• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A METHOD FOR PREPARING LUNG AIR (S) -Y-CYANO-3-PHENOXYBENZ10-10-THIRD ALCOHOL, AND 1R, CYC-2.2-DIMETR-3- (2.2-DIBROMVINSH1) -TsIRSOPROPAN-1-CARBON-3-CABLE-3-2-CARBON-3-DIMETHENE-3- (2.2-DIBROMVINSH1) -CIRSHOPROPAN-1-CARBON-3-DIMETR-3- (2.2-DIBROMVINSH1) -CIRSOPROPAN-1-CARBON-C-3-ARBON-3-2 3-phenoxybenzene alcohol with 1R, cis-2,2-dimethyl-3- (2, 2-dibromovinyl) -cyclopropan-1 carboxylic acid chloride in a monoaromatic hydrocarbon, in order to increase the yield of the desired product in as cC-cyano-3-phenoxybeneyl alcohol use it
    公开号:SU1116978A3
    申请号:SU792832611
    申请日:1979-10-15
    公开日:1984-09-30
    发明作者:Мартель Жак；Тессье Жан；Теш Андре；Демут Жан-Пьер
    申请人:Руссель-Юклаф (Фирма)；
    IPC主号:
    专利说明:

    Od sb

    00 The invention relates to a process for the preparation of ester (5) -th (g-cyano 3-phenoxybenzyl alcohol possessing insecticidal activity. A known method for the preparation of (5) -oC-ester, iano-3-phen6 oxibenyl alcohol and 1R, cis -2,2-dimetip3- (2, 2-dibromovinyl) -cyclopropane-1carboxylic acid, which implies that 1R, pds-2,2-dimethyl-3- (2,2dibromovinyl) -cyclopropane carboxylic acid or its rapoid anhydride in the environment of benzene is subjected to esterification (R, S) C-cyano-3-phenoxybenzyl alcohol and get the corresponding ester configuration (R, S). the resulting (R, S) ester is distilled and the ester is (5) -OC-cyano-3-phenoxybenzyl alcohol and TR, cis-2,2-dimethyl-3- (2,2-dibromovinyl) -cyclopropane -carboxylic acid with a yield of 50% 1. The disadvantage of this method is the low yield of the target product. The purpose of the invention is to increase the yield of the target product. The goal is achieved by the method of producing ester (3) -oC-cyano-3-phenoxybenzyl alcohol and 1R, cis-2,2-dimethyl-3- (2 ,. 2-dibromovinyl) -cyclopropane-1-carboxylic acid by esterification of cC-cyano-3-phenoxybenzyl alcohol with 1R chloride, cis-2,2 dimethyl-3 (2, 2-dibromovinyl) -cyclopropan-1-carbolic acid in a monoaromatic hydrocarbon as an oC.-cyano-3-phenoxybenzyl alcohol, it is used by its (3) -isomerism. The process is carried out at a temperature from -10 to + 20 ° C. The proposed method allows to obtain the desired product in quantitative yield. 1. Example Ester (S) - iCcyano Z-phenoxybenzyl alcohol and 1R, cis-2,2-dimethyl-3- (2,2-dibromovyl) -cyclopropan-1-phenoxybenzyl acid dissolve 640 mg of (8) -o-C- cyano-3-phenoxybenzyl alcohol in 10 cm of benzoic acid in 2 cm of toluene, and then 0.5 cm of pyridine in 2 cm of luol. It is kept for 2 hours at 20 ° C, and then for 48 hours at 0 ° C, washed with dilute hydrochloric acid and then with sodium bicarbonate solution, dried and evaporated to dryness. This gives 2.1 g of the crystalline desired product, which is purified by chromatography on silica, eluting with petroleum ether-ether (9-1). Obtain 1.3 g (99.9%) of pure in the form of crystals of the target product, T.Sh1. 100 ° C, 19 ° C (, 8%). In addition, using (5) - "1-cyano-3-phenoxy-benzyl alcohol, 2-isopropyl-2-parachlorophenyl acetic acid ester can be obtained. Example 2. a) Obtaining 2-isopropyl-2-parachlorophenyl acetic acid chloride. 10 g of D 2-isopropyl-2-chlorophenylphenyl acetic acid are added to a mixture of 50 cm-petroleum ether (b.p., ZZ-UOS) and 20 cm of thionyl chloride. The mixture is heated under reflux, refluxed for 4 hours, cooled, concentrated to dryness With a reduced pressure, 10.8 g of D 2-isopropyl-2-parachlorophenyl acetic acid chloride are obtained. b) Preparation of (8) -oC-cyano-3-phenoxy-benzyl ester of D 2-isopropyl-2 para-chlorophenylacetic acid. 3 g of (8) -o1-cyano-3-phenoxybenzyl alcohol is introduced into 50 cm of benzene, 3.1 g of the chloride of D 2-isopropyl-2-parachlorophenyl acetic acid obtained in the previous step is cooled to 15 ° C, added dropwise a mixture of 4 cm of pyridine and 10 cm of benzene, stirred for 2 hours at 20 ° C, drank 2 n. aqueous solution of hydrochloric acid, the organic layer is separated by decanting, dried, filtered, concentrated to dryness by distillation under reduced pressure, the residue is chromatographed on silica gel, eluted with benzene and 4.4 g of (8) -vC-cyano-3-phenoxybenzyl ether are obtained D 2-isopropyl-2-para-. chlorophenylacetic acid. CctJJ 13.5 ° C (, benzene), which crystallizes over time. M.p. 62 ° C. Analysis: MB (419.88). Calculated,%: C 71.50; H 5.28; every 8.44; NOj 3.34. Found,%: C 71.4; H 5.3; Cf.9.1; N0 3.3. Circular dichroism (dioxane). th +0.1 at 253 mmk (max); d
    311169784
    +0.23 at 277 mmk (max); i + 0.27sb-asymmetric carbon atom;
    at 282 mmk (max); dB +0.27 pripik at 3.17 - 3.33 ppm character 286 MMK (max). hydrogen asymmetric on the asymmetric ATMRIR spectrum (deuterochloroform). carbon acid; peak at.
    Peaks at 0.63 - 0.75 ch. / MPN, 0.88 - s6.4 ppm, characteristic hydrogen
    1.0 Ch / MPN characteristic for mineral production of me-carbon S groups of the nitrile;
    isopropyl; a peak at 2.25 ppm peaks at 6.91 - 7.25 ppm, a characteristic isopropyl hydrogen compound of aromatics to hydrogen,
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING A LAYERED ETHER OF (S) -d-CYANO-3-PHOENOXYBENZEHOLO 0 ALCOHOL, AND 1R, CIS-2,2-DIMETHYL-3- (2,2-DIBR0MVINYL) -cyclopropane-1-carboxylic acid ~ 3-phenoxybenzyl alcohol with acid chloride 1R, cis-2,2-dimethyl3- (2 1 , 2-dibromovinyl) -cyclopropane-1 carboxylic acid in a monoaromatic hydrocarbon medium, characterized in that, in order to increase the yield of the target product, as < X - cyano-3-phenoxybenzyl alcohol use its (H) -isomer and the process is carried out at a temperature of from -10 to + 20 ° C.
    1 1116978
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1116978A3|1984-09-30|Method of obtaining ester of |-alpha-cyano-3-phenoxybenzyl alcohol and ir, cis-2,2-dimethyl-3 |-cyclopropane-1-carboxylic acid
    EP0061800B1|1985-08-28|Anti srs-a carboxylic acid derivatives, processes for their production and pharmaceutical formulations containing them
    FI73966C|1987-12-10|Process for Preparation of New Cyclopropane Carboxylic Acid Esters with a Polyhalogen Substituent Useful for Control of Parasites in Warm Blood Animals
    US4260633A|1981-04-07|Pesticidal esters of amino acids
    SU1473707A3|1989-04-15|Method of producing esters of cyclopropanecarbolic acids
    EP0143153A2|1985-06-05|Insecticidal1,1&#39;-Biphenyl -3-ylmethyl esters, their production and use and compositions containing them
    Weeks et al.1980|Conversion of secondary furfuryl alcohols and isomaltol into maltol and related. gamma.-pyrones
    USRE27592E|1973-03-06|Chxchjxx
    Yamaguchi et al.1995|Chemistry and antimicrobial activity of caryoynencin analogs
    Reid et al.1978|Synthesis of methyl arylmethyl 2, 2-dimethyl-3-| cyclopropylphosphonates as potential insecticides
    Arnold et al.1980|Competitive [1, 3]-and [3, 3]-sigmatropic rearrangements
    Tsuboi et al.1987|Stereoselective synthesis of octadecapolyenoic esters as an insecticide
    US4328167A|1982-05-04|Process for the preparation of optically active cyano alcohols
    US4116998A|1978-09-26|Preparation of esters of m-phenoxybenzyl alcohol and its α-cyano and α-ethinyl derivatives with 2,2-dimethylcyclopropanecarboxylic acids
    Kuilya et al.2016|Total synthesis of cananginone C and structural revision of debilisone A
    US4233129A|1980-11-11|Process of preparation of alkyl esters of dl cis chrysanthemic acid
    Ikan et al.1971|Synthesis of. beta.-sitosteryl acetate [|-24-ethyl-3. beta.-acetoxycholest-5-ene] and its 24 S epimer
    US4994600A|1991-02-19|Process for preparing trans-β-benzoylacrylic acid ester
    Tada et al.1982|Formation of dendrolasin, sesquirosefuran, perillene and rosefuran by biomimetic autooxidation
    US4408066A|1983-10-04|Methyl cyclopropane-1,3-dicarboxylate
    US4307251A|1981-12-22|Preparation of optically active allethrolone
    EP0038575B1|1983-03-09|Cyanovinyl-cyclopropanecarboxylic acids and method of preparing these compounds
    JPH11509534A|1999-08-24|Process for producing cyclopropanecarboxylic acid and intermediates thereof
    US3887547A|1975-06-03|Process for preparing dl-strigol
    US4487955A|1984-12-11|Process for preparing cis or trans, optically active monoalkyl esters of cyclopropane-1,3-dicarboxylic acids
    同族专利:
    公开号 | 公开日
    FR2421875A1|1979-11-02|
    GB2013670A|1979-08-15|
    ZA7911B|1980-01-30|
    IE790174L|1979-07-31|
    DD142043A5|1980-06-04|
    US4273727A|1981-06-16|
    JPS54109944A|1979-08-29|
    IT7947810D0|1979-01-29|
    JPH0249759A|1990-02-20|
    GB2087385A|1982-05-26|
    FR2421875B1|1980-09-12|
    HU184198B|1984-07-30|
    AU525513B2|1982-11-11|
    BE873106A|1979-06-27|
    AT358022B|1980-08-11|
    IE790175L|1979-07-31|
    GB2087385B|1983-01-06|
    CA1125310A|1982-06-08|
    IT1116517B|1986-02-10|
    IE47910B1|1984-07-25|
    SE7812248L|1979-08-01|
    JPS61233680A|1986-10-17|
    US4344895A|1982-08-17|
    IL56313D0|1979-03-12|
    NL7900778A|1979-08-02|
    DE2902466C2|1988-03-24|
    PL117803B1|1981-08-31|
    DE2902466A1|1979-08-02|
    SE8304452L|1983-08-17|
    AU4319279A|1979-08-09|
    SE444561B|1986-04-21|
    PL213094A1|1979-10-08|
    SE8304452D0|1983-08-17|
    DK171558B1|1997-01-13|
    JPH0257067B2|1990-12-03|
    US4303585A|1981-12-01|
    DK576778A|1979-08-01|
    CH638509A5|1983-09-30|
    CS204046B2|1981-03-31|
    IL56313A|1984-07-31|
    JPS6326104B2|1988-05-27|
    ATA71479A|1980-01-15|
    DK331789A|1989-07-04|
    ES481216A1|1980-04-01|
    GB2013670B|1982-10-27|
    LU80752A1|1979-09-07|
    ES476220A1|1979-10-16|
    JPH0333704B2|1991-05-20|
    SE454087B|1988-03-28|
    DK331789D0|1989-07-04|
    SU957764A3|1982-09-07|
    CH636851A5|1983-06-30|
    DK171478B1|1996-11-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR1580474A|1968-07-12|1969-09-05|
    SE386670B|1968-07-12|1976-08-16|Roussel Uclaf|METHOD OF PREPARING INTERNAL HEMIACYLATES OF CIS-3,3-DIMETHYL-2-FORMYLcyclopropane-1-CARBONIC ACID|
    US4014918A|1968-07-12|1977-03-29|Roussel-Uclaf|Process for the preparation of cyclopropane derivatives and compounds produced therein|
    FR2045177A5|1969-06-13|1971-02-26|Roussel Uclaf|
    US3922286A|1971-03-23|1975-11-25|Sumitomo Chemical Co|Process for the production of optically active dihydrochrysanthemolactone|
    US4024163A|1972-05-25|1977-05-17|National Research Development Corporation|Insecticides|
    CH611593A5|1973-08-15|1979-06-15|Nat Res Dev|Process for the preparation of a cyclopropanecarboxylic acid ester|
    US3989654A|1973-11-22|1976-11-02|Sumitomo Chemical Company, Limited|Process for preparing cis-chrysanthemic acid|
    FR2302994B1|1975-03-06|1978-02-03|Fabre Sa Pierre|
    GB1540223A|1975-06-11|1979-02-07|Shell Int Research|Process for the preparation of alpha-cyanobenzyl alcohol derivatives|
    FR2375161B1|1976-04-23|1979-04-13|Roussel Uclaf|
    FR2348901B1|1976-04-23|1983-01-28|Roussel Uclaf|
    FR2362829B1|1976-08-27|1979-03-02|Roussel Uclaf|DE2326077C2|1972-05-25|1985-12-12|National Research Development Corp., London|Unsaturated cyclopropanecarboxylic acids and their derivatives, their preparation and insecticides containing them|
    FR2423488B1|1978-03-17|1981-12-11|Roussel Uclaf|
    FR2419939B1|1978-03-17|1980-11-28|Roussel Uclaf|
    FR2458542B1|1979-06-12|1984-09-28|Roussel Uclaf|
    FR2472570B1|1979-07-31|1983-06-17|Roussel Uclaf|
    FR2471377B1|1979-12-10|1983-02-25|Roussel Uclaf|
    JPS56133253A|1980-03-24|1981-10-19|Sumitomo Chem Co Ltd|Optical isomer of cyanohydrin ester, its production and insecticide and acaricide containing the same as effective ingredient|
    DE3040487A1|1980-10-28|1982-06-16|Hoechst Ag, 6000 Frankfurt|PHENOXY CIMAL ALCOHOLS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS AN INTERMEDIATE PRODUCT FOR THE PRESENTATION OF INSECTICIDES|
    EP0291626A3|1982-11-22|1989-05-31|E.I. Du Pont De Nemours And Company|Process for the preparation of optically-active cyanomethyl esters|
    NZ206106A|1982-11-22|1987-10-30|Shell Oil Co|Processes for the preparation of optically active cyanomethyl esters of alpha-chiral carboxylic acids and optionally substituted s-alpha-cyano-3-phenoxybenzyl alcohol|
    US4479005A|1982-12-16|1984-10-23|The Dow Chemical Company|Selective preparation of isomers and enantiomers of cyclopropane carboxylic acids|
    US4526727A|1983-01-24|1985-07-02|Shell Oil Company|Process for preparation of an S-alpha-cyano S-alpha-isopropylphenylacetate|
    AU576322B2|1983-07-22|1988-08-25|Ici Australia Limited|Alpha-substituted-alpha-cyanomethyl alcohols|
    JPH0684332B2|1985-06-20|1994-10-26|住友化学工業株式会社|Method for optical resolution of a-isopropyl-p-chlorophenylacetic acid|
    US4827013A|1985-12-31|1989-05-02|Ethyl Corporation| α-(cyano-3-phenoxy-benzyl acetate|
    US5223536A|1991-07-23|1993-06-29|Fmc Corporation|1,4-diaryl-1-cyclopropyl-4-substituted butanes as insecticides and acaricides|
    EP0601632A1|1992-12-09|1994-06-15|Duphar International Research B.V|Method of preparing optically active cyanohydrin derivatives|
    EP0601237A1|1992-12-09|1994-06-15|Duphar International Research B.V|Method of preparing optically active cyanohydrin derivatives|
    US6040130A|1997-02-10|2000-03-21|Eastman Kodak Company|Photothermographic and thermographic films containing low levels of unsaturated fatty acid to prevent fog|
    WO2006010994A1|2004-07-20|2006-02-02|Council Of Scientific And Industrial Research|Process for preparing -alpha-cyano-3-phenoxybenzyl--2--isovalerate|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7802621A|FR2421875B1|1978-01-31|1978-01-31|MD94-0272A| MD244C2|1978-01-31|1994-09-08|Method of preparation of ester of alcohol -a-cyai-3-fenoxybenzol and 1R, cis-2,2-domethyl-3--cyclopropan-1-carbonic acid|
    [返回顶部]