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Reaction mechanisms of 3-amino-4-nitro-furoxan formation by 3-amide-4-nitro-furoxan and sodium hypochlorite in water and benzene solvents
Peng, Yajing1; Sun, Shuang1; Ye, Yuqing1; Liu, Jianyong2
KeywordDehydration Chlorination Furoxan Hydrolysis Formation Mechanism
Source PublicationCOMPUTATIONAL AND THEORETICAL CHEMISTRY
2018-02-01
ISSN2210-271X
DOI10.1016/j.comptc.2018.01.006
Volume1125Pages:69-76
Indexed BySCI
SubtypeArticle
WOS HeadingsScience & Technology ; Physical Sciences
WOS SubjectChemistry, Physical
WOS Research AreaChemistry
WOS KeywordPOLARIZABLE CONTINUUM MODEL ; COUPLED-CLUSTER SINGLES ; ENERGETIC PROPERTIES ; FUROXAN ; 3,4-DINITROFUROXAN ; ISOCYANATES ; HYDROLYSIS ; CCSD ; CYTOCHROME-P450 ; MOLECULES
AbstractSynthesis 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.
Language英语
WOS IDWOS:000424963100008
PublisherELSEVIER SCIENCE BV
Citation statistics
Cited Times:1[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/168699
Collection中国科学院大连化学物理研究所
Corresponding AuthorPeng, Yajing; Liu, Jianyong
Affiliation1.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
Recommended Citation
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.
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