Preparation method of cycloprothrin optical activity isomer

Preparation method of cycloprothrin optical activity isomer

  • CN 1,970,535 B
  • Filed: 12/01/2006
  • Issued: 05/30/2012
  • Est. Priority Date: 12/01/2006
  • Status: Active Grant
First Claim
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1. the preparation method of the light of cycloprothrin isomer alive is characterized in that adopting following (1), (2) and (4), (1), (3) and (4), and four kinds of methods of (5) or (6) obtain respectively:

  • (1) in organic solvent and under 20-50 ℃


    1-(4-ethoxyl phenenyl)-2 with racemization;

    2-two Cyclopropanoyl Chlorides-1-carboxylic acid and S-(-)-Alpha-Methyl benzylamine or R-(+)-Alpha-Methyl benzylamine are 1;


    1.5 to mix with mol ratio, react 40~

    100 hours, obtain the crystal of carboxylic acid amine salt;

    With resulting crystal at ambient temperature, in organic solvent, repeat crystallization 1~

    3 time, obtain acicular crystal;

    This crystal is used organic solvent dissolution again;

    The proton aqueous acid that adds 0.1N~


    At ambient temperature, after 12~

    36 hours, crystallization gets R-(-)-1-(4-ethoxyl phenenyl)-2;

    2-two Cyclopropanoyl Chlorides-1-carboxylic acid (II) or S-(+)-1-(4-ethoxyl phenenyl)-2, the crystal of 2-two Cyclopropanoyl Chlorides-1-carboxylic acid (I);

    (2) in organic solvent and under the room temperature condition, the 2-hydroxyl-2-of racemization (3-Phenoxyphenyl) acetonitrile and aceticanhydride carried out acetylization reaction 8~

    20 hours;

    Acetylizad reaction product, butanols and unit of activity are the pseudomonas lypase of 22 units/mg, 25~

    45 ℃

    with organic solvent in reacted 5~

    10 hours, obtain the light live body of (S)-2-hydroxyl-2-(3-Phenoxyphenyl) acetonitrile;

    2-hydroxyl-the 2-of described racemization (3-Phenoxyphenyl) acetonitrile and aceticanhydride mol ratio are 1;



    The mol ratio of acetylizad 2-hydroxyl-2-(3-Phenoxyphenyl) acetonitrile and butanols is 2;


    2, and acetylizad 2-hydroxyl-2-(3-Phenoxyphenyl) acetonitrile of each mole needs the pseudomonas lypase of 22 above-mentioned~


    (3) in 0~

    10 ℃

    , organic solvent and pH are 5~

    6 inorganic salt damping fluid;

    From Semen Armeniacae Amarum, extract (the R)-oxynitrilase, Potssium Cyanide, protonic acid and the 3-phenoxy benzaldehyde that obtain and reacted 2~

    4 days, obtain R-(+)-2-hydroxyl-2-(3-Phenoxyphenyl) acetonitrile (IV);

    The mol ratio of described Potssium Cyanide, protonic acid and 3-phenoxy benzaldehyde is 1;




    The 3-phenoxy benzaldehyde of each mole needs to extract in the above-mentioned Semen Armeniacae Amarum of 200g (the R)-oxynitrilase that obtains;

    (4) in organic solvent and under the room temperature;

    The alcohol of the carboxylic acid of step (1) gained, step (2) or (3) gained, 4-(dimethylamino) pyridine and condensing agent carried out esterification 8~

    15 hours, obtained (S) type or (R) the light isomer alive of the cycloprothrin of type structural formula as follows respectively;

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