JPS62286970A - 2-phenyl-4,5,6,7-tetrahydro-2h-indazole derivative, production thereof and herbicide containing same - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [X is lower haloalkyl; Y is halogen; A is group of formula -B-D (B is O or S; D is aliphatic hydrocarbon group which may be substituted with lower alkoxy, etc.) or -COOR (R is lower alkyl which may be substituted with lower alkoxycarbonyl)]. EXAMPLE:2-[4-Chloro-2-fluoro-5-(2-propynyloxy) phenyl]-3-trifluoromethy l-4,5,6,7- tetrahydro-2H-indazole. USE:Herbicide. PREPARATION:The compound of formula I can be produced by acetylating the compound of formula II in a solvent (e.g. benzene) in the presence of a base (e.g. triethylamine) at -20 deg.C-room temperature for 30min-several hr and cyclizing the resultant compound of formula III in an organic solvent at a temperature between room temperature and the boiling point of the solvent for 1-ten odd hr.

Description

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

(Prior Art) In the cultivation of agricultural and horticultural crops, many herbicides have come to be used for weed control, which has required a great deal of labor. However, the seeds that caused chemical damage to crops remain in the environment and become polluted.
Due to the large number of people infected with the disease, there is a great deal of effort being made to develop drugs that are both effective and safe to use.

2-phenyl-4,5,6,7- similar to the compounds of the present invention
As tetrahydro-2H-indazole derivatives, compounds represented by the formula are disclosed in JP-A-59-84872.

(Problems to be Solved by the Invention) The object of the present invention is to provide a novel 2-phenyl-4,5°6.7
-Tetrahydro-2H-indazole derivatives can be industrially advantageously produced to provide a herbicide with a wide selectivity between crops and weeds, reliable efficacy, and high safety.

(Means for Solving the Problems) The present invention relates to a group represented by the general formula [wherein, X is a lower haloalkyl group, Y is a halogen atom, and A is a group represented by the formula -BD] 0 or S, D represents a lower alkoxy group or an aliphatic hydrocarbon group optionally substituted with a lower alkoxycarbonyl group) or the formula -COOR (wherein R is substituted with a lower alkoxycarbonyl group) represents a lower alkyl group. ], a method for producing the compound, and a herbicide containing the compound as an active ingredient.

The compound of the present invention exhibits high herbicidal activity against various weeds such as dogweed, pigweed, and blackberry in both soil treatment and foliage treatment under upland cultivation conditions.

In soil treatment, crops such as corn, wheat, soybeans, and peanuts are lightly damaged, and soybeans exhibit particularly high selectivity for the compounds of the present invention. In particular, the compounds of the present invention exhibit several orders of magnitude better selectivity than known compounds in soil treatment before weed germination.

It also shows high selectivity for paddy rice, and exhibits excellent herbicidal activity in soil treatment before the emergence of weeds such as rice field weeds, grasshoppers, and bulrushes.

Furthermore, the present compound can be applied to control weeds in orchards, lawns, roadside areas, vacant lots, etc.

The compound of the present invention can be manufactured by the method shown below.

The acetylation reaction is carried out in a solvent in the presence of a base at -20°C to room temperature for 30 minutes to several hours. As a solvent, chloroform, benzene, DMF, ethyl acetate, ether, water, etc. can be used. As the base, triethylamine, pyridine, sodium hydroxide, potassium carbonate, etc. can be used.

The ring-closing reaction with the hydrazine derivative represented by the general formula (III) is carried out in an organic solvent from room temperature to the boiling point of the solvent used for 1 to 10-odd hours. An organic solvent, Shiteha alcohol a, acetic acid, chloroform, benzene, 7% ethyl acetate, etc. can be used.

Further, the hydrazine derivative represented by the general formula (1) is usually used as its hydrochloride.

After the reaction is completed, the desired product can be obtained by carrying out usual post-treatments.

The structure of the compound of the present invention was determined from the results of spectrum measurements such as IRlm and MASS.

(Example) Next, examples will be given to explain the present invention in more detail.

Example 1 2-(4-chloro-2-fluoro-5-(2
-propynyloxy)phenyl) = 3-trifluoromethyl-4,5,6+ 7-tetrahydro-2H-indazole (compound number 1): 2-trifluoroacetylcyclohexanone 1.51
? (7,78mmot) of chloroform (5Tnl)
Add 0.745'(9) acetyl chloride to the solution under water cooling.
, 43 mmot), then triethylamine 0.86
f (a 50 mmot) glue aa form (10ml
) solution was added and stirred at 0°C for 2 hours.

After the reaction mixture was concentrated under reduced pressure, water was added and extracted with chloroform (3 times). The organic layer was washed with water and dried over magnesium sulfate. Concentration under reduced pressure yielded 1.45f of crude product.

Of this crude product, 0.6Of was dissolved in 15 liters of ethanol to obtain 0.64 F of 4-chloro-2-fluoro-5-(2-propynyloxy)-phenylhydrazine hydrochloride.
(2,6 mmot), sodium acetate 0.22 f
C2.7 mmol) was added thereto, and the mixture was heated under reflux for 4.5 hours. After cooling, insoluble materials were filtered, the filtrate was concentrated, and purified by silica gel chromatography (hexane-ethyl acetate 15"1) to obtain the desired product (0.249%). Melting point 87.5-90 Next, representative examples of the present invention are shown in Table 1.

Table 1 (Means for Solving 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 is similar to ordinary agricultural chemicals. It has a form. That is, the active ingredient compound is generally used by mixing an appropriate amount with a carrier and preparing it in the form of an aqueous solution, an emulsion, a granule, an aqueous solution, a flowable preparation, or the like. As a solid carrier, Merck,
Examples include white carbon, bentonite, clay, diatomaceous earth, 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 preparation mentioned above, but for example, in an irrigation agent, it is 5 to 70%, preferably 10 to 30%:
3-70%, preferably 5-20% in emulsions; 0.01-30%, preferably 0.05% in granules
A concentration of ˜10 g is used.

Irrigation agents and emulsions obtained in this way are diluted with water to a predetermined concentration to form a suspension or emulsion, and granules can be sprayed or mixed into the soil before or after weed germination. be done. In practice, the herbicide of the present invention is applied at an appropriate amount of 10 parts per part of the active ingredient IP or more.

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 achieved, but even higher effects can be expected due to the synergistic action of the mixed chemicals. In that case, combinations with multiple known herbicides are also possible. Agents suitable for use in combination with the herbicide of the present invention include penthiocarb, molinate, MY-93 (S-(2,2
-dimethylbenzyl)1-pyRlysinecarbothioate], thiocarbamate herbicides, acid amide herbicides such as butachlor, pretilacol, diphenyl ether herbicides such as chromethoxynil, bifenox, Pyrazole herbicides such as virazolate and biradixifene, sulfonylurea herbicides such as chlorsulfuron and sulfometuron-methyl, MC
Phenoxyalkanecarboxylic acid herbicides such as PlMCPB, 72Φ diphenoxypropionic acid herbicides such as diclofop-methyl, pyridyloxyphenoxypropionate herbicides such as fluazifop butyl, and others such as Pyrlofos and Daimeron. , pentacine, oxacyacin, NTN'-801 (2-benzothiazol-2-yloxy-N-methylacetanilide), nazoroanilide, HW-52 (4-ethoxymethoxybenz-27,
3/-cycloanilite), KNVv-242 [1-
(3-methylphenyl)-5-7enyl IH-1,2
, 4-) lyazole-3-carboxamide], S-47
Examples include cyclohexanedione herbicides such as (N-(2,2-dimethylbenzyl)-d-bromo tertiary-butylacetamide, setoxydim, alloxydimousodium, etc.) Also, combinations of these include vegetable oil and Oil concentrates can also be added.

(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 the present example and can be varied within a wide range.

Example 2 Hydrating agent Compound 1 of the present invention 20 parts White carbon 20 parts Cane
C ±
52 parts Sodium alkyl sulfate
Mix 8 parts or more uniformly and finely crush the active ingredient 2.
A hydrating powder of 0.0 t was obtained.

Example 3 Emulsion Compound 1 of the present invention 20 parts
Shin 5
5 parts dimethylformamide 15 parts pyrioxyethylene phenyl ether 10 parts or more were mixed and dissolved to obtain an emulsion containing 20% of the active ingredient.

Example 4 Granules Compound 1 of the present invention 5 parts
40 copies -
38 parts bentonite
10 parts alkyl sulfate soda
After uniformly mixing 7 parts or more and pulverizing finely, the diameter is 0.5~
1. The product was granulated into Ottm granules to obtain granules containing 5 active ingredients.

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

Test Example 1 Field Crop Soil Treatment Test 250eayf? The pot was filled with soil, and seeds of foxtail grass, crabgrass, Japanese wildflower, pigweed, goldenrod, Japanese knotweed, and soybean were sown on the surface layer, and the soil was sown that the seeds were no longer visible. Immediately, an emulsion of each test compound was diluted with water and a chemical solution of a predetermined concentration was sprayed on the soil surface at a ratio of 1001/10a using a small sprayer, and the soil was grown in a greenhouse.

Water was sprinkled every day to keep the soil surface moist. The permanence of each weed in the mouth was investigated for three weeks after the chemical spraying according to the following criteria, and the results shown in Table 2 were obtained.

Survey standard weed killing rate index 0% 0 20-29chi 2 40-49 arrogant j 60-69chi 6 80-89chi 8 100chi 10 Also, the numerical values of 1, 3, 5, 7, 9 are O and 2, respectively. .2 and 4
．． It shows a value between 4, 6.6, 8.8 and 10.

Claims (3)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X is a lower haloalkyl group, Y is a halogen atom, A is a group represented by the formula -B-D, O or S, D represents a lower alkoxy group or an aliphatic hydrocarbon group optionally substituted with a lower alkoxycarbonyl group, or -COOR (wherein R is substituted with a lower alkoxycarbonyl group) represents a lower alkyl group. ] A compound represented by (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X represents a lower haloalkyl group.) The compound represented by the acetylation is then produced by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ Y is a halogen atom, A is a group represented by the formula -B-D, (wherein B is O or S, and D is an aliphatic hydrocarbon optionally substituted with a lower alkoxy group or a lower alkoxycarbonyl group) ) or a group represented by the formula -COOR (wherein R represents a lower alkyl group which may be substituted with a lower alkoxycarbonyl group). ] A method for producing a compound represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (wherein, X, Y and A have the same meanings as above). . (3) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X is a lower haloalkyl group, Y is a halogen atom, A is a group represented by the formula -B-D, O or S, D represents a lower alkoxy group or an aliphatic hydrocarbon group optionally substituted with a lower alkoxycarbonyl group, or -COOR (wherein R is substituted with a lower alkoxycarbonyl group) represents a lower alkyl group. ] A herbicide characterized by containing one or more compounds represented by the following as an active ingredient.