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Untersuchungen über Steroide XLI. Umwandlungsprodukte des 17α‐Strophanthidins
Author(s) -
Manzetti Aldo,
Ehrenstein Maximilian
Publication year - 1969
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19690520215
Subject(s) - chemistry , thionyl chloride , hydrochloric acid , pyridine , hydrolysis , chloride , medicinal chemistry , organic chemistry
Pseudostrophanthidin ( 2 ) can be easily prepared by treating strophanthidin ( 1 ) with concentrated hydrochloric acid in the cold [1]. 2 has served as the initial product for the preparation of a number of analogues and homologues of steroid hormones [2] [3]. 17α‐Pseudostrophanthidin ( 4 ) is considered a suitable starting material for an extension of these investigations. It was logical to attempt the preparation of 4 from 17α‐strophanthidin ( 3 ) under conditions identical with those used in the conversion of 1 into 2. However, these experiments did not lead to 4 but, instead, by way of the unstable 14ξ‐chloro‐14‐deoxy‐17α‐strophanthidin ( 5 ) to 14‐anhydro‐17α‐strophanthidin ( 6 ). This result is essentially in agreement with findings reported in the literature [5]. To support the structure assigned to 6 , this compound was also prepared by a different, unambiguous, route. Treatment of 3 with thionyl chloride in pyridine gave mainly 3β, 5β‐O, Osulfinyl‐14‐anhydro‐17α‐strophanthidin ( 8 ), which was converted into 6 by mild hydrolysis. In turn 6 , as obtained via the unstable chloro compound 5 , gave on treatment with thionyl chloride in pyridine a product identical with 8. – 6 was characterized as the 3‐acetate 7 . As extension of these experiments, 17α‐strophanthidol ( 10 ) [6] was treated with concentrated hydrochloric acid in the cold under conditions similar to those used in the conversion of 3 into 6 by way of 5. This led to the isolation of 14‐anhydro‐17α‐strophanthidol ( 11 ), which could also be obtained by the reduction of 6 with aluminium amalgam. As is known [1] [8], strophanthidinic acid ( 13 ) can be converted into strophanthidinic acid 19,8‐lactone ( 14 ) by treatment with concentrated hydrochloric acid in the cold. In view of the negative results obtained in the attempt to transform 3 into 4 under these conditions, the question arose as to whether the conversion of 17α‐strophanthidinic acid ( 15 ) into 17α‐strophanthidinic acid 19,8‐lactone ( 16 ) by the same procedure is also impossible. 15 was prepared by treating 3 with hydrogen peroxide and was characterized as the methyl ester 17 and the methyl ester of the 3‐benzoate ( 18 ). 15 and 17 have been mentioned in the literature [5], but the physical constants reported differ from those obtained in this laboratory. It was demonstrated that after treating 15 with concentrated hydrochloric acid in the cold, no 16 could be isolated but, instead, an unstable chloro compound 19 which was converted into 14‐anhydro‐17α‐strophanthidinic acid ( 20 ). 20 was characterized as the methyl ester 21 and the 3‐acetate 22 .