Steroid TransformafJons 



133 



shown by chemical studies to have a 6p-hydroxyl group 

 present. The position of the second hydroxyl group was 

 shown to be 11a when known 1 1 a-hydroxyprogesterone 

 (XII) was incubated with a mold, Cunninghamella 



Mucorales 

 Aspergillus 



CH, 

 I 

 0=0 



CH3 

 c=o 



v^l 



Zip 



Cunninghamella ^ O'^'^^^^^'^^ 

 blakesleeana OH 



XII XXXVII 



lla-Hydroxyprogesterone g^, lla-Dihydroxy 



progesterone 

 CH3 



c=o ^^ 



Penicillium 



(Mucor) O 



XXXVIII 

 14a-Hydroxyprogestcrone 



lilacinum Thoni. O^""^"^^ 



OH 



XXXIX 



14a-Kydroxyandro- 



stenedione 



blakesleeana. The resulting compound was identical in all 

 respects to the dihydroxy-compound isolated from the 

 fermentation of progesterone, thus unequivocally proving 

 the structure as indicated in formula XXXVII. 



In a second case, the structure (16) of 14a-hydroxy- 

 progesterone (XXXVIII), obtained by incubation of pro- 

 gesterone with the Mucorales, was determined by oxidiz- 

 ing the side chain of compound XXXVIII with Penicillium 

 lilacinum Thom. The resulting compound is the known 

 14a-hydroxy-4-androstene-3,17-dione (XXXIX). The struc- 

 ture proof of this steroid by chemical means would be ex- 

 tremely laborious and difficult. 



Summary 



In summary, major emphasis has been placed upon the 

 facile and economical preparation of biologically interest- 

 ing steroids. Cortisone, hydrocortisone, estrone, and testo- 

 sterone, compounds which are ordinarily formed by mam- 



