Yukinari Kumazawa

Synthesis of the 1-N-Oxides and 1-Methoxy and N6-Methoxy Derivatives of 2-Deuterioadenines Substituted or Unsubstituted at the 9-Position

Peracid oxidations of adenine-2-d (1a) and its 9-substituted derivatives (1e) produced the corresponding 1-N-oxides (3e) in fair yields. Methylations of 9-methyl- (3b) and 9-benzyladenine-2-d 1-oxide (3e) with MeI in AcNMe 2 afforded the corresponding 1-methoxy derivatives 5b,d and 11e in good yields. Dimroth rearrangement of 5b, 5d, and 11e gave the N 6 -isomers 9b, and 9e, but their isotopic purities were unsatisfactory. Unambiguous assignments of the purine-ring proton signals in the nmr spectra of the unlabeled adenines (4e, 6b,d, and 12e) have been made by comparison with those of the labeled species (3e, 5b,d, and 11e)