JPH0341072A - Triazole carboxylic acid amide derivative and herbicide - Google Patents

Abstract

NEW MATERIAL:A triazole carboxylic acid amide derivative of formula I (R1 is lower alkyl or phenyl which may be substituted with one or more halogen atoms or low alkyl groups; R2 is H, lower alkyl or phenyl which may be substituted with one or more halogen atoms or lower alkyl groups; R3 is H, lower alkyl, lower alkoxy or phenyl which may be substituted with one or two halogen, lower alkyl, lower alkoxy or lower haloalkyl groups; R4 is H or lower alkyl). EXAMPLE:1,3-Diphenyl-5-phenylaminocarbonyl-1H-1,2,4-triazole. USE:Useful as a herbicide. Effective for preventing various weeds in rice fields or upland fields. PREPARATION:For example, an aminoether derivative of formula II is reacted with a hydrazine derivative of formula III to prepare the compound of formula I as shown in the reaction equation.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel triazole carboxylic acid ado derivatives. For more details, refer to the general formula (
The present invention relates to a novel IH-1°2,4-triazole-5-carboxylic acid amide derivative represented by I) and a herbicide containing the derivative. Therefore, the present invention is useful in the chemical industry and agriculture, particularly in the agricultural chemical manufacturing field.

Until now, there have been some literature descriptions regarding IH-1,2,4-triazole-5-carboxylic acid and ester derivatives, only regarding their production methods.

For example, for the production of 1,3-diphenyl-5-carboxylic acid ethyl ester, see Chemisch Berichte (Ch.
emische BerichtC) Volume 36, No. 248
3 (1903), the reaction of N-phenylbenzenecarboximidic acid 2-phenyl hydrazide with chlorooxoacetic acid ethyl ester was reported in Annalen der Chemie (1903).
er Che*ie) No. 653 @ pages 105-113 (
In 1963), the reaction of N-phenyl-benzenecarbohydrazonoyl chlorite with carbonocyanideic acid ethyl ester was reported by Kemisch Berichte (C
hes+1sche Berichte) Volume 98 (2
), pp. 642-649 (1965), the reaction of ethandioic acid monoethyl ester 2-phenylhydrazide monohydrochloride with benzaldoxime or benzonitrile is described.
terotsilicheskikhsoedinen
i (5) pp. 694-700 (1981) 1
．． 9-Sibidelow 1.3,7.9-tetraphenyl-
5H-imidazo(5,1-C:4.3-C”)bis(1
, 2, 4) describe the reaction of triazol-5-one with ethanol, respectively. Also Chemi5-che Berichte 1st
Volume 04 (11), pages 3510-3518 (1971)
To prepare 1,3-diphenyl-5-carboxylic acid, a reaction of 2-amino-4゜5-sibidro-3-furancarboxylic acid ethyl ester with N-phenyl-benzenecarbohydrazonoyl chlorite followed by an oxidation reaction was performed. The manufacturing method is Che■1sche
Berichte) Volume 117 (3〉No. 1194-12
14 (1984) describes l-methyl-3-phenyl-5-carboxylic acid methyl ester by the reaction of N-methyl-benzenecarbohytrazonoyl bromide monohydropromide and carbocyanideic acid methyl ester. The manufacturing method for each is described.

However, the 1,3-disubstituted-5-carboxylic acid amide derivatives of the present invention have not been described in the literature, are new compounds, and are not known to have high herbicidal effects. .

(Gadget Section) IH-1,2,4-triazole-5-carboxylic acid and its ester derivatives, which are similar to the compounds of the present invention, actually show almost no herbicidal activity, as shown in the test examples described later. However, it has not been put to practical use as a herbicide.

The object of the present invention is to provide a novel herbicide that has superior herbicidal activity and is highly safe as a herbicide for paddy rice and a field herbicide in place of conventional triazole-5-carboxylic acid derivatives. be.

In order to achieve the above object, the present inventors prepared a number of triazole carbon M! Combine the conductors.

We have carefully considered their usefulness. As a result, the IH-1゜2,4-triazole-5-carboxylic acid acto derivative represented by the general formula (I) below is a new compound that has not been described in any literature, and has high herbicidal activity and safety. It has been found that the above objective can be achieved.

Therefore, the gist of the first invention is the general formula (wherein R1 represents a phenyl group which may be substituted with M by a lower alkyl group or a halogen atom or a lower alkyl group, and R2 represents a hydrogen atom, a lower Represents an alkyl group, a phenyl group optionally substituted with a halogen atom or a lower alkyl group, and R1 is a hydrogen atom, a lower alkyl group, a lower alkoxy group, or up to two halogen atoms, a lower alkyl group, a lower alkoxy group, or a lower haloalkyl group. It is a triazolecarboxylic acid amide derivative represented by a phenyl group which may be substituted with a group, and R< is a hydrogen atom or a circle indicating a lower alkyl group.

The lower alkyl group herein refers to one having a carbon number of CI to 6.

The second aspect of the present invention resides in a herbicide characterized by containing the triazolecarboxylic acid amide derivative of formula (I) above as an active ingredient.

Next, typical examples of the compounds of the present invention represented by general formula (I) are shown in Table 1.

In addition, the compound appearance is also referred to in the following Examples and Test Examples.

The compound of the present invention represented by the general formula (I) is a new compound. The compound of general formula (1) acts as an active ingredient for controlling various weeds in paddy rice or upland fields.

The compound of general formula (I) according to the first aspect of the present invention can be prepared by either of the following two methods, namely method (A) or method (B). It can be synthesized by

Method (A) A compound of general formula (1) can be produced by reacting an iminoether derivative of general formula (n) with a hydrazine derivative of general formula (m).

(n) (m) R.

(In the formula, R,, R,, R,, R4 are the same as above,
(Rs represents a lower alkyl group, and X represents an oxygen atom or a sulfur atom) This cyclization reaction is usually carried out in an organic solvent. Usable solvents include hydrocarbons such as benzene, toluene, and hexane, chloroform, These include halogenated hydrocarbons such as chlorobenzene, ethers such as ethyl ether, dioxane, and tetrahydrofuran, alcohols such as methanol, ethanol, and propanol, amides such as dimethylformamide, dimethylacetoacetate, and dimethylsulfoxide.

Although the reaction proceeds at room temperature, the reaction time can be shortened by heating up to the boiling point of the solvent.After the reaction is complete, the target product can be obtained by distilling off the solvent, but water and benzene The compound of the present invention can also be obtained by adding an organic solvent such as toluene, tetrahydrofuran, or chloroform, separating the desired product, and distilling off the solvent. An example of producing the compound of the present invention by method (A) is shown in Example 1-2.

The compound of formula (■), which is a starting material, is obtained by preparing a nitrile derivative in an ether by a known or similar method.
It is obtained by making an iminoether hydrochloride derivative with alcohols or thiols and hydrochloric acid gas, converting it into a free form with a base, and then reacting it with achnooxoacetyl chlorites. The compound of formula (■) is a new compound,
A manufacturing example thereof is shown in Reference Manufacturing Example 1-2. Moreover, all the compounds of formula (m) are known compounds.

Method (B) The compound of formula (I) has -formula (fV)
It can be produced by reacting IH-1,2,4-)-riazole-5-carboxylic acid esters represented by formula (V) with amines represented by general formula (V).

R.

t1! (■) (V) (I) (In the formula, Ft1.R*, R3, and R4 are the same as above, and R6 represents a lower alkyl group.) This exchange reaction can be carried out by simply mixing and heating without a solvent. In many cases, the compound of formula (I) can also be obtained by using an organic solvent. As a solvent, benzene,
Hydrocarbons such as toluene and hexane, chloroform,
Halogenated hydrocarbons such as chlorobenzene, ethers such as ethyl ether, dioxane, and tetrahydrofuran, alcohols such as methanol, ethanol, and propanol, amides such as dimethylacetoacetate, dimethylacetamide, and dimethylsulfoxide, etc. The reaction proceeds even at room temperature, but the reaction time can be shortened by heating up to the boiling point of the solvent.The desired product can be obtained by distilling off the solvent after the reaction is complete; A compound of the present invention can also be obtained by adding an organic solvent such as benzene, toluene, tetrahydrofuran, or chloroform, separating the desired product, and distilling off the solvent. Example 3 shows an example of the production of the compound of the present invention by method (B).

Note that the starting material, the compound of formula (1'lr), can also be produced by the known method described in the prior art section, but in the step of producing the compound of formula (II), the starting material of method (A),
It can be produced by using alkoxyoxoacetyl chlorites instead of achnooxoacetyl chlorites. A manufacturing example of the compound of formula (■) is shown in Reference Manufacturing Example 3. Moreover, all of the compounds of formula (rV) are known compounds.

31.2 g of ethyl N-phenylaminooxoacetylbenzenecarboximidothioate and 200 mJ of ethanol
10.8 g of phenylhydrazine was added dropwise to this mixture under water cooling, and after the dropwise addition, the mixture was heated and stirred under reflux for 1 hour. After cooling, toluene was added, the resulting water was azeotropically dehydrated, and the solvent was distilled off to obtain 31.1 g of the title compound as light brown crystals.

When recrystallized from propanol, it becomes white crystals.

It showed a melting point of 198-200°C (decomposed).

N-(3-isopropoxyphenyl)aminooxoacetyl-4-methylbenzenecarboxylic acid ethyl 3
Using 6.8 g and 10.8 g of phenylhydrazine, reaction treatment was carried out in the same manner as in Example 1 to obtain 36.3 g of the title compound as pale yellow crystals. Recrystallization from ethanol gave white crystals with a melting point of 129-130°C.

1-Phenyl-3-(3-chlorol-phenyl-3-(3-chlorophenyl)-5-ethoxycarbonyl-IH-1,2,4-triazole 32
．． A mixture of 8 g, 121 g of 28% ammonium water and 200 mJl of ethanol was stirred at 30°C for 2 hours.

After distilling off the solvent and the like under reduced pressure, toluene was added and after azeotropic dehydration, toluene was distilled off to obtain 26.9 g of the title compound as light brown crystals. Recrystallization from a toluene-ethyl acetate mixed solvent gives white crystals with a melting point of 208-208.

It showed 5°C.

Benzonitrile 10.3g, ethyl mercaptan 5
．． Under water cooling, hydrochloric acid gas was blown into a mixture of 7 g of ethyl ether and 50 mJL of ethyl ether with stirring until saturation, and the mixture was left at room temperature overnight. When concentrated under reduced pressure, benzenecarboximidothioic acid ethyl salt #salt was obtained as white crystals 19.
7g was obtained.

On the other hand, 12.7 g of oxalyl chloride and 3 g of chloroform
9.3 g of aniline and 5 chloroform in a mixture of 0 mfL
0 mJl of the mixture was added dropwise under ice-water cooling for 1 hour, and the precipitated by-product acid dianilide oxalate was filtered off, and the filtrate was concentrated under reduced pressure to obtain 11.9 g of phenylachonooxoacetyl chloride as pale yellow crystals. .

Then an aqueous solution containing 9.3 g of sodium bicarbonate 20
Add benzenecarboxylic acid ethyl hydrochloride to a mixture of 0 mfL and 200 l of benzene while stirring.10.
Then, 9.2 g of phenylaminooxoacetyl chloride was added at room temperature and stirred for 30 minutes. After washing the benzene layer with water, the solvent was distilled off under reduced pressure to obtain 14.5 g of the title compound as a pale yellow oil, no'=1.
5214 was shown.

4-Methylbenzenecarpho 18.4 g of ethyl oxidate hydrochloride was obtained as white crystals.Meanwhile, using 12.7 g of oxalyl chloride C and 15, Ig of 3-isopropoxyaniline, reaction treatment was carried out in the same manner as in Reference Production Example 1 to obtain 3- 17.1 g of impropoxyphenylaminooxoacetyl chloride was obtained as light brown crystals.
-methylbenzenecarboximidate ethyl hydrochloride io
, Og and 12.1 g of 3-isopropoxyphenylaminooxoacetyl chloride were reacted in the same manner as in Reference Production Example 1 to obtain 16.4 g of the title compound as a pale yellow oil, n:''=1, 5084 was shown.

3 13.7 g of ethoxyoxoacetyl chloride was added dropwise to a mixture of 23.6 g of l-phenyl-3-3-tri-3-fluorobenzenecarboxydothioate ethyl hydrochloride, 200 mJl of chloroform, and 20.2 g of triethylamine under water cooling. After stirring at room temperature for 1 hour, 10.8 g of phenylhydrazine was added,
Water and dilute hydrochloric acid were added to the reaction mixture that was stirred at room temperature for 3 hours, the organic layer was separated, washed with water, and the solvent was distilled off to obtain 31.4 g of the title compound as pale brown crystals. Recrystallization from a hexane-ethyl acetate mixed solvent gave white crystals with a melting point of 125-126.5°C.

In addition, the second herbicide of the present invention is represented by the general formula (I) described above.
The compound can be prepared in a suitable form such as an emulsion, an aqueous solution, a liquid, a flowable (sol), a powder, one tablet of Triftless (DL) powder, one tablet of fine granules, etc. by a conventional formulation. The carrier used here can be either solid or liquid as long as it is commonly used for agricultural and horticultural chemicals, and is not limited to any particular carrier.For example, as a solid carrier, mineral powder can be used. (Kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica,
vermiculite, gypsum, calcium carbonate, apatite,
white carbon, slaked lime, silica sand, ammonium sulfate, urea, etc.),
Vegetable powders (soybean flour, wheat flour, wood flour, tobacco flour, starch, crystalline cellulose, etc.), polymer compounds (petroleum resin,
polyvinyl chloride, ketone resin, dammargum), alkyl, silicate, sugar content, highly dispersed silicic acid.

Examples include waxes. Liquid carriers include water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, 1so-propyl alcohol, butanol, ethylene glycol, benzyl alcohol, etc.), aromatic hydrocarbons (toluene, benzene, xylene, ethylbenzene, methylnaphthalene, etc.), halogenated hydrocarbons (chloroform, carbon tetrachloride, dichloromethane, chloroethylene, monochlorobenzene, trichlorofluoromethane, dichlorodifluoromethane, etc.), ethers (ethyl ether, ethylene oxide, dioxane, (tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, isophorone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate, etc.), acid amides (dimethylformamide, dimethylacetamide, etc.) , nitriles (acetonitrile, propionitrile, acrylonitrile, etc.), sulfoxides (dimethyl sulfoxide, 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, light oil, etc.).

Furthermore, various surfactants or emulsifiers are used for the purposes of emulsion dispersion, solubilization, wetting, foaming, lubrication, and spreading when preparing formulations such as emulsions, aqueous preparations, and flowable preparations. Such surfactants include nonionic type (polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester, etc.), anionic type (alkylbenzene sulfonate, alkyl sulfosuccinate, Alkyl sulfate.

polyoxyethylene alkyl sulfate, arylsulfonate, etc.), cationic type (alkylamines (laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, etc.), polyoxyethylene alkylamines))
Mono-ampholytic type (carboxylic acid (betaine type), sulfuric acid ester salt, etc.) may be mentioned, but of course it is not limited to these examples. Various adjuvants such as polyvinyl acetate, gelatin, casein, sodium alginate, gum tragacanth, etc. can be used.

In the present invention, when manufacturing the various formulations described above, the compound of the present invention is used in an amount of o,ooi% to 95% (wt%;
The same applies hereinafter), preferably in the range of 0.01% to 90%. For example, usually,
For powders, DL powders, and fine powders (F), O, 01%~
It can be contained in the range of 1% to 10% in the case of 5% single granules, and 1% to 75% in the case of wettable powders, emulsions, and liquids.

The preparations prepared in this way can be used as hydrating powders, emulsions, etc. For example, in the case of a single granule, the active ingredient may be sprayed directly on the soil surface, in the soil, or in water in an amount of about 0.3 g to 300 g. In the case of a sol, it may be diluted with water or a suitable solvent and sprayed in an amount of about 0.3 to 300 g of active ingredient.

Furthermore, when the compound of the present invention is used as a herbicide, it can be used in combination with known herbicides, insecticides, or plant regulators to expand its applicability, and in some cases, a synergistic effect can be expected. .

Tree i1 of general formula (I) described above. A method for formulating a light compound as a herbicide will be explained using Examples 4-7. However, the present invention is not limited to these examples, and can be mixed with various other additives in any proportion.
Further, other herbicides such as those mentioned above can be mixed in arbitrary proportions to prepare a formulation.

In addition, all parts in Examples indicate parts by weight.

After adding 15 parts of water to 1 part of 45 compounds, 1 part of lauryl sulfate, 1 part of calcium lignin sulfonate, 30 parts of bentonite, and 67 parts of white clay, and kneading them in a kneader. , granulated in a granulator and dried in a fluidized fluid dryer to obtain granules containing 1% of active ingredient.

Engineering 11m4i 1 Tomo Asahi Kabuto compound, 29 compounds 15 parts, white carbon
15 parts, calcium lignin sulfonate 3 parts, polyoxyethylene nonylphenyl ether 2 parts, diatom ±
5 parts of the clay and 60 parts of the clay are uniformly mixed in a grinding mixer to obtain a wettable powder containing 15% of the active ingredient.

±X straight up Compound No. 13, 20 parts, Sorbo Lure 00
20 parts of H emulsifier (manufactured by Toho Chemical Industries, Ltd.) and 60 parts of xylene are mixed to obtain an emulsion containing 20% of the active ingredient.

Engineering A powder containing 0.5% of the ingredients is obtained.

Mirizako 1 The compound of the present invention of general formula (I) has superior herbicidal activity and safety compared to known similar compounds. That is, the compound of the present invention has a wide range of effects on paddy field weeds such as Japanese barnyard grass, firefly, Japanese grasshopper, Japanese azalea, azalea, and common grass, and can completely weed these weeds by applying 50 g of the active ingredient per 10 ares. be able to. In addition, it is also effective against various upland weeds such as crabgrass, foxtail grass, whiteweed, dogweed, and knotweed.
Weeds can be completely killed with a treatment of 00g.

Furthermore, it does not cause any chemical damage to useful crops such as paddy rice, dice, corn, beets, rapeseed, and wheat, so it can be used safely.

Next, Test Examples 1 and 2 are shown to illustrate the herbicidal effect of the compound of the present invention represented by general formula (I).

A Wagner pot with a size of 115,000 are is filled with paddy soil (alluvial loam), and the surface layer is filled with barnyard grass, firefly,
Fifty seeds of each of Helaopidium japonica, Prunus elegans, Azena, and Kikashigusa were sown uniformly. Flooded one day after sowing,
The water depth was kept at 2 cm. Three days after sowing, 2 seedlings of 2.5 leaf stage paddy rice were transplanted, 3 plants per pot. One day after transplanting the paddy rice, the emulsion prepared according to Example 6 was diluted with water, and treated by dropping 10 mJL of the treatment chemical solution per pot (equivalent to 50 g per 10 are in terms of application amount of active ingredient). .

This test was conducted in duplicate per 1 drug solution concentration section, and
After a day, the herbicidal effect and the degree of phytotoxicity of paddy rice were investigated based on the evaluation index shown below.

The results are shown in Table 2.

Evaluation value of herbicidal effect Weeding 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% 9 Less than 20% wheat 1 Compounds listed in Che + 5ische Berich Le i Vol. 36 fil, p. 2483 (1903) etc.)
11) Compounds described on pages 3501 to 3518 (1971)) (Chemische Berichte Vol. 117 (
3) Compound described on pages 1194 to +214 (1984)) (Generic name: butachlor) Test Example 2 Herbicidal effect on field weeds and crops 1),
Herbicidal effect test on weeds A clay pot of 115,000 are was filled with 115,000 are field soil and 50 seeds each of various weeds such as crabgrass, hackberry, whiteberry, goldenrod, and Japanese knotweed were uniformly mixed with the 1 cm surface layer of soil.

Two days after sowing, the surface layer was lightly pressed, and an emulsion prepared according to Example 6 was made into islands with water.
equivalent) was sprayed onto the soil surface. The test was conducted in two consecutive sessions per plot, and 30 days after the chemical treatment, the herbicidal effect was investigated based on the same evaluation index as in Test Example 1.

2) Test for chemical damage to crops Field soil (alluvial loam) was filled in clay pots of 1/10,000 are, and seeds of each crop (5 soybean grains, 5 corn grains)
grains, 110 bees, rapeseed lO grains and 10 wheat grains)
The seeds were sown in separate pots, and the surface layer was lightly pressed.

One day after sowing, an emulsion prepared according to Example 6 was diluted with water, and 10,031 treatment chemicals per 10 ares (equivalent to 100 g of active ingredient per 10 ares) were sprayed onto the soil surface. The test was conducted in two consecutive plots, and 30 days after the chemical treatment, the chemical damage to each crop was investigated based on the same evaluation index as in Test Example 1. The results are shown in Table 3.

Claims (1)

[Claims] 1) General formula▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, R_1 represents a lower alkyl group or a phenyl group which may be substituted with a halogen atom or a lower alkyl group, and R_2 is hydrogen R_3 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or up to two halogen atoms, a lower alkyl group, a lower alkoxy group. or a phenyl group which may be substituted with a lower haloalkyl group, and R_4 represents a hydrogen atom or a lower alkyl group). 2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 represents a lower alkyl group or a phenyl group that may be substituted with a halogen atom or a lower alkyl group, and R_2 represents a hydrogen atom, a lower alkyl group, or Represents a phenyl group that may be substituted with a halogen atom or a lower alkyl group, and R_3 is substituted with a hydrogen atom, a lower alkyl group, a lower alkoxy group, or up to two halogen atoms, a lower alkyl group, a lower alkoxy group, or a lower haloalkyl group. A herbicide characterized by containing a triazolecarboxylic acid amide derivative represented by the following formula (representing a phenyl group which may be substituted with a phenyl group, and R_4 represents a hydrogen atom or a lower alkyl group) as an active ingredient.