JPH01139579A - Pyridyloxyphenoxypropionic acid ester derivative - Google Patents

Abstract

NEW MATERIAL:A pyridyloxyphenoxypropionic acid ester derivative expressed by formula I (X is H or Cl; Y is H, methyl or halogen). EXAMPLE:2-Thienylmethyl 2-[4-(3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy]propionate. USE:Useful as a selective herbicide, having excellent selectivity for cultivated plants, such as beans, cotton, carrot, potato or beets, without phytotoxicity and capable of exhibiting selective controlling effects on weeds, especially gramineous weeds, e.g., barnyardgrass or large crabgrass, by carrying out soil or post-emergence foliar treatment. PREPARATION:For example, a compound expressed by formula II (Hal is halogen) is reacted with a 2-thiophenemethanol derivative expressed by formula III in the presence of a suitable base, preferably at 20-100 deg.C to afford the aimed compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel pyridyloxyphenoxypropionic acid ester derivative and a selective herbicide containing the compound as an active ingredient.

[Conventional technology]

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

For example, 2-(4-(4-)U fluoromethylphenoxy)phenoxy]propionic acid methyl ester, 2-
C4-(2,4-dichlorophenoxy)phenoxy]
Propionate methyl ester, 2-C4-(3,5-dichloro-2-pyridyloxy)phenoxypropionate methyl ester, 2-[4-(5-)lifluoromethyl-2-pyridyloxy)phenoxy]propion Acid butyl esters are known and used for weed control.

However, the effectiveness of these substances is not always sufficient.

[Problem that the invention seeks to solve]

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 provides a new method represented by the general formula [1] (wherein X represents a hydrogen atom or a chlorine atom, and Y represents a hydrogen atom, a methyl group, or a halogen atom). The object of the present invention is to provide a pyridyloxyphenoxypropionic acid ester derivative (hereinafter 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.

- In clothing [1], the halogen atom represents a chlorine atom or a bromine atom.

The compound of the present invention can be produced by various methods, but
A typical manufacturing method is shown by the reaction formula below.

However, in the formula, X and Y represent the same meanings as above, and Ha
β represents a halogen atom.

= −j: ? I-1koj(J These reactions are carried out using a suitable 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 acetonitrinopedimethylformamide, 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 sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and metal hydrides such as sodium hydride, etc. used. The reaction usually proceeds at a reaction temperature of about 150°C to about 150°C, preferably about 0°C to about 100°C, and the reaction time is about several minutes to about 48 hours.

The compound of the present invention represented by general formula [1] 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 Compound Nα Physical Constant Ester When the compound of the present invention is used as a herbicide, it can be prepared using a method commonly used in pesticide formulations using pesticide adjuvants, such as emulsions, wettable powders, water solvents, oil solutions, etc. It can be used in the form of preparations such as powders and granules. 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. Solvents used as diluents include water, organic solvents, hydrocarbons, halogenated hydrocarbons, alcohols, ethers, alcohol ethers, ketones,
Examples include esters, amides, and sulfoxides.

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

- When used for boat fishing, O,OO is 1 to 10 kg/ha, preferably 0.01 to 5 kg/ha.

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 2-methyl-4-chlorophenoxyacetic acid, its salts and esters d, β-2- (4-chloro-〇-tolyloxy)propionic acid, its salts and esters octanoic acid-4-cyano-2,6-diiodophenyl 2.4-'#chlorophenyl-4'-nitrophenyl ether 2.4.6-dolichlorof Enyl-4'-nitrophenyl ether 2.4-dichlorophenyl-3'-methoxy-4'-nitrophenyl ether 3.4-Methyl dichlororuvanildoate 3-fluororuvanildoic acid isopropyldiethylthiocarbamate-3
-4-chlorobenzyl 4-nitrophenyl-3',5'--1-silyl 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(ethylamine)-6-methylthio-1,
3,5-)Ryazine2-ethylamino-4-isopropylamino-6-methylthio-1,3,5-)Ryazine2,4-bis(isopropylamino)-6-methylthio-1,3,5-triazine5 -ter, t-butyl-3-(2,4-dichloro-5
-inpropoxyphenyl)-1,3',4-oxadiazolin-2-one2.6-dichlorobenzonitrile2.6-cyclothiobenzamide2-amino-3-chloro-1,4-naphthoquinone2. 4
-Dichlorophenyl-3'-carbomethoxy-4'-nitrophenyl ether N-p-chlorobenzyloxyphenyl-3,4°5.
6-titrahydrophthalimide 2, 4-dichlorophenyl-3'-ethoxyethoxy-4'-nitrophenyl 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-diisopropyl-2-(benzenesulfonamide)-ethylenedithiophosphate 3.3'-dimethyl-4-methoxybenzophenone α-(2-naphthoxy) -Propionanilide〇-ethyl-〇-(3-methyl-6-nitrophenyl)-N-s
ec-Butylphosphorothioamidate 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide and its S-(2-methyl-1-piperidyl-carbonylmethyl)-0 ,0-di-n-propyldithiophosphate S-benzyl-N,N-dimethylthiocarbamate [Example] Next, the method for producing the compound of the present invention will be specifically explained by giving an example. The manufacturing method is not limited to these examples.

Example 1 2-(4-(3-chloro-5-trifluoromethyl-
2-pyridyloxy)phenoxy]propionic acid 2-thienylmethyl ester (compound No. 1) 0.46 g of 2-thiophenemethanol was dissolved in dichloromethane 10-, and 2-C4-(3-chloro-5-tripropionic acid) was dissolved in this solution. Fluoromethyl-2-pyridyloxy)phenoxy]
A solution of 1.05 g of propionic acid chloride dissolved in 5 d of dichloromethane was added dropwise at room temperature. Then 0.3 d of triethylamine was added and the mixture was stirred for 2 hours at room temperature. Water was added to the reaction mixture thus obtained, and the dichloromethane solution was separated and washed with water, dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The residue was purified by column chromatography (developed with silica gel chloroform) to obtain 1.10 g of the desired product.

Example 2 2-C4-(3-chloro-5-trifluoromethyl-
2-pyridyloxy)phenoxypropionic acid 2-
(5-chlorothienyl) methyl ester (compound No. 5) 2-C4-(3-chloro-5-trifluoromethyl-
2-pyridyloxy) phenoxyfupropionic acid 1.0
4 g of 2-chloro-5-(chloromethyl)thiophene, 0.67 g, and potassium carbonate 0.55 g were added to 3 Qcc of acetonitrile, and the mixture was refluxed for 2 hours with stirring. After the reaction mixture was cooled, inorganic substances were filtered off, and then acetonyl-IJ was distilled off.

The residue was purified by column chromatography [silica gel, n-
Hexane/ethyl acetate=10/1 (V/V)] to obtain 1.09 g of the desired product.

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 2g06B
(Surfactant manufactured by Toho Chemical Industries) 20 parts were uniformly stirred and mixed to form an emulsion.

Example 4 Production of a hydrating agent 10 parts of white carbon, 65 parts of Zikrite, 5 parts of Tsurupol 5039 (a surfactant manufactured by Toho Chemical Industries) and 20 parts of the compound Nα5 of the present invention were mixed and ground to form a hydrating agent. did.

Example 5 Stalk and foliage treatment test A 22 cm x 16 cm plastic bat is filled with field soil, and a certain amount of soybean, rice, wheat, corn, and oat seeds are sown, and on top of that, soil containing weed seeds such as crabgrass, wild grass, and broad-leaved weeds is added. The soil was covered with soil to a thickness of approximately 1 am.

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 inhibition was divided into five levels from 5 to 1 (5 indicates complete withering, 1 indicates no effect at all).

Effects of the Invention The compounds of the present invention have good selectivity for cultivated plants such as beans, cotton, carrots, potatoes, beets, kanranchi, currants, peanuts, radish, tobacco, tomatoes, and cucurbits, i.e., there is no phytotoxicity at normal concentrations. 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 [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] (In the formula, X represents a hydrogen atom or a chlorine atom, and Y represents a hydrogen atom, a methyl group, or a halogen atom) A pyridyloxyphenoxypropionic acid ester derivative characterized by: (2) General formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] (In the formula, X represents a hydrogen atom or a chlorine atom, and Y represents a hydrogen atom, a methyl group, or a halogen atom) A selective herbicide characterized by containing a pyridyloxyphenoxypropionate derivative as an active ingredient.