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学科主题: 物理化学
题名: Mechanisms and Risk Assessments on the N-Nitration of N-Acetylhexahydro-s-triazines: Understanding the Preparation of RDX (2)
作者: Chen, Xiao-Fang1, 2;  Yang, Kun1, 3;  Wang, Bo-Zhou2
通讯作者: 陈晓芳
刊名: JOURNAL OF PHYSICAL CHEMISTRY A
发表日期: 2013-06-20
DOI: 10.1021/jp4012203
卷: 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
类目[WOS]: Chemistry, Physical ;  Physics, Atomic, Molecular & Chemical
资助者: 1,1
研究领域[WOS]: Chemistry ;  Physics
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.
关键词[WOS]: ELECTROPHILIC AROMATIC NITRATION ;  CORRELATED MOLECULAR CALCULATIONS ;  GAUSSIAN-BASIS SETS ;  OXYGEN CENTRES ;  WAVE-FUNCTIONS ;  GAS-PHASE ;  REDUCTION ;  HYDROGEN ;  CONVERSION ;  KINETICS
语种: 英语
原文出处: 查看原文
WOS记录号: WOS:000320911000002
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/119456
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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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

Recommended Citation:
Chen, Xiao-Fang,Yang, Kun,Wang, Bo-Zhou. 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.
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