JPS5899403A - Trifluoromethylpyridoxyphenoxypropionic acid derivative and herbicide containing it - Google Patents

Abstract

NEW MATERIAL:A trifluoromethylpyridoxyphenoxypropionic acid derivative shown by the formulaI(X is H, or Cl; R is H, lower alkyl, lower alkenyl, cycloalkyl, salt-forming atom, salt-forming residue). EXAMPLE:2-[4-(5-Trifluoromethyl-2-pyridoxy)phenoxy]propionic acid ethyl ester. USE:A herbicide. Especially showing selectively herbicidal activity for withering gramineous weeds without damaging broadleaf crops such as cotton, soybean, etc., and its application amount is 1-500g/a calculated as an active ingredient. PROCESS:A compound shown by the formula CF3-Z(Z is Br orI) is reacted with a compound shown by the formula II (Y is as shown for Z; R' is H, lower alkyl, lower alkenyl, or cycloalkyl) in a solvent such as pyridine, etc. in the presence of a catalyst such as copper powder, etc., to give a compound shown by the formulaI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to herbicides containing novel triple-omethylpyri V-Schiff-X dipropionic acid derivatives.

1- (wherein, This invention relates to a herbicide containing a doxyphenoxypropionic acid derivative as an active ingredient.

In the definition of the above general formula, lower alkyl groups include methyl group, ethyl group, n-butyl group, isopropyl group,
N-butyl group, 5ee-butyl group, tert-butyl group, etc., lower fulkenyl group include allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, and dichlorofurkyl group include cyclopropyl group, cyclobutyl group. Examples of salt-forming atoms include sodium, potassium, magnesium, calcium, etc., and examples of salt-forming residues include ammonium groups, organic amines, etc.

Trifluoromethylpyridoxy of the present invention 7! Tsukidipropionic acid derivatives are usually produced, for example, by the following method.

2- 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, dinotylformamide, and dinotylsulfoxide.

Incidentally, the F-lyfluoromethylpyridoxy71-dipropionic acid and its ester produced in this manner can be further converted into other derivatives by a conventional method.

Examples of manufacturing the compounds of the present invention are described below.

Production example 1 2-(4・(5-trifluoromethyl・2
-Pyridoxy) 71-2] propionic acid ethyl ester 2-(4-(5-yol/-2-pyridoxy)phenol) propionic acid ethyl ester 4,1., trifluoromethyl iodide 2.45 g, Pyridine 40-p and 1.62 g of copper powder were mixed in an autoclave, and 120-13
After allowing the 0 reactant to react under stirring at 0°C for 12 hours,
After adding ether, all the copper salts precipitated were washed, and the ether solution was washed with water, diluted hydrochloric acid, and then water, and dried over anhydrous sulfuric acid. Thereafter, the 3-mu(m! opening solution) was purified with methylene chloride and distilled under reduced pressure.
0182-185℃/3 sn HH target 1.9
I got g.

Production example 2 2-(4・(5・trifluoromethyl・2
-Pyridoxy)phenoxy] a-pionic acid 2-(4-(5-)refluoro-amethyl-2-pyridoxy) obtained in Production Example 1 7! 3.55 g of propionic acid ethyl ester was added to a mixture of 16 g of sodium hydroxide Gs water and 16 g of 1 ethanol, and the reaction was stirred for i hours at room temperature. After completion of the reaction, ice was added to the reaction mixture. An appropriate amount was added, acidified with concentrated hydrochloric acid, and the precipitated crystals were collected by filtration, washed with water, and dried to obtain 2.5 g of the target product having a temperature of -997 to 100°C.

Production example 3 2-(4・(5-trifluoromethyl-2
-pyridoxy)phenoxy]propionic acid methyl ester 2-(4-(5-)lifluoro-amethyl-2-pyridoxy)phenoxypropionic acid obtained in Production Example 2 3.2
7. was dissolved in 33 g of methanol, and further 0.5 g of boron trifluoride ether solution was added. was added and 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 distilled off and distilled under reduced pressure to obtain a solution with a bp of 175~
3 g of 177'C/2p-75 to 177'C was obtained.

Production example 4 2-(4-(5-)lifluoromethyl 2-
Pyridoxy) 7! 2-(4-(5-)lifluoromethyl-2-pyridoxy)phenoxypropionic acid obtained in Production Example 2 3.27
．． was dissolved in a small amount of ethanol and mixed with 0.8 g of 50% aqueous sodium hydroxide solution. After reacting at room temperature for 30 minutes with stirring, it was concentrated under reduced pressure and the precipitated crystals were dried to obtain the desired product 3.0. I got it.

Production Example 5 2-(4-(3-ri0-5-trifluoromethyl-2-pyryr*shi)7e/xy)propionic acid methyl ester 2-(4-(3-chloro-5-promo) 3.9 g of 2-pyridoxy)phenoxypropionic acid methyl ester,
Trifluoromethyl iodide 2.45g, pyridine 40-0
and 1,628 ounces of copper powder are mixed in an autoclave,
After reacting at 140°C for 200 hours with stirring, heating and further reacting at 160 to 170°C for 1 hour, the reactant was allowed to cool, and then added with Nigel and the precipitated copper salt was filtered out. The ether solution was washed successively with water, diluted hydrochloric acid, and then water, and dried over anhydrous sodium sulfate. Thereafter, 1.5 g of an oily substance obtained by concentrating the ether solution was purified using a silica gel column (R liquid methylene chloride), and the solvent was distilled off to obtain 500 g of the target product with a temperature of -967 to 69°C. .

Representative examples of the compounds of the present invention produced according to the above production method or production examples are shown below.

No, 1 2.(4-(5.trifluoromethyl-2-
pyridoxy) 71] propionic acid (mp97 - 100°C) No, 2 2-(4-(3-chloro5-trifluoromethyl-2-pyridoxy)phenoxypropionic acid N
o, 3 L”(4-(5-trifluoromethyl 2-
Pyridoxy)phenol)propionate methyl ester (b9175 ~177℃72-aHg) No. 4 2
44.(3-Chloro.5-trifluoromethyl.2.pyridoxy)71-propionic acid methyl ester (-p67~69℃) No.5 2-(1(5.trifluoromethyl.2.pyridoxy) ) 7s no Sushi] propionic acid ethyl ester (
bp182 ~185℃/3-SoHg) 6-No, 6 2-(4.(3-tiyo-5-)lifluoromethyl-2-pyridoxy)phenoxy]propionic acid n-propyl ester (bp20s ~207℃ /2maHg)No, 7
2-(4-(5-)Lifluoro-amethyl-2-pyridoxy)7!7]propionic acid allyl ester (bp19B~202℃/3關H
g) No, 8 2-(4-(5-trifluoromethyl-
2-pyridoxy)phenoxy]propionic acid cyclohexyl ester (bp207~b No, 9 2-(4-(5-)lifluoromethyl-2-
Pyridoxy) phenoxy] pionic acid sodium salt N
o, 10 2-(4-(3-riao-5-)lifluoromethyl-2-pyridoxy)phenoxy]propionic acid sodium salt The trifluoromethylpyridoxyphenoxypropionic acid derivative of the present invention can be used in the test examples described below. As can be seen, it exhibits excellent activity as an active ingredient in herbicides, and is particularly notable for its selective herbicidal activity, which kills weeds of the family Grass without harming broad-leaved crops such as cotton and soybeans. The range of application as a herbicide is wide-ranging, including fields, paddy fields, orchards, mulberry orchards, mountain forests, farm roads, grounds, and factory sites, and the application method can be selected as appropriate, such as foliage treatment, soil treatment, etc. Depending on the application method, it may be used in fractions with 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 is superior when formulated and used in the form of. Furthermore, when mixed or used in combination with other agricultural chemicals such as herbicides, insecticides, and fungicides, fertilizers, and soil, even better effects may be obtained.

The appropriate application amount of the herbicide according to the present invention depends on weather conditions, soil conditions,
Although it cannot be further defined due to differences in drug formulation, application time, application method, and target weed type, the amount of active ingredient applied per are is generally 0.1 to 15,000 g, preferably 1 to 500 M, and more preferably 5 to 500 g. It is 100g.

Examples of plant tests and formulations of herbicides according to the present invention will be described below, but the present invention is not limited to these descriptions.

Test Example 1 Soil was put in a 1/3,000-area vat, and a certain amount of barnyard grass, radish, and soybean seeds were sown in a field condition, and on top of that, seeds of regular weeds such as 8-cane grass, red millet, and foxtail grass were sown. The containing soil was covered to a thickness of about 1 c@. Three days after sowing, an aqueous dispersion of the active ingredient was sprayed. The growth state of weeds was observed 200 days after the treatment and the results shown in Table 1 were obtained.The numbers in Table 0 indicate the degree of growth suppression on a scale of 10 to 1 (10 to 1).
0 indicates that growth was completely inhibited, and 1 indicates that no growth inhibition was observed.

9- Table 1 [ Tototo [ [ Test Example 2 1/10,0007- Soil was put into a container to form a field-like tube, and a certain amount of barnyard grass, radish, and soybean seeds were sown.
It was covered with soil to a thickness of 4111 mm. Thereafter, when the barnyard grass reached the two-leaf stage, a predetermined concentration of the active ingredient water extract was sprayed so as to uniformly cover the stems. The growth condition of each plant was observed 20 days after the treatment, and the degree of growth inhibition was expressed using the same criteria as in Test Example 1, and the results in Table #2 were obtained.

Formulation Example 1 (1) 2-(4-(5-)lifluoromethyl-2-
Pyridoxy) phenoxy] propionic acid ethyl ester 20 parts by weight (2) Xylene 60 #(
3) Tsuruzaru 2808B (product name; manufactured by Toho Kagaku Kogyo)
More than 20 components were uniformly mixed to form an emulsion.

Formulation example 2 (1)! /-Krite 78 parts by weight (2) White carbon 15
#<3) 5be9>8 (Product name: *-Tit@113>
2 # (4) Tsurupol 5039 (trade name; manufactured by Toho Chemical Industry Co., Ltd.) 5 # A mixture of the above components and
Trifluoromethyl 2-pyrido) 7! [Noxy] propionic acid methyl ester was mixed in a ratio of 4=1 to prepare a wettable powder.

Formulation Example 3 (1) 2-[4-(5-) 17fluoronotyl-2-pyridoxy)phenoxypropionate sodium salt 20 parts by weight 12- (2) ytelJ ethylene glycol octylphenyl ether 5 parts by weight (3 ) Sodium dodecylbenzenesulfonate 2
(4) Water 73# The components (1) to (4) above were uniformly mixed to prepare a liquid agent.

Formulation example 4 (1) Bentonite 58 parts by weight (2) Norcrite 30
#(3) Lignin phosphoric acid soda
5 Mix and granulate the above ingredients and dilute with an appropriate amount of 77 tons to prepare 2-(4-(5-trifluoromethyl-2-pyridoxy)7e7xy) allyl pionate (ally
l) 7 parts by weight of ester was sprayed onto this to form granules.

Patent applicant: Ishihara Sangyo Co., Ltd. 113 complete

Claims (1)

[Claims] trifluoromethylpyridoxy represented by A herbicide characterized by containing at least one type of phenoxypropionic acid derivative as an active ingredient.