JPS6045633B2 - Cyclohexane derivatives, manufacturing methods and herbicides - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel compound, a method for producing the same, and a use thereof.
6 is a cycloalkyl group, R2 is a lower alkyl group, R is
3 represents a lower alkyl group or a lower alkenyl group.

), a method for producing the compound, and a herbicide containing the compound as an active ingredient. The object of the present invention is to obtain these compounds industrially advantageously and to provide a simple and reliable herbicide. The present inventors have synthesized a large number of 2-acyl-3-hydroxy-2-cyclohexen-1-one derivatives, and are currently investigating those suitable for the above purpose. Both foliar and foliage spray treatments have extremely excellent herbicidal effects against weeds of the family family such as sycamore, crabgrass, oat, and hackberry grass, and are especially effective against radish, soybean, cucumber, heat, etc., which are susceptible to chemical damage by many other herbicides. The present invention was completed after further biological and physical chemistry research.

The present inventors also discovered that the compounds represented by the general formula [1] also have mitecidal activity. Japanese Patent Application Publication 1973-
46644, 50-117750 and 51-13185
No. 61, a herbicide containing a cyclohexane dione derivative similar to the compound of the present invention as an active ingredient is known.
A relatively large amount of the known compound is required in order to completely kill the weeds of the family Helicoptera.

Compounds of the present invention having a cycloalkyl group at the 5-position
Comparing 11 compounds to known compounds, 2-
It exhibits a sufficient herbicidal effect even at a moderate dosage.

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.
Among the compounds of the present invention, compounds in which R1 is a cyclohexyl group, compounds in which R2 is an ethyl or propyl group, R
Compounds in which 3 is an ethyl group or an allyl group can be sprayed onto leaves, for example, even at a dose that completely kills the weed grasshopper, it is not effective against broad-leaved crops such as radish, adzuki beans, soybeans, peas, spinach, and heat. The safety of herbicide-induced damage to broad-leaved crops is shown, with no effect observed at all, and no effect on the seeds of broad-leaved crops even at doses that completely inhibit the germination of crabgrass in pre-emergence soil treatment. It has very high properties and can be used in a wide range of applications depending on the timing, location, and concentration of application.

In addition, 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. The compound of the present invention is produced according to the following reaction formula.

(wherein Rl, R2 and R3 have the same meanings as defined above.

) That is, a 2-acyl-3-hydroxy-2-cyclohexen-1-one represented by the general formula [formula] is reacted with a lower alkoxyamine or a lower alkenyloxyamine in an inert solvent.

2-acyl-3-hydroxy-2-cyclohexene-1
Acyl of -one is acetyl, propionyl, n-
Butyryl, isoptyryl, n-pentanoyl, ethylpropionyl, α-methylpurityl, β-methylpurityl, and the like are used.

Alkoxyamines include methoxyamine, ethoxyamine, n-propoxyamine, isopropoxyamine, n-ptoxyamine, isoptoxyamine, Sec.
．． -ptoxyamine, n-amyloxyamine, isoalumiumoxyamine, n-hexyloxyamine, n-octyloxyamine, n-dodecyloxyamine, etc. are used. As the lower alkenyloxyamine, allyloxyamine, 1-propenyloxyamine, crotyloxyamine, 3-butynyloxyamine, 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, ether, benzene, toluene, chloroform, and acetate are used. After several hours of reaction, if necessary, replace the solvent and perform alkali extraction, acidify the alkaline layer with hydrochloric acid, and separate the separated oil or precipitated crystals by solvent extraction or overnight 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. Further, compounds obtained by reacting the compound represented by the general formula [1] with an acid halide or an acid anhydride to acylate it also have herbicidal activity like the compound represented by the general formula [1].

For example, the reaction formula for Yang combination when the acyl group is a benzoyl group is as follows. When carrying out the above reaction, the general formula [
1] Dissolve the compound represented by in a suitable inert solvent,
An alkali such as sodium hydroxide or potassium hydroxide is added to form an alkali metal salt.

Once separated from the reaction mixture (or as is), it is reacted with benzoyl halide or benzoic anhydride. As the reaction solvent, common organic solvents such as ether, alcohol, benzene, toluene, chloroform, and ethyl acetate are used, and the reaction temperature is from -20°C to the boiling point of the solvent used, preferably at a temperature below room temperature. After a reaction time of between 1 powder and 1 C@, if necessary, solvent replacement or solvent extraction is followed by alkali washing, water washing, drying, and distillation of the solvent under reduced pressure to obtain a crystalline or liquid form. As a product, an acylated product of the compound represented by the general formula [1] is obtained.

The acylated product is purified by recrystallization or column chromatography, and then subjected to elemental analysis, IR vector, N
The structure was confirmed by analysis results such as IVR spectrum.

The compound represented by the general formula [1] can have the following isomeric structural formula based on tautomerism.

Next, the manufacturing method of the present invention will be explained in more detail with reference to Examples.

Example 1 2-(1-allyloxyaminoptylidene)-5-cyclohexylcyclohexane-1,3-dione (compound number 1) Dissolve 2-butyryl-5-cyclohexylcyclohexane-1,3-dione 3f in 20 ml of ethanol. Then, 1.3V of allyloxyamine was added while stirring, and the mixture was allowed to react at room temperature for 5 hours.

The reaction solution was poured into ice water and the liberated oil was extracted with chloroform. The chloroform layer was washed with dilute hydrochloric acid and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain the desired compound as a colorless oil of 2.5 f. Obtained. Nrl. 53O9 Example 2 2-(-1-ethoxyaminopropylidene)-5-cyclohexylcyclohexane-1,3-dione (compound number 4) 2-propionyl-5-cyclohexylcyclo-hexane 1.9y of 1,3-dione in 20ml was dissolved in ethanol, 1f of ethoxyamine was added under stirring, and the mixture was allowed to react at room temperature for 5 hours.

The reaction solution was poured into ice water, the liberated oil was extracted with chloroform, the chloroform layer was washed with diluted hydrochloric acid, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to 1.5V.
The desired compound was obtained as a colorless oil.

n♂1.5318 Example 3 2-(1-allyloxyaminobutylidene)-5-cyclopropylcyclohexane-1,3-dione (compound number 5) 5-cyclopropyl-2-butyrylcyclohexane-1,3 -Dione 2.2y was dissolved in 20 ml of ethanol, and 0.9 ml of allyloxyamine was added with stirring, followed by reaction at room temperature for 5 hours.

The reaction solution was poured into ice water, the liberated oil was extracted with chloroform, the chloroform layer was washed with dilute hydrochloric acid, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to give 2.3 fI.
The desired compound was obtained as a colorless oil. Nrl. 5258 Reference Example 2-(N-allyloxyacetimidoyl)-5-cyclohexyl-3-benzoyloxy-2-cyclohexen-1-one 2-(1-allyloxyaminoethylidene)-
5-cyclohexylcyclohexane-1,3-dione 1
．． 2y was dissolved in 30 ml of acetone, 3 ml of 10% aqueous sodium chloride solution was added thereto, and then 0.6f of benzoyl chloride was added dropwise with stirring, and the mixture was allowed to react at room temperature for 3 hours.

The reaction mixture was poured into ice water, and the liberated oil was extracted with chloroform. The chloroform layer was washed with a 1% aqueous sodium hydroxide solution, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a colorless oil with a concentration of 0.9%. The desired compound was obtained. About n.
51.5420 Next, representative compounds of the present invention are shown in Table 1.

The herbicide of the present invention contains one or more of the compounds represented by the general formula [1] as an active ingredient, and is used in the same form as a conventional herbicide.

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, granule, or the like. Examples of solid carriers include talc, bentonite, clay, diatomaceous material, etc., and examples of liquid carriers include water, alcohol, benzene, xylene, kerosene, mineral oil, cyclohexane,
Cyclohexanone, dimethylformamide, etc. are used. 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 described above, but for example, in a wettable powder, it is 5 to 80%, preferably 10 to 60%:
in emulsions 5-70%, preferably 20-60%;
In granules, 0.5-30%, preferably 1-10%
The concentration of is used.

The wettable powders and emulsions obtained in this way are diluted with water to a predetermined concentration to form a suspension or emulsion, and the granules are sprayed or mixed into the soil before the germination of weeds, or used to weed. After germination, the foliage is sprayed.

When actually applying the herbicide of the present invention, an appropriate amount of 10y or more, preferably 25y or more of the active ingredient is applied per 10ares. 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 petanal, 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 4 Wettable powder Compound No. 2 (to) parts Talc 21 parts White carbon 41 parts*1 Sodium alkyl sulfate 8 parts or more were uniformly mixed and finely ground to obtain a wettable powder containing 30% of the active ingredient.

Example 5 Emulsion Compound No. 4 Ikube Xylene
35 parts dimethylformamide 15 parts Polyoxyethylene phenyl ether At least w parts were mixed and dissolved to obtain an emulsion containing 40% of the active ingredient.

Example 6 Granule Compound No. 45 parts Talc Habe Clay
4 田■ Bentonite
1 Sodium alkyl sulfate
After uniformly mixing 7 parts or more and pulverizing it finely, it was granulated into granules with a diameter of 0.5 to 10 TIOn to obtain granules containing 5% of the active ingredient.

Next, test examples regarding the effect of the herbicide of the present invention will be shown. Test Example 1 A pad of 10×10C7n was filled with soil, and on the surface layer were sown crabgrass, oat, pigweed, and goldenrod, and the seeds were grown in a greenhouse.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 is a cycloalkyl group having 3 to 6 carbon atoms,
R_2 represents a lower alkyl group, and R_3 represents a lower alkyl group or a lower alkenyl group. ). 2. The compound according to claim 1, wherein R_1 is a cyclohexyl group and R_2 is an ethyl group or a propyl group. 3. The compound according to claim 2, wherein R_3 is an ethyl group or an allyl group. 4 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 is a cycloalkyl group with 3 to 6 carbon atoms,
R_2 represents a lower alkyl group. ) is a general formula characterized by reacting a lower alkoxyamine or lower alkenyloxyamine with a compound represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 and R_2 are the same as those defined above. R_3 represents a lower alkyl group or a lower alkenyl group. 5 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 is a cycloalkyl group with 3 to 6 carbon atoms,
R_2 represents a lower alkyl group, and R_3 represents a lower alkyl group or a lower alkenyl group. ) A herbicide characterized by containing a compound represented by: 6. The herbicide according to claim 5, wherein R_1 is a cyclohexyl group and R_2 is an ethyl group or a propyl group. 7. The herbicide according to claim 6, wherein R_3 is an ethyl group or an allyl group.