Lactams. VII. Stereochemical Characterization and Cis-Trans Isomerization of 5-Ethyl-2-oxo-4-piperidineacetic Acid and Related Compounds

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• The stereochemistry of pairs of isomers found for 5-ethyl-2-oxo-4-piperidineacetic acid (I) and its derivatives [methyl ester (II), ethyl ester (III), and 1-benzyl derivative (IX)] has been established by interrelation of I with cincholoipon ethyl ester [(+)-VIIb], derived from the alkaloid cinchonine, through 3-ethyl-4-piperidineethanol (IV). trans-Acid IXa has been prepared by benzylation of trans-lactam ester IIIa and subsequent alkaline hydrolysis of the N-benzylated product (XIa) ; cis-acid IXb, by the alkaline hydrolysis of lactam ester Xb obtained from lactim ether VIIIb by the reaction with benzyl bromide. The lactim ether (VIIIb) has been synthesized from cis-lactam ester IIb the methylation with dimethyl sulfate in boiling benzene. It has been found that on thermal treatment at 180° either cis-acid IXb or trans-acid IXa is partially isomerized to give an equilibrated 67 : 33 mixture of IXa and IXb in 50 min. Under the same conditions the N-unsubstituted trans-acid (Ia) attains to an equilibrium faster than IXa, resulting in 33% conversion into Ib in 8 min. At 210° cis-acid Ib undergoes isomerization very rapidly to produce an equilibrated mixture of the same composition. In boiling 6 N hydrochloric acid either IXa or IXb gives an equilibrated 57 : 28 : 15 mixture of IXa, IXb, and the ring-opened product (XIII, R=C_6H_5CH_2) within 28 hr. In contrast, the methyl esters (IIa, b, Xa, b) of these acids have been found not to suffer such a cis-trans isomerization at 180° over a period of at least 1 hr. On the basis of these findings, mechanisms of the observed isomerizations are discussed.

• 社団法人日本薬学会の論文
• 1975-09-25

著者

• 吉藤 茂行

  Faculty of Pharmaceutical Sciences, Hokuriku University

• 藤井 澄三

  Faculty Of Pharmaceutical Sciences Kanazawa University

• 吉藤 茂行

  Faculty Of Pharmaceutical Sciences Of Hokuriku University

• 田井 賢

  Faculty Of Pharmaceutical Sciences Kanazawa University

• Yoshifuji Shigeyuki

  Faculty Of Pharmaceutical Sciences Of Hokuriku University

• 吉藤 茂行

  Faculty Of Pharmaceutical Sciences Hokuriku University

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