Formation mechanisms of 3,4-dinitrofuroxan via nitration reaction of furoxan

doi:10.1016/j.cplett.2016.01.038

	Formation mechanisms of 3,4-dinitrofuroxan via nitration reaction of furoxan
	Peng, Yajing 1,2; Ye, Yuqing 1; Liu, Jianyong 2; Lai, Weipeng 3
刊名	CHEMICAL PHYSICS LETTERS
	2016-03-01
卷号	647 页码:85-88
ISSN号	0009-2614
DOI	10.1016/j.cplett.2016.01.038
文献子类	Article
英文摘要	A systematic investigations on the nitration of furoxan by two typical nitration reagents nitronium tetrafluoroborate (BF4NO2) and dilute nitric acid (HNO3) in chloroform (CHCl3) solvent using density functional theory (DFT) method to reveal the formation mechanism of 3,4-dinitrofuroxan (DNFO) and explore new synthesis routes. The geometry optimizations of the minima and transition states involved in the two nitration reactions are performed at the B3LYP/6-311++G** basis set level. The CCSD single-point energy corrections at the same level are carried out on top of the optimized geometries to obtain the accurate energy. Calculated results demonstrate that the electrophilic substitutions of nitronium ions from the nitration reagents and the abstractions of protons in the complex intermediates are the main formation mechanism of DNFO. BF4- is shown to be a better proton abstracter than HNO3 and H2O due to its no barrier combination with H+. The abstraction of proton by HNO3 is predicted to be more feasible than H2O because it can supply the nitration attacker (NO2+) and release more heat. Chloroform is a feasible solvent and heating properly is necessary for the two reactions due to the relatively high barrier of 37 kcal/mol. These conclusions provide some significant indications on the new experimental synthesis of DNFO. (C) 2016 Elsevier B.V. All rights reserved.
WOS关键词	DENSITY-FUNCTIONAL THEORY ; DFT ; STEREOSELECTIVITY ; CYTOCHROME-P450 ; SELECTIVITY
WOS研究方向	Chemistry ; Physics
语种	英语
出版者	ELSEVIER SCIENCE BV
WOS记录号	WOS:000371401500017
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/171076]
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, Jianyong; Lai, Weipeng
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 3.Xian Modern Chem Res Inst, Xian 710065, Peoples R China
推荐引用方式 GB/T 7714	Peng, Yajing,Ye, Yuqing,Liu, Jianyong,et al. Formation mechanisms of 3,4-dinitrofuroxan via nitration reaction of furoxan[J]. CHEMICAL PHYSICS LETTERS,2016,647:85-88.
APA	Peng, Yajing,Ye, Yuqing,Liu, Jianyong,&Lai, Weipeng.(2016).Formation mechanisms of 3,4-dinitrofuroxan via nitration reaction of furoxan.CHEMICAL PHYSICS LETTERS,647,85-88.
MLA	Peng, Yajing,et al."Formation mechanisms of 3,4-dinitrofuroxan via nitration reaction of furoxan".CHEMICAL PHYSICS LETTERS 647(2016):85-88.