KR820000880B1 - Process for preparation of phenoxy-phenoxy-valeric acid derivatives - Google Patents

Abstract

Title compds. I (R1 = halo, CF3, C1-4 alkyl; Cat = cation of org. or inorg. base; n = 1-3) useful as herbicides against grassy weeds were prepd. by the reaction of compd. II with γ-valerolactone (III) in the presence of base. Thus, 4-(2',4'-dichlorophenoxy)-phenol was dissolved in anhydrous EtOH and Na added, distilled, then γ-valerolactone was added, heated to 210≰C for 24 hr, acidified, and recrystallized with hexane to give 90% 4-≮4'-(2",4"- dichlorophenoxy)-phenoxy≉-valeric acid (m.p. 88≰C).

Description

Method for preparing phenoxy-phenoxy vareric acid derivatives

The present invention relates to a process for the preparation of the compound of formula (I), which is effective as a herbicide.

Wherein R ₁ is halogen, CF ₃ or C ₁ -C ₄ alkyl, Cat is a cation of an inorganic or organic base and n is an integer of 1 to 3.

“Cat” refers to cations of inorganic bases such as Na ⁺ , K ⁺ , 1 / 2Ca ⁺⁺ and 1 / 2Mg ⁺⁺ or NH ₄ ⁺ and various aliphatic mono-, di- and tri-alkylamines, corresponding triethanol amines, Preference is given to cations of organic amines such as aniline, methylaniline, benzylamine and diphenylamine. Preferred halogens are chlorine and bromine.

Particularly preferred compounds are those wherein (R ₁ ) n is 4-chloro or 2,4-dichloro.

The compound of general formula (I) can be manufactured by various methods.

A) The compound of formula (III) is obtained by reacting the compound of formula (II) with the following reaction scheme.

Wherein R ₁ is halogen, CF ₃ or C ₁ -C ₄ alkyl, Z is -CN, -CS-NH ₂ , -CO-R ₂ or -CH ₂ -OR ₃ and R ₂ is hydroxy, -O- Cat, C ₁ -C ₁₂ alkoxy (optionally substituted with OH, halogen, CF ₃ , C ₁ -C ₆ alkoxy, C ₁ -C ₄ alkylthio, phenylphenoxy or halophenoxy), a radical of one of the formulas In other words

는 피롤리디닐, 피페리디닐, 모르폴리닐 또는 N-메틸-피페라지닐 래디칼을 나타냄), C₅-C₆사이클로알콕시(C₁-C₄알킬, 및/또는 할로겐으로 임의로 치환된), C₃-C₄알케닐옥시, 사이클로헥시닐옥시, C₃-C₄알키닐옥시(C₁-C₄알킬 및/또는 페닐로 1위치에서 임의로 치환된), 페녹시 (할로겐 NO₂및/또는 C₁-C₄알킬로 임의로 치환된), C₁-C₆알킬치오, 알릴치오, 페닐치오, 할로페닐치오, 아미노, 알킬아미노, 하이드록시 에틸아미노, 디-C₁-C₄알킬아미노, 피롤리디노, 피페리디노, 모르폴리노, 아닐리노(할로겐, CF₃및/또는 C₁-C₄알킬로 임의로 치환된), 또는 히드라지노이고 R₃는 수소, C₁-C₄알킬, C₁-C₄알킬카보닐, 할로-C₁-C₄-알킬카보닐, 벤조일(할로겐, NO₂및/또는 C₁-C₄알킬로 임의로 치환된), C₁-C₄알킬카바모일, 디-C₁-C₄알킬 카바모일, 페닐카바모일(할로겐 및/또는 C₁-C₃알킬로 임의로 치환된), C₁-C₄알킬설포닐, 페닐설포닐-SO₃H 또는 SO₃Cat (여기서 Cat는 유기 또는 무기염기의 양이온온이며) n은 1내지 3의 정수이고, m은 1내지 6의 정수이며 Y는 할로겐, 바람직하기로는 브롬 또는 염소 또는 메실레이트 또는 토실레이트 래디칼을 나타낸다.(here

Denotes pyrrolidinyl, piperidinyl, morpholinyl or N-methyl-piperazinyl radical), C ₅ -C ₆ cycloalkoxy (optionally substituted with C ₁ -C ₄ alkyl, and / or halogen), C ₃ -C ₄ alkenyloxy, cyclohexynyloxy, C ₃ -C ₄ alkynyloxy (optionally substituted in position with C ₁ -C ₄ alkyl and / or phenyl), phenoxy (halogen NO ₂ and And / or optionally substituted with C ₁ -C ₄ alkyl), C ₁ -C ₆ alkylthio, allylthio, phenylthio, halophenylthio, amino, alkylamino, hydroxy ethylamino, di-C ₁ -C ₄ alkyl Amino, pyrrolidino, piperidino, morpholino, anilino (optionally substituted with halogen, CF ₃ and / or C ₁ -C ₄ alkyl), or hydrazino and R ₃ is hydrogen, C ₁ -C ₄ Alkyl, C ₁ -C ₄ alkylcarbonyl, halo-C ₁ -C ₄ -alkylcarbonyl, benzoyl (optionally substituted with halogen, NO ₂ and / or C ₁ -C ₄ alkyl), C ₁ -C ₄ alkyl carbamoyl, di -C ₁ -C ₄ alkyl carbamoyl, Fe Carbamoyl (halogen and / or by C ₁ -C ₃ alkyl optionally substituted), C ₁ -C ₄ alkylsulfonyl, phenylsulfonyl -SO ₃ H or SO ₃ Cat (where Cat is a cation of an organic or inorganic base on N is an integer of 1 to 3, m is an integer of 1 to 6 and Y represents a halogen, preferably bromine or chlorine or mesylate or tosylate radical.

The reaction is preferably carried out under basic conditions at a temperature in the range of 20 ° C. to the boiling point of the mixture in an inert solvent such as toluene, xylene, dimethyl formamide or dimethyl sulfoxide. Suitable bases are alkali metal or alkaline earth metal carbonates or tertiary organic amines such as hydroxides or pyridine or triethylamine. Starting compounds of formulas (II) and (III) are well known in the literature and can be prepared by known methods.

B) Compounds of the following general formula (II) can be prepared by reacting under a temperature basic condition in the range of 100 ° C to 240 ° C with an γ-valeto-lactone equivalent or excess of the following general formula (IV). The reaction process is as follows;

The compound of the general formula (II) is preferably used in the form of its alkali metal phenolate. The reaction can be carried out in the presence or absence of a solvent.

C) The compounds of general formulas (I) and (I ′) thus obtained are subjected to known reactions, for example, saponification, esterification, salt formation, trans esterification, amidation, dehydration, hydration, reduction or oxidation, if necessary. It can be converted into other compounds of formulas (I) and (I '). Thus, for example, a compound containing functional group Z = COOH is used as an acid halide using a halogenating agent such as SOCl ₂ , an amide using an amine, a carboxylic acid salt using a base, an ester using an alcohol. Can be converted to

The ester can be obtained by reacting the corresponding acid halide with an alcohol or by alkylating a salt of the acid, for example with a halogen compound or dialkylsulfate.

는 니트릴그룹(Z=CN)에 하이드로겐 설파이드를 첨가시켜서 얻을 수 있다. 마찬가지로 관능기 Z=CONH₂는 니트릴 그룹에 물을 첨가시켜서 얻을 수 있으며, 관능기 Z=-CH₂OH는 예를들면 리치움 알루미늄 하이드라이드를 사용하여 에스테르 관능기를 환원시켜서 얻을 수 있다. 모든 이들 방법은 일반적으로 숙련된 사람에게 알려져 있다.Compounds containing functional group Z = CN can be obtained, for example, by dehydrating primary amide (Z = CONH ₂ ) with phosphorus pentoxide,

Can be obtained by adding hydrogen sulfide to the nitrile group (Z = CN). Similarly, the functional group Z = CONH ₂ can be obtained by adding water to the nitrile group, and the functional group Z = -CH ₂ OH can be obtained by reducing the ester functional group using, for example, richum aluminum hydride. All these methods are generally known to the skilled person.

Compounds of the general formula (I) according to the present invention are Avera spp., P. evergreen, D. grass, Setaria spp, Echin ochloa Spp, Digitaria Spp, Tolium spp, and Several major weeds, such as Poa spp, are treated before and after germination with excellent herbicidal effects. On the other hand, the compounds are well suited for the selective control of weeds in crops because of their good resistance to dicotyledonous plants and various grains, even at very high doses.

It is preferable that the composition of this invention contains 2 to 95% of an effective compound of general formula (I). These compounds can be manufactured by a hydrating agent, an emulsion, powder, granules, etc.

Wetting agents are agents that can be uniformly dispersed in water, in addition to active compounds, in addition to active compounds, wetting agents or wetting agents such as polyoxetylated alkylphenols, polyoxetylated orylamines, or stearylamines, alkylsulfonates or alkylphenyls. Sulfonates and dispersants such as sodium lignin-sulfonates, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate or sodium of oleyl methyl taurine.

Emulsions can be dissolved in organic solvents such as butanol, cyclohexane, dimethylformamide, xylene or high boiling aromatic compounds to form nonionic wetting agents such as polyoxetylated alkylphenols or polyoxetylated oleyl amines or stearyls. Obtained by adding amine.

Powders are obtained by grinding the active compound together with fine solids, for example talc, natural clays such as kaolin, bentonite, pyrophyllite or diatomaceous earth.

Granules may be sprayed with an active compound onto an absorbent granular inert material, or a concentrate of the active compound may be applied to sand, kaolin or granular inert material using auxiliaries such as polyvinyl alcohol, sodium polyacrylate or mineral oil. It can be prepared by spraying. Suitable formulations can be prepared by conventional methods of preparing the fertilizer by mixing with the fertilizer as necessary.

In the case of herbicides, the concentration of the active compound in the commercial formulation can be varied. In the hydrating agent, the concentration of the active compound is, for example, about 10% to 95% and the rest contains one or more of the above-mentioned additives. In emulsions the concentration of active compound is from about 10% to 80%. Powders usually contain 5 to 20% of active compound and sparse solutions contain about 2 to 20%. The content of the active compound in the granulation depends on whether the active compound is in liquid or solid form and depends on the use of auxiliaries, fillers and the like.

If necessary, commercially available solvents (concentrates) can be used by dilution with water in a conventional method, for example, a hydrating agent and an emulsion. Powders and granules can generally be used directly without dilution. The amount of active ingredient required to achieve herbicidal effects depends on external conditions such as temperature, humidity, soil type, and plant growth conditions. For example, it may vary in a wide range of 0.1 to 10.0 kg / ha, but a range of 0.1 to 5 kg / ha is preferable.

Other embodiments illustrate the invention.

Preparation Example A

The emulsion is obtained from 15 parts by weight of active compound, 75 parts by weight of cyclohexanol as solvent and 10 parts by weight of oxetylated nonylphenol (10 EO) as emulsifier.

[Example B]

A hydrating agent that can be easily dispersed in water is 25 parts by weight of an active substance, 64 parts by weight of quartz containing kaolin as an inert substance, 1 part by weight of sodium oleyl-methyl-taurine as a wetting agent and dispersant, and a pin mill ( Obtained by grinding in a pin mill).

[Example C]

The powder is obtained by mixing 10 parts by weight of active substance and 90 parts by weight of decoction as inert substance and grinding the mixture with a hammer mill.

Preparation Example D

The granules are made of, for example, about 2-15 parts by weight of active material and 98-85 parts by weight of inert granular material such as attapulgite, pumice and quartz sand.

Preparation Example 1

[4- [4 ′ (2 ″, 4 ″ -dichlorophenoxy) -phenoxy] -varerian acid]

20.3 g of 4- (2 ', 4'-dichlorophenoxy) -phenol are dissolved in 25 ml of anhydrous ethanol. 2.12 g of metallic sodium is added, the sodium is dissolved and the ethanol is distilled off.

Then 10 g of γ-baretolactone are added to solid 4- (2 ′, 4′-dichlorophenoxy) -phenol sodium and the whole is heated at 210 ° C. for 24 hours. The reaction mixture is acidified with concentrated hydrochloric acid and the residue is dissolved in toluene. The toluene layer was repeatedly extracted with methanolic bicarbonate saturated aqueous solution (50% strength). The combined extracts are acidified with concentrated hydrochloric acid and extracted with toluene. The solvent is removed under reduced pressure and then recrystallized from hexane. 23.9 g (90% of theory) of 4- [4 ′-(2 ″, 4 ″ -dichlorophenoxy) -phenoxy] -bareric acid are obtained.

Melting point 88 캜.

The following compounds are prepared in the same way.

2) 4- [4 ′-(4 ″ -chlorophenoxy) -phenoxy] -lebaric acid melting point 65 to 66 ° C.

3) 4- [4 ′-(4 ″ -trifluoromethylphenoxy) -phenoxy] -bareric acid

Production Example 4

25.9 g of 4- (2 ', 4'-dichlorophenoxy) -phenol dissolved in 150 ml of 4- [4'-(2 ", 4" -dichlorophenoxy) -phenoxy] -bareric acid butyl ester dimethylformamide 14.5 g of potassium carbonate and potassium carbonate were refluxed for 1.5 hours, 20 g of 4-chlorobaric acid butyl ester was added dropwise at 80 ° C., and the mixture was then heated to 120 ° C. for 12 hours. Distilled off The oily residue was treated with toluene, washed with dilute caustic soda solution and water and dewatered Toluene was removed under reduced pressure and the residue was distilled off at high solids.

32.1 g of 4- [4 '-(2 ", 4" -dichlorophenoxy) -phenoxy] bareric acid butyl ester (78% of theory) were obtained. The boiling point was 206 DEG C / 0.02 bar.

The following compounds are prepared in the same manner using 4-chloro vareronitrile.

5) 4- [4 ′-(4 ″ -trifluoromethylphenoxy) -phenoxy] -vareronitrile.

Preparation Example 6

[4- [4 ′-(2 ″, 4 ″ -dichlorophenoxy) -phenoxy] -bareric acid n-propyl ester]

29 g of 4- [4 ′-(2 ″, 4 ″ -dichlorophenoxy) -phenoxy] -bareric acid (Example 1) were heated to 60 ° C. with 30 ml of toluene and 12 g of thionyl chloride until gas evolution was completed. Heated to. Excess toluene and thionyl chloride are distilled off under reduced pressure. The remaining oil is treated with toluene and n-propane dissolved in 50 ml of toluene is added dropwise to a solution of 6 g and 8.5 g of triethylamine. After addition, the mixture is stirred at 50 ° C. for 1 hour and triethyl amino hydrochloride is filtered off and washed with water. After removing the solvent, the reaction product is distilled under high vacuum. 27.5 g of 4- [4 ′-(2 ″, 4 ″ -dichlorophenoxy) -phenoxy] -bareric acid n-propyl ester are obtained.

Boiling Point 2000 ℃ / 0.01bar

Production Example 7

[4- [4 ′-(4 ″ -trifluoromethylphenoxy) -phenoxy] -bareric acid secondary butyl ester]

29 g of 4- [4 ′-(4 ″ -trifluoromethylphenoxy) -phenoxy] -bareric acid, 1 ml of concentrated sulfuric acid, and 225 ml of butanol were dissolved in 300 ml of chloroform, and about 2 to 4 hours until water separation was completed. Heated to boiling point temperature. The reaction product is washed with saturated sodium bicarbonate and the solvent is distilled off under reduced pressure. The oily residue is distilled off under vacuum. Obtain 29.2 g (87.5% of theory) of 4- [4 '-(4 "-trifluoromethylphenoxy) -phenoxy] -bareric acid secondary butyl ester.

Preparation Example 8

[4- [4 ′-(4 ″ -trifluoromethylphenoxy) -phenoxy] -pentanol-1]

4- [4 ′-(4 ″ -trifluoromethylphenoxy) -phenoxy] -bareric acid isobutyl ester (Example 7) was added dropwise to a suspension suspension of 1.25 g of lithium-aluminum dissolved in 50 ml of 20.4 g ether. . After the addition was completed, the mixture was refluxed for 1 hour while stirring.

10 ml of ethyl acetate and 40 ml of water are then slowly added. Finally, 2N H ₂ SO ₄ is added with vigorous stirring until the aluminum hydroxide precipitate decomposes. The ether layer is washed with sodium bicarbonate until neutral and the solvent is distilled off under reduced pressure. Distillation under vacuum affords 15.4 g (90.5% of theory) of [4- (4 ″ -trifluoromethylphenoxy) -phenoxy] -pentanol-1.

Boiling Point 174 ℃ / 0.07 Bar

Preparation Example 9

[1-Chloroacetyloxy-4- [4 ′-(4 ″ -trifluoromethylphenoxy) -phenoxy] -pentane]

6.45 g of chloroacetyl chloride in 60 ml of anhydrous toluene was dissolved in 17.0 g of 4- [4 ′-(4 ″ -trifluoromethyl-phenoxy) -phenoxy] -pentanol-7 and 5.55 g of triethylamine at room temperature. Drop by Stirring is continued at 50 ° C. for 1 hour after addition. The precipitate is filtered off and the toluene solution is washed with dilute hydrochloric acid and water and dewatered. After removal of the solvent 18.5 g (89% of theory) of 1-chloro acetyloxy-4- [4 ′-(4 ″ -trifluoromethyl-phenoxy) -phenoxy] -pentane are obtained.

The following compounds are prepared in the same manner.

10) 1-benzoyloxy-4- [4 ′-(4 ″ -trifluoromethylphenoxy) -phenoxy] -pentane

11) 1-Methylsulfonyloxy-4- [4 ′-(4 ″ -trifluoromethyl phenoxy) -phenoxy] -pentane

12) The reaction mixture was prepared at about 10 ° C. at about 10 ° C. to prepare the compound after 1-N, N-dimethylcarbamoyloxy-4- [4 ′-(4 ″ -trifluoromethylphenoxy) -phenoxy] -pentane. Stir for time. Other compounds of the general formulas (I) and (I ·) which can be obtained according to the above examples are listed in the following table.

[table]

[Test Example I]

Weed seeds are planted in pots and sprayed onto the soil surface at various concentrations in a composition according to the invention in the form of a hydrating agent. The pot is left in the greenhouse for 4 weeks. The treatment results were evaluated according to the chart of the ball.

The test results in the following table showed excellent herbicidal effects even at low concentrations with pre-germination and post-germination treatment.

TABLE 1

Claims (1)

A process for preparing the compound of formula (I) characterized by reacting the compound of formula (II) with γ-valerolactone of formula (IV) in the presence of a base.

Wherein R ₁ is halogen, CF ₃ or C ₁ -C ₄ alkyl, Cat is a cation of an inorganic or organic base, n is an integer from 1 to 3.