Synthesis Of N-hydroxy-6-chloro-9,10-anthraquinone-2,3-dicar-boximide And Research On Its Catalytic Property

Nitroxyl radical aerobic catalysts, such as N-Hydroxyphthalimide (NHPI), showing their good to excellent performance in catalytic aerobic oxidation, have attracted people's attention recently. However, NHPI catalysis must depend on the assistance of the cocatalysts such as transition metallic or organic compounds, so that the two-component catalytic system always be used for aerobic oxidation.In this thesis, based on concluding the development of NHPI system and analyzing its mechanism, two nitroxyl radical catalysts driven by intramolecular single-electron-transfer were designed:N-hydroxy-9,10-anthraquinone-2,3-dicarboxi-mide (NHADI) and N-hydroxy-6-chloro-9,10-anthraquinone-2,3-dicarboximide (NHCADI).Using pyromellitic dianhydride and chlorobenzene as starting materials, via a four-step route including Friedel-Crafts acylation, dehydrating cyclization, acyl chlorination and bisacylimidation, NHCADI was successfully synthesized with total yield of 10.8%.Two routes was investigated to synthesize 9,10-dihydroanthracene-2,3-dicar-boxylic acid, which was the key synthetic intermediate of NHADI, using pyromellitic dianhydride and benzene, or phthalic acid anhydride and o-xylene as starting materials respectively. Both of them were successful, and the second route was more efficient. In the process of synthesizing NHADI, it was found that NHADI could not be purely obtained since it was not stable.In the following part, the oxidation of ethylbenzene was employed as template reation, the catalytic performance of NHCADI and NHCADI-Co(OAc)2 system were explored. It was found that NHCADI could catalysed the aerobic reation of ethylbenzene, the conversion of ethylbenzene could reach to 64.2% when 10 mol% NHCADI was employed, showing that the activity of NHCADI was near the couple system of NHPI and 2-chloro-9,10-anthraquinone.When the system of NHCADI (10 mol%) and Co(OAc)2 (5 mol%) was employed, the conversion of ethylbenzene could reach to 64.6%. In comparson with the Co-free datum, this meant that Co(OAc)2 could not promote the activity of NHCADI. Thus it was proved that the design of the nitroxyl radical catalysts based on intramolecular single-electron-transfer is reasonable.