JP2613047B2 - Novel 1,2,4-triazole-3-carboxylic acid amide derivative, production method thereof and herbicide containing the same as active ingredient - Google Patents

Description

The present invention relates to a 1,2,4-triazole-3-carboxylic acid amide derivative used as a herbicide component, a method for producing the same, and a herbicide containing the same as an active ingredient. Agent.

Prior art Conventionally, 1,5-diphenyl-1,2,4-triazole-3-
It is known that carboxylic acid amide derivatives have a herbicidal action, for example, JP-A-57-193406, JP-A-58-1855.
No. 72 and JP-A-59-98004 disclose examples thereof.

However, 1,5-diphenyl-1,2,4-triazole-3
-A compound having an OR group (R represents an alkyl group having 1 to 10 carbon atoms, a phenyl group or an aralkyl group) at the 3-position of the 5-phenyl group of the carboxamide has not yet been reported.

Incidentally, JP-A-58-185572 mentioned above discloses a compound having an OCH ₃ group at the 4-position of the 5-phenyl group of 1,5-diphenyl-1,2,4-triazole-3-carboxylic acid amide. Is merely exemplified.

Problems to be Solved by the Invention In recent years, useful crops, such as rice, wheat, corn, etc., and a herbicide showing a selective action of killing only weeds without harming the crops even when applied to weeds simultaneously. Agents have been strongly desired.

The present inventors have studied compounds exhibiting excellent herbicidal activity of selective action as described above, and as a result,
At the 3-position of the 5-phenyl group of 5-diphenyl-1,2,4-triazole-3-carboxylic acid amide, an OR group (R is a group having 1 carbon atom)
(Indicating up to 10 alkyl groups, phenyl groups or aralkyl groups) have been found to exhibit the above-mentioned excellent herbicidal activity.

Therefore, the present invention provides a novel 1,2,4-triazole-3-carboxylic acid amide derivative which has not been described in the literature, a herbicide containing the derivative as an active ingredient, and a method for producing the derivative. That is the task.

 Hereinafter, the present invention will be described in detail.

Constitution of the invention The feature of the present invention is that 1,2,4 represented by the following general formula (I)
A triazole-3-carboxylic acid amide derivative and a herbicide containing the same as an active ingredient; and the present invention further includes a method for producing the derivative.

(In the formula, R represents an alkyl group having 1 to 10 carbon atoms, and R may be a phenyl group or an aralkyl group.)

Means for Solving the Problems According to the present invention, represented by the general formula (I), 1,2,4-
Table 1 shows specific examples of the triazole-3-carboxylic acid amide derivative.

The compound according to the present invention has the following (A) or (B)
Can be produced by any of the methods described above.

Production method of (A): Formula (II) Is reacted with a compound represented by the following general formula (III) together with a hydrogen halide scavenger in an aprotic polar solvent.

RX (III) (wherein, R represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group, and X represents a halogen atom of Cl, Br and I).

Here, those used as the aprotic polar solvent include, for example, acetone, ketone solvents such as methyl ethyl ketone, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ether solvents such as diethylene glycol dimethyl ether, nitrile solvents such as acetonitrile, dimethyl Examples include amide-based solvents such as formamide, dimethylacetamide, N-methylpyrrolidone, and hexamethylphosphorotriamide; and sulfur-containing solvents such as dimethylsulfoxide and sulfolane.

As the hydrogen halide scavenger, caustic soda,
Caustic potash, sodium carbonate, potassium carbonate, sodium hydride,
There are inorganic bases such as metallic sodium and organic bases such as triethylamine, pyridine and N, N-dimethylaniline.

The compound of the formula (II) used as a starting material in the above-mentioned production method is obtained by the following production method (B).

That is, when a compound in which R is a hydrogen atom is used as the m-hydroxybenzaldehyde compound represented by the general formula (V) used in the production method of (B), a compound of the formula (II) is obtained.

According to the production method of the above (A), the compound is represented by the above general formula (I) (excluding a case where R is a phenyl group).
A 1,2,4-triazole-3-carboxylic acid amide derivative is obtained.

Production method of (B): Synthesized using aniline as a starting material (the synthesis method is a method described in JP-B-58-4035). A hydrazone compound having the general formula (V) (Wherein, R represents an alkyl group having 2 to 10 carbon atoms, a phenyl group or an aralkyl group).

The dehydration reaction and the dehydrogenation of the benzaldehyde derivative represented by the formula (1) are carried out in the presence of an acid catalyst.
171475) and the desired general formula (I)
A 1,5-diphenyl 1,2,4-triazole-3-carboxylic acid amide derivative is obtained.

The 1,2,4-triazole- represented by the general formula (I) obtained by the synthesis according to the methods (A) and (B) described above.
Since 3-carboxylic amide derivatives have an excellent selective herbicidal action, they can be widely used as herbicides in paddy fields, upland crops, and the like.

In order to use these compounds as herbicides, a wide variety of carriers (diluents) and auxiliaries commonly used in the preparation of agricultural chemicals are applied to wettable powders, emulsions, granules, powders, etc. Used in form.

Examples and Effects Examples will be given below to specifically describe the method for producing the compound according to the present invention, the preparation of a herbicide containing the compound as an active ingredient, and the herbicidal effect thereof.

Reference Example 1 5- (3-hydroxyphenyl) -1-phenyl-1H-
1,2,4-triazole-3-carboxylic acid amide [formula (I
Synthesis of Compound as Intermediate Having I): Oxamide phenylhydrazone [compound of formula (IV)
8.9 g (0.05 mol) was dissolved in 50 ml of acetic acid, 6.7 g (0.055 mol) of meta-hydroxybenzaldehyde was added thereto, and the mixture was stirred overnight at room temperature while keeping the system open. The acetic acid was distilled off, the residue was poured into water, and the precipitated crystals were collected by filtration, washed with water and dried.
The precipitated crystals were recrystallized from ethanol to obtain 11.8 g (84%
(Yield), mp 197-8 ° C.

Infrared absorption spectrum (KBr, cm ^-1 ) ν _{NH, OH} 3420, 3360, 3300, 3250, 3050, ν _CO 1670 Example 1 5- (3-hexyloxyphenyl) -1-phenyl-
Synthesis of 1H-1,2,4-triazole-3-carboxylic acid amide (Compound No. 3 in Table 1): 5- (3-hydroxyphenyl) synthesized in Reference Example 1.
560 mg (2 mmol) of 1-phenyl-1H-1,2,4-triazole-3-carboxylic acid amide [compound of the formula (II)] was dissolved in 20 ml of hexamethylphosphorotriamide, and 60% hydrogen was added thereto. 120mg sodium chloride (3mmol)
And stirred for 30 minutes. Next, 1.0 g (6 mmol) of hexyl bromide was further added, and the mixture was stirred at room temperature for 2 hours. The obtained reaction mixture was poured into ice water, and the aqueous layer was diluted with dilute HCl.
And then extracted with benzene. The obtained organic layer was washed with water, saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off. The resulting oil is chromatographed on silica gel (developing solvent: ethyl acetate / n-hexane = 2/1, V
/ V), and further recrystallized from ethyl acetate / n-hexane to obtain 516 mg (yield 70%) of the desired product, mp. 121 to 2 ° C.

Infrared absorption spectrum (KBr, cm ^-1 ) ν _NH 3450, ν _CO 1695 Example 2 5- (3-phenoxyphenyl) -1-phenyl-1H-
Synthesis of 1,2,4-triazole-3-carboxylic acid amide [Compound No. 7 in Table 1] 1.8 g (0.01 mol) of oxamide phenylhydrazone [compound of formula (IV)] was dissolved in 10 ml of acetic acid. Then, 2.2 g (0.011 mol) of meta-phenoxybenzaldehyde was added thereto, and the mixture was stirred overnight at room temperature while keeping the system open. Acetic acid was distilled off, water was added to the residue, and the precipitated crystals were washed with water and dried.
The precipitated crystals were recrystallized from ethyl acetate-n-hexane and 3.
1 g (86% yield) of mp.162-3 ° C. was obtained.

Infrared absorption spectrum (KBr, cm ^-1 ) ν _NH 3400, 3150, ν _CO 1690 Next, a preparation of a herbicide containing the 1,2,4-triazole-3-carboxylic acid amide derivative according to the present invention as an active ingredient Is shown.

 Parts in each example indicate weight.

Example 3 Preparation of wettable powder Compound No. 3 (Table 1) 50 parts Lignin sulfonate 5 parts Alkyl sulfonate 3 parts Diatomaceous earth 42 parts are mixed and pulverized to prepare a wettable powder and diluted with water for use.

Example 4 Preparation of Emulsion Compound No. 3 (Table 1) 25 parts Xylene 65 parts Polyoxyethylene alkyl allyl ether 10 parts are uniformly mixed to prepare an emulsion, which is diluted with water and used.

Example 5 Preparation of Granules Compound No. 4 (Table 1) 8 parts Bentonite 40 parts Clay 45 parts Lignin sulfonate 7 parts are uniformly mixed, further added with water, kneaded and granulated and processed by an extrusion granulator. Into granules.

The carriers (diluents) and auxiliaries, the mixing ratios and the active ingredients shown in Examples 3 to 5 can be varied in a wide range.

Next, test agents for demonstrating the herbicidal efficacy of the compound according to the present invention will be described.

Among these test examples, those shown as comparative examples use a compound having the following formula disclosed in JP-A-58-185572 as an active ingredient.

Test Example 1 Effect on field weeds (pre-emergence soil treatment) After a certain amount of various test plant seeds were sown and covered with soil in a planter (65 x 210 x 220 mm) in a field condition, the test was carried out. The wettable powder prepared as in Example 3 was diluted to a predetermined concentration with water, and an amount of the active ingredient of 500 g / 10a was evenly sprayed on the soil surface with a Spelegan, and then grown and controlled in a greenhouse. Twenty-one days after the treatment, the herbicidal effect on each weed and the phytotoxicity on the crop were observed and evaluated according to the following criteria, and the results shown in Table 2 were obtained.

Evaluation criteria; 0 ... no herbicidal effect 1 ... less than 30% herbicidal effect 2 ... 31-50% herbicidal effect 3 ... 51-70% herbicidal effect 4 ... 71-90% Herbicidal effect 5 …… 91-100% herbicidal effect Degree of harm; − …… Harmless ± …… Small harm + …… Medium harm …… Severe harm …… Severe harm Test Example 2 Effect on field weeds (soil treatment after germination) According to the same procedure as described in Test Example 1, seeds of various plants were sown, and water was applied when each plant reached the 1-2 leaf stage. The wettable powder diluted in (1) was sprayed uniformly on the foliage of each plant and the soil surface with a spray gun in an amount of 500 g / 10a as the active ingredient. After that, it is grown and managed again in the glass greenhouse and treated 21
After the day, evaluation was performed in the same manner as in Test Example 1, and the results shown in Table 3 were obtained.

Claims (4)

(57) [Claims] 1. The compound of the general formula (I) (Wherein, R represents an alkyl group having 1 to 10 carbon atoms, and R may be a phenyl group or an aralkyl group) . 2. Formula (I) (Wherein R represents an alkyl group having 1 to 10 carbon atoms, and R may be a phenyl group or an aralkyl group) A herbicide containing as an active ingredient. 3. The formula (II) And a compound having the general formula (III): RX (III) (wherein, R represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group, and X represents a halogen atom of Cl, Br, or I) Wherein the compound represented by the formula (I) is reacted in the presence of a hydrogen halide scavenger. (Wherein, R represents an alkyl group having 1 to 10 carbon atoms, and R may be an aralkyl group, except when it is a phenyl group). 3
-A process for producing carboxylic acid amide derivatives. 4. The formula (IV) A hydrazone compound having the general formula (V) (Wherein, R represents an alkyl group having 1 to 10 carbon atoms, a phenyl group or an aralkyl group), and a dehydration reaction and a dehydrogenation reaction in the presence of an acid catalyst. General formula (I) (Wherein, R represents an alkyl group having 1 to 10 carbon atoms, and R may be a phenyl group or an aralkyl group) of the 1,2,4-triazole-3-carboxylic acid amide derivative Manufacturing method.