CAJ | 학술논문

通过单-2-对甲苯磺酰基-β-环糊精(1)与马来二腈基二硫烯钠盐的取代反应制得单-2-马来二腈基二硫烯-β-环糊精(2),并经红外光谱、紫外光谱、热重分析、1H和13C NMR等手段对产物进行了表征.虽然化合物2的异构体--单-6-马来二腈基二硫烯9-β-环糊精在溶液中因为相互包合作用而在圆二色性光谱中产生分裂的Cotton效应峰,但是单-2-马来二腈基二硫烯-β-环糊精则显示完全的圆二色性非活性.经过时间依赖的密度泛函理论(TD-DET)计算,圆二色性光谱中的信号得到了有效的归属和确认.实验数据和理论计算结果均表明,在环糊精不同羟基面进行取代而得到的异构体在溶液中确实存在不同的组装和包合模式.
통과단-2-대갑분광선기-β-배호정(1)여마래이정기이류희납염적취대반응제득단-2-마래이정기이류희-β-배호정(2),병경홍외광보、자외광보、열중분석、1H화13C NMR등수단대산물진행료표정.수연화합물2적이구체--단-6-마래이정기이류희9-β-배호정재용액중인위상호포합작용이재원이색성광보중산생분렬적Cotton효응봉,단시단-2-마래이정기이류희-β-배호정칙현시완전적원이색성비활성.경과시간의뢰적밀도범함이론(TD-DET)계산,원이색성광보중적신호득도료유효적귀속화학인.실험수거화이론계산결과균표명,재배호정불동간기면진행취대이득도적이구체재용액중학실존재불동적조장화포합모식.
Mono [ 2-deoxy-2- (O-p-toluensulfonyl) ] -β-cyclodextrin ( 2-Ots-β-cyclodextrin, compound 1 ) was substituted with 2-butenedinitrile-2,3-dimercapto sodium salt to give the product mono [ 2-deoxy-2-( 2-butenedinitrile-2,3dimercapto sodium salt) ]-β-cyclodextrin (2-Mnt-β-cyclodextrin, compound 2). Compound 2 was characterized by IR spectroscopy, UV spectroscopy, thermogravimetry, 1H and 13C NMR spectroscopy. Different from its isomer mono[ 6deoxy-6-(2-butenedinitrile-2,3-dimercapto sodium salt)]-β-cyclodextrin(6-Mnt-~-cyclodextrin) showing splitting Cotton effects via mutual inclusion complexation, 2-Mnt-β-cyclodextrin exhibited the absence of any circular dichroism (CD) signal in solution. In the meantime, quantum chemistry methods( time dependent-density functional theory,TD-DFT) were recruited in assisting assignment and prediction of the CD signals in spectra. Based on both the theoretical approach and experimental data, the different conformations of the two ionized isomers were revealed.