Digitoxigenin-3-alkyl ethers

The synthesis of the title compounds was accomplished by (i) boron trifluoride etherate catalysed alkylation of digitoxigenin with diazoalkanes, (ii) silver tetrafluoroborate assisted solvolysis of 3-desoxy-3α-iododigitoxigen 2 d in an alcoholic medium, and (iii) m-chloroperbenzoic acid induced oxidative solvolytic displacement on the iodo compound 2 d in the presence of alcohols. The third process was the most useful for the preparation of the mono ethers 2 e and 2 f of ethylene glycol and glycerol, respectively.