Synthesis Of Novel Heterocycles And Research On Catalytic Oxidation Of N-hydroxy-1,6-methano [10] Annulene-3,4- Dicarboximide

Since aromatic 1,6-methano[10]annulene had been synthesized, all kinds of its derivatives were synthesized and showed good applications in the field of functional materials due to bioactivities. Recently, N-hydroxyimids as organic catalysts have shown the advantages of mild condition, high catalytic efficiency and selectivity in catalytic oxidation of hydrocarbons. This thesis mainly carried out the synthesis and research of catalytic oxidation based on N-hydroxy-1,6-methano[10]-annulene-3,4-dicarboximide, as well as the synthesis of a series of novel heterocycles, which revealed some innovative results.N-hydroxy-1,6-methano[10]annulene-3,4-dicarboximide was synthesized by 1,6-methano[10]annulene-3,4-dicarboxylic anhydride and hydroxylamine hydrochloride. N-hydroxy-1,6-methano [10]annulene-3,4-dicarboximide was regarded as catalyst, oxygen molecules as oxygen source and acetonitrile as solvent. Nicotinic acid was obtained up to 70% through a liquid-phase oxidation of 3-picoline under catalyst (10%mol), Co(OAc)2 (2% mol), temperature 120 ?, and 1 MPa oxygen pressure conditions,Then we investigated on catalytic oxidation of different alkylbenzenes under the catalytic system described above. In the presence of catalyst (10% mol)?Co(OAc)2 (1%mol)?100?and 1 atm of oxygen pressure, alkylbenzenes were obtained in conversion from 74% to 78%. The products are mainly carboxylic acids with small amount of aldehydes or alcohols as byproducts.N-substituted-imides were obtained under the reaction of N-hydroxy-1,6-methano[10]annulene-3,4-dicarboximide with appropriate halogenomethylarayl derivatives via an substitution reaction in the presence of triethylamine. N-substitutedimides were reduced to hydroxylactams by sodium borohydride at 0-5?. The hydroxylactams were intramolecular cyclized in trifluoroacetic acid to afford novel heterocycles (yields from 75% to 91%). All new compounds were characterized by 1HNMR?IR?MS or HRMS.