Study On Catalysis Of Biomass Char Sulfonic Acid And Sulfonic Acid Resin In Fine Organic Synthesis

Solid acid catalysts has been found to be useful in a variety of organic reactions. They had many advantages such as non-toxic, non-volatile, non-corrosive, little pollution to environment, mild reaction conditions, high reactivity and simple work-up procedures which liquid acid can’t achieve. In recent years, environmental problem had drawn increasing attention, the application of solid acid in place of liquid acid catalyzed organic reactions was one of the most important ways with the direction of the development of Green Chemistry.In this work, the application of coconut char sulfonic acid, bamboo char sulfonic acid and acidic cation exchange resin D-72 were mainly studied on the synthesis of the compounds of calix[4]resorcinarenes, amidoalkyl naphthols, a-campholenonitrile and a, a’-bis(substituted benzyliden)cycloalkanones, which were confirmed by’H NMR, MS spectra and FTIR. The influence of reaction conditions were investigated, and the yields were improved over the novel catalysts under the optimized conditions. Based on these reactions, the possible reaction mechanism for the synthesis of these compounds also were discussed.1. Coconut char sulfonic acid was prepared from coconut shell by charring and sulfonation and used as the catalyst for the synthesis of calix[4]resorcinarenes. The FTIR and XRD results showed that sulfonic group were successfully bonded to the macroporous char materials which possess condensed aromatics. The influences of the amount and the reuse of catalyst on the synthesis of calix[4]resorcinarenes were examined. The yields can reach to 49-95%.2. An efficient and direct procedure were developed for the preparation of amidoalkyl naphthols by a one-pot condensation of aromatic aldehydes,2-naphthol and amides/urea in the presence. of bamboo char sulfonic acid under solvent free conditions. Amidoalkyl naphthols can be prepared rapidly in good yields (85-92%). The structures of target compounds were confirmed by IR、1H NMR and MS. 3. The Beckmann fragmentation of camphor oxime to a-campholenonitrile over solid sulfonic acid resin had been successfully performed. The influences of solvent, reaction temperature and reaction time on the fragmentation were examined. The results indicated that the conversion of oxime can reach 100% with 90.5% of selectivity to a-campholenonitrile under the optimized reaction conditions. The kinetics show that Beckmann fragmentation of camphor oxime catalyzed by sulfonic acid resin obeys kinetics rule of the pseudo-first order reaction and the activation energy calculated from least square method is 64.6 kJ/mol.4. A series of a, a’-bis(substituted benzylidene)cycloalkanone derivatives were synthesized by cross Aldol condensations of cyclohexanone with aromatic aldehydes in presence of sulfonic acid resin under solvent-free conditions and ultrasound irradiation. The influence of the amount of catalyst, irradiation time and irradiation power were investigated. Comparaed with other X-SO3H catalysts, the target compounds can be prepared rapidly in good yields (74%-92%) catalyzed by sulfonic acid resin under the optimized conditions.