleum resin, polyvinyl chloride, ketone resin, dammal gum, etc.), alumina, silicates, sugar polymers, highly dispersible silicic acid, waxes, etc. . Further, as the liquid carrier, water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, butanol, ethylene glycol,
Benzyl alcohol), aromatic hydrocarbons (toluene, benzene, xylene, ethylbenzene, methylnaphthalene, etc.), halogenated hydrocarbons (chloroform,
Carbon tetrachloride, dichloromethane, chloroethylene, monochlorobenzene, trichlorofluoromethane, dichlorofluoromethane, etc.), ethers (ethyl ether, ethylene oxide, dioxane, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl) Ketones, isophorone, etc., Esters (ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate, etc.), Acid amides (dimethylformamide, dimethylacetamide, etc.), Nitriles (acetonitrile, propionitrile, acrylonitrile, etc.), sulfoxides (Dimethylsulfoxide, etc.), Alcohol ethers (Ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, etc.) Aliphatic or alicyclic hydrocarbons (n- hexane, cyclohexane, etc.), industrial gasoline (petroleum ether, solvent naphtha, etc.), petroleum fractions (paraffins, kerosene, etc. gas oil) and the like.

In the preparation of emulsions, wettable powders, flowable agents, etc., various surfactants (or emulsifiers) are used for the purpose of emulsification, dispersion, solubilization, wetting, foaming, lubrication, spreading and the like. .. Such surfactants include nonionic types (polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, etc.), anionic types (alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl sulphates, polysulfates). Oxyethylene alkyl sulfate, aryl sulfonate, etc.), cationic type [alkyl amines (lauryl amine, stearyl trimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, etc.), polyoxyethylene alkyl amines], amphoteric type [carboxylic acid (betaine type ), Sulfuric acid ester salt, etc.]
Of course, the present invention is not limited to these examples.

In addition to these, polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC),
Various auxiliary agents such as gum arabic, polyvinyl acetate, sodium alginate, gelatin and tragacanth gum can be used.

In the present invention, the compound of the present invention is added in an amount of 0.001% to 95% in the production of the above-mentioned various preparations.
(% By weight; the same applies hereinafter), preferably 0.01% to 75%
It can be formulated so as to contain in the range of. For example, in the case of powder, DL powder, and fine powder (F),
0.01% to 5%, in the case of granules 0.01% to 10%
%, Wettable powders, emulsions, and liquids can be contained in the range of 1% to 75%.

For example, in the case of granules, the preparation thus prepared may be sprayed as it is on the soil surface, in the soil or in water in an amount of 0.3 g to 300 g per 10 ares as an active ingredient amount. In the case of a wettable powder, an emulsion, a sol and the like, it may be diluted with water or a suitable solvent and diluted in the range of about 0.3 to 300 g per 10 ares as an active ingredient amount.

When the compound of the present invention is used as a herbicide, its applicability can be expanded by mixing it with a known herbicide, insecticide or plant regulator, and in some cases, a synergistic effect is expected. You can also do it.

Regarding the method for formulating the compound of the present invention represented by the general formula (1) as a herbicide, the following Examples 3 to 6 are given.
Explain. However, the present invention is not limited only to these examples, it can be mixed with other various additives in any proportion, and other herbicides and the like can be mixed in any proportion to prepare a formulation. You can also

Compound No. Are those shown in Table 1 above, and all parts in the examples are parts by weight.

Example 3 (Granule) Compound No. Compound 1 of 2, lauryl sulphate 1 part, calcium lignin sulfonate 1 part, bentonite 30 parts and white clay 67 parts were mixed with 15 parts of water and kneaded with a kneader, then granulated with a granulator and then fluidized dryer. And dried to obtain granules containing 1% of active ingredient.

Example 4 (Wettable powder) Compound No. 13 parts of compound 15 parts, white carbon 15 parts, calcium lignin sulfonate 3 parts, polyoxyethylene nonyl phenyl ether 2 parts, diatomaceous earth 5 parts and clay 60 parts are uniformly mixed with a pulverizer to contain 15% of active ingredient. Obtain a wettable powder.

Example 5 (Emulsion) Compound No. 4 parts 20 parts, Solpol 700H
(Emulsifier manufactured by Toho Chemical Industry Co., Ltd.) 20 parts and xylene 60 parts are mixed to obtain an emulsion containing 20% of the active ingredient.

Example 6 (powder) Compound No. Compound 9 of 0.5 part, anhydrous silicic acid fine powder
0.5 part, calcium stearate 0.5 part, clay 50 parts and talc 48.5 parts are uniformly mixed and pulverized to obtain a dust containing 0.5% of the active ingredient.

Next, Test Examples 1 to 3 are shown to demonstrate the herbicidal effect of the compound of the present invention. Test Example 1. Herbicidal effect test and phytotoxicity test for transplanted paddy rice A rice pot soil (planting loam) is filled in a plastic pot with a size of 1/5000 are, and water is added to perform scavenging. Then
Two-leaf stage paddy rice was planted at a depth of 2 cm, 2 plants per plant, 3 plants per pot, and the water depth was kept at 3 cm.

The drug treatment was carried out in the second leaf stage of Taenia muscaria in Example 5.
Dilute the emulsion prepared in accordance with 1) with water and add 10 per pot.
ml (1.3g per are in terms of the amount of active ingredient used)
(Equivalent) was added dropwise.

This test was carried out in duplicate for each chemical concentration group, and 21 days after the chemical treatment, the herbicidal effect and the phytotoxicity of paddy rice were investigated based on the following evaluation indexes. The results are shown in Table 2.

Evaluation value of herbicidal effect Herbicidal rate (%) 5 100% 4 80 to less than 100% 3 60 to less than 80% 2 40 to less than 60% 1 20 to less than 40% 0 less than 20% Evaluation of chemical damage 5 Death 4 Drug damage 3 Drug damage Medium 2 Drug damage 1 Drug damage Minor 0 Drug damage No

[0048]

[Table 2]

[0049]

Embedded image Comparative drug A; (Compounds described in JP-A-48-77030)

[0050]

Embedded image Comparative drug B; (Compounds described in JP-A-48-77030)

[0051]

Embedded image Comparative drug C; (Compounds described in JP-A-63-22083)

[0052]

Embedded image Comparative drug D; (Compounds described in JP-A-1-106883)

Test Example 2. Herbicidal effect test on paddy field weeds and phytotoxicity test on transplanted rice paddy field soil (planting loam) is filled in a plastic pot with a size of 1 / 5,000 are, and rice paddy, broad-leaved weeds (Azena, Scutellaria japonica, Mizochabe), and firefly seeds are filled. 30 seeds were seeded at a depth of 1 to 2 cm. One day after sowing, the water was flooded to keep the water depth at 2 cm. Three days after sowing, paddy rice at the 2.5 leaf stage was transplanted and grown in a greenhouse. One day after transplanting the paddy rice, 10 ml of a spray solution obtained by diluting the emulsion prepared according to Example 5 with water to a predetermined amount was dropped per pot.

This test was carried out in duplicate for each chemical concentration group, and 21 days after the treatment, the herbicidal effect and the phytotoxicity of paddy rice were investigated based on the same evaluation index as in Test Example 1. The results are shown in Table 3.

[0055]

[Table 3]

Test Example 3 Herbicidal effect on field weeds and phytotoxicity test on crops 1) Herbicidal effect test on weeds Field soil (alluvial loam soil) was packed in a bisque pot with a size of 1/5000 are, and a soil of 1 cm surface layer was prepared. Fifty seeds of each kind of weed seeds, such as crabgrass, green foxtail, white foxtail, white squirrel, swordfish, and starfish were uniformly mixed, and the surface layer was lightly pressed. Two days after sowing, the emulsion prepared according to Example 5 was diluted with water and 100 liters per 10 ares (corresponding to 100 g per 10 ares in terms of application amount of active ingredient) was sprayed onto the soil surface.

This test is carried out in a double system for each concentration of the chemical solution.
30 days after the chemical treatment, the herbicidal effect was investigated based on the same evaluation index as in Test Example 1.

2) Chemical damage test to crops Field soil (alluvial loam soil) was packed in a pot of 1 / 10,000 areal, and seeds of each crop (5 soybeans, 5 corns, 10 beets, 10 rapeseed seeds). And wheat 1
0 seeds) were sown in separate pots, and the surface layer was lightly pressed. One day after sowing, the emulsion prepared according to Example 5 was diluted with water, and 100 liters per 10 ares (corresponding to 100 g per 10 ares in active ingredient amount) was sprayed onto the soil surface.

This test is carried out in duplicate for each chemical concentration group.
30 days after the chemical treatment, the degree of phytotoxicity to each crop was investigated based on the same evaluation index as in Test Example 1. The results are shown in Table 4.

[0060]

[Table 4]

[0061]

INDUSTRIAL APPLICABILITY The compound of the present invention has an excellent herbicidal effect as compared with known similar compounds and exhibits excellent selectivity between crops and weeds. That is, in flooding treatment of paddy fields, various weeds that are problematic, for example, grass weeds such as Taenia japonicus, azena, yellow grass, broad-leaved weeds such as Mizochabe,
It can act on a wide variety of cyperaceous weeds, such as Pleurotus cornucopiae, firefly, pine nuts, cyperus edulis, and eels, urchins, etc., to be almost completely weeded, and it has no phytotoxicity to paddy rice.

In addition, the compound of the present invention is a broad-leaved weed such as buckwheat vine, dogwood, dogweed, starfish, chickweed, white lobster, agatela, nazweed, velvetleaf, malaba morning glory, etc. Crabgrass, Blue-billed anemone,
It can act on a wide range of grass weeds such as oats and cyperaceae weeds such as pearl nuts, and can almost completely weed it, and it also has a phytotoxic effect on major crops such as corn, wheat, rice, soybean, rape and beet. Don't give

Moreover, there is no human toxicity or fish toxicity. Therefore, it can be used safely.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C07D 231: 00 249: 00) (C07D 405/14 231: 00 249: 00 307: 00) (C07D 409/14 231: 00 249: 00 333: 00) (72) Inventor Masakazu Taniguchi 7-25-21 Yani, Narashino City, Chiba Prefecture (72) Inventor Hirokazu Yoshizawa 1 Clover Heights 303, 2190 Toda, Atsugi City, Kanagawa Prefecture 303 Issue (72) Inventor Masako Yoshihara, 253, Esawa, Fujisawa City, Kanagawa Prefecture

Claims (2)

[Claims] 1. A general formula: [In the formula, A represents a cyclohexyl group, a phenyl group, a furan-2-yl group or a thiophen-2-yl group,
R ₁ and R ₂ represent the same or different hydrogen atoms or lower alkyl groups, and R ₃ and R ₄ represent the same or different lower alkyl groups. ] The triazole derivative shown by these. 2. A general formula: [In the formula, A represents a cyclohexyl group, a phenyl group, a furan-2-yl group or a thiophen-2-yl group,
R ₁ and R ₂ represent the same or different hydrogen atoms or lower alkyl groups, and R ₃ and R ₄ represent the same or different lower alkyl groups. ] The herbicide containing the triazole derivative shown by these as an active ingredient.