• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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  • 优先权
    • 专利摘要:
    Compounds, such as 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime-O-(acetic acid, methyl ester) and 5-(2-chloro-4-trifluoromethylphenoxy)-2-chloroacetophenone oxime-O-(acetic acid, methyl ester), are useful for postemergence and preemergence control of weeds, and are represented by Formula I of the application.
    公开号:SU1005656A3
    申请号:SU802924049
    申请日:1980-05-08
    公开日:1983-03-15
    发明作者:Кейт Красс Деннис
    申请人:Ппг Индастриз,Инк (Фирма)；
    IPC主号:
    专利说明:

    (5) METHOD FOR OBTAINING DERIVATIVES OF OXYMES The aim of the invention is to develop, on the basis of a known method, a method for producing new compounds with herbicidal activity. This goal is achieved by the fact that according to the method of producing derivatives of oximes, the corresponding oxime of the formula. where the values of Z, X, R - are indicated, you interact with the corresponding {.halogen-substituted carboxylate compound of the formula: β | -CH (K) -CO-OR where the radical values are indicated above. The α is a halogen, and optionally the resulting compound of the formula, in which R - an alkyl group, by hydrolysis is converted into the corresponding compound, in which the hydrogen atom. Try on Synthesis of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitroaceto-phenonoxime-0- (acetic acid, methyl ester). a) Preparation of 3 (2-chloro trifluoromethylphenoxy) acetophenone. In a 250 ml flask containing a solution of 13.92 g of potassium salt 3 of hydroxyacetophenone in 30 ml of dry dimethyl sulfoxide (DMSO), 17.12 g (0.08 mol): 3, -DICHLORbenzotrifluoride are added. The reaction solution is heated for 6 hours, then cooled and stirred for 18 hours at room temperature. The DMSO was removed in vacuo and the remaining dark residue was stirred for 15 minutes with diethyl ether and filtered. Fil waste is extracted once with water, once with 1N. with a solution of sodium hydroxide, once with a saturated solution of sodium chloride, dried over anhydrous magnesium sulphate, filtered, decolorized with activated charcoal and evaporated to dryness. 16 g of a dark red oil are obtained which are 3- (2-chloro-trifluoromethylphenoxy) -acetophenone. The product is further purified on a column filled with neutral alumina III of the degree of activity. b) Nitration of 3- (2-chloro-trifluor methylphenoxy) acetophenone. In a flask with a capacity of 100 ml, containing a solution of 2b ml of concentrated sulfuric acid (H-SO) and 16 ml of ethylene dichloride (EDC), cooled to, was added dropwise 6.28 g (0.02 mol) of 3- (2-chloro). - trifluoromethylphenoxy) acetophenone. The result is a brown-black solution. After completing the addition of 3 (2-chloro- | -trifluoromethylphenoxy) acetophenone to the reaction mixture, 2.0 g (0.020 mol) of dry potassium nitrate (KNO) are added in small portions over 20 minutes so that the temperature of the reaction mixture is lower. After that the reaction mixture is stirred for 0.5 h at. Then the contents of the flask are poured into 250 ml of ice-water and the mixture is mixed with 200 ml of chloroform. The organic layer is separated, extracted twice with water, once with a saturated solution of sodium chloride, dried over anhydrous magnesium sulfate and then filtered. After removing the solvent, 6.51 g of an orange oil is obtained, which, as the analysis shows, is a mixture of two isomers, having substituents in different positions, one of which is 5 (2-chloro-trifluoromethylphenoxy) 2-nitroacetophenone. The mixture was divided into two fractions by high pressure liquid chromatography, using diethyl ether as eluent. After diethyl ether was removed from fraction 1, 2.37 g of an orange oil was obtained, which is 5- (2-chloro-4-trifluoromethylphenoxy-5-nitroacetophenone, having the following characteristics, (H11R) -surgery of deuterated chloroform (COCFj), contains chemical shifts in ppm, fractions (mod.): 2.47 m, dyyyyy (singlet signal, 3N); 6,73- 8.21 cG (multiplet signal, 6H). IR spectrum: 1710, 1575, 1520,, 1315 cmH Mass spectrum: molecular th ion at t / e 359o c) Synthesis of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitroacetophenone oxime. A solution of 2.0 g (0.0056 mol) of orange oil 5- (2- chlorine - "- trifluoromethylphenoxy) -2-nitroacetophenone in 10 ml
    absolute ethanol and 10 ml of dry. benzene. A solution of 0.77 g (0.011 mol) of hydroxylamine hydrochloride in 15 ml of absolute ethanol is then added, followed by the addition of 1.12 g (0.011 mol) of an acid acceptor (triethylamine). The reaction mixture was then boiled. After 20 ml of the solvent was distilled off, another 15 ml of benzene was added to the reaction mixture. Boiling is continued until 15 ml of the solvent is distilled off, then the remaining solution is boiled without distilling off the solvent for 1 bh, and a mixture of syn and anti-isomers of 5- (2-chloro-trifluoromethylphenoxy) -2-nitroa. Acetophenone oxime is formed . Thereafter, the solvent was removed from the reaction mixture, and the residue was dissolved in chloroform. The chloroform solution is extracted twice with water, then with a saturated solution of sodium chloride and dried over anhydrous magnesium sulfate. The chloroform solution is filtered and the solvent (chloroform) is evaporated, yielding 2.03 g of an orange oil, which is 5- (2-chloro-trifluoromethylphenoxy) -2-nitroacetophenone oxime (anti- and synisomers), having the following characteristics.
    Mass spectra molecular ion at ffl / e 37.
    NMR spectrum taken in deuterated chloroform (CDCl): 2.13 MOD, (singlet, 3N), 6.91-B, ppm (multiplet, 6H), 9.33 ppm (singlet, 1H) (syn- and anti-isomers).
    IR spectrum of syn and anti-isomers: 3100 (wide signal), i 1605, 1575, 1520, cm-1
    Go. Preparation of syn- and anti-isomers of 5- (2-chloro-trifluoromethylphenoxy) -2 nitroacetophenone oxime-0- (acetic acid, methyl ester),
    In a 25 ml flask, in which a stream of nitrogen is passed, a solution of 0.10 g (0 mol) of metallic sodium is placed in 5 ml of methanol. After all the sodium has reacted, 1.50 g (0.00 mol) prepared as described above, 5- (2-chloro-trifluoromethylphenoxy) -2-nitroacetophenone oxime (mixture of anti-synisomers) dissolved in 5 ml of methanol, and the solution is stirred. 0.68 g (0, mol) methyl bromoacetate was added to the solution obtained and the reaction mixture was stirred at room temperature for 18 hours, skipping nitrogen flow, then the mixture was boiled for 2 hours. The solvent was then removed and the residue was dissolved in chloroform (CHCf) The chloroform solution is extracted twice with water, once with a saturated solution of sodium chloride and dried over anhydrous magnesium sulphate. The solution is filtered, the solvent is evaporated, the result is 1.68 g of orange oil, which is a mixture of isomers 5 (2-chloro-trifluoromethylphenoxy) -2-nitroacetophenone-oxime-0- (acetic acid, methyl ester). The orange oil is purified by chromatography), by dissolving it in 3 ml of ethyl ether and applying this solution to the top of a 7 inch long column (approximately 16.8 cm) and a diameter of 21 mm filled with alumina III degree of activity, as eluent use diethyl ether and collect the desired fractions. The solvent is removed to give Q, 72 g of a yellow oil, which is a mixture of anti- and synisomers 5 (2-chloro-trifluoromethylphenoxy) -2-nitroacetophenone oxime-0- (acetic acid, methyl ester), having the following characteristics.
    Mass spectrum: molecular ion at m / e,
    IR spectrum of syn-anti-isomers: 17: 1605, 1575, 1520, 1320 cM-t
    NMR spectrum of syn- and anti-isomers, taken in deuterated i: chloroform (CDCE): 2.23 ppm (singlet, ZN), 3.67 m. Do ({and 3.72 m, d, (f (singlet, ZN), k, kl and, 67 sG (singlet, -2H), 6.78-8, 25 ppm, (G (multiplet, 6H).
    When the yellow oil is dissolved in ethanol (methanol), pale yellow crystals are obtained with a mp. 89-92 S.
    Example 2. Synthesis of anti- and sinisomers of 5- (2-chloro-β-trifluoromethylphenoxy) -2-nitroacetophenone oxime-O- (acetic acid, ethyl ester).
    A solution of 0, Hg (0.0060 mol) of metallic, tallic sodium in B ml of methanol is charged into a 50 ml flask, while passing a stream of nitrogen. After all of the sodium has reacted, 2.0 g (0.0053 mol of orange oil of a mixture of anti- and synisomers of 5- (2-chloro-trifluoromethyl71 phenoxy) -2nitroacetophenioxime (Gc-arsenic, as described in Example 1c and solution stirring. 1.0b g (0.0059 mol of ethyl 2-romompropionate is added to the reaction mixture and the resulting mixture is stirred at room temperature for 51 hours, the nitrogen flow is passed. The solvent is removed from the solution, the remaining oil is stirred in diethyl ether, filtered and washed thoroughly with diethyl ether. Phil the waste is washed twice with water, once with a saturated solution of sodium chloride and dried over anhydrous magnesium sulfate. After that, the ether solution is filtered, the solvent is removed by evaporation. 2.23 g of orange oil, which is a mixture of anti- and synisomers (- 2-chloro-trifrprmethyl phenoxy) -2-nitro-L-acetophenone oxime-0- (acetic acid, ethyl ether) Orange oil is purified by chromatography by dissolving it in diethyl ether and applying it on an 8-inch (19 $ 2 cm) column top and a diameter of 21 mm zap Dilute neutral alumina of the III degree of activity. Diethyl ether is used as the eluent, and the first component leaving the column is the desired product. The solvent is removed to obtain 1.13 g of a yellow oil, which is a mixture of anti- and synisomers 5- (2-chloro-4-trifluoromethylphenoxy) 2- nitroacetophenone oxime-0- (acetic acid, ethyl ester). PRI me R 3. Synthesis of 5 (2-chloro-trifluoromethylphenyl) -2-chlorobenzaldoxime-0- (acetic acid, melt tilrvogo ether). a) Preparation of 3 (2-chloro-4-trifluoromethylphenoxy) -benzeldehyde dimethyl acetal; To a solution of 80.7 g (0.39 mol) of the potassium salt of dimethyl acetal 3 hydroxybenzaldehyde, 170 ml of dry dimethyl sulfoxide was added to 77.0 g (0.3b mol 3) -dichlorobenzene trifluoride. The solution is heated on an oil base with a temperature for k h and then stirred overnight at room temperature-i re. The solvent is then removed under vacuum and the residue is stirred with chloroform and filtered. The filtrate is washed with water, 0.5N sodium hydroxide and saturated solution 6 and dried over sodium chloride with anhydrous magnesium sulfate. After filtering off the drying agent with activated carbon and removing the solvent receive 11, B g of light orange oil, which is 3- (2-chloro-trifluoromethylphenoxy) benzaldehyde dimethyl acetal ”b) Preparation of 5- (2-chloro-trifluoromethylphenoxy) -2-chlorobenzaldehyde, B A 200 ml flask is placed with 10.0 g (0.029 mol) of the above 3- (2-chloro-trifluoromethylphenoxy) benzaldehyde dimethyl acetal and 90 ml of dry ethylene dichloride. The solution is cooled in an ice bath and then a catalytic amount (approximately 0.2 g) of ferric chloride is added to the solution. After that, chlorine gas is flowed into the reaction mixture at a moderate rate and the transmission is continued for 1 hour at the end. After completion of passing chlorine gas, the solution is stirred for another 2 hours at which time. The reaction solution is then extracted with water (N.0) and the aqueous layer is extracted with chloroform (,) The organic layers of ethylene dichloride and chloroform are combined and washed again with water (the pH value of the water is adjusted to 6 with 1 But sodium hydroxide solution). The organic layer is then washed with a saturated solution of sodium chloride and dried over anhydrous magnesium sulphate. After filtering off the dryer and removing the solvent, 11.7 g of a pale yellow oil, 5 (2-chloro-4-trifluoromethylphenoxy) -2-chlorobenzaldehyde, having the following characteristics, NMR spectrum in deuterated chloroform, are obtained: 6, ppm | | | cG (multiplet, 6H), 10.37 MOD cG (singlet, 1H). IR spectrum: 1695, 1605, 1590, 1500, Y15, 1320 cm Mass spectrum: molecular ion with m / e 33. c) Preparation of 5 (2-chloro-trifluoromethylphenoxy) -2-chlorobenzaldoxime. In a 100 ml flask, 3.3 g (0.01 mol) of the resulting 5 (2-chloro-trifluoromethylphenoxy) -2-chlorobenzaldehyde, 20 ml of tetrahydrofuran (THF) and 12 ml of absolute ethanol are placed. To this solution 0, 83 g (0.012 mol) of hydroxylamine hydrochloride in 10 ml of water and then. S 0.60 g (0.015 mol) of sodium hydroxide in 5 ml of water. After stirring the solution at room temperature, the organic solvent is removed from the solution for about an hour in vacuum, and the aqueous residue is treated with a water-chloroform mixture. The organic layer is separated, washed with a saturated solution of sodium chloride and dried over anhydrous magnesium sulphate. After filtering off the drying agent and removing the solvent, 3.01 g of a beige solid are obtained. This substance is recrystallized from 0 ml of -20 rekcaha, which results in 1.24 g of a beige crystalline substance, which is a mixture of anti-synisomers of 5- (2-chloro-4-trifluoromethylphenoxy) -2-chlorobenzaldoxime, 5 with m.p. 109-112 C and the following characteristics.
    NMR spectrum in deuterated chloroform; 6.83-7.70 ppm, {G (multiplet, 6H), 8.45 M, A. (G (singlet # 1H), Sv 8.97 MOD with s inglet, 1H).
    IR: 33 0-3110, 1b05, 1590, 1570, 1400, 1320.
    d. Preparation of 5 (2-chloro-4-trifluoromethylphenoxy) -2-chlorobenzaldoxime-jj -O- (acetic acid, methyl ester).
    A 25 ml flask is purged with dry nitrogen (Nj) and then 0.09 g (0.0037 mol) of metallic sodium and 5 ml of dry methanol are placed into it. When all of the sodium reacts, 1, g, 10.00355 mol / 5- (2-chloro-4-trifluoromethylphenox1 |) -2-chlorobenzaldoxic in 4 ml of methanol is introduced into the flask. After stirring for 15 minutes, 0.57 g (0.0037 mol) of methyl bromoacetate was added to the reaction mixture and the solution was stirred overnight at room temperature (a stream of nitrogen was blown into the flask). The solvent was then removed in vacuo, the residue was dissolved in chloroform and extracted with water and a saturated solution of sodium chloride, after which the organic layer was dried with anhydrous magnesium sulfate. After filtering off the dryer and evaporating the solvent
    1.53 g of pale yellow oil are obtained. It is dissolved in 2 ml of chloroform. This solution is applied to a top part, a column filled with silica gel (60/35 g silica gel, 70-230 mesh, activity 2-3), and eluted with chloroform. The eluate is collected in fractions of 10 ml each and analyzed by thin layer chromatography (TLC). Evaporation of the solvent from COOTs of these fractions (the first component coming from the column) allows to obtain 1.02 g of pure colorless oil, which is 5 (2-chloro). 4-trifluoromethylphenoxy) -2-chlorobenzaldoxime-0- (acetic acid, methyl ester), having the following characteristics,.
    NMR spectrum in deuterium chloroform: 3.75 ppm (GHsinglet, GN), 4.71 ppm (f (singlet, 2H); multiplet with centpOM at 7.31 ppm of exhaust gas (6H), 8.5b ppm of i (f (singlet, 1H).
    IR spectrum: 1760, 1740, 1595, 15b5, 1500, 1465, 1320 CM
    i Mass spectrum: molecular ion at m / e 421 ..
    , Example 4. Synthesis of 5-and-chloro-4-t (5fluoromethylphenoxy) -2-xLorbenzaldoxime-0-: (2-propionic acid, methyl ester). f
    A 25 ml flask is flushed with dry nitrogen and then 6 ml of dry methanol and g (0.005 mol) of metallic sodium are charged. After all the sodium has reacted, 2.09 g (O, 006 mol) of 5- (2-chloro-4-trifluoromethylphenoxy) -2-chlorobenzaldoxime) are added in one portion to the solution, obtained (as described in Example 1a , in 6 ml of methyl alcohol, after which the reaction mixture is stirred for approximately 15 minutes at room temperature.
    To this solution, 1.12 g (0.0062 mol) of ethyl 2-br1Omopropionate was added in one portion. Received by
    the solution is stirred under a stream of dry nitrogen overnight at room temperature. The solvent is then distilled off and the residue is dissolved in chloroform-water, the phase is separated and the chloroform layer is extracted with a saturated solution of sodium chloride and dried over anhydrous magnesium sulfate. After filtering off the drying agent and evaporating the solvent, a gram of crude (crude) oil is obtained. The oil is dissolved in 2 ml of chloroform and this solution is applied to the top of a column filled with silica gel (g silica gel, 70-230 mesh, activity 2-3, the column is filled with a wet method, silica gel is introduced into the column as a suspension in chloroform), chloroform is used as eluent. The eluate is collected in 10 ml fractions and analyzed by the method of those. After removal of the solvent from the appropriate fractions (6 to 13), 1.9 g of a clear, colorless oil, which is 5- (2-chloro-trifluoromethylphenoxy) -2-chlorobenzaldoxime-0 (2-propionic acid, methyl ester having the following characteristics. The NMR spectrum measured in deuterium chloroform contains the following chemical shifts in ppm: 1, k6 (f (doublet, 3N); 3,670 (singlet, 3N), 73 sG (quadruplet, 1H); 7.18 cG (mule tiplet, 6H); 8, cG (singlet, 1H). IR spectrum: 1760, 1610, 1600, 15b5 1500, U65, 1320 CM-t Mass spectrum: molecular ion at m / e 35 .. The following: connection The results were obtained according to the procedure described above. EXAMPLE 5 “5- (2-Chloro-4-trifluoromethylphenoxy) -2-nitroacetophenone oxime-0- (2-propionic acid, methyl ester) - to a yellow oil, has The following characteristics are about the CNR spectrum, taken in deuterated chloroform: 1.29 m; Up to 1.51 ppm cG (two doublets, GN), 2.25 m / d eG (singlet, 3H) i 2 , 25 m, d. B Sslinglet, ZN) 3.69 ppm and 3.73 MOD, SG (two singlet ZN),, 6A MOD. and 4.80 m, d „sG (two quadruplets, 1H), 7.0-8.25 ppmw, (multiplets, 6H)" IR spectrum: 1750, 1575, 1525, 1315 cm-1 Mass spectrum: molecular ion at m / e 360, Example 2 J3 6o 5- (2-Chloro-trifluor methylphenoxy) -2-nitroacetophenone oxime. The -0-acetic acid (yellow oil) obtained by conversion of methyl ester has the following characteristics. NMR spectrum (at 2.19 Mod. X O (singlet, 50 ppm, 71m, d ij (9 singlets, 2H), 6.93, g8.2 ppm (G (multiplet, 6H ), 10.92 ppm (Siiglet, 1H). IR spectrum: ZOOO-Z OO (wide signal); 1730, 1575, 1525, 1315 Example 7. 5-12-Chlor-4 - trifluoromethylphenoxy) -2-nitrobenzaldoxime is a viscous semi-solid substance with the following characteristics: NAN spectrum in deuterated chloroform: 6,, 13 MoD sG (multiplet, 6H) j 8,13 MoD cG (singlet, 1H); 9.9 m .d, and (broadened singlet, 1H). IR spectrum: 3310 (broad signal), 1605, 1570, 1520,, UOO, 1315 cM-t Mass spectrum: molecular ion with m / z BdO. meper 8o 5 (2-chloro-trifluoromethylphenoxy) -2-nor robenzaldoxime-0- (acetic acid, methyl ether), after recrystallization from methyl alcohol, a pale yellow solid is obtained (topl. 72-76 0), having the following characteristics: NANR spectrum in deuterated chloroform: 3.76 m.To d (singlet, ZN) I, 72 ppm cG (singlet, 2H); 6.937, 79 MODs of SG (multiplet, 5H); 8.13 md, (doublet, 1H); 8.78 m. Before singlet, 1H), IR spectrum: 1755, 1bOO, 15b5, 1515, 1315 Mass spectrum: molecular ion at m / e, Example 9 "5- (2-Chloro-trifluoromethylphenoxy) -2-nitrobenzaldoxime -0- (2-propionic acid, methyl ether) liquid substance pale yellow ETA with the following characteristics. NMR spectrum taken in deuterated chloroform (CDCE) - (1.52 m / d, (doublet, 3N); 3.72 ppm (singlet, 3N); k, 8k m, To (quartet, 1H ); multiplet with a center in the region of 7.35 ppm, (5H), 8.12 MD (doublet, 1H); 8.75 ppm (singlet, 1H). IR spectrum: 1750 , 1b05, 15b5, 1520, 1315 cm Mass spectrum: molecular ion with m / n NbO Example 10. 5 (2-Chloro-trifluoromethylphenoxy) -2-nitrobenzaldoxime-0- (acetic acid, isopropyl ether) is a crystalline solid yellow color, having the following characteristics, NMR spectrum, taken in deuterated chloroform (CDCf,): (fl, 23 ppm, (doublet, 6H)) A, 63 md (singlet, 5.06 ppm . (heptet, 1H), multiplet with the center in the region of 7.33 ppm (5I),
    权利要求:
    Claims (2)
    [1]
    Claim
    A method of obtaining derivatives of oximes of General formula I
    ΟΉ-Ο-Ο-Ο-Ο-Κ 2 g to (“m, where X is the nitro group (N0 ^) or the halogen atom j. U is the chlorine atom (Cp), J
    Z is a hydrogen atom, *
    R is a hydrogen atom or an alkyl group comprising up to three atoms
    4 new carbon ',
    R is a hydrogen atom or methyl
    [2]
    2 groupJ
    R is a hydrogen atom, a lower alkyl group, with the fact that the oxime of formula IV.
    Z '. where Y, Z, X, R - have the above meanings, they are reacted with a carboxylate of the formula Hal - CHiR ^ -CO-OR 2 ·, where r r ^ are shown above, Hal is halogen, and, if desired, the obtained compound of formula I in which R 2 represents an alkyl group, by hydrolysis is converted into the corresponding compound in which R 1 · represents a hydrogen atom.
    Priority by signs:
    05/11/79 at X-NO ^, * У- С I, Z-hydrogen, R is hydrogen, the alkyl group С DO 3J is hydrogen, СН3, · R T is hydrogen, the lower alkyl group,
    04/15/80. when X-MO g , halogen U-Cp ( 'Z is hydrogen, R is hydrogen, the alkyl group is up to C ^, R 4 is hydrogen, CTC j R ^ is hydrogen, a lower alkyl group.
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    同族专利:
    公开号 | 公开日
    YU121080A|1983-12-31|
    PL224072A1|1981-02-13|
    PT71222A|1980-06-01|
    FI71731B|1986-10-31|
    SE8003512L|1980-11-12|
    NL181430C|1987-08-17|
    PL134026B1|1985-07-31|
    ES491327A0|1981-04-16|
    GB2049695B|1983-07-20|
    KR830002698A|1983-05-30|
    NO149587B|1984-02-06|
    FI71731C|1987-02-09|
    AU5826880A|1980-11-13|
    CS221909B2|1983-04-29|
    IE800961L|1980-11-11|
    GB2120233A|1983-11-30|
    HU183134B|1984-04-28|
    CA1236851C|1988-05-17|
    GB2049695A|1980-12-31|
    CH644588A5|1984-08-15|
    DE3017795C2|1988-11-24|
    NO801373L|1980-11-12|
    KR840001968B1|1984-10-26|
    GB2120233B|1984-05-02|
    AU526031B2|1982-12-16|
    IL59958A|1984-05-31|
    NO149587C|1984-05-16|
    AR230986A1|1984-08-31|
    DD151861A5|1981-11-11|
    FI801303A|1980-11-12|
    BR8002850A|1980-12-23|
    EG14625A|1985-03-31|
    DE3051060C2|1988-08-18|
    FR2456088A1|1980-12-05|
    FR2456087A1|1980-12-05|
    AT366883B|1982-05-10|
    NL181430B|1987-03-16|
    ATA248480A|1981-10-15|
    BG38333A3|1985-11-15|
    YU42506B|1988-10-31|
    GB8300942D0|1983-02-16|
    CH652385A5|1985-11-15|
    IT8067734D0|1980-05-09|
    IT1133087B|1986-07-09|
    RO79871B|1983-01-30|
    ES8104212A1|1981-04-16|
    FR2456087B1|1983-02-25|
    LU82433A1|1980-12-16|
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    IE49793B1|1985-12-11|
    PH16450A|1983-10-12|
    FR2456088B1|1983-02-25|
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    GR67695B|1981-09-07|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4071686A|1968-12-17|1978-01-31|U.S. Philips Corporation|Novel benzylidene amino-oxyalkyl carboxylic acids and carboxylic acid derivatives|
    US3652645B1|1969-04-25|1984-07-24|
    US3776715B1|1969-04-25|1984-08-28|
    US4039588A|1969-05-28|1977-08-02|Rohm And Haas Company|Herbicidal 4-nitro-diphenyl ethers|
    US3979437A|1973-09-19|1976-09-07|Mobil Oil Corporation|Substituted phenoxybenzoic acids and derivatives thereof|
    US3914300A|1971-12-23|1975-10-21|Shell Oil Co|Phenyl ketoxime derivatives|
    US4093446A|1972-03-14|1978-06-06|Rohm And Haas Company|Herbicidal 4-trifluoromethyl-4-nitrodiphenyl ethers|
    US3928416A|1972-03-14|1975-12-23|Rohm & Haas|Herbicidal 4-trifluoromethyl-4{40 nitrodiphenyl ethers|
    US3798276A|1972-03-14|1974-03-19|H Bayer|Herbicidal 4-trifluoromethyl-4'-nitrodiphenyl ethers|
    US4063929A|1973-02-12|1977-12-20|Rohm And Haas Company|Herbicidal 4-trifluoromethyl-4'nitrodiphenyl ethers|
    US3983168A|1973-08-13|1976-09-28|Mobil Oil Corporation|Halophenoxy benzoic acid salts|
    US4060686A|1973-12-21|1977-11-29|Janice Bradshaw|Cephalosporins having a 7- group|
    JPS577122B2|1973-12-24|1982-02-09|
    US3907866A|1974-06-07|1975-09-23|Mobil Oil Corp|Higher halophenoxy benzoic acid esters|
    US3976470A|1975-07-23|1976-08-24|Stauffer Chemical Company|Diphenyl ether amides|
    GB1543964A|1976-04-08|1979-04-11|Ici Ltd|Method of antagonising herbicides on soyabean and cotton|
    US4059435A|1976-08-31|1977-11-22|Rohm And Haas Company|Herbicidal 4-trifluoromethyl-3-cyanoalkoxy-4-nitro diphenyl ethers|
    CH632130A5|1977-03-02|1982-09-30|Ciba Geigy Ag|Compositions on the basis of oxime ethers, oxime esters or oxime carbamates which are suitable in agriculture for crop protection|
    DE2803317C2|1977-03-05|1989-03-02|Koerber Ag, 2050 Hamburg, De|
    BE870068A|1978-08-30|1979-02-28|Ciba Geigy|METHOD OF SELECTIVE CONTROL AGAINST WEEDS AND HERBICIDAL AGENT APPLIED TO THIS EFFECT|
    US4490167A|1979-08-06|1984-12-25|Ciba-Geigy Corporation|Oxime derivatives of diphenyl ethers and their use in herbicidal compositions|
    US4551171A|1980-02-01|1985-11-05|Rhone-Poulenc, Inc.|2-Nitro-5- phenylalkanone oxime and imine derivatives as herbicides|
    AU6651581A|1980-02-01|1981-08-06|Rhone-Poulenc, Inc.|2-nitro- benzoyl derivatives as herbicides|
    JP5246286B2|2011-03-15|2013-07-24|カシオ計算機株式会社|Image recording apparatus, image recording method, and program|US4633000A|1980-02-01|1986-12-30|Rhone Poulenc Agrochimie|2-nitro-5- phenylalkanone oxime and imine derivatives as herbicides|
    US4551171A|1980-02-01|1985-11-05|Rhone-Poulenc, Inc.|2-Nitro-5- phenylalkanone oxime and imine derivatives as herbicides|
    DE3044810A1|1980-11-28|1982-07-01|Bayer Ag, 5090 Leverkusen|SUBSTITUTED PHENOXYCIMATE ACID DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF AS HERBICIDES, AND INTERMEDIATE PRODUCTS AND THEIR PRODUCTION|
    US4509970A|1981-12-17|1985-04-09|Zoecon Corporation|Substituted phenylphosphinyloxy- and phosphinylthio-iminocarboxylates useful for the control of weeds|
    DE3220526A1|1982-06-01|1983-12-01|Bayer Ag, 5090 Leverkusen|TRIFLUORMETHYLPHENOXY-PHENYL DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS HERBICIDES|
    DK416583A|1982-10-06|1984-04-07|Hoffmann La Roche|BENZOIC ACID DERIVATIVES WITH HERBICIDE EFFECT|
    US4504671A|1982-10-15|1985-03-12|Ppg Industries, Inc.|Method for preparing aldoxime or ketoxime-O-alkanoic acid|
    US4900862A|1983-03-28|1990-02-13|American Cyanamid Company|Herbicidally active substituted diphenyl ether oxime derivatives|
    US4584403A|1983-04-11|1986-04-22|Ppg Industries, Inc.|Herbicidally active substituted diphenyl ether oxime derivatives|
    GB8309774D0|1983-04-11|1983-05-18|Ici Plc|Herbicidal compounds|
    FR2549047B1|1983-07-12|1986-03-21|Rhone Poulenc Agrochimie|NOVEL HERBICIDES DERIVED FROM ARYLOXYBENZENES CARBONIMIDES|
    EP0149268A3|1983-12-14|1985-11-06|Shell Internationale Researchmaatschappij B.V.|Herbicidal composition and method of combating plant growth|
    US4571255A|1983-12-29|1986-02-18|Ppg Industries, Inc.|Subsituted phenoxybenzisoxazole herbicides|
    HU190222B|1984-01-17|1986-08-28|Budapesti Vegyimuevek,Hu|Fungicide comprising substituted phenoxy-benzaldehyde as active substance|
    DE3410105A1|1984-03-20|1985-10-03|Hoechst Ag, 6230 Frankfurt|HERBICIDAL AGENTS|
    ZA851378B|1984-03-22|1986-09-24|Ppg Industries Inc|Diphenylether oxime ester derivatives|
    US4596883A|1984-07-05|1986-06-24|Ppg Industries, Inc.|Herbicidally active substituted diphenyl ethers|
    AU574236B2|1984-11-12|1988-06-30|Sumitomo Chemical Company, Limited|Herbicidal composition comprising 2- -4,5,6,7-tetrahydro-2h-isoindole-1,3-dione|
    CN1005376B|1984-12-12|1989-10-11|旭化成工业株式会社|Herbcide comprising as an active ingredient 5--2-nitro-alpha substituted acetophenone and/or oxime derivative|
    CA1276647C|1984-12-12|1990-11-20|Teruyuki Misumi|5--2-nitro-a- substituted-acetophenone, oxime derivative thereof, process for preparing thereof, herbicidal composition,and method for the destruction of undesirable weeds|
    US4738709A|1985-01-10|1988-04-19|Ppg Industries, Inc.|Herbicidally active substituted benzisoxazoles|
    GB8520774D0|1985-08-20|1985-09-25|Shell Int Research|Diphenyl ether herbicides|
    US4710582A|1986-07-14|1987-12-01|Ppg Industries, Inc.|Herbicidally active substituted diphenyl ether oxime derivatives|
    JPH01233203A|1988-03-12|1989-09-19|Mitsubishi Petrochem Co Ltd|Herbicide composition|
    GB9013352D0|1990-06-14|1990-08-08|Ici Plc|Herbicidal compounds|
    KR20040012102A|2002-08-01|2004-02-11|이동수|Method of manufacturing a soft and light knitting yarn|
    US20110232180A1|2010-03-23|2011-09-29|Schultz Sr Shane Blake|Method of applying calcium magnesium acetate to affect growth of unwanted broadleaf weeds in lawn grasses|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US3804379A| true| 1979-05-11|1979-05-11|
    US06/136,171|US4344789A|1979-05-11|1980-04-15|Acids and esters of 5--2-nitro, -halo, or-cyano alpha substituted phenyl carboxy oximes, and method of controlling weeds with them|
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