Excerp
The convenient method due to Sommelet and Ferrand [1] for the preparation of trimethylamine from ammonium formate, formaldehyde and formic acid, though its usefulness has recently been demonstrated
[2]in the case of anabasine, appears not to have attained general recognition as a means for the methylation of amines.
This process furnishes excellent yields of tertiary bases from simple primary and secondary aliphatic amines, including piperidine. Its ready applicability is illustrated by the complete methylation of tetramethylenediamine, the hydrochloride of which is extensively decomposed by heating at 125° with aqueous formaldehyde,
[3] and yields the tetramethyl derivative only when heated to 200° with dry paraformaldehyde. [4]
The reaction appears to be specific for formaldehyde, in contrast to its homologs, which apparently require higher temperatures [5] for corresponding changes to take place. Thus, a mixture of acetaldehyde, formic acid and ammonium formate yielded no carbon dioxide on heating on the steam-bath, and from the resulting bases only 2-methyl-5-ethylpyridine could be isolated. The reaction also fails with compounds which strongly polar groups are attached to nitrogen, such as amides,urea, guanidine and hydroxylamine; these appear to yield hydroxymethyl derivatives only.
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