KR830001714B1 - Process for the preparation of diphenyl ether derivatives - Google Patents

Abstract

Title compds. I (X,Y = halogen, CF3; R = methyl, chloromethyl, phenyl, lower alkoxy, dimethylamino), useful as herbicides, were prepd. by reacting compds. II suspended in acetic anhydride-water mixed soln. with Cl2 to give compds. III, which was reacted with ammonia to give IV followed by reaction of compds. V and K2CO3 in acetone to give I. Thus, 2'-chloro-4'-trifluoromethyl-3-methoxycarbonylaminosulfonyl-4-nitrodiphenylether was prepd. from 2'-chloro-4'-trifluoromethyl-3-benzylmercapto-4-nitrodiphenylether suspended in acetic anhydride-water mixed soln.

Description

Method for preparing diphenyl ether derivative

The present invention relates to a process for the preparation of the novel diphenyl ether derivatives of the general formula (E).

Wherein X and Y represent a halogen atom or a trifluoromethyl group, provided that Y is a trifluoromethyl group when X is a halogen atom, and Y is a halogen atom when X is a trifluoromethyl group.

R represents a methyl group, a chloromethyl group, a phenyl group, a lower alkoxy group or a dimethylamino group.

A large number of herbicides using diphenyl ether derivatives as active ingredients have been proposed since the past and are not commercially available. Examples thereof include NIP (active ingredient: 2 ', 4'-dichloro-4-nitro diphenyl ether) and CNP (2). And herbicides such as ', 4', 6'-trichloro-4-nitro diphenyl ether) and TOPE (3'-methyl-4-nitro diphenyl ether).

These conventionally known diphenyl ether herbicides are generally excellent in soil treatment ability for annual weeds occurring in paddy fields, but the ability to treat foliage on all weeds, or annual broadleaf weeds or perennials. It has a common property of low herbicidal effect on weeds. Alternatively, derivatives of these types may cause unexpected changes in the presence or absence of herbicidal effects, small or large, speed or damage to crops due to differences in chemical structure due to differences in the type, number or position of substituents as in the case of other organic compounds. There are many cases.

The present inventors have conducted various studies for the purpose of obtaining industrially useful diphenyl ether derivatives not described in the prior art. As a result, the synthesis of novel diphenyl ether derivatives represented by the following general formula (E) was successful, and the novel diphenyl ether derivatives have excellent herbicidal effects on all weeds, The present invention was found to have no toxicity or strange smell to human body, animals and shellfish.

In formula, X, Y. R is as above-mentioned.

The diphenyl ether derivative of the present invention combines both the ability to kill weeds before and after development, so-called soil treatment ability and foliage treatment ability, and also results in annual or perennial rice plant growing in paddy fields or feet. It is effective against a wide range of weeds such as weeds and broadleaf weeds. Therefore, the herbicide of the present invention is effective as an early herbicide before or after seeding, or a medium-term herbicide for 1-2 weeks after seeding for perennial weeds and broadleaf weeds, and in the case of fields, soil treatment type before and after sowing of crops. It can be used as a herbicide or a herbicide-treated herbicide for all weeds in orchards, tea fields, mulberry fields, and non-crop lands.

Table 1 lists the derivatives of the novel diphenyl ether produced by the present invention. It is useful as a salt of these diphenyl ether derivatives or an active ingredient of the herbicide of the present invention.

TABLE 1

The diphenyl ether derivative according to the present invention can be synthesized by the following reaction step.

1st process

2nd process

3rd process

X, Y, and R in the formulas of the above steps are as described above.

An embodiment of each process will be described in detail as follows.

Example 1

Synthesis of 2'-chloro-4'-trifluoromethyl-3-methoxycarbonylaminosulfonyl-4-nitro diphenyl teier (compound of compound No. 4).

15.0 g (0.034 mol) of 2'-chloro-4'-trifluoromethyl-3-benzylmercapto-4-nitrodiphenyl ether was suspended in a mixture of 70 ml glacial acetic acid and 10 ml mol and chlorine at 10-20 DEG C while stirring. The gas was blown and reacted for 2 hours, followed by stirring at room temperature for 1 hour.

The contents were then poured into water, the freed oil was extracted with benzene, washed with extract, dehydrated with sodium sulfate and the solvent was distilled off to remove 2'-chloro-4'-trifluoromethyl-3-chloro. Sulfonyl-4-nitro diphenyl ether was obtained.

This was then dissolved in ethyl acetate and added dropwise into an ethyl acetate solution saturated with ammonia. After completion of the dropwise addition, the mixture was stirred for 1 hour at room temperature, water was added, the reaction solution was washed with water, then dehydrated in sodium sulfate, the solvent was distilled off, and the residue was recrystallized from isopropaol. 10.5 g (yield: 78%) of -4'-trifluoromethyl-3-aminosulfonyl-4-nitro diphenyl ether were obtained.

After dissolving 2.2 g (0.0055 mol) of this compound in 50 ml of acetone, 1.1 g (0.008 mol) of potassium carbonate and 0.7 g (0.008 mol) of methyl chlorosilicate were added and the mixture was boiled and refluxed for 3.5 hours.

After distilling off the acetone, 50 ml of water was added to the residue, and the insoluble substance was filtered off.

The filtrate is made acidic with infectious acid, and the precipitated crystals are collected by filtration, dried and recrystallized from a mixed solution of benzene and n-hexane, and then 2'-chloro-4'-trifluoromethyl-3-methoxy is obtained as a pale yellow prismatic crystal. 2.1g (yield: 84%) of carbonylaminosulfonyl-4-nitro diphenyl ethers (melting point: 127-130 degreeC) were obtained.

Example 2

2'-Chloro-4'-trifluoromethyl-3-acetyl amino sulfonyl-4-nitro diphenyl ether (synthesis of compound of compound No. 1).

2.4 g (0.006 mol) of 2'-chloro-4'-trifluoromethyl-3-aminosulfonyl-4-nitro diphenyl ether obtained in the same manner as in Example 1 was dissolved in 60 ml of acetone, followed by 1.2 g of potassium carbonate. (0.009 mol) and acetone solution of 0.6 g (0.008 mol) of acetyl chloride were added and the mixture was boiled under reflux for 8 hours. Subsequently, the acetone is distilled off, the residue is diluted with aqueous sodium hydroxide solution, and the insoluble substance is filtered off. The filtrate is made of strong hydrochloric acid. The precipitated crystals are collected by filtration, dried and recrystallized from a mixed solution of benzene and n-hexane. 2.4 g (yield: 91%) of 2'-chloro-4'-trifluoromethyl-3-acetyl amino sulfonyl-4-nitro diphenyl ether (melting point: 152-155 degreeC) of a prism phase crystal was obtained.

Example 3

Synthesis of 2'-bromo-4'-trifluoromethyl-3-N, N-dimethylcarbamoylaminosulfonyl-4-nitrodiphenyl ether (compound of compound No. 1).

After dissolving 1.5 g (0.0034 mole) of 2'-bromo-4'-trifluoromethyl-3-aminosulfonyl-4-nitrodiphenyl ether synthesized according to Example 1 in 60 ml of acetone, 0.6 g of potassium carbonate was dissolved. (0.0044 moles) and 0.5 g (0.0045 moles) of N, N-dimethylcarbamoyl chloride were added and refluxed for 8 hours. Subsequent operations were carried out in accordance with Example 2 and were subjected to colorless powdery crystals of 2'-bromo-4'-trifluoromethyl-3-N, N-dimethylcarbamoylaminosulfonyl-4-nitrodiphenyl ether (melting point). : 160-162 degreeC) obtained 0.8g (yield: 46%).

In the case of using the diphenyl ether derivative according to the present invention as a herbicide, granules, powders, emulsions, hydrates, tablets, emulsions are used by using an inert solid carrier, a liquid carrier, an emulsion dispersant, etc., in accordance with the practice of pesticide preparation. It can be used as arbitrary formulations, such as aerosol and a smoke agent. Examples of these inert carriers include acryltalc, clay, kaolin, diatomaceous earth, calcium carbonate, potassium chlorate, saltpeter, wood flour, nitrocellulose, starch, benzene, xylene, n-hexane, arivia rubber, vinyl chloride, carbon dioxide, and freon , Propane, butane and the like. In addition, an adjuvant on a formulation, for example, an electrodeposition agent, a diluent, a surfactant, a solvent, and the like can be appropriately blended. Moreover, it may be mixed with fungicides, insecticides and other pesticides, urea, decoy, phosphorus, kali salts and other fertilizers, soil improvers.

Next, the formulation example of a herbicide is described. The part in a formulation example means a weight part.

[Example 1]

50 parts of 2'-chloro-4'-trifluoromethyl-3-methoxycarbonylaminosulfonyl-4-nitrodiphenyl ether (compound of compound No. 4), 30 parts of xylene, 10 parts of isophorone, emulsifier Ten parts of solpol (trade name) were dissolved and mixed to obtain an emulsion.

[Example 2]

50 parts of 2'-bromo-4'-trifluoromethyl-3-N, N-dimethylcarbamoyl aminosulfonyl-4-nitrodiphenyl ether (compound No. 12), 30 parts of kaolin, bentodite 15 parts and 5 parts of soda lignin sulfonic acid were mixed and ground to obtain a hydrate.

[Example 3]

5 parts of 2'-chloro-4'-trifluoromethyl-3-acetylaminosulfonyl-4-nitrodiphenyl ether (compound of compound No. 1), 30 parts of bentonite, 60 parts of talc, 2 parts of naphthalene sulfonic acid After mixing and grinding three parts of lignin sulfonic-acid sodium, an appropriate amount of water was added and mixed, the particle | grains were manufactured using the granulator and the granules were obtained.

[Example 4]

5 parts of 2'-chloro-4'-trifluoromethyl-3-N, N-dimethylcarbamoylaminosulfonyl-4-nitrodiphenyl ether (compound No. 7), 50 parts of talc, 45 parts of kaolin uniform Mixed and ground to obtain a powder.

Next, the effect of the herbicide of the present invention will be described in detail according to the experimental example. In addition, the test compound number is the same as the compound number mentioned above.

Experimental Example 1

Testing of Herbicidal Effects on Water Soil Treatment

(아아르)·와그너포트(pot)에 논의 토양을 채우고, 표층에 반야드그래스(barnyardgrass), 투스컵(tooth cup), 홈스핌퍼넨(false pimpernel), 스몰 플라워 엄브렐라플렌드(Small flower Umbrella Plant), 호타루이(Hotarui), 헤라오모다카(Heraomodaka)의 각종 잡초종자를 파종하고, 물을 가하여 써레질한다.

Fill up the soil in the (ar) and wagnerpots, and fill the surface with barnyardgrass, tooth cup, false pimpernel, small flower Umbrella Plants, Hotarui and Heraomodaka are sown and sown by adding water.

Next, we bought tubers of Slander Spike rush, Urikawa and Mizu-gaya tsuri, and transplanted 4,5 rice seedlings and added 3 cm of water. It was in the state of deep water.

Subsequently, three days later, the dilution liquid (active ingredient amount: 40, 20, 10 g equivalent amount per a) of each hydration agent prepared according to Formulation Example 2 was uniformly dispersed in the deep water surface. Growth control was carried out in a glass chamber at 25 ° G, and the herbicidal effect of each test compound was examined for 3 weeks after dispersion. The results are shown in Table 2. In addition, the indication of the herbicidal effect was based on the following criteria.

5: Complete Examination 4: Daehan (大 害) 3: Middle Sea 2: Minor Sea 1: Minor Sea 0: Harmless (normal growth)

[Table 2]

Experimental Example 2

Test of gymnastic effect on the field (pretreatment soil treatment)

·와그너포트예 밭의 토양을 채우고 소맥, 옥수수, 콩 및 목화종자를 파종하고 만나그래스(manna grass), 콤몬 펄스레인(Common purslane), 화이트 구즈 훗(white hoose foot), 와일드 아마란스(wild amaranth), 추파(chufa)의 각 잡초종자를 혼합한 토양으로 복토하고, 적량의 관수를 했다. 1일후, 제제예 2에 따라서 제조한 각 수화제의 희석액(유효성분량 : a당 40, 20, 10g 상당량)을 토양 표면에 분무 산포하였다. 25℃의 유리방내에서 생옥 관리하고, 산포후 3주일째에 각 시험화합물의 제초효과를 조사했다. 그 결과를 표 3에 표시하였으며 제초효과의 표시기준은 실험예 1의 경우와 동일하다.

Fill the soil of the Wagnerporte field, sowing wheat, corn, soybeans and cotton seeds, manna grass, common purslane, white hoose foot, wild amaranth Were covered with soil mixed with each of the weed seeds of chufa and watered appropriately. After 1 day, the dilution liquid (active ingredient amount equivalent to 40, 20, 10 g per a) of each hydration agent prepared according to Formulation Example 2 was spray-spread on the soil surface. The jade control was carried out in a glass chamber at 25 ° C., and the herbicidal effect of each test compound was examined three weeks after scattering. The results are shown in Table 3, and the criteria for labeling the herbicidal effect is the same as in Experiment 1.

Table 3

Experimental Example 3

Assay of foliage foliar herbicidal effect

·와그너 포트에 밭의 토양을 채우고, 만나그래스(manna grass), 와일드 아마란스(wild ama-ranth), 화이트 구즈 홋(white goose foot)을 파종하고, 25℃의 유리방내에서 발아 생육시켰다. 만나그래스 3엽기, 와일드 아마란스, 화이트 구즈 훗이 2장의 떡잎이 나왔을때 제제예 2에 따라서 제조한 각 수화제의 희석액(유효성분 농도 : 0.4, 0.2, 0.1%)을 포트당 5ml 채우고, 경엽에 분무산포하였다. 25℃의 유리방내에서 생육관리하여, 산포후 3주일째에 각 시험약제의 제초효과를 조사하였다.

Wagner pots were filled with soil in the fields, manna grass, wild ama-ranth and white goose foot were sown and germinated and grown in a glass chamber at 25 ° C. When three leaves of Mannagrass, Wild Amaranth and White Goose Fut were found, two ml of each cotyledon were filled with 5 ml per pot of diluent (active ingredient concentration: 0.4, 0.2, 0.1%) of each hydrating agent prepared according to Preparation Example 2. It was. Growth control was performed in a glass chamber at 25 ° C., and the herbicidal effects of each test drug were examined at 3 weeks after dispersal.

The results are shown in Table 4, and the labeling criteria of the herbicidal effect is the same as in Experiment 1.

Table 4

Claims (1)

Next, the compound of formula (A) was suspended in a mixed solution of glacial acetic acid and water, and chlorine gas was introduced and stirred while stirring to obtain a compound of formula (B), which was then reacted with ammonia to obtain a compound of formula (C). A method for producing diphenyl ether represented by the following general formula (E), which is reacted with potassium carbonate and the following general formula (D) in the next acetone.

Wherein X and Y represent a halogen atom or a trifluoromethyl group, provided that Y represents a trifluoromethyl group when X is a halogen atom, and Y represents a halogen atom when X is a trifluoromethyl group. R represents a methyl group, a chloromethyl group, a phenyl group, a lower alkoxy group, or a dimethylamino group.