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系統識別號 U0002-1109201515394100
中文論文名稱 新式含氮橋基雙氮雜菲衍生之化合物合成、結構與性質研究
英文論文名稱 The New Bis(1,10-phenanthrolin-2-yl)amine Derivatives: Synthesis,Structure and Properties
校院名稱 淡江大學
系所名稱(中) 化學學系碩士班
系所名稱(英) Department of Chemistry
學年度 103
學期 2
出版年 104
研究生中文姓名 張翔
研究生英文姓名 Hsiang Chang
學號 601160525
學位類別 碩士
語文別 中文
口試日期 2015-07-21
論文頁數 50頁
口試委員 指導教授-王文竹
委員-劉陵崗
委員-賴重光
中文關鍵字 含氮橋基雙雜菲  酸解離常數  關聯性磁振頻譜 
英文關鍵字 Bis(1,10-phenanthrolin-2-yl)  Acid dissociation constant  COSY 
學科別分類 學科別自然科學化學
中文摘要 以1,10-二氮雜菲(1,10-phenanthroline)為基礎,所形成特殊類大環分子HDPA (bis(1,10-Phenanthrolin-2-yl)amine)的衍生物有別以往合成,L1。L1是與HDPA以往衍生物在不同氮上的取代,選擇其中一邊雜菲環上的外側氮加成而非在於橋雞氮上做取代,這樣的反應形成了一個不對稱的分子結構。而由於純化上替換陰離子所形成L2化合物。

在L1以及L2的NMR光譜圖之間沒有太大差異,圖譜中由於不對稱性使得圖譜呈現許多個積分值為1的雙重峰,而且許多訊號峰有重疊情況難以判別因此利用二維的光譜技術,H-H COSY、HMQC及HMBC的方法來準確判別氫及碳的NMR光譜,並用ESI-MS確認其質量而確定是離子化合物以及有成功置換陰離子形成L2,並測量兩化合物的電化學性質。在酸鹼滴定實驗中,利用電子吸收光譜來偵測,經由計算後知道兩化合物的pKa值為3.31與2.98,並與起始物HDPA及橋基氮上取代衍生物做比較。並初步的測量兩化合物的電化學性質。

這樣的結果是形成一個離子化合物,反應上有別於HDPA橋基氮上取代的簡易的反應程序以及最後的高產率。這樣的衍生物雖然與金屬上配位是不太可行的,但由於烷鏈末端是高反應性的碘,而有高反應性,在於衍生上還是有很大的可能。

英文摘要 In this research, new ionic compounds base on 1,10-phenanthroline, L1 and L2 were synthesized with high yield. L1 was synthesised by the reaction of macrocyclic molecule HDPA (bis(1,10-phenanthrolin-2-yl)amine) with 1,6-diiodohexane. The L1 was designed for different reaction site with HDPA derivatives synthesized in other research.
L1 is synthesized by the modification of phenanthroline instead of bridge nitrogen of HDPA and generate an asymmetric structure. L2 was synthesized by the exchange of anion for the solubility.
The H-H COSY, HMQC and HMBC technology were used for solving the aromatic signal of L1 and L2. And L1 and L2 were identified by ESI-MS. The acid titration UV-Vis experiments shows Pka of L1 was 3.13 and Pka of L2 was 2.98. The oxidation potential of L1 were -0.19 eV, -0.89 eV and L2 were -0.73 eV, -1.07 eV. The reduction otenrial of L1 were 0.68 eV, 0.93 eV and L2 were 0.76 eV, 0.88 eV.
論文目次 目錄

中文摘要
英文摘要

第一章 緒論 1
1-1 環芳烴化合物 1
1-2 橋基雜菲分子 2
1-3 含氮橋基雜菲分子 3
1-4 設計 4

第二章 實驗 5
2-1 實驗藥品 5
2-2 實驗儀器 6
2-2-1 核磁共振光譜 6
2-2-2 電子吸收光譜儀 6
2-2-3 電灑法質譜分析儀 6
2-2-4 電化學儀 7
2-3 酸滴定實驗 7
2-4 電化學實驗 7
2-5 合成 8

第三章 結果與討論 14
3-1 分子的合成 14
3-1-1 HDPA的合成 15
3-1-2 L1的合成 15
3-1-3 L2的合成 15
3-2 一般光譜圖 17
3-2-1 1H-NMR光譜圖 17
3-2-2 13C-NMR光譜圖 20
3-2-3 電灑離子化質譜 21
3-2-4 電子吸收光譜 25
3-2-5 循環伏安譜圖 29
3-3 二維核磁共振光譜圖 31
3-3-1 1H-1HCOSY 31
3-3-2 HMQC 33
3-3-3 HMBC 35
3-4 酸滴定 36
3-4-1 L1酸滴定光譜 37
3-4-2 L2酸滴定光譜 39
3-4-3 酸解離常數計算 41

第六章 結論 43

參考文獻 44

附錄 45

圖目錄

Figure 3-1 1H-NMR 300 MHz of L1 in DMSO-d6 . 18
Figure 3-2 1H-NMR 600 MHz of L1 in DMSO-d6 . 19
Figure 3-3 1H-NMR 300 MHz of L2 in DMSO-d6. 19
Figure 3-4 150 MHz 13C-NMR spectrum of the L1 in DMSO-d6 . 20
Figure 3-5 ESI-MS spectrum of L1 ( c = 1 x 10-5 M) in CH3OH (full scan). 21
Figure 3-6 ESI-MS spectrum of L1 ( c = 1 x 10-5 M) in CH3OH ,zoom scan for 584 m/z. 22
Figure 3-7 ESI-MS spectrum of L2 ( c = 1 x 10-5 M) in CH3OH 23
Figure 3-8 ESI-MS spectrum of L2 ( c = 1 x 10-5 M)in CH3OH (zoom scan for 584 m/z ) 23
Figure 3-9 ESI-MS spectrum of L2 ( c = 1 x 10-5 M) in CH3OH zoom scan for 292 m/z ) 24
Figure 3-10 ESI-MS spectrum of L2 ( c = 1 x 10-5 M) in CH3OH for anion detection.( zoom scan for
PF6- m/z =145) 24
Figure 3-11 ESI-MS spectrum of L2 ( c = 1 x 10-5 M) in CH3OH for anion detection.( zoom scan for I-
m/z =127) 25
Figure 3-12 UV-vis spectrum of L1 in CH3CN in 298K , normailize abs. to 1.0 for wavelength
214nm. 26
Figure 3-13 Variable-concentration UV-Vis spectra of L1 for different concentration. 26
Figure 3-14 Variable-concentration UV-Vis fitting spectra of L1 in CH3CN for different
concentration in 320 nm fitting. ( red line is fit linear of L1 ) 27
Figure 3-15 UV-vis spectrum of L2 in CH3CN in 298K, normailize abs. to1.0 for wavelength
214nm. 28
Figure 3-16 Uv-vis of PeDPA,HDPA L1and L2 normailize absorbance to1.0 for the highest peak in
210~250 nm.( all in CH3CN ). 29
Figure 3-17 Cyclic voltammograms of L1 in CH3CN solution at 298K.( 0.05M NBu4PF6 , Glassy
carbon electtode, 100m V/s scan rate) 30
Figure 3-18 Cyclic voltammograms of L2 in CH3CN solution at 298K.( 0.05M NBu4PF6 , Glassy
carbon electtode, 100m V/s scan rate) 31
Figure 3-19 600 MHz 1H-1H COSY spectrum of the L1 in DMSO-d6 ( for long alkyl chain). 32
Figure 3-20 600 MHz 1H-1H COSY spectrum of the L1 in DMSO-d6 ( for aromatic part ). 33
Figure 3-21 HMQC spectrum of the L1 in DMSO-d6. 34
Figure 3-22 HMQC spectrum of the L1 in DMSO-d6. ( for long alkyl chain ) 34
Figure 3-23 HMQC spectrum of the L1 in DMSO-d6. ( for aromatic part ) 35
Figure 3-24 NMR 600 MHz HMBC spectrum of the L1 in DMSO-d6 (for aromatic part) 36
Figure 3-25 UV-vis absorption spectra pH acid titration of L1 ( c = 1.04 x 10-5 M ) in CH3CN drop
by HCl(aq) in CH3CN. 37
Figure 3-26 UV-vis absorption spectra pH acid titration of L1 ( 1.04 x 10-5 M in CH3CN ) as
function of pH between 6.85 and 4.40. 38
Figure 3-27 UV-vis absorption spectra pH acid titration of L1 ( 1.04 x 10-5 M in CH3CN ) as
function of pH between 4.40 and 2.26. 38
Figure 3-28 UV-vis absorption spectra pH acid titration of L2 (c = 3.23 x 10-5 M ) in CH3CN drop
by (c = 1.00x 10-2 M or 1.00 x 10-3 M ) HCl(aq) in CH3CN. 39
Figure 3-29 UV-vis absorption spectra pH acid titration of L2 ( 3.23 x 10-5 M in CH3CN ) as
function of pH between 6.70 and 4.13. 40
Figure 3-30 UV-vis absorption spectra pH acid titration of L2 ( 3.23 x 10-5 M in CH3CN ) as
function of pH between 4.13 and 1.87. 40
Figure 3-31 Variation of absorbance as s fouction of pH for L2 ( 3.23 x 10-5 M ) for slection of
wavelength. (point are the experimental point.) 41
Figure 3-32 Plot of log [ ( Ai – A / A - Af ) ] vs. pH for wavelength 320 nm with L1 ,
pKa = 3.13 ± 0.10 and Ka = 7.61 ( ± 1.73 ) x 10-4. 42
Figure 3-33 Plot of log [ ( Ai – A / A - Af ) ] vs. pH for wavelength 320 nm with L2,
pKa = 2.98 ± 0.03 and Ka = 1.05 ( ± 0.5 ) x 10-3. 43
Figure A-1 1H-NMR 300 MHz of L1 in DMSO-d6 . 46
Figure A-2 1H-NMR 300 MHz of L2 in DMSO-d6 . 47
Figure A-3 1H-NMR 600 MHz of L1 in DMSO-d6 . 48
Figure A-4 1H-NMR 600 MHz of L1 in DMSO-d6 (for long alkyl chain). 49
Figure A-5 1H-NMR 600 MHz of L1 in DMSO-d6 (for aromatic part). 50

表目錄

Scheme 1 Scheme 1 Synthesis of L1 and L2. 16
Scheme 2 Scheme 2 A reaction mechanism of CP reacted to HDPA. 17
Table 5-1 Table of HDPA, NpDPA, L1 and L2 ( in CH3CN ) with pKa1 and pKa2 value. 43


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15. 高憲章, 博士論文, 私立淡江大學化學研究所, 民國99年5月
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