JPS63152362A - Butenoic acid derivative, its production and herbicide containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R is ethyl, isopropyl or cyclopropyl; Z is O or S) and its acid addition salt. EXAMPLE:2-Methyl-3-( 5'-isopropyl-5'-methyl-4'-oxoimidazolidin-2'-yl )-(Z)-2-buten oic acid. USE:A herbicide. PREPARATION:The compound of formula I can be produced by reacting an imidazolinone derivative of formula II with sodium cyanoborohydride under acidic condition with hydrochloric acid, sulfuric acid, etc., in a lower alcohol solvent at 0 deg.C-room temperature for 10min-5hr.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula [wherein R represents an ethyl group, isopropyl group or cyclopropyl group, and Z represents an oxygen atom or a sulfur atom]. ] The present invention relates to a butene derivative or its acid adduct 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 compounds of the present invention can be used to treat various weeds that are problematic in the treatment of foliage and soil in upland fields, such as freckle weeds, snail knotweed, purslane, chickweed, whiteweed, Japanese radish, daikon radish, shepherd's purse, shepherd's purse, American hornwort, snail grass, Japanese commonweed, and American goldenrod. Mosquitoes, field pansies, Japanese morning glories, American morning glories, Maruba morning glories, Western bindweed, Japanese odorifera, hotokenoza, Japanese morning glories, Japanese Physalis, Japanese Physalis, Japanese Physalis, Japanese firs, Sunflowers, Japanese chamomiles,
Broad-leaved weeds such as corn marigolds, barnyard grass, and barnyard grass,
Weeding for grass family weeds such as foxtail grass, grasshopper, sycamore, grasshopper, oat, oat, seiban sorghum, grass barley, horseweed, blackberry, etc., cyperaceae weeds such as dayflower, and cyperaceae weeds such as cyperus spp. In addition, the compounds of the present invention do not cause any problematic phytotoxicity to major crops such as cotton, corn, wheat, etc.

The compound of the present invention is also particularly suitable as a herbicide for treating soil in cotton fields. The compound of the present invention is also suitably used as a herbicide for non-agricultural land.

The compound of the present invention has the general formula [wherein R and Z have the same meanings as above]. It can be produced by reacting the imidazolinone derivative represented by ] with sodium cyanoborohydride under acidic conditions in a solvent.

The reaction temperature and reaction time range for this reaction are respectively O to 50'C, preferably 0C to room temperature, and 10 minutes to 5 hours.
Based on the equivalent amount, the sodium cyanoborohydride is present in an amount of 1 equivalent to an excess of 1 equivalent, preferably 1 to 2 equivalents.

Examples of acids used to create acidic conditions include hydrochloric acid and sulfuric acid. Moreover, this reaction is preferably carried out under a nitrogen atmosphere.

Examples of the solvent include lower alcohols such as methanol and ethanol.

After the reaction is complete, is the reaction solution treated with an acid such as hydrochloric acid? After setting the pH to 1, return the pH to 2 to 8 using an alkali such as a purple sodium carbonate aqueous solution, pour into water, extract with an organic solvent, and concentrate, or evaporate the solvent and remove the resulting residue with an organic solvent such as methanol. The desired compound of the present invention can be obtained by performing post-treatments such as concentrating the ν solution, or further performing operations such as chromatography and recrystallization as necessary. Can you get it?

Examples of the acid adduct of the butenoic acid derivative [■] include hydrochloride, hydrobromide, etc., while blowing hydrogen chloride gas or hydrogen bromide gas in a solvent into the butenoic acid derivative [I]. It can be produced by reaction.

The reaction temperature range for this reaction is 0.5 to 5 hours, the reaction time range is 0 to 50°C, and the amount of reagent used in the reaction is hydrogen chloride per equivalent of butenoic acid derivative [■]. Or hydrogen bromide is in an amount of 1 to excess. Examples of the solvent include halogenated hydrocarbons such as methylene chloride, chlorobenzene, and dichlorobenzene, and ethers such as diethyl ether, dioxane, and tetrahydrofuran.

After the reaction is completed, the reaction solution is subjected to usual post-treatments such as collecting precipitated crystals and drying, or, if necessary, is purified by operations such as recrystallization.

Next, Table 1 shows some of the compounds of the present invention produced according to this production method.

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

Production Example 1 2-Methyl-8-(5'-isopropyl-51-methyl-4'-oxo-2'-imidacillin-2'-yl)-
Dissolve 1.0 g of (Z)-2-butenoic acid in 50 liters of methanol and add 2N hydrochloric acid in methanol to adjust the pH to 2.
~8.

Sodium cyanoborohydride 800q under nitrogen atmosphere
was added and stirred at room temperature for 80 minutes.

During this time, 2N hydrochloric acid in methanol was added little by little to keep the pH of the reaction solution at 2 to 8, and the mixture was further stirred at the same temperature for 1 hour. After the reaction was completed, concentrated hydrochloric acid was added to adjust the pH to 1, and then an aqueous sodium hydrogen carbonate solution was added to adjust the pH to 2-8. The reaction solution was then poured into water, extracted with chloroform, dried over anhydrous magnesium sulfate, and concentrated to give 2-methyl-8
-(5'-isopropyl-5'-methyl-4'-oxoimidazolidin-2'-yl) -CZ) -2-butenoic acid (trans form) 840Wl was obtained o map,
174-176°CNMRδCCDC15) (pl
)m): 0.8-1.0 (6H.

m), 1.45 (8H, s), 1.8-2.0 (6H
, m) Production Example 2 2-Methyl-8-(5'-isopropyl-5'-methyl-4'-oxo-2'-imidacillin-2'-yl)
-(Z) 2.0g of -2-butenoic acid and 80t of methanol
Dissolve in ttl and add 2N hydrochloric acid methanol solution to adjust the pH to 2-8. Under a nitrogen atmosphere, 580q of sodium cyanoborohydride was added, and the mixture was stirred at room temperature for 80 minutes.

During this time, to maintain the pH of the reaction solution at 2 to 8, a 2-stock hydrochloric acid methanol solution was added little by little. Furthermore, 5801q of sodium cyanoborohydride was added, and the mixture was stirred for 8 () minutes while maintaining the pa 2 to 8. This operation was repeated two more times and then stirred at room temperature for 1 hour. After the reaction is complete, add concentrated hydrochloric acid and
After adjusting to H1, add sodium hydrogen carbonate aqueous solution to adjust the pH.
Adjusted to 2-8. The resulting reaction solution was concentrated under reduced pressure, 501" of methanol was added to the residue, insoluble salts were filtered out, and the P solution was concentrated to give 2-methyl-8 (5'-isopropyl-5'
-Methyl-4'-oxo-imidazolidin-2'-yl)-(Z)-2-butenoic acid (cis and trans
A mixture of bodies) was obtained. This was subjected to silica gel column chromatography (eluent: hexane/acetone/methanol), and the previously eluted portion was added to 2-methyl-8-(5'
2-methyl-8-(5'-isopropyl-5 '-Methyl-4'-oxo-imidazolidine-2'-ih ) -(Z) -
The cis form of 2-butenoic acid 180 was obtained.

trans body: m, T), 174-176℃ NMRa
CCDC(?s) (ppm): 0.8-1.
0 (6H, m), 1.45 (8H, s), 1.8-2.
0(6H, m) cis body: m, pm 5t) -57°CNl'l/
IRδ (CDC&) (ppm): 0.6~
1.6 (15H, m) Production Example 8 2-Methyl-8-(5'-isopropyl-5'-methyl-41-thioxo-2'-imidacillin-2'-yl)
-(Z) -1.0f of -2-butenoic acid was added to 50% of methanol.
Vtl and add 2N hydrochloric acid methanol solution to adjust the pH to 2-8.

Sodium cyanoborohydride 800w under nitrogen atmosphere
and stirred at room temperature for 80 minutes.

During this time, 2N hydrochloric acid in methanol was added little by little to keep the pH of the reaction solution at 2 to 8, and the mixture was further stirred at the same temperature for 1 hour. 300q of sodium cyanoborohydride was added again to adjust the pH to 2-8, and the mixture was stirred for 1 hour. After the reaction was completed, concentrated hydrochloric acid was added to adjust the pH to 1, and then an aqueous sodium hydrogen carbonate solution was added to adjust the pH to 2-8. The reaction solution was then poured into water, extracted with chloroform, dried over anhydrous magnesium sulfate, and concentrated to give an oily 2-methyl-8-(5'-isopropyl-5'-methyl-4'-thioxoimidazolidine). -2'-yl) -(Z) -2-butenoic acid (cis
A mixture of trans isomer and trans isomer) was obtained. The obtained oil was subjected to column chromatography (eluent: hexane-acetone), and 2-methyl-8-(5
'-Isopropyl-5'methyl-4'-thioxoimidazolidin-2'-yl)-(Z)-2-butenoic acid trans isomer was added to the later eluted portion of 2-methyl-8-
The cis form of (5'-isopropyl-5'-methyl-4'-thioxoimidazolidin-2'-yl)-(Z)-2-butenoic acid was obtained.

Trans body: n p” L 565 ONMRδ C
CDCl5) (1) pm): 0.6 to 1.1
(6H, m), 1.88 (8H, s), 1.7-1.9
(6H, m) cis body: m, pm 9F1~97°CNMRδ (
CDC1g) (ppm): 0. '7~1.4
(15H, m) Next, some of the compounds of the present invention produced according to this production method are shown in Table 2.

Table 2 When using the compound of the present invention with the general formula as an active ingredient of a herbicide,
It is usually mixed with solid carriers, liquid carriers, surfactants, and other formulation auxiliaries to formulate emulsions, wettable powders, suspensions, granules, solutions, etc.

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

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

Surfactants used for emulsification, dispersion, wetting, etc. include anionic surfactants such as alkyl sulfate salts, alkylaryl sulfonate salts, dialkyl sulfosuccinate salts, and polyoxyethylene alkylaryl ether phosphate salts. Examples include nonionic surfactants such as polyoxyethylene alkyether, polyoxyethylene alkylaryl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester.

As formulation adjuvants, lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC
(carboxymethylcellulose), PAP (isopropyl acid phosphate), and the like.

Examples of formulations are shown below. Note that parts indicate parts by weight.

Formulation Example 1 A wettable powder is obtained by thoroughly grinding and mixing 1 or 4.50 parts of the compound of the present invention, 8 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic hydrous silicon oxide.

Formulation Example 2 1 or 8.10 parts of the compound of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 70 parts of methyl alcohol are thoroughly mixed to obtain an emulsion.

Formulation Example 8 1 or 3.2 parts of the compound of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium ligninsulfonate, 8 parts of bentonite
0 parts and 65 parts of kaolin clay are thoroughly ground and mixed, water is added and the mixture is thoroughly kneaded, and then granulated and dried to obtain granules.

Formulation Example 4 1 or 8.25 parts of the compound of the present invention, 8 parts of polyoxyethylene sorbitan monooleate, 8 parts of CMC, and 69 parts of water are mixed and wet-pulverized until the particle size becomes 5 microns or less to obtain a suspension agent. .

Formulation Example 6 1 or 4.80 parts of the compound of the present invention, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate, and 15 parts of synthetic hydrous silicon oxide are thoroughly ground and mixed to obtain a wettable powder.

The compound of the present invention thus formulated is applied to soil or foliage before or after the emergence of weeds. Soil treatment includes soil surface treatment, soil mixing treatment, etc., and foliage treatment includes treatment from above the plant body, as well as local treatment that treats 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, it can be used in combination with insecticides, acaricides, nematicides, fungicides, plant growth regulators, fertilizers, soil conditioners, and the like.

The compound of the present invention can be used as an active ingredient of a herbicide for fields, orchards, pastures, lawns, forests, non-agricultural lands, and the like.

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 is usually 0.00% per are in upland fields. 19 to 50 g, preferably 0.1 f to 40 y, and in non-agricultural land, 1
1-20 Of per are, preferably 2-100
Emulsions, wettable powders, suspension agents, etc. are usually diluted in a specified amount with 1 to 10 liters of water per are (if necessary, an auxiliary agent such as a spreading agent is added). Granules, etc. are usually processed as is without any dilution.

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

Next, test examples demonstrate that the compounds of the present invention are useful as active ingredients of herbicides. The compounds used for comparison are indicated by the compound symbols in Table f.

Table i In addition, the herbicidal efficacy is determined by visually observing the degree of inhibition of budding and growth of the test plants during the survey, and ``0'' indicates that there is no or almost no difference from the case where no compound is used. If the plant is withered or its growth is completely inhibited, it is evaluated as "5", and evaluated on a scale of θ to 5, 0.1.2.
8.4.5.

Test Example 1 Upland Soil Surface Treatment Test A cylindrical plastic pot with a diameter of lOα and a depth of 10 cI11 was filled with upland soil, sown with barnyard grass, oats, morning glory, and Japanese radish, and covered with soil. The test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with water equivalent to 10 liters per are, and the emulsion was applied to the soil surface using a small sprayer. After treatment, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 4.

Table 4 Test Example 2 Upland Stem and Leaves Treatment Test A cylindrical plastic pot with a diameter of 10σ and a depth of 1Qz was filled with upland soil, and millet, oat, radish, and 1.5-year-old Japanese radish were sown and grown in a greenhouse for 101 years. Thereafter, the test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount of the emulsion was diluted with water containing a spreading agent equivalent to 0 liter per are, and the grass leaves were treated from above the plants with a small sprayer. . 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 5 Test Example 8 Upland Soil Treatment Test A vat with an area of 88 x 28 d and a depth of 11 was filled with upland soil, and sown with diver, cotton, corn, wheat, Physalis, Physalis, Japanese millet, Japanese grasshopper, Seiban sorghum, hackberry, and oat; 1~
It was covered with soil to a thickness of 2cIII. The test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with water equivalent to 10 liters per are, and the emulsion was applied to the soil surface using a small sprayer. After treatment, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated.

The results are shown in Table 6.

＼, °), "°゛151,'ノTable 6 Test Example 4 Upland grass treatment test Area 88 x 28 d, depth 11 c!M vat was filled with upland soil, and cotton, corn, dive, mulva morning glory, Physalis Physalis, and Physcomitrella spp. , sowing of barnyard grass, Saban sorghum, hackberry, and oat
It was grown for days. Thereafter, the test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount of the emulsion was added to
It was diluted with a liter of water and uniformly applied to the entire stem and leaves from the top of the plant using a small sprayer. At this time, the growth conditions of weeds and crops vary depending on the grass species, but at the 1-4 leaf stage,
The plant height was 2 to 12 crK. The herbicidal efficacy was investigated 20 days after the treatment. The results are shown in Table 7. Note that this test was conducted in a greenhouse throughout the entire period.

Table 7

Claims (1)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R represents an ethyl group, isopropyl group, or cyclopropyl group, and Z represents an oxygen atom or a sulfur atom. ] A butenoic acid derivative or an acid adduct thereof. (2) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R represents an ethyl group, isopropyl group, or cyclopropyl group, and Z represents an oxygen atom or a sulfur atom. ] The general formula is characterized by reacting the imidazolinone derivative represented by the formula with sodium cyanoborohydride in a solvent under acidic conditions ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R and Z are It has the same meaning as above. ] A method for producing a butenoic acid derivative or an acid adduct thereof. (8) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R represents an ethyl group, isopropyl group, or cyclopropyl group, and Z represents an oxygen atom or a sulfur atom. ] A herbicide characterized by containing a butenoic acid derivative or an acid adduct thereof as an active ingredient.