The synthesis of oxime reagents from natural and semi‐synthetic phenolic lipid and alkanoic acid resources for the solvent recovery of copper(II)

Abstract

In a study of the relationship between structure and efficiency towards recovery of copper(II) by chelation/solvent extraction, a series of homologous aldoximes has been synthesised from natural phenolic lipidic, and fatty lipidic renewable sources, for comparison with commercial reagents prepared from petrochemical sources. From cardanol, in technical cashew nut-shell liquid, isoanacardic aldoxime, [2-hydroxy-4-pentadec(en)yl]aldoxime, and from the natural phenolic lipid, anacardic acid, the isomer, 2-hydoxy-6-pentadec(en)ylaldoxime, have been synthesised. A C 11 analogue of anacardic aldoxime from Anacardium giganteum has been prepared. The isomeric n-octyl aldoximes have been synthesised, the o-and p-isomers from the readily available fatty acid n-octanoic acid and the m-isomer from cardanol. Related m-aldoximes have been prepared from the ketonic intermediates methyl isoamyl and methyl amyl ketones. The solvent extraction properties for copper(II) of the synthesised aldoximes have been compared with those of a current commercial reagent, 2-hydroxy-5-t-nonylbenzaldoxime (Acorga 5100, Cytec), and two former extractants, 2-hydroxy-5-t-nonylacetophenone ketoxime (SME 529, Shell) and 2-hydroxy-5-t-nonylbenzophenone ketoxime (LIX 65N, Henkel). All the aldoximes possessed useful properties in extraction efficiency, notably the isoanacardic and the C 8 aldoximes with the C 8 oisomer, 2-hydroxy-3-n-octylbenzaldoxime, exhibited optimal extraction, stripping and phase separation characteristics.

Synthesis and Antioxidancy of Some n‐Alkyl, t‐Alkyl, Homologous and Isomeric Lipidic Alkylthiobisphenols

“…Reduction of the resultant alkenes from the Wittig reaction [14], by catalytic hydrogenation, gave the required alkylphenols. 2-and 4-Alkylphenols were obtained by Fries rearrangements of phenyl esters (from phenol and n-alkanoic acids) to give the ketoalkyl intermediates which were reduced to give the 2-and 4-n-alkylphenols [9]. 2-(1,1,3,3-tetramethylbutyl) phenol was obtained by a described procedure [15].…”

“…Cardanol monoene was obtained by the catalytic hydrogenation of mixed cardanol in ethanol containing Raney nickel or by chemical reduction [9] and mixed cardanol by the base addition method [7] and vacuum distillation. Saturated cardanol (3-pentadecylphenol was prepared by catalytic hydrogenation with a Pd/C catalyst and by chemical reduction of mixed cardanol with hydrazine/air [7].…”

“…In the present paper we describe syntheses of a range of compounds with different n-alkyl chain lengths, branching, isomeric positions of the n-alkyl group in the aryl ring and of certain n-pentadecyl compounds bearing unsaturation. 3-Alkylphenols are readily accessible only from natural resources and their 2-and 4-alkyl isomers in the present work by synthesis from n-alkanoic sources as studied in the aldoxime series [9]. Surfactant compounds with n-alkyl chains are more biodegradable than those with branched chains [10] and it seems likely that the same probability applies to sulphur analogues.…”

Effect of the Structure of Alkyl Salicylaldoxime on Extraction of Copper(II)

“…In this group of chemical compounds, the para-directing R group has great impact on their charge distribution, steric-hindrance effect, and so on, which determines their extraction ability for Cu(II) [8,9]. At present, AS are produced by bio-extraction and artificial synthesis, with the artificial synthesis route being the dominant technique for the production of AS [10,11]. It was reported that many types of AS with different R groups (e.g., nonyl, decyl, and dodecyl) have been synthesized in the laboratory [12][13][14][15][16].…”

Liquid–liquid synthesis of oximes from carbonyl compounds: formation under neutral conditions and degradation at acidic hydrometallurgical process conditions

“…Several synthetic methods to increase oximation rates have been proposed in the literature. These include application of micelles and phase‐transfer catalysis in liquid–liquid systems, solid‐organic systems and single organic phase systems …”