臺灣博碩士論文加值系統

鄰氨基苯甲酸是具有非常豐富的物理化學生物及藥性特質，是一種重要的β胺基酸。目前已經知道鄰氨基苯甲酸有三種不同的晶體結構：
一、 室溫下，乙醇溶液揮發生成結晶，空間群為Pna21。
二、 攝氏80度下，昇華生成結晶，空間群為Pbca；大量真空昇華，生成結晶，空間群為P21/c。
三、 加熱至攝氏150度融化成液態後，降溫凝固生成結晶，空間群為P21/c。
在本研究中，我們鑑定了三種晶體各自的晶體結構，並確認了這三種晶體從低溫 -100 °C到室溫都是穩定存在的。透過熱重分析、熱差分析的實驗結果，我們也得到了三種晶體各自的昇華速率、活化能、反應熱焓等動力學數據。透過分析動力學數據的差異，確認了加熱過程中觀察到的Pna21晶體晶相轉變應是轉變為P21/c。透過氫譜的鑑定分析，確認了鄰氨基苯甲酸受熱裂解的產物為苯胺和二氧化碳並粗略探討溫度對裂解速率的影響。最後根據文獻方法將鄰氨基苯甲酸應用在含鎳金屬染料的合成上，將2-吡啶甲醛與氨基苯甲酸縮合成鉗合配體並配位至鎳，製備出紅色染料結晶。

Anthranilic acid has various properties in chemistry, physics and medicinal activities. In addition to these, anthranilic acid has three known polymorphic forms:
1. Crystals in pace group Pna21 are formed with slow evaporation from EtOH at room temperature.
2. Sublimation of crude anthranilic acid at 80 °C produces crystals in space group Pbca; vacuum sublimation of crude anthranilic acid at 80 °C however produces crystals in space group P21/c.
3. Upon heating anthranilic acid to a melt at 150 °C then cooling to a solidification anthranilic acid crystalizes in space group P21/c.

In this study, all three polymorphic forms were studied with X-ray crystallography without phase transition from -173 °C to room temperature. Kinetic data such as sublimation rate, activation energy, enthalpy ΔH‡ were determined by TGA and DSC experiments using the transition state theory. We also acknowledged that Pna21 phase transition before melt is the transition to P21/c. 1H NMR experiments showed that anthranilic acid decomposes to aniline and carbon dioxide at high temperature. Above all, anthranilic acid was employed as a starting material to the synthesis of a metal dye complex, which was an imine condensed by anthranilic acid and pyridine-2-carboxaldehyde and coordinated to a nickel metal ion.

摘要..........................I
Abstract....................II
目錄........................III
圖目錄.......................IV
表目錄.......................IV
第一章 緒論...................1
一、 前言.....................1
二、 研究動機.................3
第二章 結果與討論..............4
一、 晶體結構.................4
二、 昇華速率................10
三、 熱差分析................15
四、 熱裂解實驗..............17
五、 動力學探討..............22
六、 衍生物合成..............23
七、 結論....................24
第三章 實驗部分..............25
一、 儀器部分................25
二、 鄰氨基苯甲酸晶體製備.....26
三、 熱重分析................26
四、 熱差分析................26
五、 熱裂解實驗..............27
六、 衍生物合成..............27
參考文獻....................28
附錄........................29
一、 TGA實驗數據.............29
二、 熱裂解實驗氫譜數據.......46

1.Zapała, L.; Kalembkiewicz, J.; Sitarz-Palczak, E. Biophys. Chem. 2009, 140, 91-98.
2.Yoon, U. C.; Mariano, P. S. Arc. Chem. Res. 1992, 25, 233.
3.Hardy, G. E.; Kaska, W. C.; Chandra, B. P.;Zink, J. I. J. Am. Chem. Soc. 1981, 103, 1074-1079.
4.Davidson, R. S.; Harrison, K.; Steiner, P. R. J. Chem. Soc. C 1971, 3480.
5.Bergmark, W. R.; Whitten, D. G. J. Am. Chem. Soc. 1990, 112, 4042.
Bergmark, W. R.; Whitten, D. G. Mol. Cryst. liq. Cryst. 1991, 194, 239.
6.Rodríguez-Molina, B.; Ochoa, M. E.; Romero, M.; Khan, S. I.; Farfán, N.; Santillan, R.; Garcia-Garibay, M. A.; Cryst. Growth Des. 2013, 13, 5107-5115.
7.Wiltzius, J. J. W.; Landau, M.; Nelson, R.; Sawaya, M. R.; Apostol, M. I.; Goldschmidt, L.; Soriaga, A. B.; Cascio, D.; Rajashankar, K.; Eisenberg, D. Nat. Struct. Mol. Biol. 2009, 16, 9.
8.Thallapally, P. K.; Jetti, R. K. R.; Katz, A. K.; Carrell, H. L.; Singh, K.; Lahiri, K.; Kotha, K.; Boese, R.; Desiraju, G. R. Angew. Chem. Int. Ed. 2004, 43, 1149-1149.
9.Arnold, P. R.; Jones, F.; Mol. Cryst. liq. Cryst. 1972, 19, 133-140.
10.Kumar, S. S.; Nangia, A. Cryst. Growth Des. 2014, 14, 1865-1881.
11.Buvaylo, E. A.; Kokozay, V. N.; Rubini, K.; Vassilyeva, O. Y.; Skelton, B. W. J. Mol. Struct. 2014, 1072, 129-136.