Reaction Mechanism of 3,4-Dinitrofuroxan Formation from Glyoxime: Dehydrogenation and Cyclization of Oxime
文献类型：期刊论文
| 作者 | Peng, Ya-Jing2,3; Jiang, Yan-Xue2; Peng, Xie3; Liu, Jian-Yong3; Lai, Wei-Peng1 |
| 刊名 | CHEMPHYSCHEM
 |
| 出版日期 | 2016-02-16 |
| 卷号 | 17期号:4页码:541-547 |
| 关键词 | Cyclization Dehydrogenation Furoxans Radical Reactions Reaction Mechanisms |
| ISSN号 | 1439-4235 |
| DOI | 10.1002/cphc.201500968 |
| 文献子类 | Article |
| 英文摘要 | The reaction pathway of the formation of 3,4-dinitrofuroxan from glyoxime is theoretically investigated under experimental conditions with 25% nitric acid and dinitrogentetroxide reagents to clarify the mechanism of formation of a furoxan ring by glyoxime. The geometric configurations of minima and transition-state species are optimized at the (U)B3LYP/6-311++G** level. The CCSD(T) and CASSCF(10e,8o)/CASSCF(9e,8o) single-point energy corrections at the same level are performed on top of the optimized geometries. A subsequent dynamic correlation by using NEVPT2/6-311++G**-level single-point energy calculations based on the CASSCF results is also performed to obtain accurate energy values. The formation reaction is analyzed from two processes: glyoxime nitration and 3,4-dinitroglyoxime (nitration product) oxidative cyclization. Calculation results indicate that the electrophilic substitution of nitronium ions from the protonated HNO3 and the abstraction of hydrogen ions by HNO3 molecules are requisites of glyoxime nitration. The formation of a furoxan ring from 3,4-dinitroglyoxime involves two possible mechanisms: 1)oxydehydrogenation by NO2 molecules and the subsequent torsion of NO radical groups to form a ring and 2)the alternation of dehydrogenation and cyclization. The intermediates and transition states in both routes exhibit monoradical and diradical characteristics. Singlet and triplet reactions are considered for the diradical species. Results show that the singlet reaction mechanism is more favorable for cyclization than the triplet reaction. The formation of a furoxan ring from oxime is in accordance with the stepwise intermolecular dehydrogenation and intramolecular torsion to the ring. |
| WOS关键词 | DENSITY-FUNCTIONAL THEORY ; AB-INITIO ; FUROXAN ; STEREOSELECTIVITY ; CYTOCHROME-P450 ; CYCLOADDITION ; BUTADIENE ; PATHWAYS ; ETHER ; OXIDE |
| WOS研究方向 | Chemistry ; Physics |
| 语种 | 英语 |
| WOS记录号 | WOS:000371145100014 |
| 出版者 | WILEY-V C H VERLAG GMBH |
| 源URL | [http://cas-ir.dicp.ac.cn/handle/321008/171270]  |
| 专题 | 大连化学物理研究所_中国科学院大连化学物理研究所 |
| 通讯作者 | Liu, Jian-Yong; Lai, Wei-Peng |
| 作者单位 | 1.Xian Modern Chem Res Inst, Xian 710065, Peoples R China 2.Bohai Univ, Dept Phys, Jinzhou 121013, Peoples R China 3.Chinese Acad Sci, State Key Lab Mol React Dynam, Dalian Inst Chem Phys, Dalian 116023, Peoples R China |
| 推荐引用方式 GB/T 7714 | Peng, Ya-Jing,Jiang, Yan-Xue,Peng, Xie,et al. Reaction Mechanism of 3,4-Dinitrofuroxan Formation from Glyoxime: Dehydrogenation and Cyclization of Oxime[J]. CHEMPHYSCHEM,2016,17(4):541-547. |
| APA | Peng, Ya-Jing,Jiang, Yan-Xue,Peng, Xie,Liu, Jian-Yong,&Lai, Wei-Peng.(2016).Reaction Mechanism of 3,4-Dinitrofuroxan Formation from Glyoxime: Dehydrogenation and Cyclization of Oxime.CHEMPHYSCHEM,17(4),541-547. |
| MLA | Peng, Ya-Jing,et al."Reaction Mechanism of 3,4-Dinitrofuroxan Formation from Glyoxime: Dehydrogenation and Cyclization of Oxime".CHEMPHYSCHEM 17.4(2016):541-547. |
入库方式： OAI收割
来源：大连化学物理研究所
浏览0
下载0
收藏0
其他版本
除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。