JPH01230555A - 2-(4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-phenoxy)propionic acid ester derivative - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R is formulas II-V). EXAMPLE:(3,5-Dimethyl-isoxazol-4-yl)-methyl 2-[4-(3-chloro-5-trifluoromethyl-2- pyridyox)-phenoxy]propionate. USE:A selective herbicide capable of exhibiting excellent selectivity for cultivated crops, such as beans, cotton, carrot, potato, beet, cabbage and mustard, and showing controlling effects on gramineous weeds, such as barnyard grass, large crabgrass, goosegrass, grem foxtail and wild oats. PREPARATION:A compound expressed by formula VI is reacted with a compound expressed by the formula HOR in the presence of a base (e.g., potassium carbonate) in the presence or absence of a solvent (e.g., acetonitrile) at 0-150 deg.C temperature to afford the aimed compound expressed by formula I.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides novel 2-C4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxyfupropionic acid ester derivatives and The present invention relates to a selective herbicide contained as an ingredient.

[Conventional technology]

It has been reported that many phenoxypropionate derivatives have herbicidal activity.

For example, 2-(4-(4-)lifluoromethylphenoxy)phenoxy]propionic acid methyl ester, 2-
C4-(2,4-dichlorophenoxy)phenoxyfupropionate methylesterenope 2-[4-(3,5-dichloro-2-pyridyloxy)phenoxyfupropionate methylesternope 2-(4-(5 -) Lifluoromethyl-2-pyridyloxy) phenoxyfupropionic acid butyl ester and the like are known and used for weed control. However, the effectiveness of these substances is not always sufficient.

[Problem to be solved by the invention]

Beet, soybean, cotton, alfalfa, rapeseed, potato,
In the cultivation of broad-leaved crops such as sunflowers, radish, Chinese cabbage, cabbage, and tomatoes, without harming these useful crops,
There is still a strong market demand for a selective herbicide that can kill regular weeds using either pre-emergence soil treatment or post-emergence foliage treatment, even though many herbicides have already been developed and sold. . In particular, when foliage treatment is performed after weed emergence, the conventional phenoxypropionate esters described above take more than 8 days to achieve post-treatment effects, which has caused many dissatisfaction among crop growers. It was strongly desired.

The object of the present invention is to obtain said compounds industrially and to provide even more improved selective herbicides that meet the demands of the market.

[Means and effects for solving the problems] The present invention is a general hole CI] C4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxyfupropionic acid ester derivative (hereinafter referred to as , referred to as the compound of the present invention) and a novel selective herbicide containing the compound of the present invention as an active ingredient.

The compound of the present invention can be produced by various methods, and a typical production method is shown by the following reaction formula. However, in the formula, Hal represents a halogen atom, and R represents the same meaning as above.

These reactions are carried out using an appropriate base in the presence or absence of a solvent.

Examples of solvents include ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene, and xylene, ethers such as ethyl ether, tetrahydrofuran, and dioxane, and carbon halides such as chlorobenzene, chloroform, carbon tetrachloride, and dichloroethane. hydrogen,
Tertiary amines such as triethylamine, pyridine, and dimethylaniline, and polar solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide, and hexamethyltriamide phosphate are used.

As a base, triethylamine, pyridine, 1.8-
Diazabicyclo-(5,4,0)-7-undecene, tertiary amines such as dimethylaniline, sodium hydroxide,
Alkali hydroxides such as potassium hydroxide, alkaline earth hydroxides such as calcium hydroxide, alkali carbonates such as IJium, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and hydrogenation such as sodium hydride. Metal etc. are used. The reaction is usually carried out at a temperature of 0°C to about 150°C,
Preferably proceeding at a reaction temperature of about 0°C to about 100°C,
The reaction time is about several minutes to about 48 hours.

The compound of the present invention represented by general formula [I] can be synthesized by any of the methods described above. Regarding the specific example, Part 1
Shown in the table. However, the compounds of the present invention are not limited to these.

Table 1: When the compound of the present invention is used as a herbicide, it can be prepared by using a pesticide auxiliary and a commonly used method for pesticide formulation, such as emulsions, wettable powders, aqueous solutions, oil solutions, powders, granules, etc. It can be used in the form of a formulation. In actual use, these various preparations can be used as they are or diluted with water to a predetermined concentration.

Specific examples of pesticide adjuvants include diluents, surfactants, stabilizers, sticking agents, aerosol propellants, and synergists. Examples of the solvent as a diluent include water, organic solvents, hydrocarbons, 10-genated hydrocarbons, alcohols, ethers, alcohol ethers, ketone necks, esters, amides, and sulfoxides. .

In addition, fillers and solid carriers include inorganic powders such as slaked lime, magnesium lime, gypsum, calcium carbonate, sand, perlite, pumice, diatomaceous earth, aluminium, mina, zeolite, clay minerals (talc, vermiculite, kaolinite).
Examples include plant powder (for example, starch, grain, glucose, etc.), synthetic resin powder (for example, phenol resin, carbon resin, vinyl chloride resin), and the like. Examples of the surfactant include anionic surfactants (e.g. alkyl sulfates, aryl sulfonic acids, succinates, polyethylene glycol alkyl aryl ether sulfate salts), cationic surfactants (e.g. alkyl amines,
Examples include polyoxyethylene alkyl amines), nonionic surfactants (for example, polyoxyethylene glycol ethers, polyoxyethylene glycol esters, and polyhydric alcohol esters), and amphoteric surfactants. Other examples include stabilizers, fixing agents, efficacy extenders, dispersion stabilizers, and synergists.

The amount of the compound of the present invention used as an active ingredient can be appropriately changed depending on the form of the preparation, the method of application, purpose, timing, weed growth status, etc.

-0.001~1000g/10a when used for boat fishing
and preferably 0.01 to 100 g/10a.

The herbicide of the present invention can be applied in combination with other agricultural chemicals used in the same field, such as insecticides, fungicides, herbicides, plant growth regulators or fertilizers. In particular, it may be appropriate to add and mix the following herbicides for the purpose of reducing spraying labor or expanding the range of grass species that can be effectively controlled.

2.4-dichlorophenoxyacetic acid, its salts, esters and alkylamine salts 2-methyl-4-chlorophenoxyacetic acid, its salts and esters d, f-2-(4-chloro-〇-tolyloxy)propionic acid, its salts and ester octanoic acid-4-cyano-2,6-diiodophenyl 2.4-';chlorophenyl-4'-nitrophenyl ether 2.4.6-) dichlorophenyl-4'-nitrophenyl ether 2.4-dichlorophenyl- 3'-Methoxy-4'-nitrophenyl ether 3.4-Methyl dichlororuvanillide 3-Dichlororuvanillide isopropyldiethylthiocarbamate
3-4-chlorobenzyl 4-nitrophenyl-3',5'4silyl ether hexahydro-IH-azepine-1-carbothioic acid-8
-Ethyl 3.4-dichloropropionanilide 2-chloro-2',6'-diethyl-N-(butoxymethyl)acetanilide 2-chloro-2',6'-diethyl-N-(m-propoxyethyl)acetanilide 1 -(α,α-dimethylbenzyl)-3-p-tolylurea2.4-bis(ethylamino)-6-methylthio-1,
3,5-triazine 2-ethylamino-4-isopropylamino-6-methylthio-1,3,5-) riazine 2.4-bis(isopropylamino)-6-methylthio-1,3,5-) riazine 5 -tert-butyl-3-(2,4-dichloro-5-
isopropoxyphenyl)-1,3,4-oxadiazolin-2-one 2.6-dichlorobenzonitrile 2.6-cyclothiobenzamide 2-amino-3-chloro-1,4-naphthoquinone 2.4
-Dichlorophenyl-3'-carbomethoxy-4'-nitrophenyl ether N-p-chlorobenzyloxyphenyl-3,4°5.
6-titrahydrophthalimide 2,4-dichlorophenyl-3'-ethoxyethoxy'
z-4'-Ditrophenyl ether N(1-ethylpropyl)-2,6-sinitro 3,4-xylidine 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-pyrazol-5-yl- p-) Luenesulfonate 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-5-(benzoylmethoxy)-pyrazole 4-(2,4-dichloro-3-methylbenzoyl)-1
, 3-dimethyl-5-(benzoylmethoxy)-pyrazole 0.0-'; isopropyl-2-(benzenesulfonamide)-ethylenedithiophosphate 3.3'-dimethyl-4-methoxybenzophenone α-(2-naphthoxy )-propionanilide 0-ethyl-〇-(3-methyl-6-nitrophenyl)-N-s
ec-Butylphosphorothioamidate 3-isopropyl-2,,1,'3-benzothiadiazinone-(4)-2,2-dioxide and its derivatives 5-(2-methyl-1-piperidyl-carbonylmethyl )-〇,〇-Di-n-propyldithiophosphate S-benzyl-N,N-dimethylthiocarbamate [Example] Next, the method for producing the compound of the present invention, the production of the preparation, and the processing test will be explained in detail with reference to Examples. However, the present invention is not limited to these examples.

Example 1 2-C4-(3-chloro-5-trifluoromethyl-2
-Pyridyloxy)-phenoxypropionic acid 3.
Preparation of 5-dimethyl-isoxazol-4-yl)-methyl ester (compound Nα3) 2-(4-(3-chloro-5-trifluoromethyl-
2-pyridyloxy)-phenoxypropionic acid 1.
0 g, 3.5-dimethyl-4-chloromethyl-inoxazole 0.47 g and anhydrous potassium carbonate 0.44
Add 6 g to 30 ml of acetonitrile and add 6.
Refluxed for an hour. After the reaction mixture was cooled, inorganic substances were filtered off, and acetonitrile was distilled off. The residue was purified by column chromatography [developed with silica gel, benzene/ethyl acetate = 10/1 (v/v)] to obtain 0.62 g (glassy oil) of the target product.

Example 2 2-(4-(3-chloro-5-trifluoromethyl-
Preparation of cyclohexyl 2-pyridyloxy)-phenoxypropionic acid ester (compound Nα4) 0.36 g of cyclohexanol was added to 3Q dichloromethane.
mji! 2-C4-(3-chloro-
A solution of 1.12 g of 5-trifluoromethyl-2-pyridyloxy)-phenoxypropionic acid chloride dissolved in 10 ml of dichloromethane was added dropwise at room temperature. 1
After 0 minutes, 0.4 g of triethylamine was added and the mixture was stirred for a further 2 hours at room temperature. Water was added to the reaction mixture thus obtained, and the dichloromethane solution was separated, washed with water, dried over anhydrous magnesium sulfate, and then the solvent was distilled off.

The residue was purified by column chromatography [silica gel, developed with benzene/ethyl acetate 10/1 (V/V)],
1.52 g (no. 1.5182) of the target product was obtained.

Example 3 Preparation of emulsion 20 parts of the present compound Nα1 (parts indicate parts by weight, the same applies hereinafter), 60 parts of xylene, and Tsurpol 2806B.
(Surfactant manufactured by Toho Chemical Industries) 20 parts were uniformly stirred and mixed to form an emulsion.

Example 4 Preparation of a wettable powder 20 parts of the compound Nα4 of the present invention, 10 parts of white carbon, 65 parts of Zeekrite, and 5 parts of Tsurupol 5039 (a surfactant manufactured by Toho Chemical Industries) were mixed and ground to form a wettable powder. did.

Example 5 Stalk and foliage treatment test A 22 cm x 16 cm plastic vat was filled with field soil, and a certain amount of soybean, rice, wheat, corn, and oat seeds were sown. It was covered with soil to a thickness of approximately 1.0CI11. When the gramineous plants reached the 3.0 to 3.5 leaf stage, a prescribed chemical was uniformly sprayed on the foliage.

The growth state of the weeds was observed on the 14th day after the chemical treatment, and the results shown in Table 2 were obtained. The numerical value of the degree of growth suppression is 5 levels from 5 to 1 (
5 indicates complete death, 1 indicates no effect).

Example 6 Soil Treatment Test Fill a 22cm x 16cm plastic vat with field soil, sow a certain amount of soybean, rice, wheat, corn, and oat seeds, and then soil containing weed seeds such as crabgrass, field weed, and broad-leaved weeds. It was covered with soil to a thickness of approximately 1.0 Cffl. The next day, the soil was uniformly treated with the specified chemicals.

The growth state of the weeds was observed on the 14th day after the chemical treatment, and the results shown in Table 3 were obtained. The numerical value of the degree of growth inhibition is the same as in Example 5.

Effects of the Invention The compounds of the present invention have good selectivity for cultivated plants such as beans, cotton, carrots, potatoes, beets, citrus fruits, mustard, peanuts, radish, tobacco, tomatoes, cucumbers, etc., that is, they do not cause phytotoxicity at normal concentrations used. Soil treatment before germination and foliage treatment after germination were carried out on weeds, especially weeds of the regular family, such as Japanese millet, blackberry, blackberry, foxtail grass, wild oat, golden foxtail, grasshopper, silver grass, johnson grass, etc., without causing any problems. In this case, it shows an excellent selective control effect.

Claims (2)

[Claims] (1) General formula [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] (In the formula, R is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ Mathematical formulas, There are chemical formulas, tables, etc.▼,▲mathematical formulas, chemical formulas,
A 2-[4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy]propionic acid ester derivative characterized by being represented by ▼. (2) General formula [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] (In the formula, R is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ Mathematical formulas, There are chemical formulas, tables, etc.▼,▲mathematical formulas, chemical formulas,
Contains as an active ingredient a 2-[4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy]propionate derivative characterized by the following: A selective herbicide characterized by: