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题名: DFT Study of Intermolecular [4+2] versus [3+2] Cycloadditions in the Dimerization of 2,4,6-Trinitrotoluene (TNT): Regioselectivity and Stereoselectivity
作者: Chen, Xiao-Fang1;  Hou, Chun-Yuan1;  Han, Ke-Li1
刊名: JOURNAL OF PHYSICAL CHEMISTRY A
发表日期: 2010-01-21
DOI: 10.1021/jp909670w
卷: 114, 期:2, 页:1169-1177
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Physical ;  Physics, Atomic, Molecular & Chemical
研究领域[WOS]: Chemistry ;  Physics
英文摘要: Two novel types of intermolecular hetero cycloadditions in the participation of the nitro group are put forward in the dimerization of TNT, in comparison with Diels-Alder cross-linking of benzene ring skeletons. Possible transition States and products; for example, their geometrical details, vibrational frequencies, and energies are verified at the B3LYP/6-31+G(d,p) level. Contrary to the hetero Diels-Alder reaction, the folding of the benzene ring side endo is slightly selective specific in 1,3-dipolar cycloaddition. The substituent pattern on reactivity indicates that the methyl group at the bridged sites significantly retards the reaction. Two new sigma bonds are formed kinetically and thermodynamically through the single state; however, the first sigma bond is more easily generated by the triplet state. The shock-wave-produced chemically bound dimer of TNT is most likely to be the oxygen-carbon linkage product. The initial chemical events in TNT under high pressure can be extended to interpret the shock insensitivity of other unsaturated nitro-explosives. The calculated results agree well with some experimental observations.
关键词[WOS]: DENSITY-FUNCTIONAL THEORY ;  TRANSIENT HIGH-PRESSURE ;  SHOCK WAVE COMPRESSION ;  DIELS-ALDER REACTION ;  AB-INITIO ;  UNIMOLECULAR DECOMPOSITION ;  LEWIS-ACID ;  PHOTOCHEMICAL NITRATION ;  THERMAL-DECOMPOSITION ;  IMPACT SENSITIVITIES
语种: 英语
WOS记录号: WOS:000273400600060
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/142020
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

Recommended Citation:
Chen, Xiao-Fang,Hou, Chun-Yuan,Han, Ke-Li. DFT Study of Intermolecular [4+2] versus [3+2] Cycloadditions in the Dimerization of 2,4,6-Trinitrotoluene (TNT): Regioselectivity and Stereoselectivity[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2010,114(2):1169-1177.
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