INVESTIGATIONS ON STEROIDS. IV. NEW DEGRADATION PRODUCTS OF CHOLIC ACID AND STUDIES ON THE SYNTHESIS OF 7,12-DIHYDROXYPROGESTERONE¹

INVESTIGATIONS ON STEROIDS. X. REVISION OF NOMENCLATURE OF PREVIOUSLY DESCRIBED COMPOUNDS1

“…He presented convincing evidence that the monoacetoxy compound present in the resulting mixture of reaction products is methyl 3(a), 12(a)-dihydroxy-7(a)acetoxyetiocholanate. In a paper dealing with some degradation products of cholic acid (19) we described the partial saponification of 3(a), 7(a), 12(a)triacetoxypregnane-20-one which yielded a monoacetoxy compound interpreted to be 12(a)-acetoxypregnane-3(a), 7(a)-diol-20-one. The identical substance was subsequently described by others (20).…”

“…The identical substance was subsequently described by others (20). On account of his findings in connection with the partial hydrolysis of methyl 3(a), 7(a), 12(a)-triacetoxyetiocholanate Lardón (18) presumes that the 12-acetoxypregnane-3(a), 7(a)diol-20-one described by us (19) and Miescher ( 20) is in reality 7(a)-acetoxypregnane-3(a), 12(a)-diol-20-one. This assumption is probably correct and hence the product of the oxidation of the latter compound with chromic acid (19) should be called 7(a)-acetoxypregnane-3,12,20-trione rather than 12(a)acetoxypregnane-3,7,20-trione.…”

“…On account of his findings in connection with the partial hydrolysis of methyl 3(a), 7(a), 12(a)-triacetoxyetiocholanate Lardón (18) presumes that the 12-acetoxypregnane-3(a), 7(a)diol-20-one described by us (19) and Miescher ( 20) is in reality 7(a)-acetoxypregnane-3(a), 12(a)-diol-20-one. This assumption is probably correct and hence the product of the oxidation of the latter compound with chromic acid (19) should be called 7(a)-acetoxypregnane-3,12,20-trione rather than 12(a)acetoxypregnane-3,7,20-trione. In like manner the product of the partial dehydrogenation of the compound by means of the Oppenauer method (19) should be named 7(a)-acetoxypregnane-12(a)-ol-3,20-dione rather than 12(a)acetoxypregnane-7(a)-ol-3,20-dione.…”

“…This assumption is probably correct and hence the product of the oxidation of the latter compound with chromic acid (19) should be called 7(a)-acetoxypregnane-3,12,20-trione rather than 12(a)acetoxypregnane-3,7,20-trione. In like manner the product of the partial dehydrogenation of the compound by means of the Oppenauer method (19) should be named 7(a)-acetoxypregnane-12(a)-ol-3,20-dione rather than 12(a)acetoxypregnane-7(a)-ol-3,20-dione.…”

Synthesis of Steroids of the Progesterone Series.

“…The physiological activity of 6-dehydroprogesterone (LXXXVII) is about one-third to one-half that of progesterone. The diacetate of 7(a), 12(a)-dihydroxyprogesterone (XCIV) was prepared by Ehrenstein and Stevens (9,11) by a procedure starting with cholic acid (LXXXVIII). A side-chain degradation involving many steps yielded 3(a), 7(a), 12(a)-triacetoxypregnan-20-one (LXXXIX), a compound which is now much more easily available by means of Miescher's new degradation method (27, 28).…”