Synthesis And Properties Of New Molecular Hydroxamic Extractrant

China has abundant resource of copper. However as high-grade copper becomes dwindling now, efficiently separate and comprehensive utilization low-grade, high-performance and complex multi-component copper deposit has became an effective way to solve the shortage of resources. Copper hydrometallurgy technology which using for efficient separate copper and other irons in acidity and dilute solution becomes mainstream in copper metallurgy. The research and development of effective copper extractant was significant.Firstly, This article has explored the synthesis of new structures with new molecules containing hydroxyl oxime unit. With dicationic imidazolium salt as catalyst and P-methyl(fluorine/chlorine) benzaldehyde as starting material, substituted a-benzoin as an important intermediate was synthesized through the mechanism of nitrogen heterocyclic carbine. Then oximation with hydroxylamine hydrochloride and get trans substituted a-benzoin which were separated by column chromatography using gradient elution. the product was confirmed by’HNMRResponse of a-benzoin oxime certain compounds to copper ions has studied by UV spectrum. The results showed that when1equivalent of copper ions was added in the compound of the trans compounds, new absorption peaks and stable chelates were appeared. It has showed better selective for copper which could judge from the unchanged UV spectrum when Na+, K+, Ag+, Mg2+, Ca2+, Ba2+, Pb2+, Zn2+, Co2+, Ni2+, Fe3+, Al3+et metal ions were added in. Job’s Plot curve shows that the combined ratio was1:1.The performance of compounds containing hydroxyl oxime units to extract and strip copper was studied. Preparation of two-phase extraction with compounds and copper iron at ratio1:1, O/A=1:1, got extraction rate in different pH. The results showed that extraction rate increases with the pH increases and when pH=5, extraction rate were12%、34%、28%、16%. Order of extraction ability was methyl>fluorine>chlorine>none. Compare with the conventional commercial extraction(like M5640), this compounds’extraction ability wasn’t good, the reason could be:①molecular structure was too neat, lack of lipophilic groups, oil-soluble poor②larger steric around the reactive grounds, small elastic structure, limit their extraction ability. However this give the compounds better selective for copper, they can use for potential selective chemical sensors. Through the transformation of the carbon chain, improve their oil-soluble, they can be potential efficient copper extraction.4-t-octylphenol, acetylchloride, aluminum chloride, hydroxylamine hydrochloride, isooctanoate as the raw materials, tetrachloroethane as reaction solvent, three reaction steps synthesis of2-hydroxy-5-t-octylacetophenone oxime were studied. The optimum reaction conditions for Fries rearrangement were as follow:tetrachloroethane as reaction solvent, n(aluminum chloride):n(4-t-octylphenol)=1.2:1, reaction temperature120℃, reaction time6h. The target product yield of90.8%, with89.2%purity.Compare of the Fries rearrangement reaction with titanium-(4-nonyl)-phenyl ester and titanium-(4-t-octyl)-phenyl ester. The results showed that larger steric substituent can suppress the occurrence of side reactions rearrangement, significantly reduce product impurities.