Heterocyclic steroids. X. 2-Aza-4-oxa-steroid analogs

Two 2-aza-4-oxa steroids have been synthesized from acid Ia. In addition the Beckmann rearrangement of the C-1 amide Ij has been explored.     

Novel synthesis of 2-isoxazolyl steroids

Novel examples of the reaction of 20-hydroxy-20-isoxazolinyl steroids to 20-isoxazolyl steroids using acetic acid in the presence of hydrobromic acid are reported. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 759–761, May, 2007.     

Translational energy release and stereochemistry of steroids. 14. Epimeric dihydroxy steroids of the androstane series

The stereochemistry of dihydroxy steroids, both the mode of the A/B ring junctions and the configuration of OH groups, may be determined from translational energy (T50%) measurements for the loss of a CH.3 radical, from the ratios of metastable-ion peak heights to those of the main beam (determined for the dehydration reactions), and by comparing unimolecular and collision-induced, mass-analysed ion kinetic energy spectra of the new main beam of [M-H2O]+ ions (i.e. those formed via dehydration of metastable molecular ions of epimeric hydroxy steroids in the first field-free region of a double-focusing mass spectrometer.     

Analysis of steroids. XVI

Summary ⁴-3-Hydroxy- or -acetoxysteroids can be determined as 3,5-dienes by spectrophotometry at 236 nm. This method has been employed for the determination of ethynodiol in contraceptive pills. Possible interferences by co-extracted foreign substances have been prevented by differential spectrophotometry. A combination of this method with the reduction by means of sodium borohydride made possible a determination of ⁴-3-ketosteroid contamination in norethynodrel.

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Analyse von Steroiden. XVI

Zusammenfassung ⁴-3-Hydroxy- oder Acetoxysteroide können in Form von 3,5-Dienen spektrophotometrisch bei 236 nm bestimmt werden. Das Verfahren wurde zur Bestimmung von Ethynodiol in Anticoncipientia verwendet, wobei Störungen durch mitextrahierte Fremdsubstanzen durch Differentialspektrophotometrie verhindert wurden. Durch Kombination dieser Methode mit der Reduktion durch Natriumborhydrid konnte eine Verunreinigung von ⁴-3-Ketosteroid in Norethynodrel bestimmt werden.

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Part of the lecture Differential Spectrophotometry in Pharmaceutical Analysis presented to the F.I.P. Congress, London, September, 1969. Part XV.: Mikrochim. Acta (in press).

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The authors thank Mrs. G. Berhidai, Miss M. Kapàs and Miss J. Sütö for their technical assistance.