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A 1 H NMR anomaly for steroidal alcohols? Reactions of a steroidal γ‐ketoacid
Author(s) -
Piatak David M.,
Ashline Kirk A.,
Angelos George,
Swenson Rebecca P.,
Caspi Eliahu
Publication year - 1982
Publication title -
lipids
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.601
H-Index - 120
eISSN - 1558-9307
pISSN - 0024-4201
DOI - 10.1007/bf02535110
Subject(s) - chemistry , methylene , hydrolysis , diol , nmr spectra database , singlet state , epimer , proton nmr , nuclear magnetic resonance spectroscopy , medicinal chemistry , stereochemistry , organic chemistry , spectral line , excited state , physics , astronomy , nuclear physics
The chemical and spectroscopic properties of several reaction products of 17β‐hydroxy‐1,3‐seco‐2‐nor‐5α‐estran‐1‐oic acid and 17β‐hydroxy‐1,3‐seco‐2‐nor‐4‐oxo‐5α‐estran‐1‐oic acid were examined and found to be atypical. For instance, the methyl ester of the first acid was resistant to basic hydrolysis conditions but partly hydrolyzed with 100% H 2 SO 4 . Reduction of the ester by LiA1H 4 gave 1,3‐seco‐2‐nor‐5α‐estrane‐1,17β‐diol from which diacetate, ditosylate and 17‐monotosylate derivatives were prepared. The C‐1 methylene protons of each appeared as a singlet in 60, 100 and/or 270 MHz NMR spectra. The methyl ester and the diacetate of the diol were synthesized by alternate methods to verify the assigned structures. A 470‐MHz spectrum eventually resolved the C‐1 methylene protons of the monotysylate into the AB portion of an ABX pattern, further confirming the assigned structures. Also, 2,3‐seco‐1‐oxo‐5α‐estran‐17β‐ol 17‐nitrate was synthesized.