Synthesis Of Dehydroabietic Amine Derivatives And Their Application In Asymmetric Phase-Transfer Catalytic Reaction And Chiral Separation

Part Ⅰ: Five chiral quaternary ammonium salts deriving from dehydroabietylamine were designed and synthesized as chiral phase-transfer catalysts. And these catalysts were applied to catalyse asymmetric redcution of hypnone and epoxidation of chalcone. Especially, the epoxidation of chalcone was studied systematically. The results showed that these catalysts could catalyse the epoxidation of chalcone (yield 33%~99%, e.e. 2.0%~20.7%.), and the structure and dosage of these catalysts, oxidants and solvents can affect the asymmetric epoxidation reaction. Furthermore, the relations of catalytic activities and molecular structure by diversification of the structure of catalyst were also studied. PART Ⅱ: Four chiral crown ethers deriving from natural rosin were designed and synthesized as chiral phase-transfer catalysts. And these catalysts were applied to catalyse asymmetric Michael addition of 2-nitropropane to chalcone and epoxidation of chalcone. The results showed that these catalysts could catalyze the Michael addition of 2-nitropropane to chalcone (yield 43%~51%, e.e. 7%~35%). and epoxidation of chalcone (yield 47%~69%, e.e. 0%~4%). Furthermore, the relations of catalytic activities and molecular structure by diversification of the size of crown ring and the substituent at the nitrogen atom were studied. PART Ⅲ: Two novel chiral fluorescence derivatization reagents dehydroabietyl-thioisocyanate (DHA-NCS) and degrading-dehydroabietyl-thioisocyanate (DDHA-NCS) were synthesized . In acetonitrile,DHA-NCS present ultraviolet at λmax=224 nm, Fluorescence: λex=280 nm, λem=314 nm; DDHA-NCS present ultraviolet at λmax=224 nm, Fluorescence: λex=276 nm, λem=318 nm. At 60 oC, DHA-NCS could readily react with D,L-Ala, D,L-Cys, D,L-Thr, D,L-Ser and D,L-Val etc. in 1.5% triethylamine acetonitrile solution to product the corresponding derivatives,and the derivatives could be separated easily with high performance capillary electrophoresis (HPCE). At 70oC, DDHA-NCS could readily react with D,L-Asn, D,L-Val, D,L-Met, D,L-Leu, D,L-Phe and D,L-Trp etc. in 5% triethylamine acetonitrile solution get the corresponding derivatives,and the derivatives could be easily separated with high performance capillary electrophoresis (HPCE).