联苯型[11],[14]和[17]环系氮杂支链套索冠醚的合成  

Studies on Synthesis of New Biphenyl 11,14 and 17 - Membered Ring N - Pivot Lariat Crown Ethers

作　　者：刘刚[1] 牛长荣[2] 吴成泰[2] 

机构地区：[1]湖南怀化师范高等专科学校化学系,湖南怀化418008 [2]武汉大学化学系,湖北武汉430072

出　　处：《有机化学》1996年第1期23-28,共6页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金

摘　　要：以碳酸钾为缩合剂２，２’－二羟基联苯分别与二对甲苯磺酸酯Ⅱａ～ｃ，Ⅳｂ，Ⅵｂ反应合成尚未见文献报道的联苯型单氮杂冠醚（１～３），二氮杂冠醚９和１１，３，９和１１分别用氢溴酸去甲苯磺酰基得到亚胺型氮杂冠醚４，１０和１２。４与溴代烃ＲＢｒ（ｒ＝－（ＣＨ２）３ＣＨ３－ＣＨ２ＣＨ＝ＣＨ２－（ＣＨ２）７ＣＨ３－（ＣＨ２）２Ｏ（ＣＨ２）２ＯＣ４Ｈ９）反应分别合成（１１）环系氮支套索冠醚（５～８）。New diphenyl 11 - membered ring aza crown ethers(l - 3), 14 and 17 - membered ring diazacrown ethers(9, 11) were prepared by ome step reaction of 2, 2' - dihydroxydephenyl with com-pouds TsO(CH2CH2N)m(CH2CH2O)nCH2CH2NCH2CH2OT3( Ⅱ a: m = n = 0, R = C6H5 - ; Ⅱ b: m =n=0,R=p-CH3C6H4;22222c:m = n = 0, R = Ts;Ⅳ b: m = 1, n = 0, R = Ts;Ⅵ b: m = n =1,R=Ts; Ts= tosy1) in DMF at 100 - 110℃ , using anhydrous patassium carbonate as condensing agent. The tosyl groups of 3, 9 and 11 were removed by treatment with 40 % HBr in ACOH in the presence of a large amount of phenol. Three new azacrown ethers 4, 10 and 12 were formed from 3, 9 and 11 respectively. New N - pivot lariat crown ethers 5 -8 and 13 were prepared by one step reaction of 4 and 12 with RBr in CH3Cn at reflux temperature, using anhydrous K2CO3 as condensing ageny. They were characterized by elemental analysis, IR, 1H NMR and MS.

关 键 词：二羟基联苯 氮朵冠醚 合成 

分 类 号：O626.5[理学—有机化学]