71426-76-1Relevant academic research and scientific papers
Methylene group transfer in carbonyl compounds discovered in silico and detected experimentally
Gridnev, Ilya D.,Zherebker, Alexander,Kostyukevich, Yury,Nikolaev, Eugene
, p. 361 - 365 (2019)
A previously unknown transformation of aldehydes, ketones, and carboxylic acid derivatives leads to the formation of substituted oxiranes, aziridines, and azirines as shown by DFT and MP2 computations. Formations of 2,2-dimethyloxirane-d8 from acetone-d6, phenylazirine-d2 from benzonitrile and 2- methyl-2-(4-hydroxyphenyl)-oxirane from 4-hydroxyacetophenone were detected experimentally by electrospray ionization mass-spectrometry with a heated desolvating capillary. This reaction is a truly concerted process characterized by high activation barriers (activation enthalpies 320-480 kJmol-1).
