附加试剂及反应介质对TPPFeCl催化环己烷仿生氧化反应性能的影响

研究了某些附加试剂及反应介质对四苯基卟吩合铁(Ⅲ)[TPPFeCl或(TPPFe)₂O]模拟细胞色素P-450催化PhIO羟化环己烷反应的影响。发现适量的异丙醇、吡啶及NaOH能促进反应,加入盐酸及增大介质的极性对反应不利。证明了副产物环己酮主要是由PhIO直接氧化主产物环己醇生成的,TPPFeCl的存在不利于酮的生成,醇的存在能延长催化剂的寿命。

The Influence of Additive Reagent and Reaction Medium on the Catalytic Characteristics of TPPFeCl in the Biomimetic Oxidation of Cyclohexane with PhIO

The influence of additive isopropyl alcohol, pyridine, hydrochloric acid and sodium hydrate in different quantities on the catalytic characteristics of chloro tetraphenyl-porphinato iron TPPFeCl and (TPPFe)2O in above reaction was studied. It is found that isopropyl alcohol and pyridine in small amounts could increase the yield of oxidation product of cyclohexane. The presence of cyclohexanol could give a longer catalytic lifetime of TPPFeCl. The catalytic oxidation of cyclohexane could be favourable as a small amount of aqueous NaOH was added; but unfavourable as hydrochloride acid was added. This reaction was unfavourable either when the polarity of solvent increased. One of the oxidation products of cyclohexane, cyclohexanone, was verified to be mainly produced by oxidizing cyclohexanol directly by PhIO. The presence of TPPFeCl was unfavourable to form cyclohexanone.