KR820000627B1 - Process for the preparation of phenoxy phenylthio alkane carboxylic acid derivatives - Google Patents

Abstract

Title compds.(I; A = CN or COB where B = ONR1R2 where R1,R2 = alkyl, etc.; C = H, halo, CN, alkyl, or alkoxyl; D = H, halo, CN, NO3, or CF3; E = H, halo, CN, NO2, alkyl, etc.; Hal = halo; n = 0, 1, or 2; = alkylene, alkoxy, etc.) are herbicides and plant growth regulators. Thus, 1 kg Na Me 3-(2',4'-dichlorophenoxy)-6-cyanophenylthioacetate/ha controlled Echinochloa crus-galli, Sagittaria pygmaea, Cyperus difformis, Ammania, and Rotala in rice paddies.

Description

Method for preparing phenoxyphenyl thioalkane carboxylic acid derivative

The present invention relates to a process for the preparation of novel phenoxyphenylthioalkane carboxylic acid derivatives useful as herbicides and plant growth regulators, to compositions comprising them as active ingredients, and to their use.

The novel phenoxyphenyl thioalkane carboxylic acid derivative has the following structural formula (1).

In the above structural formula

A represents a cyano group or a -COB group.

B represents -ON = CR ₁ R ₂ , -OR ₃ , -SR ₄ or -NR ₅ R ₆ .

C represents hydrogen, halogen, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy

D represents hydrogen, halogen, cyano, nitro, trifluoromethyl.

E represents hydrogen, halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, methylsulfonyl, dimethylsulfamoyl

Hal represents halogen.

n is 0, 1 or 2.

Q is branched and straight chain C ₁ -C ₄ alkylene bridge which is unsubstituted or substituted by halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxycarbonyl or cyano.

R ₁ and R ₂ are each C ₁ -C ₄ alkyl or one of them represents hydrogen.

의 양이온을 나타내는데 상기에서 M은 알칼리금속 또는 알칼리토금속의 양이온, 철, 구리, 아연, 망간 또는 니켈양이온 또는 암모니오기이고R ₃ and R ₄ are hydrogen: acetoxy, acetyl or methyl unsubstituted or substituted, alkyl or base having 2 to 18 carbon atoms

Where M is a cation of alkali metal or alkaline earth metal, iron, copper, zinc, manganese or nickel cation or ammonium

m is an integer corresponding to the valence of the cation 1, 2 or 3, and Ra, Rb, Rc and Rd are each independently substituted with hydrogen in the presence of benzyl or -OH, -NH ₂ or C ₁ -C ₄ alkoxy C ₁ It represents a -C ₄ alkyl group. R ₃ and R ₄ are also C ₁ -C ₁₈ alkyl groups substituted by unsubstituted or halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylthio, C ₃ -C ₈ cycloalkyl, nitro or cyano , C ₃ -C ₁₈ alkenyl group, C ₃ -C ₁₈ alkynyl group, phenyl or unsubstituted or halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ Benzyl groups substituted with alkylthio, cyano, nitro or trifluoromethyl.

R ₅ and R ₆ are independently of one another and are hydrogen, unsubstituted or C ₁ -C ₄ alkoxy, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxy substituted with halogen hydroxyl, or nitrogen attached together Together represent a 5 to 6 membered heterocycle, which may include nitrogen, oxygen or sulfur as the secondary complex element and may be substituted by C ₁ -C ₄ alkyl or phenyl.

Alkyl groups in the above formulas may or may not have side chains and include the indicated number of carbons.

Alkylene bridges may represent methylene bridges, 1- or 2-ethylene bridges, straight chain 1- or 2-ormethylethyl or 1,1-dimethylmethylene, branched propylene bridges and straight or corresponding branched butylene bridges.

Form a 5- to 6-membered heterocycle with nitrogen to which R ₅ and R ₆ are attached together to form a pyrrole, pyrrolidine, pyridine and piperadine ring, in which case the heterocycle contains a secondary complex Piperazine, oxazole, thiazole, morpholino and thiomorpholino rings may also be represented.

These rings may be substituted by C ₁ -C ₄ alkyl and the piperazine ring may also be substituted by phenyl.

The compounds of the present invention are low in toxicity to warm-blooded animals and have no problems in their application. These are stable compounds soluble in common organic solvents such as alcohols, ketones, dimethyl formamide, dimethyl sulfoxide and the like. Normal application rates range from 0.1 to 5 kg per hectare.

The active compound of formula (I) of the present invention has herbicidal activity, which is particularly good for pre-germination and post-germination applications and can be used as a weed remover in monocotyledonous and dicotyledonous crops. They also have beneficial growth control effects (growth inhibition) and especially inhibit the growth of dicotyledonous plants.

Examples of useful applications of the compounds of the present invention are as follows.

Increased hydration is obtained by inhibiting the growth of soybeans and similar legumes.

-It is possible to promote the formation of larger and better leaves by inhibiting unnecessary bleeding and growth of cuts that have been cut off in tobacco crops.

-Inhibit the growth of fruit trees, ornamental waters, shrubs and shrubs in order to save cutting labor.

The novel compounds of formula (I) can be prepared by the following schemes.

In the above structural formulas A, C, D, E, Hal, n and are as defined in formula (I).

Recently, many patent documents regarding various substituted diphenyl ethers having herbicidal activity have been published. Many known phenoxythioalkane carboxylic acid derivatives are also known.

Reference: German Publication No. 2,223,894.

However, the herbicidal activity of extremely low concentrations of known phenoxy phenylthioalkane carboxylic acid derivatives was not satisfactory.

The compounds of formula (I) of the present invention have strong herbicidal properties and also have selective herbicidal activity.

The following examples detail how to obtain the compound of formula (I). Other active compounds prepared by the corresponding methods are listed in the following table. Percent is related to weight.

Example 1

[3- (2 ', 4'-Dichlorophenoxy) -6-cyano-phenylthio acetic acid methyl ester]

a) 12 g of 4-chloro-2-methylmercapto-nitrobenzene are heated to 160 ° C. in 50 ml of dimethyl sulfoxide containing 10 g of 2,4-dichlorophenol and 2.5 g of sodium hydroxide. After 2 hours it is poured on ice and extracted with ethyl acetate. The organic solution was concentrated and the residue was recrystallized from toluene / hexane to yield 16 g of 2,4-dichloro-3'-methylmercapto-4'-nitrophenyl ether having a melting point of 120 ° to 122 ° C. Catalytic reduction in dioxane with Ranickel yields 2,4-dichloro-3'-methylmercapto-4'-aminodiphenyl ether in quantitative yield. The melting point is 40 ° to 43 ° C.

b) 65 g of this compound are mixed with 300 ml of water and 144 ml of concentrated sulfuric acid and the mixture is cooled to 0 ° C. A diazonium salt solution is prepared by reacting a 5% sodium nitrite solution at 0 ° to 5 ° C. After 1 hour, a solution of 39.5 g of potassium iodide dissolved in 370 ml of water was added dropwise at 0 ° C. A crude precipitate is formed which is added to methylene chloride and dissolved after 2 hours. The organic phase is separated and concentrated. The residue is repeatedly extracted with warm hexane and the combined hexane extracts are concentrated and cooled. Crystallization gives 67 g of 2,4-dichloro-3'-methylmercapto-4-urido-diphenylether.

c) 15 g of this compound are stirred in a nitrogen atmosphere with 3.5 g of copper cyanide in 50 ml of N-methyl-2-pyrrolidone at 140 ° C. After 3 hours the reaction mixture is cooled and stirred with 500 ml of water and 20 ml of ammonia. The precipitate was collected, dried and recrystallized from toluene / hexane to yield 10 g of 2,4-dichloro-3'-methylmercapto-4'-cyano-diphenylether at 84 ° C.

d) 5 g of this compound are refluxed in 20 ml methyl bromoacetate. After 8 hours, methyl bromacetate was distilled off and the residue was purified by chromatography to give the title compound at 95 ° C. with unreacted starting material.

Example 2

[3- (2 ', 4'-Dichlorophenoxy) -6-urido-phenylthioacetic acid methyl ester]

10 g of 2,4-dichloro-3'-methylmercapto-4'-urido-diphenyl ether and 20 ml methylbromo acetate are refluxed for 10 hours and purified by silica gel column chromatography using cyclohexane as a solvent. Evaporating off the solvent yields 7 g of a clear oil with a refractive index n ₂₄ ^D : 1.6528.

Example 3

[β- [3- (2'-Chloro-4-trifluoromethylphenyl) -phenylthio] propionic acid ethyl ester]

71 g of 3-methylmercaptophenol, 118.5 g of 3,4-dichloro benzotrifluoride and 22.5 g of sodium hydroxide are reacted for 4 hours at 140 ° C. in 400 ml of dimethyl sulfoxide. Pour the reaction mixture onto ice. The precipitated oil is taken up in ether and purified by distillation. 32 g of 4-trifluoromethyl-2-chloro-3'-methylmercapto-diphenylether (boiling point 115 ° to 120 ° C./0.02 torr) obtained in good yield of the result was 90 g of ethyl 3-bromopropio. The crystals of nate and potassium iodide are stirred at 170 ° C. for 10 hours. Distillation produces the title compound slowly with unreacted starting material. Boiling Point: 250 ° C / 0.03 Torr (in Bulb Tube)

Example 4

α- [3- (2 ', 4'-dichlorophenoxy) -6-chlorophenylthio] propionic acid methyl ester

a) To a solution of 400 g di- (2 ', 4'-dichlorophenoxy) nitrobenzene, 64 g 85% potassium hydroxide and 700 ml dioxane add 45 g of methylene mercaptan at 50 ° to 70 ° C. After 1 hour the solvent is stirred off in vacuo and the residue is taken up in toluene. The solution is washed with dilute sodium hydroxide solution and liberated from 2,4-dichlorophenyl which is added dropwise to a mixture of 500 g of iron powder, 500 g of ethanol and 50 ml of concentrated hydrochloric acid. After refluxing for 15 hours, the alkaline residue was alkalized with 30% sodium hydroxide solution, and iron residue was removed by suction filtration and the filter cake was washed with toluene. Concentration and distillation of the organic phase of the filtrate yields 192.5 g of compound of Example 1a, having a boiling point of 170 ° C./0.1.

b) The compound of Example 3 a) is dissolved in 1.5 liter of glacial acetic acid and 153 ml of hydrochloric acid are added to the solution. A solution of 41.5 g of sodium nitrite dissolved in 100 ml of water at 5 ° C. was added dropwise to prepare a diazo solution. The excess nitrite is decomposed to sulfamic acid and the diazo solution is added dropwise to 75 liters of 90 캜 and 2 liters of 18% hydrochloric acid and 118 g of copper chloride (I). After 1 hour it is extracted with toluene and the organic phase is concentrated. Distillation of the residue gave 3- (2 ', 4'-dichloro phenoxy) -6-chloro methylmercapto benzene having a boiling point of 158 ° C / 0.05.

c) 140 g of the compound of Example 3 b) is refluxed for 16 h in 10 ml of crystals of methyl 2-bromopropionate and potassium iodide. Subsequent distillation yields 150 g of the title compound having a boiling point of 186 ° C./0.09.

Example 5

α- [3- (2'-chloro-4'-trifluoromethylphenoxy) -6-chlorothio] propionic acid methyl ester

a) After sufficient stirring, 241 g of 2-chloro-5-methoxy-aniline are added to 310 ml of water and 385 ml of concentrated hydrochloric acid followed by 750 g of ice. The mixture is cooled to -10 ° C, a solution of 111 g of sodium nitrite dissolved in 150 ml of water is added all at once, and the temperature is raised to 10 ° C. After 30 minutes excess nitrite is broken down into sulfamic acid and the solution is filtered off. Add this diazo solution to a solution of 300 ml of water, 800 ml of toluene, 225 g of sodium methylxanthogenate, 85 g of sodium bicarbonate and 75 ml of 30% sodium hydroxide at 55 to 60 ° C. This is separated, which is washed with water, dried over sodium sulfate and 100 ml of triethylamine are added dropwise at 70 ° C. After refluxing for 2 hours and cooling and adding 200 ml of 30% sodium hydroxide solution, the organic phase is separated and distillation produces 4-chloro-3-methylmercaptoanisole having a boiling point of 138 ° to 145 ° C / 11.

152.2 g of this compound was prepared using J. Am. Chem. Soc. Similar to the method described in 79,720, saponification yields 110 g of 4-chloro-3-methylmercaptophenol.

Boiling Point: 117 ° to 121 ° C / 0.03

b) 50 g of 4-chloro-3-methylmercaptophenol, 62 g of 3,4-dichloro benzotrifluoride and 12 g of sodium hydroxide are stirred at 142 ° C. for 6 hours in 150 ml dimethylsulfoxide. The reaction mixture is poured into ice and extracted with toluene. Distillation of the organic phase gave 81 g of 3- (2'-chloro-4-trifluoromethylphenoxy) -6-chlorothioanisole having a boiling point of 158 ° C / 0.4.

20 g of the compound of Example 4 b) are stirred with 190 ml methyl 2-bromopropionate at 190 ° C. for 20 h and then distilled in a bulb tube.

Product: 21 g of α-[-3- (2'-chloro-4'-trifluoro methylphenoxy) -6-chlorophenylthio] propionic acid methyl ester

Boiling Point: 200 ℃ / 0.13

Example 6

α- [3- (2'-chloro-4'-trifluoromethylphenoxy) -6-methoxythio] propionic acid methyl ester

a) 187 g hydroquinone monomethyl ether, 324 g 3,4-dichlorobenzotrifluoride and 60 g sodium hydroxide are stirred in 500 ml dimethylformamide at 140 ° C. for 5 hours. The reaction mixture is poured onto ice and collected by suctioning off the precipitate 2-chloro-4-trifluoromethyl-4'-methethoxydinyl ether. 315 g of foreign compound (melting point: 60 ° to 63 ° C.) are treated dropwise at 10 ° C. in a mixture of 170 g of mixed acid of 67 g of fuming nitric acid and 103 g of concentrated sulfuric acid and 1 liter of glacial acetic acid. After stirring for 3 hours, the precipitate was collected by suction and dried to give 291 g of 4- (2'-chloro-4'-trifluoromethyl-phenoxy-2-nitroanisole having a melting point of 90 ° to 92 ° C. .

b) 318 g of the compound of Example 5a) is hydrogenated with nickel as a catalyst in dioxane. The catalyst is separated off and the reaction solution is concentrated.

Product: 300 g 4- (2'-chloro-4'-trifluoromethyl-phenoxy) -2-amino-anisole.

Boiling Point: 185 ° C / 0.4 (Distilled in Bulb Tube)

Melting Point: 36 ° to 38 ° C

c) 97 g of the compound of Example 5 b) is diazotized with sodium nitrite by Example 4a) in 100 ml of dimethyl formamide, 100 ml of concentrated hydrochloric acid and 100 ml of water and the idiazo solution is reacted with potassium methylxanthogenate To give 4- (2'-chloro-4'-trifluoromethyl-phenoxy) -2-methylmer capto-anisole.

Boiling Point: 150 ° to 155 ° C / 0.01

d) Reacting 8 g of the compound of Example 5c) with 2-bromo-propionate in Example 3c) yields the title compound.

Boiling Point: 190 ° C / 0.0001 (Distilled in Bulb Tube)

The novel compounds of formula (I) are stable compounds that are soluble in common organic solvents such as alcohol ethers, ketones, dimethylformamide, dimethyl sulfoxide and the like.

The composition of the present invention is obtained by uniformly mixing and grinding the compound of formula (I) together with a suitable carrier, with or without a dispersant or solvent which is inactive with the active ingredient in a known manner. The active substance can be processed into the following formulation.

[Solid formulation:

Powders, powders, granules (coatings, saturated granules, and homogeneous granules): Active substances which can be dispersed in water:

Hydrating, Pasting, Emulsion:

Liquid formulation: Solution

The concentration of the active ingredient in the composition is from 1 to 80% by weight and low concentrations of 0.05 to 1% by weight is possible. The composition of the present invention can be used in combination with other pesticide active substances or compositions.

The active compound of formula (I) may be formulated as follows. (Part is about weight)

[Emulsion]

The following ingredients are mixed to produce 25% emulsion.

25 parts Active substance of formula (I)

Mixture of 5 parts nonylphenolpolyoxyethylene and calcium dodecylbenzenesulfonate

15 parts cyclohexanone

55 parts xylene

This concentrate can be diluted with water to form an appropriate emulsion of 0.1 to 10%. This emulsion is suitable for removing weeds from plant cultivation.

[Mouth]

5% granules are prepared using the following materials.

Part 5 Active substance of structural formula (I)

0.25 parts epichlorohydrin

0.25 parts cetyl polyglycol ether

3.50 parts of polyethylene glycol

91 parts kaolin (0.3-0.8 mm particle size)

The active material is mixed with epichlorohydrin and dissolved in 6 parts of acetone followed by addition of polyethylene glycol and cetyl polyglycol ether. The resulting solution is sprayed on kaolin and then evaporated in vacuo.

[Handmade]

The following components are used to prepare a) 70% and b) 10% hydrating agent.

a) 70 parts of active substance of formula (I)

5 parts sodium dibutylnaphthalene sulfate

3 parts naphthalenesulfonic acid / phenolsulfonic acid / formaldehyde concentrate (3: 2: 1)

10 kaolins

12 Champagne Chokes

b) 10 parts of active substance of formula (I)

Mixture of sodium salt of 3 parts saturated fatty alcohol sulfate

5 parts naphthalenesulfonic acid / formaldehyde concentrate

82 kaolins

Each active substance is attached to the corresponding carriers (kaolin and choke), mixed and ground to produce highly hydrated hydrating agents and suspending agents. Dilution of this hydrous with water gives a suspension containing 0.1-80% of the active material. This suspension is suitable for removing weeds from plant cultivation.

[Paste]

45% paste was prepared using the following materials.

45 parts Active substance of formula (I)

5 parts sodium aluminum silicate

14 parts cetylpolyglycol ether and 8 moles of ethylene oxide

1 part oleyl polyglycol ether and 5 moles of ethylene oxide

Part 2 Spindle Oil

10 parts polyethylene glycol

23 parts water

The active material is mixed with the above ingredients and ground. Dilution with water gives a paste to prepare a suspension of the desired active substance concentration.

The 3-phenoxy-α-phenyl thioalkane carboxylic acid derivatives of the novel structural formula (I) and compositions comprising them have excellent selective herbicidal activity against vegetative weeds in various cultivated crops, and also have plant growth regulation.

A particularly preferred field of use is the use of grain crops, in particular for the selective weeding of dicotyledonous weeds in rice.

The novel active substance of formula (I) is effective for both pre-germination and post-emergence applications, but is preferably used as a post-emergence contact herbicide, but it is also safe to use before germination.

This active compound is suitable for post-germination application to crop plants when formulated in a diluted state of 25% hydrating agent, emulsion concentrate, and water.

Herbicidal activity when the active substance is applied after plant germination (after germination)

Various cultivated plants and vegetational weeds are grown until 4-6 leaves emerge from the greenhouse beds. These plants are sprayed with an aqueous emulsion of active material (obtained from 20% emulsion concentrate) at various application rates. Treated plants are stored under optimal light, water, temperature (22 ° to 25 ° C) and humidity (50 to 70% relative humidity) conditions. Results are evaluated 15 days after treatment.

In this test, all dicotyledonous plants and weeds were severely damaged by compound (I), monocotyledonous crops were hardly damaged, and vegetative weeds were moderately damaged.

Selective herbicidal activity against rice during germination

After germination, the 25-day-old rice is transferred to large asbestos cement containers in the greenhouse, and the weed seeds from the rice cultivation such as blood, olme, alpine garden, ammania and water flowers are placed between the rows of rice. Sprinkle. The water in the container is well controlled and maintained at 25 ° C and high humidity. After 12 days, weeds germinate, and when 2 or 3 leaves emerge, the soil of each container is filled with 2.5 cm high water. The active substance is applied with a pipette in the form of an emulsion concentrate or sprayed between the rows of plants in the form of granules. Emulsion concentrates are diluted to provide a ratio of 2 and 1 kg of active ingredient per hectare. Results are evaluated 4 weeks after treatment. In this test, compound (I) caused severe damage to dicotyledonous weeds such as ammonia and water flowers, and also caused significant damage to alpine acids. Rice was not damaged.

The test compounds of the present invention have strong contact herbicidal activity against some plants and growth inhibition against many other plantings.

[Inhibit growth of grasses]

Seeds of grasses, such as Lolium perenne King Poaful Gimbal, and Dactillis Glomerata, are sown on a plastic plate filled with a mixture of soil / eaten / sand (6: 3: 1). The germinated grass is cut about 4 cm from soil every week and sprayed with a mixture of active substances of formula (1) 1 day after the last cut. The application rate is 5 kg of active substance per hectare. Pasture growth is assessed 10 to 21 days after application.

[Growth Inhibition]

Seeds of Triticum aestivum, Summerde (Hordeum vulgare) and Rye (Secale) are sown in plastic beakers containing sterilized soil in the greenhouse. Five days after seeding, the young shoots of the grains are sprayed with a dilute solution of the active substance. It is applied to foliar at the rate of 6 kg of active substance per hectare. The results are evaluated after 21 days. The active substance of the present invention significantly inhibits the growth of grasses and cereals.

Claims (1)

Reaction of the alkylthiodiphenyl ether of formula (II) with the α-halocarboxylic acid derivative of formula (III) in an aprotic solvent, in the presence of a base as an acid acceptor and at temperature conditions between normal pressure and the boiling point of the reaction mixture To prepare a phenoxyphenylthio alkanecarboxylic acid derivative of formula (I).

In the above structural formula, A represents a cyano group or a -COB group. B represents -ON = CR ₁ R ₂ , -OR ₃ , -SR ₄ or -NR ₅ R ₆ . C represents hydrogen, halogen, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy and D represents hydrogen, halogen, cyano, nitro, trifluoromethyl. E represents hydrogen, halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, methylsulfonyl, dimethylsulfamoyl and Hal represents halogen. n is 0, 1 or 2. Q is branched and straight chain C ₁ -C ₄ alkylene bridge which is unsubstituted or substituted by halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxycarbonyl or cyano. R ₁ and R ₂ are each C ₁ -C ₄ alkyl or one of them represents hydrogen. R ₃ and R ₄ are hydrogen: methyl unsubstituted or substituted with acetoxy, acetyl or methyl; Alkyl of 2 to 18 carbon atoms; Or base

Wherein M is a cation of alkali metal or alkaline earth metal, iron, copper, zinc, manganese or nickel cation or ammonia group

m is an integer corresponding to the valence of the cation 1, 2 or 3, and Ra, Rb, Rc and Rd are each independently substituted with hydrogen in the presence of benzyl or -OH, -NH ₂ or C ₁ -C ₄ alkoxy C ₁ It represents a -C ₄ alkyl group. R ₃ and R ₄ are also C ₁ -C ₁₈ alkyl groups substituted by unsubstituted or halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₃ -C ₈ cycloalkyl, nitro or cyano, C ₃ -C ₁₈ alkenyl group, C ₃ -C ₁₈ alkynyl group, phenyl or unsubstituted or halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl unsubstituted or substituted with halogen Benzyl groups substituted with thio, cyano, nitro or trifluoromethyl. R ₅ and R ₆ are independently of one another and are hydrogen, unsubstituted or C ₁ -C ₄ alkoxy, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkoxy substituted with halogen hydroxyl, or nitrogen attached together Together represent a 5 to 6 membered heterocycle, which may include nitrogen, oxygen or sulfur as the secondary complex element and may be substituted by C ₁ -C ₄ alkyl or phenyl.