碘化1-甲基-2-异丙基(或丙基)-3-苯磺酰基咪唑啉的合成及基团转移反应  

Synthesis and Group Transfer Reaction of 1-Methyl-2-isopropyl(or propyl)-3-benzenesulfonyl Imidazolidinium Iodide

作　　者：温雪山[1,2] 霍明章[3] 陈建新[1] 

机构地区：[1]山西师范大学化学与材料科学学院,临汾041004 [2]宁夏环境监测站宁东能源化工基地,银川750000 [3]山西大同大学医学院,大同037008

出　　处：《高等学校化学学报》2015年第5期893-898,共6页Chemical Journal of Chinese Universities

基　　金：山西省留学回国人员基金(批准号:0713);山西省自然科学基金(批准号:2012011046-9);山西师范大学基金(批准号:SD2014CXXM-53)资助~~

摘　　要：合成了新的四氢叶酸辅酶(THF)模型化合物碘化1-甲基-2-异丙基-3-苯磺酰基咪唑啉(5a)和碘化1-甲基-2-丙基-3-苯磺酰基咪唑啉(5b),研究了其反应性能.结果表明,化合物5与双官能团亲核体邻苯二胺或邻氨基苯酚反应,完全转移了4个碳的异丁基和正丁基单元,基于此探索了合成2-取代苯并咪唑及2-取代苯并唑的新方法;化合物5a与单官能团亲核体胺类反应部分转移了4个碳的异丁基单元,生成不同基团取代的N,N,N'-三取代乙二胺盐;化合物5a在Na BH4作用下可发生还原反应,在Na OH水溶液中可发生水解反应,也可与碳负离子基团(硝基甲基负离子或二腈基甲基负离子)发生亲核加成反应,生成了3类不同基团取代的N,N,N'-三取代乙二胺衍生物,探索了此类化合物的简易合成方法.这些反应模拟了四氢叶酸辅酶在生物体内转移一碳单元的功能,并将其扩展到4个碳原子单元,获得了可应用于有机合成的新方法和新试剂.In the course of developing synthetic methods based upon mechanisms of biochemical processes,1-methyl-2-isopropyl-3-benzenesulfonyl imidazolidinium iodide（5a） and 1-methyl-2-propyl-3-benzenesulfonyl imidazolidinium iodide（5b） were prepared as the tetrahydrofolate model compounds at the oxidation level of formate,which reacting with bifunctional nucleophiles o-phenylenediamine and 2-aminophenol.In the synthetic process,four carbon fragments were transferred completely and we found a way directly to benzimidazoles,benzoxazoles.The reaction of the model compound 5a with monofunctional nucleophiles（butylamine,aniline,benzylamine,p-methoxyaniline） afforded the products transferred part of four carbon fragments,containing three different groups of N,N,N＇-trisubstituted ethylenediamine salt.Sodium borohydride reduction of 5a afforded compound 9.Treatment of compound 5a with Na OH caused hydrolysis and the corresponding carbonyl compound 10 was formed.The nucleophilic addition reaction of compound 5a with some carbanion（nitromethane carbanion and malononitrile carbanion） gave compounds 12 and 13,respectively.Compounds 9,10,and 12 or 13 are three kinds of containing different groups of N,N,N＇-trisubstituted ethylenediamine.

关 键 词：四氢叶酸 咪唑啉盐 转移反应 模型 加成反应 

分 类 号：O621.3[理学—有机化学]