ISSN:
0941-1216
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
New Products by Ring Expansions of Solid 17-Hydroxy-20-ketosteroids with Gaseous Hydrochloric AcidGaseous hydrogen chloride reacts directly with crystalline 17-hydroxy-20-ketosteroids like 17α-hydroxy-progesterones (1, 5, 6, 8) to give enlargement of ring D. In addition to the known acyloine rearrangement, new reaction types are observed which give rise to the products of substitutive rearrangement with elimination of water, 16β-Chloro-(3) and 16α-chloro-16β-methyl-17-oxo-D-homosteroids (7, 9) are formed stereoselectively. The drying agent magnesium sulfate may keep the reaction products solid. Mechanistic proof is provided spectroscopically (IR) and by the isolation of 17aβ-hydroxy-17aα-methyl-D-homoandrost-4-ene-3,17-dione (2) and its conversion to 16β-chloro-17aβ-methyl-D-homoandrost-4-ene-3,17-dione (3) with gaseous hydrogen chloride. The new reaction types do not occur in solution.
Additional Material:
1 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/prac.19943360808
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