臺灣博碩士論文加值系統

本論文主要分為兩大主題，第一個主題是在探討對苯二胺衍生物的合成、電化學與光譜電化學研究。本研究探討對苯二胺衍生物的苯環及甲基取代對於氧化電位的影響，並研究其光譜電化學。研究發現，當對苯二胺上的氫以苯環的取代數目越多時，氧化電位越正，表示苯環數目越多，越不易氧化；而當甲基的取代數目越多時，氧化電位越負，表示甲基取代數目越多，越容易氧化。
第二個主題則是研究對苯二胺衍生物藉由滴定不同pKa的含氮鹼，以電化學的方式觀察化合物氧化後誘導與不同的鹼產生氫鍵的能力。在循環伏安法中可以得知，此類的對苯二胺衍生物，當含氮鹼加入後，第二個氧化波隨著含氮鹼濃度的增加會出現新的氧化波，且含氮鹼的pKa大小會影響第三個氧化還原波的電位。這指出，當對苯二胺上的氫經過氧化後會與含氮鹼的氮原子誘導產生氫鍵。

This work has included two topics. The first one has been concerned with p-phenylenediamines synthesis, electrochemistry and spectroscopy. The phenyl and methyl substituents of p-phenylenediamine derivatives exhibit effects on the oxidation potential and spectra. Phenyl group substitution on p-phenylenediamines caused the oxidation potential to be more positive while methyl groups made the compounds easier to oxidize. A correlation of oxidation potential with the number of substituents was delineated.
The second topic is about the electrochemically induced hydrogen bonding of the p-phenylenediamine derivatives with pyridines and imidazoles. During the oxidative scans of p-phenylenediamine derivatives in presence of bases, a new redox couple was observed and the second oxidation wave disappeared gradually. The potential of the new redox couple exhibited linearity with the pKa of the base. A reaction scheme involving complex formation upon redox reactions is thus proposed.

第一章 緒論 1
第一節 價間電子傳導 (Intervalence charge transfer, IVCT) 1
第二節 氫鍵與受體 3
(i) 氫鍵 (Hydrogen bond) 3
(ii) 受體 (receptor) 7
第三節 研究目的 9
第二章 實驗 10
第一節 藥品 10
第二節 對苯二胺衍生物的合成 12
(i) N, N-diphenyl-p-phenylenediamine, (3) 12
(ii) N, N, N』 -triphenyl-p-phenylenediamine, (5) 12
(iii) N, N, N』, N』 -tetraphenyl-p-phenylenediamine, (6) 13
(iv) N, N, N』 -trimethyl-N』-phenyl- p-phenylenediamine, (9) 13
(v) N, N-dimethyl-N』, N』 -diphenyl- p-phenylenediamine, (10) 13
(vi) N, N』 -dimethyl-N, N』 -diphenyl- p-phenylenediamine, (11) 14
(vii) N-methyl-N, N』, N』 -triphenyl- p-phenylenediamine, (12) 14
第三節 儀器設備與方法 15
(i) 電化學儀器 15
(ii) 光譜電化學裝置 15
第三章 對苯二胺之電化學與光譜電化學 16
化合物p-phenylenediamine (1) 16
化合物N-phenyl-p-phenylenediamine (2) 19
化合物N, N-diphenyl-p-phenylenediamine (3) 20
化合物N, N』 -diphenyl-p-phenylenediamine (4) 22
化合物N, N, N』 -triphenyl-p-phenylenediamine (5) 24
化合物N, N, N』, N』 -tetraphenyl-p-phenylenediamine (6) 26
化合物N, N, -dimethyl-p-phenylenediamine (7) 28
化合物N, N, N』, N』 -tetramethyl-p-phenylenediamine (8) 31
化合物N, N, N』 -trimethyl-N』-phenyl-p-phenylenediamine (9) 34
化合物N, N-dimethyl-N』, N』 -diphenyl-p-phenylenediamine (10) 35
化合物N, N』 -dimethyl-N, N』 -diphenyl-p-phenylenediamine (11) 38
化合物N-methyl-N, N』, N』 -triphenyl-p-phenylenediamine (12) 40
第四章 對苯二胺之氧化態與吡啶之作用 50
化合物 N, N』 -diphenyl-p-phenylenediamine (4) 51
化合物N, N, N』 -triphenyl-p-phenylenediamine (5) 57
第五章 對苯二胺之氧化態與咪唑之作用 73
化合物 p-phenylenediamine (1) 73
化合物 N-phenyl-p-phenylenediamine (2) 74
化合物 N, N』 -diphenyl-p-phenylenediamine (4) 75
化合物 N, N, N』-triphenyl-p-phenylenediamine (5) 77
化合物 N, N, N』, N』-tetraphenyl-p-phenylenediamine (6) 79
化合物 N-methyl-N, N』, N』 -triphenyl-p-phenylenediamine (12) 81
結論 83
參考文獻 84

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