KR19990077459A - Novel oxyacetanilide substituted with a fluoroalkenyl group and process for the preparation thereof - Google Patents

Abstract

The present invention relates to a novel oxiacetanilide derivative substituted with a fluoroalkenyl group of the general formula (I) having strong herbicidal activity, excellent selectivity, low toxicity, and improved drug sustainability, and a herbicide composition containing the same.

Wherein R ¹ represents a phenyl group or a phenyl group substituted with one or more substituents selected from the group consisting of alkyl, haloalkyl, alkoxy, chlorine, fluorine and cancellation having 1-2 carbon atoms, and R ² represents an alkyl group having 1-3 carbon atoms R ³ represents a phenyl group or a thiophene group substituted with a phenyl group, a thiophene group, or one or more substituents selected from the group consisting of alkyl, haloalkyl, alkoxy, methylenedioxy, chlorine, fluorine and cancellation having 1-2 carbon atoms. And R ⁴ represents CF ₃ or CF ₂ CF ₃ .

Description

Novel oxyacetanilide substituted with a fluoroalkenyl group and process for the preparation according to the present invention

The present invention relates to a novel oxiacetanilide derivative substituted with a fluoroalkenyl group having herbicidal activity and a method for producing the same.

Currently used herbicides despite the excellent herbicidal effect of the same structure is continuously developed and used, resulting in a change in the weed group according to the continued use of the pesticides is a problem.

For example, changes in the weed population caused by the use of herbicides were the major weeds in the 1970s and 1980s, including blood, barley, and the like.In the 1980s and 1990s, sputum, olme, algae, beetle Perennial weeds such as Ryu) have been investigated as major weeds, and since the 1990s, the annual annual weeds have been a problem. This change in weed group is very closely related to the properties of herbicides developed and used at the time, such as amides, carbamate herbicides in the 1970s and 1980s, and sulfonylurea herbicides in the 1980s and 1990s.

As pointed out above, there are ways to use amide and carbamate herbicides that have been developed in the past to control annual weeds, such as blood, which has emerged again as problem weeds since the 1990s. 1-4kg) is very high, so it is very likely to cause a variety of environmental problems, and also has a weak effect on the weeds, and lacked in a variety of factors that must be provided as a herbicide, such as the harmful effects on crops, selectivity, drug efficacy. In an effort to solve this problem, oxacetamide compounds having high activity of herbicidal activity, which have been recently transformed from amide compounds, have emerged. Such compounds are described, for example, in German patents DE 2903966, DE 3038636, DE 3323334, DE 3344236, DE 3418167, DE 3422861, DE 440596 and Bayer WO 95/34560. Known from WO 96/08488, WO 96/11575, WO 96/28434 A1, WO 97/08160 A1 and the like. However, the herbicides mentioned in the patent do not have superior drug efficacy compared to conventional drugs, the range of herbicidal activity is narrow, there is room for improvement such as short duration of the drug efficacy.

The inventors of the present invention propose a novel herbicide having a fluoroalkenyl group in order to develop a compound that satisfies the above requirements, that is, a herbicide having a stronger herbicidal activity, a lower toxicity, a higher herbicidal spectrum, and a higher economical efficiency with improved drug sustainability than conventional herbicides. The present invention has been completed from the results of synthesizing oxiacetanilide compounds of these compounds, which are toxic to crops such as rice, wheat, corn, and barley and exhibit high herbicidal activity to weeds.

Therefore, an object of the present invention is not only excellent in the manufacturing process and excellent herbicidal power, but also high herbicidal activity against flower and weeds, including the annual weed, which is abundantly grown in rice fields and fields, and for rice, corn, barley, wheat, etc. It is to provide a novel acetanilide derivative substituted with a nontoxic fluoroalkenyl group.

It is also an object of the present invention to provide a method for preparing a novel acetanilide derivative substituted with a fluoroalkenyl group and a herbicide composition having the same as an active ingredient.

According to the present invention there is provided a novel oxiacetanilide derivative substituted with a fluoroalkenyl group represented by the following general formula (I):

Formula 1

Wherein R ¹ represents a phenyl group or a phenyl group substituted with one or more substituents selected from the group consisting of alkyl, haloalkyl, alkoxy, chlorine, fluorine and cancellation having 1-2 carbon atoms, and R ² represents an alkyl group having 1-3 carbon atoms R ³ represents a phenyl group or a thiophene group substituted with a phenyl group, a thiophene group, or one or more substituents selected from the group consisting of alkyl, haloalkyl, alkoxy, methylenedioxy, chlorine, fluorine and cancellation having 1-2 carbon atoms. And R ⁴ represents CF ₃ or CF ₂ CF ₃ .

It is most preferable when R <^1> is a phenyl group, R <^2> is a methyl or i-propyl group, and R <^3> is phenyl substituted by chlorine, a fluorine, a methoxy group, etc. among the compound of the said general formula (I).

In particular, R in the compound of the general formula (I)^OneAnd R²Are each different substituents^OneIs a phenyl group and R²Is a methyl group and R³Is phenyl or phenyl substituted with chlorine, fluorine, methoxy group or the like, exhibits excellent herbicidal activity and excellent selectivity between crops and weeds.^OneAnd R²Are each different substituents^OneIs a phenyl group and R²Is i-propyl and R³Is phenyl, or phenyl substituted with chlorine, fluorine, methoxy groups, etc., it has excellent herbicidal activity, no rice and no direct damage to the leek rice. It is shown.

According to the present invention, the novel oxacetanilide derivatives in which the fluoroalkenyl group represented by the general formula (I) is substituted can be prepared by the method shown in Scheme 1 below.

In the above scheme, R^One, R², R³And R⁴Are as defined above, respectively.

Specifically, the compound (I) of the present invention prepares an alcoholic compound of the following general formula (II), which is substituted with an alkenyl compound and a base substituted with a trifluoromethyl group or a pentafluoroethyl group of the general formula (III) The reaction can be carried out under high yield.

Wherein R ¹ , R ² , R ³ and R ⁴ are as defined above.

The alcoholic compound of the general formula (II) used as a starting material for the preparation of the general formula (I), which is the target compound of the present invention, may be substituted with amines (VI) as a raw material, as shown in Scheme 2 below. Synthesis can be carried out by known methods such as acetylation reaction and hydrolysis reaction. [Reference: Hamm, PC et al., J. Amer. Chem. Soc., 78, 2556 (1956); Hartman, W. W. et al. Org. Syn., Coll. Vol. 3, 650 (1955) and Brasen, W. R. et al., Org. Syn., Coll. Vol. 4, 582 (1963).

Wherein R ¹ and R ² are each as defined above.

In addition, the vinyl fluoride compound of the general formula (III), which is required for the preparation of the general formula (I), which is the target compound of the present invention, has a Greenia reaction based on a halide (VIII) as shown in Scheme 3 below, Synthesis may be carried out via known methods such as the Wittig reaction. See Herkes, FE et al., J. Org. Chem., 32, 1311 (1967); And Wheaton, G. A. et al., J. Org. Chem., 48, 917 (1983).

In the above scheme, X is Br or Cl, and R ³ and R ⁴ are as defined above.

Alkenyl compounds substituted with an alcoholic compound of formula (II) and a trifluoromethyl group or pentafluoroethyl group of formula (III) prepared by the above-described preparation methods are shown in Scheme 1 By reacting in the presence of a base, the compound of the general formula (I), which is the target compound of the present invention, can be prepared.

In the above reaction, the amount of the compound of the formula (II) and the compound of the formula (III) is equimolar, and it is preferable to use 1 to 2 equivalents of the base with respect to these compounds. In this case, benzene, toluene, tetrahydrofuran, acetone, acetonitrile, dichloromethane, dimethylformamide or dimethyl sulfoxide may be used as the solvent, and these organic solvents may be mixed with water. Bases which can be used include inorganic bases such as sodium hydride, potassium hydride, potassium t-butoxide, sodium hydroxide, gallium hydroxide, sodium carbonate and potassium carbonate and organic bases such as triethyl amine and pyridine. The temperature of the reaction is appropriate from room temperature to 100 ℃, the end time of the reaction is when the reaction is consumed, which can be easily confirmed by TLC.

The compound of the general formula (I), which is the target compound of the present invention, has a double bond in one place in the molecule, and accordingly, depending on what steric configuration of the substituents F and R ⁴ with respect to the double bond, the following formulas (Ia), There may be two isomers of the cis (Z) and trans (E) isomers of (Ib).

In which R is^One, R², R³And R⁴Are as defined above, respectively.

The final product of the present invention is the Z-isomer (Ia) and E-isomer formed from the reaction of the alcoholic compound of formula (II) with the alkenyl compound substituted with the trifluoromethyl group of formula (III). Obtained as a mixture of two isomers of (Ib), these isomers are identified by the difference in chemical shift of methylene groups bound to oxygen of vinyl groups by ¹ H-NMR analysis (reference material: CHCl ₃ ). It became. That is, when the compound of Example 1 is described as an example, in case of Z-form (Ia), methylene proton appears as a single line at about 4.30 ppm, and in case of E-form (Ib), methylene proton is formed at about 4.49 ppm. This can be interpreted as a middle line, because in the case of E-Ib, methylene protons and trifluoromethyl groups are located on the same side, and methylene protons move about 0.2 ppm of low magnetic field, thus integrating these methylene protons. The ratio of the Z-form (Ia) and the E-form (Ib) (about 2: 1) can be calculated. More specifically, these isomers are determined by chemical shifts of fluorine and trifluoromethyl groups substituted with vinyl groups and their coupling constants as a result of ¹⁹ F-NMR analysis (reference material: CFCl ₃ ). Confirmed. That is, in the case of the Z-form (Ia), the fluorine substituted in the vinyl group is represented by a quartet having a coupling constant of 24.08 Hz at the position of -84.99 ppm, and the fluorine of the trifluoromethyl group is a couple of 25.07 Hz at the position of -57.36 ppm. It appears as a double line with a ring constant. In the case of the E-form (Ib), the fluorine substituted in the vinyl group is represented by a quartet having a coupling constant of 12.43 Hz at the position of -83.40 ppm, and the fluorine of the trifluoromethyl group is a couple of 12.66 Hz at the position of -57.95 ppm. It was confirmed that it appeared as a double line with a ring constant. On the other hand, the ratio of the Z-form (Ia) and the E-form (Ib) is about 2: 1, which is calculated as the F integral value on the ¹⁹ F-NMR.

Finally, the compound of the general formula (I) prepared by the preparation method of the present invention is actually obtained as a mixture of Z-form (I-a) and E-form (I-b).

On the other hand, the present invention provides a herbicide composition comprising a novel acetamide compound having a vinyloxy group substituted with the trifluoromethyl group or pentafluoroethyl group of the general formula (I) as an active ingredient. The composition according to the present invention may be used by first mixing one or more of the compounds of the general formula (I) with a suitable carrier and diluent in the form of a suitable formulation, for example, emulsions, wetting agents, powders, granules, etc. In this case, the content of the active ingredient is, for example, 10-90% by weight when the preparation is an emulsion or a hydrating agent, 0.1-10% by weight when the powder, and 1-30% by weight when the granule is used. However, some changes are possible depending on the purpose of the preparation.

Suitable carriers for use in the compositions according to the invention include liquid carriers and solid carriers. Examples of the liquid carrier include water, alcohols (monohydric alcohols such as methanol, dihydric alcohols such as ethylene glycol, trihydric alcohols such as glycerin), ketones (acetone, methyl ethyl ketone, etc.), ethers (dioxane, tetrahydrofuran, cellosolve, etc.). Etc.), aliphatic hydrocarbons (gasoline, kerosene, etc.), halogenated hydrocarbons (chloroform, carbon tetrachloride, etc.), acid amides (dimethylformamide, etc.), esters (ethyl acetate, butyl acetate, fatty acid glycerin esters, etc.), aceto Nitrile and the like, and in the present invention, these may be used alone or in combination of two or more thereof. As the solid carrier, mineral particles (kaolin, clay, bentonite, acidic clay, talc, silica, silica, sand, etc.), vegetable powders (wood, etc.) and the like may be used. In addition, an emulsifier, an adhesive, a dispersant, or a wetting agent may be used in the composition of the present invention. For example, nonionic, anionic or cation such as fatty acid soda polyoxy alkyl esters, alkyl sulfonates, polyethylene glycol esters, and the like. A surfactant can be used.

In addition, the composition of the present invention may be used by mixing different kinds of agrochemically active ingredients, such as insecticides, fungicides, herbicides, plant growth regulators, etc., if necessary, fertilizers, etc. may be mixed together.

It will be described in more detail with reference to the following preparation examples and examples of the production method of the novel oxiacetanilide derivatives substituted with the fluoroalkenyl group of the general formula (I) which is the target compound of the present invention prepared by the above method do.

In the present invention, when the separation is possible among the stereoisomer compounds, the separation was evaluated for physiological activity for each compound, and in the case of separation, the activity was evaluated in the form of a mixture.

Preparation Example 1 Preparation of N-Methyl-2-hydroxyacetanilide (II)

First Step: Preparation of N-methyl-2-chloroacetanilide (V)

After dissolving 10.7 g (0.1 mol) of N-methylaniline (VI) in 150 ml of dichloromethane and 10.12 g (0.1 mol) of triethylamine, 13.55 g (0.12 mol) of chloroacetyl chloride was slowly added dropwise under ice cooling to room temperature. After stirring for 1 hour at, the reaction solution was washed 2-3 times with water. The separated organic layer was dried and recrystallized with n-hexane to obtain 17.6 g of a product N-methyl-2-chloroacetanilide (V) as a tan solid. (Yield 96%)

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.68-7.12 (m, 5H), 3.92 (s, 2H), 3.45 (s, 3H)

MS (m / e): 183 (M ⁺ , 37), 134 (51), 106 (100), 90 (52), 51 (59)

Melting Point: 61 ~ 62 ^o C

Second Step: Preparation of N-methyl-2-acetoxyacetanilide (IV)

18.3 g (0.1 ml) of N-methyl-2-chloroacetanilide (V) obtained in the first step was mixed with 50 ml of dried dimethylformamide (DMF), and then 9.8 g (0.12 mol) of sodium acetate was added thereto. Heated for 1 hour. The reaction mixture was cooled, 50 ml of water was added and the organic layer obtained by extracting with ethyl acetate two or three times was dried and concentrated, separated by gallum chromatography (eluent: n-hexane: ethyl acetate = 9: 1) to give a liquid product N. 19 g of -methyl-2-acetoxy acetanilide (IV) was obtained. (Yield 92%)

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.78-7.21 (m, 5H), 4.48 (s, 2H), 3.36 (s, 3H), 2.21 (s, 3H)

MS (m / e): 207 (M ⁺ , 8), 107 (61), 77 (30), 43 (100)

Third Step: Preparation of N-methyl-2-hydroxyacetanilide (II)

To 100 ml of methanol, 20.7 g (0.1 ml) of N-methyl-2-acetoxyacetanilide (IV) obtained in the second step was mixed with 100 ml of methanol, and 4.8 g (0.12 mol) of sodium hydroxide was gradually added. Heated to reflux for 1 hour. The reaction mixture was cooled, methanol was removed under reduced pressure, 50 ml of water was added thereto, and the organic layer obtained by extraction with ethyl acetate two or three times was dried, concentrated and recrystallized with n-hexane. 14 g of product N-methyl-2-hydroxyacetanilide (II) as a white solid was obtained. (Yield 85%)

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.54-7.15 (m, 5H), 3.82 (d, 2H), 3.38 (t, 1H), 3.32 (s, 3H)

MS (m / e): 165 (M ⁺ , 34), 134 (41), 106 (100), 77 (81)

Melting Point: 41 ~ 42 ^o C

Preparation Examples 2 to 31

Preparation Example 1 shows a method using N-methylaniline among various amines (VI) that can be used as initial raw materials in the preparation of alcoholic compounds of general formula (II). Thus, as described in Preparation Example 1, N-substituted 2-hydroxyacetanilide of general formula (II) used in the present invention was similarly prepared from various amines (VI), and the melting point of these compounds, NMR and MS analysis results are shown in Tables 1a to 1c.

Preparation Example 32 Preparation of 2,2-Difluoro-1-trifluoromethyl-4′-methoxystyrene (III)

First Step: Preparation of 2,2,2-trifluoromethyl-4'-methoxyphenylketone (VII)

Nitrogen gas was passed through a dried container, magnesium (5.1 g, 0.21 mol) and 300 ml of dried ether were added thereto, and p-bromoanisole (37.4 g, 0.2 mol) was slowly added dropwise to prepare a GREEN reagent. The reaction solution was added dropwise with ethyl trifluoroacetate (28.4 g, 0.2 mol) under cooling to -78 ° C and stirred for 0.5-1 hour. The reaction solution was mixed with ice, acidified with concentrated hydrochloric acid and extracted 2-3 times with ether. After drying the organic layer, the solvent was removed under reduced pressure and distilled under reduced pressure (pressure: 20 mmHg, temperature: 72-73 ° C.) to give a colorless oily product, 2,2,2-trifluoromethyl-4'-methoxyphenylketone. 35.09 g was obtained (yield 86%).

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.62-6.81 (m, 4H), 3.86 (s, 3H)

MS (m / e): 204 (M ⁺ , 56), 135 (100), 107 (86), 92 (66), 77 (92)

Second step; Preparation of 2,2-difluoro-1-trifluoromethyl-4'-methoxystyrene (III)

Tetrahydrofuran (THF, 250 ml) and triphenylphosphine ((C ₆ H ₅ ) ₃ P, 26.2 g, 0.1 mol) dried under nitrogen stream were added to the flask, and the reaction temperature was maintained at 10 ^° C. or lower. Modifluoromethane (CF ₂ Br ₂ , 25.2 g, 0.12 mol) was added dropwise. After stirring for 30 minutes, 2,2,2-trifluoromethyl-4'-methoxyphenylketone (10.2 g, 0.05 mol) generated in the first step was added and heated to reflux for 12 hours. The reaction mixture was cooled and distilled under reduced pressure to distill the oily product (pressure: 10 mmHg, temperature: 72-74 ^° C.) to give a colorless liquid compound, 2,2-difluoro-1-trifluoromethyl-4. 9.36 g of '-methoxystyrene (III) was obtained. (Yield 78.7%).

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.48-6.79 (m, 4H), 3.79 (s, 3H)

MS (m / e): 238 (M ⁺ , 69), 195 (14), 145 (35), 74 (33), 59 (100)

Preparation Examples 33-48

Preparation Example 32 shows a method using 4-bromoanisole among various halides (VIII) that can be used as an initial raw material in the preparation of the vinyl fluoride compound of formula (III). Compounds of the general formula (III) used in the present invention were prepared by analogy with various halides (VIII) as described in Preparation Example 32, depending on the product, distillation or silica gel column chromatography ( Eluent: n-hexane).

The yield and analysis of the intermediate and final compound in each step in their preparation are shown in Tables 2a and 2b. In Tables 2a and 2b, distillation temperature and pressure were displayed when distilled, and "column" when separated by column chromatography.

Preparation Example 49

The same procedure as in Step 1 of Preparation Example 32 was carried out using bromobenzene and ethylpentafluoropropionate to obtain phenylpentafluoroethylketone, and the same procedure as in Step 2 of Preparation Example 32 was used. This gave 2,2-difluoro-1-pentafluoroethylstyrene.

The yield and analysis results of the phenylpentafluoroethyl ketone and 2,2-difluoro-1-pentafluoroethyl styrene are shown in Tables 2a and 2b. In Tables 2a and 2b, distillation temperature and pressure were displayed when distilled, and "column" when separated by column chromatography.

Example 1: Preparation of N-methyl- (2'-fluoro-1'-trifluoromethylstyryl-2'-oxy) acetanilide

In a dried container, N-methyl-2-hydroxyacetanilide (330 mg, 2 mmol) obtained in Preparation Example 1 was mixed with acetone (10 ml), followed by adding 0.22 ml (2.2 mmol) of an aqueous sodium hydroxide solution (10 M concentration). The reaction solution was stirred for 30 minutes. Thereafter, 2,2,2-difluoro-1-trifluoromethylstyrene (416 mg, 2 mmol) obtained in Preparation Example 27 was slowly added and stirred for 1 to 2 hours. Acetone in the reaction solution was removed under reduced pressure, mixed with water, and extracted with ethyl acetate. After drying the organic layer, the solvent was removed under reduced pressure and purified by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 9: 1) to give 655 mg of the title compound (compound 1) as a colorless liquid (yield 92.8%). .

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.52-6.91 (m, 10H), 4.49 (E-form) 4.30 (Z-form) (s, 2H), 3.30 (s, 3H)

MS (m / e): 353 (M ⁺ , 12), 177 (42), 120 (100), 91 (72), 77 (96)

¹⁹ F-NMR (CDCl ₃ , CFCl ₃ ) δ (ppm): -57.36 (Z-form), -57.95 (E-form) (d, 3F), -83.40 (E-form), -84.99 (Z- Sieve) (q, 1F)

Example 2 Preparation of (E) -N-methyl- (2'-fluoro-1'-trifluoromethylstyryl-2'-oxy) acetanilide

N-methyl- (2'-fluoro-1'-trifluoromethylstyryl-2'-oxy) acetanilide prepared in Example 1 was a mixture of E- and Z-forms, which was then subjected to column chromatography. (Eluent: n-hexane: ethyl acetate = 9: 1) was purified by separation to prepare only the E- sieve.

(E-form): Colorless solid compound Melting point: 91-92 ^o C

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.54-6.90 (m, 10H), 4.49 (s, 2H), 3.31 (s, 3H)

MS (m / e): 353 (M ⁺ , 43), 177 (48), 120 (100), 91 (68), 77 (82)

¹⁹ F-NMR (CDCl ₃ , CFCl ₃ ) δ (ppm): -57.95 (d, 3F), -83.40 (q, 1F)

Example 3 Preparation of (Z) -N-methyl- (2'-fluoro-1'-trifluoromethylstyryl-2'-oxy) acetanilide

N-methyl- (2'-fluoro-1'-trifluoromethylstyryl-2'-oxy) acetanilide prepared in Example 1 was a mixture of E- and Z-forms, which was then subjected to column chromatography. (Eluent: n-hexane: ethyl acetate = 9: 1) was purified by separation to prepare a Z- sieve only.

(Z-body): Colorless liquid compound

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.51-7.11 (m, 10H), 4.30 (s, 2H), 3.30 (s, 3H)

MS (m / e): 353 (M ⁺ , 57), 177 (40), 120 (100), 91 (70), 77 (97)

¹⁹ F-NMR (CDCl ₃ , CFCl ₃ ) δ (ppm): -57.36 (d, 3F), -84.99 (q, 1F)

Examples 4 to 220

By using the alcoholic compounds (hydroxyacetanilide) of the general formula (II) prepared in Preparation Examples 1 to 31 and the vinyl fluoride compounds of the general formula (III) prepared in Preparation Examples 32 to 49 Selected alcoholic compounds and vinyl fluoride compounds corresponding to the structures of the compounds shown in Table 3, and carried out similarly to those described in Example 1, the target compounds of the present invention as shown in Table 3 (compound 4 to 220) were obtained. The melting point, NMR, and MS analysis results of the oxyacetanilide compound substituted with the fluoroalkenyl group thus prepared are shown in Tables 3a to 3v.

Drug test

Herbicidal activity assay test in paddy conditions (freshwater conditions)

An appropriate amount of fertilizer is mixed with the paddy soil, water is mixed, and then it is put in a predetermined amount in a screening square pot having a surface area of 140 cm ² . As a weed seed for experiment, sowing seeds of blood, tadpole, and cochlea, which are annual weeds, and planting 1 ~ 2 tubers of perennial weeds and algae (1st experiment, 2nd experiment: rice (3 Bizarre, quinoa seeds), blood, tadpoles, water squirrels, beetles, olme; 3rd experiment: 1st experiment weed species, mantis grass, node flowers, beetle grass, egg plant, algae, peel grass, As sputum), the direct soybeans are sown 5 grains of each young seed, and the rice plants are planted at a depth of about 2cm, each of two seedlings of 2.5 ~ 3.0 leaves (see Table 4 Plant Abbreviations, PADDYLAND WEED SPECIES). The prepared pots are transferred to a greenhouse and freshwater to a depth of about 3 cm. Two days after sowing, the test compounds of the examples are weighed, and Tween-20 is dissolved in 50% acetone added with 0.1%, followed by dripping 4 ml per pot on fresh water surface. Doses are formulated and treated so that primary screening (PRS) is at 4 kg per ha and secondary screening is at 4, 1, 0.25, 0.0625, 0.0156 kg per ha. After treating the drug and growing it in a greenhouse for 2-3 weeks, the herbicidal effect against weeds and the damage against rice are shown in Table 5 (Frans et al., 1986, Experimental design and techniques for measuring and analyzing plant). responses to weed control practices, In research methods in weed sciencs, ed. by Camper.p.29-70, Southern Weed Science Society, p.486; Cho, Kwang-Yeon, 1988, Establishment of a Screening System for New Pesticide Development, Korea Research Institute of Chemical Research Report, p. 916). The herbicidal activity test results of the compounds under freshwater conditions are shown in Tables 6a to 6u.

Plant abbreviation (PADDYLAND WEED SPECIES) ABRV. GENUS-SPECIES NAME Hangul Name ENGLISH NAME ORYSA Oryza sativa L. rice plant Rice ECHOR Echinochlora crus-galli P. BEAUV.var. oryzicola OHWI blood Barnyardgrass SCPJU Scirpus juncoides ROXB. Tadpole Bulrush CYPDI Cyperus difformis L. Albangdongi Umbrellaplant CYPSE Cyperus serotinus ROTTB. You too Flat-sedge. ANEKE Aneilema keisak HASSK. Mantis grass Dayflower MOOVA Monochoria vaginalis PRESL Water pinnacle Monochoria ROTIN Rotala indica KOEHE Flower Toothcup SAGPY Sagittaria pygmaea MIQ Olme Arrow head

Herbicide Effectiveness Criteria Table shame General technology crops weed 0 radish No harm at all. No control at all, 102030 about Weak steel Although there are visible signs of weakness visible in the eye, the final yield will not be affected. A slight inhibition is apparently observed but the control effect cannot be expected. 405060 medium Weak steel Although the recovery is very severe, the final yield will be lost. Inhibitory effect is recognized but sufficient control effect cannot be expected. 708090 River Weak steel Severe damage is unlikely to recover, and above 80, nearly all individuals die. Practical control effects are recognized, and above 80 almost all individuals are killed. 100 very Completely killed Fully controlled

As can be seen from the results of the efficacy test, the novel oxyacetanilide derivatives substituted with the fluoroalkenyl group according to the present invention exhibit excellent herbicidal activity even at low concentrations and have a very broad herbicide range (Spectrum) against weeds. In particular, it exhibits very excellent herbicidal activity on the grass and weeds, including the main weeds of rice, and has excellent selectivity between weeds and crops, such as improved sustainability of the drug and very low toxicity to rice, the main crop. Moreover, it has the advantage of being a herbicide for dry and dry weaves because of its excellent selectivity between crops and weeds. Also in the case of the field, it exhibits excellent herbicidal activity on the flowers and weeds such as blood and barley.

Claims (5)

Oxyacetanilide derivatives substituted with a fluoroalkenyl group of the general formula (I) Formula 1 Wherein R ¹ represents a phenyl group or a phenyl group substituted with one or more substituents selected from the group consisting of alkyl, haloalkyl, alkoxy, chlorine, fluorine and cancellation having 1-2 carbon atoms, and R ² represents an alkyl group having 1-3 carbon atoms R ³ represents a phenyl group or a thiophene group substituted with a phenyl group, a thiophene group, or one or more substituents selected from the group consisting of alkyl, haloalkyl, alkoxy, methylenedioxy, chlorine, fluorine and cancellation having 1-2 carbon atoms. And R ⁴ represents CF ₃ or CF ₂ CF ₃ . The method of claim 1, In the general formula (I), R ¹ is a phenyl group, R ² is a methyl or i-propyl group, and R ³ is a phenyl group or a phenyl group substituted with chlorine, fluorine or methoxy group. Oxiacetanilide derivatives. The method of claim 2, In the general formula (I), R ¹ is a phenyl group, R ² is a methyl group, and R ³ is a phenyl group or a phenyl group substituted with chlorine, fluorine or methoxy group. Oxyacet substituted with the fluoroalkenyl group of the general formula (I) according to claim 1 comprising reacting an alcoholic compound of the general formula (II) with an alkenyl compound of the general formula (III) in the presence of a base: Process for preparing anilide derivatives: Formula 2 Formula 3 Wherein R ¹ , R ² , R ³ and R ⁴ are each as defined in claim 1. A herbicide composition comprising an effective amount of a oxiacetanilide derivative substituted with a fluoroalkenyl group of the general formula (I) according to claim 1 and a carrier or a diluent.