UV-Induced C-H Functionalization of Alkanes with NO2 in Supercritical Carbon Dioxide

被引：7
|
作者：
Ivanov, Roman E. [1 ]
Zharkov, Mikhail N. [1 ]
Zlotin, Sergei G. [1 ]
机构：
[1] Russian Acad Sci, IN Nazarov Lab Fine Organ Synth, ND Zelinsky Inst Organ Chem, Leninsky Prospect 47, Moscow 119991, Russia
来源：
CHEMPHOTOCHEM | 2022年 / 6卷 / 08期
基金：
俄罗斯科学基金会;
关键词：
nitrogen oxides; alkanes; radical reactions; photochemistry; supercritical fluids; NITROGEN-DIOXIDE; NITRATION; CYCLOHEXANE; ACID; NITROCYCLOHEXANE; PERSPECTIVES; OXIDE;
D O I：
10.1002/cptc.202200084
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
A novel catalyst-free method for functionalization of unbranched alkanes via radical nitration with UV-activated nitrogen oxide (IV) in supercritical carbon dioxide medium has been developed. The method allows to transform these inactive substrates into corresponding nitrates and nitro compounds with outstanding yields (up to 65%), using available reagents (NO2, O-2) under mild reaction conditions (35-50 degrees C), and exhibits lower hazards compared to conventional analogues. An improved selectivity towards the nitrates has been achieved by adding pure oxygen to the reaction. Based on changes in reaction rate and product composition, the plausible reaction mechanism for the UV-induced C-H functionalization of alkanes with nitrogen oxide (IV) and pure oxygen has been proposed.
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页数：5
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