Nitrogen derivatives of fatty acids

Fatty amines are nitrogen derivatives of fatty acids, olefins, or alcohols prepared from natural sources, fats and oils, or petrochemical raw materials. Commercially available fatty amines consist of either a mixture of carbon chains or a specific chain length from C The amines are classified as... 

S. H. Shapiro, "Commercial Nitrogen Derivatives of Fatty Acids," in E. Pattison, ed., Patty A.cids and Their Industrial Applications, Marcel Dekker, Inc., New York, 1968, pp. 77—154. 

C. W. Glankler, J. Am. Oil Chem. Soc. 56, 802A-805A (1979) . .Nitrogen Derivatives of Fatty Acids, Secondary and Tertiary Amines, Quaternary Salts, Diamines, Imidazolines". 

Fatty Amines. Fatty amines are the most important nitrogen derivatives of fatty acids. They are produced by the reaction of fatty acids with ammonia and hydrogen. They are the bases for the manufacture of quaternary ammonium compounds used as fabric softeners and biocides. Fatty amine oxides are mild to the skin with good cleaning and foaming properties and find application as a shampoo ingredient. The above mentioned products are but some of the oleochemical derivatives from coconut fatty acids (5). 

Fatty Amines Fatty amines are the most important nitrogen derivatives of fatty acids. They are produced by the reaction of fatty acids with ammonia and hydrogen. 

Nitrogen derivatives of fatty acids in the context of this article refer for the most part to surfactants derived via conversion of the acid to an amine, or via condensation of the fatty acid with an amine such as an alkanolamine. The manufacture of such derivatives has been reviewed in detail by the author and co-workers [4] and will be discussed in less detail here. 

To improve the separation of the derivatives of fatty acids with the same effective carbon number, e.g., palmitoleic (C16 1), linoleic (18 2), andmyristic (C14 0), Baty et al. (33) reported the preparation of the anthrylmethyl esters derivatives of several fatty acids (with 9-hydroxy-methylanthracene and the catalyst 2-bromo-l-methylpyridinium iodide (BMPI)) with a view to analysis by HPLC and LC-MS (with gradient elution on a ZORBAK 5-/zm Cl8 column) (see Chemical Structure 1). The excess reagents were evaporated under nitrogen at 50°C, and the de-rivatized acids were taken up in 1 ml of mobile phase prior to chromatography. This method did not allow the resolution of the C16 1, 08 2, and C14 0 esters, although HPLC data obtained for the other acids correlated well with that obtained by capillary gas-liquid chromatography. 

This cold saponification is recommended especially when vitamin-containing lipids or derivatives of fatty acids containing conjugated double bonds, are present. Generally about 1—12 h heating rmder reflux in a nitrogen atmosphere is required. The duration depends on the lipids to be hydrolysed. 10—20% toluene or xylene can be added to raise the boiling point of the hydrolysis mixture if difficultly hydrolysable compounds are present. 

The preparation of the methyl ester derivatives of fatty acids must be by far the commonest chemical reaction performed by lipid analysts, yet it is often poorly understood the topic has been comprehensively reviewed [160,205,839], There is no need to hydrolyse lipids to obtain the free fatty acids before preparing the esters as most lipids can be transesterified directly. No single reagent will suffice, however, and one must be chosen that best fits the circumstances. Esters prepared by any of the following methods can be purified if necessary by adsorption chromatography (see below). Care should be taken in the evaporation of solvents as appreciable amounts of esters up to C14 can be lost if this step is performed carelessly. In particular, an over vigorous use of nitrogen to blow off solvents must be avoided. Esters other than methyl may be required from time to time for specific purposes. 

Fatty amines and their derivatives represent the most important nitrogen compounds of fatty acids. They possess great ionization constants compared with other alkyl derivatives of ammonia. They are cationic, basic, biologically active, and strongly adsorbed on many surfaces due to their high adsorption potential. They are indispensable in many surface-related physicochemical processes. They are the starting materials for the manufacture of quaternary ammonium compounds and various cationic and amphoteric substances. 

Presence of various nitrogen-containing compounds, or of fatty acids or their derivatives, controls the vigorous interaction of the ether and chlorosulfuric acid at above 40°C, producing higher yields of 4,4/-oxybisbenzenesulfonyl chloride. 

FADAs are nitrogen derivatives of coconut oil synthesised from fatty acid and diethanolamine. Equimolar amounts of the two starting compounds yield water-insoluble monoethanolamides, whereas the reaction of two moles of diethanolamine with one of the acids results in water-soluble FADA possessing the typical alkyl chain distribution with the C12/C14 homologues prevailing [33]. 

The main raw material is the fatty nitrile derived from the reaction of fatty acid with ammonia. Catalytic hydrogenation of the nitrile produces the amines. The amines are available as primary, secondary, and tertiary amine, depending on the number of the alkyl groups attached to the nitrogen atom. 

Plant metabolites that are capable of becoming toxic in sunlight or UVA are produced by a wide variety of biochemical pathways and thus are a structurally diverse group of natural products. Both linear and cyclic photosensitizers are known from plants. Linear phototoxins are generally derived from fatty acid precursors and typically possess conjugated double and triple bond systems. The majority of cyclic photosensitizers, on the other hand, are bi- and tricyclic aromatic molecules that may contain nitrogen, oxygen or sulfur as heterocyclic elements. 

Amino acids derived from dietary or body proteins are also potential fuels that can be oxidized to acetyl CoA, or converted to glucose and then oxidized (see Fig. 2). These oxidation pathways, like those of fatty acids, generate NADH or FAD(2H). Ammonia, which can be formed during amino acid oxidation, is toxic. It is therefore converted to urea in the liver and excreted in the urine. There are more than 20 different amino acids, each with a somewhat different pathway for oxidation of the carbon skeleton and conversion of its nitrogen to urea. Because of the complexity of amino acid metabolism, use of amino acids as fuels is considered separately in Section Seven, Nitrogen Metabolism. 

In the mass spectrometric analysis of fatty acids in general, certain nitrogen-containing derivatives have proved to be especially useful in that they permit location... 

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