Nitrogen derivatives (Amides, diamides, nitriles, primary amines and oxides)

Abstract

Without a doubt the nitrogen derivatives are the most broadly diversified family of fatty acid derivatives. Today they account collectively for perhaps 400 million pounds of products per year in the USA alone. Although fatty amides may be produced by a large number of synthetic routes, industrially only two are of any commercial importance. Diamides are the difunctional analogs of simple amides, and a typical one that is in medium scale production volume is ethylene bis(stearamide). Industrially, the production of fatty nitriles in the fatty acid derivative industry is exclusively by ammonolysis of fatty acids at temperatures somewhat above those required to produce amides, or roughly, 300–320 C. Both vapor phase catalytic and liquid phase ammonolysis processes may be employed. Nitriles have limited uses as such, but find their utility as fatty derivative intermediates only. The primary amines, RNH2, are produced industrially by the catalytic hydrogenation of nitriles. The general conditions for the conversion of nitriles to primary amines with a minimum content of secondary or tertiary amines is with nickel catalyst using an excess of ammonia at relatively low temperatures (130–140 C). Amine oxides are derived from tertiary amines by a controlled reaction with hydrogen peroxide. In addition to tertiary amines, the monoalkyl diethoxylated amines can be considered as in the same class. These are made by the addition of ethylene oxide to primary amine. Two moles of ethylene oxide can be added without catalyst. Additional ethoxylation does require a basic catalyst. These amines, besides having end uses of their own, can be converted to amine oxides or can be converted to ethoxylated quaternary ammonium salts.

N,N′‐ethylenediyl‐bis‐alkanamides: Differential scanning calorimetry studies

“…However, its temperature increased as the chainlength increased. This is in keeping with most observations made on fatty acids and their derivatives (16)(17)(18)(19)(20)(21)24,25). This endotherm may represent a phase change, which in turn might indicate that the compounds are liquid crystals (10).…”

“…The melting points (second endotherms in Table 1) of the long-chain symmetrical bis-alkanamides of EDA decreased from 166.3~ (C 9 alkanoyl) to 143.4~ (C20 a!kanoyl) as the carbon chainlength and the RMM increased. This was another paradoxical observation that would not be expected from the melting points of the saturated straight-chain fatty acids (17), fatty acid methyl esters (18), fatty acid esters of glycerol (19), fatty acid amines (21), and most of their other derivatives, which all increase with increasing chainlength. However, similar depressions of melting temperatures with increasing carbon number have been reported for the 2-alkyl- benzimidazoles (22) and the bis-amides of 4,4'-diaminodiphenylmethane (23).…”

Pyrolytic Fractionation: A Promising Thermochemical Technique for Processing Oleaginous (Algal) Biomass

“…samples pyrolyzed at 420 °C. It is possible that N-derivatives of fatty acids were formed as a result of reactions of the free fatty acids (produced in this step due to breakdown of triglycerides) with polymerized (charred) proteins from the previous pyrolysis step . Since fatty nitriles have been considered as fuel additives to improve lubricating properties, − the presence of these compounds at low concentrations may, in fact, enhance the fuel value of triglyceride-derived bio-oil from pyrolytic fractionation.…”

“…It is possible that N-derivatives of fatty acids were formed as a result of reactions of the free fatty acids (produced in this step due to breakdown of triglycerides) with polymerized (charred) proteins from the previous pyrolysis step . Since fatty nitriles have been considered as fuel additives to improve lubricating properties, − the presence of these compounds at low concentrations may, in fact, enhance the fuel value of triglyceride-derived bio-oil from pyrolytic fractionation. Trace amounts of toluene and 4-methylphenol were also observed in the triglyceride-derived bio-oils from both the oleaginous algal feedstocks and could have formed from degradation of recalcitrant or charred proteins.…”