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METHOD FOR MANUFACTURING OPTICALLY ACTIVE CARBOXYLIC ACID ESTER

Foreign code F130007423
File No. S2013-0218-N0
Posted date Jun 20, 2013
Country WIPO
International application number 2012JP064647
International publication number WO 2012169575
Date of international filing Jun 7, 2012
Date of international publication Dec 13, 2012
Priority data
  • P2011-130572 (Jun 10, 2011) JP
Title METHOD FOR MANUFACTURING OPTICALLY ACTIVE CARBOXYLIC ACID ESTER
Abstract A method that manufacturers an optically active carboxylic acid ester at high yield and high enantioselectivity is provided. An optically active carboxylic acid ester is manufactured at high yield and high enantioselectivity by reacting a racemic carboxylic acid and a specific alcohol or phenol derivatives in a polar solvent having a dipole moment of 3.0 or higher in the presence of an acid anhydride and an asymmetric catalyst, esterifying one enantiomer of the racemic carboxylic acid at high selectivity, and increasing the amount of esterified carboxylic acid by racemizing the optically active carboxylic acid which is the other enantiomer not used in esterification.
Outline of related art and contending technology BACKGROUND ART
An optically active carboxylic acid esters, pharmaceutical, intermediate of a physiologically active substance, as intermediates for synthesis of natural products, used in a variety of applications.
Conventional, in a method for producing an optically active carboxylic acid ester, an alcohol with an asymmetric catalyst and a carboxylic acid is reacted with a known.
And an optically active carboxylic acid ester as a method of manufacturing an optically-active alcohol, tetramisole or benzo tetramyristoyl sole (tetramisole) (benzotetramisole) is used as a catalyst, an acid anhydride in the presence of a tertiary benzyl alcohols from racemic 2 a method of producing an optically active carboxylic acid ester is known (see non-patent document 1). In addition, benzo tetramyristoyl sole is used as a catalyst, an acid anhydride in the presence of an optically active carboxylic acid from racemic propargyl alcohols also known a method for producing esters (see non-patent document 2). Further, as a method to improve the substrate generality, tetramisole is used as a catalyst or benzo tetramyristoyl sole, benzoic anhydride or a derivative thereof with a primary alcohol in the presence of the racemic 2 is reacted with a carboxylic acid and a method for producing an optically active carboxylic acid ester also known (see Patent Document 1).
On the other hand, an optically active carboxylic acid ester and as a production method for an optically active carboxylic acid, benzo tetramyristoyl sole or tetramisole is used as a catalyst, benzoic anhydride or a derivative thereof in the presence of the racemic carboxylic acids and alcohols by reacting an optically active carboxylic acid ester also known a method of manufacturing (see Patent Document 2).
Scope of claims (In Japanese)請求の範囲 [請求項1]
 動的速度論的光学分割による光学活性カルボン酸エステルの製造方法であって、
 ラセミのカルボン酸と、下記式(a)で表されるアルコール又は下記式(b)で表されるフェノール誘導体とを、酸無水物と不斉触媒との存在下、双極子モーメント3.0以上の極性溶媒中で反応させ、前記ラセミのカルボン酸のうち一方のエナンチオマーを選択的にエステル化するとともに、他方のエナンチオマーをラセミ化することを特徴とする光学活性カルボン酸エステルの製造方法。
[化1]

(式(a)中、R aは置換基を有していてもよいフェニル基、ナフチル基、アントリル基、又はフェナントリル基を示す。)
[化2]

(式(b)中、R bは置換基を有していてもよいフェニル基、ナフチル基、アントリル基、又はフェナントリル基を示し、nは1~5の整数を示す。複数のR bが存在する場合、それらは同一であっても異なっていてもよい。)

[請求項2]
 前記不斉触媒が下記式(c)~(f)で表されることを特徴とする請求項1記載の光学活性カルボン酸エステルの製造方法。
[化3]

(式(c)~(f)中、Xは下記の置換基
[化4]

のいずれかを示し、Rは保護基を示す。)

[請求項3]
 前記ラセミのカルボン酸が下記式(g)で表されることを特徴とする請求項1又は2記載の光学活性カルボン酸エステルの製造方法。
[化5]

(式(g)中、R g1、R g2は互いに異なる有機基を示す。)

[請求項4]
 前記式(g)中、R g1、R g2のいずれか一方は、多重結合を有する炭素原子を介して不斉炭素と結合する有機基であり、他方は、多重結合を有さない炭素原子を介して不斉炭素と結合する有機基であることを特徴とする請求項3記載の光学活性カルボン酸エステルの製造方法。






  • Applicant
  • ※All designated countries except for US in the data before July 2012
  • TOKYO UNIVERSITY OF SCIENCE EDUCATIONAL FOUNDATION ADMINISTRATIVE ORGANIZATION
  • Inventor
  • SHIINA, Isamu
  • NAKATA, Kenya
  • ONO, Keisuke
IPC(International Patent Classification)
Specified countries National States: AE AG AL AM AO AT AU AZ BA BB BG BH BR BW BY BZ CA CH CL CN CO CR CU CZ DE DK DM DO DZ EC EE EG ES FI GB GD GE GH GM GT HN HR HU ID IL IN IS JP KE KG KM KN KP KR KZ LA LC LK LR LS LT LU LY MA MD ME MG MK MN MW MX MY MZ NA NG NI NO NZ OM PE PG PH PL PT QA RO RS RU RW SC SD SE SG SK SL SM ST SV SY TH TJ TM TN TR TT TZ UA UG US UZ VC VN ZA ZM ZW
ARIPO: BW GH GM KE LR LS MW MZ NA RW SD SL SZ TZ UG ZM ZW
EAPO: AM AZ BY KG KZ RU TJ TM
EPO: AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR
OAPI: BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG
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