JPH04297455A - 4-heterocyclic-3-(substituted phenyl)butyric acid derivative and herbicide - Google Patents

Abstract

PURPOSE:To obtain a new 4-heterocyclic-3-(substituted phenyl)butyric acid derivative having excellent herbicidal activity and safety as a herbicide for paddy rice plant and a herbicide for upland crop. CONSTITUTION:A compound shown by formula I (X is H, halogen or lower alkyl; R is lower alkenyloxy, lower alkynyloxy or isoxazolidyl; A is group shown by formula II to formula VII) such as allyl-4-cyano-3-phenyl-4-(1-triazolyl) butanoate. The compound is obtained by subjecting a substituted acetonitrile shown by formula VIII and a cinnamic acid derivative shown by formula IX to Michael addition reaction in the presence of a base by using an inert solvent in the reaction. The herbicide is applied in a rate of 0.3-300g calculated as an amount of active component based on 10 ares to surface of soil, soil or water.

Description

[Detailed description of the invention]

0001

[Purpose of the invention]

[Industrial Application Field] The present invention provides novel 4-cyano-4
-Heterocyclic-3-(substituted phenyl)butyric acid derivatives. More specifically, the novel 4 represented by the general formula (I) below
-Heterocyclic-3-(substituted phenyl)butyric acid derivatives and herbicides containing the derivatives as active ingredients. Therefore, the present invention is useful in the chemical industry and agriculture, particularly in the agricultural chemical manufacturing field.

0002

BACKGROUND OF THE INVENTION Several substituted butyric acid derivatives have been known so far. For example, JP-A-62-289553 describes that a compound represented by the following general formula has herbicidal activity.

0003

[C5] (In the formula, R1 is OH, OR4, R2 and R3 are both

[
is a group selected from the group consisting of: and pyridyl, and R4
represents alkyl, monohaloalkenyl, monohaloalkynyl, alkoxyalkyl, hydroxyalkynyl,
Y and Y independently represent hydrogen, halogen, or alkyl. ).

However, the substituted butyric acid derivatives described in this publication have insufficient herbicidal activity and cannot be said to be necessarily satisfactory, and there is a desire to develop herbicides that do not have these drawbacks.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to provide a new herbicide having superior herbicidal activity and safety as a herbicide for paddy rice and field crops.

[0006]

[Structure of the invention]

[Means for Solving the Problems] In order to achieve the above object, the present inventors synthesized a large number of 4-heterocyclic-3-(substituted phenyl)butyric acid derivatives and conducted extensive studies on their usefulness. . As a result, we found that the 4-cyano-4-heterocyclic-3-(substituted phenyl)butyric acid derivative represented by the general formula (I) below is a new compound that has not been described in the literature and has high herbicidal activity and safety. I found it.

Therefore, the gist of the first invention is that the following general formula (I)

embedded image (wherein, X represents a hydrogen atom, a halogen atom, or a lower alkyl group, R represents a lower alkenyloxy group, a lower alkynyloxy group, or an isoxazolidyl group, and A represents a group

00
08]

[Chemical formula 8] is shown. ) is a 4-heterocyclic-3-(substituted phenyl)butyric acid derivative.

[0009] The lower alkyl group, lower alkenyloxy group, and lower alkynyloxy group referred to herein may be linear or branched. Moreover, the term "lower" as used herein refers to those having a carbon number of C1 to C6.

[0010] Furthermore, the gist of the second invention is as follows:
4-heterocycle-3-(substituted phenyl) of the above general formula (I)
A herbicide characterized by containing a butyric acid derivative as an active ingredient.

Next, typical examples of the compound of general formula (I) of the present invention are shown in Tables 1 to 4. However, compound No. is also referred to in the following Examples and Test Examples.

0012

[Table 1]

[0013]

[Table 2]

[0014]

[Table 3]

[0015]

[Table 4]

[0016]

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

EXAMPLES Method for producing the compound of the present invention The compound of general formula (I) according to the present invention can be produced by the method described below. That is, it can be produced by Michael addition of a substituted acetonitrile represented by general formula (II) and a cinnamic acid derivative represented by general formula (III) in the presence of a base using a solvent inert to the reaction.

[0018]

[Chemical formula 9] (In the formula, X, R, and A have the same meanings as above.)

0
Solvents that can be used in this addition reaction include tetrahydrofuran, dioxane, dimethylformamide, and the like. As the base, sodium hydride, sodium amide, etc. can be used. The reaction proceeds at room temperature. After the reaction is completed, the compound of the present invention can be obtained by adding water and an organic solvent such as toluene to separate the desired product and distilling off the solvent. Examples of production using this method are shown in Examples 1 to 3. Incidentally, both the starting materials, the formula (II) compound and the formula (III) compound, can be obtained by known methods.

Example 1 Preparation of allyl-4-cyano-3-phenyl-4-(1-triazolyl)butanoate (compound No. 1) 100
Allyl cinnamate 5.9 in a 4-necked flask with a volume of ml
g, 0.2 g of sodium hydride, and 20 ml of tetrahydrofuran, and 3.0 g of 1-triazolyl acetonitrile was added dropwise to this mixture, followed by stirring 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, it was dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure to obtain 8.2 g of the title compound as an orange oil. When this was purified by silica gel column chromatography, it became a colorless oil with n23D=1.55
It showed 37.

Example 2 Production of isoxazolyl-4-cyano-4-(2-(1-methylpyrrolyl))-3-phenylbutanamide (compound No. 22) Isoxazolyl was placed in a 100 ml four-necked flask. Add 5.1 g of lucinnamamide, 0.2 g of sodium hydride, and 20 ml of tetrahydrofuran, and add 3.0 g of 2-(1-methylpyrrolyl)acetonitrile to this mixture.
was added dropwise, and the mixture was stirred at room temperature for 2 hours. When treated in the same manner as in Example 1, 8.0 g of the title compound was obtained as a yellow oil. When this was purified by silica gel column chromatography, it became a colorless oil, n23D = 1.566
2 was shown.

Example 3 Isoxazolyl-4-cyano-3-phenyl-4-(
Production of 2-quinolyl)butanamide (Compound No. 28) In a 100 ml four-necked flask, add 3.6 g of isoxazolidyl cinnamamide, 0.1 g of sodium hydride,
and 20 ml of tetrahydrofuran, and 3.0 g of 2-quinolyl acetonitrile was added dropwise to this mixture, followed by stirring at room temperature for 2 hours. When treated in the same manner as in Example 1, 6.6 g of the title compound was obtained as an orange oil. When this was purified by silica gel column chromatography, it became a colorless oil with n23D=1.5973.

Example Method for Preparing a Herbicide The second herbicide of the present invention is prepared by preparing an emulsion, a wettable powder, a liquid, a flowable (sol), or It can be prepared in an appropriate form such as powder, driftless (DL) powder, granules, fine granules, tablets, and the like. The carrier used here can be either solid or liquid, as long as it is commonly used for agricultural and horticultural chemicals.
It is not limited to a specific thing. 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 flour, starch) , crystalline cellulose, etc.), polymer compounds (petroleum resin, polyvinyl chloride, ketone resin, dammargum, etc.), alumina, silicates, sugar polymers, highly dispersed silicic acid, and waxes. In addition, as a 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, trichloro fluoromethane, 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.), 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 distillates (paraffins, kerosene,
(light oil, etc.).

[0024] In addition, various surfactants (or emulsifiers) are used for the purposes of emulsification, dispersion, solubilization, wetting, foaming, lubrication, spreading, etc. when preparing formulations such as emulsions, wettable powders, and flowables.
is used. Such surfactants include nonionic types (polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, etc.) and anionic types (alkylbenzene sulfonates, alkyl sulfosuccinates, etc.).
alkyl sulfate, polyoxyethylene alkyl sulfate, aryl sulfonate, etc.), cationic type (alkylamines (laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, etc.), polyoxyethylene alkylamines), amphoteric type [carvone acids (betaine type), sulfuric acid ester salts, etc., but of course the present invention is not limited to these examples.

[0025] In addition to these, polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC)
, gum arabic, polyvinyl acetate, gelatin, sodium alginate, gum tragacanth, and the like can be used.

[0026] In the present invention, when producing the various preparations described above, the compound of the present invention is added in an amount of 0.001% to 95%.
(wt%; same below), preferably 0.01% to 90
The formulation can be formulated to contain within a range of %. For example, for powders, DL powders, and fine powders (F),
0.01% to 5%, in the case of granules, 0.01% to 10%
In the case of , wettable powders, emulsions, and solutions, the content can be in the range of 1% to 75%.

[0027] When the preparation thus prepared is, for example, a granule, it may be directly sprayed onto the soil surface, into the soil, or into water in an amount of active ingredient in the range of about 0.3 g to 300 g per 10 ares. In the case of wettable powders, emulsions, and sol preparations, they may be diluted with water or a suitable solvent and sprayed in an amount of about 0.3 to 300 g of active ingredient per 10 ares.

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. You can also.

The method for formulating the compound of the present invention of general formula (I) as a herbicide is described in Examples 4 to 4 below.
7 will be explained. However, the present invention is not limited to these examples, and can be mixed with various other additives in any proportion, and may also be formulated by mixing other herbicides as described above in any proportion. You can also. The compound numbers are shown in Tables 1 to 4 above, and all parts in the examples are parts by weight.

Example 4 (granules) 1 part of compound No. 1, 1 part of lauryl sulfate, 1 part of calcium lignin sulfonate, 3 parts of bentonite
After adding 15 parts of water to 0 parts and 67 parts of white clay and kneading them in a kneader, they are granulated in a granulator and dried in a fluidized fluid dryer to obtain granules containing 1% of the active ingredient.

Example 5 (Wettable powder) 15 parts of Compound No. 8, 15 parts of white carbon, 3 parts of calcium lignin sulfonate, 2 parts of polyoxyethylene nonylphenyl ether, 5 parts of diatomaceous earth, and 60 parts of clay were mixed in a pulverizing mixer. Mix evenly with the active ingredient 1
A hydrating powder containing 5% is obtained.

Example 6 (emulsion) 20 parts of compound No. 10, Solpol 700H (
20 parts of emulsifier (manufactured by Toho Chemical Industries, Ltd.) and 60 parts of xylene were mixed to obtain an emulsion containing 20% of the active ingredient.

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

[0034]

EFFECT OF THE INVENTION The compound of the present invention represented by 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 grasshopper, Japanese aphrodisiac, and other paddy field weeds. Many weeds can be almost completely eradicated. In addition, various upland weeds such as crabgrass, hackberry, whiteweed, dogweed, and knotweed can be almost completely weeded by applying 100 g of the active ingredient per 10 ares. Furthermore, it does not cause any chemical damage to useful crops such as paddy rice, soybeans, corn, beets, rapeseed, and wheat. Furthermore, it is not toxic to humans or fish. Therefore, it can be used safely.

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

Test Example 1 Herbicidal effect test on paddy field weeds and phytotoxicity test on transplanted paddy rice Paddy soil (alluvial loam) was filled in a Wagner pot with a size of 1/5000 are, and the surface layer was 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, paddy rice seedlings at the 2.5 leaf stage were transplanted with two plants per pot, three plants per pot. One day after transplanting paddy rice, the emulsion prepared according to Example 6 was diluted with water,
10 ml per pot (equivalent to 50 g per 10 ares of active ingredient) was added dropwise.

[0037] This test was conducted in duplicate per leaf fluid concentration group.
Based on the evaluation index shown below after 30 days of drug treatment,
The herbicidal effect and the degree of chemical damage to paddy rice were investigated. The results are shown in Tables 5 and 6.

[0038] Evaluation value of herbicidal effect
Weeding rate (%)
5
100%
4
80-less than 100%
3
Less than 60-80%
2
Less than 40-60%
1
Less than 20-40%
0
less than 20%

[0039]

[0040]

[Table 5]

[0041]

[Table 6]

Test Example 2 Herbicidal effect on field weeds and chemical damage test on crops 1) Test of herbicidal effect on weeds Field soil (
Alluvial loam) was packed, and 50 seeds each of various weed seeds such as crabgrass, hackberry, whiteweed, Japanese knotweed, and Japanese knotweed were uniformly mixed with the soil in the surface layer of 1 cm, 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 treatment agent per 10 ares (equivalent to 100 g per 10 ares of active ingredient) was sprayed onto the soil surface for treatment. This test was conducted twice per chemical solution concentration area, and the herbicidal effect was investigated 30 days after the chemical treatment based on the same evaluation index as in Test Example 1.

2) Phytotoxicity test on crops 1/10,
Field soil (alluvial loam) was filled in 000 are clay pots, and seeds of each crop (5 soybeans, 5 corn, 10 beets, 10 rapeseed, and 10 wheat) were sown in separate pots. One day after sowing, an emulsion prepared according to Example 6 was diluted with water and 10
100 liters of treatment agent per are (equivalent to 100 g of active ingredient per 10 are) was sprayed onto the soil surface.

[0044] This test was conducted in duplicate per drug solution concentration area.
Thirty days after the chemical treatment, the degree of chemical damage to each crop was investigated based on the same evaluation index as in Test Example 1. The results are shown in Tables 7 and 8.

[0045]

[Table 7]

[0046]

[Table 8]

Claims (2)

[Claims] Claim 1: General formula [Formula 1] (wherein, X represents a hydrogen atom, a halogen atom, or a lower alkyl group; R represents a lower alkenyloxy group, a lower alkynyloxy group, or an isoxazolidyl group; is a group [chemical formula 2]
] Indicates. ) 4-Heterocyclic-3-(substituted phenyl)butyric acid derivative. Claim 2: General formula [Formula 3] (wherein, X represents a hydrogen atom, a halogen atom, or a lower alkyl group; R represents a lower alkenyloxy group, a lower alkynyloxy group, or an isoxazolidyl group; is the group [chemical formula 4]
] Indicates. ) A herbicide characterized by containing a 4-heterocyclic-3-(substituted phenyl)butyric acid derivative represented by the following as an active ingredient.