Insight into the acidic group-induced nitration mechanism of 2-methyl-4,6-dihydroxypyrimidine (MDP) with nitronium

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	Insight into the acidic group-induced nitration mechanism of 2-methyl-4,6-dihydroxypyrimidine (MDP) with nitronium
	Wang, Kuan; Chen, Jian-Gang; Wang, Bozhou; Ji, Yueping; Liu, Fengyi; Liu, Zhao-Tie; Wang, Wenliang; Liu, Zhong-Wen; Hao, Zhengping; Lu, Jian
刊名	RSC ADVANCES
	2016
卷号	6 期号:83 页码:80145-80157
英文摘要	The strong desire for developing promising candidates of insensitive nitro energetic materials has spurred numerous attempts to discern the nitration details. The nitration mechanism of 2-methyl-4,6-dihydroxypyrimidine (MDP) with nitronium (NO2+) to form 2-dinitromethylene-5,5-dinitropyrimidine-4,6-dione is studied via DFT-B3LYP/6-311G(d,p) method. The possible nitration pathways are excavated and illustrated. Herein, a unique/incredible induction/enhancement of the co-existing acidic group of HSO4- to the targeted nitration is definitively proposed. The impact of the introduction order of four nitro groups (-NO2) on the title nitration is systematically demonstrated. It is suggested that the proposed induction of HSO4- may effectively promote/catalyze not only the NO2+ attack, but the H-transfer and H-abstraction as well, and thus dramatically decreases the activation free energy of the nitration system. Moreover, the NO2+ attack may be dynamically affected by the pre-introduced -NO2 and the resulted fluctuation of charge distribution in the pre-intermediates, which has been primarily supported via the calculated atomic charge, Coulomb attraction and Fukui function. It is indicated that the preferential dinitration on -CH3 with the induction of HSO4- (path A) is the most likely pathway. It is optimistically expected that the present study may provide a theoretical basis to the research and engineering tests of the title nitration, and promote the exploration of related insensitive energetic materials.
收录类别	SCI
内容类型	期刊论文
源URL	[http://ir.rcees.ac.cn/handle/311016/35993]
专题	生态环境研究中心_环境纳米材料实验室
推荐引用方式 GB/T 7714	Wang, Kuan,Chen, Jian-Gang,Wang, Bozhou,et al. Insight into the acidic group-induced nitration mechanism of 2-methyl-4,6-dihydroxypyrimidine (MDP) with nitronium[J]. RSC ADVANCES,2016,6(83):80145-80157.
APA	Wang, Kuan.,Chen, Jian-Gang.,Wang, Bozhou.,Ji, Yueping.,Liu, Fengyi.,...&Lu, Jian.(2016).Insight into the acidic group-induced nitration mechanism of 2-methyl-4,6-dihydroxypyrimidine (MDP) with nitronium.RSC ADVANCES,6(83),80145-80157.
MLA	Wang, Kuan,et al."Insight into the acidic group-induced nitration mechanism of 2-methyl-4,6-dihydroxypyrimidine (MDP) with nitronium".RSC ADVANCES 6.83(2016):80145-80157.