JPS6026362B2 - Herbicides containing trifluoromethylpyridoxyphenoxypropionic acid or its derivatives - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel herbicide containing trifluoromethylpyridoxyphenoxypropionic acid or a derivative thereof.

More specifically, the present invention is based on the following: The invention relates to a herbicide containing trifluoromethylpyridoxyphenoxypropionic acid (which is an ammonium group or dimethylammonium group) or a derivative thereof as an active ingredient.

In the definition of the above general formula, lower alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group,
n-butyl group, sec-butyl group, rt-butyl group, etc.; lower alkenyl groups include allyl group, isoprobenyl group, 1-butenyl group, 2-butenyl group; and cycloalkyl groups include cyclopropyl group, cyclobutyl group, Examples of the alkali metal atom or alkali metal atom include sodium, potassium, magnesium, and calcium.

The trifluoromethylpyridoxyphenoxypropionic acid or derivative thereof of the present invention is usually produced, for example, by the following method.

In the above reaction formula, Y and Z are a bromine atom or an iodine atom, X is as described above, and R is a hydrogen atom, a lower alkyl group, a lower alkenyl group, or a cycloalkyl group.

Examples of the solvent used include pyridine, sulfolane, dimethylformamide, and dimethylsulfoxide. The trifluoromethylpyridoxyphenoxypropionic acid and its ester thus produced can be further converted into other derivatives by conventional methods. Examples of manufacturing the compounds of the present invention are described below.

Production Example 1 2-[4-(5-trifluoromethyl-2-pyridoxy)phenoxy]propionic acid ethyl ester 2-[4-(5-iodo-2-pyridoxy)phenoxy] propionic acid ethyl ester 4.1 night, tri-iodide 2.45 ml of fluoromethyl, 40 ml of pyridine and 1.62 ml of copper powder were mixed in an autoclave and reacted at 120-130 qC for 1 hour under a light bulb.

After the reaction mixture was allowed to cool, ether was added to separate the precipitated copper salt, and the ether solution was washed with water, diluted hydrochloric acid, and then dried over sodium bran sulfate. Thereafter, the oily substance obtained by concentrating the ether solution was purified using a silica gel column (developing solution: methylene chloride), and distilled under reduced pressure to obtain a BP182
The desired product of ~185° C./3 Yanagi Hg was obtained for 1.9 min. Production Example 2 2-[4-(5-trifluoromethyl-2-pyridoxy)phenoxy]probionic acid 2-[4-(5-trifluoromethyl-2-pyridoxy)phenoxy]probionic acid obtained in Production Example 1 above
4-(5-trifluoromethyl-2-pyridoxy)phenoxy].

Ethyl pionate 355 ml Sodium hydroxide 4
In the evening, the mixture was added to a mixture of 16 parts of water and 16 parts of ethanol, and reacted under a rope frame at room temperature for 2 hours. After the reaction, add an appropriate amount of ice to the reaction mixture, make it acidic with concentrated hydrochloric acid, filter out the precipitated crystals, wash with water, and dry to obtain the desired product 2 with an mp of 97 to 10.
．． I got 5 nights. Production Example 32-[4-(5-trifluoromethyl-2-pyridoxy)phenoxy]propionic acid methylestere 2-[4-(5-
3.27 g of trifluoromethyl-2-pyridoxy)phenoxy]propionic acid was dissolved in methanol 33', 0.5 g of boron trifluoride ether solution was added, and the mixture was reacted at reflux temperature for 3 hours. .

After the reaction was completed, a small amount of water was added, and the mixture was concentrated under reduced pressure and extracted with methylene chloride. After washing the extracted layer with water and drying with anhydrous sodium sulfate, methylene chloride was removed and distilled under reduced pressure to obtain bp.
2.3 days of target material with a Hg of 175 to 1770/2 were obtained.
Production example 42-[4-(5-trifluoromethyl-2-
Pyridoxy)phenoxy]propionic acid sodium salt 2-[4-(5-trifluoromethyl-2-pyridoxy)phenoxy]propionic acid obtained in Production Example 2 3.27
The solution was dissolved in a small amount of ethanol and mixed with 0.8% of a 50% aqueous sodium hydroxide solution.

After reacting for 3 minutes at room temperature under condensation, the reaction mixture was concentrated under reduced pressure and the precipitated crystals were dried to obtain the desired product 3.0 minutes. Manufacturing example
5 2-[4-(3-kuro.

-5-Trifluoromethyl-2-pyridoxy)phenoxy)propionic acid methyl ester 2-[4-(3-chloro-5-bromo-2-pyridoxy)phenoxy]probionic acid methyl ester 3.9 nights, trifluoromethyl iodide 2.45 nights, pyridine 40°C and 1.62°C of steel powder were mixed in an autoclave, reacted under rope at 140°C for 20 hours, heated and further heated to 160°C to 17°C.
Allowed time to react.

After the reaction product was allowed to cool, ether was added to separate the precipitated steel salts, and the ether solution was washed with water, diluted hydrochloric acid, and then with water, and dried over anhydrous sodium sulfate. Thereafter, the ether solution was concentrated and the obtained oil was purified using a silica gel column (developing solution: methylene chloride), and the solvent was distilled off.
Obtained 50 false o's of 55-570 objects. Representative examples of the compounds of the present invention produced according to the above production methods or production examples are shown below.

M. 1 2-[4-(5-trifluoromethyl-2-pyridoxy)phenoxy]propionic acid (mp97-10
Pi○) Yuzu. 2 2-[4-(3-chloro-5-trifluoromethyl-2-pyridoxy)phenoxy]propionic acid M. 3 2-[4-(5-trifluoromethyl-2-pyridoxy)phenoxy]propionic acid methyl ester (bp175-1770/2 style Hg) 4 2-[4-(3-chloro-5-trifluoromethyl-2-pyridoxy)phenoxy] propionic acid methyl ester (mp55-570) M. 5 2-[4-(5-trifluoromethyl-2-pyridoxy)phenoxy]propionic acid ethyl ester (bpI 82-185°C/3 Hg) M. 6 2-[4-(3-chloro-5-trifluoromethyl-2-pyridoxy)phenoxy]propionic acid n-propylester (bp205-207C/2 style Hg) M. 7 2-[4-(5-trifluoromethyl-2-pyridoxy)phenoxy]propionate (ally
l) Ester (bpl Satoshi ~ 2020/3 broadside Hg) M. 8 2-[4-(5-trifluoromethyl-2-pyridoxy)phenoxy]propionic acid cyclohexyl ester (bp 207-21 pC/1 g) M. 9 2-[4-(5-trifluoromethyl-2-pyridoxy)phenoxy]probionic acid sodium salt ratio. 10 2-[4-(3-chloro-5-trifluoromethyl-2-pyridoxy)phenoxy]propionate sodium salt rudder. 11 2-[4-(3-chloro-5-trifluoromethyl-2-pyridoxy)phenoxy]calcium propionate salt. 12 2-[4-(5-trifluoromethyl-2-pyridoxy)phenoxy]propionate ammonium salt M. 13 2-[4-(5-trifluoromethyl-2-pyridoxy)phenoxy] propionic acid dimethylammonium salt The trifluoromethylpyridoxyphenoxypropionic acid or its derivatives of the present invention can be found in the test examples described below.
Shows excellent activity as an active ingredient in herbicides.

In particular, it is attracting attention as a unique selective herbicidal activity that kills weeds of the grass family without harming broad-leaved crops such as cotton and soybeans. The scope of its application as a herbicide is in fields, paddy fields,
It can be applied to a wide variety of areas, including orchards, mulberry orchards, forests, foundation roads, grounds, and factory sites, and the application methods can be selected as appropriate, such as hollyhock treatment and soil treatment. Depending on the application method, it may be dispersed in water or mixed with various auxiliary agents such as diluents, solvents, emulsifiers, and spreading agents to form emulsions, solutions, wettable powders, powders, and granules. It can be formulated and used in the following form. Furthermore, it can be mixed or used in combination with other agricultural chemicals such as herbicides, insecticides, and fungicides, fertilizers, soil, etc. In this case, even better effects may be exhibited. Although the appropriate application amount of the herbicide according to the present invention cannot be determined unconditionally due to differences in weather conditions, soil conditions, drug formulation, application timing, application method, type of target weed, etc., it is generally the amount of active ingredient applied per are. as 0.
1 to 1,000 evenings, preferably 1 to 500 evenings, and more preferably 5 to 100 evenings.

Examples of herbicide plant experiments and formulations according to the present invention are described below, but the present invention is of course not limited to these descriptions.

Test Example 1 Soil is placed in a 1/3,000-area pot, and a certain amount of grasshoppers, daikon radish, and soybean seeds are sown in a field condition, and on top of the soil, a gutter of regular weeds such as crabgrass, red-winged grass, and foxtail grass is added. The soil was covered to a thickness of about 1 layer.

Three days after sowing, an aqueous dispersion of the active ingredient was sprayed. The growth and condition of the weeds were observed on the 20th day after the treatment, and the results shown in Table 1 were obtained. The numerical values in the table indicate the degree of growth inhibition by dividing it into a scale of 10 to 1 (10 indicates that growth was completely inhibited, and 1 indicates that no growth inhibition was observed). Table 1 Test Example 2 Put soil in a 1/10,000 are pot to prepare a field, sow a certain amount of radish, radish, and soybean seeds, and
It was covered with a thick layer of gong.

Thereafter, when the grasses reached the second hollyhock stage, an aqueous dispersion of the active ingredient at a predetermined concentration was sprayed evenly over the established stalks. The growth condition of each plant was observed on the 20th day after the treatment, and the degree of growth inhibition was expressed using the same criteria as in Test Example 1 to obtain the results shown in Table 2. Table 2 Formulation Example 1 [1}21 [41 (5-trifluoro.

Parts by weight of methyl-2-pyridoxy)phenoxypropionic acid ethyl ester 2 [2' xylene 60
〃Glue Sorball 280 Bait (Product name: Toho Chemical Industry Co., Ltd.)
Each of the above 20 components was uniformly mixed to form an emulsion.

Formulation example 2'11 Sickleite
7 parts by weight of milk [2] White carbon
15 〃'3' Lavelin S (product name; manufactured by Daiichi Kogyo Seiyaku) 2 〃[4} Solbol 5039 (product name; manufactured by Toho Chemical Industries)
5 [Mixture of each of the above components, and 2-[
A wettable powder was prepared by mixing 4-(3-chloro-5-trifluoromethyl-2-pyridoxy)phenoxy-pionic acid methyl ester in a ratio of 4:1.

Formulation Example 3 '1' Part by weight of 2-[4-(5-trifluoromethyl-2-pyridoxy)phenoxy]propionate sodium salt 2 '21 Polyethylene glycol octyl phenyl ether 5 '3' Sodium dodecylbenzenesulfonate 2 〃 [41 Water 73'' Each of the above components '1-2' was mixed uniformly to prepare a liquid.

Formulation example 4 [1'pentonite $ parts by weight]
, Siegrite 30" Sodium lignin sulfonate 5 The above ingredients were mixed and granulated, and diluted with an appropriate amount of acetone to form 2-[4-(5
-trifluoromethyl-2-pyridoxy)phenoxy]
Granules were prepared by spraying 7 parts by weight of allyl propionate onto the mixture.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, A herbicide characterized by containing as an active ingredient at least one type of trifluoromethylpyridoxyphenoxypropionic acid or its derivatives represented by a metal atom, an alkaline earth metal atom, an ammonium group, or a dimethylammonium group. agent.