Synthesis,Characterization And Properties Of Dethydroabietyl Ammonium Phosphotungstates

(1) Three kinds of new organic-inorganic hybrid catalytic materials:lacunary dawson-type dehydroabietyl ammonium phosphotungstate (DHPW), N,N-dimethyl-N-benzyl-N-dehydroabietic chloride (NDHA) and N,N-dimethyl-N-benzyl-N-dehydroabietyl ammonium peroxo phosphotungstate (PNHPW) were synthesized by using dehydroabietylamine and keggin-type phosphotungstic acid(HPW) raw meterials and structurally characterized by means of elemental analysis, ICP-AES, IR spectroscopy, UV spectroscopy, Nuclear magnetic resonance and thermogravemetric.(2) Three kinds of new organic-inorganic hybrid catalytic materials catalyzed-oxidation of 1-octene, styrene, cinnamaldehyde, alpha-pinene and terpen-4-ol with 30% H2O2 under free-solvent condition were investigated by means of GC/MS and gave 1,2-epoxy octane, benzaldehyde, 2,3-dihydroxy-1,8-cineole and p-menthane-1,2,4-triol, respectively; With N-dimethyl-N-benzyl-N-dehydroabietyl quaternary ammonium cation or dehydroabietyl quaternary ammonium cation as counter ion, they are with good phase transfer catalysis effects and higher catalytic activity relative to HPW.(3) Effects of reaction conditions on DHPW catalyzed-oxidation of 10octene were investigated by means of GC and GC/MS. The results obtained show that DHAP is with oxidation-acid bifunctional catalysis for the conversion of 1-octene in the presence of hydrogen peroxide to 1,2-epoxy octane,1,2-dihydroxy octane and 2-hydroxy-octane; the selectivity of 1,2-epoxy octane in non-polar solvents at ambient temperature reached more than 90% and decreased in free-solvents or polar solvents because 1,2-epoxy octane can be decomposed by the ring-opening of epoxide.(4) PNHPW catalyzed-oxidation of terpen-4-ol with hydrogen peroxide to p-menthane-1,2,4-triol was also studied. Effect of reaction condition on conversion rate of terpen-4-ol and selectivity of p-menthane-1,2,4-triol were investigated for the optimum condition(terpen-4-ol 5mmol,1,2-dichloroethane 5 mL, PNHPW 0.025g, hydrogen peroxide 5mmol, reaction temperature 30℃,reaction time 3 hour), under the optimum conditions the conversion rate of terpen-4-ol is 89.7% and the selectivity of main product p-menthane-1,2,4-triol is 82.9%.