Sterically Hindered Carbonyl O‐Oxides and Dioxiranes − (6‐tert‐Butyl‐2,3,4‐trimethylphenyl)phenylcarbonyl O‐Oxide and (6‐tert‐Butyl‐2,3,4‐trimethylphenyl)phenyldioxirane

Abstract

(6-tert-Butyl-2,3,4-trimethylphenyl)phenylcarbonyl O-oxide (1b) was generated by photooxidation of diazo compound 6b in an organic glass and in solution and characterized by UV/ Vis spectroscopy and by its photo-and thermochemistry. With 4.5 min at 230 K the half-life of 1b is considerably smaller than that of dimesityl ketone O-oxide (1a). The only clearly detected thermal product of 1b is the corresponding ketone 3b. The isomeric (6-tert-butyl-2,3,4-trimethylphenyl)-

Three‐Membered Heterocycles. Structure and Reactivity

“…There are certainly isolated alternative conditions that lead to the formation of the dioxirane system, such as the photolytic oxidation of diaryl diazoalkanes (e.g., 837 ! 838, Scheme 2.119) [805]; however, to date they have not been widely adopted by the synthetic laboratory.…”

Generation of Mono- and Bis-dioxiranes from 2,3-Butanedione

“…The comparison of 1 with butane-2,3-bisacetal ( 2 ), such as the 1,1,2,2-oxygenation generated as a protecting group for 1,2-diols, led us to raise the following question: Can more than one dioxirane center occupy a molecule? Despite the intense interest in the synthesis of dioxiranes, in studies gauging dioxirane stability, and in oxone-mediated cleavage of 1,2-dicarbonyl compounds, no studies have yet focused on molecules containing adjacent α-dioxirane groups (1,2-bis-dioxiranes). The juxtaposition of two dioxirane groups would represent a new type of structure in dioxirane chemistry.…”