JPH05255315A - 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 (R1 and R3 are H or lower alkyl; R2 is lower alkyl; R4 and R5 are lower alkyl), e.g. 1-diethylcarbamoyl-3-(3,5- dimethyl-4-methylthio-1-pyrazolyl)sulfonyl-1,2,4-triazole. The compound can be produced by reacting an indole 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 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] [Wherein R ₁ and R ₃ represent the same or different hydrogen atoms or lower alkyl groups, R ₂ represents a lower alkyl group, and R ₄ and R ₅ 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 ₅ has 1 to 6 carbon atoms, and may be linear or branched, for example, methyl group, ethyl group, 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.

[0015]

[Table 1]

[Chemical 7]

[0016] Note) In the table, Me is a methyl group, Et is an ethyl group, nPr
Is n-propyl group, iPn is isopropyl group, nBu is n-butyl group, secBu is sec-butyl group, tBu
Represents a t-butyl group.

[0017]

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.

[0018]

EXAMPLES (Production Method of the Compound of the Present Invention) Next, the production method of 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 _Four, R _FiveRepresents 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, R ₁, R₂, R₃Means the same as above
You ) Reacting with a pyrazole derivative
By the general formula (1)

[Chemical 10](In the formula, R ₁, R ₂, R ₃, R_FourAnd R_FiveIs the same as above
Express meaning. 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 a usual post-treatment 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 the 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).

[0025]

【Example】

Example 1 Preparation of 1-diethylcarbamoyl (3,5-dimethyl-4-methylthio-1-pyrazole) sulfonyl-1,2,4-triazole (Compound No. 2) 3,5-Dimethyl-4-methylthiopyrazole 3 ．
0 g, anhydrous potassium carbonate 3.0 g, acetonitrile
1-diethylcarbamoyl-1, 70 ml of the mixture,
2,4-triazole-3-sulfonyl chloride 5.
6 g was added and stirred at 50 ° C. for 1 hour. Then, the reaction solution was concentrated under reduced pressure, 100 ml of toluene was added to the residue, and the mixture was washed with water. This was dried over anhydrous sodium sulfate, the solvent was evaporated under reduced pressure, and the residue was purified by silica gel chromatography (developing solvent, toluene: ethyl acetate = 15: 1) to give the title compound as a colorless oil. .1
g (yield 83%, n ²³ _D 1.5438) was obtained.

Example 2 1-Diethylcarbamoyl-3- (3-t-butyl-4)
-Methylthio-1-pyrazolyl) sulfonyl-1,2,
Preparation of 4-triazole (Compound No. 13) 3-t-
To a mixture of 3.0 g of butyl-4-methylthiopyrazole, 2.0 g of anhydrous sodium carbonate and 70 ml of acetonitrile was added 4.0 g of 1-dimethylcarbamoyl-1,2,4-triazole-3-sulfonyl chloride, and the mixture was stirred at room temperature for 1 hour. It was stirred. Then, the reaction solution was concentrated under reduced pressure, 60 ml of chloroform was added to the residue, and the mixture was washed with water.
The organic layer was dried over anhydrous sodium sulfate, the solvent was evaporated under reduced pressure, and the residue was purified by silica gel chromatography (developing solvent: toluene: ethyl acetate = 30: 1) to give the title compound as a colorless oil (6.2 g). (Yield 89%, m.p.
p. 108-111 ° C).

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 obtained 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.
20 g (yield 88%, melting point 77-78 ° C.) were obtained.

80 g of 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. 62.5 g of the title compound as white crystals when air-dried overnight.
(Yield 85%, melting point 60-61 ° C).

Example (Method for formulating 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 carrier. ,
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%.

In the case of granules, for example, the thus-prepared preparation may be sprayed as it is on the soil surface, in the soil or in water in an amount of about 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, it can be used in combination with a known herbicide, insecticide or plant regulator to expand its applicability, and in some cases, a synergistic effect is expected. You can also do it.

The method of formulating the compound of the present invention represented by the general formula (1) as a herbicide is described in Examples 3 to 6 below.
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 illustrate 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 soil) is filled in a plastic pot with a size of 1 / 5,000 are, and water is added to perform scavenging, and 50 seeds of Tainubie seeds are sown on the surface layer of 0 to 2 cm. Then, 2 leaves of paddy rice are planted at a depth of 2 cm, 2 plants per plant, 3 plants per pot, and the depth of water is 3 c.
kept m.

The drug treatment was carried out in the second leaf stage of Taenia japonica 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

[0047]

[Table 2]

[0048]

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

[0049]

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

[0050]

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

[0051]

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

Test Example 2. Herbicidal effect test for paddy field weeds and phytotoxicity test for transplanted paddy rice Paddy soil (planting soil) is filled in a plastic pot with a size of 1 / 5,000 are, and rice paddy, broad-leaved weeds (Azena, Kishigusa, Mizohakobe) and firefly seeds are filled. 30 seeds were seeded at a depth of 1-2 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, the emulsion prepared according to Example 5 was diluted with water to a predetermined amount to obtain a spray solution,
0 ml was dropped.

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

[0054]

[Table 3]

Test Example 3 Herbicidal effect on upland weeds and phytotoxicity test on crops 1) Herbicidal effect test on weeds Field soil (alluvial loam soil) was packed in a biscuit 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 was 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 for crops Clay pots of 1 / 10,000 are are filled with field soil (alluvial loam soil), and seeds of each crop (5 soybeans, 5 corns, 10 beets, 10 rapeseed seeds) And wheat 1
0 grains 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 a double system for each concentration of the chemical solution.
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.

[0059]

[Table 4]

[0060]

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 and cyperus edulis, eels, and urchins and can almost completely weed it, and it does not cause any phytotoxicity to paddy rice.

Further, the compound of the present invention is a broad-leaved weed such as buckwheat vine, indigo, indactyla, chickweed, white azalea, blue-toothed apricot, apricot, chinensis, malva morning glory, etc., which is a problem in foliar treatment and soil treatment of upland fields, barnyardgrass, millet, green locust, 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 animal toxicity or fish toxicity. Therefore, it can be used safely.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hirokazu Yoshizawa 1 Clover Heights 303 at 2190 Toda, Atsugi City, Kanagawa Prefecture (72) Inventor Masako Yoshihara 253, Esawa, Fujisawa City, Kanagawa Prefecture (72) Yoko Yoko Morimoto, Kanagawa Prefecture 5-37-12 Asahi-cho, Atsugi-shi

Claims (2)

[Claims] 1. A general formula: [Wherein R ₁ and R ₃ represent the same or different hydrogen atoms or lower alkyl groups, R ₂ represents a lower alkyl group, and R ₄ and R ₅ represent the same or different lower alkyl groups .. ] The triazole derivative shown by these. 2. A general formula: [Wherein R ₁ and R ₃ represent the same or different hydrogen atoms or lower alkyl groups, R ₂ represents a lower alkyl group, and R ₄ and R ₅ represent the same or different lower alkyl groups .. ] The herbicide containing the triazole derivative shown by these as an active ingredient.