KR19990074863A - Novel fluorinated propenyloxyacetamides and preparation method thereof - Google Patents

Abstract

The present invention relates to novel fluorinated propenyloxyacetamide derivatives of the following general formula (I), which have strong herbicidal activity, good selectivity, low toxicity and improved sustainability of medicament and herbicide compositions containing the same:

Wherein R ¹ represents an unsubstituted or substituted phenyl or thiophene group having 1 to 2 carbon atoms, alkyl, haloalkyl, alkoxy, methylenedioxy or one or more chlorine, fluorine or cancelled, and R ² and R ³ are each Alkyl or benzyl group having 1 to 4 carbon atoms, alkenyl or benzyl group having 1 to 4 carbon atoms, or R ² and R ³ together with the nitrogen atom to which they are attached, are unsubstituted or have 1 to 2 alkyl groups at the 2 or 6 position. Or two substituted piperidino, hexamethyleneimino, morpholino, 1,2,3,6-tetrahydropyridino or 1,2,3,4-tetrahydroquinolino groups.

Description

Novel fluorinated propenyloxyacetamides and preparation method thereof

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

The ideal herbicide requirement is not only to show excellent weed control effect in one small amount of treatment during the entire growth period of the weeds, but also to be non-toxic and fundamentally harmless to the crops to which the herbicide is applied. And low pollution non-toxicity that does not cause toxicity to the ecosystem. Conventional herbicides have been somewhat problematic to recognize as the ideal herbicides described above. In addition, herbicides are currently being used, despite the excellent herbicidal effect of the same series of analogues are continuously developed and used, causing a change in the weeds in the ecosystem, the continued use of the pesticides is a problem.

For example, changes in the weed group caused by the use of herbicides. For example, annual weeds such as blood and barley were the major weeds in the 1970s and 1980s. Perennial weeds have been investigated as the major weeds, and since the 1990s, the annual annual weeds have been a problem. This change in the weed group is very closely related to the properties of herbicides developed and used at the time, that is, amide-based, carbamate-based herbicides in the 1970-1980s, and sulfonylurea herbicides in the 1980-1990s.

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 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 solve the above-mentioned disadvantages of conventional herbicides and meet the requirements of the ideal herbicide, that is, the herbicide activity is stronger and lower toxicity than the conventional herbicides, the herbicidal spectrum is wider, and the economical efficiency of the improved drug sustainability is improved. In order to develop a compound, a new acetamide compound having a fluorine-substituted propenyloxy group was synthesized. The present invention has been completed.

Therefore, the 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 annual weeds, which are grown in paddy fields and fields, and the main crops of rice, corn, barley, etc. Is to provide a novel acetamide derivative substituted with a non-toxic fluorinated propenyloxy group.

It is also an object of the present invention to provide a method for producing a novel acetamide derivative having a fluorine-substituted propenyloxy group and a herbicide composition having the same as an active ingredient.

According to the present invention there is provided a novel acetamide derivative having a fluorine substituted propenyloxy group represented by the following general formula (I):

Formula 1

Wherein R ¹ represents unsubstituted or substituted or substituted phenyl or thiophene group having 1 to 2 carbon atoms, alkyl, haloalkyl, alkoxy, methylenedioxy or one or more chlorine, fluorine or cancelled, and R ² and R ³ are Each is an alkyl of 1-4 carbons, an alkenyl or benzyl group of 1 to 4 carbon atoms, or R ² and R ³ together with the nitrogen atom to which they are attached, an unsubstituted or an alkyl group of 1-2 carbon atoms in the 2 or 6 position Form 1 or 2 substituted piperidino, hexamethyleneimino, morpholino, 1,2,3,6-tetrahydropyridino or 1,2,3,4-tetrahydrocurolino group).

Among the compounds of the general formula (I), R ¹ is phenyl which is unsubstituted or substituted with chlorine, fluorine or methoxy group, R ² and R ³ together with the nitrogen atom to which they are bonded, piperidino, hexamethyleneimino, Most preferably, a morpholino or 1,2,3,6-tetrahydropyridino group is formed.

According to the present invention, the novel fluorinated propenyloxyacetamide derivative represented by the general formula (I) can be produced by the method shown in the following Scheme 1.

(In the above scheme, R^One, R²And R³Are as defined above, respectively)

Specifically, the compound (I) of the present invention is an alcoholic compound of the general formula (II)

(Wherein R ² and R ³ are each as defined above)

To prepare an alkenyl compound substituted with a trifluoromethyl group of the general formula (III)

(Wherein R ¹ is as defined above)

It can be manufactured in high yield by reacting in the presence of a base.

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 ² and R ³ 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).

(Wherein X represents Br or Cl, and R ¹ is as defined above)

The alcoholic compound of formula (II) and the alkenyl compound substituted with the trifluoromethyl group of formula (III) prepared by the above-mentioned preparation methods are reacted in the presence of a base as shown in Scheme 1 above. The compound of the said general formula (I) which is an objective compound of this invention can be manufactured.

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 that can be used include inorganic bases such as sodium hydride, potassium hydride, t-butoxylate, sodium hydroxide, potassium 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 CF ₃ have 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, R²And R³Are as defined above, respectively.

The final product of the present invention is the Z-isomer (Ia) and the 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, the methylene proton is represented by the singlet in the position of about 4.67 ppm in the case of Z-form (Ia), and the methylene proton is in the position of about 4.79 ppm in the case of E-form (Ib). 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) to the E-form (Ib) (about 2: 1) can be calculated (from ¹ H-NMR of 16550). More specifically, these isomers were analyzed by ¹⁹ F-NMR analysis (reference Substance: CFCl ₃ ) The results were confirmed by chemical shifts of fluorine and trifluoromethyl groups substituted with vinyl groups and their coupling constants. That is, in the case of Z-form (Ia), the fluorine substituted in the vinyl group is represented by a quartet having a coupling constant of 25.15 Hz at the position of -84.28 ppm, and the fluorine of the trifluoromethyl group is a couple of 24.85 Hz at the position of -57.38 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 12.46 Hz at the position of -82.24 ppm, and the fluorine of the trifluoromethyl group is a couple of 12.32 Hz at the position of -57.83 ppm. It was confirmed that it appeared as a double line with a ring constant. On the other hand, Z- body (Ia) and the ratio is about 2 in E- body (Ib): (from ¹⁹ F-NMR of 16550) 1 is calculated on the F integral values long, ¹⁹ F-NMR.

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

On the other hand, this invention provides the herbicide composition which uses the novel acetamide compound which has the vinyloxy group by which the trifluoromethyl group of said general formula (I) was substituted 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.

The preparation method of the novel acetamide derivatives having the fluorinated propenyloxy group of the above formula (I), which is the target compound of the present invention prepared by the above method, will be described in more detail with reference to Preparation Examples and Examples below.

In the present invention, the activity was evaluated in the form of a mixture of the stereoisomer compound.

Preparation Example 1 Preparation of N-2-hydroxyacetylpiperidine (II)

First step: preparation of N-2-chloroacetylpiperidine (V)

8.52 g (0.1 mol) of piperidine was mixed with 150 ml of dichloromethane and 10.12 g (0.1 mol) of triethylamine, and then slowly added dropwise 13.55 g (0.12 mol) of chloroacetyl chloride under ice cooling. The reaction solution was stirred at room temperature for 1 hour, washed 2 ~ 3 times with water, and the organic layer was separated and dried and separated by column chromatography (eluent: n-hexane: ethyl acetate = 4: 1) to give a brown liquid product N. 14.8 g of 2-chloroacetylpiperidine was obtained. (Yield: 92%)

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 4.08 (s, 2H), 3.76-3.18 (m, 4H), 1.98-1.21 (m, 6H)

MS (m / e): 161 (M ⁺ , 26), 126 (100), 69 (37), 41 (68)

Second Step: Preparation of N-2-acetoxyacetylpiperidine (IV)

16.1 g (0.1 mol) of N-2-chloroacetylpiperidine obtained in the first step was mixed with 50 ml of dried dimethylformamide (DMF), followed by adding 9.8 g (0.12 mol) of sodium acetate and heating for 1 hour. It was. 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 column chromatography (eluent: n-hexane: ethyl acetate = 4: 1) to give a liquid product N. 16.5 g of 2-acetoxyacetylpiperidine was obtained. (Yield 89%)

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 4.67 (s, 2H), 3.68-3.10 (m, 4H), 2.12 (s, 3H), 1.68-1.38 (m, 6H)

MS (m / e): 185 (M ⁺ , 21), 112 (51), 69 (73), 43 (100)

Third Step: Preparation of N-2-hydroxyacetylpiperidine (II)

18.5 g (0.1 mol) of N-2-acetoxyacetylpiperidine obtained by separation in the second step was mixed with 150 ml of methanol, and 4.8 g (0.12 mol) of sodium hydroxide was slowly added thereto, followed by heating to reflux for 1 hour. The reaction mixture was cooled, the methanol was removed under reduced pressure, 50 ml of water was added, and the organic layer obtained by extracting with ethyl acetate two to three times was dried and concentrated to give a column of brown liquid, which was purified by column chromatography (eluent: n-hexane: ethyl acetate = 2). : 1) was isolated to obtain 11.7 g of N-2-hydroxyacetylpiperidine. (Yield 82%)

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 4.08 (d, 2H), 3.97 (t, 1H), 3.67-3.02 (m, 4H), 1.75-1.15 (m, 6H)

MS (m / e): 143 (M ⁺ , 35), 112 (86), 69 (77), 43 (100)

Preparation Examples 2 to 17

Preparation Example 1 shows a method using piperidine among various amines (VI) that can be used as initial raw materials in the preparation of alcoholic compounds of general formula (II). The same procedure as described in Preparation Example 1 was conducted to prepare substituted 2-hydroxyacetamide of general formula (II) used in the present invention from various amines (VI). Shown in 1a and 1b.

Preparation Example 18 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, 100 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: 10mmHg, temperature: 72 ~ 74 ^° C) to give a colorless liquid product, 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 19-33

Preparation Example 18 shows a method using p-bromoanisole among various halides (VIII) that can be used as an initial raw material in the preparation of the vinyl fluoride compound of general formula (III). The same procedure as described in Preparation Example 18 was carried out to prepare a compound of formula (III) used in the present invention from various halides (VIII), depending on the product, distillation or silica gel column chromatography ( Eluent: n-hexane). The analysis results of each step intermediate and final compound 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.

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

In a dried container, N-2-hydroxyacetylpiperidine (286 mg, 2 mmol) obtained in Preparation Example 1 was mixed with acetone (20 ml), followed by adding 0.22 ml (2.2 mmol) of sodium hydroxide solution (10 M concentration). The solution was stirred for 30 minutes. Thereafter, 2,2-difluoro-1-trifluoromethylstyrene (416 mg, 2 mmol) obtained in Preparation Example 25 was slowly added and stirred for 1-2 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 = 2: 1) to give 600 mg of the title compound (compound 1) as a colorless solid (yield 90.6%). . Colorless solid, compound melting point: 78-79 ^o C

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.58-7.17 (m, 5H), 4.79 (E-form) 4.67 (Z-form) (s, 2H), 3.71-3.05 (m, 4H) , 1.78-1.35 (m, 6H)

MS (m / e): 331 (M ⁺ , 40), 126 (85), 98 (76), 84 (100)

¹⁹ F-NMR (CDCl ₃ , CFCl ₃ ) δ (ppm): -57.38 (Z-form), -57.83 (E-form) (d, 3F), -82.24 (E-form), -84.28 (Z- Sieve) (q, 1F)

Examples 2 to 74

Substituted hydroxyacetamide compounds of formula (II) prepared in Preparation Examples 1-17 above and substituted 2,2-difluoro- of formula (III) prepared in Preparation Examples 18-33 above An object of the present invention is repeated by repeating the same procedure as described in Example 1 by selecting an alcoholic compound and a vinyl fluoride compound corresponding to the structures of the final compounds shown in Table 3 below among the 1-trifluoromethylstyrene compounds. Compounds (compounds 2 to 74) were obtained. The analysis results of the fluorinated propenyloxyacetamide compound thus prepared are shown in Tables 3a to 3h.

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 prepared so that primary screening (PRS) is at 4 kg / ha and secondary screening is at 4, 1, 0.25, 0.0625, 0.0156 kg / ha. The herbicidal efficacy criteria for weeding and weeding against rice after growing in the greenhouse for 2-3 weeks (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 Screening System for New Pesticide Development, Korea Research Institute of Chemical Research, See page 916). The herbicidal activity test results of the compounds in fresh water are shown in Tables 6a to 6g.

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

Example Weight (kg / ha) Rice (three seasons) blood Tadpole Water pinnacle You too Olme One 1.0000 80 100 100 100 100 90 0.2500 0 100 100 90 100 80 0.0625 0 100 60 90 100 0 0.0156 0 95 20 60 0 0 0.0040 0 20 0 0 0 0 2 1.0000 80 100 100 100 - 70 0.2500 70 100 100 100 - 60 0.0625 20 100 40 90 - 30 0.0156 0 70 10 80 - 0 0.0040 0 30 0 40 - 0 3 4.0000 100 100 100 100 100 0 1.0000 60 100 100 100 100 0 0.2500 20 100 100 100 0 0 0.0625 0 100 50 80 0 0 0.0156 0 30 0 30 0 0 4 1.0000 0 100 100 90 - 50 0.2500 0 100 60 90 - 10 0.0625 0 95 10 80 - 0 0.0156 0 40 0 50 - 0 0.0040 0 0 0 0 - 0 5 1.0000 30 100 100 90 - 50 0.2500 30 100 100 90 80 20 0.0625 0 80 20 80 80 0 0.0156 0 60 0 50 70 0 0.0040 0 0 0 20 0 0 6 1.0000 70 100 100 90 - 60 0.2500 40 100 100 80 90 30 0.0625 0 85 30 80 40 0 0.0156 0 50 10 50 0 0 0.0040 0 0 0 20 0 0 7 4.0000 100 100 100 100 0 100 1.0000 50 100 100 100 0 100 0.2500 30 100 100 90 0 100 0.0625 0 100 100 90 0 40 0.0156 0 90 40 70 0 0 8 1.0000 40 100 100 100 100 60 0.2500 10 100 70 90 100 40 0.0625 0 90 0 50 0 10 0.0156 0 30 0 0 0 0 0.0040 0 0 0 0 0 0 9 1.0000 65 100 100 100 - 70 0.2500 0 100 90 90 - 50 0.0625 0 80 30 70 - 20 0.0156 0 30 0 40 0 0 0.0040 0 0 0 20 0 0 10 4.0000 80 100 100 100 100 0 1.0000 60 100 100 100 100 0 0.2500 20 100 40 90 100 0 0.0625 20 100 0 80 20 0 0.0156 20 90 0 50 0 0 11 4.0000 90 100 100 100 100 100 1.0000 90 100 100 100 100 100 0.2500 70 100 100 100 100 60 0.6250 0 100 100 100 100 30 0.0156 0 70 40 60 0 0

Example Weight (kg / ha) Rice (three seasons) blood Tadpole Water pinnacle You too Olme 12 1.0000 65 100 100 100 - 50 0.2500 30 100 100 90 - 50 0.0625 0 100 100 90 - 0 0.0156 0 90 50 80 50 0 0.0040 0 70 10 50 0 0 13 1.0000 65 100 100 90 - 80 0.2500 20 100 50 90 60 50 0.0625 0 95 10 70 - 0 0.0156 0 80 0 70 0 0 0.0040 0 0 0 20 0 0 14 1.0000 60 100 100 100 100 70 0.2500 20 100 100 100 100 50 0.0625 0 100 60 100 100 20 0.0156 0 80 10 30 0 0 0.0040 0 30 0 0 0 0 15 1.0000 0 100 30 100 100 50 0.2500 0 100 0 90 20 20 0.0625 0 95 0 80 0 0 0.0156 0 30 0 10 0 0 0.0040 0 0 0 0 0 0 16 4.0000 60 100 100 100 100 100 1.0000 50 100 100 100 100 100 0.2500 30 100 60 100 0 100 0.0625 10 80 40 60 0 0 0.0156 0 60 0 40 0 0 17 1.0000 60 100 100 100 100 70 0.2500 10 100 100 100 100 50 0.0625 0 100 40 100 100 30 0.0156 0 95 0 80 0 0 0.0040 0 60 0 20 0 0 18 1.0000 50 100 100 100 100 100 0.2500 20 100 80 100 90 60 0.0625 0 100 30 60 0 0 0.0156 0 60 0 20 0 0 0.0040 0 0 0 0 0 0 19 4.0000 100 100 100 100 100 50 1.0000 50 100 100 100 100 30 0.2500 20 100 30 100 100 0 0.0625 0 90 20 60 20 0 0.0156 0 20 0 30 0 0 20 1.0000 10 100 60 100 100 60 0.2500 0 100 30 90 0 0 0.0625 0 90 0 70 0 0 0.0156 0 60 0 0 0 0 0.0040 0 0 0 0 0 0 21 1.0000 10 100 40 90 100 60 0.2500 0 95 10 90 10 10 0.0625 0 90 0 90 0 0 0.0156 0 60 0 10 0 0 0.0040 0 0 0 0 0 0 22 1.0000 20 100 60 100 100 60 0.2500 10 100 0 100 80 40 0.0625 0 80 0 40 0 10 0.0156 0 50 0 10 0 0 0.0040 0 0 0 0 0 0

Example Weight (kg / ha) Rice (three seasons) blood Tadpole Water pinnacle You too Olme 23 1.0000 40 100 100 90 100 50 0.2500 10 100 90 90 100 0 0.0625 0 100 10 90 0 0 0.0156 0 90 0 30 0 0 0.0040 0 0 0 0 0 0 24 1.0000 20 100 60 100 70 90 0.2500 0 100 40 50 50 0 0.0625 0 100 0 30 40 0 0.0156 0 50 0 0 0 0 0.0040 0 0 0 0 0 0 25 1.0000 20 100 100 90 100 0 0.2500 0 100 100 90 100 0 0.0625 0 95 30 70 80 0 0.0156 0 60 0 0 0 0 0.0040 0 0 0 0 0 0 26 1.0000 50 100 100 100 - 60 0.2500 30 100 50 90 - 60 0.0625 10 95 0 80 80 30 0.0156 0 40 0 40 - 0 0.0040 0 10 0 20 0 0 27 1.0000 50 100 100 100 100 80 0.2500 0 100 70 90 100 40 0.0625 0 100 40 70 0 10 0.0156 0 80 10 40 0 0 0.0040 0 60 0 10 0 0 28 1.0000 70 100 100 100 100 90 0.2500 10 100 100 90 90 40 0.0625 0 100 50 90 80 20 0.0156 0 95 20 80 0 0 0.0040 0 80 0 10 0 0 29 1.0000 20 100 100 100 100 40 0.2500 10 100 50 100 30 30 0.0625 0 100 50 100 0 30 0.0156 0 70 50 50 0 30 0.0040 0 50 50 50 0 0 30 1.0000 10 100 100 100 100 40 0.2500 0 100 100 100 100 40 0.0625 0 80 50 80 100 20 0.0156 0 50 30 50 0 10 0.0040 0 0 0 10 0 0 31 1.0000 10 100 70 90 100 20 0.2500 0 90 50 90 100 60 0.0625 0 60 0 20 0 0 0.0156 0 60 0 0 0 0 0.0040 0 0 0 0 0 0 32 1.0000 20 100 100 100 - 20 0.2500 20 90 70 90 0 0 0.0625 10 80 20 80 0 0 0.0156 0 60 0 80 0 0 0.0040 0 0 0 30 0 0 33 4.0000 70 100 100 100 100 100 1.0000 40 100 100 100 100 90 0.2500 0 100 30 80 100 50 0.0625 0 100 0 70 30 0 0.0156 0 60 0 40 0 0

Example Weight (kg / ha) Rice (three seasons) blood Tadpole Water pinnacle You too Olme 34 4.0000 50 100 100 100 100 100 1.0000 40 100 80 100 100 100 0.2500 20 100 50 90 0 0 0.0625 0 95 0 40 0 0 0.0156 0 50 0 0 0 0 35 1.0000 20 100 50 100 100 60 0.2500 10 100 20 90 100 0 0.0625 0 90 0 70 0 0 0.0156 0 40 0 30 0 0 0.0040 0 40 0 0 0 0 36 4.0000 60 100 100 100 100 0 1.0000 0 100 50 100 100 0 0.2500 0 100 0 60 0 0 0.0625 0 80 0 20 0 0 0.0156 0 0 0 0 0 0 37 1.0000 0 100 40 100 100 0 0.2500 0 100 20 90 100 0 0.0625 0 95 0 40 0 0 0.0156 0 40 0 10 0 0 0.0040 0 0 0 0 0 0 38 1.0000 10 95 10 90 0 20 0.2500 0 80 0 40 0 10 0.0625 0 70 0 10 0 0 0.0156 0 0 0 0 0 0 0.0040 0 0 0 0 0 0 39 4.0000 70 100 100 100 100 90 1.0000 50 100 100 100 100 60 0.2500 20 90 40 70 0 0 0.0625 0 80 0 30 0 0 0.0156 0 80 0 0 0 0 40 4.0000 90 100 100 100 100 100 1.0000 80 100 100 100 100 80 0.2500 50 100 90 100 100 50 0.0625 20 100 40 70 40 0 0.0156 0 60 0 0 0 0 41 4.0000 100 100 100 100 100 90 1.0000 90 100 100 100 100 0 0.2500 20 90 90 60 100 0 0.0625 0 70 30 20 100 0 0.0156 0 0 0 0 0 0 42 2.0000 0 100 0 100 50 50 0.5000 0 100 0 100 20 0 0.1250 0 100 0 90 0 0 0.0310 0 60 0 30 0 0 0.0080 0 20 0 0 0 0 43 4.0000 0 100 20 100 100 50 1.0000 0 100 0 100 100 0 0.2500 0 100 0 100 100 0 0.0625 0 95 0 100 50 0 0.0156 0 80 0 30 0 0 44 4.0000 90 100 100 100 100 100 1.0000 80 100 100 100 100 90 0.2500 60 100 100 90 50 80 0.0625 10 100 100 90 30 30 0.0156 0 70 20 70 0 0

Example Weight (kg / ha) Rice (three seasons) blood Tadpole Water pinnacle You too Olme 45 1.0000 50 100 100 100 - 80 0.2500 10 100 60 90 - 0 0.0625 0 95 10 90 - 0 0.0156 0 80 0 70 - 0 0.0040 0 20 0 60 - 0 46 1.0000 100 100 100 100 - 90 0.2500 0 100 90 90 - 60 0.0625 0 100 20 90 90 20 0.0156 0 70 10 80 0 0 0.0040 0 30 0 60 0 0 47 1.0000 10 100 50 90 - 80 0.2500 0 100 40 80 - 0 0.0625 0 95 30 80 70 0 0.0156 0 60 0 50 0 0 0.0040 0 0 0 0 0 0 48 1.0000 40 100 100 90 - 60 0.2500 0 100 90 90 - 40 0.0625 0 95 10 80 60 30 0.0156 0 65 0 70 0 0 0.0040 0 20 0 50 0 0 49 1.0000 70 100 90 100 - 80 0.2500 10 100 30 90 - 50 0.0625 0 95 0 80 - 10 0.0156 0 70 0 80 0 0 0.0040 0 0 0 40 0 0 50 1.0000 90 100 100 100 - 80 0.2500 50 100 30 90 - 50 0.0625 30 100 20 90 - 10 0.0156 10 70 10 80 0 0 0.0040 0 20 10 60 0 0 51 1.0000 10 100 90 90 - 80 0.2500 0 100 50 80 - 0 0.0625 0 90 10 70 60 0 0.0156 0 70 0 60 - 0 0.0040 0 0 0 50 0 0 52 1.0000 50 100 100 100 100 60 0.2500 0 100 30 80 20 0 0.0625 0 100 0 70 20 0 0.0156 0 70 0 20 0 0 0.0040 0 0 0 0 0 0 53 1.0000 50 100 100 100 - 90 0.2500 20 100 100 90 - 70 0.0625 0 100 30 90 60 20 0.0156 0 70 20 80 30 0 0.0040 0 30 0 30 30 0 54 1.0000 60 100 100 100 - 100 0.2500 0 100 100 100 - 90 0.0625 0 100 30 90 - 40 0.0156 0 80 30 80 80 0 0.0040 0 60 0 50 0 0 55 1.0000 20 100 100 100 - 70 0.2500 0 100 50 90 - 50 0.0625 0 90 10 80 50 10 0.0156 0 70 0 50 0 0 0.0040 0 0 0 30 0 0

Example Weight (kg / ha) Rice (three seasons) blood Tadpole Water pinnacle You too Olme 56 1.0000 20 100 70 100 - 70 0.2500 0 100 30 90 - 20 0.0625 0 95 20 80 - 0 0.0156 0 75 0 50 - 0 0.0040 0 20 0 40 0 0 57 1.0000 20 100 10 100 0 50 0.2500 0 95 0 90 0 10 0.0625 0 30 0 70 0 0 0.0156 0 30 0 50 0 0 0.0040 0 0 0 0 0 0 58 1.0000 0 100 90 90 50 50 0.2500 0 90 70 90 - 0 0.0625 0 75 10 70 - 0 0.0156 0 50 0 50 0 0 0.0040 0 10 0 20 0 0 59 4.0000 90 100 100 100 100 100 1.0000 80 100 100 100 100 70 0.2500 10 100 90 80 100 50 0.0625 0 90 70 70 40 30 0.0156 0 60 0 30 0 0 60 4.0000 100 100 100 100 100 60 1.0000 40 100 100 90 100 50 0.2500 10 100 100 90 100 0 0.0625 0 90 30 30 0 0 0.0156 0 20 0 0 0 0 61 4.0000 40 100 100 100 70 0 1.0000 20 100 100 100 0 0 0.2500 0 90 0 40 0 0 0.0625 0 70 0 0 0 0 0.0156 0 20 0 0 0 0 62 4.0000 0 100 40 90 0 0 1.0000 0 100 0 50 0 0 0.2500 0 60 0 0 0 0 0.0625 0 40 0 0 0 0 0.0156 0 0 0 0 0 0 63 4.0000 70 100 100 100 100 0 1.0000 30 100 100 100 100 0 0.2500 0 100 50 100 100 0 0.0625 0 90 0 90 100 0 0.0156 0 90 0 20 10 0 64 4.0000 80 100 100 100 100 0 1.0000 40 100 100 100 100 0 0.2500 0 100 0 100 100 0 0.0625 0 80 0 80 100 0 0.0156 0 80 0 0 0 0 65 4.0000 80 100 100 100 100 100 1.0000 50 100 100 100 100 100 0.2500 40 100 90 90 100 100 0.0625 30 100 60 80 60 60 0.0156 0 60 0 50 0 0 66 4.0000 80 100 100 100 100 0 1.0000 40 100 40 100 100 0 0.2500 20 100 30 90 90 0 0.0625 0 80 20 80 20 0 0.0156 0 60 0 50 10 0

Example Weight (kg / ha) Rice (three seasons) blood Tadpole Water pinnacle You too Olme 67 4.0000 60 100 100 100 100 100 1.0000 40 100 80 100 100 100 0.2500 30 100 40 100 50 100 0.0625 0 80 30 100 30 100 0.0156 0 80 0 60 30 50 68 4.0000 50 100 40 90 50 0 1.0000 0 100 0 40 0 0 0.2500 0 90 0 0 0 0 0.0625 0 50 0 0 0 0 0.0156 0 10 0 0 0 0 69 4.0000 0 80 0 40 100 60 1.0000 0.2500 0.0625 0.0156 70 4.0000 100 100 100 100 100 80 1.0000 40 100 100 100 100 80 0.2500 10 100 100 100 100 50 0.0625 0 100 50 70 40 0 0.0156 0 70 0 20 0 0 71 4.0000 100 100 100 100 100 0 1.0000 40 100 100 100 100 0 0.2500 10 100 0 100 100 0 0.0625 0 100 0 80 100 0 0.0156 0 80 0 0 0 0 72 4.0000 60 100 100 100 100 0 1.0000 30 100 100 100 100 0 0.2500 0 100 0 50 0 0 0.0625 0 95 0 0 0 0 0.0156 0 20 0 0 0 0 73 4.0000 70 100 100 100 100 90 1.0000 0 100 100 100 30 90 0.2500 0 100 100 100 30 0 0.0625 0 100 0 80 20 0 0.0156 0 50 0 20 0 0 74 4.0000 50 100 90 100 100 40 1.0000 20 100 60 100 20 - 0.2500 0 100 30 80 0 - 0.0625 0 80 0 80 0 0 0.0156 0 0 0 70 0 0

As can be seen from the results of the efficacy test, the novel acetamide derivatives substituted with fluorinated propenyloxy groups according to the present invention are toxic to major crops, and exhibit excellent herbicidal activity even at low concentrations. Is very wide. In particular, the continuity of the medicinal effect is improved, and the weeds and crops are excellent because the toxicity of the main crop, rice, is very low because of excellent herbicidal activity on the grass and weeds, including the main weeds of rice. In addition, even in the case of the field is a major crops such as corn, barley, wheat, etc. is safe and exhibits excellent herbicidal activity on the flowers and weeds such as blood and barley.

Claims (5)

Fluorinated propenyloxyacetamide derivatives of the general formula (I) Formula 1 Wherein R ¹ represents an unsubstituted or substituted phenyl or thiophene group having 1 to 2 carbon atoms, alkyl, haloalkyl, alkoxy, methylenedioxy or one or more chlorine, fluorine or cancelled, and R ² and R ³ are each Alkyl or benzyl group having 1 to 4 carbon atoms, alkenyl or benzyl group having 1 to 4 carbon atoms, or R ² and R ³ together with the nitrogen atom to which they are attached, are unsubstituted or have 1 to 2 alkyl groups at the 2 or 6 position. Or two substituted piperidino, hexamethyleneimino, morpholino, 1,2,3,6-tetrahydropyridino or 1,2,3,4-tetrahydrocurololino groups. The method of claim 1, R ¹ is unsubstituted or substituted with chlorine, fluorine or methoxy groups, R ² and R ³ together with the nitrogen atom to which they are attached, piperidino, hexamethyleneimino, morpholino or 1,2,3, A fluorinated propenyloxyacetamide derivative, which forms a 6-tetrahydropyridino group. The method of claim 2, In general formula (I), R ¹ is a phenyl group which is unsubstituted or substituted with chlorine or fluorine, and R ² and R ³ form a piperidino group together with the nitrogen atom to which they are bonded. Acetamide derivatives. Represented by the general formula (I) according to claim 1 which comprises reacting an alcoholic compound of the following general formula (II) in the presence of a base Process for preparing fluorinated propenyloxyacetamide derivatives: Formula 2 Formula 3 Wherein R ¹ , R ² , and R ³ are each as defined in claim 1. A herbicide composition comprising an effective amount of a novel fluorinated propenyloxyacetamide derivative of formula (I) according to claim 1 and a pharmaceutically acceptable carrier.