JPH03209362A - 4,4,5-trimethyl-2-(2,3-dimethyl-4-methylsulfonylbenzoly) cyclohexane-1,3-dione, production thereof and use as herbicide - Google Patents

Abstract

NEW MATERIAL:4,4,5-Trimethyl-2-(2,3-dimethyl-4-methylsulfonylbenzoyl) cyclohexane-1,3-dione shown by formula I. USE:Useful as a herbicide having excellent selectivity to crops. An application amount can be reduced by blending the herbicide with a well-known herbicide, the blending has high synergistic effects and brings about save of labor and high effects. PREPARATION:4,4,5-Trimethylcyclohexane-1,3-dione shown by formula II is reacted with 2,3-dimethyl-4-methylsulfonylbenzoyl chloride shown by formula III in the presence of a base. Then the prepared reaction product shown by formula IV or formula IV' is subjected to rearrangement reaction in the presence of a base and a cyanide compound to give a compound shown by formula I. Potassium cyanide is preferable as the cyanide compound. The rearrangement reaction is preferably carried out 20-40 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention provides 4,4.!'l-trimethyl-2-(23-
dimethyl-4-methylsulfonylbenzoyl)cyclohexane-1,3-sion (hereinafter referred to as the compound of the present invention)
, its production method and use as a herbicide. [Prior Art] The compound of the present invention is included in the claims of JP-A-61-155347, but is not mentioned at all in the detailed description of the invention.

[Problem to be solved by the invention]

The object of the present invention is to provide a herbicide with excellent herbicidal efficacy and good selectivity with crops. (!l 11
[Means for solving the problem] The compound of the present invention can be produced by the following two-step reaction. [Iff] [1v] [rV] []] The bases used in step (a) are K O H, N
These include alkali metal hydroxides such as aOH, alkaline earth metal hydroxides, tri(C1-Ch)alkylamines, pyridine, sodium carbonate, sodium phosphate, etc. Compound (Iff) is used with 1 molar or excess base.

As the solvent used, water, methylene chloride, toluene, ethyl acetate, DM, THF, dimethoxyethane, acetonitrile, etc. are used.

The anti-core mixture is stirred at O'C to 50°C until the reaction is complete. The reconstituted mixture is processed in a conventional manner.

In step (b), 1 mol of compound (IV) is added to 1 to 4
mol of base, preferably 2 mol of base and from 0.01 mol to more than 0.5 mol, preferably 0. React with 1 mole of cyanide. The base used here is the step (
Any of the bases listed under a) can be used.

Further, as the cyanide compound, potassium cyanide, acetone cyanohydrin, hydrogen cyanide, etc. are used.

In addition, by adding a small amount of a phase transfer catalyst such as Krasun ether, the reaction can be completed in a shorter time.

The rearrangement is carried out by stirring the reaction mixture at a temperature below 80°C, preferably between 20 and 40°C, until the reaction is complete.

The catalysts used are I,2-dichloroethane, toluene, acetonitrile, methylene chloride, ethyl acetate, DMF.
, methyl isobutyl titone, THF1 dimethoxyethane, etc. The compound [■] which is the original #1 compound and the compound of the present invention each have the following mutability. In addition, in the following structural formula, the substituent on the benzene ring is omitted.

(II) ['') [''] ↓1 ↓↑ After the reaction is completed, the desired product can be obtained by carrying out the usual treatment. The structure of the compound of the present invention is I
Determined from R, NMI<, MASS, etc.

[Example 1 Compound j Next, the compound of the present invention will be explained in detail with reference to Examples.

Example 1 4,5-trimethyl-2-(2,3-dimethyl-4-
Methylsulfonylbenzoyl)cyclohegyusan-1.3
-dione 4,5-trimethylcyclohexane-1,3-sion I
g (6.5 mmol) triethylamine (TEA), 0.8 g (7.2
mmol) then 1.6 g (6.5 mmol) of 2.3-dimethyl=4-methylsulfonylhene,zoyl chloride
of methylene chloride fPi 5 an was added at room temperature.
The reaction solution was stirred at room temperature for 1 hour, washed with water, and then washed with M
The mixture was dried with g S O a and the solvent was removed under reduced pressure. (Dissolve the distillate in 30 #l of acetonitrile, then add 0.72 g (7.1 mmol) of triethylamine and KC
0.23 g (3.5 mmol) of N was added and stirred at room temperature for 10 hours. After the reaction, the solvent was distilled off under reduced pressure,
The obtained residue was dissolved in a mixed solution of chloroform and dilute hydrochloric acid. Separate the chloroform layer, extract the chloroform layer with dilute alkaline water, then acidify the aqueous layer with dilute hydrochloric acid,
Extracted with chloroform. The chloroform layer was washed with water, then dried with MgSO4, and the solvent was distilled off under reduced pressure. The obtained residue was crystallized with methanol to obtain 1.3 g of the desired product. Yield 55%, mp134~6°C0 cg! 1,000-step herbicide for solving JAs] The herbicide of the present invention contains one or more of the compounds represented by the above formula (1) as an active ingredient, and has a form similar to that of ordinary agricultural straw. That is, an effective compound is generally used by mixing an appropriate amount with the body and formulating it in the form of a permanent agent, emulsion, granule, aqueous solution, flowable agent, or the like. Solid 11! Examples of liquid substances include talc, white carbon (silica), hentonite, clay, and diatomaceous substances. Examples of liquid substances include water, alcohol, henzhen, xylene, kerosene, mineral oil,
Cyclohexane, cyclohexanone, dimethylformamide, etc. are used. Surfactants can be added to these preparations if necessary to obtain a uniform and stable form. The concentration of the active ingredient in the herbicide of the present invention varies depending on the form of the drug mentioned above, but for example, in an aqueous phase preparation, it is 5 to 70%, preferably 10 to 30%; In emulsions, 3-70%, preferably 5-20%; in emulsions, 0.01-30%.
%, preferably a concentration of 0.05 to 10% is used.

The permanent agent or emulsion thus obtained is diluted with water to a predetermined concentration to form a suspension or emulsion, and the granules are sprayed or mixed onto the soil before or after weed germination. Ru. In actual weeding according to the present invention, an equivalent amount of 1 g or more of the effective ingredient is applied per 10 ares.

In addition, the herbicide of the present invention can be used with known bactericides, insecticides, acaricides,
It can also be applied in combination with herbicides, plant growth regulators, etc. In particular, by applying it in combination with a herbicide, it is possible to reduce the application efficacy. Moreover, it not only brings about labor saving, but also high effects can be expected due to the synergistic action of the mixed drugs.

In that case,? Combination with I number of known herbicides is also possible. Examples of agents suitable for mixed application with the herbicide of the present invention include carbamate herbicides such as hentiocarb, molinate, and dimepiverate, thiocarbamate herbicides, acid amide herbicides such as butachlor, pretilachlor, and mefenacet, and chlormethoxynil and bifenox. Diphenyl ether herbicides, triazine herbicides such as atrazine and cyanazine, sulfonylurea herbicides such as chlorsulfuron and sulfometuron-methyl, M
Phenoxyalkanecarboxylic acid herbicides such as CP, MCPB, phenoxyphenoxybrivionic acid herbicides such as diclofop-methyl, biridyloxyphenoxybrobionic acid herbicides such as fluazifosobutyl, penzoylpro Penzoyla ξ nobrobionic acid thread herbicides such as nbuethyl and furanprop ethyl; others include biverofos, Daimeron, Benxone, Guifenzocort,
Naproanilide, HW-52 (4-ethoxymethoxyhenz-2,3-dichloroanilide), KNW-241
Cl- (3-methylphenyl)-5-phenyl I
F{-1,2,4-triazole-3-carpoxamide], quinclorac (3,7-dichloro-8-quinolinecarboxylic acid), and cyclohexanedione herbicides such as setoxydim and alloxydimousodium. It will be done. Also, these silks are mixed with vegetable ura and oil.
It is also possible to add condensates.

[Example 1 herbicide]

Next, some formulation 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 over a wide range.

Example 2 Water phase agent Compound of the present invention 20 parts White carbon (silica) 2 parts Diatomaceous earth
70 parts alkyl sulfate soda
2 parts Sodium ligninsulfonate
More than 6 parts were uniformly mixed and finely ground to obtain a permanent agent with an effective precept of 20%.

Example 3 Emulsion Compound of the present invention 20 parts xylene 55 parts dimethylformamide 15 parts calcium alkylbenzenesulfonate 4 parts polyoxyethylene alkylphenyl ether 6 parts or more were mixed and dissolved to obtain an emulsion with an effective content of 20%.

(Effects of the Invention) Next, test examples regarding the effects of the herbicide of the present invention will be shown. Test Example 1 Soil was packed in a 20M pot, and cuttings of crabgrass, A. japonica, Ichibi, Inubu, and Cyperus were sown on the surface layer, and after being lightly covered, they were grown in a greenhouse. When each weed grew to a height of 5 to 10 cm, 125 and 63 ppm chemical solutions prepared by diluting an emulsion of each test compound with water were added at a ratio of 1001/I O a (12.0 ppm per 10 a).
(equivalent to 5 and 6.3 g) was used to destroy the stems and leaves of weeds using a small sprayer. Three weeks later, the weed-killing effect was investigated according to the following investigation criteria, and the results are shown in Table 1. Survey criteria: Weed killing rate: 0% 20-29% 40-49% 60-69% 80-99% 100% 1, 3, 5, 2 and 4, 4 and 6, 6 and 8, between 8 and 10 Showing clay.

Above-ground grass weight in untreated area - 015 fresh weeder on the ground in the treatment area Weed killing rate (%)・ XIOO Above-ground grass weight in untreated area No. 1 table Control compound: 4, 4, 6-trimethyl-2- (2-methyl-4 Methylsulfonylbenzoy ) cyclohexane-1, 3-Shion (Compound drug described in JP-A-61-155347)

Claims (3)

[Claims] (1) 4,4,5-trimethyl-2-(2,3-dimethyl-4-methylsulfonylbenzoyl)cyclohexane-1,3-dione. (2) 4,4,5-trimethylcyclohexane-1,3
-Dione and 2,3-dimethyl-4-methylsulfonylbenzoyl chloride are reacted in the presence of a base, and the resulting product is subjected to a rearrangement reaction in the presence of a base and a cyanide compound. A method for producing the compound according to item 1. (3) A herbicide characterized by containing the compound according to claim 1 as an active ingredient.