KR790001079B1 - Process for preparation of benzyl-phenoxy-alkanecarboxylic acids - Google Patents

Abstract

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Description

[Name of invention]

Method for preparing benzyl-phenoxyalkane carboxylic acid

Detailed description of the invention

The present invention relates to a process for preparing benzyl-phenoxyalkanecarboxylic acid and its derivatives of the following formula (1).

In the above formula

R is halogen, (C ₁ -C ₄ ) alkyl, halo (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, halo (C ₁ -C ₄ ) alkoxy, phenyl, -NO ₂ , -NH ₂ or -CN;

R 'is (C ₁ -C ₄ ) alkyl or halogen;

n is an integer of 1 to 3;

n ₁ is 0 or an integer of 1 to 3;

Y is (C ₁ -C ₆ ) alkylene;

X is _{-COOH, -COO- (C 1 -C 8} ) alkyl, -CONH _2, -CONH-NH _2, or -CN, -COO-Cat, and;

"Cat" is a cation of an inorganic or organic base.

In the above formula (I), R is preferably 4-, 2, or 4-position halogen (especially chlorine or cancellation), and n ₁ is preferably 0, that is, an unsubstituted preferred benzene ring is preferred, but chlorine or methyl It may be substituted by n ₁ is preferably 1 at this time. The -OYX group is preferably in the 0- or P-position relative to the benzyl group, particularly in the P-position.

Y especially represents a -CH (CH ₃ )-group. When X is a carboxyl ester group, the group preferably contains 1 to 4 carbon atoms. "Cat" is preferably an alkali or alkaline earth cation, in particular Na ⁺ , K ⁺ or Ca ⁺⁺ / 2.

Benzylphenoxy-alkanecarboxylic acid and its derivatives corresponding to formula (I) are prepared by the following method.

Benzylphenol of the following formula (II) is prepared by reacting with a halocarboxylic acid derivative of the following formula (III).

Wherein Hal is chlorine or canceled and X is -COO- (C ₁ -C ₈₎ - represents an alkyl, -CONH _2, -CONH-NH ₂ or -CN.

The reaction is generally methanol, ethanol at a temperature of 50-150 ° C. (80-120 ° is suitable) in the presence of stoichiometric amounts of inorganic or organic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate pyridine or triethylamine. The reaction is carried out in an inert organic solvent such as benzene, petroleum ether, diethyl ketone, dioxane, DMF or DMSO. Free carboxylic acids or salts thereof are preferably prepared by known methods from reaction products obtained by saponification of esters or nitriles.

Starting materials of formula (II) are prepared by reacting the corresponding substituted benzylchloride and phenol in the presence of a condensing agent such as AlCl ₃ or ZnCl ₃ by known methods (Ind. Eng. Chem. 28, 505 (1936)). This reaction yields benzylphenol substituted at the O- and P-positions, which are separated by fractional distillation.

The compound of formula (I) has excellent selective activity against weed grass. In the pre- and post-germination treatment of weeds, these weeds are destroyed in small quantities and do not harm or even cause very little damage to broad-leaved cultivated plants or broad-leaved weeds.

In addition, the compounds prepared according to the present invention do not harm various cultivated plants such as rice, barley, wheat, sugar cane, etc., even at a capacity sufficient to destroy weeds. Therefore, the present compounds can be used for weed removal in dicot plants and grains such as beets, legumes, cotton, vegetables, cucumber plants, cutting boards, tobacco and the like.

In particular, the herbicidal effect is particularly strong against foxtail gyass, wild locusts, van yardgrass, foxtail millets and crab grasses. It can be used before and after germination of plants which is not possible with known herbicides.

For example, trichloroacetic acid, alacro (2-chloro-2, 6-diethyl-N- (methoxymethyl) -acetanilide), and trifluirarin (N, N-di- (n-propyl) ), 2, 6-dinitro-4-trifluoromethylaniline) and the like can be used only for the pre-germination treatment, barban (4-chloro-2-butynyl-N- (3-chlorophenyl)-carbamate) In addition, chlorophenpropmethyl (2-chloro-3- (4-chlorophenyl) -propionic acid methyl ester) can be used only for post-germination treatment. In addition, the concentration of the drug required for complete destruction of the weeds is significantly lower than that of the above-mentioned herbicides.

The compounds of the present invention can be used as conventional preparations such as hydrating agents, emulsions, solutions, powders, granules.

Hydrating agents are preparations that are homogeneously dispersed in water and, in addition to the active substance, wetting agents such as polyoxyethylated alkylphenols, polyoxyethylated oleyl or stearylamines, alkyl or alkylphenylsulfonates, and the like, lignin sulfonic acid sodium salts, 2 And diluents such as dispersants such as 2'-dinaphthyl-methane-6, 6'-disulfonic acid, dibutyl-naphthalene-sulfonic acid and the like, or an inert substance.

An emulsion is obtained by dissolving the active substance in an organic solvent such as cyclohexanone, xylene, or a high boiling aromatic hydrocarbon, and may be added with an emulsifier in order to emulsify it well in water.

Powder is obtained by grinding the active ingredient with a solid material which is finely ground with talc or natural aluminum compound such as kaolin, bentonite, pyropyrite or diatomaceous earth.

Commercially applicable solutions as nebulizers dissolve the active ingredient in an organic solvent and may contain an expanding agent such as a fluoride mixture of hydrocarbons.

The granules are sprayed with a powdered active ingredient through the nozzle to the absorbent granulating inert material, or the active ingredient is an adhesive such as polyvinyl alcohol, sodium salt of polyacrylic acid or mineral oil such as sand, kaolin or granulating inert material. It is prepared by coating the surface of the carrier. The active substance may also be granulated by the method used for the preparation of the fertilizer granulation material by mixing with one or more fertilizers if necessary. In commercial herbicide formulations the concentration of the active substance according to the invention can vary in various ways. For example, in the hydrating agent, the concentration of the active ingredient can be varied in the range of about 10% to 50%, with the remainder consisting of adducts of the above formulations. The concentration of active ingredient in the emulsion can vary from about 10% to 50%. Powders generally contain 5 to 20% and the solution contains about 3 to 20% of active material. In the case of granules, the content of the active ingredient may vary in part depending on whether the active ingredient is a liquid or a solid and the granulating agent, filler or other adduct used, but is generally 3 to 10%.

In practical applications, commercial thickeners may be optionally diluted in conventional manner. For example, in the case of a hydrating agent and an emulsion, it is diluted with water. Powders, granules and solutions are no longer diluted before use. The amount of active material required for practical application varies considerably with external conditions (eg temperature, humidity, etc.), but in general 0.1 to 10.0 kg / ha (0.2 to 2.5 kg / ha is preferred) is used. .

Preparation Example

10-40% by weight of wet ingredient containing 10-40% by weight of active substance

Active substance 30-40% (weight)

Finely dispersed adsorbent silicic acid (silicic acid) 8% by weight

Sodium salt of dinaphthylmethane-disulfonic acid (Tamol ^R NNO) 8% by weight

Sodium salt of alkylnaphthalene sulfonic acid (Leonil ^R DB) 2% (weight)

Sodium salt of oleylmethyltauride (Hostapon ^R T) 0.5% by weight

Diatomaceous earth

Emulsions containing 20 to 50% by weight of active substance

20-50% of active substance (weight)

Calcium salt 5% (weight) of dodecylbenzenesulfonic acid

Nonylphenol-polyglycol ether 7% (weight)

Oleyl alcohol-polyglycol ether 3% (weight)

The rest is xylene

Granules containing 3 to 5% by weight of active substance

3-5% active substance

2% by weight of emulsifier mixture of dodecylbenzenesulfonate calcium salt and castor oil-polyglycol ether / or ester

Diatomaceous earth or finely dispersed silicic acid (silic acid), remaining quartz sand (diameter 0.3 to 1 mmφ) 5% (weight)

The novel herbicides of the present invention may also be used in admixture with the following recited substances which are known herbicides.

Urea derivatives: linuron, monolinuron, chlorotoluron, ifuron, diuron, methoxuron, fluorometron, metabenzthiazuron,

Triazine derivatives: simazine, atrazine, amethrin, promethrin, desmethrin, metoprotrin, metrizin;

Uracil derivatives: lenacil, bromacil;

Pyrazone derivatives: pyrazone;

Phenoxy-alkanecarboxylic acids: 2, 4-D, MCPA, dichloroprop, mecoprop, 2, 4-DP, TBA;

Carbamic acid derivatives: banvan, phenmedipham, dialate, trialate, benolate, bench ocarb, swipe;

Dinitrophenol derivatives: dinitro-0-cresol, dinoceb (DNBP), dinotub and esters or salts thereof;

Chlorinated fatty acids: TCA, Dalapon;

Amides: defenamide, isocarbamide;

Dipyridium derivatives: paraquat, diquat;

Anilides: propanyl, solan, monalide, arachrol, proparkrol, ventacrol;

Aniline: trifluoroaniline, nitraniline, urizarin, dinitramine;

Other active substances: Diclobenyl, isoxinyl, cyanazine, pyrazone, bromophenoxime, chlorotalmethyl, benzoylpropetyl, chlorophenpropmethyl, MSMA, DSMA, nitrophene, florenyl, bentazole, fluorine Lodifen;

Next, examples of the present invention are illustrated.

Production Example 1

2 [P- (4-chlorobenzyl) -phenoxy] -propionic acid ethyl ester

A solution of 22 g of 4- (4-chlorozenzyl) -phenol and 18.5 g of α-bromopropionic acid ethyl ester in 100 ml of dimethyl formamide was stirred with 16 g of potassium carbonate at 100 ° C. for 2 hours. After cooling, the reaction mixture is placed in 1 l of water, and the precipitated oily substance is separated and dehydrated with a forget-me-not. Distillation under vacuum afforded 23.3 g of 2- [P- (4-chlorobenzyl) -phenoxy] -propionic acid ethyl ester of the following structural formula.

Boiling Point: 146 to 151 ° C / 0.1mmHg / n ²² _D : 1.5527

Production Example 2

2- [P- (2, 4-dichlorobenzyl) -phenoxy] -propionic acid amide

A solution of 25.3 g of 4- (2,4-dichlorobenzyl) -phenol and 15.2 g of α-bromopropionic acid amide in 100 ml of dimethylformamide is stirred with 16 g of potassium carbonate at 100 ° C. for 2 hours. After cooling, the reaction mixture is poured into 1 L of water, and the precipitated viscous oil is absorbed into methylene chloride and washed with water. After dehydration with forget-me-not, the solvent is removed under reduced pressure. The remaining colorless crystals are recrystallized from methanol.

Yield: 25.8 g, Melting point: 148 to 149 ° C

Production Example 3

2- [P- (2,4-dichlorobenzyl) -phenoxy] -propionic acid sodium salt

A 2- [P- (2,4-dichlorobenzyl) -phenoxy] -propionic acid ethyl ester was added to 100 ml of methanol and stirred, while a solution of 2.5 g of sodium hydroxide in 100 ml of water was added and stirred at 50 ° C. for 3.5 hours. Next, the mixture is left at room temperature overnight, and the solvent is distilled off under reduced pressure. The remaining sodium salt was dried at 60 ° C. under reduced pressure to obtain 19.6 g of a sodium salt of 2- [P- (2,4-dichlorobenzyl) -phenoxy] -propionic acid having the following structural formula.

Production Example 4

2- [P- (2, 4-dichlorobenzyl) -phenoxy] -butyl acid ethyl ester

A solution of 25.3 g of 4- (2,4-dichlorobenzyl) -phenol and 15 g of α-chlorobutyl acid ethyl ester in 100 ml of dimethylpramide was stirred with 16 g of potassium carbonate at 100 ° C. for 2 hours. After cooling, the reaction mixture is placed in 1 l of water, and the precipitated oil is separated and dehydrated with forget-me-not. Distillation under vacuum affords 2- [P- (2,4-dichlorobenzyl) -phenoxy] -butyl acid ethyl ester of the following structural formula.

Boiling Point: 180 to 183 ° C / 0.8mmHg / n ²¹ _D = 1.5912

The following compounds are prepared by the above examples.

[table]

Production Example 33

2- [P- (2, 4-dichlorobenzyl) -phenoxy] -propionic acid

17.5 g of 2- [P- (2,4-dichlorobenzyl) -phenoxy] -propionic acid ethyl ester was refluxed for 2 hours in a solution of 2.5 g of sodium hydroxide dissolved in 100 ml of methanol. After cooling, 100 ml of water is added and the mixture is acidified with 2n-hydrochloric acid, whereby propionic acid precipitates as a colorless oil to separate. When it is cooled with ice water, it solidifies and becomes a waxy colorless substance.

Yield: 15.3 g

Biological Experimental Example

Example 1

Seeds of weeds belonging to different plant families are potted and covered with soil. On the same day the soil is sprayed with a hydrating agent in which the compound of Example (5) is suspended in water. In the same manner, dichloroprop 2, (2 ', 4'-dichlorophenoxy) propionic acid, which is a known substance, is used as a control, in the above procedure. In addition, the above quoted material is already germinated and sprayed on plants having 2 to 3 leaves to be tested.

The results were expressed as percent plant destruction as follows.

In the above chart, number 4 has a significant herbicidal effect on weeds and is considered to have a satisfactory preservation effect on cultivated plants (see Bolle, Nachrichtenblatt des Deutschen pflanzenschutzdienstes 16, 1964, pages 92-94).

As a result of the following Table (1), compared to the dichloroprop, the compound of the present invention can be seen that even at high dose of 2.5kg / ha has no effect or little effect on the hardwood plants. The potency of the compounds of the invention is limited only to species of the family Lolium, Alopecurus and Echinochloa, while dichloroprop is effective against the above mentioned plants and other weeds. Shows none. As a matter of fact, it can be seen that the material of the present invention is completely different from the known herbicide dichloroprop, although its chemical structure is similar.

TABLE 1

Example 2

Wheat, barley, Alopecurus myosuroides and avena fatua seeds are potted and germinated in a greenhouse. Three to four leaves sprout and then spray the aqueous suspension of the present invention. As a control agent, chlorophenpropmethyl having the following structure used commercially is used.

The following table (2) shows the results after 4 weeks of treatment, and the Foxtailgrass and wild medley are basically removed by the compound of the present invention even at low dose rates (for example, 0.62 kg / ha), while the cultivated plants Can be found to be harmless at all or very little. However, chlorophenprop methyl can be seen that even at high doses of 1.25 kg / ha, wild locusts are only slightly injured and foxtailgrass is not harmed.

TABLE 2

The compounds of Examples 18, 19, 30 and 31 have similar titers as the Examples 5 and 7 compounds.

Example 3

Echinochloa is one of the most important weeds in rice cultivation in rice cultivation countries. This is the same as sowing directly in rice fields or planting them in seedlings. The following experiments A and B show that the material of the present invention is most suitable as a herbicide for half yardgrass in rice cultivation by the two cultivation methods.

In Experiment A, half yardgrass and rice are planted at the same time. After sprouting 3 to 4 leaves, the compounds of the present invention are sprayed onto the plants in the form of an aqueous suspension. The results of Table 3 (after 4 weeks of treatment) are sufficient for half yardgrass weeding even at a very low dosage of 0.31 kg / ha of the active substance of the present invention, and do not cause significant damage to rice even at twice the dose. Is showing.

In Experiment B, rice was transplanted three weeks after germination and at the same time half yardgrass was planted. After a few days, when half yardgrass germinates, the pot is filled with water, and the compound of the present invention is added to the deceased. The results after 4 weeks of treatment are shown in Table (3).

TABLE 3

Example 4

Corn crop growth in soybean fields is also a major problem in soybean crop crops after large corn harvesting (for example, in large areas such as the United States). To test whether the compounds of the present invention are suitable for the removal of native corn in soybean fields, corn and soybeans are planted in pots and, after germination, are treated with a suspension of the material prepared by the method of the present invention (see Table 4). As a result of Table (4) it can be seen that for this purpose the compounds of the invention destroy unwanted corn plants without harming soybeans.

TABLE 4

Example 5

Seeds of Echinochloa and Setale are planted with sugarcane and cotton. After germination, these plants are sprayed with a suspension of the compounds of the invention (see Table 5).

As a result of the above Table (5), it can be seen that the substance according to the present invention has a very good destructive effect on the weeds without harming sugarcane and cotton at 0.31 and 0.62 kg / ha dose rates.

TABLE 5

Example 5a

Examples 5 and 7 in the form of an aqueous suspension, the compound is administered to the cultivated plants in the form of 2-3 leaves at the dose of 2.5 kg / ha of the active substance. At this time, the following plants were not harmed.

Beet, Beetroot, Spinach, Cucumber, Melon, Watermelon, Red Clover, Lucerne, Groundnut, Soybean, Kidney Bean, Pea, Pea, Flax, Carrot, Celery, Rape, Cabbage, Tomato, Tobacco , Potatoes, cotton and so on.

According to this experiment, it can be seen that the compound according to the present invention can be used for dicotyledonous plants even at high dose rate without harming the cultivated plant.

Example 6

Seeds of sugarcane and bony (digital), wild locust (echinocloe) and foxtail millet (setaria) are potted. On the same day, the material of the present invention is sprayed on the soil surface in the form of a suspension solution at different dose ratios (pre-germination treatment). The results of this experiment are shown in Table (6). As a result, the compound of the present invention destroys the weed plants at 0.31 or 0.62 kg / ha dose, but does not harm sugar cane, etc. Moreover, it can be seen that it can be used even at a high concentration of 1.25 kg / ha dose. Can be. Alachlor, a comparator of the following structural formula, is commonly used as a weed herbicide in soil pretreatment in agriculture, but cannot actually be used for this plant because it harms sugarcane.

In addition, Propacchlor of the following structural formula is used as a herbicide, but weed plants are not completely removed even when administered at a high dose of about 1.25 kg / ha.

Example 7

In a similar experiment, two compounds of the invention were tested on crops, their action on Foxtail Grass (Allopecurus). As a result shown in Table (7), it can be seen that these two substances are suitable for selective weeding on foxtail grasses, which are weeds in crops.

Example 8

The weed plant seeds listed in Table (9) are planted in pots and the soil is sprayed with the compound suspension solution of the present invention. The herbicidal efficacy obtained after 4 weeks of administration is shown in Table (9). From the above data, the material of the present invention is a weed plant, Foxtailgrass (Allopecurus), Foxtail Millet (Cetaria), Poaple (Poa Speco), Raygrass (Rollium) and Vanyard. It can be seen that the grass has a good herbicidal action.

TABLE 6

TABLE 7

TABLE 8

The compounds of Examples (6), (8), (13), (23), (2), (3), (26) and (29) have similar effects.

Claims (1)

A method for preparing benzyl-phenoxyalkanecarboxylic acid and its derivatives of formula (I) by reacting benzylphenol of formula (II) with a halocarboxylic acid derivative of formula (III).

In the above structural formula R is halogen, (C ₁ -C ₄ ) alkyl, halo (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, halo- (C ₁ -C ₄ ) alkoxy, phenyl, -NO ₂ ,- NH ₂ or —CN; R 'is (C ₁ -C ₄ ) alkyl or halogen; n is an integer of 1 to 3, n ₁ is 0 or an integer of 1 to 3; Y is (C ₁ -C ₆ ) alkylene; X is _{-COOH, -COO- (C 1 -C 8} ) _{alkyl, -CONH 2 -CONH-NH 2,} -CN or -COO-Cat (where Cat is an inorganic or organic cation); Hal is chlorine, or cancellation.