JPH0558979A - 3,4-Di (substituted phenyl) butyric acid derivative and herbicide - Google Patents

Abstract

(57) [Abstract] [Objective] An object of the present invention is to provide a 3,4-di (substituted phenyl) butyric acid derivative having excellent herbicidal activity. [Structure] The 3,4-di (substituted phenyl) butyric acid derivative of the present invention is represented by the general formula (I). General formula [Chemical formula 1] (In the formula, X or Y may be the same or different and each represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a trifluoromethyl group, a phenoxy group or a trifluoromethyl-substituted pyridyloxy group. ,
R represents a lower alkenyloxy group, a propargyloxy group, an isopropylideneaminooxy group, an isoxazolidyl group, and n represents 1 or 2.)

Description

Detailed Description of the Invention

[0001]

[Object of the Invention]

FIELD OF THE INVENTION The present invention relates to novel 3,4-di (substituted phenyl) butyric acid derivatives and herbicides. More specifically, it relates to a novel 3,4-di (substituted phenyl) butyric acid derivative represented by the general formula (I) described below, and a herbicide containing the derivative as an active ingredient. Therefore, the present invention is useful in the chemical industry as well as agriculture, especially in the field of agrochemical manufacturing.

[0002]

2. Description of the Related Art Several substituted butyric acid derivatives have been known so far. For example, JP-A-62-289553
The publication describes that a substituted butyric acid derivative represented by the following general formula (IV) has herbicidal activity.

[0003]

[Chemical 3] (In the formula, R ¹ is OH, OR ⁴ , and R ² and R ³ are both

[Chemical 4] And R ⁴ is a group selected from the group consisting of
Represents alkyl, monohaloalkenyl, monohaloalkynyl, alkoxyalkyl or hydroxyalkynyl, and X and Y independently represent hydrogen, halogen or alkyl).

However, the substituted butyric acid derivative described in this publication has insufficient herbicidal activity and is not necessarily satisfactory.

[0005]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a novel compound having excellent herbicidal activity and safety as a herbicide for paddy rice and a field-acting herbicide, and a herbicide containing the same.

[0006]

[Constitution of the invention]

[Means for Solving the Problems] In order to achieve the above-mentioned object, the present inventors have synthesized many 3,4-di (substituted phenyl) butyric acid derivatives, and have diligently studied their usefulness. As a result, 3, which is represented by the following general formula (I),
It was found that a 4-di (substituted phenyl) butyric acid derivative is a novel compound not described in the literature, has high herbicidal activity and safety, and achieves the above object.

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

[Chemical 5] (In the formula, X or Y may be the same or different and each represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a trifluoromethyl group, a phenoxy group or a trifluoromethyl-substituted pyridyloxy group. ,
R represents a lower alkenyloxy group, a propargyloxy group, an isopropylideneaminooxy group, an isoxazolidyl group, and n represents 1 or 2), and a 3,4-di (substituted phenyl) butyric acid derivative represented by is there.

The lower alkyl group, lower alkoxy group and lower alkenyloxy group referred to herein may be linear or branched. Also it refers to the number of carbon atoms of the C ₁ -C ₄ The lower here.

The gist of the second invention is as follows.
A herbicide containing the 3,4-di (substituted phenyl) butyric acid derivative of the above general formula (I) as an active ingredient.

Next, typical examples of the compounds of the general formula (I) of the present invention are shown in Tables 1-6.

The compound No. of the present invention is also referred to in the following examples and test examples.

[0012]

[Table 1]

[0013]

[Table 2]

[0014]

[Table 3]

[0015]

[Table 4]

[0016]

[Table 5]

[0017]

[Table 6]

[0018]

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

EXAMPLES (Method for Producing Compound of the Present Invention) The compound of the general formula (I) according to the present invention can be produced by the method described below.

That is, a substituted benzyl cyanide represented by the general formula (II) and a substituted cinnamic acid derivative represented by the general formula (III) are subjected to Michael addition in the presence of a base using a solvent inert to the reaction. Can be manufactured.

[0021]

[Chemical 6] (In the formula, X, Y, R and n have the same meanings as described above)

As the solvent that can be used in this addition reaction,
Tetrahydrofuran, dioxane, dimethylformamide and the like. As the base, sodium hydride, sodium amide, etc. can be used. Also, the reaction proceeds at room temperature.

After completion of the reaction, the compound of the present invention can be obtained by adding water and an organic solvent such as toluene to fractionate the desired product and distill off the solvent.

Examples of production by this method are shown in Examples 1 to 3.

The starting compound (II) compound and
All the compounds of formula (III) can be obtained by known methods.

Example 1 Allyl-4- (3-chlorophenyl) -4-cyano-3
-Preparation of phenylbutanoate (Compound No. 1) In a four-necked flask with a capacity of 100 ml, 3.8 g of allyl cinnamate, 0.4 g of sodium hydride and 20 ml of tetrahydrofuran were placed, and 3-chlorobenzyl cyanide 3 was added to this mixture. 0.0 g was added dropwise, and the mixture was stirred at room temperature for 10 hours. Water and toluene were added to the reaction solution, and the organic layer was separated.
After washing with water and drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 5.6 g of the title compound as an orange oil. This was purified by silica gel column chromatography to give a colorless oily substance, showing n _D ²³ = 1.5572.

Example 2 Isoxazolyl-4- (3-chlorophenyl) -4-
Cyano-3-phenylbutanamide (Compound No. 60)
Preparation of 100 ml 4-necked flask was charged with 3.1 g of isoxazolyl cinnamamide, 0.2 g of sodium hydride and 20 ml of tetrahydrofuran, and 2.3 g of 3-chlorobenzyl cyanide was added dropwise to this mixture at room temperature. Stir for 2 hours. Treatment as in Example 1 yielded 5.2 g of the title compound as an orange oil. This was purified by silica gel column chromatography to give a colorless oily substance, showing n _D ²³ = 1.5677.

Example 3 Isoxazolyl-4- (3-chlorophenyl) -4-
Preparation of cyano-3- (2-fluorophenyl) butanamide (Compound No. 77) Isoxazolyl-2 in a 100 ml four neck flask.
4.2 g of fluorocinnamamide, 0.4 g of sodium hydride and 20 ml of tetrahydrofuran were added, 3.2 g of 3-chlorobenzyl cyanide was added dropwise to this mixture, and the mixture was stirred at room temperature for 2 hours. Treatment as in Example 1 yielded 6.9 g of the title compound as a yellow oil.
This was purified by silica gel column chromatography to give a colorless oily substance, showing n _D ²³ = 1.5664.

[Examples] (Method for formulating herbicide) The herbicide of the present invention comprises an emulsion, a wettable powder, a liquid preparation and a flowable (sol) preparation of the compound of the general formula (I) according to a conventional formulation. , Powder, driftless (DL) powder, granules, fine granules, tablets and the like. 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, crystals) (Eg, cellulose), polymer compounds (petroleum resin, polyvinyl chloride, ketone resin, dummar gum, etc.), alumina, silicates, sugar polymers, highly dispersible silicic acid, waxes and the like. Further, as the liquid carrier, water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-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, dichlorofluoromethane, 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.), nitrites (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 fraction (paraffins, kerosene, light oil, etc.) And so on.

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) and carboxymethyl cellulose (CM
Various auxiliary agents such as C), gum arabic, polyvinyl acetate, gelatin, sodium alginate and tragacanth can be used.

In the present invention, when the above-mentioned various preparations are produced, the compound of the present invention is added in an amount of 0.001% to 95%.
(% By weight; the same applies hereinafter), preferably 0.01% to 90
It can be formulated 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%,
In the case of a wettable powder, an emulsion, and a liquid preparation, it 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 and a sol, it may be diluted with water or a suitable solvent and sprayed as an active ingredient in the range of about 0.3 to 300 g per 10 are.

When the compound of the present invention is used as a herbicide, its applicability can be increased 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.

A method for formulating the above-mentioned compound of the present invention of the general formula (I) as a herbicide will be described in Examples 4 to 7 below. However, the present invention is not limited to these examples, and can be mixed with various other additives in an arbitrary ratio, and the above-mentioned other herbicides and the like can be mixed in an arbitrary ratio to prepare a formulation. You can also do it.

The compound Nos. Are shown in Tables 1 to 6 above, and all parts in the examples are parts by weight.

Example 4 (Granule) 1 part of the compound of Compound No. 1, lauryl sulfate 1
Water, 1 part calcium lignin sulfonate, 30 parts bentonite and 67 parts clay and 15 parts water and kneaded with a kneader, then granulated with a granulator and dried with a fluid dryer to give 1% active ingredient. To obtain granules containing.

Example 5 (Wettable powder) 15 parts of compound No. 8 compound, white carbon 15
Parts, 3 parts of calcium lignin sulfonate, 2 parts of polyoxyethylene nonylphenyl ether, 5 parts of diatomaceous earth and 60 parts of clay are uniformly mixed with a pulverizing mixer to obtain a wettable powder containing 15% of the active ingredient.

[Example 6] (Emulsion) Compound No. 10 (20 parts), Solpol 700H
20 parts (emulsifier manufactured by Toho Chemical Industry Co., Ltd.) and 60 parts of xylene are mixed to obtain an emulsion containing 20% of the active ingredient.

[Example 7] (Dust) 0.5 part of the compound of Compound No. 19, fine powder of silicic acid anhydride
5 parts, calcium stearate 0.5 parts, clay 50
Parts and 48.5 parts of talc are uniformly mixed and ground to obtain a powder containing 0.5% of the active ingredient.

[0041]

INDUSTRIAL APPLICABILITY The compound of the present invention represented by the general formula (I) has excellent herbicidal activity and safety as compared with known similar compounds.

That is, the compounds of the present invention act broadly on paddy field weeds such as millet, firefly, herring mold, eel, azalea, and yellow grass, at an application rate of 50 g per 10 are as an active ingredient. Many weeds can be almost completely weeded. In addition, various kinds of field weeds such as crabgrass, green foxtail, white squirrel, white squirrel, Amaranthus serrata, etc. can be almost completely weeded at an application rate of 100 g as an active ingredient per 10 ares. Moreover, it does not cause chemical damage to useful crops such as paddy rice, soybean, corn, beet, rapeseed and wheat. Moreover, there is no animal or fish toxicity. Therefore, it can be used safely.

Test Examples 1 and 2 are shown to illustrate the herbicidal activity of the compounds of the present invention of general formula (I).

[Test Example 1] Herbicidal effect test on paddy field weeds and phytotoxicity test on transplanted paddy rice Paddy soil (alluvial loam soil) was filled in a Wagner pot having a size of 1/5000 are, and a fly, firefly,
50 seeds of Heliomodaka, Konagi, Azena, and Oenothera were evenly sown. 1 day after sowing,
The water depth was kept at 2 cm. Three days after sowing, two 2.5-leaf stage seedlings of paddy rice were planted in one plant, two plants, and three plants were planted per pot. Rice transplant 1
After a day, the emulsion prepared according to Example 6 was diluted with water, and 10 ml per pot (equivalent to 50 g per 10 are in terms of the amount of active ingredient used) was added dropwise.

This test is carried out in a double system for each concentration of the chemical solution,
30 days after drug treatment, based on the evaluation index shown below,
The herbicidal effect and the degree of phytotoxicity of paddy rice were investigated. The results are shown in Tables 7 to 10.

[0046]Evaluation value of herbicidal effect Weeding rate (%)  5 100% 4 80 to less than 100% 3 60 to 80 〃 2 40 to 60 〃 1 20 to 40 〃 0 20 〃Evaluation value of drug damage Degree of phytotoxicity  5 Death 4 Large chemical damage 3 Medium 2 Small 1 Small 1 Small 0 No

[0047]

[Table 7]

[0048]

[Table 8]

[0049]

[Table 9]

[0050]

[Table 10] Comparative drug A:

[Chemical 7] (Compound described in JP-A-62-289553) Comparative drug B:

[Chemical 8] (Compounds described in JP-A-62-289553)

[Test Example 2] 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 1/5000 ares pot of unglazed clay, and a soil of 1 cm surface layer And 50 seeds of various kinds of weed seeds such as crabgrass, locust, white foxtail, white squirrel, white squirrel, sardine, and starfish were uniformly mixed, and the surface layer was lightly pressed.
Two days after sowing, the emulsion prepared according to Example 6 was diluted with water, and 100 liters of the treatment agent per 10 ares (corresponding to 100 g per 10 ares in terms of the application amount of the active ingredient) was sprayed on the soil surface.

This test is carried out in duplicate for each chemical concentration group.
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 Field soil (alluvial loam soil) was filled in a pot of 1 / 10,000 ares, and the seeds of each crop (5 soybeans, 5 corns, 10 beets, 10 rapeseed seeds) Wheat 10
Granules) were seeded in separate pots, and the surface layer was lightly pressed. One day after sowing, the emulsion prepared according to Example 6 was diluted with water, and 100 liters of the treatment agent per 10 ares (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 Tables 11 to 13.

[0056]

[Table 11]

[0057]

[Table 12]

[0058]

[Table 13]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07D 213/63 6701-4C 261/02 9283-4C (72) Inventor Hirokazu Yoshizawa Toda, Atsugi, Kanagawa Prefecture 1 at 2190 Clover Heights 303 (72) Inventor Yoko Morimoto 5-37-12 Asahi-cho, Atsugi-shi, Kanagawa Rose Heights 103

Claims (2)

[Claims] 1. A general formula: (In the formula, X or Y may be the same or different and each represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a trifluoromethyl group, a phenoxy group or a trifluoromethyl-substituted pyridyloxy group. ,
R represents a lower alkenyloxy group, a propargyloxy group, an isopropylideneaminooxy group, an isoxazolidyl group, and n represents 1 or 2), which is a 3,4-di (substituted phenyl) butyric acid derivative. 2. A general formula: (In the formula, X or Y may be the same or different and each represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a trifluoromethyl group, a phenoxy group or a trifluoromethyl-substituted pyridyloxy group. ,
R represents a lower alkenyloxy group, propargyloxy group, isopropylideneaminooxy group, isoxazolidyl group, and n represents 1 or 2, and a 3,4-di (substituted phenyl) butyric acid derivative represented by A herbicide which is contained as an active ingredient.