• 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:
    Stereoisomerically-enriched cyanomethyl esters are prepared by treating a non-symmetrical ketene or an alphachiral carboxylic acid halide or reactive derivative thereof with an optically-active alphahydroxynitrile. Certain optically-active optionally substituted S-alphacyano-3-phenoxy-benzyl alcohol intermediates are prepared by treating the corresponding aldehyde of ketone with a source of hydrogen cyanide in the presence of a substantially water-immiscible, aprotic solvent and a cyclo(D-phenylalanyl-D-histidine) as a catalyst.
    公开号:SU1542412A3
    申请号:SU833675006
    申请日:1983-11-21
    公开日:1990-02-07
    发明作者:В.Стаутэмайр Дональд；Х.Тиман Чарльз；Донг Вальтер
    申请人:Шелл Ойл Компани (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a new process for the preparation of 5-o-cyano-3 -pheno-sibeneyl alcohol or its sedimentation with the R-isomer, which is used to prepare pyrethroid esters.
    The purpose of the invention is the iDeody process.
    EXAMPLE 1 A 00 ml three-neck flask was charged with 43 mg of cyclo-B phenylalanyl-P-histidine and placed in a nitrogen atmosphere. 3.5 ml of hydrogen cyanide are then added with a syringe, causing the catalyst to swell and gel. After 5 minutes, 30 ml of toluene is added, causing additional swelling of the catalyst.
    5.95 g of 3-phenoxybenzaldehyde is added at the same time. Reactionary
    the mixture is stirred for 4.75 hours and then quickly cooled with 20 ml of water containing 10 drops of concentrated hydrochloric acid. The toluene rastigor is separated, washed twice with water and diluted to 50 ml with toluene for analysis by liquid chromatography. The analysis showed that the obtained product with a yield of 31%, containing 80% S-c-cyano-Z-phenoxybenzyl alcohol and 20% R-isomer,
    PRI me R 2, 3-l-cyano-3-phenoxybenzyl alcohol.
    The method is carried out according to Example 1, but using 171 mg of cyclo-D-phenylalanyl-B-histidine. After certain intervals, the resulting product is taken up in 0.25 ml and determined by means of an i-routine chromatography of its SOGTLR:
    SP
    Ј 1chE
    th
    n "
    Yu

    cm

    % conversion of aldehyde 20 76 96
    After 7 hours, the reaction mixture is rapidly cooled by adding 10 ml of 1 N hydrochloric acid. The organic phase is separated and washed twice with water, dried over magnesium sulfate, JQ is filtered off and stored at -10 ° C. The filtrate is diluted to 50 ml with toluene and the optical rotation is determined to be - 54 at 21 ° C in a well ( 1 dm). A sample of the product was acetylated with p-nitrophenyl acetic anhydride, and using the high pressure liquid chromatography (HP C), the resulting product was determined on a Pirkle chiral column, which was co-2Q from 71% of 8-o-cyano-3-phenoxyben -. 31st alcohol and 29% I-cl-cyano-2phenoxybenzyl alcohol. Yield 95%.
    Example 8-с6-Щано-3-фенокг sibenzyl alcohol.
    Two small round bottom flasks with magnetic stirrers and septum lids are loaded into each 22.5 mg of cyclo-B-phenylalanyl-B-histidine and placed under nitrogen. 0.98 ml of hydrogen cyanide is taken, which is diluted to 25 ml with toluene, and 5 ml of the solution is added to each flask with a syringe. After 5 minutes, 0.87 ml of 3-phenoxybenzaldehyde (POA1) is added to each flask. The contents of flask No. I are mixed in an oil bath at 35 ° C, and the contents of the flask W 2 are mixed in a water bath at 24-26 ° C
    The results are shown in the table.
    PRI me R 4. S-dt-Cyano-3-phenoxybenzyl alcohol.
    The reaction is carried out by contacting 0.0099 m of cyclo-B-phenylalanyl-B-histidine with 0.99 mol of 3-phenoxy-benzaldehyde, followed by the addition of 2.2 mol of hydrogen cyanide and 190 ppm of water. Reaction: Conducted in toluene at 25 ° C. Conversion - aldehyde is 93%. Product ... was obtained in 88% yield and is 88% S-ot-cyano-3-phenoxybenzene alcohol and 12% R-isomer.
    PRI me R 5. 8-o (cyano-3-phenoxybenzyl alcohol.
    To 0.2933 g of cyclo-B-phenylalanyl-D-gnstidine in 15 ml of diethyl ether, at 25ffC, add 2,907 g of 3-feoxybenzaldehyde, followed by
    The addition of 0.940 g of hydrogen cyanide. After 2 hours, the conversion of 3-phenoxybenzaldehyde is 94% and the product obtained consists of 94% S-rf-cyano-3-phenoxybenzyl alcohol and 6% of the R-isomer. Yield 93%. ,
    Example: 6. 8 - (/ - Cyano-3-pheno-sibeneoyl alcohol.
    The reaction is carried out in the presence of 0.0200 g of cyclo-B-phenylalanyl-B-histidine at 25 ° C and 1.4037 g of 3-phenoxy-benzaldehyde in a nitrogen atmosphere, followed by the introduction of 2.1812 g of toluene with 13.65 wt. % hydrogen cyanide. After 2.7 hours, the conversion of 3-phenoxy-benzaldehyde is 93% and the product has a 88-, 6% enantiomeric excess of S-pf-cyano-3-phenoxybenzyl alcohol and 11% of the R-isomer.
    515
    Example. S-rf-Cyano-3-phenoc-snbeneyl alcohol.
    The reaction is carried out at 25 ° C by contacting 0.0519 g of cyclo-Phenyl-alanylNO-hisTidine in 9.32 ml of diethyl ether with 1.811 g of 3-phenoxy-sibenzaldegnd, followed by the addition of 0.617 g of hydrogen cyanide. After 3.6 hours, the conversion of 3-phenoxbenzaldehyde is 99.4% and the product contains 86% S-Y-cyano-3-phenoxy-sibeneyl alcohol and 14% R-isomer. The yield is 99.4%.
    The proposed method allows to obtain the target product more simple
    126
    technology in one stage instead of three
    by a known method.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of obtaining 8-o / -cyano-3-phenoxybasic alcohol or its mixture with the R-isomer, from the fact that, in order to simplify the process, 3-phenoxbenzaldehyde is reacted with hydrogen cyanide in toluene or diethyl of lovy ether in the presence of a catalyst cyclo-P-phenylalanylCH histidine at 24-35 ° C.
    类似技术:
    公开号 | 公开日 | 专利标题
    Kobayashi et al.1994|A chiral scandium catalyst for enantioselective Diels-Alder reactions
    Martin et al.1994|Enantio-and diastereoselectivity in the intramolecular cyclopropanation of secondary allylic diazoacetates
    SU1542412A3|1990-02-07|Method of producing s-alpha-cyano-3-phenoxybenzene alcohol or its mixture with r-isomer
    IL127058A|2001-07-24|Process for the synthesis of protected esters of |-3,4- dihydroxybutyric acid
    Molander et al.1994|Intramolecular nucleophilic acyl substitution reactions mediated by samarium | iodide: a convergent approach to the preparation of enantiomerically enriched 4-hydroxy ketones from 3-iodopropyl carboxylates
    SU1547707A3|1990-02-28|Method of producing trans-ethyl-1,2,3,4-tetrahydro-6,7-methylenedioxy-4-oxo-1|naphthalene-2-carboxylate
    JP2008508193A|2008-03-21|Method for producing optically active compound
    CN1042129C|1999-02-17|Process for preparing sertraline intermediates
    Ohga et al.1970|A Study on the Photochemistry of α, β-Unsaturated γ-Lactones. I. The Structures of the Photodimers of 4-Hydroxycrotonic Acid γ-Lactone
    Bolm et al.2003|A novel asymmetric synthesis of highly enantiomerically enriched norbornane-type diamine derivatives
    CN86107090A|1987-04-22|The preparation method of Clausenamide
    Naruse et al.1988|Asymmetrization of meso-cyclic ketones using homochiral acetal templates
    CN112694376A|2021-04-23|Kinetic resolution method of allyl tertiary alcohol catalyzed by chiral phosphoric acid
    Hudlicky et al.1991|Yeast-mediated resolution of. beta.-keto esters of prochiral alcohols
    US4720558A|1988-01-19|Process for inverting the configuration of secondary alcohols
    US5145993A|1992-09-08|Process for preparing D-2-|-propionic acid and intermediate thereof
    Carreño et al.1996|Diels-Alder reactions of [| R]-|-1-p-tolylsulfinyl-1, 3-pentadiene: the unexpected evolution of maleic anhydride adducts
    JPH0859554A|1996-03-05|Asymmetric hydrogenation of ketoisophorone derivative
    IE47907B1|1984-07-25|Process for preparing aromatic aldehydes
    Ballini et al.1999|Synthesis of ω‐Nitro Acids and ω‐Amino Acids by Ring Cleavage of α‐Nitrocycloalkanones
    Youn et al.2001|Highly diastereoselective additions of methoxyallene and acetylenes to chiral α-keto amidesElectronic supplementary information | available: synthesis and spectroscopic data for 4b, 5g, 6b and 7b. See http://www. rsc. org/suppdata/cc/b1/b100355k
    US5179208A|1993-01-12|Process for preparing d-2-|-propionic acid and intermediate thereof
    Marotta et al.1994|The Conversion of 3-Hydroxy-6-heptenoic Acids into Bicyclo [3.2. 0] hept-3-en-6-ones
    US4304942A|1981-12-08|Producing substituted 2-cyclopentenones
    SU640991A1|1979-01-05|Method of obtaining 3-thenylalkylketones
    同族专利:
    公开号 | 公开日
    JPH03238053A|1991-10-23|
    YU222783A|1986-12-31|
    PT77685B|1986-03-27|
    CA1263800A|1989-12-05|
    IL70155A|1989-09-10|
    NO834257L|1984-05-23|
    KR890003660B1|1989-09-29|
    ES527417A0|1985-11-01|
    DK532383A|1984-05-23|
    NZ206106A|1987-10-30|
    HU200584B|1990-07-28|
    OA07593A|1985-03-31|
    GR79041B|1984-10-02|
    MX167266B|1993-03-12|
    IN161692B|1988-01-16|
    EP0451927A1|1991-10-16|
    EP0109681B1|1992-03-11|
    BR8306312A|1984-07-03|
    YU43429B|1989-06-30|
    YU43197B|1989-04-30|
    ES8601860A1|1985-11-01|
    HUT37915A|1986-03-28|
    DE3382524D1|1992-04-16|
    DK532383D0|1983-11-21|
    AU577032B2|1988-09-15|
    FI834259A0|1983-11-21|
    FI834259A|1984-05-23|
    PL244585A1|1985-11-05|
    IL70155D0|1984-02-29|
    AU2155583A|1984-05-31|
    EP0109681A2|1984-05-30|
    EP0109681A3|1986-01-15|
    YU36986A|1986-12-31|
    PT77685A|1983-12-01|
    DD216453A5|1984-12-12|
    JPH02270852A|1990-11-05|
    BG40805A3|1987-02-16|
    KR840007715A|1984-12-20|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2383137A|1939-12-05|1945-08-21|American Cyanamid Co|Acetylation of cyanohydrins|
    NL295592A|1963-07-22|
    ZA7911B|1978-01-31|1980-01-30|Roussel Uclaf|Optically-active substituted benzyl alcohol and process for preparing it|
    FR2458542B1|1979-06-12|1984-09-28|Roussel Uclaf|
    DE3116474A1|1981-04-25|1982-11-11|Basf Ag, 6700 Ludwigshafen|METHOD FOR PRODUCING OPTICALLY ACTIVE CARBONIC ACIDS|
    JPH0153665B2|1981-08-17|1989-11-15|Nippon Kayaku Kk|
    AU527142B2|1981-12-16|1983-02-17|Bayer Aktiengesellschaft|Phenoxy benzyl alcohols|
    ZA837994B|1982-11-22|1984-06-27|Shell Oil Co|Process for the preparation of optically-active cyanomethyl esters|
    AU576322B2|1983-07-22|1988-08-25|Ici Australia Limited|Alpha-substituted-alpha-cyanomethyl alcohols|AU576322B2|1983-07-22|1988-08-25|Ici Australia Limited|Alpha-substituted-alpha-cyanomethyl alcohols|
    US4554102A|1983-09-26|1985-11-19|Shell Oil Company|Cyanohydrination catalyst comprising non-crystalline or amorphous dipeptide|
    EP0172380A3|1984-08-20|1987-06-16|E.I. Du Pont De Nemours And Company|Preparation of cyanomethyl esters|
    US4611076A|1985-06-26|1986-09-09|Shell Oil Company|Chiral cyanohydrination process|
    US4611077A|1985-06-26|1986-09-09|Shell Oil Company|Increasing enantiomeric selectivity in chiral cyanohydrination|
    JPH064578B2|1986-12-15|1994-01-19|鐘淵化学工業株式会社|Process for producing optically active cyano compound|
    JP2924000B2|1989-09-29|1999-07-26|住友化学工業株式会社|Asymmetric induction catalyst|
    CA2062233A1|1991-03-12|1992-09-13|Atsunori Mori|Catalyst for asymmetric induction|
    GB0304132D0|2003-02-24|2003-03-26|Syngenta Ltd|Chemical process|
    AU2010334164B2|2009-12-25|2014-09-11|Suntory Beverage & Food Asia Pte. Ltd.|Learning motivation improvers|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US44376382A| true| 1982-11-22|1982-11-22|
    US44376482A| true| 1982-11-22|1982-11-22|
    US44351382A| true| 1982-11-22|1982-11-22|
    [返回顶部]