KR820000879B1 - Process for preparation of phenoxy (or benzyl)-phenoxy propionic acid derivatives - Google Patents

Abstract

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Description

[Name of invention]

Method for preparing phenoxy (or benzyl) -phenoxy propionic acid derivatives

Detailed description of the invention

The present invention relates to a process for preparing the following general formula (I) compound having herbicidal and fungicidal action.

그룹이고, A는 치환되지 않거나 또는 메틸, 에틸, 아세틸 또는 일반식 -COOR′₃의 기타 잔기로 치환될 수 있는 메틸렌 그룹, 치환되지 않거나 또는 환상에서 할로겐 또는 (C₁-C₄)-알킬 및 니트로 그룹중에서 선택된 동일 또는 상이한 치환체 하나 또는 두개로 치환된 페닐렌 또는 스티릴 그룹이고, R₃와 R₃′는 같거나 다를 수 있으며 각각은 (C₁-C₄)-알킬 그룹이다.Wherein n and n ₁ are the same or different and are each an integer of 0 to 3 and R and R ₁ are each halogen or (C ₁ -C ₄ ) -haloalkyl, (C ₁ -C ₄ ) -alkyl, nitro, ( C ₁ -C ₄ ) -alkoxy or (C ₁ -C ₄ ) -alkylthio group and at least two of R and R ₁ may be the same or different and X is —0- or —CH ₂ — and Y is —0 -, -S- or -NH- and Z is cyanoethyl or a general formula

And A is a methylene group which may be unsubstituted or substituted with methyl, ethyl, acetyl or other moiety of the general formula -COOR ′ ₃ , unsubstituted or cyclically halogen or (C ₁ -C ₄ ) -alkyl and Or a phenylene or styryl group substituted with one or two of the same or different substituents selected from nitro groups, R ₃ and R ₃ ′ may be the same or different and each is a (C ₁ -C ₄ ) -alkyl group.

Preferred compounds of formula (I) are those wherein halogen is chlorine and / or bromine, the alkyl group has 1 or 2 carbon atoms, n is 1 or 2, n ₁ is 0 and Y is an oxygen atom.

Especially preferred are compounds wherein (R) n is 4-Cl, 2, 4-Cl, 4-Br, 2-Cl, 4-Br or 4-CF ₃ and n ₁ is 0 and X and Y are oxygen. Preferred Z is a cyanoethyl group, such as 2-cyanoethyl, or A-COOR ₃ group, wherein A is -CH _2- , -CH (CH ₃ )-or -CH (C ₂ H ₅ )- Compound.

The present invention relates to a process for preparing the compound of general formula (I) as follows:

The compound of formula (III) is prepared by reacting with the compound of formula (III).

Wherein n, n ₁ , R, R ₁ , X, Y and Z are as described above, one of the B and D residues is halogen and the other is a -YH group where H is substituted with an alkali or ammonium cation Can be).

In the general formulas (II) and (III), halogen is preferably chlorine or bromine.

The general formula (I) compound has excellent herbicidal activity against a wide range of weeds, both before and after germination. Thus, the compounds of the present invention are herbicidal against herbaceous weeds, such as Avena, Alopecurus, Lolium and Pork, Poultry and Burdock (Setaria, Echinocloa and Digitaria) among dicotyledonous crops. Has

Some compounds can selectively kill even herbaceous weeds in crops.

Soy, peanuts, dwarf beans, beans, peas, alfalfa, flax, cabbage, rapeseeds, cucumbers, sunflowers, tobacco, carrots, cedars and beets are generally not affected by high doses.

Due to the specific action on weeds, in particular oat grass, ragweed, barley, millet, the compounds of the present invention may be used in the preparation of Many good known herbicides, such as, can be used preferentially on strong weed breeding grounds.

Also, the amount necessary to completely remove the weeds is generally much smaller than the known herbicides mentioned above.

Another advantage of the compounds of the invention is their low toxicity to warm blooded animals.

Accordingly, the present invention relates to a method for removing weeds by spraying or weeding in an area or soil that is easily or invaded by weeds.

Surprisingly, compounds of general formula (I) also contain Piricularia oryzae, Pseudomonas aeruginosa, Botrytis cinerea, Plasmopara viticola, as well as harmful fungi that occur in useful substances. , Phytophora infestans, powdery mildew, Rhizoctonia solani, Septoria nodorum, Ustilago nuda, Phoma betae It also has excellent effects on plant diseases such as Pythium ultimum and Helminthosporium gramineum.

Therefore, the present invention also includes a method for preventing fungal infection by spreading the compound of the present invention to a fungus or a substance or area infected with or prone to fungus.

When used as a fungicide in useful articles, the compounds can be used as additives in lacquers, varnishes and paints. When used as a plant protection agent, the compound may be formulated as a powder, spray powder, dispersion or emulsion concentrate. The total amount of active ingredient is generally 2 to 80% by weight, depending on the formulation. They may also contain conventional tackifiers, wetting agents, dispersants, fillers and carriers. They can also be mixed with other fungicides.

The present invention therefore provides herbicides and / or fungicides containing a compound of formula (I) and a suitable carrier material.

Herbicides or fungicides may contain one or more conventional formulation aids and inert materials and generally contain from 2 to 95 (by weight) of the active substance of formula (I). For example, the preparations may be in the form of hydrating powders, emulsion concentrates, spray solutions, powders or granules.

Hydrated powders are preparations that can be uniformly dispersed in water and are polyoxethylated alkylphenols, polyoxethylated oleyl or stearyl amines or alkyl or alkylphenyl sulfonates, in addition to the active ingredient, separately from diluents or inert ingredients. And humectants such as lignin sulfonic acid, dispersing agents such as sodium salts of 2,2'-dinaphthylmethane-6,6'-disulfonic acid or oleoylmethyllauric acid.

Emulsifying concentrates are obtained by dissolving the active ingredient in organic solvents such as butanol, cyclohexanone, dimethylformamide, xylene or aromatics with relatively high boiling points.

Powders or spray powders may be obtained by counting the active ingredient as natural earth, such as talc or kaolin, benzoite, pyrophyllite or diatomaceous earth and grinding it together with the body material.

Spray solutions widely used in spray cans contain active ingredients dissolved in organic solvents and other sprays such as mixtures of fluorochlorohydrocarbons and / or carbon dioxide.

Granules may be sprayed onto granulated inert materials which adsorb the active ingredient or by using an adhesive such as polyvinyl alcohol, sodium salt of polyacrylic acid or mineral oil to concentrate the active ingredient concentrate such as sand, kaolinite or granulated inert materials. It can be prepared by adhering to the surface of the carrier material. Alternatively, suitable actives can be formulated by mixing with fertilizers as needed in the conventional manner for preparing fertilizer granules.

The concentration of active ingredient in the herbicide formulation can vary depending on the formulation. For hydrating powders, the concentration of the active ingredient is 10 to 80% and the rest are the above-mentioned formulation additives. The concentration of active ingredient in the emulsion concentrate is from 10 to 80%. Powders usually contain from 5 to 20% of the active ingredient and from spraying solutions are from 2 to 20%. The amount of active ingredient in the granules to some extent depends on whether the active ingredient is liquid or solid and also on the choice of granulation aids, fillers and other substances.

When a commercially available commercial concentrate is used, it can be diluted by the conventional method as needed, for example, in the case of a hydrating powder or an emulsion concentrate, using water. Powders, granules and spray solutions are generally not diluted with other inert materials before use. The amount required for spraying depends on external conditions such as temperature and humidity, and 0.1 to 10 kg / ha of active ingredient may be used, but it is preferable to spray 0.1 to 3 kg of active ingredient. The active ingredient according to the invention can be combined with one or more other herbicides and / or soil pesticides.

The following examples illustrate the invention.

[Production example]

Example 1

[2- [4 ′-(4 ″ -chlorophenoxy) -phenoxy] -propionyl lactic acid methyl ester]

81 g of 2- [4 ′-(4 ″ -clophenoxy) -phenoxy] -propionic acid and 48 g of 2-bromopropionic acid methyl ester solution dissolved in 160 ml of acetone were stirred for 8 hours with 40 g of potassium carbonate. Boil together and heat. After cooling to 20 ° C., inorganic salts are filtered out. Acetone is distilled from the filtrate and the residue is distilled under vacuum.

91 g (yton yield 87%) of the following structural compound is obtained. Boiling Point: 190 to 191 ° C / 0.1.

Example 2

[2- [4 ′-(2 ″, 4 ″ -dichlorophenoxy) -phenoxy] -propionylglycolic acid methyl ester]

61 g of 2- [4 ′-(2 ″, 4 ″ -diclophenoxy) -phenoxy] -propionic acid and 24 g of chloroacetic acid methyl ester are dissolved in 200 ml of butanone. After adding 26 g of potassium carbonate, the mixture is stirred and heated to boiling for 8 hours. The reaction mixture is cooled to 20 ° C. and inorganic salts are filtered out. The butanone in the filtrate is distilled off and the resulting ester is purified by vacuum distillation.

67 g (90.9% of theoretical yield) of the following structural compound are obtained. Advantage: 207-208 ° C./0.05.

Example 3

[2- [4 ′-(2 ″, 4 ″ -dichlorophenoxy) -phenoxy] -propionylthiogly- glycolic acid methyl ester]

48 g of thioglycolic acid methyl ester is dissolved in 200 ml of toluene. 156 g of 2- [4 ′-(2 ″, 4 ″ -dichlorophenoxy) -phenoxy] -propionic acid chloride dissolved in 150 ml of toluene at a temperature of 20 to 40 ° C. and 48 g of anhydrous tree dissolved in 50 ml of toluene Ethylamine is added dropwise at the same time. The mixture is then stirred at 40 ° C. for 2 hours. The resulting triethylamine chloro hydrate is suction filtered. Toluene in the filtrate is distilled off and the residue is purified by distillation at 0.2 Torr.

180 g (96% of theoretical yield) of the following structural compound are obtained. Boiling Point: 230 to 232 ° C / 0.2.

Example 4

[2- [4- (4 ″ -bromophenoxy) -phenoxy] -propionic acid 2-cyanoethyl ester]

30 g of 3-hydroxypropionic nitrile are dissolved in 150 ml of toluene. 143 g of 2- [4 ′-(4 ″ -bromophenoxy) -phenoxy] -propionic acid chloride dissolved in 100 ml of toluene at 20 to 40 ° C. and 40 g of anhydrous triethylamine dissolved in 50 ml of toluene simultaneously Add it down. The mixture is then stirred at 40 ° C. for 2 hours, cooled to 20 ° C., suction filtered and the toluene is distilled from the filtrate. 151 g of residue are obtained. This residue is distilled off to give 138 g (88%) of the following structural compound. Boiling Point: 208 to 210 ° C / 0.1.

Example 5

[2- [4 ′-(4 ″ -trifluoromethylphenoxy) -phenoxy] -propionic acid 4-methoxycarbonylphenyl ester]

23 g of 4-hydroxybenzoic acid methyl ester and 17 g of mousse triethylamine are dissolved in 120 ml of toluene. 52 g 2- [4 ′-(4 ″ -trifluoromethylphenoxy) -phenoxy] -propionic acid chloride in 80 ml of toluene at 20-40 ° C. is added dropwise. The mixed solution was stirred at 40 ° C. for 2 hours, cooled to 20 ° C., and triethylamine chlorohydrate was suction filtered to distill toluene from the filtrate. The oily material obtained is recrystallized from n-hexane.

64 g (theoretical yield 92%) of the following structural compound are obtained. Melting Point: 78 ~ 79 ℃

Example 6

[2- [4 ′-(2 ″, 4 ″ -dichlorophenoxy) -phenoxy] -propionyloxy (2acetoacetic acid methyl ester)]

70 g of sodium salt of 2- [4 ′-(2 ″, 4 ″ -dichlorophenoxy) -phenoxy] -propionic acid are suspended in 300 ml of benzene and 32 g of 2-chloroacetoacetic acid methylester are added. After stirring at 80 ° C. for 8 hours, the mixture is cooled and sodium chloride is filtered off. Toluene is distilled off.

76 g of the following structural formula is obtained as a yellow oily substance. n _D ²⁵ = 1.5593

The compounds in the following table are prepared according to the method of Examples 1-6.

TABLE 1

TABLE 2

Example 88

[2- [4 ′-(2 ″, 4 ″ -dichlorobenzyl) -phenoxy] -propionyl lactic acid methyl ester]

44 g of 2- [4 ′-(2 ″, 4 ″ -dichlorobenzyl) -phenoxy] -propionic acid, 27 g of 2-bromopropionic acid methyl ester, 21 g of anhydrous potassium carbonate and 100 ml of acetone at 60 ° C. for 8 hours Stir while. After cooling to 20 ° C., inorganic salts are filtered out. Acetone is distilled off from the filtrate and the residue is distilled under vacuum.

51 g (91.6% of theoretical yield) of the following structural compound are obtained. Boiling Point: 165-166 ℃ / 0.05.89

Example 89

[2- [4 ′-(4 ″ -chlorophenoxy) phenoxy] -propionyl taronic acid diethyl ester]

32 g of 2- [4 ′-(4 ″ -chlorophenoxy) phenoxy] -propionic acid sodium salt, 27 g bromomalonic acid diethyl ester, 1 ml of dimethylformamide and 150 ml of toluene at 80 ° C. for 18 hours Stir. After suction filtration of sodium bromide, toluene and excess bromomalonic acid diethyl ester are distilled off from the filtrate.

Obtain 43g (theoretical yield 96.0%) of the following structural formula, pale yellow oily matter. n _D ²⁵ : 1.5300

Example 90

[2- [4 ′-(2 ″, 4 ″ -dichlorophenoxy) -phenoxy] -propionyl tatronic acid diethyl ester]

35 g of 2- [4 ′-(2 ″, 4 ″ -dichlorophenoxy) -phenoxy] -propionic acid, 27 g of bromomalonic acid diethyl ester, 1 ml of dimethylformamide and 150 ml of toluene were subjected to 80 ° C. for 18 hours. Stir in After cooling to 20 DEG C, sodium bromide was filtered by suction, and toluene and excess bromomalonic acid diethyl ester were distilled off from the filtrate in vacuo.

Obtain 47 g of the following structural formula, a pale yellow oily substance (97% of theoretical yield).

n _D ²⁵ : 1.5337

Example 91

[2- [4 ′-(2 ″, 4 ″ -dichlorophenoxy) -phenoxy] -propionyl glycine methyl ester]

14 g in 80 ml of toluene was added 24 g (0.076 mol) of 2- [4 ′-(2 ″, 4 ″ -dichlorophenoxy) -phenoxy] -propionic chloride in 40 ml of toluene at a temperature of 10-15 ° C. (0.152 mol) of glycine methyl ester chlorohydrate freshly liberated glycine ester over 30 minutes dropwise. The mixture is then stirred at 15-22 ° C. for 2 hours. The resulting glycine methyl ester chlorohydrate is suction filtered. Distillation in vacuo from toluene filtrate.

Obtain 30 g of the following structural formula, a pale yellow oily substance.

Also mentioned are 2- [4 ′-(4 ″ -chlorophenoxy) -phenoxy] -propionyl thioglycolic acid methyl esters.

Biological Example

[Production]

In this example the results were evaluated according to the Bolle's plot of reference. [Reference: Nachrichtenblatt des. Deutschen pflanzen schutzdienstes 16, 1964, 92-94].

[Rating chart]

Example I Before Germination

Various weed seeds are sprayed on experimental seedlings, and sprayed bonsai or emulsified concentrates containing various compounds of the present invention are sprayed on the soil surface at different capacities. Fluorodiphene and mekoptops are used as comparative formulations. The seedlings are then transferred to the hotbed for 4 weeks and the results are evaluated according to Bolle's chart. The results are shown in Table A. As it turns out, the compounds according to the invention listed in Table A show very good action against weeds. It works at very low doses for almost all types of weeds, i.e. 0.15 kg / ha. Fluorodiphene and mecoprop are much weaker in herbicides.

TABLE A

Example II Post Germination Treatment

Various weed seeds are sown in seedlings and grown on hotbeds. Three weeks after sowing, various compounds of the present invention are sprayed to the plants at different doses as spray powders or emulsified concentrates and placed on a hotbed for four weeks, and the action of the compounds is evaluated according to the Bolle's diagram. Fluorodiphene and mekoptops are used as comparative formulations.

As can be seen from Table B, the compounds of the present invention have a very good action against weeds and are better than the known agents fluorodifen and mekoptop.

Example III Post-germination Treatment

Using a method such as Example II (post-germination treatment), various crops are spray sprayed with a suspension or emulsion of the compound according to the invention mentioned in Examples I and II. High doses of 2.5 kg / ha showed no damage to soybeans, peanuts, dwarf beans, soybeans, peas, purple crab, cabbage, cucumber, sunflower tobacco, carrots, cereals and beets. For barley and wheat, the formulations according to Examples 1,2,8,11,37,38,43,47,53,56 and 57 had no action.

Similar results are obtained when the compound is sprayed onto the soil surface by pre-germination treatment.

TABLE B

Biological Example

[Fungicide]

In this case, the following is used as a comparative preparation.

A = 5,6-dihydro-2-methyl-1,4-oxatiin-3-carboxanilide and methoxyethyl Hg silicate

B = manganese ethylene-1,2-bis-dithiocarbamate

D = tetramethylthiuram-disulfide (TMTD)

E = S-ethyl-N- (3-dimethylaminopropyl) -thiolcarbamate hydrochloride (prothiocarb)

Example IV

15% infected barley seeds infected with Ustilago nuda are divided into compounds according to the invention at the concentrations indicated in Table C, sprinkled on seedlings, initially at low temperatures and then at higher temperatures (20 ° C.) Grow in. Mixture A is used as a comparative formulation. After 10 to 12 weeks, the number of fresh stems and intact stems infected with Ustiagogo and Nuda is counted, and the degree of infection is measured, respectively, and finally the activity is calculated. The results are shown in Table C.

TABLE C

Table C shows that in comparison to Comparative Formulation A, the compounds of the present invention have an excellent action against Ustiida.

Example V

Summer barley seeds naturally infected with about 24% with Helminthosprium gramineum are divided into 50% aliquots of various concentrations containing the compounds listed in Table D. The seeds are sown in seedlings and then transferred to the greenhouse. The number of fresh and fresh plants infected with Helmitosporium gramene is then counted, and in each case the degree of infection is measured and finally the activity is calculated. The results are shown in Table D.

TABLE D

The results in Table D show that the compounds of the present invention have a superior effect on the genus Helmintosporium and have no mercury-containing compounds compared to the non-mercury comparable solvent B and the mercury-containing comparable solvent A. It shows excellent action.

Example VI

Beet, which is approximately 60% naturally infected with Phoma betae, is divided into Comparative D with the compounds of the present invention listed in Table E, seeded in seedlings and grown at 20 ° C. Three weeks after sowing, the beet plants are tested for the degree of infection with poma beta to determine the activity of the compounds of the present invention. The results are shown in Table E.

TABLE E

EXAMPLE VII

The compounds in Table F are mixed to be uniform but uniformly distributed in soil heavily infected with Pythium ultimum. The soil treated in this way is placed in plastic seedlings and 10 peas are sown in each seedling. The same operation is repeated about E which is a comparative formulation. After 8-10 days of sowing, the test evaluation is carried out by counting the number of germinated fresh plants and calculating the functionality of the compounds of the present invention. The control rate used is seedlings with infected untreated soil.

TABLE F

Tables E and F show that the compounds of the present invention have a much better fungicidal action than comparative formulations D and E.

Claims (1)

A process for preparing a compound of formula (I), characterized by reacting a compound of formula (II) with a compound of formula (III):

Wherein n and n ₁ may be the same or different and are each an integer of 0 to 3, and R and R ₁ are each a halogen atom or a halogen substituted with-(C ₁ -C ₄ ) -alkyl, (C ₁ -C ₄ ) -Alkyl, nitro, (C ₁ -C ₄ ) -alkoxy or (C ₁ -C ₄ ) -alkylthio group and at least two of R and R ₁ can be the same or different and X is -0- or -CH _2- And Y is -0-, -S- or -NH- and Z is cyanoethyl group or general formula

Moiety, wherein A is a methylene group unsubstituted or substituted with a methyl, ethyl, acetyl or moiety of the formula -COOR ₃ ', an unsubstituted or cyclic halogen atom, (C ₁ -C ₄ ) -alkyl and nitro Or a phenylene or styryl moiety substituted with one or two of the same or different substituents selected from R ₃ and R ₃ ′ may be the same or different and each is a (C ₁ -C ₄ ) -alkyl group and is a B or D residue. One is halogen and the other is -YH group, where H can be substituted with alkali or ammonium cation.