【作者】 唐莅东；

【导师】 王恒山； 潘英明；

【作者基本信息】 广西师范大学 ， 有机化学， 2005， 硕士

【摘要】 一、以脱氢松香胺为原料设计并合成了五个手性季铵盐相转移催化剂。并用这些催化剂催化了苯乙酮的不对称还原和查尔酮的不对称环氧化反应,其中对查尔酮的环氧化反应进行了较为系统的研究,发现这些催化剂都能催化查尔酮的环氧化反应（产率33%⁹9%, e.e. 2.0%²0.7%）。且发现催化剂的结构和用量以及氧化剂、溶剂对催化活性和对映选择性都有一定的影响。并通过各种基团的引入以改变分子的刚性,研究了催化活性与分子结构的关系。二、设计并合成了四个含脱氢松香骨架的手性冠醚相转移催化剂。并用这些催化剂催化了2-硝基丙烷与查尔酮的不对称Michael加成和查尔酮的不对称环氧化反应。发现这些催化剂都能催化2-硝基丙烷与查尔酮的Michael 加成（产率43%⁵1%, e.e. 7%³5%） 和查尔酮的环氧化反应（产率47%⁶9%, e.e. 0%⁴%）。并根据冠环的大小、N 原子上的支链等,研究了催化活性与分子结构的关系。三、设计并合成了两种手性荧光衍生试剂脱氢松香基异硫氰酸酯（DHA-NCS）和降解脱氢松香基异硫氰酸酯（DDHA-NCS）。在乙腈溶液中,DHA-NCS 的紫外吸收为λ_max=224 nm, 荧光为λ_em=280 nm, λ_em=314 nm; DDHA-NCS 的紫外吸收为λ_max=224 nm, 荧光为λ_ex=276 nm, λ_em=318 nm. DHA-NCS在1.5%三乙胺的乙腈溶液中,在65 oC 可以与D,L-丙氨酸、D,L-半胱氨酸、D,L-苏氨酸、D,L-丝氨酸、D,L-丙氨酸和D,L-缬氨酸等氨基酸对映体生成相应的衍生物,这些衍生物在高效毛细管电泳上得到了很好的分离。DDHA-NCS 在5%三乙胺的乙腈溶液中,在70℃可以与D,L-门冬酰胺、D,L-缬氨酸、D,L-甲硫氨酸、D,L-亮氨酸、D,L-苯丙氨酸和D,L-色氨酸等氨基酸对映体生成相应的衍生物,这些衍生物在高效毛细管电泳上也得到了很好的分离。更多还原

【Abstract】 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).更多还原