含 β-胺基-α, β-不飽和酮及蔥基三唑取代芳杯之合成及其金屬離子感測研究

Abstract

本論文成功的在1,3-alternate 構形芳杯兩端分別利用即合化學與1,3-偶極環化加成反應合成出具有蔥基三唑基團與異咢唑(isoxazole)基團的化合物60，接著使用Mo(CO)6進行開環得到具β-胺基-α,β-不飽和酮的雙位接收器化合物61。我們亦合成了用雙丙基選擇性將其中一端保護起來的控制化合物48及56，進行紫外-可見光、螢光及氫核磁共振光譜量測來了解化合物61與多種金屬離子間的錯合能力。由紫外-可見光光譜與螢光光譜得知在CHCl3/CH3CN = 1：499溶劑體系下，化合物61對於Na+與Pb2+較有選擇性。Job Plot與氫核磁共振滴定光譜顯示出Na+與Pb2+分別以1：1比例錯合在化合物61下緣醚基的氧原子與不飽和酮羰基的氧原子上。我們也發現芳杯上苯環有輔助金屬錯合的現象。在金屬競爭實驗中顯示Pb2+對於61的錯合能力較Na+強，低濃度時即可使紫外-可見光與螢光變化達飽和。由non-linear fitting method計算出Pb2+ 對於61•Na+ 的錯合常數約為1.28×106 M-1,我們也利用了non-linear fitting method 在Na+ 對於61•Pb2+ 的實驗中得到錯合常數為56.9 M-1。 我們也進行了化合物61在較高極性溶劑下的金屬離子篩選實驗，在CHCl3/CH3OH = 1：49溶劑體系下發現 61 對Ag+有極佳的篩選能力，錯合Ag+後螢光可增強4.6倍。氫核磁共振滴定光譜顯示化合物61與Ag+的錯合比例為1：2，在化合物48與56的氫核磁共振光譜滴定實驗中顯示三唑基團與不飽和酮基團皆會錯合Ag+離子。在快原子撞擊質譜(FAB)中也發現了61與Ag+錯合比例為1：2的質譜訊號m/z = 750，因此我們推論Ag+會同時錯合於芳杯61的三唑基團與β-胺基-α,β-不飽和酮基團上並形成1：2的錯合。

In this thesis, we synthesized a new chemosensor based on 1,3-alternate calix[4]arene 60 with isoxazole and triazole units which were introduced by 1,3-dipolar cycloaddition and click reaction. Followed by Mo(CO)6 mediated ring-opening reaction of isoxazole, a novel ditopic receptor calix[4]arene 61 constructed by anthrylmethyl-triazole and β-amino-α,β-unsaturated ketone groups was obtained. Two control compounds 48 and 56 were also synthesized. The metal ions binding abilities of 48, 56, and 61 toward were invesitigated by UV-vis, fluorescence and 1H-NMR spectroscopy. Using UV-Vis and fluorescence spectra for screening, we found that 61 was selective toward Na+ and Pb2+ in CHCl3/CH3CN = 1:499. Job Plot and 1H-NMR titration experiment show that the binding ratio of 61 toward Na+ and Pb2+ was 1:1, respectively. The binding site of 61 toward Na+ and Pb2+ was proposed to be between phenolic-O and the C=O group on the β-amino-α,β-unsaturated ketone, we also found that Na+ and Pb2+ were chelated on 61 with the help of phenol at calixarene. The competitive experiment of 61 with Na+ and Pb2+ showed that even at low concertation can make the absorption and fluorescence saturated. The Ka of 61•Na+ + Pb2+ caculated by non-linear fitting method were 1.28×106 M-1, we also get the Ka of 61•Pb2+ + Na+ from non-linear fitting method is 56.9 M-1。 Futhermore, the metal ions screening of 61 by UV-vis and fluorescence experiments of 61 spectroscopy were carried out in more polar solvent. In the CHCl3/CH3OH = 1:49 solvent system, 61 was found to be selectivity toward Ag+, which caused an enhancement of its fluorescence by 4.6-fold. According to 1H-NMR titration experiment, we proposed that the binding ratio of 61 with Ag+ is 1:2. Further evidence of the formation of complex 61•(Ag+)2 came from the observation of m/z = 750 in FAB Mass spectrum. In the 1H-NMR titration experiments of control compounds 48 and 56 also showed that Ag+ can be chelated by both of β-amino-α,β-unsaturated ketone and triazole units. So we proposed that 61 can bind 2 eq of Ag+ at the same time, one at the β-amino-α,β- unsaturated ketone and the other at triazo units, to form a 1:2 complex.