Abstract
Syntheses of DL-2-piperidinemethanol (XXXIII) and meso-cis-2, 6-piperidinedimethanol (XXXIV) were accomplished through a few steps from 2-picoline (I) and 2, 6-lutidine (II) respectively. The configuration of XXXIV was confirmed. The following reactions of synthetic intermediates were also examined. 6-Methylpicolinaldehyde (IX) was obtained by acetolysis followed by hydrolysis from 2-bromomethyl-6-methylpyridine 1-oxide (X) through α-bromo-6-methyl-2-pyridinemethanol acetate (XIV) in a yield, 16.2% and from 2-ethylthiomethyl-6-methylpyridine 1-oxide (XII) through α-ethylthio-6-methyl-2-pyridinemethanol acetate (XVII) in a yield, 84.2%. Unusually enough, alkaline treatment at room temperature converted 2-bromomethylpyridine 1-oxide (XIX) to 2, 2'-oxydimethyldipyridine 1, 1'-dioxide (XXVI) in a yield as high as 88.3%. The ether formation was found in the same treatment of analogues.
