The Synthesis Of Hydroxamates And N-hydroxamides And Their Synergic Catalytic Action In The Oxidation Of Aromatic Hydrocarbon

The investigation of biomimetic oxygen carriers not only has important theoretic significance to reveal reversible bonding and activating oxygen as well as the mechanism of oxidation reaction in organism, but also is potentially applicable in chemical separating oxygen and realizing high efficiency and selectivity of catalytic oxidation reaction under a moderate condition. Recent investigations have been concentrating on metalloporphin and Schiff base type biomimetic oxygen carriers. But their practical application was restricted by difficult preparation and expensive price. On the contrary, hydroxamates have simple and convenient preparation and their structure can be regulated to a great extent as new models of biomimetic oxygen carriers, so the studies on hydroxamates have great theoretic significance and practical value.In this thesis, the two series of 9 hydroxamic acid ligands and their 13 transition-metal complexes were synthesized, among which 4 ligands and their 8 transition-metal complexes were unreported and were characterized by 1H NMR, IR, MS and analysis of elements.The synergic catalytic action of hydroxamates and N-hydroxyphthimide(NHPI) in the oxidation of aromatic hydrocarbon was first studied in this thesis. The results showed that the catalytic activity of hydroxamates can be promoted by NHPI to some extent. But due to the poor solubility of NHPI in aromatic hydrocarbon, the synergic catalytic action is not very strong. If some additive was put into the reaction system to make NHPI more soluble in aromatic hydrocarbon, the oxidation can proceed more quickly.From the analysis of published articles and our experiment results, we can draw a conclusion that the synergic effects of hydroxamates and NHPI can produce Phthimide-N-oxyl(PINO), which is a more active radical and makes the oxidation catalyzed by hydroxamates and NHPI more reactive.