JPH024217B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel cyclohexane derivative, its preparation method and its use, and more specifically, the general formula: (In the formula, R is a hydrogen atom, an alkyl group, an alkylthioalkyl group, a phenyl group, or a substituted phenyl group, and R ₁ is an alkyl group, a benzyl group, a substituted benzyl group, a phenethyl group, a phenoxymethyl group, a 2-
Indicates a thienylmethyl group, an alkoxymethyl group, or an alkylthiomethyl group. The present invention relates to a cyclohexane derivative represented by (), a method for producing the same, and a plant growth regulator containing the same as an active ingredient. Conventionally, in so-called chemical control, which regulates plant growth with chemical substances, maleic acid hydraside (MH), N,N-dimethylaminosuccinic acid amide (B-nine), or 2-chloroethyltrimethylammonium chloride (CCC) has been used. etc. have been used to suppress plant growth, suppress the germination of lateral buds, and prevent lodging, etc., but all of these methods are not only limited in terms of application situations, applicable plants, and application times, but also have unstable effects. However, they had various disadvantages such as chemical damage and high cost. As a result of intensive research to eliminate the drawbacks of these conventionally used plant growth regulators, the present inventors have found that the compound represented by the above general formula () has an excellent plant growth regulating effect. Heading: This completes the invention. Compounds represented by the general formula () of the present invention are illustrated in Table 1. In addition, the compound number will be referred to in the following description.

【table】

【table】

[Table] The compound of the present invention can be produced, for example, as follows. (In the formula, R and R ₁ have the same meanings as above,
M represents an alkali metal atom. ) That is, [ ] can be produced by reacting the compound shown in [ ] with a base in the presence of a solvent at a temperature ranging from room temperature to the boiling point of the solvent for 1 to 10 hours. Here, as a base,
sodium methylate, sodium ethylate,
Examples of the solvent include sodium hydride and potassium tert-butoxide, and examples of the solvent include methanol, ethanol, benzene, toluene, xylene, N,N-dimethylformamide, dimethyl sulfoxide, and dimethyl cellosolve. [] can be produced by treating [] with an acid such as hydrochloric acid. [] is [] or [] and acid chloride in the presence or absence of γ-picoline, in the presence or absence of a base, in the presence of a solvent, in the temperature range from -20 ° C. to the boiling point of the solvent, Preferably below room temperature 10
It can be produced by reacting for minutes to seven hours. The base here can be arbitrarily selected from bases commonly used in dehydrohalogenation reactions. Examples of such substances include organic bases such as trimethylamine, triethylamine, diethylamine, dimethylamine, and pyridine, and inorganic bases such as sodium hydroxide and potassium hydroxide. Examples of solvents include toluene, benzene, and xylene. , dichloromethane,
Examples include organic solvents such as 1,2-dichloroethane, chloroform, carbon tetrachloride, N,N-dimethylformamide, dimethyl sulfoxide, and methyl cellosolve, and/or water. γ-Picoline is considered to have a phase transfer catalytic action. The compound of the present invention can be produced by reacting [] in the presence of a catalyst and a solvent at a temperature ranging from room temperature to the boiling point of the solvent for 1 to 10 hours. Examples of the catalyst here include pyridine derivatives such as 4-N,N-dimethylaminopyridine, 4-N,N-diethylaminopyridine, and 4-pyrrolidinoaminopyridine, or N- such as N-methylimidazole and N-ethylimidazole. Mention may be made of alkylimidazole derivatives. The compound of the present invention can also be produced without isolating the aforementioned intermediate [], [] or []. The compound of the present invention can have the tautomeric structural formula shown below. Next, examples of methods for producing the compounds of the present invention will be shown. Example 1 Method for producing compound 15 Add diethyl acetonyl succinate to 150 ml of ethanol solution containing 3.4 g of sodium while stirring at room temperature.
31 g was added dropwise over about 1 hour. After further boiling and refluxing for 2 hours, the temperature was returned to room temperature and ethanol was distilled off under reduced pressure.
100 ml of toluene, 50 ml of ice-cold water, and 0.3 g of γ-picoline were added to the obtained brown candy-like substance, and the mixture was stirred.
-15 g of butyryl chloride was added dropwise at room temperature over about 2 hours. After stirring for an additional 30 minutes, the toluene layer was separated, washed with water, and dried to form 4-N,N-dimethylaminopyridine.
0.8 g was added and heated at 80 to 90° C. for 3 hours while stirring. After completion, toluene was distilled off under reduced pressure and separated and purified using silica gel column chromatography (developed with benzene).
19.5 g (yield 55.9%) of the target product was obtained. Compounds 1-14 and 16-44 in the same manner as in Example 1
can also be manufactured. Example 2 Method for producing compound 26 5-ethoxycarbonyl-cyclohexane-
After dissolving 2.1 g of 1,3-dione in 20 ml of dichloromethane and adding 1.7 g of triethylamine, 1.9 g of n-valeryl chloride was added dropwise over 30 minutes with stirring. After stirring for 3 hours, the reaction solution was washed with water, and the organic layer was dried and concentrated. The obtained liquid was dissolved in 20 ml of toluene and 4-
After adding 0.6 g of N,N-dimethylaminopyridine, the mixture was heated at 80 to 90°C for 4 to 5 hours to complete the reaction. After removing toluene under reduced pressure, it was separated and purified using silica gel column chromatography (developed with benzene) to obtain 2.2 g of the target product.
(yield 71.9%). Compounds 1-25 and 27-
44 can also be manufactured. The plant growth regulating effect of the compound of the present invention represented by the general formula [] is mainly a growth-inhibiting effect, but is not limited to this, and the plant growth control effect can be changed by changing the applied plants, application method, application timing, and applied dosage. Various plant growth regulating effects are expressed by For example, rooting promotion effect, lodging reduction effect, lateral bud development promotion effect, rooting promotion effect, stem and leaf green keeping effect, flowering promotion or delay effect, fruit set promotion effect, seed ripening promotion effect, temperature disturbance and herbicide. It has the effect of increasing resistance to drug damage or disease damage due to
These various plant growth regulating effects are not necessarily expressed simultaneously. By applying the compound of the present invention to the foliage or soil of plants, it is possible to suppress the elongation of internodes of rice, wheat, corn, etc., and prevent or reduce lodging. By applying it, it is possible to improve seedling quality and produce healthy seedlings with excellent rooting after transplantation and resistance to low-temperature damage. In addition, by applying it to the stems and leaves of rice, wheat, etc. during the growing season, it shortens the upper leaf height and improves the three-dimensional arrangement of the leaf blades, increasing the light utilization efficiency and improving the ripening rate. Yield can be increased. Furthermore, the elongation of flowers, horticultural crops, etc., which occurs due to high temperatures and lack of sunlight in greenhouses, plastic greenhouses, etc., can also be suppressed by applying the compounds of the present invention. The various plant growth regulating effects of the compounds of the present invention are extremely useful not only in agriculture and horticulture, but also in controlling the growth of plants in non-agricultural lands. For example, by applying the compound of the present invention to lawns such as parks, sports fields, golf courses, airports, and river slopes, undergrowth in orchards, or pastures, the growth and overgrowth of plants can be suppressed. It can reduce the number of times of mowing and make mowing work easier. Furthermore, when applied to lawns, it can promote the development of lateral buds and increase the growth density of lawns. When using the plant growth regulator of the present invention, the compound of the present invention alone or in combination with carriers, surfactants, dispersants, adjuvants, etc., can be used to form wettable powders, emulsions, granules, and powders. It can be formulated into various forms such as pastes, diluted to an appropriate concentration and sprayed, or applied directly. Formulations containing the compound of the present invention as an active ingredient are listed below as formulation examples, but the present invention is not limited to this range. In each formulation example, parts indicate parts by weight. Formulation Example 1 (Wettable powder) 10 parts of Compound 1, 85 parts of diatomaceous earth, 2 parts of sodium dinaphthylmethane disulfonate, and 3 parts of sodium ligninsulfonate are uniformly mixed and pulverized to prepare a wettable powder. Formulation Example 2 (Emulsion) 30 parts of Compound 15, 20 parts of cyclohexanone, 11 parts of polyoxyethylene alkylaryl ether, 4 parts of calcium alkylbenzenesulfonate, and 35 parts of methylnaphthalene are uniformly dissolved to prepare an emulsion. Formulation Example 3 (Granules) 5 parts of Compound 13, 2 parts of sodium salt of lauryl alcohol sulfate, 5 parts of sodium lignin sulfonate, 2 parts of carboxymethylcellulose and 86 parts of clay are uniformly mixed and ground. 20 parts of water are added to 80 parts of this mixture and kneaded, processed into 14 to 32 mesh granules using an extrusion granulator, and dried to form granules. Formulation Example 4 (Powder) 4 parts of Compound 16, 5 parts of diatomaceous earth, and 91 parts of clay are uniformly mixed and ground to obtain a powder. Formulation Example 5 (Paste) 5 parts of Compound 9, 1 part of xylene, 5 parts of polyoxyethylene sorbitan monolaurate, and 89 parts of white petrolatum are uniformly mixed to form a paste. The application amount of the compound of the present invention varies depending on the crops to which it is applied, the time of application, the application method, etc., but the amount of active ingredient per hectare is 0.01 to 50 kg, preferably 0.05 to 10 kg.
It is. Next, the effects of the compounds of the present invention will be specifically explained using test examples. Test Example 1 Rice growth inhibition test Paddy rice with fully expanded second leaves (variety: Kinnanpu)
A wettable powder of the compound of the present invention prepared according to Formulation Example 1 was diluted with 1,000 g of water per hectare so that the active ingredient was 1 kg/ha, and sprayed on the foliage. The length of stems and leaves was measured on the day of chemical treatment and 3 weeks after treatment, and the inhibition rate was calculated according to the following formula. The inhibition rate was rounded to the nearest whole number and shown as an integer. The results are shown in Table 2.

【table】

[Table] 〓 Ward stem and leaf length Ward stem and leaf length〓
Test Example 2 Lawn Growth Suppression Test Bentgrass (variety:
A hydrating agent of the compound of the present invention prepared according to Formulation Example 1 was diluted with 1,000 g of water per hectare so that the active ingredient was 1 kg/ha, and sprayed on the leaves and foliage. The investigation was conducted according to Test Example 1 after 5 weeks of treatment.
The inhibition rate was calculated. The results are shown in Table 3.

[Table] Test Example 3 Seedling quality improvement test for paddy rice box seedlings In a 30 x 60 cm paddy rice seedling box, sprouting rice of paddy rice (variety: Kinnanfu) was sown, covered with soil, and then watered from above. Thereafter, a predetermined amount of the emulsion of the compound of the present invention prepared according to Formulation Example 2 was diluted with water, and 20ml per box was prepared.
Sprayed on the soil surface. After treatment, they were grown in a thermostatic chamber at 30°C for 3 days, and then electrostatically placed in a greenhouse. When the leaf age of the untreated plot reached 2.5 leaves, the plant height, leaf age, and dry weight of the stem, leaf, and root portions were measured. In addition, some of the seedlings were washed with water, the roots were cut to a length of 2 cm, and the seedlings were placed in a pot filled with water to a depth of 2 cm at a 45 degree angle. The content was measured.
The rising angle is a real value, and the other values are shown in Table 4 as a percentage of the untreated plot, rounded to the nearest whole number. Table 4 shows that the compounds of the present invention have the effect of suppressing the elongation of box seedlings, promoting root growth, and promoting the establishment of paddy rice after transplantation.

[Table] Test Example 4 Paddy rice internodal elongation inhibition test 1/2000 are Three-leaf stage paddy rice (variety: Kinnanfu) was transplanted into a Wagner pot with two plants per plant, and 3 plants were added on the 35th day after transplanting. An emulsion of the compound of the present invention prepared according to Example 2 was diluted with water and dropped into submerged water so that the amount of active ingredient was 1 kg per hectare. Three months after the treatment, the culm length, internodal length, and unit internodal weight were investigated, and the percentages relative to the untreated plot are shown in Table 5 as integers rounded to the nearest whole number. Incidentally, the internodes are numbered 1 to 5 from the top, and the unit internodal weight indicates the dry weight per 1 cm of internodes.

【table】

Claims (1)

[Claims] 1. General formula (In the formula, R is a hydrogen atom, an alkyl group, an alkylthioalkyl group, a phenyl group, or a substituted phenyl group, and R ₁ is an alkyl group, a benzyl group, a substituted benzyl group, a phenethyl group, a phenoxymethyl group, a 2-
Indicates a thienylmethyl group, an alkoxymethyl group, or an alkylthiomethyl group. ) A cyclohexane derivative represented by 2 A compound represented by the general formula [Formula] or [Formula] (wherein R represents a hydrogen atom, an alkyl group, an alkylthioalkyl group, a phenyl group, or a substituted phenyl group, and M represents an alkali metal atom); general formula (In the formula, R ₁ is a hydrogen atom, benzyl group, substituted benzyl group, phenethyl group, phenoxymethyl group, 2
- Represents a thienylmethyl group, an alkoxymethyl group or an alkylthiomethyl group. ) in water and/or an organic solvent in the presence or absence of a base to form a compound represented by the general formula (In the formula, R and R ₁ have the same meanings as above.)
After producing a compound represented by the general formula, the compound is rearranged in the presence of a catalyst. (In the formula, R and R ₁ have the same meanings as above.)
A method for producing a cyclohexane derivative represented by 3 General formula (In the formula, R is a hydrogen atom, an alkyl group, an alkylthioalkyl group, a phenyl group, or a substituted phenyl group, and R ₁ is an alkyl group, a benzyl group, a substituted benzyl group, a phenethyl group, a phenoxymethyl group, a 2-
Indicates a thienylmethyl group, an alkoxymethyl group, or an alkylthiomethyl group. 1. A plant growth regulator comprising a cyclohexane derivative represented by ) as an active ingredient.