3-胺基-1,2,4-三氮肼及其衍生化合物之化學與理論計算研究

The Chemistry and Theoretical Calculation Studies on 3-Amino-1,2,4-triazines

樊忠良(Chung-Liang Fan)

指導教授 ： 黃 龍 池

高雄醫學大學/藥學院/藥學研究所碩士在職專班/碩士(2004年)

摘要

本研究進行3-胺基-1,2,4-三氮肼單環雜環之製備、反應性、理論計算及反應機制探討。
由3-胺基-1,2,4-三氮肼 (3-amino-1,2,4-triazine) 及其衍生化合物共四顆單環雜環及一顆雙環雜環化合物之X-ray單晶繞射資料與理論計算所得計算數值做比較。理論計算軟體包括分子力學 (Molecular mechanics) MM2法及量子力學全初始法 (ab initio methods)：Hartree-Fock配合STO-3G或3-21G或6-31G基底函數組合；MP2配合STO-3G或3-21G或6-31G基底函數組合與半經驗法 (semiempirical methods) AM1、MINDO/3、MNDO和PM3，進行理論計算。尋求較適於3-胺基-1,2,4-三氮肼類化合物之計算軟體，作為3-胺基-1,2,4-三氮肼類化合物之各種化學計算，與實驗值比照或推求新知或預測反應。
理論計算軟體做結構的最低能量計算，以鍵長及鍵角與X-ray單晶繞射資料做比較，結果顯示以ab initio (Hartree-Fock) 6-31G基底函數組所運算出來的數值最近似於X-ray單晶繞射值，其次是MM2及ab initio (Hartree-Fock) 3-21G法。
本研究於反應性探討其結果顯示，化合物3-amino-1,2,4- triazin-5(2H)-one (52) 的矽化中間體當做親核性試劑時可得到N-2取代及N-6取代的產物，若矽化中間體當做親電子性試劑時可得到N-5取代的產物，總產率皆優，因此矽化中間體可應用於N-2、N-5與N-6取代之反應。本研究並從化合物之單晶繞射完整結構消息、質譜與反應結果來推敲三種反應的反應機制。

關鍵字

3-胺基-1 ； 2 ； 4-三氮肼

並列摘要

In this research, we investigated the preparation, reactions, theoretical calculations and mechanism of monoheterocyclic 3-amino-1,2,4-triazine.
Data of single crystal X-ray diffraction of five compounds, four monocyclic crystals of 3-amino-1,2,4-triazine and its derivatives and one bicyclic crystal of the parent compound, were compared with the data from theoretical calculations. The theoretical calculation methods used were molecular mechanics (MM2) and quantium mechanics (ab initio methods with Hartree-Fock and M?ller-Plesset operators by basis sets of STO-3G, 3-21G and 6-31G, and semiempirical methods with models of AM1, MINDO/3, MNDO and PM3).
Among them, data of calculated bond lengths and angles obtained from the ab initio (Hartree-Fock by 6-31G basis set) method were in good agreement with those from the X-ray results. The methods of MM2 and ab initio (Hartree-Fock by 3-21G basis set) showed the second well agreement.
As to the aspects of reactions, the sililated intermediate of 3-amino-1,2,4-triazin-5(2H)-one can act either as a nucleophile to afford N-2 and N-6 substitutes or as an electrophile to get N-5 substitutes, which the total yield rates were both good. The reaction mechanism was proposed according to the X-ray data, mass data and chemical reactions.

並列關鍵字

3-amino-1 ； 2 ； 4-triazines

參考文獻

伍、參考文獻

1. L.C. Hwang, C. H. Tu, J. H. Wang, G. H. Lee, and Y. Wang, Analytical Sciences, 18, 853 (2002).

2. D. H. Ford, L. R. Guse, J. W. Hooks, C. E. Moore, and S. J. Parka, Ger. Offen. 2, 361, 464 (June 12, 1974); C. A., 82, 27229m (1975).

3. E. Jeney and T. Zsolnai, Zentralbl. Bakteriol. Parasitenkd. Abt. I, Orig. 177, 220 (1960); C. A., 54, 21498h (1960).

4. J. Skoda, A. Cihak, J. Gut, M. Prystas, A. Piskala, C. Parkanyi, and F. Sorm, Collect. Czech. Chem. Commun., 27, 1736 (1962).