How neutral nitrogen-containing compounds are oxidized in oxidative-denitrogenation of liquid fuel with TiO2@carbon. Issue 14 (1st April 2021)

• Record Type: Journal Article
• Authors: Bhadra, Biswa Nath; Baek, Yong Su; Choi, Cheol Ho; Jhung, Sung Hwa
• Is Part Of: Physical chemistry chemical physics. Volume 23:Issue 14(2021)
• Page Start: 8368
• Page End: 8374
• Publication Date: 2021-04-01
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d1cp00633a
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : In oxidative denitrogenation of neutral nitrogen-containing compounds, it was found that oxygen firstly attacks the nitrogen atom, via electrophilic addition of an active oxygen atom; and oxygen on nitrogen moves to the nearby carbon atom because of the relative stability of the intermediates and products. Abstract : Oxidative-denitrogenation (ODN) of indole (IND) and methyl-substituted INDs (methyl-INDs), representative neutral nitrogen-containing compounds (NCCs), was carried out with TiO2 @C and H2 O2 as heterogeneous catalyst and oxidant, respectively, under ultrasound irradiation. The oxidation of INDs progressed through radical formation, as evidenced by electron spin resonance and radical scavenger experiments. The oxidized position of INDs in the ODN process was checked via characterization of the obtained products. It was observed that the oxidation finally occurred on the carbon rather than on the nitrogen atom of INDs, unlike the oxidation of basic NCCs ( e.g., oxidation on the nitrogen atom, as respective N -oxides were formed) and sulfur-containing compounds. To understand the relative reactivity and oxidation position, electron density (ED) on the nitrogen atom of the studied INDs and relative stability of representative intermediates/products were calculated. It could be confirmed that ED on the nitrogen atom of the INDs is very important in the oxidation of INDs since the ODN reactivity of INDs was enhanced with increasing ED on the nitrogen atom of the investigated INDs. Moreover, theoretical analyses of the relative stability of substrate and intermediates/products (especially for IND) can explain the route for the observed final products in ODN. In other words, oxygen on the nitrogen atom, obtained via the first step of oxidation (electrophilic addition of an active oxygen atom on nitrogen), moves to the nearby carbon atom, because of the relative stability of the intermediates and products.