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Herstellung von Dihydro‐, Tetrahydro‐ und Hexahydrochelidamsäure‐Derivaten

 

作者: Kurt Hermann,   André S. Dreiding,  

 

期刊: Helvetica Chimica Acta  (WILEY Available online 1976)
卷期: Volume 59, issue 2  

页码: 626-642

 

ISSN:0018-019X

 

年代: 1976

 

DOI:10.1002/hlca.19760590227

 

出版商: WILEY‐VCH Verlag GmbH

 

数据来源: WILEY

 

摘要:

Preparation of dihydro‐, tetrahydro‐ and hexahydro‐chelidamic‐acid derivatives.Three methods for the preparation of 4‐oxo‐2,6‐piperidine‐dicarboxylic acid (3) and derivatives, required as a synthon for betalaine pigments, were explored.The best method was found to be the catalytic hydrogenation of chclidamic acid (1) with 5% Rh/Alox in water under 2.7 atm. H2for 33 h at 70° and subsequent esterification with methanol which gave 42% ofcis,cis‐4‐hydroxy‐2,6‐piperidine‐ (7) and 10% of 2,6‐cis‐piperidine‐dicarboxylic acid dimethyl ester (8), readily separable by chromatography. Oxidation of7with dimethylsulfoxide and a carbodiimide attached to a polymer afforded 90% of 4‐oxo‐2,6‐cis‐piperidine‐dicarboxylic acid dimethyl ester (19). Other methods of oxydizing7to19were less successful.The electrochemical reduction of1followed by esterification with methanol led in a low yield to a mixture of 4‐oxo‐0‐2,6‐trans‐piperidine‐dicarboxylic acid dimethylester (24), its dimethyl acetal25and presumablytrans‐4‐hydroxy‐r‐2,cis‐6‐piperidine‐dicarboxylic acid dimethyl ester (26).Reaction of 4‐oxo‐hepta‐2E, 5E‐dienoic acid (35) with aqueous ammonia gave a 98% yield of a 3 : 2 mixture ofcis‐ andtrans‐ammonium‐4‐oxo‐2, 6‐piperidine‐dicarboxylate (39and40).The above mentioned catalytic hydrogenation method was also applied to N‐ethyl‐chelidamic acid (16) to give a 4:6 mixture of the N‐ethyl derivatives17and18. Furthermore, a number of functional derivatives of5, of19, of39and of40were prepared.Oxidation of the hydroxy‐diester7with dimethylsulfoxide and a carbodiimidc derivative in the presence of trifluoroacetic acid afforded 4‐oxo‐1,2,3,4‐tetrahydro‐2, 6‐pyridine‐dicarbo

 

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