JPS591698B2 - Method for producing cyclohexane derivatives - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel compound, and more specifically, it has the general formula ONH-O-R2 X represents an alkyl group, a phenyl group substituted with a halogen atom or an alkoxy group, a styryl group, a furyl group, or a thienyl group.

) and a method for producing a metal salt thereof.

Compounds produced according to the present invention are useful as herbicides.

The object of the present invention is to obtain these compounds industrially advantageously and to provide a simple and highly effective herbicide.

The inventors of the present invention are currently investigating a variety of cyclohexane-1,3-dione derivatives suitable for the above-mentioned purpose, and found that they are represented by the general formula (wherein R1 and X have the same meanings as defined above).

) for the compound represented by the general formula (In the formula, R2 has the same meaning as defined above.

) was reacted with the compound represented by the general formula [
The compounds represented by 1] can be obtained industrially advantageously, and they also show extremely excellent herbicidal activity against weeds of the family Weeds such as Sparrow weed, Sparrow gnome, and Cucifera in both soil treatment and foliar spraying, and especially against many other weeds. discovered that it has a selectivity that is almost harmless to broad-leaved crops, including adzuki beans and soybeans, which are susceptible to chemical damage caused by herbicides, and after further biological and physicochemical research, they completed the present invention. did.

A herbicide containing a 4-hydroxy-6-methyl-α-pyrone derivative as an active ingredient is known from Patent Application Publication No. 46-16916. One drawback of this herbicide is that it requires a fairly large dose.

However, the compound of the present invention exhibits a sufficient herbicidal effect even at a lower dose than known compounds. Furthermore, the compounds of the present invention exhibit excellent herbicidal efficacy against weeds even when treated at any growth period, whether before or after germination. The compound of the present invention has no effect on broad-leaved crops such as daikon radish, adzuki beans, soybeans, peas, spinach, and beads when applied to leaves, even at doses that can completely kill the weed grasshopper, for example. In addition, in the pre-emergence soil treatment of weeds, even at a dose that completely inhibits the germination of crabgrass, there is no effect on the seeds of broad-leaved crops.The safety of herbicides against broad-leaved crops is extremely high, and their application is They can also be used in a very wide range of application times, locations and concentrations. Furthermore, the compounds of the present invention can be used safely without concerns about residual toxicity in soil or plants or acute toxicity to livestock and fish. In producing the compound of the present invention, the compound represented by the general formula [] and the amine represented by the general formula [] are reacted in an inert solvent.

The reaction temperature is from room temperature to the boiling point of the solvent used, preferably at room temperature or under mild heating conditions. Alcohol, acetone, ether,
Common organic solvents such as benzene, toluene, chloroform, acetate, dimethylformamide, acetonitrile, dimethyl sulfoxide, and tetrahydrofuran are used. After 30 minutes to several hours of reaction, if necessary, the solvent is replaced and alkali extraction is performed, and the alkaline layer is acidified with hydrochloric acid, and the precipitated oil or crystals are separated by solvent extraction or filtration to obtain the desired product.

After purification by recrystallization or column chromatography, the structure was confirmed by the results of elemental analysis 1R spectrum, NMR spectrum, etc. In producing the metal salt of the compound of the present invention, the compound represented by the general formula [1] and a caustic alkali such as caustic soda or caustic potash are mixed in water or an organic solvent such as acetone, methanol, ethanol, dimethylformamide, etc. The sodium salt and potassium salt are obtained by mixing and reacting with heating if necessary, and then the desired metal salt is obtained by reacting the same with the desired metal salt in the same manner.

Metal salts often precipitate or crystallize out in the above-mentioned solvents. Examples of metal salts that form metal salts with the compound represented by the general formula [1] include Na, . K. Ca
、． Mg. ．． Ba,. Ni. ．． CulMn,. CO,.
Zn,. Fe,. Salts of monovalent or divalent metals such as Agl, such as chlorides, hydroxides, sulfates, nitrates, acetates, and other metal salts soluble in water or organic solvents are used.
Note that Ca salt can also be obtained by directly reacting the compound represented by the general formula [1] with calcium hydroxide in an organic solvent.

Some of the metal salts of the present invention produced in this way do not show a clear melting point due to some chemical changes or decomposition at high temperatures, but they do not show a clear melting point due to a chemical change or decomposition at high temperatures. The formation of metal salts can be determined by changes in absorption intensity.

That is, the raw material compound represented by the general formula [1] has a wave number of 1
The carbonyl group shows absorption at 655 and 16011, whereas metal salts show absorption at longer wavelengths. Note that in the obtained metal salt, an anion such as 0H may be simultaneously coordinated with the metal atom.

The following tautomeric structural formulas can be considered for the present compound [1] and the starting material compound []. Next, Table 1 shows examples of compounds produced by the method of the present invention. The manufacturing method of the present invention will be explained in detail by giving Examples.

Example 1 2-(1-ethoxyaminopropylidene)-5(4-chlorophenyl)-cyclohexane-1,3-dione 5-(4-chlorophenol-3-hydroxy-2-propionyl-2-cyclohexene- 1-
Add 1.27 ethoxyamine to a solution containing 5.6 t of
was added and reacted at room temperature for 3 hours with stirring.

After the reaction is completed, ethanol is removed under reduced pressure to obtain crude crystals. When this is recrystallized from ethanol, the desired product 5.
1t is obtained. (White columnar crystals) Melting point: 92-3°C Yield: 75% Example 2 2-(1-allyloxyaminobutylidene) 5-(4-
methoxyphenyl)-cyclohexane-1,3-dione In a solution of 4,37 2-butyryl-3-hydroxy-5-(4-methoxyphenyl)-2-cyclohexen-1-one dissolved in 50 cc of ethanol, Add 1.247 g of allyloxyamine and react at room temperature for 3 hours with stirring.

After the reaction is complete, ethanol is distilled off under reduced pressure, the residue is dissolved in a 5% aqueous sodium hydroxide solution, insoluble materials are extracted and removed with ether, and the alkaline layer is acidified with hydrochloric acid. The precipitate was extracted with ether, washed with water, and dried over magnesium sulfate. By distilling off the ether under reduced pressure, the desired product 4y can be obtained.
(yellow crystal) Melting point 52-3°C Yield 73.3% Example 3 2-(1-ethoxyaminopropylidene)-5(4-methylphenyl)-cyclohexane 1,3-dione copper salt Acetone 15CC 1-Ethoxyaminoflopylidene)-5-(4-methylphenyl)-cyclohexane An aqueous solution of 0.137 ml of caustic soda dissolved in 1 cc of water is added to a solution of 1,3-dione 17 at room temperature and stirred for 1 hour. .

Thereafter, acetone was distilled off under reduced pressure, and 15 cc of water was added.
A solution of 0.467 ml of copper sulfate dissolved in 50 cc of water was added dropwise to this at room temperature, and the reaction was stirred for an additional 10 minutes. After washing the precipitate with water, acetone and ether, and drying, 0.9 t of the desired product as a green powder is obtained. Melting point 183
~4°C (decomposition) Yield 40% Example 42-(1-allyloxyaminopropylidene)-5-styrylcyclohexane-1,3-dione 3-hydroxy-2-propionyl-5-styryl-2-cyclohexene- 5.4 t1 (0.02 mol) of 1-one was dissolved in a mixed solution of 30 cc of chloroform and 30 cc of ethanol, 1.6 t (0.022 mol) of allyloxyamine was added, and after reacting at room temperature for 3 hours, the mixture was further refluxed. React for 10 minutes.

After the reaction is complete, the solvent is distilled off under reduced pressure, and the residue is dissolved in chloroform. The chloroform solution is extracted twice with 5 to 10% aqueous sodium hydroxide solution (14 to 16 cc), and the alkaline layer is acidified with hydrochloric acid to separate an oily substance. After extracting the oily substance twice with 10 CC of chloroform, the chloroform solution was extracted with 1 cc of chloroform.
Wash with 0cc water. After drying with magnesium sulfate,
The residue was filtered and chloroform was distilled off under reduced pressure to obtain the desired product 6.27 as a colorless oil. Yield 95% n℃1.5
851 Example 5 2-(1-allyloxyaminopropylidene)5-(2
-Furyl)cyclohexane-1,3dione 5-(2-furyl)-3-hydroxy-2-propionyl-2-cyclohexen-1-one 2.37 was dissolved in 40cc of ethanol, allyloxyamine 17 was added, and the mixture was heated at room temperature. After stirring for 2 hours, the solvent was distilled off under reduced pressure, and the residue was dissolved in 30 cc of 5% aqueous sodium hydroxide solution.

After washing the insoluble matter with ether, it was neutralized by adding hydrochloric acid, and the liberated yellow oil was extracted with chloroform. After washing with water and drying with anhydrous magnesium sulfate, the chloroform was distilled off.
The target object 2.3y was obtained. Nl. 5452 Yield 80% Example 6 2-(1-ethoxyaminopropylidene)-5(2-thienyl)cyclohexane-1,3dione 3-hydroxy-2-propionyl-5-(2-thienyl)-2-cyclohexene- 1-one 37 was dissolved in 40 cc of ethanol, 0.9 t of ethoxyamine was added, and after stirring at room temperature for 2 hours, the solvent was distilled off under reduced pressure to obtain crude crystals.

Recrystallize with n-hexane to obtain the desired product 2.5V in the form of white needles. Melting point 68-69°C Yield 71% Example 7 2-(1-ethoxyaminopropylidene)-5(2-furyl)-cyclohexane-1,3dione Copper salt 2-(1-ethoxyaminopropylidene)-5 Dissolve 0.57 of (2-furyl)-cyclohexane-1,3-dione in 10 cc of acetone, add 0.2 t of sodium hydroxide to 1 cc of water.
A solution dissolved in C was added, and after stirring at room temperature for 30 minutes, the solution was distilled off under reduced pressure, and 20 cc of water was added to the residue.

Then, an aqueous solution of 0.6 t of copper sulfate dissolved in 5 cc of water was added dropwise, and the mixture was stirred at room temperature for 20 minutes. The obtained green product is separated, washed with water, and then dried to obtain 0.8 t of the desired proboscis. Melting point: 197-8°C Yield: 70% The herbicide produced by the present invention contains one or more of the compounds represented by the above general formula [1] as an active ingredient.

The active ingredient compound is generally used by mixing an appropriate amount with a carrier and preparing it in the form of a wettable powder, emulsion, powder, granule, or the like. Examples of solid carriers include talc, bentonite, clay, and diatomaceous earth. Examples of liquid carriers include water, alcohol, benzene, xylene, kerosene, mineral oil, cyclohexane, cyclohexanone, and dimethylformamide. If necessary, a surfactant may be added in order to obtain a uniform and stable form in these preparations. The concentration of the active ingredient as a herbicide of the compound produced according to the present invention varies depending on the form of the formulation mentioned above, but for example, in a wettable powder, the concentration is 5 to 8.
0%, preferably 10-60%; in emulsions 5-7
0%, preferably 20-60%; for powders and granules, concentrations of 0.5-30%, preferably 1-10% are used.

The wettable powders and emulsions thus obtained are diluted with water to a predetermined concentration to form a suspension or emulsion; the powders and granules are directly sprayed or mixed into the soil before weed germination; Alternatively, foliar spray treatment is applied after weed germination.

When actually applying the herbicide produced according to the present invention, an appropriate amount of the active ingredient is 107 or more, preferably 507 or more per 10 ares. The herbicide produced according to the present invention can also be used in combination with known bactericides, insecticides, acaricides, herbicides, plant growth regulators, and the like.

In particular, when used in combination with herbicides, not only can the amount of chemicals used be reduced and labor-saving, but even higher effects can be expected due to the synergistic action of both chemicals. Chemicals suitable for use in combination with the herbicide produced by the present invention include triazine herbicides such as simazine, propazine, and promethrin; cabamate herbicides such as betanal;
Examples include urea herbicides such as linuron and tribunyl, and heterocyclic herbicides such as bendazone, pyrazone and renacil. Next, some production examples regarding herbicides produced according to the present invention will be shown, but the active ingredient compounds, additives, and addition ratios are not limited to these production examples and can be varied within a wide range.

Manufacturing example 1 hydrating agent Mix the above evenly, finely crush it, A 20% hydrating agent was obtained.

Manufacturing example 2 emulsion Active ingredient Mix and dissolve the above ingredients to form the active ingredient 4. Obtained.

Production Example 3 Granules After uniformly mixing the 0% emulsion and pulverizing it finely, the powder had a diameter of 0.5-1.
The mixture was granulated into granules of 0 mm to obtain granules containing 7% of the active ingredient.

Next, test examples regarding the effect of the herbicide of the present invention will be shown.

Test Example 1 Flooded Soil Treatment Test A pot with a surface area of 60 cd was filled with soil, about 60 millet seeds were sown thereon, and the soil was lightly covered with soil, followed by a flooded state to the extent that the soil surface was moistened.

10 cc of a solution of a predetermined concentration prepared by diluting an emulsion of each test compound with water was poured into a pot and placed in a greenhouse. Two weeks later, the growth status of the barnyard grass was investigated.

The growth status was expressed in six stages from O to 5, with O indicating the same level of growth as without treatment and 5 indicating withering or non-germination, and the results shown in Table 2 were obtained. Test example 2 Single leaf stage treatment test surface area 60c? A pot was filled with soil, and about 50 grains of Japanese millet were sown on top, lightly covered with soil, and allowed to grow within the temperature range.

When the Japanese millet grew to the single-leaf stage, each pot was flooded with water at a depth of about 3 CTL, and a chemical solution of a predetermined concentration prepared by diluting an emulsion of each compound with water was irrigated into each pot. Two weeks later, the growth status of the Japanese millet was investigated.

Expressing the growth state according to the same criteria as Test Example 1,
The results shown in Table 3 were obtained. Test Example 3 Stem and Leaf Treatment Test Pots with a surface area of 100 cr were filled with soil, and seeds of crabgrass and pigweed were sown, lightly covered with soil, and grown in a greenhouse.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R_1 is an alkyl group, X is an alkyl group,
Indicates a phenyl group, styryl group, furyl group or thienyl group substituted with a halogen atom or an alkoxy group. ) is reacted with a compound represented by the general formula R_2-O-NH_2 (wherein R_2 represents an alkyl group or an alkenyl group). Yes▼ (However, in the formula, R_1 represents an alkyl group, R_2 represents an alkyl group or an alkenyl group, and X represents an alkyl group, a phenyl group, a styryl group, a furyl group, or a thienyl group substituted with a halogen atom or an alkoxy group.) A method for producing a compound represented by