臺灣博碩士論文加值系統

論文主要研究之方向為兩部份，分別為掌性芳杯之合成與對掌
性分子之辨識研究，以及掌性芳杯對金屬離子之感測討論。
首先，我們成功合成出在芳杯下緣鄰位具有 (S)-(-)-BINOL 冠醚
之芳杯衍生物(S)-(-)-42a-b，以及進一步衍生化至(S)-(-)-43a-b、
(S)-(-)-44a-b 與(S)-(-)-49a-b，分別進行一系列紫外可見光光譜之量測，將化合物(S)-(-)-44a-b 與 (S)-(-)-49a 針對八類掌性小分子50-57進行螢光光譜篩選，觀察到螢光增強的現象，利用非線性回歸方法得到主客間之結合常數。以(S)-(-)-44a 而言，由大至小分別為：(S)-53 (S)-55 (S)-54 (S)-52 (S)-50 (S)-51 (S)-56 ? (S)-57，從中討論並且比較其掌性辨識能力，發現其中對53 有最佳的辨識效果（Kass(R)= 3.41*104 M-1, Kass(S) = 3.21*105 M-1, Kass(R)/Kass(S) = 1/9.41）。另外，在與其他客體的錯合中，我們可以歸納整理出各種情況之辨識特性，希望藉由相互比較來推論得到合理的錯合模式並探究影響掌性辨識的行為因素。

In this thesis, a series of binaphthyl-derived chiral calix[4]crowns were synthesized and their recognition abilities toward chiral amino alcohols and metal ions were studied.
We have synthesized a series of (S)-(-)-binaphthyl-appended calix[4]crown-n ether (n = 6, 8) 41-49, which were substituted with mono- or proximal bis-carboxyl groups. The complexation properties of binaphthyl hosts (S)-(-)-44a-b and (S)-(-)-49a toward chiral amines, amino alcohols, alcohols and diols 50-57 were investigated by the
UV-visible, fluorescence and CD spectroscopies. Possible binding modes of these chiral hosts toward amino alcohols 50 and 52-55 were discussed. The association constants (Kass)63 of 44a, 44b or 49a with chiral guest molecules were calculated by the nonlinear fitting method of the fluorescence spectra. Furthermore, the binding ratio of 44a-b and 49a with chiral guests were determined by Job plots. The results showed that the binding abilities of 44a toward guests decrease in the order of (S)-53 (S)-55 ? (S)-54 ? (S)-52 ? (S)-50 (S)-51 (S)-56 ? (S)-57. Furthermore, 44a exhibited a great performance for 53 in enantiomeric discrimination (Kass(R) = 3.41*104 M-1, Kass(S) = 3.21*105 M-1, Kass(R)/Kass(S) = 1/9.41). The comparisons of these complexes would gives an insight into the chiral recognition.

中文摘要............................................. I
英文摘要............................................. III
目錄 ............................................. IV
圖目錄 ............................................. VI
式圖目錄.............................................. XIV
表目錄 .............................................. XVI
式目錄 ..............................................XVII
附圖目錄...............................................XVII
化合物對照表...........................................XXV
第一章 緒論............................................... 1
1.1 前言.................................................. 1
1.2 掌性辨識之起源與發展原理.............................. 1
1.3 螢光化學感測器之作用原理.............................. 5
1.4 BINOL 之起源與發展.................................... 7
1.5 冠醚之起源與發展..................................... 16
1.6 芳杯之起源與發展..................................... 19
第二章 .研究動機與合成................................... 34
2.1 含芳杯之掌性辨識感測器的設計與合成................... 35
第三章 結果與討論........................................ 37
3.1 p-tert-Butylcalix[4]arene 20 之合成.................. 37
3.2 Calix[4]arene 21 之合成.............................. 38
3.3 1,1'-Binaphthyl-2,2'-diol rac-1 之合成............... 39
3.4 雙對甲苯磺酰基取代BINOL 之醚類衍生物 38a、.38b 及rac-38b 之合成............................................... 41
3.5 p-tert-Butylcalix[4]arene 下緣鄰位端修飾冠醚衍生物
.之合成.................................................. 42
3.6 探討BINOL 修飾冠醚之芳杯衍生物之合成............. 53
3.7 圓二色光譜（Circular Dichroism spectra）之量測.... 64
3.8 對-第三丁基芳杯修飾BINOL 之冠醚衍生物莫耳
.吸收係數之量測.......................................... 69
3.9 對-第三丁基芳杯修飾BINOL 之冠醚衍生物對掌
.性分子篩選能力之量測.................................... 71
3.10 對-第三丁基芳杯修飾BINOL 之冠醚衍生物對掌
.性分子結合常數之量測.................................... 79
3.11 對-第三丁基芳杯修飾BINOL 之冠醚衍生物對金
.屬離子篩選能力之量測................................... 112
第四章 結............................................... 120
第五章 實驗部份......................................... 123
5.1 試藥及測試方法...................................... 123
5.2 實驗步驟及光譜資料.................................. 125
第六章 參考文獻......................................... 151
第七章 附圖............................................. 160
6.1 部分1H-NMR 及13C-NMR 光譜圖......................... 161
6.2 化合物(S)-(-)-49a 的ORTEP 圖與晶體參數..... 236
簡歷 ................................................... 244

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