JPS591696B2 - Method for producing spirodicyclohexane derivatives - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel compound, in particular, a method for producing a novel compound of the general formula o
NH-O-R* (wherein R1 represents an alkyl group, and R2 represents an alkyl group or an alkenyl group.

) The present invention relates to a method for producing novel spirodicyclohexanes 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 Unruz pyrocin clohexanedione derivatives, and are currently investigating those suitable for the above-mentioned purpose.

) and the general formula (wherein R2 has the same meaning as defined above).

) is represented by the above general formula [I]. Spirodicyclohexanediones are industrially advantageously obtained, and they exhibit extremely excellent herbicidal activity against weeds of the family Weeds, such as Sparrow weed, Sparrow gnome, and Hemlockweed, both in soil treatment and in foliage treatment, and are particularly effective against many other herbicides. They discovered that it has selectivity to be almost harmless to broad-leaved crops, including azuki beans and soybeans, which are susceptible to chemical damage, and after conducting further biological and physicochemical research, they completed the present invention.

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.

Surprisingly, 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 when treated at any growing season, whether before or after germination, but treatment during the growing season is preferable. The compound of the present invention can be applied to radish, azuki beans, soybeans, peas, spinach, etc. even at a dose that completely kills, for example, the weed of the family Helicoptera by foliage spraying.
There is no effect on broad-leaved crops such as bead, and even at a dose that completely inhibits the germination of crabgrass in the pre-emergence soil treatment of weeds, no effect is observed on the seeds of broad-leaved crops. Herbicides are extremely safe against herbicide damage, and can be applied in a 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 the general formula [1], R1 and R2 are lower alkyl and lower alkenyl groups, which have particularly excellent herbicidal effects. In producing the compound of the present invention, the general formula [
] 4-Unluz pyrocin chlohexane-3
- 5-dione and the alkoxyamine, alkenyloxyamine, etc. represented by the above general formula [] are reacted in an inert solvent.

Acetyl, propionyl, n-butyryl, isoptyryl, n-pentanoyl, ethylpropionyl, α-methylbutyryl, β-methylbutyryl, and the like are used as the acyl of 4-unloos pyrocin chlohexane-3,5 dione.

As the alkoxyamine, methoxyamine nitoxyamine, n-propoxyamine, isopropoxyamine,
n-butoxyamine, isofoxyamine, Sec. −
Butoxyamine, n-amyloxyamine, isoamyloxyamine, n-hexyloxyamine, n-octyloxyamine, n-dodecyloxyamine, etc. are used. As the alkenyloxyamine, allyloxyamine, 1-propenyloxyamine, crotyloxyamine, 3-butenyloxyamine, methallyloxyamine, etc. are used.

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, and acetate are used. After 30 minutes to several hours of reaction, if necessary, the solvent is replaced and alkali extraction is performed, the alkali layer is acidified with hydrochloric acid, and the separated 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 elemental analysis, R spectrum, NMR spectrum, etc. The compound of the present invention may have the following tautomeric structural formula. Further, the general formula [] of the pre-raw material is also considered to have a tautomeric structural formula similar to the above.

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

Example 1 4-(1-allyloxyaminopropylidene) spirodicyclohexane-3,5-dione 4-propionyl-spirodicyclohexane 3,5-dione 1.2f7 (0.
005 mol) was dissolved in 10 cc of ethanol, 0.47 (0.0055 mol) of allyloxyamine was added, and the mixture was reacted at room temperature for 3 hours.

After the reaction is complete, ethanol is distilled off under reduced pressure, and the residue is dissolved in chloroform. The chloroform solution is extracted twice with 7 to 8 CC of a 5 to 10% aqueous solution of caustic soda, and the alkaline layer is acidified with hydrochloric acid to separate an oily substance. The oil was extracted twice with 10 cc of chloroform, and the chloroform was distilled off under reduced pressure to obtain 1.37 g of a colorless oil.
Yield 89%, NOl. 5336 The herbicide of 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, 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 preparation mentioned above, but for example, in the case of a hydrate, it is 5 to 80%, preferably 10 to 80%.
60%: 5-70% in emulsions, preferably 20-70%
60%: For powders and granules, a concentration of 0.5 to 30%, preferably 1 to 10% is used.

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

When actually applying the herbicide of the present invention, an appropriate amount of 10 y or more, preferably 30 y or more of the active ingredient is applied per 10 are. 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, probazine, 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.

Example 2 hydrating agent Mix the above ingredients evenly, grind them finely, A 20% hydrating agent was obtained.

Example 3 emulsion Active ingredient The above ingredients were mixed and dissolved to obtain an emulsion containing 40% of the active ingredient.

Example 4 After uniformly mixing the above ingredients and pulverizing them finely, the mixture was made into a powder having a diameter of 0.5 to 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 chemical 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 One-leaf stage treatment test A pot with a surface area of 6 Ocd was filled with soil, and about 50 grains of Japanese millet were sown thereon, lightly covered with soil, and grown in a greenhouse.

When the Japanese millet grows to the single-leaf stage, the water depth is approximately 3 (V
7! 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 Soil surface treatment test Soil mixed with crabgrass and pigweed seeds was placed on a surface area of 1
The cells were packed in 0.00 cwL pots and grown in a greenhouse.

Before the germination of crabgrass and pigweed, a chemical solution of 5 CC of a predetermined concentration prepared by diluting an emulsion of each test compound with water was sprayed onto the soil surface, and 21 days later, the growth status of crabgrass and pigweed was investigated. The growth status was expressed according to the same criteria as Test Example 1, and the results shown in Table 4 were obtained. Test Example 4 Leaf Treatment Test A pot with a surface area of 100 cd was filled with soil, and seeds of crabgrass and pigweed were sown, lightly covered with soil, and grown in a greenhouse.

Claims (1)

[Claims] 1 A compound represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. or alkenyl group) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 represents an alkyl group, R_2 represents an alkyl group or an alkenyl group ) A method for producing a compound represented by