JPS591697B2 - 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, specifically having the general formula NH-O-R2.

□1゛''...(In the formula, R1 is an alkyl group,
R2 is an aralkyl group, an alkoxycarbonylalkyl group, an alkoxyalkyl group, or an alkylthioalkyl group, X is a different or similar alkyl group in which the hydrogen atom of the cyclohexane ring is substituted at the 5th position, and n is 1 or 2
shows.

) The present invention relates to a method for producing novel cyclohexane-1,3-diones represented by:

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 present inventors have synthesized a large number of cyclohexane-1,3 dione derivatives, and are currently examining those suitable for the above purpose. .

) 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 compound represented by I] can be obtained industrially advantageously, and it also shows extremely excellent herbicidal activity against weeds of the family Weeds, such as Psyllium japonica, Psyllium japonica, and Cucifera, in both soil and foliage treatments, and is particularly effective against many other herbicides. They discovered that it has a selectivity that makes it almost harmless to broad-leaved crops, including azuki beans and soybeans, which are susceptible to chemical damage.
The invention has been completed.

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 in a smaller 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 wide range of application times, locations and concentrations.

Furthermore, the compounds of the present invention can be used completely without concerns about residual toxicity in soil or plants or acute toxicity to livestock and fish. In producing the compounds of the present invention, 3-hydroxy-2-cyclohexen-1-ones represented by the above general formula [] and amines represented by the above 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. As the reaction solvent, common organic solvents such as alcohol, acetone, ether, benzene, toluene, chloroform, acetic acid ester, dimethylformamide, acetonitrile, dimethyl sulfoxide, and tetrahydrofuran are used. After 30 minutes to several hours of reaction, if necessary, replace the solvent and perform alkaline extraction.
The alkaline layer is acidified with hydrochloric acid, and the precipitated crystals or separated oil are separated by solvent extraction or filtration to obtain the desired product.

After purification by recrystallization or column chromatography, the structure was confirmed by elemental analysis, IR spectrum, NMR spectrum, etc. The compound of the present invention may have the following tautomeric structural formula.

Next, Table 1 shows examples of compounds produced by the method of the present invention.

Next, the method for producing the compound of the present invention will be explained in detail with reference to Examples.

Example 1 2-(1-benzyloxyaminopropylidene)-5.
5-dimethylcyclohexane-1,3-dione 5,5-
7.8 y of dimethyl-3-hydroxy-2-propionyl-2-cyclohexen-1-one and 87 y of benzyloxyamine hydrochloride are dissolved in 50 cc of ethanol, and 15 cc of aqueous ethanol containing 2.1 y of caustic soda is added dropwise at room temperature.

After reacting for 1 hour and 30 minutes at the same temperature, the precipitated Na
The Cl was thoroughly filtered off, and the ethanol was distilled off under reduced pressure. 5 for residue
% caustic soda aqueous solution is added, and insoluble matter is extracted with ether. When the alkaline layer is neutralized with hydrochloric acid, an oily substance is obtained. This is extracted with chloroform, washed with water, dried over magnesium sulfate, and the chloroform is distilled off under reduced pressure to obtain a colorless oil. If you leave it for a while, it will crystallize, but if you recrystallize it with petroleum ether, the white crystal target will become 8.07
can get. Yield 66%, melting point 58-59°C Example 2 2-(1-ethoxycarbonylmethyloxyaminopropylidene)-5,5-dimethylcyclohexane-1,3
-dione 5,5-dimethyl-3-hydroxy-2-propionyl-2-cyclohexen-1-one 1.967 (
0.01 mol) and 1.567 (0.01 mol) of ethyl ethyl aminooxyacetate hydrochloride in 30 cc of ethanol.
An ethanol solution containing 0.68y (0.01 mol) of sodium ethylate dissolved in the solution was added to neutralize the hydrochloride, and the mixture was allowed to react overnight at room temperature.

Ethanol was distilled off from the reaction solution under reduced pressure, and the residue was dissolved in water and extracted with ether to obtain 2.8y of pale yellow liquid.
This is purified by silica gel column chromatography to give the desired product as a colorless transparent liquid. Yield 94% N2ll. 5
Ol9lD゜Example 3 2-(1-methoxyethoxyaminopropylidene)-5
・5-dimethylcyclohexane-1,3-dione 5,5
-dimethyl-3-hydroxy-2-propionyl-2-
Cyclohexen-1-one 1.967 (0.01 mol)
and methoxyethyloxyamine hydrochloride 1.

Dissolve 287 (0.01 mol) in 30 cc of ethanol, add an ethanol solution containing 0.68 y (0.01 mol) of sodium ethylate to neutralize the hydrochloride, and then leave to react day and night at room temperature. let

After the reaction is completed, ethanol is distilled off under reduced pressure, water is added to the residue to dissolve it, extracted with ether, and the solvent is distilled off to obtain the desired product 2.5y as a colorless transparent liquid. Yield 93.5%, N2
l) 1.5100. The herbicide of the present invention has the general formula [1]
It consists of containing one or more of the compounds shown in 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, diatomaceous earth, etc., and examples of liquid carriers include water, alcohol, benzene, xylene, kerosene, mineral oil, cyclohexane, cyclohexanone, dimethylformamide, and the like. 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 in the herbicide of the present invention varies depending on the form of the formulation mentioned above, but for example, in the case of a wettable powder, the concentration is 5 to 5.
80%, preferably 10-60%; in emulsions 5-60%
70%, preferably 20-60%; for powders and granules, concentrations of 0.5-30%, preferably 1-10% are used.

The wettable powders and emulsions obtained in this way are diluted with water to a predetermined concentration to form a suspension or emulsion; the powders and granules are left as they are and are sprayed or mixed into the soil before weed germination. Or, after weed germination, foliar spray treatment is applied.

When actually applying the herbicide of the present invention, an appropriate amount of the active ingredient is applied in an amount of 107 or more, preferably 307 or more per 10 ares. The herbicide of 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 of the present invention include triazine herbicides such as simazine, propazine, and promethrin, carbamate herbicides such as betanal, linyuron,
Examples include urea herbicides such as tribunyl agents, and heterocyclic herbicides such as bentazone agents, pyrazone agents, and renacil agents. Next, some examples regarding the herbicide of the present invention will be shown, but the active ingredient compounds, additives, and addition ratios are not limited to these examples and can be varied within a wide range.

The above was mixed uniformly and finely pulverized to obtain a wettable powder containing 20% of the active ingredient.

The above ingredients were mixed and dissolved to obtain an emulsion containing 40% of the active ingredient.

Example 6 Granule Compound 3 7 parts Talc 38 parts Clay 3 8 parts Bentonite 10 parts Sodium alkyl sulfate 7 parts or more were uniformly mixed and finely ground to a diameter of 0.5 to l.
．． The mixture was granulated into particles 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 test surface area of 6 ocd 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.

A chemical solution IOCC 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 0 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: 6 Ocwl pots were filled with soil, and approximately 50 grains of Japanese millet were shaken and lightly covered with soil, and grown in a greenhouse.

When the Japanese millet grew to the single-leaf stage, each pot was flooded with water to a depth of about 3 cm, and a chemical solution of a predetermined concentration prepared by diluting an emulsion of each compound with water was poured 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 Leaf treatment test surface area 100crii. The pots were filled with soil, and the seeds of mehishi niva 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, n represents 1 or 2), a compound represented by the general formula R_2-O-NH_2 (wherein R_2 represents an aralkyl group, an alkoxycarbonylalkyl group, an alkoxyalkyl group, or an alkylthioalkyl group). It is characterized by causing a reaction. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the formula, R_1 is an alkyl group, R_2 is an aralkyl group, alkoxycarbonylalkyl group, alkoxyalkyl group, or alkylthioalkyl group, and X is a hydrogen atom of the cyclohexane ring. A method for producing a compound represented by a different or the same alkyl group substituted at the position, n represents 1 or 2.