基于脱氢松香酸芳环二胺合成手性荧光衍生试剂的研究-有机化学专业论文.docxVIP

Study on the synthesis of novel chiral fluorescence derivatizing reagents deriving from Methyl 13,14-diaminodeisopropyldehydroabietate Postgraduate: Li Fang-Yao Supervisor: Prof. Wang Heng-Shan Abstract Dehydroabietic acid (DAA) is one of important renewable resource. It is widely used in many fields such as paint, adhesives, printing ink, papermaking, rubber, food additive,biological product, etc. DAA is a natural chiral compound with three chiral carbon atom and a reactive carboxy group. Like some natural drug, it has a aromatic diterpene structure with three ring . For above reasons, DAA might be hopefully modified to some multifunctional derivatives and novel fluorescence derivatization reagents through constructing aromatic or heteroaromatic ring on DAA’ s skeleton. Part I, starting from dehydroabietic acid which was purified from disproportionated rosin, two important intermedias, Methyl 12-bromo-13, 14-dinitro- deisopropyldehydroabietate (MBDDDA) and Methyl 13, 14-dinitro- deisopropyldehydroabietate were synthesized through methylation, bromination, nitration and reduce. Then two phena-zines (methyl(1R,4aS,18aS)-1,4a- dimethyl-1, 2, 3, 4, 4a, 17, 18, 18a-octahydro-dibenzo [a, c] naphtho [2, 1-h] phenazine- 1-carbixylate and methyl (1R, 4aS, 18aS) -1, 4a-dimethyl- 1, 2, 3, 4, 4a, 17, 18, 18a- octahydronaphtho [2, 1-h] dipyrido [3, 2-a: 2, 3-c] phenazine-1-carboxylate) were synthesized by the reaction between MDDDA phen-5, 6-dione. Compared with DAA’s methyl ester, both the products’ maximal excitation wavelengths and emission wavelengths are bathochromic shifted with with fluorescent λex/λem of 406-420nm/450-460nm and their excitation wavelengths meet with our demand. Then, a chiral fluorescence derivatization reagent was synthesized through two steps. Part II, methyl (1R, 4aS, 16aS) -1, 4a-dimethyl-1, 2, 3, 4, 4a, 15, 16, 16a- octahydroacenaphtho [2, 1-f] quinoxaline-1-carboxylate was synthesized from Methyl 13, 14- diaminodeisopropyl- dehydroa