JPS63174983A - Aminobutenolide derivative, production thereof and herbicide comprising said derivative as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [R<1>-R<3> are H, lower alkyl or lower haloalkyl; R<4> is group shown by formula II or formula III (X is lower alkyl, lower alkoxy, lower haloalkyl or halogen; n is 0-5; R<5> and R<6> are lower alkyl)]. EXAMPLE:1-Phenyl-8-(2,5-dihydro-2,2,4-trimethyl-5-oxo-3-furyl)urea. USE:A herbicide. PREPARATION:A furanone derivative [e.g. 4-amino-8,5,5-trimethyl-2(5H)-furanone, etc.] shown by formula IV is reacted with an isocyanic acid derivative (e.g. phenyl isocyanate, etc.) shown by formula V usually in a solvent such as THF, etc., in the presence of a base (e.g. sodium hydride, etc.) preferably at 0-150 deg.C for 1-10hr.

Description

Detailed Description of the Invention The present invention relates to compounds of the general formula CI) [wherein R1, R2, and R3 are the same or different, a hydrogen atom, a lower alkyl group, or a lower represents an alkoxy group, a lower haloalkyl group or a halogen atom, and n is O-5
R5 and R6 are the same or different and represent lower alkyl groups. ] The present invention relates to an aminobutenolide derivative represented by (hereinafter referred to as the compound of the present invention), a method for producing the same, and a herbicide containing the same as an active ingredient.

The compound of the present invention can be used to treat mild weeds that are problematic in the treatment of foliage and earthen walls in upland areas, such as purslane, chickweed, whiteweed, blueberry, Japanese radish, Japanese radish, and other weeds.
The compound of the present invention has a herbicidal effect on a wide range of weeds such as shepherd's purse, grass weed, Japanese grass, Japanese goldenrod, and Japanese dogwood, as well as grass weeds such as barnyard grass, Japanese barnyard grass, and foxtail grass. It does not cause any phytotoxicity to major crops such as.

In addition, the compound of the present invention can be applied to mild weeds that are problematic in the waterlogging treatment of rice fields, such as grass weeds such as Japanese millet, broad-leaved weeds such as azalea, japonica, and chickweed; It has a herbicidal effect on weeds, grasshoppers, etc., and does not cause any harmful effects on rice.

Furthermore, the compound of the present invention can be used as a herbicide for paddy fields, fields, orchards, pastures, lawns, forests, non-agricultural lands, etc., and can also be used in combination with other herbicides. It can be expected to increase the potency of the herb. Additionally, insecticides, acaricides, nematicides, fungicides, plant growth regulators, and fertilizers.

It can also be used in combination with soil conditioners and the like.

Among the compounds of the present invention, R4 is represented by the formula -Q-" [wherein, X and n have the same meanings as above]. It can be produced by reacting a furanone derivative represented by the following formula with an isocyanic acid derivative represented by the general formula [■] [wherein X and n have the same meanings as above].

The reaction is usually carried out in a solvent in the presence of a base, typically at a reaction temperature of 0 to 159" C1 reaction time of 0.1 to 10 hours, and the amount of reagents used for the reaction is determined according to the general formula For 1 equivalent of the furanone derivative represented by [I], the general formula
The amount of the isocyanic acid derivative represented by is 0.5 to 2 equivalents, and the amount of the base is 0.5 to 2 equivalents.

As a solvent, aliphatic hydrocarbons such as hexane, heptane, ligroin, petroleum ether, benzene, toluene,
Examples include aromatic hydrocarbon layers such as xylene, halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, and mixtures thereof.

As the base, potassium t-butoxide, sodium hydride, sodium methoxide, sodium ethoxide,
Lithium N-isopropyl cyclohexylamide, trityl sodium, etc. may be used. After the reaction, the reaction solution is treated with a carboxylic acid such as acetic acid or propionic acid, or with water, and then subjected to conventional treatments such as organic solvent extraction and concentration. If so, the desired compound of the present invention can be obtained by purification by heat treatment such as chromatography or recrystallization.

Furthermore, among the compounds of the present invention, R4 is of the formula -NCONHR'■ [In the formula, R11 and R6 represent the same meanings as above.

] The compound represented by the above is a reaction between a furanone derivative represented by the general formula ("l) and an isocyanic acid derivative represented by the general formula C■] R' -NCOrff) C, where R5 represents a lower alkyl group. After that, it can be produced by further reacting with an isocyanic acid derivative represented by the general formula CV3R'-NCO(Y) [wherein R6 represents a lower alkyl group].

The reaction is usually carried out in a solvent in the presence of a base, typically at a reaction temperature of θ to 150°C and a reaction time of 0.1 to 10 hours. The isocyanic acid derivative represented by the general formula (ff) is 0.6 to 2 equivalents per equivalent of the furanone derivative represented by [l], and the isocyanic acid derivative represented by the general formula [v] is 0.6 to 2 equivalents. , the base is 0.5 to 4 equivalents.

As a solvent, aliphatic hydrocarbons such as hexane, heptane, ligroin, petroleum ether, benzene, toluene,
Examples include aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, and diethylene glycol dimethyl ether, and mixtures thereof.

Examples of the base include potassium t-butoxide, sodium hydride, sodium methoxide, sodium ethoxide, lithium N-isopropylcyclohexylamide, trityl sodium, and the like.

After the reaction is complete, the reaction solution is treated with a carboxylic acid such as acetic acid or propionic acid, or with water, followed by conventional treatments such as organic solvent extraction and concentration, and if necessary, chromatography, recrystallization, etc. - By purification, the desired compound of the present invention can be obtained.

Next, the compound of the present invention produced by this production method @1
Shown in the table.

Table 1 General formula [1] Next, production examples of the compounds of the present invention will be shown.

Production Example 1 (Production of Compound (1) of the Present Invention) Sodium hydride 58* (0,0024 mol).

Anhydrous tetrahydrone 7- and 4-amino-8゜5.5-
Trimethyl-2(5H)-furanone 881(0,00
After stirring 27 mol) at 40 to 50°C for 20 minutes, 0.28 d (0,0021 mol) of phenyl isocyanate was added, and the mixture was stirred at 50°C for 40 minutes. After adding acetic acid to the reaction solution, the solvent was distilled off under reduced pressure, and the residue was treated with silica gel column chromatography (eluent: ethyl acetate/n-hexane = 8/2, volume ratio) to obtain 1-phenyl. -8-(2,5-dihydro-2,2,4-)samethyl-5-oxo-8-furyl)urea 481*(in @
p*l9(i~8°C0 yield 88X:
a) Schiff:/acid phenyl standard) was obtained.

(s, 8H), 6.9-7.6 (m, 5H), 8.
7 (brs, IH), 9.1 (br s, 1f () mass hector m/z 260 (M+).

Production Example 2 (Production of Compound (8) of the Present Invention) Sodium hydride 58q+ (0,0024 mol), anhydrous tetrahydrofuran 7 sg and 4-amino-5-methyl-2(5) 1
)-furanone 804 cape (0,0027 mol) from 40 to 5
After stirring for 20 minutes at 0°C, phenyl isocyanate 0.
28+d (0,0021 mol) was added to the reaction mixture and stirred for 80 minutes at 60°C. After adding 9.5 m of acetic acid, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: 1-phenyl-8-(2,5-dihydro-2-methyl-
6-oxo-8-furyl) urea 447q (m.

1), 216-8゛C1 yield 92%: based on phenyl isocyanate) was obtained.

5.16 (Q, J=6.9Hz, IH), 5
．． 76 (s, IH), 7.8-7.6 (m,
5H), 9.0 (br s, IH), 9.5 (br 3
．． 1f()2 mass spectrum m/z 2 B 2 CM
” ).

Elemental analysis value CHN Analysis value 81.8 4.96 11.7 Calculated value
62,06 5.21 12.06 When the compound of the present invention is used as an active ingredient of a herbicide, it is usually mixed with a solid carrier, a liquid carrier, a surfactant, and other formulation auxiliaries to form an emulsion, a wettable powder, Formulate into suspensions, granules, etc.

These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 1 to 90×1, preferably 2 to 80%.

Solid carriers include kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite,
Examples include fine powders or granules such as talc, diatomaceous earth, calcite, walnut powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide. Liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, isopropanol, and ethylene. Alcohols such as glycol and cellosolve, ketones such as acetone, cyclohexanone and isophorone, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, N, N-
Examples include dimethylformamide, acetonitrile, water, etc.

Surfactants used for emulsification, dispersion, wet carbonization, etc. include alkyl sulfate salts, alkyl sulfonate salts, alkylaryl sulfonate salts, dialkyl sulfosuccinate salts, polyoxyethylene alkylaryl ether phosphate salts, etc. Anionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. etc. can be mentioned.

As formulation aids, lignin sulfonate, alginate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethylcellulose), PA
Examples include P (acidic IJ isopropyl phosphate).

The compound of the present invention thus formulated can be used for soil treatment, foliage treatment, or flooding treatment before or after weed germination. In addition to treatment from above the plant body, there are local treatments that treat only weeds so that they do not attach to crops.

Furthermore, by mixing it with other herbicides, it can be expected to increase the herbicidal efficacy. Furthermore, the compound of the present invention can be used in combination with insecticides, acaricides, nematicides, plant growth regulators, fertilizers, soil volume improvers, etc. earth,
It can be used as an active ingredient in herbicides for lawns, forests, non-agricultural lands, etc.

When the compound of the present invention is used as an active ingredient of a herbicide, the amount to be treated will vary depending on weather conditions, formulation form, treatment time, method, location, target weeds, target crops, etc., but usually 1.
11~aoog per are, preferably 5g~15
0f, and emulsions, wettable powders, suspension agents, etc., are diluted in a specified amount with 1 liter to 10 liters of water per are (if necessary, auxiliary agents such as spreading agents are added). Granules and the like are usually processed as they are without any dilution.

In addition to the above-mentioned surfactants, the spreading agents include polyoxyethylene 18M acid (ester), lignin sulfonate, abietate, dinaphthylmethane disulfonate,
Examples include paraffin.

Examples of formulations are shown below. In addition, in the compound of the present invention, 5 parts indicated by the compound number in Table 1 is 2 parts of W.

Formulation Example 1 50 parts of the compound (2) of the present invention, 8 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic hydrous silicon oxide are thoroughly ground and mixed to obtain a wettable powder.

Formulation Example 2 10 parts of the compound (1) of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, and 70 parts of dode and cyclohexanone are thoroughly mixed to obtain an emulsion.

Formulation Example 8 2 parts of the compound of the present invention (4), 1 part of synthetic hydrated silicon oxide, 2 parts of calcium lignosulfonate, 80 parts of bentonite and 65 parts of kaolin clay were thoroughly ground and mixed, and water was added and kneaded thoroughly. , granulation and drying to obtain granules.

Formulation Example 4 A test example shows that 25 parts of the compound (8) of the present invention, 8 parts of polyoxyethylene sorbitan monooleate, 69 parts of water, and a particle size of 5 microns are useful. The compounds of the present invention are indicated by the compound numbers in Table 1, and the compounds used for comparison are indicated by the compound symbols in Table 2.

Table II2 In addition, the evaluation of herbicidal efficacy and phytotoxicity is based on whether the germination and growth conditions of the test plants (weeds and crops) at the time of the survey have no or almost no difference compared to untreated plants.
OJ is defined as "10" when the test plant is completely dead or the budding or growth is completely suppressed, and θ ~ 1
Divided into 11 stages of 0.0.1.2.8.4.5.6.7
．． 8.9.10.

Test Example 1 Upland Soil Surface Treatment Test A cylindrical plastic pot with a diameter of 10 cIn and a depth of 10 m was filled with upland soil, sown with barley, corn, sugar beet, chickweed, and Japanese radish, and covered with soil. The test compound was made into a wettable powder according to Formulation Example 1, a predetermined amount of the wettable powder was diluted with water equivalent to 1.0 liter per are, and the solution was applied to the soil surface using a small sprayer. After treatment, the plants were grown in a greenhouse for 20 days and their phytotoxicity and herbicidal efficacy were investigated. The results are shown in Table 8.

Table 8 Test Example 2 Upland Soil Surface Treatment Test A cylindrical plastic pot with a diameter of 103 cm and a depth of 10 cm was filled with upland soil,
Ichibi was sown and covered with soil. The test compound was made into a wettable powder according to Formulation Example 1, a predetermined amount of the wettable powder was diluted with water equivalent to 10 liters per are, and the solution was applied to the soil surface using a small sprayer. After treatment, the plants were allowed to grow in a greenhouse for 20 days, and phytotoxicity and herbicidal efficacy were investigated. The results are shown in Table 1.

Table 4 Test Example 8 Upland Stem and Leaves Treatment Test A cylindrical plastic pot with a diameter of 10 cm and a depth of 10 z was filled with upland soil, and corn, Japanese radish, Japanese radish, and Japanese radish were sown and grown in a greenhouse for 10 days. Thereafter, the test compound was made into a wettable powder as in Formulation Example 1, and a predetermined amount of the wettable powder was diluted with water containing a spreading agent equivalent to 10 liters per are, and a small spray was applied. The stems and leaves were treated from above the plant using a container. After treatment, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 5.

Table 6 Test Example 4 Paddy field flooding treatment test A cylindrical plastic pot with a diameter of 8 bacteria and a depth of 12 cIR was filled with paddy earthen walls, and 1 to 2 seeds of Japanese millet, broad-leaved weeds (Azaena, Kikashigusa, Chickweed), and firefly were added to the pot. After mixing to a deep depth and creating a paddy field by flooding, rice at the two-leaf stage was transplanted and grown in a greenhouse. After 6 days (at the beginning of each weed's emergence), the test compound was made into a wettable powder according to Formulation Example 1, a predetermined amount of the wettable powder was diluted with 5 milliliters of water, and the solution was applied to the water surface. The plants were grown in a greenhouse for 20 days after treatment, and their herbicidal efficacy and phytotoxicity were investigated. The results are shown in Table 6.

Table 6

Claims (4)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ^4 represents a group represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ where X is a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, or a halogen. represents an atom, n represents an integer of 0 to 5, and R^5 and R^6 are the same or different and represent lower alkyl groups.] Aminobutenolide derivatives represented by (2) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R^1, R^2, and R^3 are the same or different and represent a hydrogen atom, a lower alkyl group, or a lower haloalkyl group. ] Furanone derivatives represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. represent. ] A general formula characterized by reacting with an isocyanic acid derivative represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. express the same meaning. ] A method for producing an aminobutenolide derivative represented by (3) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R^1, R^2, and R^3 are the same or different and represent a hydrogen atom, a lower alkyl group, or a lower haloalkyl group. ] A furanone derivative represented by the general formula R^5-NCO [wherein R^5 represents a lower alkyl group]. ] After reacting with an isocyanic acid derivative represented by the general formula R^6-NCO [wherein R^6 represents a lower alkyl group]. ] There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by reacting isocyanic acid derivatives shown in [In the formula, R^1, R^2, R^3, R^5 and R^6
has the same meaning as above. ] A method for producing an aminobutenolide derivative represented by (4) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R^1, R^2, R^3 are the same or different and represent a hydrogen atom, a lower alkyl group, or a lower haloalkyl group, ^4 represents a group represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Here, X represents a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, or a halogen atom, n represents an integer of 0 to 5, and R^5 and R^6 are the same or different and represent a lower alkyl group. ] A herbicide characterized by containing an aminobutenolide derivative represented by the following as an active ingredient.