JPH02726A - Cyclohexenone derivative, production thereof and herbicide - Google Patents

Abstract

NEW MATERIAL:A cyclohexenone derivative expressed by formula I [X is halogen, hydroxy, nitro, cyano, alkyl, haloalkyl, haloalkenyl, etc., n is 0 or 1-5; X may be same or different when n is 2; Y is straight chain or branched lower alkylene; m is 0 or 1; R<1> is hydroxy, cyano, nitro, alkylcarbonyl, etc.; R<2> is halogen, alkyl, alkoxycarbonyl, haloalkenyl, etc.; l is 0 or 1-5 (R<2> may be same or different when l is >=2); R is H, alkylcarbonyl, arylcarbonylalkyl, etc., except that R<1> is furyl group which may have a substituent group when m is 0]. USE:Useful as a herbicide capable of exhibiting effects on weeds, such as large crabgrass or barnyardgrass, and showing selectivity for corn, etc. PREPARATION:A compound expressed by formula II and a compound expressed by formula III (Q is halogen) are used as starting raw materials to afford the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel cyclohexenone derivative, a method for producing the same, and a herbicide containing the derivative as an active ingredient.

[Conventional technology]

In the cultivation of agricultural and horticultural crops, many herbicides have come to be used to control weeds, which have traditionally required a great deal of labor. Because it causes chemical damage to crops and remains in the environment and contaminates it, there is a desire to develop a drug that is effective at lower doses and can be used safely.

Compounds similar to the compounds of the present invention are disclosed in JP-A-60-87238, JP-A-60-87239, JP-A-61-152642, JP-A-61-152649, JP-A-61-155347, and JP-A-61-155347. 62-123145 is known.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a herbicide that can be industrially advantageously synthesized, is highly effective with lower dosages, is highly safe, and has good selectivity with respect to crops.

[Means for solving problems]

The present invention is based on the general formula (1) [wherein X: halogen, hydroxy group, nitro group, cyano group, alkyl group, haloalkyl group, haloalkenyl group,
Alkoxy group, haloalkoxy group, haloalkenyloxy group, alkylthio group, haloalkylthio group, haloalkenylthio group, monoalkylamino group, dialkylamino group, alkoxydicarbonyl group, alkylcarbonylalkoxy group, alkylcarbonyl group, alkoxyamino group , alkylsulfonyl group, haloalkylsulfonyl group, alkoxycarbonylalkylthio group, alkoxycarbonylalkylsulfinyl group, alkoxycarbonylalkylsulfonyl group, phenyl group optionally having substituents neo, 1,2,3,4.5 (n is 2 or more, X may be the same or different;) Y: a straight chain or branched lower alkylene group m: O or I , a heterocyclic group which may have 210 groups, or Z-R'Z: oxygen, so+,
(k is 0.1 or 2), -N-S-5-R": Furkyl group, haloalkyl group, alkenyl group, alkynyl group, alkoxyalkyl group, alkylthioalkyl group, alkoxycarbonylalkyl group, having a substituent Phenyl group, aralkyl group, optionally substituted heterocyclic group R1: phenyl group I optionally have halogen, alkyl group, alkoxycarbonyl group, haloalkenyl group, IA group !, :0.t, 2, 3, 4.5 R when i is 2 or more
2 may be the same or different.) R: hydrogen, alkylcarbonyl group, arylcarbonylalkyl group, arylsulfonyl group, residue of an inorganic or organic base. However, when m-0, R1 has a substituent. (excluding optional furyl group), its production method, and herbicide.

The compound of the present invention exhibits high herbicidal activity in both soil and foliage treatments under field conditions, particularly in foliage spraying.
Crab grass, Cyperus japonica, Ichibi.

It also contains compounds that are highly effective against various field weeds such as grasshopper, and are selective for crops such as corn, wheat, and soybeans.

In addition, the compounds of the present invention have excellent herbicidal efficacy against weeds such as paddy field weeds such as field weeds, Japanese grasshopper, Japanese cypress, and firefly, and also include compounds that exhibit selectivity for rice.

Furthermore, the compounds of the present invention can be applied to control weeds in orchards, lawns, railroad tracks, vacant lots, etc.

The compound of the present invention can be produced by the following two-step reaction.

In the above formula, R', R", X, Y, n, m, I
! .

has the same meaning as above, Q is halogen, al step (
The bases used in a) are KOH, alkali metal hydroxides such as Na011, alkaline earth metal hydroxide tri(C+Cb alkyl)amines, pyridine, sodium carbonate, sodium phosphate, etc., each with 1 mol. Compound (If) and compound (I[l) are used together with 1 molar or excess base.

The solvent used is water, methylene chloride, toluene, ethyl acetate, dimethylformamide, TIIF, dimethoxyethane, acetonitrile, etc. The reaction mixture is stirred at O'C ~ 50 °C until the reaction is completed. The zero-reacted product is treated in a conventional manner.

In step (b), 1 mol of compound (IV,) is added to
4 moles of base, preferably 2 moles of base and 0.01
The reaction is carried out with mol to 0.5 mol or more, preferably 0.1 mol of a cyanide compound. 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.

Note that by adding a small amount of a phase transfer catalyst such as crown ether, the reaction can be completed in a shorter time.

The temperature at which the dislocation occurs is below 80°C, preferably between 20'C and 40°C.
The reaction mixture is stirred at °C until the reaction is complete. Solvents used include 1,2-dichloroethane, toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, methyl isobutyl ketone, THF, dimethoxyethane, and the like.

-a In the case of RH in the starting compound represented by formula (III) and the compound of the present invention, the following tautomerism exists. In addition, in the following structural formula, the substituents on the cyclohexene ring and benzene ring are omitted.

OHi at the H 1-position is converted into an OR group by a conventional method.

[Here, l1aj! is halogen, W is -cnzc.

:alkyl group) etc.] After the reaction is completed, the desired product can be obtained by carrying out a usual post-treatment. The structure of the compound of the present invention was determined from IR, NMR, MASS, etc.

[Example - Compound]

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

Example 5 - Synthesis of methoxyethyl-2-(2-nitro-4-chlorobenzoyl)cyclohexadione (Compound No. 11
6) 5-methoxyethylcyclohexane-1,3-sion 1
．． 7 g (0.01 mol) and 2.2 g (0.01 mol) of 2-nitro-4-chlorobenzoyl chloride were dissolved in 20 d of methylene chloride, and while stirring while cooling with ice water, 1.1 g (0.0109 mol) of triethylamine was dissolved. mol) was added. After returning to room temperature and stirring for 3 hours, the reaction solution was washed with water, and the organic layer was dried over magnesium sulfate. The solvent was distilled off to obtain an oily crude product. After adding 20 rnl of acetonitrile to this crude product and dissolving it, 1.1 g (0,0109 mol) of triethylamine, KC No. 06
g (0,00092 mol) and 1 day - crown-60
,02g was added and stirred at room temperature for 10 hours.After the reaction was completed, the solvent was distilled off, and 50g of ethyl acetate was added to the obtained oily substance.
ml and 10 ml of water were added and dissolved. The aqueous layer was made acidic using dilute hydrochloric acid.

The machine layer is diluted hydrochloric acid 10mj! It was washed twice, then washed with saturated brine, and dried over magnesium sulfate.

The solvent was distilled off, and the resulting crude product was purified using silica gel column chromatography (eluent: hexane-methylene chloride 1:
1) L, 1.9 g (yield 53.8%) of the oily target product was obtained. n D"1.5713 Representative examples of the compounds of the present invention, including the above examples, are shown in Table 1.

[Means for Solving the Problems - Herbicide] The herbicide of the present invention contains one or more of the compounds represented by the general formula (1) as an active ingredient, and has a form similar to that of ordinary agricultural chemicals. That is, the active ingredient compound is first mixed with a carrier in an appropriate amount and prepared in the form of a wettable powder, emulsion, granule, aqueous solution, flowable preparation, or the like. Examples of solid carriers include talc, white carbon, bentonite, clay, and diatomaceous materials, and examples of liquid carriers include water, alcohol, benzene, xylene, kerosene, mineral oil, cyclohexane, cyclohexanone, and dimethylformamide. 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 mentioned above, but for example, in a wettable powder, it is 5 to 70%, preferably 10 to 30%:
3 to 70% for emulsions, preferably 5 to 20%; 0.01 to 30% for double grains, preferably 0.05 to 20%;
A concentration of 10% is used.

The wettable powders and emulsions thus obtained are diluted with water to a predetermined concentration to form a suspension or emulsion, and the granules are treated with a cloth on the soil before or after weed germination. Or mixed treatment. When actually applying the herbicide of the present invention, an appropriate amount of 1 g or more of the active ingredient is applied per 10 ares.

In addition, the herbicide of the present invention is a known bactericide, insecticide, acaricide,
It can also be used in combination with herbicides, plant growth regulators, etc. In particular, when used in combination with herbicides, not only the amount of chemicals used can be reduced and labor savings can be achieved, but even higher effects can be expected due to the synergistic effects of the mixed chemicals. In that case, combinations with multiple known herbicides are also possible. Examples of drugs suitable for mixed use with the herbicide of the present invention include bentiocarb, molinate, MY-93 (S-(2°2-
dimethylbenzyl) 1-piperidine carbothioate]
Carbamate herbicides such as, thiocarbamate herbicides, acid amide herbicides such as butachlor, pretilachlor, mefenacet, diphenyl ether herbicides such as chromethoxynil and bifenox, triazine herbicides such as atrazine and cyanazine, chlorsulfuron, Sulfonylurea herbicides such as sulfometuron-methyl, phenoxyalkanecarboxylic acid herbicides such as MCPSMCPB, phenoxyphenoxypropionic acid herbicides such as diclofop-methyl, and pyridyloxyphenoxypropionic acid herbicides such as fluazifop butyl. , benzoylprop-ethyl, furanprop-ethyl, and other penzoylaminoflohionic acid herbicides; cycloanilide), KNW
-242 (1-(3-methylphenyl)-5-phenyl-IH-1,2,4-1-riazole-3-carboxamide], quinclorac (3,7-dichloro-8-quinolinecarboxylic acid), and Examples include cyclohexanedione herbicides such as setoxydim and alloxydim-sodium.

Vegetable oils and oil concentrates can also be added to these combinations.

[Example - 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 (they can be varied within a wide range).

Example 2 Wettable powder Compound 66 of the present invention 20 parts White carbon 20 parts Diatomycin + 52 parts Sodium alkyl sulfate 8 parts or more were mixed uniformly and finely ground to obtain a wettable powder containing 20% of the active ingredient.

Example 3 Emulsion Compound 91 of the present invention 20 parts xylene
55 parts dimethylformamide 15 parts polyoxyethylene phenyl ether 10 parts or more were mixed and dissolved to obtain an emulsion containing 20% of the active ingredient.

Example 4 Granule Compound No. 111 5 parts Tal
ri 4
0 copies -
38 part bentonite
10 parts or more of alkyl sulfate soda 7 parts or more are mixed uniformly and finely ground, and the diameter is 0.5 to 1.
OIIIm was granulated to obtain granules containing 5% of the active ingredient.

〔Effect of the invention〕

Next, test examples regarding the effect of the herbicide of the present invention will be shown.

Test Example 1 Paddy Soil Treatment Test A 150 cdl pot was filled with paddy soil, and seeds of Novie, Kumagayari, Omodaka, and Hotarui were sown and lightly covered with soil. The next day, the water depth was maintained at 2 to 3 cm, and the granules of each compound were treated with a predetermined dose and grown in a greenhouse. Three weeks after the chemical treatment, the herbicidal effect of each weed was investigated according to the following criteria, and the results shown in Table 2 were obtained.

Survey standard weed killing rate Weed killing index 0% 0 20-29% 2 40-49% 4 60-69% 6 80-89% 8 100% 10 The values for 13.5.7.9 are o and 2. 2 and 4.
It shows a value between 4, 6.6, 8.8 and 10.

Ilk was applied to the stems and leaves of weeds in one container. Three weeks later, the herbicidal effect on weeds was investigated according to the adjustment criteria of Test Example 1, and the results are shown in Table 3.

* Control compound (compound described in JP-A-60-87238) Example 2 Stalk and leaf spraying treatment

Claims (3)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X: halogen, hydroxy group, nitro group, cyano group, alkyl group, haloalkyl group, haloalkenyl group,
Alkoxy group, haloalkoxy group, haloalkenyloxy group, alkylthio group, haloalkylthio group, haloalkenylthio group, monoalkylamino group, dialkylamino group, alkoxycarbonyl group, alkylcarbonylalkoxy group, alkylcarbonyl group, alkoxyamino group, Alkylsulfonyl group, haloalkylsulfonyl group, alkoxycarbonylalkylthio group, alkoxycarbonylalkylsulfinyl group, alkoxycarbonylalkylsulfonyl group, phenyl group that may have a substituent n: 0, 1, 2, 3, 4, 5 ( When n is 2 or more, X may be the same or different.) Y: linear or branched lower alkylene group m: 0 or 1 R^1: hydroxy group, cyano group, nitro group, alkylcarbonyl group, Alkoxyamino group, optionally substituted heterocyclic group, or Z-R^3Z: oxygen, SO_x
(k is 0, 1 or 2), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (r: hydrogen or alkyl group), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, -S-S- R^3: Alkyl group, haloalkyl group, alkenyl group,
Alkynyl group, alkoxyalkyl group, alkylthioalkyl group, alkoxycarbonylalkyl group, phenyl group that may have a substituent, aralkyl group, heterocyclic group that may have a substituent R^2: halogen, alkyl group, alkoxycarbonyl group, haloalkenyl group, phenyl group which may have a substituent l: 0, 1, 2, 3, 4, 5 (when l is 2 or more, R^2
may be the same or different. ) R: Hydrogen, alkylcarbonyl group, arylcarbonylalkyl group, arylsulfonyl group, residue of inorganic or organic base However, when m = 0, R^1 represents a furyl group which may have a substituent. A compound represented by (2) Compounds represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (in the formula, R^1, R^2, Y, m, l
has the same meaning as above. ) is represented by the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (wherein, There are chemical formulas, tables, etc. ▼ ) and a base to form a compound shown in the following formula ▲ Mathematical formulas, tables, etc. ▼ , and then this compound is reacted with a base and a cyanide compound. A method for producing a compound represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. (3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R, R^1, R^2, X, Y, n, m, l have the same meanings as above.) one or two compounds
A herbicide characterized by containing seeds or more as active ingredients.