Reaction mechanisms of 3-amino-4-nitro-furoxan formation by 3-amide-4-nitro-furoxan and sodium hypochlorite in water and benzene solvents
文献类型：期刊论文
| 作者 | Peng, Yajing1; Sun, Shuang1; Ye, Yuqing1; Liu, Jianyong2 |
| 刊名 | COMPUTATIONAL AND THEORETICAL CHEMISTRY
 |
| 出版日期 | 2018-02-01 |
| 卷号 | 1125页码:69-76 |
| 关键词 | Dehydration Chlorination Furoxan Hydrolysis Formation Mechanism |
| ISSN号 | 2210-271X |
| DOI | 10.1016/j.comptc.2018.01.006 |
| 文献子类 | Article |
| 英文摘要 | Synthesis of new furoxan-based compounds has been a hot research topic in order to explore the energetic materials with good application prospect. 3-amino-4-nitro-furoxan is a precursor for synthesis of furoxan derivatives because that the amino groups are prone to be substituted by nucleophiles. A theoretical research is conducted for the formation reaction of 3-amino-4-nitro-furoxan by 3-amide-4-nitrofuroxan and sodium hypochlorite in water and benzene solvents using the density functional theory (DFT) and CCSD coupled cluster method to reveal the formation mechanism and explore new synthesis routes. The structures and energies of intermediates and transition states in the possible reaction pathways are given, and the potential energy surfaces of the every reaction channels are mapped. The results indicate that the formation mechanism is mainly through two stages: generation and hydrolysis of isocyanate. Hydrogen bond plays an important role for the hydrolysis process. The formation mechanism is shown to be dependent on the polarity of solvent. The hydroxyl ion (OH-), originated from the basic properties of sodium hypochlorite solution, is shown to be more likely first attacker than the hypochlorite ion (OCI-) for the reactant 3-amide-4-nitro-furoxan due to the low active barrier in the polar water solvent. But the OCI- dominates the reaction in benzene solvent where the isocyanate is formed via the dehydration chlorination by OCI- and Hofmann rearrangement with the elimination of chloride ion. The isocyanate is then hydrolyzed through addition of a H2O molecule to the N=C double bonds, rotation of the hydroxyl hydrogen, transfer of hydrogen to the N atom in the amide group and the removal of a CO2 molecule to form the final product. The benzene solvent is more suitable than water solvent for the formation reaction due to the lower active barrier of 46.4 kcal/mol. The reaction is not feasible at room temperature and raising properly temperature of system would be requisite to realize the synthesis reaction. (C) 2018 Elsevier B.V. All rights reserved. |
| WOS关键词 | POLARIZABLE CONTINUUM MODEL ; COUPLED-CLUSTER SINGLES ; ENERGETIC PROPERTIES ; FUROXAN ; 3,4-DINITROFUROXAN ; ISOCYANATES ; HYDROLYSIS ; CCSD ; CYTOCHROME-P450 ; MOLECULES |
| WOS研究方向 | Chemistry |
| 语种 | 英语 |
| WOS记录号 | WOS:000424963100008 |
| 出版者 | ELSEVIER SCIENCE BV |
| 源URL | [http://cas-ir.dicp.ac.cn/handle/321008/168698]  |
| 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 | Peng, Yajing; Liu, Jianyong |
| 作者单位 | 1.Bohai Univ, Dept Phys, Jinzhou 121013, Peoples R China 2.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China |
| 推荐引用方式 GB/T 7714 | Peng, Yajing,Sun, Shuang,Ye, Yuqing,et al. Reaction mechanisms of 3-amino-4-nitro-furoxan formation by 3-amide-4-nitro-furoxan and sodium hypochlorite in water and benzene solvents[J]. COMPUTATIONAL AND THEORETICAL CHEMISTRY,2018,1125:69-76. |
| APA | Peng, Yajing,Sun, Shuang,Ye, Yuqing,&Liu, Jianyong.(2018).Reaction mechanisms of 3-amino-4-nitro-furoxan formation by 3-amide-4-nitro-furoxan and sodium hypochlorite in water and benzene solvents.COMPUTATIONAL AND THEORETICAL CHEMISTRY,1125,69-76. |
| MLA | Peng, Yajing,et al."Reaction mechanisms of 3-amino-4-nitro-furoxan formation by 3-amide-4-nitro-furoxan and sodium hypochlorite in water and benzene solvents".COMPUTATIONAL AND THEORETICAL CHEMISTRY 1125(2018):69-76. |
入库方式： OAI收割
来源：大连化学物理研究所
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