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学科主题物理化学
Mechanisms and Risk Assessments on the N-Nitration of N-Acetylhexahydro-s-triazines: Understanding the Preparation of RDX (2)
Chen, Xiao-Fang1,2; Yang, Kun1,3; Wang, Bo-Zhou2; Chen XF(陈晓芳)
刊名JOURNAL OF PHYSICAL CHEMISTRY A
2013-06-20
ISSN1089-5639
DOI10.1021/jp4012203
117期:24页:5007-5014
收录类别SCI
合作性质
文章类型Article
部门归属11
项目归属1101
产权排名待补充
WOS标题词Science & Technology ; Physical Sciences
资助者1,1 ; 1,1 ; 1,1 ; 1,1
类目[WOS]Chemistry, Physical ; Physics, Atomic, Molecular & Chemical
研究领域[WOS]Chemistry ; Physics
关键词[WOS]ELECTROPHILIC AROMATIC NITRATION ; CORRELATED MOLECULAR CALCULATIONS ; GAUSSIAN-BASIS SETS ; OXYGEN CENTRES ; WAVE-FUNCTIONS ; GAS-PHASE ; REDUCTION ; HYDROGEN ; CONVERSION ; KINETICS
英文摘要Although the N-nitration by nitric acid is widely used to synthesize nitramines in biological, medical, and explosive industries, little is known about the microscopic behavior when the nitrated substrates are tertiary amines. Hexahydro-1,3,5-triacetyl-s-triazine (TRAT) nitrated into hexahydro-1,3,5-trinitro-s-triazine (RDX) was theoretically investigated at the MP2/cc-PVDZ level. An O-to-N-transnitration mechanism was put forward for the N-nitration of N-acetyl tertiary amines, including the formation of diverse complexes R'N(COCH3)RNO2+ and deacetylate. The electron transfer results in the complex formation, and the acetyl-to-nitro electrophilic displacement leads to deacetylate. Presumably, the carbonyl groups (C=O) in N-acetyl tertiary amines serve as the hinged joint in the electron transfer. Three successive N-nitrations transform TRAT into RDX; their electron transfers are strongly exothermic by 21.1, 19.5, and 15.4 kcal/mol relative to TRAT + 3NO(2)(+), repectively, and their electrophilic displacements possess low activation Gibbs free energies of 9.0, 6.8, and 7.5 kcal/mol relative to the a-complexes 6, 11, and 14, respectively. The rate constants of the single electron transfer (SET) and the acetyl-to-nitro displacement were estimated roughly by Marcus and transition-state (TS) theories, respectively, indicating that they are both fast with the strong exothermicity. The available experimental phenomena were well interpreted by the computational results.
语种英语
资助者1,1 ; 1,1 ; 1,1 ; 1,1
原文出处查看原文
WOS记录号WOS:000320911000002
引用统计
被引频次:2[WOS]   [WOS记录]     [WOS相关记录]
文献类型期刊论文
条目标识符http://cas-ir.dicp.ac.cn/handle/321008/119456
专题中国科学院大连化学物理研究所
通讯作者Chen XF(陈晓芳)
作者单位1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China
2.Xian Modern Chem Res Inst, Xian 710065, Peoples R China
3.Dalian Maritime Univ, Dept Phys, Dalian 116026, Peoples R China
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Chen, Xiao-Fang,Yang, Kun,Wang, Bo-Zhou,et al. Mechanisms and Risk Assessments on the N-Nitration of N-Acetylhexahydro-s-triazines: Understanding the Preparation of RDX (2)[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2013,117(24):5007-5014.
APA Chen, Xiao-Fang,Yang, Kun,Wang, Bo-Zhou,&陈晓芳.(2013).Mechanisms and Risk Assessments on the N-Nitration of N-Acetylhexahydro-s-triazines: Understanding the Preparation of RDX (2).JOURNAL OF PHYSICAL CHEMISTRY A,117(24),5007-5014.
MLA Chen, Xiao-Fang,et al."Mechanisms and Risk Assessments on the N-Nitration of N-Acetylhexahydro-s-triazines: Understanding the Preparation of RDX (2)".JOURNAL OF PHYSICAL CHEMISTRY A 117.24(2013):5007-5014.
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