Study On Synthesis Of Perillartine

Perillartine is a new synthetic perfume product with high sweetness and low calorific. It is widely used in tobacco, food, medicine, health and other industries. In this paper, perillartine was synthesized via epoxidation, isomerization, oxidation and oximation from raw material ofβ-pinene. This research obtained 2,10-epoxypinane, perillyl alcohol, perillyl aldehyde and perillartine with this method; Structures of these four products and the main by-products' were characterized by data of infrared spectra, GC-MS spectra and 1H NMR spectra; Reaction conditions of each step were optimizated and the total yield of perillartine was 44.5%.2,10-Epoxypinane was prepared via epoxidation ofβ-pinene with peractetic acid. The experimental results show that the reaction temperature is a important factor on the yield. Single factor experiments show that 0-5℃is the best reaction temperature and 2,10-epoxypinane is prepared with 80.32% purity and 72.2% yield based on the optimum conditions.The perilly alcohol was prepared via ismerization reaction of 2,10-epoxypinane catalyzed by amine nitrae. The optimum conditions are established as follows: perillyl alcohol can be obtained from isomerization of 2,10-epoxypinanecatalyzed by morpholinium nitrate, with the amount of catalyst of 15% of 2,10-epoxypinane(mol), in mixture solvent DMF/CH₃NO₂(v/v,1/5) at 80-85℃for 2.5h, with 84.33% purity and 70.2% yield.Prepared 5 inorganic carriers oridants, the activity of the supported PCC was studied on the selective oxidation reaction of perilly alcohol to perilly aldehyde. The optimum conditions are established as follows: The yield was 84.9%(PCC/activated carbon), 90.2%(PCC/Al₂O₃), 96.5%(PCC/ Silica gel), 85.2%(PCC/4A molecular sieve), 80.7%(PCC) with dry mixing method and 92.8%( PCC/Silica gel) with immersion method, respectively, when the reaction was carried out with the content of PCC of 2.0mmol/g and reaction time of 8h at room tempreture.Perillartine were synthesized via oximation of perillyl aldehyde and hydroxylamine hydrochloric in acid-base buffer solution (NaCO₃-NaHCO₃). The effects on yield of perillartine of the reaction system's pH, the reaction temperature and the mole ratio of perillyl aldehyde to hydroxylamine were investigated. The optimal reaction conditions were determined as follows: the pH of 6.5, the mole ratio of perillyl aldehyde to hydroxylamine hydrochloric of 1:7 and reaction temperature of 40℃for 6h. The yield of perillartine was 91.1% with the purity of 98.20%.