37615-53-5

Two primary amines, 1-hexylamine 2, 1-dodecylamine 19, one secondary amine, di-1-hexylamine 18, and three tertiary amines, N,N-dimethyl-1-hexylamine 6, N,N-dimethyl-1-butylamine 3, and N,N-dimethyl-1-dodecylamine 22 were each heated at 150°C, 250°C or 350°C with 49% aqueous formic acid for varying periods of time. The aliphatic primary amines underwent easy N-formylation and subsequent reduction to give N-methyl- and N,N-dimethylalkylamines. Especially at higher temperatures, other reactions intervened including elimination of NH3 to the corresponding alkenes followed by partial double bond isomerization. Tertiary amines were more reactive at higher temperatures undergoing hydrolysis and reductive cleavages to secondary and primary amines, which subsequently followed the reaction sequences seen for primary amines. This series of saturated amines showed none of the cleavage into smaller fragments that was observed in the reductive alkylation of pyridine and 4-methylpyridine to a series of N-alkylpiperdines. This result reinforces the bis-aza-retro-Aldol-fragmentation mechanism postulated for the formation of the N-alkylpiperidines. Johann Ambrosius Barth 1997.

N-Methyl and N,N-dimethylalkylamines are converted into N-methyldialkylamines in good yields when heated at 180 deg C in the presence of a catalytic amount of RuCl2(Ph3P)3.

N,N-dimethylalkyl- or N,N-dialkylmethyl-amines are selectively obtained from the reaction between aliphatic amines and methanol at 180 deg C for 7 h in the presence of RuCl2(Ph3P)3 catalyst.