JPS58164543A - Cyclohexane derivative, its preparation and plant growth regulator containing the same - Google Patents

Abstract

NEW MATERIAL:The titled compound of formulaI(R is H, alkyl, alkylthioalkyl, phenyl, substituted phenyl; R1 is alkyl, benzyl, substituted benzyl, phenethyl, phenoxymethyl, 2-thienylmethyl, alkoxymethyl, alkylthiomethyl). EXAMPLE:2-Methylcarboxyl-5-ethoxycarbonyl-cyclohexane-1,3-dione. USE:Plant growth regulator: it mainly suppresses growth, however, further shows promotion of rooting, reduction in lodging, promotion of lateral bud generation, green holding in buds and leaves, promotion or retardation of flowering, stimulation of heat generation in seeds. PREPARATION:The reaction of a compound of formula II (M is alkali metal) or formula III with an acid chloride of formula IV in water and/or an organic solvent in the presence or absence of a base to give a compound of formula V, then the rearrangement of the product is effected in a solvent in the presence of a catalyst to give the compound of formulaI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to cyclohexane derivatives, processes for their preparation and uses thereof, and more particularly.

10 (Formula CLR is a hydrogen atom, an alkyl group, an alkylthioalkyl group, a phenyl group, or a substituted 7□nyl group).

R3 is an alkyl group, a benzyl group, or a km pencil group.

Cyclohexane fermentation conductor represented by @) representing a methyl group, alkoxymethyl group, or alkylthiomethyl group, its production method, and a plant growth regulator characterized by containing the same as an active ingredient. Adjustment with substances. Conventionally, in so-called chemical controls, maleic acid hydrazide (MW), N,N-dimethylaminosuccinic acid amide (B-nine), or 2-chloroethyltrimethylammonium chloride (000) has been used to inhibit plant growth. It has been used to suppress the germination of buds and to prevent lodging, but these are all applicable situations.

Not only were there restrictions on the plants to which it could be applied and when it could be applied, but it also had a number of drawbacks, such as unstable growth, phytotoxicity, and high price. is the result of extensive research to eliminate the drawbacks of these previously used **tone 11 agents.

The compound wisdom represented by the above general formula (1), *Growth of seeds 1llI! It has been found that the present invention has the following effect.

Compounds of the present invention represented by general formula (I) - Compound numbers exemplified in Table 1 are referred to in the following description.

The compound of the present invention can be produced, for example, as follows.

(In the formula, R and R1 have the same meanings as above, and 2M represents an alkali metal atom.) That is, Ijll represents the reaction between the compound represented by 0 and a base in the presence of a solvent. 2! Or solvent I! lI
It can be produced by reacting 1 to 1 for 10i1@ in a temperature range of 1. Examples of the base include sodium methylate, sodium ethylate, sodium hydride, potassium tertiary butoxide, etc., and examples of the solvent include methanol, ethanol, benzene, toluene, and xylene.

Examples include N,N-dimethylformamide, dimethyl sulfoxide, and dimethyl cellosolve.
It can be produced by acid precipitation with an acid such as hydrochloric acid.

In the presence or absence of (b) or 4', acid chloride and ty-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 It can be produced by reacting for 10 minutes to 7 hours at room temperature or below.

The base here can be arbitrarily selected from 9 bases commonly used in dehydrogenation reactions. Examples of such substances include trimethylaone, triethylaone, and diethylaion.

Examples of organic bases such as dimethyl hydroxide, pyridine organic bases, sodium hydroxide, and inorganic bases with hydration power IJ 1>5 can be mentioned. , organic solvents such as chloroform, carbon tetrachloride, N,N-dimethylformamide, dimethyl sulfoxide, and methyl selon, and/or water. l-Picoline is considered to have phase transfer catalytic action. The compound of the present invention can be produced by reacting (1) in the presence of a catalyst and a solvent at a temperature between room temperature and the boiling point of the solvent for 1 to 10 hours.

Examples of the catalyst here include 4-N,N-dimethylaminopyridine and 4-M,N-diethylaminopyridine.

Pyridine derivatives such as 4-pyrrolidinobiridine,
Alternatively, N-alkyl, such as N-methyliodazole and N-ethylimidazole, can include dazole derivatives. The compound of the present invention may have the tautomeric structural formula shown below.Next, examples of the method for producing the compound of the present invention will be shown.

Example 1 Method for producing compound 3 Ethanol 150+a containing sodium 3.4 f t-
31f of diethyl acetonylsuccinate was added dropwise to the solution over about 1 hour while stirring at room temperature. Boil for another 2 hours! P.I.
After refluxing, the mixture was returned to room temperature and ethanol was distilled off under reduced pressure.
Add 100% toluene, 5Qm of ice-cold water, and 5t of l-picoline α to the brown candy-like substance and press ff.
Butyryl chloride 15F was added dropwise at room temperature over about 2 hours. After further stirring for 30 minutes, the toluene layer was separated, washed with water, and dried.
- 0.8f of N,N-dimethylminopyridine was added and heated at 80 to 90°C for 3 hours without stirring. After completion, toluene was distilled off under reduced pressure and separated and purified using silica gel column chromatography (Pensen M@) to obtain the target product 19.5 f (defeated army 5
5.9) Compounds 12 and 4 to 44 can also be produced in the same manner as in Example 1.

Example: Production method of compound 26 5-ethoxysulfonyl-cyclohexane-dione 2.1f was dissolved in dichloromethane 2011J, triethylamine t7F was added, and n-valeryl chloride t9f was added dropwise over 30 minutes with stirring. . After stirring for 3 hours, the two reaction solutions were washed with water, and the organic layer was dried and condensed.

The obtained liquid was dissolved in toluene 201, and 4-M, M
- after addition of dimethylaminopyridine α6f.

The reaction was completed by heating at 80-90°C for 4-5 hours. After removing toluene under reduced pressure, it was separated and purified using silica gel column chromatography (developed with benzene) to obtain the target product 22F (defeated army 7t 91
1) was obtained. Compounds 1 to 25 and 27 to
44 can also be manufactured. General formula [! ] The plant growth regulating action of the compound of the present invention is mainly a growth-inhibiting action, but is not limited to this, and may be affected by the application, method of application, timing of application, and dosage. By changing Gongon no Dan - Growth 1. Enriching effect can be expressed. For example, rooting promotion effect, growth reduction effect, lateral bud generation promotion effect 2. Rooting promotion effect, stem and leaf green keeping effect, flowering promotion or delay effect 2. Effect on promoting fruit set. 9. Effect on promoting ripening of seeds.

It has the effect of increasing resistance to temperature disturbances, herbicides, etc., and resistance to diseases, but these effects of controlling plant growth are not necessarily expressed at the same time.

By applying the compound of the present invention to the stems and leaves of plants, it suppresses the interpartial elongation of rice, wheat, corn, etc.
It can prevent or reduce lodging, and by applying it when raising seedlings of paddy rice and soybean crops, it can improve fh quality and improve rooting after transplanting and resistance to low humidity damage. It is possible to create 6 healthy bacteria.

In addition, by applying it to the stems and leaves of rice, wheat, etc. during the growing season, it shortens the length of the upper leaf blade and improves the three-dimensional arrangement of the leaf blade, resulting in a light utilization efficiency of i%. The ripening rate is improved and the grain yield can be increased.

moreover,! When growing indoors or in greenhouses, high temperatures 9 and lack of sunlight can also cause the growth of red flowers and other garden crops.
This can be inhibited by the IIWI compound of the present invention.

The ability of the compounds of the present invention to regulate plant growth is extremely useful not only in agriculture and horticulture, but also in controlling the growth of cuttings in non-cultivable lands. ! ? By applying 7 to lawns in parks, golf courses, airports, river slopes, undergrowth in orchards, and pastures in pasturelands, it suppresses plant growth and overgrowth, reducing the number of mowings. It can reduce the amount of water and make the mowing process easier. In addition, when applied sequentially to the lawn, it can also promote the development of lateral buds and increase the growth density of the lawn.

When using the plant medium length 1IiI preparation of the present invention, the compound of the present invention may be used alone, or it may be mixed with a carrier, a surfactant, a dispersant, a m-adjuvant, etc., to form a wettable powder, an emulsion, a powder, a powder, etc. It is formulated into various forms such as pastes, diluted to an appropriate concentration and sprayed, or directly consumed.

Examples of formulations containing all the active ingredients of the compounds of the present invention are listed below, but the invention is not limited to these. In each formulation example, 2 parts are heavy wAt-O.Blend example 1 (hydrating agent) 10 parts of compound (1), 85 g of diatomaceous earth, 2 parts of sodium 7-methylmethane disulfonate, and 3 parts of sodium ligninsulfonate are uniformly added. Mix and grind to make a wettable powder.

Formulation example 2 (emulsion) Dissolved in 530 parts of compound α, 220 parts of cyclohexane, 11 parts of phosphoryl diethylene alkyl ether, 4Nk of rubenzenesulfone dicalcium in alcohol and 35 parts of methylnaphthalene. and remove the emulsion.

Formulation Example 3 (Granules) Compound Q: 15%, 2 parts of sodium salt of lauryl alcohol sulfur ester, 5 parts of sodium lignin sulfonate, 2 parts of dimethyl cellulose in carboxylic acid, and 8 parts of clay
6 pieces can be mixed and ground uniformly. 20 parts of water was added to 80 parts of this mixture and kneaded.

After processing into 14 to 32 mesh granules using an extrusion granulator.

Formulation Example 4 (Powder) 4 parts of compound +1, 5 parts of diatomaceous earth, and 91 parts of clay are uniformly mixed and pulverized to obtain a powder.

Formulation Example 5 (Paste) Compound M (915 parts, 1 part of xylene, 5 parts of polyethylene 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 depends on the crop to which it is applied and the time of application.

Although it varies depending on the application method etc., the active ingredient is Q per hectare, 01-50 & 9. Preferably α05 to 10 kg.

Next, the effects of the compounds of the present invention will be specifically explained using test examples.

Test Example 1 Growth Suppression Test on Paddy Rice A hydrating powder of the compound of the present invention prepared according to Formulation Example 1 was applied to paddy rice (product S+: Zeng-Fu) with the second leaf fully developed. The solution was diluted with water and sprayed on the foliage at a concentration of 100 In per hectare.

Drug processing day and processing 3M! Determine the stem and leaf length after i.

The inhibition rate was calculated according to the following formula. The suppression rate is rounded off to the nearest whole number and is shown in II numbers.The results are shown in the t*2 table.

× 100 Table 2 Test Example 2 Lawn Growth Suppression Test A hydrating agent of the present compound prepared in 1llIll according to Formulation Example 1 was applied to bentgrass (Product 11 = Seaside) and Japanese grass grass cut to the height of 2-. 100 (l) of water per hectare so that the ingredients are 1 to 97 ha,
& The leaves were sprayed.

The investigation was conducted in accordance with Test Example 1 5 weeks after the treatment.

The suppression rate was calculated @ The results are shown in section sti.

jll go! Germination-promoting fir of paddy rice (product 413 Zengnanfeng) was sown in a 0x60- rice seedling box, and after the St was excavated, it was watered from the top.

Thereafter, a predetermined amount of an emulsion of the compound of the present invention prepared according to Formulation Example 2 was diluted with water, and sprayed onto 100ml of clay bottles per box.

After the treatment, the plants were grown for 3 days in a 50°C chamber, and then left in a greenhouse. When the number of leaves in the untreated plot reached 2.5, the plant height, t# age, and dry weight of the stem, leaf, and root portions were measured. Also, after washing some of the seedlings, a! The seedlings were cut to a length of Yr2am and placed in a pot flooded with water at a 45 degree angle, and 10 days later, the rising angle of the fungus and the 1s green content of the second leaf were measured. The other values are percentages of the untreated area below the decimal point [&
! j14 as an integer of g15 people! From Table 4 shown in Table 1, it can be seen that the uninvented compound suppresses the elongation of m seedlings, promotes root growth, and promotes the establishment of paddy rice after transplanting.

No. 41F Test Example 4 Adviser Elongation Suppression Test on Paddy Rice 1/2000 Plants Wagnerpo, S-concentrated Paddy Rice (
Variety! (Kinnanfu) Planted 2 Yt plants and transplanted 5 plants.

On the 55th day after transplantation, an emulsion of the compound of the present invention was prepared in accordance with Formulation Example 2, diluted with water, and dropped into submerged water at a concentration of 1 kI4:1 per hectare of the active ingredient. Treatment 5+ About the culm length, S spacing length, and unit internodal type in the monthly bale - eat it, and calculate the percentage of the untreated plot as an integer rounded to the nearest whole number! Shown in I.

The 9 internodes are numbered 1st to 5th from higher order, and the unit internodal type indicates the dry weight per 1aa of 2goseki. 132 0 Applicant Kumiai Chemical Industry Co., Ltd. 1-4-26 Ikenohata, Taito-ku, Tokyo

Claims (1)

[Claims] (In the formula, R is a hydrogen atom, an alkyl group, an alkylthioalkyl group,), a nyl group, or an enyl group. Group, Fu, Tsukidimethyl group. A cyclohexane derivative represented by ◎) representing a 2-chenylmethyl group, an alkylthiomethyl group, or an alkylthiomethyl group. (In the formula, 11!Hydrogen, an alkyl group, an alkylthioalkyl group, an aunyl group, or a substituted), a nyl group, and 9M is an atom of an atom. Middle RI is an alkyl group, a benzyl group, a benzyl group substituted with 6), a netyl group, and a 71-dimethyl group. A compound represented by 0 ) representing a 2-chenylmethyl group, alkyldimethyl group or an alkylthiomethyl group and [,
After producing a compound which is reacted with the general formula (wherein R and R have the same meanings as above) by reacting in water or/and IIIA solvent: in the presence or absence of a base, It is characterized by carrying out the transfer in the presence of a catalyst. General formula (in the formula,
R and R have the same meanings as above. ) 〇(3) General formula (wherein, i is a Mizuki atom, an alkyl group, an alkylthioalkyl group, a 7.nyl group or a substituted), a nyl group is l R1 is an alkyl group, a pencil i , **benzyl group, fluorine, netyl group, 7□tsukidimethyl group. A plant growth-1I agent containing a cyclohexane fermentation conductor represented by a 2-chenylmethyl group, an alkoxymethyl group, or an alkylthiomethyl group (T) as an active ingredient.