【作者】 石乐君；

【导师】 郭永恩；

【作者基本信息】 天津科技大学 ， 微生物与生化药学， 2009， 硕士

【摘要】 1,1’-联萘-2,2’-二酚(BINOL)及其衍生物已在不对称合成、分子识别、新功能材料等研究领域得到了广泛应用。本课题基于现有的BINOL研究进展,设计了在分子识别和手性高效液相色谱固定相制备方面有潜在应用价值的2’-烷氧基-2-羟基-1,1’-联萘-3-甲醛,并完成了用于该化合物合成的某些重要中间体的制备。首先,以BINOL为主要原料,依次经过双羟基保护、有机锂参与的2,2’-二(甲氧基甲氧基)联萘环的3-位甲酰化、羟基保护基脱除等四步反应合成了骨架化合物2,2’-二羟基-1,1’-联萘-3-甲醛。并采用核磁共振谱图对其进行了表征,并进一步考察了物料比、催化剂加入量、反应时间及反应温度对产率的影响,使其产率最高可达63%。其次,设计了两条路线合成侧链化合物5-氯甲基-2-[2-(1,3-二氧环戊环基)]苯胺,该化合物为首次合成,是以3-硝基-4-甲基苯甲酸为主要原料,依次经过还原、缩合、氧化、醛基的缩醛保护、氨基还原等反应制得了合成该侧链的重要中间体。并对可行的实验路线进行了工艺改进,进一步考察了催化剂、物料比、溶剂、反应温度和反应时间等不同因素对各步产物产率的影响,提高了每一步的产率。最终产物及重要中间体的结构采用红外光谱、质谱、核磁共振氢谱等进行了表征。最后,利用Williamson醚合成法制得了上述骨架与侧链中间体相连结的模型化合物,并考察了实验条件对上述重要中间体收率的影响,而且得到了较高的收率(90%左右),还对其中的一种产物采用红外光谱、质谱、核磁共振氢谱等进行了表征。更多还原

【Abstract】 1,1’-Binaphthyl-2.2’-diol (BINOL) and its derivatives were widely applicated in asymmetric synthesis, molecular recognition, new functional materials and other research fields. Based on recent BINOL research development,2’-alkyloxy-1,1’-binaphthyl-3-carboxamide with potential applications in molecular recognition and HPLC chiral stationary phase manufacture was designed, and some of its important intermediates were synthesized.Firstly, skeleton compound 2,2’-dihydroxy-1,1’-binaphthyl-3-aldehyde was obtained from BINOL, successively by two hydroxy groups’protection, di-MOM BINOL’s metallation by n-BuLi and reaction with DMF, deprotection. The product was characterized by IR, MS, 1H NMR, etc. The effects were inpecteted by molar ratio, catalyst, time and temperature on yield, and the yield can reach 63%.Secondly, the synthetic routes of two side-chain compounds, i.e.5-chloromethyl-2-[2-(1,3-dioxolanyl)]aniline were designed, and their important intermediates were preapared form 3-nitro-4-methylbenzoic acid, by its esterification, condensation, oxidation, aldehyde group’s protection as acetal, and nitro group’s reduction to amine as well as acetamidation in turn. The effects were inpecteted by catalyst, molar ratio, resolve, time and temperature on yield, and the yield was improved. The structures of intermediates and some other important compounds were characterized by IR, MS and 1H NMR, etc.Finally, model coupling compound between skeleton compound and an intermediate of side-chain compound metioned above was prepared by Williamson reaction, and whose reaction conditions affecting some intermediates’yields were studied. The yield can reach about 90%. And the product was characterized by IR, MS,1H NMR, etc.更多还原