【作者】 程习星；

【导师】 王建平； 陈庆华； 张玉清；

【作者基本信息】 河南科技大学 ， 化学工艺， 2006， 硕士

【摘要】 氮杂环丙烷类化合物在有机合成中是一类很重要的起始原料,这类化合物作为反应底物可以用来合成多官能的胺,氨基醇,氨基酸,生物碱,β-内酰胺以及聚合物等多种有机分子,也可以用作不对称合成中的配体和辅助剂。许多天然产物中均含有氮杂环丙烷的结构组份,且表现出抗病毒,抗肿瘤,酶抑制性等生物活性。然而,国内对氮杂环丙烷及其衍生物合成方法的报道仍十分有限,基于氮杂环丙烷在光学活性及抗生活性等方面的潜在应用前景,本课题合成了一些结构新颖的手性氮杂环丙烷类化合物,主要结果如下:(1)以廉价的糠醛为原料,经过光化、缩醛化、溴化等一系列化学反应得到了手性合成子5-(L-孟氧基)-2(5H)-呋喃酮3和5-(L-孟氧基)-3-溴-2(5H)-呋喃酮5a。(2)氮气保护下,在碱性介质中5a作为Michael受体,用四丁基溴化铵(TBAB)催化与氮亲核试剂伯胺进行串联的不对称Michael加成及分子内亲核取代反应,合成得到了目标分子手性5-(R)-(1R,2S,5R)-孟氧基-丁内酯[3,4-b]-2(S)-6(R)-1-N-烷基氮杂环丙烷7a-7d,ee≥98%,并从分子角度研究了化合物7a、7b的晶体结构。(3)氮气保护下,在THF溶剂中用LiAlH4对化合物7进行有效的还原,柱层析分离,纯化后得到高产率含有两个羟基的功能性2(S),3(R)-二羟基甲基-N-烷基氮杂环丙烷8a-8d,并从分子角度研究了8a、8b、8c的晶体结构。(4)新方法合成了含氮化合物苯腙基乙酰基二取代乙酸乙酯9和2,2-二氯乙酸环己铵盐10,并描述了其晶体结构。化合物9中有分子内氢键,整个分子处于热力学稳定状态。化合物10相邻分子间的多种氢键,使得该分子结构非常稳定。更多还原

【Abstract】 The versatility and high reactivity of the aziridines make them attractive intermediates for the synthesis of various types of organic molecules, such as chiral amines, aminoacids, amino alcohols, alkaloid,β-lactamic, polymers. Moreover, chiral aziridines have been utilized as ligands and auxiliaries in efficient asymmetric synthesis. A number of synthetic aziridines have found biological applications as antitumor agents,antibiotics and as enzyme inhibitors. Several naturally occurring aziridines have been shown to exhibit antibiotic and antitumor activity. Despite these interests, the methods for the synthesis of these compounds in enantiomerically pure form are rather limited. In this paper, some aziridines with new structure have been synthesized based on the patented applied prospects and the main results as follows: (1) chiral sythons for 5-menthyloxy-2-(5H)-furanone (3) and 3-bromo-2(5H) -furanone (5a) were synthesized via photochemical reaction, acetalization, bromine addition and elimination reaction for hydrogen bromide using furfural, a very cheap material. The synthesis of racemic 5-menthyloxy-2-(5H)-furanone (3) was conveniently achieved in good yield through acetalization of the resulting 5-hydroxy-2(5H)-furanone (2) in menthol under refluxing, which is easily obtained by the photooxidation of furfural. 5-menthyloxy-3-bromo-2(5H)-furanone 5a was easily prepared in four steps in good yield from furfural (1) on large scale.(2) 5-(R)-menthyloxy-butyrolacto[3,4-b]-2(S)-6(R)-1-N-alkyl-aziri-更多还原