摘要
Six sterically hindered chloro meso-tetra-ortho-alkylphenylporphinato irons (T(o-R)PPFe(III)Cl, R = Me, Et, n-Pr, i-Pr, n-Bu, t-Bu) were synthesized and used to catalyze the monooxygenation of cyclohexane with PhIO. Both the yields of cyclohexanol and the relative rates of monooxygenation of cyclohexane catalyzed by T(o-R) PPFe(IIl)Cl were higher than those of TPPFe(III)Cl respectively. The order of the yields(%) of cyclohexanol and the rate of cyclohexanol formation in the monooxygenation of cyclohexane catalyzed by T(o-R)PPFe(III)Cl for the different substituents are: i-Pr(58) > Et(57) > n-Pr(52) > Me(51) > n-Bu(48) > t-Bu(46) > H(35) and i-Pr > Et > t-Bu > n-PT greater than or equal to Me greater than or equal to n-Bu greater than or equal to H respectively. The special steric effect on the catalytic character of these different alkyl substituents in T(o-R)PPFe(III)Cl is proposed on the basis of the results.
Six sterically hindered chloro meso-tetra-ortho-alkylphenylporphinato irons (T(o-R)PPFe(III)Cl, R = Me, Et, n-Pr, i-Pr, n-Bu, t-Bu) were synthesized and used to catalyze the monooxygenation of cyclohexane with PhIO. Both the yields of cyclohexanol and the relative rates of monooxygenation of cyclohexane catalyzed by T(o-R) PPFe(IIl)Cl were higher than those of TPPFe(III)Cl respectively. The order of the yields(%) of cyclohexanol and the rate of cyclohexanol formation in the monooxygenation of cyclohexane catalyzed by T(o-R)PPFe(III)Cl for the different substituents are: i-Pr(58) > Et(57) > n-Pr(52) > Me(51) > n-Bu(48) > t-Bu(46) > H(35) and i-Pr > Et > t-Bu > n-PT greater than or equal to Me greater than or equal to n-Bu greater than or equal to H respectively. The special steric effect on the catalytic character of these different alkyl substituents in T(o-R)PPFe(III)Cl is proposed on the basis of the results.
基金
Project supported by the National Natural Science Foundation of China.
