PROCEEDED OF TRANSFORMATION Of an ESTER Of CHIRAL SECONDARY ALCOHOL ACID A-CYANE OPTICALLY ACTIVE OF STRUCTURE (R) INTO ESTER Of CHIRAL SECONDARY ALCOHOL ACID A-CYANE OF STRUCTURE (S) 机翻标题: 暂无翻译,请尝试点击翻译按钮。

公开号/公开日
FR2375161 A1 1978-07-21 [FR2375161]FR2375161 B1 1979-04-13 [FR2375161] / 1978-07-211979-04-13
申请号/申请日
1976FR-0012094 / 1976-04-23
发明人
;
申请人
ROUSSEL UCLAF;
主分类号
IPC分类号
A01N-037/34A01N-053/00A01N-053/08A01N-053/14A01P-007/04A61K-031/545C07B-031/00C07B-055/00C07B-057/00C07C-067/00C07C-069/74C07C-069/743C07C-253/00C07C-253/30C07C-255/32C07C-255/38C07C-255/39C07C-255/53C07D-501/06
摘要
(FR2375161) A process for the preparation of an ester of chiral (A) acid with an optically active (S) alpha -cyano-3-phenoxybenzyl alcohol by reacting an ester of chiral (A) acid with alpha -cyano-3-phenoxybenzyl alcohol of the formula <IMAGE> B in its optically active (R) form or a racemic (R,S) mixture or a mixture of esters of said (R) alcohol and (S) alcohol in non-equimolecular proportions designated herein as "ester (R+S)" with a base selected from the group consisting of ammonium hydroxide, primary, secondary and tertiary amines, quaternary ammonium compounds, liquid amines of high molecular weight, ion exchange resins of a basic character and a catalytic amount of a strong base in at least one solvent in which the ester of the (R) alcohol is soluble and in which the ester of the (S) alcohol is insoluble and recovering from the resulting medium the chiral (A) acid ester of the (S) alcohol which is insoluble.  (From US4133826 A)
机翻摘要
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地址
代理人
代理机构
;
优先权号
1976FR-0012094 1976-04-23
主权利要求
(FR2375161) 1. Proceeded of transformation of an ester of chiral acid (A) alcohol (B) optically active of structure (R) or racemic of structure (R, S) of formula B (B) (R) or (R, S) or of a mixture in proportion not equimoleculaire, of ester of chiral acid alcohol (A) (B) optically active of structure (R) and ester of chiral acid alcohol (A) (B) optically active of structure (S), mixture indicated by “ester (R + in an ester of chiral acid alcohol (A) (B) optically active of structure (S), characterized in that one subjects the ester of chiral acid alcohol (A) (B) optically active, of structure (R), or of racemic structure (R, S), or mixes itesters says “ester R + S”, with the action of a basic agent selected in the group consisted ammonia, the amines secondary, the tertiary amines and the strong bases which, they, are used in catalytic quantity, within a solvent or of a mixture of solvents in which ester of chiral acid alcohol (A) (B) of structure (S) is insoluble and ester of chiral acid alcohol (A) (B) of structure (R) is soluble, then isolates from the reactional medium, - the ester of chiral acid alcohol (A) (B) of structure (S) thus rendered insoluble. 2. Proceeded according to the revendication1, characterized in that the chiral acid is an acid having an asymmetrical carbon. 3. Proceeded according to claim 1, characterized in that the chiral acid (A) is an acid having two asymmetrical carbon atoms. 4. Proceeded according to any of the revendicatipns 1 and 3, characterized in that the chiral acid (A) is a carboxylic acid cyclopropane of which two of carbons of the cycle are asymmetrical carbons. 5. Process - according to any of claims 1,3 - and 4 characterized in that the chiral acid (A) is an acid optically active carboxylic cyclopropane of structure cis or trans of formula: .0. Hal'- 'Hal in which Hal represents an atom of - chlorine or bromine. 6. Proceeded according to any of the claims 1 and 3 to 5, characterized in that the chiral acid is the 2,2-dimethyl acid 3R- (2 1 2-dibromovinyl) cyclopropane-1R-carboxylic or acid 1R, cis 2,2-dimethyl 3 (2,2-dibromovinyl) carboxylic cyclopropane. 7. Proceeded according to any of the claims 1 and 3 to 5, characterized in that the chiral acid is - the 2,2-dimethyl acid 3R- (2,2-dichlorovinyl) cyclopropane-1R-carboxylic or acid 1R, cis 2,2-dimethyl 3 (2,2-dichlorovihyl) carboxylic cyclopropane. 8. Proceeded according to any of claims 1 to 7, characterized in that the basic agent is selected in the group consisted ammonia, the triethyiamine, the diethylamine, the morpholine L pyrrolidine, piperidin, and used in catalytic quantity, it solid, the potash, alkaline alcoholates alkaline, amidures, `alkaline hydrides. 9. Proceeded according to claim 8, characterized in that the basic agent is ammonia. 10. Proceeded according to claim 8, characterized in that the basic agent is the triethylamine. 11. Proceeded according to any of claims 1 to 10, characterized in that the solvent or the mixture of solvents used is selected in the group consisted racetonitrile, the alcanols, and the mixtures of alcanol, and oil ether, in particular the mixtures of alcanol and pentane, hexane, or heptane. 3. 0 12. Proceeded according to claim 11, characterized in that the solvent or the mixture of solvents is selected in the group consisted the acetonitrile, the propanol the isopropanol, the butanols linear and ramified and by the mixtures of preceding alcohols with the gasoline G, the gasoline B, gasoline 0, the gasoline B, pentane, hexane or heptane. 13. Process according to the claim) of transformation of an ester of the 2,2-dimethyl acid 3R- (2,2-dibromovinyl) cyclopropane-1Rcarboxylique of alcohol a-cyano 3-phenoxy benzylic, optically active of structure (R) or racemic of structure (R, S) of formula (13): (B) (R) or (R, S) or of a mixture, in proportion not equimoleculaire, of 2,2-dimethyl 3R- (2,2-dibromovinyl) cyclopropane-1R-carboxylate of (R) a-cyano 3-phenoxybenzyle and 2,2-dimethyl 3R- (2,2-dibromovinyl) cyclopropane-1R-carboxylate of (S) a-cyano - 3-phenoxybenzyle, mixture indicated by “ester dibromo R S”, into 2,2-dimethyl 3R- (2,2-dibromovinyl) cyclopropane-1R-carboxylate of (S) a-cyano 3-phenoxybenzyle, characterized in that one subjects the optically active alcohol ester of structure (R), the racemic alcohol ester of structure (R, S), or the mixture says “ester dibromo R S ", previously definite, with the action of a basic, selected agent in the group consisted ammonia, the amines secondary, the tertiary amines, and the bases strong which, ellesisont used in catalytic quantity, within a solvent or from a mixture of solvents in which 2,2-dimethyl the 3R- (2,2-dibromovinyl) cyclopropane-1R-carboxylate of (S) a-cyano 3-phenoxybenzyle is insoluble, and in which 2,2-dimethyl the 3R- (2,2-dibromovinyl) cyclopropane-1R-carboxylate of (R) a-cyano-3-phenoxybenzyle is soluble, then isolates from the reactional medium alcohol ester of structure (S), thus rendered insoluble. 14. Proceeded according to claim 13, characterized in that the basic agent is selected in the group consisted ammonia, there triethylamine, la' diethylamine, the morpholine, pyrrolidine, piperidin, and used in catalytic quantity, the edlude, it: mug up, the alkaline alcoholates alkaline, amidures, the alkaline hydrides. 15. Proceeded according to the claim 14, characterized in that the basic agent is ammonia or the triethylamine. 16. Proceeded according to any of claims 13 to 15, characterized in that the solvent or mixed of solvents used is selected in the group made up parl' acetonitrile, the alcanols, - and the mixtures of alcanol and oil ether, in particular mixtures of alcanol and pentane, hexane or heptane. 17. Proceeded according to claim 16, characterized in that the solvent or the mixture of solvents used is selected-in the group consisted the acetonitrile, propanol, the isopropanol, the 1 5 butanols linear and ramified and by a mixture of preceding alcohols with the gasoline G, the gasoline B, the gasoline C, the gasoline E, pentane, hexane where heptane. 18. Proceeded according to claim 17, Characterized in that the solvent is the isopropanol. - 20 19. Process according to any of claims 13 to 18 of transformation from 2,2-dimethyl the 3117 (42-dibramovinyl) cyclopropane 1. R-carboxylate of (R) a-cyano 3-phenoxybenzyle in 2 -, 2-dimethyl 5R- (2,2-dibromoVinyl) cyelopropane-1R-Carboxylate of (8) - a-cyano 3-phenoxybenzyle; characterized in that one subjects the optically active alcohol ester of structure (R) k-l' action of a basic agent selected in the group consisted the amaoniaque one, secondary amines, the strong amineetertiaires, and bases which, they, are used in catalytic qmqntity, within a solvent chosen in it group-made up by llacetonitrile, the alcanols and the-mixtures of alcanol and oil ether, in particular mixtures of alcanol. and of pentane, - of hexane or heptane. 20. Proceeded according to claim 19, characterized in that the basic agent is ammonia or the triethylamine and solvent is the isopropanol. 21. Process according to one queIconque of claims 13 to 18 of transformation of 2,2-dimethyl 3R7 (2,2dibromovinyl) 1R-carboxylate cyclopropane - of (R, S) a-cyano 3-phenoxybenzyle into 2,2-dimethyl 3R- (2,2-dibromovinyl) cyclopropane-1R-carboxylate of (S) a-cyano 3. Phenoxybenzyle, characterized in that one subjects the racemic alcohol ester, with the action of a basic agent selected in the group consisted ammonia, the amines secondary, the tertiary amines, and the strong bases, which, they, are used in catalytic quantity, within a solvent chosen in the group consisted the acetonitrile, the alcanols and the mixtures of alcanol and oil ether in particular the mixtures of alcanol and pentane, hexane or heptane. 22. Proceeded according to revendidation 21, characterized in that the basic agent is ammonia or the triethylamine and solvent is the isopropanol. 23. Process according to any of claims 13 to 18 of transformation of a mixture into proportion not equimoleculaire of 2,2-dimethyl 3R- (42-dibromovinyl) cyclopropane-1R-carboxylate of (R) a-cyano 3-phencxybenzyle and 2,2-dimethyl 3R- (2,2-dibromovinyl) cyclopropane-1R-carboxylate of (S) a-cyano 3-phenoxybenzyle into 2,2-dimethyl 3R- (2,2-dibromovinyl) cyclopropane-1R-carboxylate of - (S) m-cyanO 3-phenoxybenzyle, characterized in that one subjects the mixture of esters to the action of a basic agent selected in the group consisted ammonia, the secondary amines, the tertiary amines and the bases strong which, they L are used in catalytic quantity, within a solvent chosen in the group consisted the acetonitrile, them alcanols, and them. mixtures of alcanol and oil ether, in particular mixtures 2 5 of alcanO1 and pentane, hexane or dlheptane. 24. Proceeded according to the claim 23, characterized in that the basic agent is ammonia or the triethylamine and solvent is the isopropanol. Process according to claim 1 of transformation of an ester of the 2,2-dimethyl acid 3R- (2,2-dichlorovinyl) carboxylic cyclopropane-1R 7. Of alcohol E. - cyano 3-phenoxy benzylic, optically active, of structure (R) or racemic of structure (R, S), of formula: H Cn (B) (R), (R, S) or of a mixture in proportion not equimoleculaire of 2,2-dimethyl 3R- (2,2-dichlorovinyl) cyclopropane-1R-carboxylate of (R) a-cyano 3-phenoxybenzyle and 2,2-dimethy1-3R- (2,2-dichlorovinyl) cyclopropane-1R-carboxylate of (S) u-cyano 3-phenoxybenzyle, mixture indicated by “ester dichloro R + 8”, 2,2-dimethyl 3R- (2,2-dichlorovinyl) cyclopropane-1R-carboxylate of (S) a-cyano 3-phenoxybenzyle, characterized in that one subjects the optically active alcohol ester of structure (R), ester-of the alcohol raceaique one (R, S) or the melangeA.it “ester dichloro R + S”, with the action of a basic agent selected in the group constituted by ammonia, the amines senondaires, the amines tertiary, and the strong bases which, ellea, are used in catalytic quantity, within a solvent or of a mixture of solvents - in which 2,2-dimethyl the 3R- (2,2-dichlorovinyl) cyclopropane-1R-carboxylate of (S) a-cyano 3-phenoxybenzyle is insoluble and in which 2,2-dimethyl the 3R- (2,2-dichloroviny1) cyclopropane-1R-carboxylate of (R) a-cyano 3-phenoxybenzyle is soluble, then isolates from the reactional medium alcohol ester of structure (S), thus rendered insoluble. 26. Proceeded according to claim 25, characterized in that the basic agent is selected in the group constitute par. ammonia, the triethylamine, the diethylamine, the morpholine, pyrrolidine, piperidin and used in catalytic quantity, soda, the potash, the alkaline alcoholates alkaline, amidures, alkaline hydrides. 2. 5 27. Proceeded according to claim 26, characterized in that the basic agent is ammonia or the triethylamine. 28. Proceeded according to any of claims 25 to 27, characterized in that the solvent or. the Mixture of solvents used/is selected /in the group consisted the acetonitrile, the alcanols, and the mixtures of alcanol and oil ether: in particular mixtures of alcanoi and pentane, hexane or heptane. 29. Proceeded according to claim 28, characterized in that the solvent or the-mixture of solvents used is selected in the group consisted the acetonitrile, propanol, the isopropanol, butanols tertiary and ramified, and by the mixtures of preceding alcohols with the gasoline G, the gasoline B, the gasoline C, the gasoline E, pentane, hexane or heptane. 30. Process according to. claim 25 of transformation of the 2,2dimethyl 3R- (2,2-dichlorOvinyl) cyclopropane-1R-carboxylate of (R) a-cyano 3-phenoxybenzyle into 2,2-dimethyl 3R- (2,2-dichlorovinyl) cyclopropane-1R-carboxylate of (S) a-cyano 3-phenaxybenzyle, characterized in that one subjects the alcohol ester cptiquement active of structure (R) to the action of a basic agent selected in the group consisted ammonia, the amines secondary, the tertiary amines, and the strong bases which, they, are used in catalytic quantity, within a solvent chosen in the group consisted the acetonitrile, the alcanols and the mixtures of alcanol and oil ether, in particular the mixtures of alcanol and pentane, of hexane or heptane. 31. Proceeded according to claim 30, characterized in that the basic agent is ammonia Or the triethylamine and solvent is the isopropanol. 32. Proceeded according to claim 25 of transformation of 2,2dimethyl 3R- (2,2-dichlorovinyl) cyclopropane-1R-carboxylate of (R, S) a-cyano 3-phenoxybenzyle into 2,2-dimethyl 3R- (2,2-diChlorovinyl) cyclopropane-1R-carboxylate of (S) a-cyano 3-phenoxybenzyle, characterized in that one subjects the racemic alcohol ester (R, S) with the action of a basic agent selected in the group consisted ammonia, the amines secondary, the tertiary amines, and the bases strong which, ellestsont used in catalytic quantity, within a selected organic solvent dana the group consisted the acetonitrile, the alcanols and the mixtures of Al boat and oil ether, in particular the mixtures of alcanol and pentane, hexane or heptane. 33. Proceeded according to claim 32, characterized in that the basic agent used is ammonia or the triethylamine and solvent used is the isopropanol. R uf 34. Proced' according to claim 25, of transformation of a proportion mixture not equimoleculaire of 2,2-dimethyl 3R- (2,2dichlorovinyl) cyclopropane-1R, - carboxylate of (R) a-cyano 3-phenoxy benzyl and of 2,2-dimethyl 3R- (2,2-dichlorovinyl) cyclopropane-1Rcarboxylate of (S) a-cyano 3-phenoxybenzyle, into 2,2-dimethyl 3R- (2,2-dichlorovinyl) cyclopropane-1R-car' boxylate of (S) cccyano 3-phenoxybenzyle, mixture indicated parftester dichloro R + S ", characterized in that one subjects it - mixture of esters to the action of a basic agent selected in the group consisted ammonia secondary amines, the strong amines.tertiaires, and bases which, they, are used in catalytic quantity, within an organic solvent - chosen in the group consisted the acetonitrile, alcanols, and breadths mixtures of aloanol and oil ether, in particular mixtures of alcanol, pentane, hexane, or heptane. - 35. Proceeded according to the claim 34, characterized in that ragent basic is ammonia or the triethylamine and the solvent are the isopropanol.
法律状态
(FR2375161) LEGAL DETAILS FOR FR2375161  Actual or expected expiration date=1996-04-23    Legal state=DEAD    Status=EXPIRED     Event publication date=1976-04-23  Event code=FR/APP  Event indicator=Pos  Event type=Examination events  Application details  Application country=FR FR7612094  Application date=1976-04-23  Standardized application number=1976FR-0012094     Event publication date=1978-07-21  Event code=FR/A1  Event type=Examination events  Application for patent of invention, (first publ.)  Publication country=FR  Publication number=FR2375161  Publication stage Code=A1  Publication date=1978-07-21  Standardized publication number=FR2375161     Event publication date=1979-04-13  Event code=FR/B1  Event indicator=Pos  Event type=Event indicating In Force  Patent of invention (second publication)  Publication country=FR  Publication number=FR2375161  Publication stage Code=B1  Publication date=1979-04-13  Standardized publication number=FR2375161     Event publication date=1989-06-02  Event code=FR/CL  Event type=License agreements  Event type=LICT  Concession to grant licences Concession de licence    Event publication date=1992-09-04  Event code=FR/CC  Event type=Extension of term of duration of protection  Supplementary certificate of protection laid open to the public (law of 25 june 1990) Demande de certificat complementaire de protection rendu publique (loi du 25 juin 1990) 92C0305, 920526     Event publication date=1992-10-23  Event code=FR/CB  Event type=Extension of term of duration of protection  Supplementary certificate of protection granted (law of 25 june 1990) Demande de certificat complementaire de protection delivre (loi du 25 juin 1990) 92C0305, 760423     Event publication date=1993-04-23  Event code=FR/CL  Event type=License agreements  Event type=LICT  Concession to grant licences Concession de licence    Event publication date=1996-01-05  Event code=FR/CD  Event type=Change of name or address  Event type=Reassignment  Change of name or company name Changement de nom de denomination    Event publication date=1996-01-05  Event code=FR/CA  Event type=Change of name or address  Change of address Changement d'addresse    Event publication date=1996-04-23  Event code=FR/EEDX  Event indicator=Neg  Event type=Event indicating Not In Force  Patent has expired    Event publication date=1998-04-17  Event code=FR/TP  Event type=Change of name or address  Event type=Reassignment  Transmission of property Transmission de propriete    Event publication date=1998-05-22  Event code=FR/TP  Event type=Change of name or address  Event type=Reassignment  Transmission of property Transmission de propriete CORRECTION
专利类型码
A1B1
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