WO2003037085A1 - Optically active herbicidal (r)-phenoxypropionic acid-n-methyl-n-2-fluorophenyl amides - Google Patents

Optically active herbicidal (r)-phenoxypropionic acid-n-methyl-n-2-fluorophenyl amides Download PDF

Info

Publication number
WO2003037085A1
WO2003037085A1 PCT/KR2001/001845 KR0101845W WO03037085A1 WO 2003037085 A1 WO2003037085 A1 WO 2003037085A1 KR 0101845 W KR0101845 W KR 0101845W WO 03037085 A1 WO03037085 A1 WO 03037085A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
hydrogen
methyl
halogen
formula
Prior art date
Application number
PCT/KR2001/001845
Other languages
French (fr)
Inventor
Dae Whang Kim
Hae Sung Chang
Young Kwan Ko
Jae Wook Ryu
Jae Chun Woo
Dong Wan Koo
Jin Seog Kim
Bong-Jin Chung
Oh-Yeon Kwon
Original Assignee
Dongbu Hannong Chemical Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=19198468&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2003037085(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to BRPI0117166-6A priority Critical patent/BRPI0117166B1/en
Priority to JP2003539442A priority patent/JP2005507402A/en
Priority to AU2002212806A priority patent/AU2002212806B2/en
Priority to PCT/KR2001/001845 priority patent/WO2003037085A1/en
Priority to CN01823753.3A priority patent/CN1279031C/en
Application filed by Dongbu Hannong Chemical Co., Ltd. filed Critical Dongbu Hannong Chemical Co., Ltd.
Priority to CA002465342A priority patent/CA2465342C/en
Priority to EP01981146A priority patent/EP1448058A4/en
Priority to US10/494,084 priority patent/US20050043180A1/en
Priority to HU0402057A priority patent/HU230485B1/en
Publication of WO2003037085A1 publication Critical patent/WO2003037085A1/en
Priority to BG108697A priority patent/BG66413B1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles

Definitions

  • the present invention relates to optically active herbicidal (R)- phenoxypropionic acid N-methyl-N-2-fluorophenyl amide compounds represented in the following formula (1), a method for preparing thereof, their use to prevent generation of barnyard grass produced from rice and composition as suitable herbicides,
  • X is hydrogen, halogen, hydroxy, NH 2 , C0 2 H, C ⁇ -C 6 alkylamino substituted with 1 or 2 of C1-C3 alkyl, ⁇ - _ alkyl, C ⁇ -C 6 alkoxy, CL-C 3 haloalkyl, C -C3 haloalkoxy, C 2 -C alkoxyalkoxy, Q-Ci alkylthonyl, C ⁇ -C 4 alkylsulfonyl, C 2 -C 6 alkenyl, C 2 -C 6 alkinyl, C 2 -C 6 alkenyloxy, C 2 -C 6 alkinyloxy, C ⁇ -C 3 alkoxycarbonyl, or Q-C3 alkylcarbonyl; Y is hydrogen or fluoro; and n is an integer of 0 to 2, wherein X can be a combination of other substituents when n is 2. [Background Art]
  • (R ⁇ ) m is hydrogen, halogen, CF 3 , N0 2 , CN or alkyl; A is O, S or NH; R 2
  • R3 and R may be identical or different and represent hydrogen, C ⁇ -C 6 alkyl, Ci-C ⁇ hydroxyalkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, or phenyl substituted with 1 to 3 substituents chosen from C ⁇ -C alkyl, Ci-C 6 alkoxy, halogen and CF 3 .
  • R5 is , where R 6 is hydrogen or halogen; R7 is hydrogen or alkyl ; and Z is , where R3 and R may be identical or different and represent hydrogen, Ct-Ce alkyl, Ci-C ⁇ hydroxyalkyl, C3-C6 cycloalkyl, O-Q alkoxy, or phenyl substituted with 1 to 3 substituents chosen from C ⁇ -C 4 alkyl, Ci-C ⁇ alkoxy, halogen and CF3.
  • C ⁇ -C 6 alkyl identical or different and represent hydrogen, C ⁇ -C 6 alkyl, Ci-C ⁇ hydroxyalkyl, C 3 -C ⁇ cycloalkyl, C ⁇ -C 4 alkoxy, or phenyl substituted with 1 to 3 substituents chosen from C ⁇ -C alkyl, C ⁇ -C 6 alkoxy, halogen and CF3.
  • JP Patent publication 2-11580 discloses the compound represented in the following formula (5),
  • L is low alkyl, halogen, methoxy, methoxyphenoxy, benzyloxy, methylthio or methylvinyl; and n is an integer of 0 to 2.
  • JP Patent publication sho 53-40767 and sho 54-112828 also disclose that phenoxypropionic acid amide derivatives have herbicidal activity.
  • inventors of the present invention disclosed herbicidal phenoxypropionic acid N-alkyl-N-2-fluorophenyl amide compounds in International Pat. Publication No. WO 2000/05956.
  • the inventors have intensively studied to provide herbicides to effectively control barnyard grass, and particularly, to find out selective herbicidal activity of phenoxypropionic acid N-alkyl-N-2-fluorophenyl amide compounds of formula (6).
  • phenoxypropionic acid N-alkyl-N-2-fluorophenyl amides of formula (6) exist as (R)- or (S)-stereoisomer, and (R)-stereoisomers provide higher stability to rice and better herbicidal activity compared to (S)-stereoisomers or mixtures thereof. This superior activity of (R)-stereoisomers is distinguished from the conventional inventions.
  • an object of the present invention is to provide optically active herbicide compounds which exhibit excellent selectivity toward rice and prevent the production of harmful barnyard grass.
  • the present invention is to provide optically active herbicide phenoxypropionic acid N-methyl-N-2-fluorophenyl amides of formula (1) with an excellent herbicidal activity as well as selective and remarkable stability toward rice,
  • X is hydrogen, halogen, hydroxy, NH 2 , CO2H, Ci-C ⁇ alkylamino substituted with 1 or 2 of Ci-C3 alkyl, Ci-C ⁇ alkyl, C ⁇ -C 6 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C 2 -Q alkoxyalkoxy, Ci-Q alkylthonyl, d-C 4 alkylsulfonyl, C 2 -C 6 alkenyl, C 2 -C 6 alkinyl, C 2 -C 6 alkenyloxy, C 2 -C 6 alkinyloxy, C1-C3 alkoxycarbonyl, or O-C3 alkylcarbonyl; Y is hydrogen or fluoro; and n is an integer of 0 to 2, wherein X can be a combination of other substituents when n is 2.
  • optically active compounds of formula (1) according to the present invention may be specified as the following Table 1.
  • optically active compounds of formula (1) according to this invention may be synthesized by employing a conventional method represented in the following Scheme 1, reacting a compound of formula (7) with a compound of formula (8),
  • X' is OH, CI, Br, or phenoxy;
  • X is hydrogen, halogen, hydroxy, NH 2 , C0 2 H, C ⁇ -C 6 alkylamino substituted with 1 or 2 of Ci-C 3 alkyl, Ci-C ⁇ alkyl, Ci- C ⁇ alkoxy, Q-C?
  • haloalkyl C1-C3 haloalkoxy, C 2 -Q alkoxyalkoxy, C1-C4 alkylthonyl, Ci-Q alkylsulfonyl, C 2 -C 6 alkenyl, C2-C6 alkinyl, C 2 -C 6 alkenyloxy, C 2 -C 6 alkinyloxy, Ci-C 3 alkoxycarbonyl, or C1-C3 alkylcarbonyl; Y is hydrogen or fluoro; and n is an integer of 0 to 2, wherein X can be a combination of other substituents when n is 2.
  • a binder such as triphenylphosphine and an organic base such as triethylamine or pyridine at a temperature of 0 to 100 ° C in an inert solvent such as ethers like tetrahydrofuran, ethyethyl acetate, acetonitrile, toluene, xylene, hexane, methylene chloride, carbon tetrachloride, dichloroethane or the like. After the solvent is evaporated, the crude product is purified by column chromatography.
  • an inert solvent such as ethers like tetrahydrofuran, ethyethyl acetate, acetonitrile, toluene, xylene, hexane, methylene chloride, carbon tetrachloride, dichloroethane or the like.
  • X is CI, Br, I, benzenesulfonyloxy, toluenesulfonyloxy, methanesulfonyloxy or low alkyl sulfate; and X is hydrogen, halogen, hydroxy, NH 2 , CO2H, Ci-C ⁇ alkylamino substituted with 1 or 2 of C1-C3 alkyl, Ci-C 6 alkyl, Ci-C ⁇ alkoxy, Ci-C 3 haloalkyl, C1-C3 haloalkoxy, C 2 -C 4 alkoxyalkoxy, Ci-C alkylthonyl, Ci-Q alkylsulfonyl, C 2 -C 6 alkenyl, C 2 -C 6 alkinyl, C 2 -C 6 alkenyloxy, C 2 -C ⁇ alkinyloxy, G-C3 alkoxycarbonyl, or O-C3 alkylcarbonyl;
  • a strong base which is enough to pull out a hydrogen from amide, NH.
  • a strong base include NaOH, KOH, LiOH, NaH, n-BuLi, LDA, and the like.
  • the reaction is performed at a temperature of -78 to 50 ° C in an inert solvent such as ethers like ethylether, dioxane or tetrahydrofuran or hydrocarbons like hexane.
  • Y' is halogen, alkylsulfonyloxy, haloalkylsulfonyloxy, benzenesulfonyloxy or toluenesulfonyloxy;
  • X is hydrogen, halogen, hydroxy, NH 2 , CO2H, Ci-C ⁇ alkylamino substituted with 1 or 2 of C1-C3 alkyl, Ci-C ⁇ alkyl,
  • Y is hydrogen or fluoro
  • n is an integer of 0 to 2, wherein X can be a combination of other substituents when n is 2.
  • examples of the base include inorganic bases of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrogen carbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate; and organic bases such as triethylamine, N,N- dimethylaniline, pyridine and l,8-diazabicyclo[5,4,0]undec-7-ene.
  • phase transition catalyst such as tetra-n-butylammonium bromide or 18-crown-6-[l,4,7,10,13,16-hexaoctacyclooctadecane] may be added to rapidly complete the reaction, if necessary. Further, one or more than two solvents may be used, if deemed necessary.
  • the inert organic solvent examples include ketones such as acetone; aromatic hydrocarbons such as toluene, xylene and chlorobenzene; aliphatic hydrocarbons such as petroleum ether and ligroin; ethers such as diethylether, tetrahydrofuran and dioxane; nitrites such as acetonitrile and propionitrile; and amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.
  • a reaction is carried out at a temperature of from 0 ° C to reflux, preferably at 5 to 50 ° C , for 1 to 24 hour(s) to afford the desired product with high yield.
  • Y' is halogen, alkylsulfonyloxy, haloalkylsulfonyloxy, benzenesulfonyloxy or toluenesulfonyloxy;
  • X is hydrogen, halogen, hydroxy, NH 2 , C0 2 H, Ci-C ⁇ alkylamino substituted with 1 or 2 of Ci-C 3 alkyl, Ci-C 6 alkyl, Ci-C ⁇ alkoxy, C1-C3 haloalkyl, Ci-C 3 haloalkoxy, C 2 -C alkoxyalkoxy, Ct-C alkylthonyl, C1-C4 alkylsulfonyl, C2-C0 alkenyl, C 2 -C 6 alkinyl, C 2 -C 6 alkenyloxy, C 2 -C ⁇ alkinyloxy, C1-C3 alkoxycarbonyl, or Q-C3 alkylcarbonyl;
  • examples of the base include inorganic bases of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrogencarbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate; and organic bases such as triethylamine, N,N- dimethylaniline, pyridine, picoline, quinoline, and l,8-diazabicyclo[5,4,0]undec- 7-ene.
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
  • alkali metal carbonates such as sodium carbonate and potassium carbonate
  • alkali metal hydrogencarbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate
  • organic bases such as triethylamine, N,N- dimethylaniline, pyridine, picoline, quinoline, and l,8-diazabicyclo[5,4,0]undec- 7-ene.
  • phase transition catalyst such as tetra-n-butylammonium bromide or 18-crown-6[l,4,7,10,13,16-hexaoctacyclooctadecane] may be used, if necessary. Further, more than one solvent may be used if deemed necessary.
  • the inert organic solvent examples include ketones such as acetone and butanone; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; aliphatic hydrocarbons such as petroleum ether, and ligroin; ethers such as diethylether, tetrahydrofuran and dioxane; nitriles such as acetonitrile or propionitrile; and amides such as N,N-dimethylformamide, N,N-dimethyl acetamide and N-methylpyrrolidone.
  • a reaction is carried at a temperature of from 0 ° C to reflux, preferably at 20 to 100 ° C for 1 to 24 hour(s) to afford the desired product with high yield.
  • Example 1 Preparation of (S)-2-bromo-propionic acid-N-(2-fluorophenyl)-N- methyl amide
  • Example 5 Preparation of (R)-2-[4-(6-chloro-2-benzoxazolyloxy)- phenoxyjpropionic acid-N-(2-fluorophenyl)-N-methyl Amide (R)-2-[4-(6-chloro-2-benzoxazoyloxy)-phenoxy]propionic acid-N-(2- fluorophenyl) amide (100 mg, 0.24 mmol) was dissolved in 10 ml of anhydrous tetrahydrofuran and 60% NaH(10 mg, 0.24 mmol) and CH 3 I(34 mg, 0.24 mmol) were added sequentially at 0 ° C . The reaction mixture was stirred at room temperature for 5 hours.
  • the reaction mixture was cooled to room temperature and acidified with 5% hydrochloric acid.
  • the acidified reaction mixture was extracted three times with ethyl acetate.
  • the combined organic solvent layer was dried over magnesium sulfate, filtered and concentrated under reduced pressure.
  • the acidified reaction mixture was extracted three times with ethyl acetate.
  • the combined organic solvent layer was dried over magnesium sulfate, filtered and concentrated under reduced pressure.
  • the compounds according to the present invention should be formulated in such a suitable type such as wettable powder, emulsions, granules, dusts, suspensions and solutions by combining a carrier, a surfactant, a dispersing agent or a supplement agent. Many of these may be applied directly or after diluted with suitable media.
  • Formulations can be prepared at spray volume of from hundreds liters to thousands liters per hectare. The formulations contain about 0.1% to 99% by weight of active ingredient(s) and 0.1% to 20% surfactant(s) or 0% to 99.9% solid or liquid diluent(s) are recommended to be added. The formulations will contain these ingredients in the following approximate proportions shown in Table 3. Table 3
  • the proportion of active ingredients depends on the intended use. Higher ratio of a surfactant is sometimes desired to active ingredients and is achieved by incorporation into the formulation or tank mixing.
  • Solid diluents with high absorption are preferred for wettable powder.
  • Liquid diluents and solvents are preferred to be stable against phase separation at 0 ° C . All the formulations may contain a small amount of additives to prevent forming, caking, corrosion and growth of microorganisms.
  • solutions can be made only by blending ingredients and fine solids by blending and pulverizing with hammer-mill.
  • Suspensions can be made by wet-milling and granules can be made by spraying the active ingredients on performed granular carrier.
  • Formulation 1 Wettable Powder
  • the ingredients are thoroughly blended, re-blended after spraying liquid surfactant on the solid ingredients and hammer-milled until all the solids are essentially under 100 ⁇ m.
  • Active ingredient (Compound of Example 3) 20 wt. %
  • Formulation 2 Wettable Powder
  • the ingredients are blended, hammer-milled until all the solids are under 25 ⁇ m and packaged.
  • Active ingredient (Compound of Example 3) 80 wt. % Sodium alkyl naphthalenesulf onate 2 wt.%
  • the ingredients are mixed and homogeneously dissolved to give emulsions.
  • Active ingredient (Compound of Example 3) 30 wt. % Cyclohexanone 20 wt. % Polyoxyethylene alkylaryl ether 11 wt.%
  • the formulations according to this invention were sprayed with diluting to a certain concentration.
  • the compounds according to the present invention represent high activity as leaf treatment herbicides for rice and especially effective in rice due to an excellent control of barnyard grass.
  • the active ingredients can be used from 10 g to 4 kg per hectare, preferably from 50 g to 400 g.
  • the amount of the compounds of the present invention depends on the amount and size of weeds and formulations.
  • the herbicides of the present invention can be used as alone or in combination with other herbicides, insecticides or bactericides.
  • one agent selected from the group consisting of bentazon, quinclorac, propanil, simetryn, 2,4-D, fenoxaprop-ethyl, linuron, MCPA, azafenidin, carfentrazone, molinate, thiobencarb, pendimethalin, bensulfuron-methyl, pyrazosulfuron- ethyl, metsulfuron-methyl, thifensulfuron-methyl, tribenuron-methyl, trifluralin, amidosulfuron, bromoxynil, butachlor, mecoprop, metribuzin, bifenox, benfuresate, isoproturon, cyhalofop-butyl, mefenaset, fentrazamide, pyriminobac-methyl, bispyribac sodium, azimsulfruon, cyclosulfamuron, pyanchor, and mixtures thereof
  • the active compound(s) of formula (1) according to the invention exhibited an excellent selectivity toward the plants and herbicidal activity against weeds.
  • optically active (R)-stereoisomers of the present invention exhibit excellent selectivity toward rice and superior herbicidal activity against barnyard grass to racemic mixtures and (S)- stereoisomers thereof. Therefore, the optically active compounds of the present invention may be very effective in rice farming. Further, it is proved that the optically active compounds are very stable for wheat, barley, beans, and corn and useful to control weeds.

Abstract

The present invention relates to optically active herbicidal (R)-phenoxypropionic acid N-methyl-N-2-fluorophenyl amide compounds represented in the following formula (1), a method for preparing thereof, their use to prevent generation of barnyard grass produced from rice and composition as suitable herbicides, (I) wherein X is hydrogen, halogen, hydroxy, NH2, CO2H, C1-C6 alkylamino substituted with 1 or 2 of C1-C3 alkyl, C1-C6 alkyl, C1-C6 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C2-C4 alkoxyalkoxy, C1-C4 alkylthonyl, C1-C4 alkylsulfonyl, C2-C6 alkenyl, C2-C6 alkinyl, C2-C6 alkenyloxy,C2-C6 alkinyloxy, C1-C3 alkoxycarbonyl, or C1-C3 alkylcarbonyl; is hydrogen or fluoro; and n is an integer of 0 to 2, wherein X can be a combination of other substituents when n is 2.

Description

OPTICALLY ACTIVE HERBICIDAL (R)-PHENOXYPROPIONIC ACID-N-METHYL-N-2-FLUOROPHENYL AMIDES
[Technical Field]
The present invention relates to optically active herbicidal (R)- phenoxypropionic acid N-methyl-N-2-fluorophenyl amide compounds represented in the following formula (1), a method for preparing thereof, their use to prevent generation of barnyard grass produced from rice and composition as suitable herbicides,
Figure imgf000002_0001
wherein X is hydrogen, halogen, hydroxy, NH2, C02H, Cι-C6 alkylamino substituted with 1 or 2 of C1-C3 alkyl, \- _ alkyl, Cι-C6 alkoxy, CL-C3 haloalkyl, C -C3 haloalkoxy, C2-C alkoxyalkoxy, Q-Ci alkylthonyl, Cι-C4 alkylsulfonyl, C2-C6 alkenyl, C2-C6 alkinyl, C2-C6 alkenyloxy, C2-C6 alkinyloxy, Cι-C3 alkoxycarbonyl, or Q-C3 alkylcarbonyl; Y is hydrogen or fluoro; and n is an integer of 0 to 2, wherein X can be a combination of other substituents when n is 2. [Background Art]
U.S. Pat. No. 4,130,413 discloses the compounds represented in the following formula (2),
Figure imgf000003_0001
wherein (Rι)m is hydrogen, halogen, CF3, N02, CN or alkyl; A is O, S or NH; R2
is hydrogen or alkyl; Z is
Figure imgf000003_0002
, where R3 and R may be identical or different and represent hydrogen, Cι-C6 alkyl, Ci-Cό hydroxyalkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, or phenyl substituted with 1 to 3 substituents chosen from Cι-C alkyl, Ci-C6 alkoxy, halogen and CF3.
U.S. Pat. No. 4,531,969 discloses the compounds represented in the following formula (3),
Figure imgf000003_0003
wherein R5 is
Figure imgf000003_0004
, where R6 is hydrogen or halogen; R7 is hydrogen or alkyl ; and Z is
Figure imgf000004_0001
, where R3 and R may be identical or different and represent hydrogen, Ct-Ce alkyl, Ci-Cό hydroxyalkyl, C3-C6 cycloalkyl, O-Q alkoxy, or phenyl substituted with 1 to 3 substituents chosen from Cι-C4 alkyl, Ci-Cβ alkoxy, halogen and CF3.
U.S. Pat. No. 5,254,527 discloses the compounds represented in the following formula (4),
Figure imgf000004_0002
Figure imgf000004_0003
identical or different and represent hydrogen, Cι-C6 alkyl, Ci-Cβ hydroxyalkyl, C3-Cό cycloalkyl, Cι-C4 alkoxy, or phenyl substituted with 1 to 3 substituents chosen from Cι-C alkyl, Cι-C6 alkoxy, halogen and CF3.
Even though some compounds of formula (1) of the present invention are disclosed in the above patents, none of the patents teach the synthesis of the compound of formula (1) and have tested the same for herbicidal activity.
JP Patent publication 2-11580 discloses the compound represented in the following formula (5),
Figure imgf000005_0001
wherein L is low alkyl, halogen, methoxy, methoxyphenoxy, benzyloxy, methylthio or methylvinyl; and n is an integer of 0 to 2.
JP Patent publication sho 53-40767 and sho 54-112828 also disclose that phenoxypropionic acid amide derivatives have herbicidal activity.
Further, inventors of the present invention disclosed herbicidal phenoxypropionic acid N-alkyl-N-2-fluorophenyl amide compounds in International Pat. Publication No. WO 2000/05956.
Figure imgf000005_0002
Even though many of herbicides for rice have been recently developed and used, barnyard grass among weeds is the biggest problem in rice paddy.
Development of herbicides to control barnyard grass is an urgent to one who is in the field of agriculture. After transplanting young rice, herbicides, developed until now, cannot effectively control the production of barnyard grass so that it causes a huge damage to harvest. It has been reported that the amount of rice harvest is decreased by 2% when barnyard grass is produced 1 week per 1 m2, decreased by about 10% when produced 5 weeks per 1 m2, decreased by about 19% when produced 10 weeks per 1 m2 and decreased by about 35% when produced 20 weeks per 1 m2. Many different kinds of herbicides have been used for the purpose of controlling barnyard grass that damages in amount of harvest of rice. However, the herbicide with a broader herbicidal activity, environment-friendly property and cost-effectiveness is still in demand.
The inventors have intensively studied to provide herbicides to effectively control barnyard grass, and particularly, to find out selective herbicidal activity of phenoxypropionic acid N-alkyl-N-2-fluorophenyl amide compounds of formula (6). As a result, we completed this invention by finding that some phenoxypropionic acid N-alkyl-N-2-fluorophenyl amides of formula (6) exist as (R)- or (S)-stereoisomer, and (R)-stereoisomers provide higher stability to rice and better herbicidal activity compared to (S)-stereoisomers or mixtures thereof. This superior activity of (R)-stereoisomers is distinguished from the conventional inventions.
Therefore, an object of the present invention is to provide optically active herbicide compounds which exhibit excellent selectivity toward rice and prevent the production of harmful barnyard grass.
[Disclosure of Invention]
The present invention is to provide optically active herbicide phenoxypropionic acid N-methyl-N-2-fluorophenyl amides of formula (1) with an excellent herbicidal activity as well as selective and remarkable stability toward rice,
Figure imgf000007_0001
(1)
wherein X is hydrogen, halogen, hydroxy, NH2, CO2H, Ci-Cό alkylamino substituted with 1 or 2 of Ci-C3 alkyl, Ci-Cό alkyl, Cι-C6 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C2-Q alkoxyalkoxy, Ci-Q alkylthonyl, d-C4 alkylsulfonyl, C2-C6 alkenyl, C2-C6 alkinyl, C2-C6 alkenyloxy, C2-C6 alkinyloxy, C1-C3 alkoxycarbonyl, or O-C3 alkylcarbonyl; Y is hydrogen or fluoro; and n is an integer of 0 to 2, wherein X can be a combination of other substituents when n is 2.
The optically active compounds of formula (1) according to the present invention may be specified as the following Table 1.
Table 1
Figure imgf000008_0001
Figure imgf000009_0001
Figure imgf000010_0001
Figure imgf000011_0001
The optically active compounds of formula (1) according to this invention may be synthesized by employing a conventional method represented in the following Scheme 1, reacting a compound of formula (7) with a compound of formula (8),
Scheme 1
Figure imgf000012_0001
wherein X' is OH, CI, Br, or phenoxy; X is hydrogen, halogen, hydroxy, NH2, C02H, Cι-C6 alkylamino substituted with 1 or 2 of Ci-C3 alkyl, Ci-Cό alkyl, Ci- Cό alkoxy, Q-C? haloalkyl, C1-C3 haloalkoxy, C2-Q alkoxyalkoxy, C1-C4 alkylthonyl, Ci-Q alkylsulfonyl, C2-C6 alkenyl, C2-C6 alkinyl, C2-C6 alkenyloxy, C2-C6 alkinyloxy, Ci-C3 alkoxycarbonyl, or C1-C3 alkylcarbonyl; Y is hydrogen or fluoro; and n is an integer of 0 to 2, wherein X can be a combination of other substituents when n is 2.
In the method according to Scheme 1, it is performed preferably to use a binder such as triphenylphosphine and an organic base such as triethylamine or pyridine at a temperature of 0 to 100 °C in an inert solvent such as ethers like tetrahydrofuran, ethyethyl acetate, acetonitrile, toluene, xylene, hexane, methylene chloride, carbon tetrachloride, dichloroethane or the like. After the solvent is evaporated, the crude product is purified by column chromatography.
Another method for preparing the compounds (1) represented in the following Scheme 2 is an alkylation of a compound of formula (9) to a compound of formula (10), Scheme 2
Figure imgf000013_0001
( 9 ) wherein X" is CI, Br, I, benzenesulfonyloxy, toluenesulfonyloxy, methanesulfonyloxy or low alkyl sulfate; and X is hydrogen, halogen, hydroxy, NH2, CO2H, Ci-Cό alkylamino substituted with 1 or 2 of C1-C3 alkyl, Ci-C6 alkyl, Ci-Cό alkoxy, Ci-C3 haloalkyl, C1-C3 haloalkoxy, C2-C4 alkoxyalkoxy, Ci-C alkylthonyl, Ci-Q alkylsulfonyl, C2-C6 alkenyl, C2-C6 alkinyl, C2-C6 alkenyloxy, C2-Cό alkinyloxy, G-C3 alkoxycarbonyl, or O-C3 alkylcarbonyl; Y is hydrogen or fluoro; and n is an integer of 0 to 2, wherein X can be a combination of other substituents when n is 2.
In scheme 2, it is performed preferably using a strong base which is enough to pull out a hydrogen from amide, NH. Examples of a strong base include NaOH, KOH, LiOH, NaH, n-BuLi, LDA, and the like. The reaction is performed at a temperature of -78 to 50 °C in an inert solvent such as ethers like ethylether, dioxane or tetrahydrofuran or hydrocarbons like hexane.
Another method for preparing the compounds (1) represented in the following Scheme 3 is a reaction of a compound of formula (11) with a compound of formula (12) in the presence of a base, Scheme 3
Figure imgf000014_0001
( 11 ) ( 12 ) wherein Y' is halogen, alkylsulfonyloxy, haloalkylsulfonyloxy, benzenesulfonyloxy or toluenesulfonyloxy; X is hydrogen, halogen, hydroxy, NH2, CO2H, Ci-Cό alkylamino substituted with 1 or 2 of C1-C3 alkyl, Ci-Cό alkyl,
Ci-Cό alkoxy, C1-C3 haloalkyl, 0-C3 haloalkoxy, C2-C4 alkoxyalkoxy, 0-C alkylthonyl, Ci- alkylsulfonyl, C2-C6 alkenyl, C2-C6 alkinyl, C2-C6 alkenyloxy,
C2-Cό alkinyloxy, Ci-C3 alkoxycarbonyl, or C1-C3 alkylcarbonyl; Y is hydrogen or fluoro; and n is an integer of 0 to 2, wherein X can be a combination of other substituents when n is 2.
In Scheme 3, examples of the base include inorganic bases of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrogen carbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate; and organic bases such as triethylamine, N,N- dimethylaniline, pyridine and l,8-diazabicyclo[5,4,0]undec-7-ene.
A phase transition catalyst such as tetra-n-butylammonium bromide or 18-crown-6-[l,4,7,10,13,16-hexaoctacyclooctadecane] may be added to rapidly complete the reaction, if necessary. Further, one or more than two solvents may be used, if deemed necessary. Examples of the inert organic solvent include ketones such as acetone; aromatic hydrocarbons such as toluene, xylene and chlorobenzene; aliphatic hydrocarbons such as petroleum ether and ligroin; ethers such as diethylether, tetrahydrofuran and dioxane; nitrites such as acetonitrile and propionitrile; and amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. A reaction is carried out at a temperature of from 0°C to reflux, preferably at 5 to 50 °C , for 1 to 24 hour(s) to afford the desired product with high yield.
Another method for preparing the optically active compound (1) represented in the following Scheme 4 is a reaction of a compound of formula (13) with a compound of formula (14) in the presence of a base,
Figure imgf000015_0001
( 13 ) ( 14 )
wherein Y' is halogen, alkylsulfonyloxy, haloalkylsulfonyloxy, benzenesulfonyloxy or toluenesulfonyloxy; X is hydrogen, halogen, hydroxy, NH2, C02H, Ci-Cό alkylamino substituted with 1 or 2 of Ci-C3 alkyl, Ci-C6 alkyl, Ci-Cό alkoxy, C1-C3 haloalkyl, Ci-C3 haloalkoxy, C2-C alkoxyalkoxy, Ct-C alkylthonyl, C1-C4 alkylsulfonyl, C2-C0 alkenyl, C2-C6 alkinyl, C2-C6 alkenyloxy, C2-Cό alkinyloxy, C1-C3 alkoxycarbonyl, or Q-C3 alkylcarbonyl; Y is hydrogen or fluoro; and n is an integer of 0 to 2, wherein X can be a combination of other substituents when n is 2.
In Scheme 4, examples of the base include inorganic bases of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrogencarbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate; and organic bases such as triethylamine, N,N- dimethylaniline, pyridine, picoline, quinoline, and l,8-diazabicyclo[5,4,0]undec- 7-ene.
A phase transition catalyst such as tetra-n-butylammonium bromide or 18-crown-6[l,4,7,10,13,16-hexaoctacyclooctadecane] may be used, if necessary. Further, more than one solvent may be used if deemed necessary. Examples of the inert organic solvent include ketones such as acetone and butanone; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; aliphatic hydrocarbons such as petroleum ether, and ligroin; ethers such as diethylether, tetrahydrofuran and dioxane; nitriles such as acetonitrile or propionitrile; and amides such as N,N-dimethylformamide, N,N-dimethyl acetamide and N-methylpyrrolidone. A reaction is carried at a temperature of from 0°C to reflux, preferably at 20 to 100 °C for 1 to 24 hour(s) to afford the desired product with high yield.
The present invention will be further illustrated by the following examples. However, they should not be construed as limiting the scope of this invention defined by the appended claims. [Examples] Example 1: Preparation of (S)-2-bromo-propionic acid-N-(2-fluorophenyl)-N- methyl amide
(S)-2-Bromopropionic acid(3.4 g, 0.022 mol) and 2-fluoroaniline(3 g, 0.024 mol) were dissolved in 50 ml of chloroform and cooled to 0°C . Dicyclohexylcarbodiimide(5 g, 0.024 mol) dissolved in 10 ml of chloroform was slowly injected through a syringe. The temperature of the reaction mixture was raised to room temperature and the reaction mixture was stirred for 1 hour. Solid remained during the reaction was filtered out and washed twice with 20 ml of chloroform. The filtrate was concentrated under reduced pressure and the crude product was purified by column chromatography (eluent; ethyl acetate/ -hexane=l/ 3) to afford 5 g of the target product.
Η-NMR(CDC13) : δl.7(3H, d), 3.24(3H, s), 4.16(0.7H, q), 4.34(0.3H, q), 7.13- 7.48(4H, m)
Example 2: Preparation of (R)-2-(4-hydroxyphenoxy)propionic acid-N-(2- fluorophenyl)-N-methyl amide
(S)-2-bromo-propionic acid-N-(2-fluorophenyl)-N-methyl amide (18.2 g, 0.07 mol), hydroquinone (7 g, 0.064 mol), potassium carbonate (10.54 g, 0.076 mol) and tetra-n-butylammonium bromide (1 g) were dissolved in 350 ml of acetonitrile and heated at reflux for 6 hours. The reaction mixture was cooled to room temperature and solid remained during the reaction was filtered out. The filtrate was concentrated under reduced pressure and the crude product was purified by column chromatography (eluent: ethyl acetate/ -hexane=l/ 2) to afford 16 g of the target product.
Η-NMR(CDC13) : δl.42(3H, t), 3.25(3H, s), 4.56(1H, q), 6.5-7.4(8H, m)
Example 3: Preparation of (R)-2-[4-(6-chloro-2-benzoxazolyloxy)- phenoxyjpropionic acid-N-(2-fluorophenyl)-N-methyl amide
(R)-2-(4-hydroxyphenoxy)propionic acid-N-(2-fluorophenyl)-N-methyl amide (11.5 g, 0.04 mol), 2,6-dichlorobenzoxazole (6.85 g, 0.036 mol), potassium carbonate (6 g, 0.043 mol) and tetra-n-butylammonium bromide (1 g) were dissolved in 300 ml of acetonitrile and heated at reflux for 7 hours. The reaction mixture was cooled to room temperature and solid remained during the reaction was filtered out. The filtrate was concentrated under reduced pressure and the crude product was purified by column chromatography (eluent: ethyl acetate/ n-hexane=l/ 3) to afford 12.5 g of the target product.
Η-NMR(CDC13) : δl.42(3H, t), 3.3(3H, s), 4.62(1H, m), 6.8-7.4(HH, m)
Example 4: Preparation of (R)-2-[4-(6-chloro-2-benzoxazolyloxy)- phenoxy]propionic acid-N-(2-fluorophenyl)-N-methyl amide
(R)-2-[4-(6-chloro-2-benzoxazoyloxy)-phenoxy]propionic acid (346.7 mg, 1 mmol) was dissolved in 10 ml of tetrahydrofuran. 2-Fluoroaniline(111.12 mg, 1 mmol), triphenylphosphine(393.4 mg, 1.5 mmol), triethylamine(0.15 ml, 1 mmol) and carbon tetrachloride(l ml) were added sequentially and heated at reflux for 8 hours. The reaction mixture was cooled to room temperature and acidified with 5% hydrochloric acid, followed by addition of water. The acidified reaction mixture was extracted three times with ethyl acetate. The combined organic layer was dried over magnesium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by column chromatography (eluent: ethyl acetate/ n-hexane=T/ 4) to afford 200 mg of the target product.
m.p : 132-136 °C Η-NMR(CDC13) : δl.7(3H, d), 4.81(1H, q), 7.05-7.45(10H, m), 8.35(1H, m), 8.5(1H, br)
Example 5: Preparation of (R)-2-[4-(6-chloro-2-benzoxazolyloxy)- phenoxyjpropionic acid-N-(2-fluorophenyl)-N-methyl Amide (R)-2-[4-(6-chloro-2-benzoxazoyloxy)-phenoxy]propionic acid-N-(2- fluorophenyl) amide (100 mg, 0.24 mmol) was dissolved in 10 ml of anhydrous tetrahydrofuran and 60% NaH(10 mg, 0.24 mmol) and CH3I(34 mg, 0.24 mmol) were added sequentially at 0°C . The reaction mixture was stirred at room temperature for 5 hours. Ice water was poured to the reaction mixture and it was extracted three times with ethyl acetate. The combined organic solvent layer was dried over magnesium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by column chromatography(eluent: ethyl acetate/ n-hexane=l/ 2) to afford 75 mg of the target product. Η-NMR(CDC13) : δl.42(3H, t), 3.3(3H, s), 4.62(1H, m), 6.8-7.4(HH, m)
Example 6: Preparation of (R)-2-[4-(6-chloro-2-benzoxazolyloxy)- phenoxyjpropionic acid-N-(2-fluorophenyl)-N-methyl amide
(R)-2-[4-(6-chloro-2-benzoxazoyloxy)-phenoxy]propionic acid(346.7 mg, 1 mmol) was dissolved in 10 ml of tetrahydrofuran and N-methyl-2- fluoroaniline(125 mg, 1 mmol), triphenylphosphine(393.4 mg, 1.5 mmol), triethylamine(0.15 ml, 1 mmol) and carbon tetrachloride(l ml) were added sequentially and the reaction was heated at reflux for 12 hours. The reaction mixture was cooled to room temperature and acidified with 5% hydrochloric acid, followed by addition of water. The acidified reaction mixture was extracted three times with ethyl acetate. The combined organic solvent layer was dried over magnesium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by column chromatography (eluent: ethyl acetate/ -hexane=l/ 2) to afford 100 mg of the target product.
Example 7: Preparation of (R)-2-[4-(6-chloro-2-benzoxazolyloxy- phenoxy)propionic acid-N-methyl-N-(2,4,5-trifluorophenyl)amide (R)-2-[4-(6-chloro-2-benzoxazoyloxy)-phenoxy]propionic acid (0.693 g, 2 mmol) was dissolved in 15 ml of tetrahydrofuran and N-methyl-2,4,5- trifluoroaniline(0.322 g, 2 mmol), triphenylphosphine(0.78g, 2 mmol), triethylamine(0.4 ml) and carbon tetrachloride(2 ml) were added sequentially and then the reaction mixture was heated at reflux for 18 hours. The reaction mixture was cooled to room temperature and acidified with 5% hydrochloric acid. The acidified reaction mixture was extracted three times with ethyl acetate. The combined organic solvent layer was dried over magnesium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by column chromatography (eluent: ethyl acetate/ -hexane=l/ 2) to afford 250 mg of the target product.
Η-NMR(CDC13) : δl.42(3H, d), 3.2(3H, s), 4.65(1H, m), 6.6-7.4(9H, m)
Example 8: Preparation of (R)-2-[4-(6-chloro-2-benzoxazolyloxy)- phenoxyjpropionic acid-N-methyl-N-(2,6-difluoro-phenyl)amide
(R)-2-[4-(6-chloro-2-benzoxazoyloxy)-phenoxy]propionic acid(0.693 g, 2 mmol) and N-methyl-2,6-difluoroaniline(0.284 g, 2 mmol) were dissolved in 20 ml of tetrahydrofuran and triphenylphosphine(0.78 g, 2 mmol), triethylamine(0.42 ml) and carbon tetrachloride(2 ml) were added sequentially. The reaction mixture was heated at reflux for 16 hours. The reaction mixture was cooled to room temperature and acidified with 5% hydrochloric acid. The acidified reaction mixture was extracted three times with ethyl acetate. The combined organic solvent layer was dried over magnesium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by column chromatography (eluent: ethyl acetate/ n-hexane=l/ 2) to afford 205 mg of the target product.
Η-NMR(CDC13) : δl.4(3H, d), 3.3(3H, s), 4.62(1H, q), 6.8-7.4(10H, m) Example 9: Preparation of (R)-2-[4-(6-chloro-2-benzoxazolyloxy)- phenoxyjpropionic acid-N-(2,4-difluorophenyl)-N-methyl amide
(R)-2-[4-(6-chloro-2-benzoxazoyloxy)-phenoxy]propionic acid(0.693 g, 2 mmol) was dissolved in 15 ml of tetrahydrofuran and N-methyl-2,4- difluoroaniline(0.284 g, 2 mmol), triphenylphosphine(0.78 g, 2 mmol), triethylamine(0.42 ml) and carbon tetrachloride(2 ml) were added sequentially. The reaction mixture was heated at reflux for 12 hours. The reaction mixture was cooled to room temperature and acidified with 5% hydrochloric acid, followed by addition of water. The acidified reaction mixture was extracted three times with ethyl acetate. The combined organic solvent layer was dried over magnesium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by column chromatography (eluent: ethyl acetate/ n- hexane=l/2) to afford 230 mg of the target product.
Η-NMR(CDC13) : δl.4(3H, d), 3.2(3H, s), 4.6(1H, q), 6.6-7.2(10H, m)
Example 10: Preparation of (R)-2-[4-(6-chloro-2-benzoxazolyloxy)- phenoxyjpropionic add-N-methyl-N-(2,3,6-trifluorophenyl)amide
(R)-2-[4-(6-chloro-2-benzoxazoyloxy)-phenoxy]ρropionic acid(0.693g, 2 mmol) was added to 6 ml of thionyl chloride and the reaction mixture was heated at reflux for 2 hours. Excess of thionyl chloride was removed under reduced pressure and 3 ml of anhydrous tetrahydrofuran was added to it. A solution of N-methyl-2,3,6-trifluoroaniline(0.32 g, 2 mmol) and triethyl amine(0.42 ml) in anhydrous tetrahydrofuran(10 ml) was added slowly to the reaction mixture at 0°C . The mixture was stirred at 0°C for 30 minutes and stirred at room temperature for additional 1 hour. After pouring water the reaction mixture was extracted three times with ethyl acetate. The combined organic solvent layer was dried over magnesium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by column chromatography (eluent: ethyl acetate/ n-hexane=l/ 2) to afford 240 mg of the target product.
'H-NMRCCDCb) : δl.45(3H, d), 3.25(3H, s), 4.6(1H, q), 6.7-7.4(9H, m)
Examples 11-16
The compounds represented in the following Table 2 were prepared by the same procedure of example 10 except using of aniline compounds instead of N-methyl-2,3,6-trifluoroaniline.
Table 2
Figure imgf000024_0001
Formulation
In order to use the compounds according to the present invention as herbicides, they should be formulated in such a suitable type such as wettable powder, emulsions, granules, dusts, suspensions and solutions by combining a carrier, a surfactant, a dispersing agent or a supplement agent. Many of these may be applied directly or after diluted with suitable media. Formulations can be prepared at spray volume of from hundreds liters to thousands liters per hectare. The formulations contain about 0.1% to 99% by weight of active ingredient(s) and 0.1% to 20% surfactant(s) or 0% to 99.9% solid or liquid diluent(s) are recommended to be added. The formulations will contain these ingredients in the following approximate proportions shown in Table 3. Table 3
Figure imgf000025_0001
The proportion of active ingredients depends on the intended use. Higher ratio of a surfactant is sometimes desired to active ingredients and is achieved by incorporation into the formulation or tank mixing.
Solid diluents with high absorption are preferred for wettable powder. Liquid diluents and solvents are preferred to be stable against phase separation at 0 °C . All the formulations may contain a small amount of additives to prevent forming, caking, corrosion and growth of microorganisms.
According to conventional methods to prepare the composition, solutions can be made only by blending ingredients and fine solids by blending and pulverizing with hammer-mill. Suspensions can be made by wet-milling and granules can be made by spraying the active ingredients on performed granular carrier.
Preparation examples of typical formulations are as follows. Formulation 1: Wettable Powder
The ingredients are thoroughly blended, re-blended after spraying liquid surfactant on the solid ingredients and hammer-milled until all the solids are essentially under 100 μm.
Active ingredient (Compound of Example 3) 20 wt. %
Dodecylphenol polyethylene glycol ether 2 wt. %
Sodium ligninsulf onate 4 wt. %
Sodium silicon aluminate 6 wt. %
Montmorillonite 68 wt.%
Formulation 2: Wettable Powder
The ingredients are blended, hammer-milled until all the solids are under 25 μm and packaged.
Active ingredient (Compound of Example 3) 80 wt. % Sodium alkyl naphthalenesulf onate 2 wt.%
Sodium ligninsulf onate 2 wt. %
Synthetic amorphous silica 3 wt. %
Kaolinite 13 wt.%
Formulation 3: Emulsion
The ingredients are mixed and homogeneously dissolved to give emulsions.
Active ingredient (Compound of Example 3) 30 wt. % Cyclohexanone 20 wt. % Polyoxyethylene alkylaryl ether 11 wt.%
Calcium alkylbenzenesulf onate 4 wt. %
Methylnaphthalene 35 wt.%
Formulation 4: Granule
The ingredients were thoroughly blended. 20 parts by weight of water was added to 100 parts of weight the ingredient mixture. The ingredient mixture was granulated with a size of 14 to 32 mesh by using extrusive granulator and dried. Active ingredient (Compound of Example 3) 5 wt.%
Sodium laurylalcoholsulf onate 2 wt. %
Sodium ligninsulf onate 5 wt. %
Carboxymethyl cellulose 2 wt. %
Potassium sulfate 16 wt. % Plaster 70 wt.%
The formulations according to this invention were sprayed with diluting to a certain concentration.
Utility
The compounds according to the present invention represent high activity as leaf treatment herbicides for rice and especially effective in rice due to an excellent control of barnyard grass. The active ingredients can be used from 10 g to 4 kg per hectare, preferably from 50 g to 400 g. The amount of the compounds of the present invention depends on the amount and size of weeds and formulations. The herbicides of the present invention can be used as alone or in combination with other herbicides, insecticides or bactericides. Especially it is essential to add one agent selected from the group consisting of bentazon, quinclorac, propanil, simetryn, 2,4-D, fenoxaprop-ethyl, linuron, MCPA, azafenidin, carfentrazone, molinate, thiobencarb, pendimethalin, bensulfuron-methyl, pyrazosulfuron- ethyl, metsulfuron-methyl, thifensulfuron-methyl, tribenuron-methyl, trifluralin, amidosulfuron, bromoxynil, butachlor, mecoprop, metribuzin, bifenox, benfuresate, isoproturon, cyhalofop-butyl, mefenaset, fentrazamide, pyriminobac-methyl, bispyribac sodium, azimsulfruon, cyclosulfamuron, pyanchor, and mixtures thereof.
The herbicidal effect of the compounds of this invention was tested and the examples are as follows.
Experimental Example 1: Leaf Treatment Test
Seeds of rice, wheat, barley, corn, cotton, barnyard grass, common sorgum, large crabgrass and fall panicum were seeded at a pot with a surface area of 600 cm2. When barnyard grass grown in a green house kept at 20 - 30 °C had three leaves, wettable powder prepared by mixing 1 part by weight of the active compound, 5 parts by weight of acetone and 1 part by weight of emulsifier and diluted with water was applied directly to the leaves in 2000 L per hectare. The concentration of the spray liquid was so chosen the particular amounts of the active compound desired. 14 days after the treatment, the degree of damage to the plants was rated in % damage in comparison to the development of untreated control.
0% no effect (same as untreated control)
20% slight effect
70% herbicidal effect
100% total destruction
In the test, the active compound(s) of formula (1) according to the invention exhibited an excellent selectivity toward the plants and herbicidal activity against weeds.
Table 4
Figure imgf000029_0001
Among the compounds of formula (1), herbicidal activity of (R)-2-[4- chlor o-2-benzoxazoyloxy] -phenoxy ] propionic acid-N-(2-f luroropheny 1)-N- methyl amide (Example 3) was compared to the (S)-stereoisomer and racemic mixture thereof and the result is summarized in table 5. Table 5
Figure imgf000030_0002
(R)-Compound
Figure imgf000030_0001
R,S-Racemic compound
Figure imgf000031_0001
(S)-Compound
Figure imgf000031_0002
[Industrial Applicability]
As described above, it is noted that optically active (R)-stereoisomers of the present invention exhibit excellent selectivity toward rice and superior herbicidal activity against barnyard grass to racemic mixtures and (S)- stereoisomers thereof. Therefore, the optically active compounds of the present invention may be very effective in rice farming. Further, it is proved that the optically active compounds are very stable for wheat, barley, beans, and corn and useful to control weeds.

Claims

[CLAIMS]What is claimed is:
1. A herbicidal compound, (R)-phenoxypropionic acid-N-methyl-N-2- fluorophenyl amide of formula (1), having stability toward rice and preventing the generation of barnyard grass:
Figure imgf000032_0001
wherein X is hydrogen, halogen, hydroxy, NH2, CO2H, C1-C0 alkylamino substituted with 1 or 2 of C1-C3 alkyl, Cι-C6 alkyl, Ci-Cό alkoxy, 0-C3 haloalkyl, C1-C3 haloalkoxy, C2-Q alkoxyalkoxy, Ci-Q alkylthonyl, Cι-C alkylsulfonyl, C2-C6 alkenyl, C2-Cό alkinyl, C2-C6 alkenyloxy, C2-C6 alkinyloxy, C1-C3 alkoxycarbonyl, or C1-C3 alkylcarbonyl; Y is hydrogen or fluoro; and n is an integer of 0 to 2, wherein X can be a combination of other substituents when n is 2.
2. The herbicidal compound according to claim 1, wherein said X is H, F, CI, Br, CN, CH3, or OCH3; Y is H or F; and n=l.
3. The herbicidal compound according to claim 1, wherein said X is H; and Y is H.
4. The herbicidal compound according to claim 1, wherein said X is 5-CH3; and Y is H.
5. The herbicidal compound according to claim 1, wherein said X is 4,5-F2; and Y is H.
6. A method of controlling barnyard grass produced while growing rice without inflicting any substantial harm to said rice which comprises applying an effective amount of at least one compound of formula (1):
Figure imgf000033_0001
wherein X is hydrogen, halogen, hydroxy, NH2, C02H, O-Cs alkylamino substituted with 1 or 2 of G-C3 alkyl, Ci-Cό alkyl, Ci-Cό alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, C2-Q alkoxyalkoxy, C1-C4 alkylthonyl, Ci-C4 alkylsulfonyl, C2-C6 alkenyl, C2-C0 alkinyl, C2-C6 alkenyloxy, C2-Cό alkinyloxy, C1-C3 alkoxycarbonyl, or C1-C3 alkylcarbonyl; Y is hydrogen or fluoro; and n is an integer of 0 to 2, wherein X can be a combination of other substituents when n is 2.
7. A herbicidal composition comprising at least one compound of formula (1) together with at least one member selected from the group consisting of: an agriculturally acceptable carrier, a supplement agent, a surfactant and at least one other herbicidal compound:
Figure imgf000034_0001
wherein X is hydrogen, halogen, hydroxy, NH2, CO2H, Ci-Cό alkylamino substituted with 1 or 2 of Cι-C3 alkyl, Ci-Cό alkyl, Ci-Cό alkoxy, C1-C3 haloalkyl, Ci-C3 haloalkoxy, C2-C4 alkoxyalkoxy, C1-C4 alkylthonyl, Cι-C alkylsulfonyl, C2-C6 alkenyl, C2-Cό alkinyl, C2-C6 alkenyloxy, C2-Cό alkinyloxy, Cι-C3 alkoxycarbonyl, or C1-C3 alkylcarbonyl; Y is hydrogen or fluoro; and n is an integer of 0 to 2, wherein X can be a combination of other substituents when n is 2.
PCT/KR2001/001845 2001-11-01 2001-11-01 Optically active herbicidal (r)-phenoxypropionic acid-n-methyl-n-2-fluorophenyl amides WO2003037085A1 (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
HU0402057A HU230485B1 (en) 2001-11-01 2001-11-01 Optically active herbicidal (r)-phenoxypropionic acid-n-methyl-n-2-fluorophenyl amide
JP2003539442A JP2005507402A (en) 2001-11-01 2001-11-01 Photoactive (R) -phenoxypropionic acid-N-methyl-N-2-fluorophenylamide compound having herbicidal activity
AU2002212806A AU2002212806B2 (en) 2001-11-01 2001-11-01 Optically active herbicidal (R)-phenoxypropionic acid-N-methyl-N-2-fluorophenyl amides
PCT/KR2001/001845 WO2003037085A1 (en) 2001-11-01 2001-11-01 Optically active herbicidal (r)-phenoxypropionic acid-n-methyl-n-2-fluorophenyl amides
CN01823753.3A CN1279031C (en) 2001-11-01 2001-11-01 Optically active herbicidal (R)-phenoxypropionic acid-N-methyl-N-2-fluorophenyl amides
BRPI0117166-6A BRPI0117166B1 (en) 2001-11-01 2001-11-01 Herbicidal composition to prevent the generation of barnyard grass and method to control the generation of barnyard grass produced
CA002465342A CA2465342C (en) 2001-11-01 2001-11-01 Optically active herbicidal (r)-phenoxypropionic acid-n-methyl-n-2-fluorophenyl amides
EP01981146A EP1448058A4 (en) 2001-11-01 2001-11-01 Optically active herbicidal (r)-phenoxypropionic acid-n-methyl-n-2-fluorophenyl amides
US10/494,084 US20050043180A1 (en) 2001-11-01 2001-11-01 Optically active herbicidal (r)-phenoxypropionic acid-n-methyl-n-2-fluorophenyl amides
BG108697A BG66413B1 (en) 2001-11-01 2004-04-26 Optically active herbicidal (r)-phenoxypropionic acid-n-methyl-n-2-fluorophenyl amides

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/KR2001/001845 WO2003037085A1 (en) 2001-11-01 2001-11-01 Optically active herbicidal (r)-phenoxypropionic acid-n-methyl-n-2-fluorophenyl amides

Publications (1)

Publication Number Publication Date
WO2003037085A1 true WO2003037085A1 (en) 2003-05-08

Family

ID=19198468

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2001/001845 WO2003037085A1 (en) 2001-11-01 2001-11-01 Optically active herbicidal (r)-phenoxypropionic acid-n-methyl-n-2-fluorophenyl amides

Country Status (10)

Country Link
US (1) US20050043180A1 (en)
EP (1) EP1448058A4 (en)
JP (1) JP2005507402A (en)
CN (1) CN1279031C (en)
AU (1) AU2002212806B2 (en)
BG (1) BG66413B1 (en)
BR (1) BRPI0117166B1 (en)
CA (1) CA2465342C (en)
HU (1) HU230485B1 (en)
WO (1) WO2003037085A1 (en)

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009005297A3 (en) * 2007-07-03 2009-03-12 Kyung Nong Corp Optically active (r)-aryloxypropionic acid amides and herbicidal composition comprising same
WO2013040021A1 (en) 2011-09-13 2013-03-21 Monsanto Technology Llc Methods and compositions for weed control
WO2013040117A1 (en) 2011-09-13 2013-03-21 Monsanto Technology Llc Methods and compositions for weed control
WO2014151255A1 (en) 2013-03-15 2014-09-25 Monsanto Technology Llc Methods and compositions for weed control
WO2015108982A2 (en) 2014-01-15 2015-07-23 Monsanto Technology Llc Methods and compositions for weed control using epsps polynucleotides
US9121022B2 (en) 2010-03-08 2015-09-01 Monsanto Technology Llc Method for controlling herbicide-resistant plants
US9416363B2 (en) 2011-09-13 2016-08-16 Monsanto Technology Llc Methods and compositions for weed control
US9422558B2 (en) 2011-09-13 2016-08-23 Monsanto Technology Llc Methods and compositions for weed control
US9422557B2 (en) 2011-09-13 2016-08-23 Monsanto Technology Llc Methods and compositions for weed control
US9540642B2 (en) 2013-11-04 2017-01-10 The United States Of America, As Represented By The Secretary Of Agriculture Compositions and methods for controlling arthropod parasite and pest infestations
US9777288B2 (en) 2013-07-19 2017-10-03 Monsanto Technology Llc Compositions and methods for controlling leptinotarsa
US9850496B2 (en) 2013-07-19 2017-12-26 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
US10041068B2 (en) 2013-01-01 2018-08-07 A. B. Seeds Ltd. Isolated dsRNA molecules and methods of using same for silencing target molecules of interest
US10240161B2 (en) 2012-05-24 2019-03-26 A.B. Seeds Ltd. Compositions and methods for silencing gene expression
US10378012B2 (en) 2014-07-29 2019-08-13 Monsanto Technology Llc Compositions and methods for controlling insect pests
US10557138B2 (en) 2013-12-10 2020-02-11 Beeologics, Inc. Compositions and methods for virus control in Varroa mite and bees
US10609930B2 (en) 2013-03-13 2020-04-07 Monsanto Technology Llc Methods and compositions for weed control
US10612019B2 (en) 2013-03-13 2020-04-07 Monsanto Technology Llc Methods and compositions for weed control
US10655136B2 (en) 2015-06-03 2020-05-19 Monsanto Technology Llc Methods and compositions for introducing nucleic acids into plants
US10683505B2 (en) 2013-01-01 2020-06-16 Monsanto Technology Llc Methods of introducing dsRNA to plant seeds for modulating gene expression
US10760086B2 (en) 2011-09-13 2020-09-01 Monsanto Technology Llc Methods and compositions for weed control
US10801028B2 (en) 2009-10-14 2020-10-13 Beeologics Inc. Compositions for controlling Varroa mites in bees
US10808249B2 (en) 2011-09-13 2020-10-20 Monsanto Technology Llc Methods and compositions for weed control
US10806146B2 (en) 2011-09-13 2020-10-20 Monsanto Technology Llc Methods and compositions for weed control
US10829828B2 (en) 2011-09-13 2020-11-10 Monsanto Technology Llc Methods and compositions for weed control
US10883103B2 (en) 2015-06-02 2021-01-05 Monsanto Technology Llc Compositions and methods for delivery of a polynucleotide into a plant
US10888579B2 (en) 2007-11-07 2021-01-12 Beeologics Inc. Compositions for conferring tolerance to viral disease in social insects, and the use thereof
US10968449B2 (en) 2015-01-22 2021-04-06 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
US10988764B2 (en) 2014-06-23 2021-04-27 Monsanto Technology Llc Compositions and methods for regulating gene expression via RNA interference
US11091770B2 (en) 2014-04-01 2021-08-17 Monsanto Technology Llc Compositions and methods for controlling insect pests
US11807857B2 (en) 2014-06-25 2023-11-07 Monsanto Technology Llc Methods and compositions for delivering nucleic acids to plant cells and regulating gene expression

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101822262A (en) * 2010-05-18 2010-09-08 东莞市瑞德丰生物科技有限公司 Weeding composition
CN105820134A (en) * 2016-03-24 2016-08-03 山东海诺格生物科技有限公司 Compound with herbicidal activity and preparation method and application thereof
CN110863020B (en) * 2019-12-19 2022-12-23 湖南速博生物技术有限公司 Method for synthesizing metamifop by enzyme method
CN112314610A (en) * 2020-10-28 2021-02-05 安徽润农腾辉生物科技有限公司 Weeding composition containing metamifop, halosulfuron-methyl and butachlor
CN113068703A (en) * 2021-04-09 2021-07-06 安徽海日农业发展有限公司 Compound herbicide for rice based on metamifop and butachlor
CN113717123B (en) * 2021-09-10 2023-10-10 内蒙古蓝科生物科技有限公司 Preparation method of metamifop

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5833742A (en) * 1996-10-11 1998-11-10 Rohm And Haas Company Phenylamides as marine antifouling agents
WO2000005956A1 (en) * 1998-07-25 2000-02-10 Dongbu Hannong Chemical Co., Ltd. Herbicidal phenoxypropionic acid n-alkyl-n-2-fluorophenyl amide compounds

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5254527A (en) * 1977-12-24 1993-10-19 Hoechst Aktiengesellschaft Optically active herbicidal ethyl-2-(4-(6-chloro-benzoxazol-2-yloxy)-phenoxy)-propionate
JPH0211580A (en) * 1988-06-30 1990-01-16 Kumiai Chem Ind Co Ltd Phenoxypropionic acid amide derivative and herbicide
US6600048B2 (en) * 1998-07-25 2003-07-29 Dongbu Hannong Chemical Co., Ltd. Herbicidal phenoxypropionic acid N-alkyl-N-2-fluorophenyl amide compounds
ES2211573T3 (en) * 1999-08-03 2004-07-16 Dongbu Hannong Chemical Co., Ltd. ALCOXICARBONIL ANILIDE COMPOUNDS OF HIGHLY SELECTIVE PHENOXIPROPIONIC ACID AND METHOD FOR PREPARATION.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5833742A (en) * 1996-10-11 1998-11-10 Rohm And Haas Company Phenylamides as marine antifouling agents
WO2000005956A1 (en) * 1998-07-25 2000-02-10 Dongbu Hannong Chemical Co., Ltd. Herbicidal phenoxypropionic acid n-alkyl-n-2-fluorophenyl amide compounds

Cited By (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2183213A4 (en) * 2007-07-03 2013-08-07 Kyung Nong Corp Optically active (r)-aryloxypropionic acid amides and herbicidal composition comprising same
EP2183213A2 (en) * 2007-07-03 2010-05-12 Kyung Nong Corporation Optically active (r)-aryloxypropionic acid amides and herbicidal composition comprising same
US8293774B2 (en) 2007-07-03 2012-10-23 Kyung Nong Corporation Optically active (R)-aryloxypropionic acid amides and herbicidal composition comprising same
WO2009005297A3 (en) * 2007-07-03 2009-03-12 Kyung Nong Corp Optically active (r)-aryloxypropionic acid amides and herbicidal composition comprising same
US10888579B2 (en) 2007-11-07 2021-01-12 Beeologics Inc. Compositions for conferring tolerance to viral disease in social insects, and the use thereof
US10801028B2 (en) 2009-10-14 2020-10-13 Beeologics Inc. Compositions for controlling Varroa mites in bees
US11812738B2 (en) 2010-03-08 2023-11-14 Monsanto Technology Llc Polynucleotide molecules for gene regulation in plants
US9988634B2 (en) 2010-03-08 2018-06-05 Monsanto Technology Llc Polynucleotide molecules for gene regulation in plants
US9121022B2 (en) 2010-03-08 2015-09-01 Monsanto Technology Llc Method for controlling herbicide-resistant plants
US10808249B2 (en) 2011-09-13 2020-10-20 Monsanto Technology Llc Methods and compositions for weed control
US9422558B2 (en) 2011-09-13 2016-08-23 Monsanto Technology Llc Methods and compositions for weed control
US9422557B2 (en) 2011-09-13 2016-08-23 Monsanto Technology Llc Methods and compositions for weed control
US10829828B2 (en) 2011-09-13 2020-11-10 Monsanto Technology Llc Methods and compositions for weed control
US10806146B2 (en) 2011-09-13 2020-10-20 Monsanto Technology Llc Methods and compositions for weed control
US9416363B2 (en) 2011-09-13 2016-08-16 Monsanto Technology Llc Methods and compositions for weed control
EP3434779A1 (en) 2011-09-13 2019-01-30 Monsanto Technology LLC Methods and compositions for weed control
EP3296402A2 (en) 2011-09-13 2018-03-21 Monsanto Technology LLC Methods and compositions for weed control
WO2013040117A1 (en) 2011-09-13 2013-03-21 Monsanto Technology Llc Methods and compositions for weed control
US10760086B2 (en) 2011-09-13 2020-09-01 Monsanto Technology Llc Methods and compositions for weed control
EP3382027A2 (en) 2011-09-13 2018-10-03 Monsanto Technology LLC Methods and compositions for weed control
WO2013040021A1 (en) 2011-09-13 2013-03-21 Monsanto Technology Llc Methods and compositions for weed control
EP3434780A1 (en) 2011-09-13 2019-01-30 Monsanto Technology LLC Methods and compositions for weed control
US10240162B2 (en) 2012-05-24 2019-03-26 A.B. Seeds Ltd. Compositions and methods for silencing gene expression
US10934555B2 (en) 2012-05-24 2021-03-02 Monsanto Technology Llc Compositions and methods for silencing gene expression
US10240161B2 (en) 2012-05-24 2019-03-26 A.B. Seeds Ltd. Compositions and methods for silencing gene expression
US10041068B2 (en) 2013-01-01 2018-08-07 A. B. Seeds Ltd. Isolated dsRNA molecules and methods of using same for silencing target molecules of interest
US10683505B2 (en) 2013-01-01 2020-06-16 Monsanto Technology Llc Methods of introducing dsRNA to plant seeds for modulating gene expression
US10612019B2 (en) 2013-03-13 2020-04-07 Monsanto Technology Llc Methods and compositions for weed control
US10609930B2 (en) 2013-03-13 2020-04-07 Monsanto Technology Llc Methods and compositions for weed control
WO2014151255A1 (en) 2013-03-15 2014-09-25 Monsanto Technology Llc Methods and compositions for weed control
US10568328B2 (en) 2013-03-15 2020-02-25 Monsanto Technology Llc Methods and compositions for weed control
US9856495B2 (en) 2013-07-19 2018-01-02 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
US10597676B2 (en) 2013-07-19 2020-03-24 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
US9850496B2 (en) 2013-07-19 2017-12-26 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
US9777288B2 (en) 2013-07-19 2017-10-03 Monsanto Technology Llc Compositions and methods for controlling leptinotarsa
US11377667B2 (en) 2013-07-19 2022-07-05 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
US10927374B2 (en) 2013-11-04 2021-02-23 Monsanto Technology Llc Compositions and methods for controlling arthropod parasite and pest infestations
US10100306B2 (en) 2013-11-04 2018-10-16 Monsanto Technology Llc Compositions and methods for controlling arthropod parasite and pest infestations
US9540642B2 (en) 2013-11-04 2017-01-10 The United States Of America, As Represented By The Secretary Of Agriculture Compositions and methods for controlling arthropod parasite and pest infestations
US10557138B2 (en) 2013-12-10 2020-02-11 Beeologics, Inc. Compositions and methods for virus control in Varroa mite and bees
WO2015108982A2 (en) 2014-01-15 2015-07-23 Monsanto Technology Llc Methods and compositions for weed control using epsps polynucleotides
US10334848B2 (en) 2014-01-15 2019-07-02 Monsanto Technology Llc Methods and compositions for weed control using EPSPS polynucleotides
US11091770B2 (en) 2014-04-01 2021-08-17 Monsanto Technology Llc Compositions and methods for controlling insect pests
US10988764B2 (en) 2014-06-23 2021-04-27 Monsanto Technology Llc Compositions and methods for regulating gene expression via RNA interference
US11807857B2 (en) 2014-06-25 2023-11-07 Monsanto Technology Llc Methods and compositions for delivering nucleic acids to plant cells and regulating gene expression
US11124792B2 (en) 2014-07-29 2021-09-21 Monsanto Technology Llc Compositions and methods for controlling insect pests
US10378012B2 (en) 2014-07-29 2019-08-13 Monsanto Technology Llc Compositions and methods for controlling insect pests
US10968449B2 (en) 2015-01-22 2021-04-06 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
US10883103B2 (en) 2015-06-02 2021-01-05 Monsanto Technology Llc Compositions and methods for delivery of a polynucleotide into a plant
US10655136B2 (en) 2015-06-03 2020-05-19 Monsanto Technology Llc Methods and compositions for introducing nucleic acids into plants

Also Published As

Publication number Publication date
CA2465342C (en) 2009-09-08
US20050043180A1 (en) 2005-02-24
BG108697A (en) 2005-03-31
HU230485B1 (en) 2016-08-29
EP1448058A1 (en) 2004-08-25
HUP0402057A3 (en) 2005-10-28
AU2002212806B2 (en) 2006-06-08
BG66413B1 (en) 2014-02-28
JP2005507402A (en) 2005-03-17
CN1558717A (en) 2004-12-29
BRPI0117166B1 (en) 2015-04-22
CA2465342A1 (en) 2003-05-08
HUP0402057A2 (en) 2005-01-28
BR0117166A (en) 2004-10-26
EP1448058A4 (en) 2005-01-26
CN1279031C (en) 2006-10-11

Similar Documents

Publication Publication Date Title
CA2465342C (en) Optically active herbicidal (r)-phenoxypropionic acid-n-methyl-n-2-fluorophenyl amides
AU2002212806A1 (en) Optically active herbicidal (R)-phenoxypropionic acid-N-methyl-N-2-fluorophenyl amides
EP1100332B1 (en) Herbicidal phenoxypropionic acid n-alkyl-n-2-fluorophenyl amide compounds
US6600048B2 (en) Herbicidal phenoxypropionic acid N-alkyl-N-2-fluorophenyl amide compounds
US6489268B1 (en) Highly selective herbicidal phenoxypropionic acid alkoxycarbonyl anilid compounds and method of preparing the same
KR100419853B1 (en) Optically active herbicidal (R)-phenoxypropionic acid-N-methyl-N-2-fluorophenyl amides
RU2264392C2 (en) Optically active herbicide (r)-phenoxypropionic acid n-methyl-n-2-fluorophenylamide, method for control of barnyard- grass and herbicide composition
KR100419856B1 (en) Herbicidal phenoxypropion amides
KR100545784B1 (en) 3,4,5,6-Terahydrophthalimides having herbicidal activity
KR20010106604A (en) Herbicidal haloxyfop amides
CN113912537A (en) 2- (quinoline-8-yl) carbonyl-cyclohexane-1, 3-diketone compound and preparation method and application thereof
PL205136B1 (en) Optically active herbicidal (r)-phenoxypropionic acid-n-methyl-n-2-fluorophenyl amides
JPH02264767A (en) N-(2-methylphenyl)-2-(4-(6-chlorobenzothiazolyl-2-oxy) phenoxy)propanamide and herbicide containing the compound as active component
JPH1179914A (en) Herbicidal composition containing aniline derivative

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PH PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 1-2004-500565

Country of ref document: PH

ENP Entry into the national phase

Ref document number: 10869701

Country of ref document: BG

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 108697

Country of ref document: BG

WWE Wipo information: entry into national phase

Ref document number: 2465342

Country of ref document: CA

Ref document number: 20018237533

Country of ref document: CN

Ref document number: 2002212806

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 01173/DELNP/2004

Country of ref document: IN

Ref document number: 1173/DELNP/2004

Country of ref document: IN

Ref document number: 2003539442

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 2001981146

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 1200400548

Country of ref document: VN

WWP Wipo information: published in national office

Ref document number: 2001981146

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 10494084

Country of ref document: US