Erich Röhm

Über 5-Hydroxymethyl-cytidin und 5-Hydroxymethyl-cytosin-N-3-β-D-glucopyranosid sowie über reaktionsfähige Vorstufen

5-Benzyloxymethyl-NNH2-benzoyl-cytosine (4) is formed from 5-hydroxymethyl-cytosine (1) in 80% yield by benzylation and subsequent benzoylation. The benzylation readily takes place with benzyl alcohol and catalytic amounts of hydrochloric acid in tetrahydrothiophen-1.1-dioxide as solvent. — 4 is quantitatively converted in pyridine at room temperature to a toluene soluble mercury (II) salt 5. 5 condenses easily with 2.3.5-tribenzoyl-D-ribofuranosyl chloride to give the β-nucleoside 6, no a-anomer being found. — The removal of all protecting groups by catalytic hydrogenation and treatment with sodium methoxide or ammonia leads to cristalline 5-hydroxymethyl cytidine 10 (ca. 60% yields based on 1). — In an analogous manner N-3-β-D-glucosyl-5-hydroxymethyl-cytosine 15 is prepared. — Selective removal of certain of the protecting groups in 6 and 11 yields potentially valuable synthetic intermediates.