Reaction of Aliphatic Amines with 49% Formic Acid. 1-Hexylamine, di-1-hexylamine,N,N-dimethyl-1-hexylamine, 1-dodecylamine,N,N-dimethyl-1-dodecylamine andN,N-dimethyl-1-butylamine

Abstract

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.

Selenium‐Containing Heterocycles From Isoselenocyanates: Synthesis of1,3‐Selenazolidine and Perhydro‐1,3‐selenazine Derivatives

“…[34a] Formanilide and N-cyclohexylformamide are commercially available (Fluka and Aldrich), N-(4-chlorophenyl)-, N-(4-bromophenyl)-, and N-(4-methoxyphenyl)formamide were prepared from the corresponding anilines and 95 % formic acid by a slightly modified literature protocol: [60] the solution was heated to reflux for 30 min and the solvents were evaporated to dryness in vacuo. The residue was dissolved in Et 2 O and washed with dilute AcOH (5 %), H 2 O, and aqueous NaHCO 3 (5 % aq.).…”

Enzymatic synthesis of 2,5-furandicarboxylic acid-based semi-aromatic polyamides: enzymatic polymerization kinetics, effect of diamine chain length and thermal properties

“…The acid end group was produced by a N435-catalyzed hydrolysis of esters during the polymerization; 31,41 and the formation of the amide end group was due to the reaction between the amine groups and formic acid at the purication step. 31,41,56 Thermal properties of the obtained FDCA-based semiaromatic polyamides…”

Radical Addition to Isonitriles: A Route to Polyfunctionalized Alkenes through a Novel Three-Component Radical Cascade Reaction

“…Diphenyl disulfide (1a), 4-methoxythiophenol, 4-chlorothiophenol, 4-hydroxybenzonitrile, p-anisidine, n-dodecylamine, phenylacetylene (2), tert-butyl isonitrile ( 14), trimethylsilylacetylene ( 17 benzonitrile (1b), 33 bis(4-methoxyphenyl) disulfide (1c), 34 and bis(4-chlorophenyl) disulfide (1d) 35 were prepared according to the literature. N-(4-Methoxyphenyl)formamide 36 and N-ndodecylformamide 37 were synthesized from the corresponding amines by treatment with boiling formic acid. 36 4-Methoxyphenyl isonitrile (3) 38 and n-dodecyl isonitrile (24) 39 were prepared from the corresponding formamides by reaction with diisopropylamine and phosphorus oxychloride in dichloromethane.…”