Generation of mono- and bis-dioxiranes from 2,3-butanedione.
Biacetyl reacts with oxone to give bis-dioxirane [3,3'-dimethyl-3,3'-bidioxirane, 3B] and mono-dioxirane [1-(3-methyl-dioxiran-3-yl)ethanone, 3A)]. Bis-dioxirane 3B is formed when two oxygens are incorporated into biacetyl, while mono-dioxirane 3A incorporated only one. A greater stability is observed in 3B compared to 3A, which is attributed to an alpha-dioxiranyl (anomeric) effect in the former. In contrast, 3A suffers from a destabilizing pi-electron withdrawing effect from the adjacent carbonyl group.
Sawwan
Nahed
N
Department of Chemistry, Graduate Center and The City University of New York (CUNY), Brooklyn College, Brooklyn, New York 11210, USA.
Greer
Alexander
A
D002384:Catalysis; D003931:Diacetyl / Q000737:chemistry*; D019281:Dimerization; D004852:Epoxy Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D008401:Gas Chromatography-Mass Spectrometry; D009682:Magnetic Resonance Spectroscopy
D004852:Epoxy Compounds; C061799:dioxirane; D003931:Diacetyl