臺灣博碩士論文加值系統

本論文旨在模擬高能化合物1,3,3-三硝基氮雜環丁烷（1,3,3-trinitro azetidine, TNAZ）的合成，參考近期文獻研究所述硝基甲烷法及1,3-二鹵-2-丙醇法兩種方法，合理地建立了反應相關的機構步驟，並藉Gaussian 09程式軟體，選用密度泛函數理論B3LYP/6-31G（d,p）計算法，完成所有階段過程物種之最佳化計算，並獲取一般實驗法不易獲得之反應活化能數值，憑以擇選出利於反應進行的路徑。
研究結果顯示，在硝基甲烷法合成目標高能物的模擬過程中，可考量採行由硝基甲烷與甲醛經離子型態轉變生成2,2-二硝基-1,3-丙二醇，再與溴化氫生成1,3-二溴-2,2-二硝基丙烷，進一步與第三丁胺反應製得1-第三丁基-3,3-二硝基氮雜環丁烷，最後進行硝化而得到TNAZ。由於部分原子基團產生的取代基效應，此階段克服1386.6 kJ/mol總活化能障即可完成，此外，藉由1,3-二鹵-2-丙醇法進行反應合成的模擬過程中，可採行由丙三醇製成1,3-二溴-2-丙醇後，隨之與硝基胺行胺化及環化，接續經氧化、肟化及硝化等合宜的路徑，所須跨越的總能障約只需1163.5 kJ/mol。

關鍵詞：1,3,3-三硝基-氮雜環丁烷（TNAZ）、密度泛函數理論（DFT）、取代基效應、活化能障、胺化反應。

This study is aimed at the simulation modeling of synthesis of 1,3,3-trinitro azetidine （TNAZ） high-energy compound. Based on the experimental nitrometane and 1,3-dihalo-2-propanol raw material methods in latest literatures, we suggested reasonably reaction mechanisms. Using quantum mechanical theory, i.e.,electronic density functional theory（DFT）B3LYP/6-31G（d,p） in the version of Gaussian 09 program, we have completed optimization work for all species in relatrd reaction stage and have obtained energy barrier data, which were referred to pick out the more feasible reaction path ways.
From the research results：Nitromethane was used to react with formaldehyde through ionic type transition to produce 2,2-dinitro-1,3-propandiol,followed by reacting with hydrogen bromide to produce 1,3-dibromo-2,2-dinitro propane; further reacting with tertiary amine to produce 1-tertiary amino-3,3-dinitro azetidine, and undergo nitration to obtain TNAZ. Substituent effect of some atomic groups were found in this part of synthesis modeling, and a total activation energy of 1386.6 kJ/mol has to be conquered to complete the reaction. Furthermore, synthesis modeling with 1,3-dihalo-2-propanol raw material method, the suggested reaction routes could be bromination of glycerol to 1,3-dibromo-2-propanol; followed by reacting with nitromethane to undergo amination, and further cyclization, oxidation, oximization, nitration in sequence to produce the target TNAZ product. An overall 1163.5 kJ/mol of energy barrier has to be crossed over in this part of computation.

Keywords：1,3,3 - trinitro azetidine（TNAZ）, density functional theory（DFT）, substituent effect, activation energy, amination reaction.

目 錄
誌謝…………………………………………………………………………………ii
摘要…………………………………………………………………………………iii
ABSTRACT………………………………………………………………………..iv
目錄…………………………………………………………………………………..v
表目錄………………………………………………………………………………vii
圖目錄………………………………………………………………………………viii
1. 緒論………………………………………………………………………………1
1.1 研究動機..…………………………………………………………………1
1.2 研究目的……………………………….…………………………………3
1.3 研究背景……………………………………………………………………3
1.3.1 TNAZ之開發及應用介紹…………………………………………3
1.3.2 實驗合成分法……………………………………………………4
1.3.3 影響反應合成之取代基效應……………………………………5
1.4 研究架構……………………………………………………………………7
1.5 反應合成系統之設計………………………………………………………8
1.5.1 硝基甲烷合成法…………………………………………………8
1.5.2 1,3-二鹵-2-丙醇合成法…………………………………………13
2. 研究方法…………………………………………………………………………15
2.1 分子結構之建立…………………………………………………………15
2.2 分子系統幾何最適化計算………………………………………………15
2.2.1 Ab inito / Hartree-Fock法………………………………………16
2.2.2 Density Functional Theory (DFT)/ B3LYP法……………………16
2.2.3 底函數組………………………………………………………17
2.3 反應過渡態之模擬………………………………………………………19
2.4 取代基定位效應之探討…………………………………………………19
2.5 離去基團之影響…………………………………………………………21
3. 結果與討論………………………………………………………………………23
3.1 最適化的分子幾何………………………………………………………23
3.2 分子的熱力學能量………………………………………………………23
3.3 硝基甲烷合成法…………………………………………………………31
3.3.1 2,2-二硝基-1,3-丙二醇之合成…………………………………31
3.3.2 1,3-二鹵-2,2-二硝基丙烷之合成………………………………35
3.3.3 1-烷基-3,3-二硝基氮雜環丁烷之合成…………………………38
3.3.4 1,3,3-三硝基氮雜環丁烷（TNAZ）的合成………………………39
3.4 1,3-二鹵-2-丙醇合成法……………………………………………………44
3.4.1 1,3-二鹵-2-丙醇之合成…………………………………………44
3.4.2 1-硝基-3-氮雜環丁醇之合成……………………………………44
3.4.3 1,3,3-三硝基-氮雜環丁烷（TNAZ）之合成…………………44
4. 結論………………………………………………………………………………49
參考文獻……………………………………………………………………………51
附錄…………………………………………………………………………………55
自傳…………………………………………………………………………………72

表目錄
表3.1 TNAZ合成反應穩定態物種的熱力學能量…………………………………24
表3.2 TNAZ合成反應過渡態物種的熱力學能量…………………………………29

圖目錄
圖1.1 環氧氯丙烷法合成TNAZ……………………………………………………1
圖1.2 TNAZ反應合成法（1）………………………………………………………4
圖1.3 TNAZ反應合成法（2）………………………………………………………5
圖1.4 芳香環取代基的位向效應……………………………………………………6
圖1.5 高能氮雜環化合物TNAZ合成理論分析研究流程…………………………7
圖1.6 硝基甲烷法之離子型態合成TNAZ…………………………………………9
圖1.7 硝基甲烷法之自由基型態合成TNAZ………………………………………11
圖1.8 1,3-二鹵-2-丙醇合成TNAZ…………………………………………………14
圖3.1 2,2-二硝基-1,3-丙二醇合成之離子型態轉變能障…………………………33
圖3.2 2,2-二硝基-1,3-丙二醇合成之自由基型態轉變能障………………………34
圖3.3 1,3-二鹵-2,2-二硝基丙烷合成之離子型態轉變能障………………………36
圖3.4 1,3-二鹵-2,2-二硝基丙烷合成之自由基型態轉變能障……………………37
圖3.5 1-烷基-3,3-二硝基氮雜環丁烷合成之離子型態轉變能障…………………41
圖3.6 氮雜環烷合成TNAZ之離子型態轉變能障…………………………………43
圖3.7 1,3-二鹵-2-丙醇合成之能障比較……………………………………………46
圖3.8 1-硝基-3-氮雜環丁醇合成之能障比較……………………………………47
圖3.9 氮雜環丁醇合成TNAZ之反應能障…………………………………………48

[1] Archibald　, T. G., Gilardi, R. D., Baum, K. and George, C., “Synthesis and x-ray crystal structure of 1,3,3-trinitroazetidine,” Journal of Organic Chemistry, Vol. 55, pp. 2920-2924, 1990.
[2] Curtiss, L. A., Carpenter, J. E., Raghavachari, K. and Pople, J. A., “Validity of Additivity Approximations Used in Gaussian-2 Theory,” Journal of Chemical Physics, Vol. 96, p. 9030, 1992.
[3] Curtiss, L. A., Raghavachari, K. and Pople, J. A., “GAUSSIAN-2 Theory Using Reduced Moller-Plesset Orders,” Journal of Chemical Physics, Vol. 98, p. 1293, 1993.
[4] Curtiss, L. A., Raghavachari, K. and Pople, J. A., “Gaussian-2 Theory: Use of Higher Level Correlation Methods, Quadratic Configuration Interaction Geometries, and Second-Order Moller-Plesset Zero-Point Energies,” Journal of Chemical Physics, Vol. 103, p. 4192, 1995.
[5] Curtiss, L. A., McGrath, M. P., Blaudeau, J.-P., Davis, N. E., Binning, R. C. J. and Leo Radom, “Extension of Gaussian-2 theory to molecules containing third-row atoms GA-Kr.” American Institute of Physics, Vol. 103, p. 6104, 1995.
[6] Curtiss, L. A., Redfern, P. C., Smith, B. J. and Radom, L. , “Gaussian-2 (G2) theory: Reduced basis set requirements,” Journal of Chemical Physics, Vol.104, p.5148, 1996.
[7] Curtiss, L. A., Raghavachari, K., Redfern, P. C. and Pople, J. A., “Assessment of Gaussian-2 and Density Functional Methods for the Computation of Enthalpies of Formation,” Journal of Chemical Physics, Vol. 106, p. 1063, 1997.
[8] Curtiss, L. A., Raghavachari, K., Redfern, P. C., Rassolov, V. and Pople, J. A., “Gaussian-3 theory for molecular energies of first- and second-row compound,” Journal of Chemical Physics, Vol. 109,p. 7764, 1998.
[9] Curtiss, L. A., Redfern, P. C., Raghavachari, K. and Pople, J. A., “Assessment of Gaussian-2 and Density Functional Methods for the Computation of Ionization Energies and Electron Affinities,” Journal of Chemical Physics, Vol. 109, p. 42, 1998.
[10] Curtiss, L. A., Redfern, P. C., Raghavachari, K., Rassolov, V. and Pople, J. A., “Gaussian-3 Theory Using Reduced Moller-Plesset Orders,” Journal of Chemical Physics, Vol. 110,p. 4703, 1999.
[11] Curtiss, L. A., Redfern, P. C., Raghavachari, K. and Pople, J. A., “Gaussian-3 Theory: A Variation Based on Third-Order Perturbation Theory and an Assessment the Contribution of Core-Related Correlation,” Chemical Physics Letters, Vol. 313, pp. 600-607, 1999.
[12] Kedziora, G. S., Pople, J. A., Rassolov, V. A., Ratner, M., Redfern, P. C. and Curtiss, L. A., “The Relativistic Dirac-Coulomb-Fock Effect on Atomizatiom Energies, ” Journal of Chemical Physics, Vol. 110, p. 7123, 1999.
[13] Curtiss, L. A., Raghavachari, K., Redfern, P. C. and Pople, J. A., “Assessment of Gaussian-3 and Density Functional Theories for a Larger Test Set,” Journal of Chemical Physics, Vol. 112, p. 7374, 2000.
[14] Redfern, P. C., Zapol, P., Curtiss, L. A. and Raghavachari, K., “Assessment of Gaussian-3 and Density Functional Theories for Enthalpies of Formation of C1-C16 Alkanes,” Journal of Physical Chemistry, Vol. A104, pp. 5850-5854, 2000.
[15] Curtiss, L. A., Redfern, P. C., Raghavachari, K. and Pople, J. A., “Gaussian-3x (G3X) Theory: Use of Improved Geometries, Zero-Point Energies, and Hartree-Fock Basis Sets,” Journal of Chemical Physics, Vol. 114, pp. 108-117, 2001.
[16] 張光全，“1,3,3-三硝基氮雜環丁烷（TNAZ）的工業合成現狀及其應用進展”，含能材料，第10卷，第4期，第174-177頁，2002。
[17] Bottaro, J. C., “Recent advances in explosives and solid propellants,” Chemistry and Industry, Vol. 7, pp. 249-252, 1996.
[18] Chapman R. D., Fronabarger J. W., and Sanborn, W. B., “Phase behavior in TNAZ-based and other explosive formulations[DAAA21-93-C-0017],” USA Government Reported. 1994.
[19] Liu, M. H., Cheng, K. F., Chen, C. and Hong, Y. S., “A guiding Simulation research on developing promising energetic materials” International Journal of Quantum Chemistry, Vol. 109, pp. 1618-1625, 2009.
[20] Cheng, K. F., Liu, M. H., and Hong, Y. S. “Computational Optimum Conditions for FOX-7 Synthesis - A Comparative Synthesis Route,” Journal of Molecular Structure (THEOCHEM), Vol. 957, pp. 6-14, 2010.
[21] Liu, M. H., Cheng, K. F., Chen, C., and Hong, Y. S. “Computational Study on the Comparative Synthesis of Energetic FOX-7 Derivatives,” International Journal of Quantum Chemistry, Vol. 110, pp. 813-820, 2010.
[22] Liu, M. H., Cheng, K. F., Chen, C., and Hong, Y. S. “Computational study of FOX-7 synthesis in a solvated reaction systemInt,” International Journal of Quantum Chemistry, Vol. 111, pp. 1859-1869, 2011.
[23] Cheng, K. F., Liu, M. H., Yang, P-H. “Computational study of the catalytic synthesis of 5-nitro-1,2,4-triazol-3-one,” International Journal of Quantum Chemistry, Vol. 112, pp. 703-712, 2012.
[24] Singha, A., Sikderb, N., and Sikder, A. K., “Improved synthesis of an energetic material, 1,3,3-trinitroazetidine (TNAZ) exploiting 2-iodoxy benzoic acid (IBX) as an oxidising agent,” Indian Journal of Chemistry, Vol. 44B, pp. 2560-2563, 2005.
[25] Jadhav, H. S., Talawar, M. B., Dhavalea, D. D., Asthanab, S. N., & Krishnamurthyc, V. N., “Alternate method for synthesis of 1,3,3-trinitroazetidine (TNAZ): Next generation melt castable high energy material,” Indian Journal of Chemical Technology, Vol. 13, pp. 41-46, 2006.
[26] Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Zakrzewski,V. G., Montgomery, J. A., Stratmann, Jr, R. E., Burant, J. C., Dapprich, S., Millam, J. M., Daniels, A. D., Kudin, K. N., Strain, M. C., Farkas, O., Tomasi, J., Barone,V., Cossi, M., Cammi, R., Mennucci, B., Pomelli, C., Adamo, C., Clifford, S., Ochterski, J., Petersson, G. A., Ayala, P. Y., Cui, Q., Morokuma, K., Malick, D. K., Rabuck, A. D., Raghavachari, K., Foresman, J. B., Cioslowski, J., Ortiz, J. V., Stefanov, B. B., Liu, G., Liashenko,A., Piskorz, P., Komaromi, I., Gomperts, R., Martin, R. L., Fox, D. J., Keith, T., Al-Laham, M. A., Peng, C. Y., Nanayakkara, A., Gonzalez, C., Challacombe, M., Gill, P. M. W., Johnson, B., Chen, W., Wong, M. W., Andres, J. L., Gonzalez, Head-Gordon, C., M., Replogle, E. S., and Pople, J. A., Gaussian, Inc., Pittsburgh PA, 2003.
[27] Bock, C. W., and Hargittai, I., “Geometrical Consequences of Resonance- Assisted Intramolecular Hydrogen-Bond Formation from Ab Initio MO Calculations on 2-Nitroresorcinol,” Structural Chemistry, Vol. 5, pp. 307-312, 1994.
[28] Markham, G. D., and Bock, C. W., “Intramolecular Sulfur-Oxygen interactions: An Ab Initio Molecular Orbital and Density Functional Theory Investigation,” Journal of Molecular Structure (Theochem), Vol. 418, pp. 139-154, 1997.
[29] Lee, C., Yang, W., and Parr, R. G., “Development of the Colle-Salvetti Correlation-energy Formula into a Function of the Electron Density,” Physical Reviews B, Vol. 37, pp. 785-789, 1988.
[30] Frisch, M. A., Popie, John, A., and Binkley, J. S., “Self-Consistent Molecular Orbital Methods 25. Supplementary Functions for Gaussian Basis Sets,” Journal of Chemistry Physical, Vol. 80, pp. 3265-3279, 1984.
[31] Schlegel, H. B., “Optimization of Equilibrium Geometries and Transition Structures,” Journal of Computational Chemistry, Vol. 3, No. 2, pp. 214-218, 1982.
[32] Levine, I. N., Quantum Chemistry Third Edition, New Jersey, pp. 256-263, 1983.
[33] Lee, C., Yang, W., and Parr, R. G., “Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density,” Physical Review B, Vol. 37, pp. 785-789, 1998.
[34] Becke, A. D., “Density-Functional Thermochemistry. III. The Role of Exact Exchange,” Journal of Chemical Physics, Vol. 98, pp. 5648-5652, 1993.
[35] Hoheuberg, P., and Kohn, W., “Inhomogeneous Electron Gas,” Physical Review, Vol. 136, pp. B864-B871, 1964.
[36] Kohn, W., and Shan, L. J., “Self-Consistent Equations Including Exchange and Correlation Effects,” Physical Review, Vol. 140, pp. A1133-A1138, 1965.
[37] Clark, T., Chandrasekhar, J., Spitznagel, G. W., and Schleyer, P. V., “Efficient Diffuse Function-Augmented Basis Sets for Anion Calculations Ⅲ. The 3-21G Basis Set for First-Row Elements, Li-F,” Journal of Computational Chemistry, Vol. 4, No. 3, pp. 294-301, 1983.
[38] Peng, C., and Schlegel, H. B., “Combining Synchronous Transit and Quasi-Newton Methods to Find Transition States,” Israel Journal of Chemistry, Vol. 33, pp. 449-454, 1993.
[39] Peng, C., Ayala, P. Y., Schlegel, H. B. and Frisch, M. J. “Using redundant internal coordinates to optimize equilibrium geometries and transition states,” Journal of Computational Chemistry, Vol. 17, pp. 49-56, 1996.