Study For Selective Catalytic Oxidation Of The Chain Of Aryl Hydrocarbon

The selective oxidations of aryl hydrocarbon to benzoic acid catalyzed byN-hydroxyphthalimide(NHPI)/transition metal ion were studies in this thesis, and thisthesis divider into four parts as follows:The first part is about the oxidation reaction of substituted toluenes catalyzed byNHPI/Co(Salen). The substrates were oxidized by molecular oxygen which catalyzedby NHPI/M(Salen) in acetic acid. The catalytic performances of various catalyticsystems and catalysts had been studied in this part. The results show that the systemof NHPI/Co(Salen) has better performance, meanwhile, the conversion of toluene isabove 95% and the yield of benzoic acid is about 85%. Some substrates withdonating-electron group, catalyzed by this catalytic system, were oxidized easily at80℃under atmospheric pressure.The second part is about the oxidation reaction of toluene catalyzed by supportedcobalt catalyst. Toluene which catalyzed by NHPI and Co/Al(OH)x-150 is oxidized bymolecular oxygen at 110℃under atmospheric pressure in acetic acid. The resultsshow that the reaction catalyzed by this no soluble catalyst has higher selectivity andthe conversion of toluene is about 42%.The third part is about the oxidation of substituted toluenes which catalyzedNHPI/Co/Mn is carried out in nonacid solvents. The study shows that the conversionsand yields of p-chlorotoluene and p-methyl-(t)-butylbenzene are more than 90%. Thecatalytic performance of cobalt acetate for the oxidation of substitute toluenes ispromoted by added manganese acetate. The substrate with donating-electron group iseasily converted to benzoic acid. However, the substrate with withdrawing-electrongroup is oxidized difficultly. The fourth part is about the synthetic technology of nicotinic acid. The oxidation of 3-methylpyridine to nicotinic acid catalyzed by NHPI/Co(OAc)2 in mixed solvent of acetic acid and bromobenzene has good yield. The optimized reaction condition: NHPI (10 mol%), cobalt acetate (1.5mol%), 3-methylpyridine(4 mmol), 160℃and oxygen(2.0MPa). The yield of nicotinic acid is about 81% under this optimized condition.