The Influence Of Chlorine Substitutents On The Catalytic Performance Of Organic Free Radicals

The catalytic oxidation of hydrocarbons is an important transformation in both petrochemical and fine chemcal industry. A new organic catalyst, N-hydroxyphthalimide (NHPI) can efficiently realize the activation of C-H and attracts much attention because of its highly catalytic efficiency.The following is the major content in this thesis:(1) Chlorine atoms were introduced on the aromatic ring of NHPI, and accordingly 4-chloro-N-hydroxyphthalimide (CNHPI) and 3,4,5,6-tetrchloro-N-hydroxy-phthalimide (TCNHPI) were synthesized. On the other hand, chlorine atoms were introduced on the aromatic ring of anthraquinone (AQ), and therefore 1,2,3,4-tetrchloro-9,10-anthraquinone (TCAQ),2-chloro-9,10-anthraquinone (2-MCAQ) and 1,2,3,4,6-penta-chloro-9,10-anthraquinone (PCAQ) were synthesized. All the products were characterized with1HNMR or IR spectroscopy.(2) Choosing the aerobic oxidation of ethylbenzene as the template reaction, the catalytic activities of the catalytic systems constituted by different anthraquinones and different NHPIs were studied. And the influences of the number of chlorine atoms on the catalytic activities were also studied. It shows that the catalytic activity can be improved by the chlorine substituents.(3) In acetonitrile, TCNHPI/TCAQ, which are more chlorine atoms substituted, performs more efficiently.67.9% conversion of ethylbenzene with 95.7% selectivity for acetophenone could be obtained at 100℃under 0.4 MPa of dioxygen in 5 h, and there was almost no PEPH generated.(4) Under solvent-free conditions, the influence of the number of chlorine atoms substituted was also studied. TCNHPI/TCAQ was more efficient than NHPI/TCAQ, and the reaction rate was faster. And it is found that PEPH was genetated if TCNHPI was used more than 0.2 mol%.