30 



T. F. Gallagher 



to the hormones we wished to prepare. The platinum- 

 catalysed exchange reaction first studied in sterols by Bloch 

 and Rittenberg seemed to offer the means for this end. It 

 was found that, with suitable compounds, the incorporation 

 of isotope was satisfactory and the yield was good. The best 

 yields were obtained with unsaturated ketones of the type 

 exemplified by androst-4-ene-3:17-dione. This compound 

 upon heating in 70 per cent deuterated acetic acid and 



OH 



dz- !I,I2 TESTOSTERONE 



CH3 

 I 



c=o 



o?^ 



CH. 

 I 



c=o 



^.^ 



,^^.AJ 



d2- 11,12 PROGESTERONE 



HO 



CH3 



I 



c = o 



dz-M,I2 ETIOCHOLANOLONE 



CHzOAc 

 I 



c=o 



rs^ j^ .^:" 



17* - HYDROXY- 

 d2- 11,12 PROGESTERONE 



d2- 11,12 



Substonce "s" ocetote 



Fig. 1. Steroid hormones and metabolites prepared from 



d2-ll,12-pregnanolone. 



deuterium oxide in the presence of an active catalyst was 

 recovered in over 90 per cent yield with approximately 2 • 5 

 atoms per cent excess deuterium. Similar results were 

 obtained with other ketones. The reaction thus constitutes 

 an excellent preparative procedure for certain compounds 

 closely related to the steroid hormones. The synthesis of 

 deuterium testosterone from androst-4-ene-3:17-dione labelled 

 by exchange is shown in Fig. 2. The results obtained in the 

 catalysed exchange with cestrone are illustrated in Fig. 3. 

 The incorporation of radioactive tritium into steroid hormones 



