Transformed steroids. 123. Synthesis of 5α(H)- and 5α(OH)-6-ketosteroids with an additional 17α,20ξ-dihydroxytetrahydropyran ring E
The paper is devoted to the synthesis of 3,17α,20-trihydroxy-16β,23-epoxy-21,24-dinor-5αH-cholan-6-one and 3,5α,17α,20-tetrahydroxy-16β,23-epoxy-21,24-dinorcholan-6-one and derivatives of them. It has been shown that the reduction of 3,17α-dihydroxy-16β,23-epoxy-21,24-dinorchol-5-en-20-one with sodium tetrahydroborate and with diborane takes place stereospecifically with different spatial directivities: in the products of diborane reduction, ring E exists in the boat form, as has been shown by1H and13C NMR methods. The trans linkage of rings A/B in the modified steroids has been confirmed by their circular dichroism spectra.
3,7-disubstituted bicyclo[3.3.1]nonanes—III: Synthesis and conformation of bicyclo[3.3.1]nonane-3α,7α-dicarboxylic acid, its dimethyl ester and some other 3,7-disubstituted bicyclo[3.3.1]nonanes; adamantane as an integrated holding system
Abstract The conformation of bicyclo[3.3.1]nonane-3α,7α-dicarboxylic acid and its dimethyl ester has been studied by comparing 1 H NMR and 13 C NMR spectra of these compounds with those of some model 3,7-disubstituted bicyclo[3.3.1]nonanes, fixed in a single conformation by the use of adamantane as an integrated holding group or by means of suitable substitution. It is shown that the dicarboxylic acid and its dimethyl ester exist predominantly as two rapidly interconverting (identical) chair-boat conformations with distinctly flattened rings; the population of the double-boat conformation appears to be very small.
A study of the local tissue reactions in man to cortisone and compound F. VI. Histopathological studies of the local effect of compound F in normal and pathologic skin of man.
After our previous negative studies (1) of the local effect of cortisone acetate in the skin of man, a year ago, a parallel study of 17-hydroxycorticosterone-21-acetate, Compound F, was outlined. Theoretically, Compound F should be the active steroid. It was so suggested by Rothman (2), that in all probability Compound F and not cortisone would be active locally in the skin of man.