Syntheses Of Water-soluble Cu(Ⅱ) Coordination Complexes And Their Catalytic Properties

The oxidation of alcohols to the corresponding carbonyl compounds is one of the most important reactions in organic synthesis, and extensive efforts have been focused on the development of metal-catalyzed aerobic oxidation methods. In this thesis, the reactions of five Cu(II) salts with 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)acetic acid(pypzacac H) yielded five coordination complexes. They exhibited excellent catalytic performance in the aerobic oxidation of alcohol to aldehyde and the ammoxidation of alcohol to nitrile in water. The catalytic aqueous solution could be reused several cycles without obvious decay of catalytic efficiency. In addition, we designed and synthesized4-((3,5-dicarboxybenzyl)oxy)-2,2,6,6-tetramethylpiperidinyloxy ligand, which could promote the aerobic oxidation of alcohol catalyzed by Cu2+ in water.1. Reactions of Cu(OAc)2, Cu(NO3)2, Cu SO4, Cu(Cl O4)2 or Cu Cl2 with2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl) acetic acid(pypzacac H) ligand produced four dinuclear Cu(II) complexes [{(Me OH)Cu(OAc)}(μ-κ2:κ1-pypzacac)]2·0.5H2O(1·0.5H2O), [{Cu(pypzacac)}(μ-κ2:κ1-pypzacac)2{Cu(H2O)2}](NO3)·2(Me OH)0.5·6H2O(2·2(Me OH)0.5·6H2O), [{(Me OH)Cu(mpypzacac)}(μ-SO4)]2·2Me OH(3·2Me OH),[{Cu(mpypzacac)2}(μ-κ2:κ1-pypzacac){Cu(mpypzacac)}](Cl O4)3·Me OH(4·Me OH) and one polymeric Cu(II) complex [(Cu Cl)(μ-κ3:κ1-pypzacac)]n(5), respectively. Complexes1–5 exhibited excellent catalytic performance in the aerobic oxidation of alcohol to aldehyde and the ammoxidation of alcohol to nitrile in water. The reaction could tolerate a wide range of aromatic functional groups including electron donating groups such as methoxyl and methyl, aryl chloride, nitro groups and aromatic heterocyclic molecules.The catalytic aqueous solution was easily separated and could be reused for several cycles without any obvious decay of catalytic efficiency.2. The new TEMPO-containing organic compound4-((3,5-dicarboxybenzyl)oxy)-2,2,6,6-tetramethylpiperidinyloxy(H2TEMPO-BDC) was designed and synthesized. This ligand was employed to promote the aerobic oxidation of alcohol mediated by Cu2+ in water under the mild conditions. The correspondingaldehyde products were obtained in good to excellent yields. The yields of electron-donating substrates are obviously higher than the yields of electron withdrawing substrates.