Premium
On the Reaction of Aminoxyls with Dioxiranes
Author(s) -
Dinoi Anna,
Curci Ruggero,
Carloni Patricia,
Damiani Elisabetta,
Stipa Pierluigi,
Greci Lucedio
Publication year - 1998
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(199805)1998:5<871::aid-ejoc871>3.0.co;2-f
Subject(s) - dioxirane , chemistry , dimethyldioxirane , yield (engineering) , deoxygenation , acetone , radical , trifluoromethyl , adamantane , organic chemistry , photochemistry , decomposition , reaction mechanism , medicinal chemistry , catalysis , materials science , alkyl , metallurgy
In the reactions of dimethyldioxirane ( 1a ) and methyl(trifluoromethyl)dioxirane ( 1b ) with 2,2,6,6‐tetramethylpiperidinyl‐1‐oxyl ( 2 ) (TEMPO) in acetone, the corresponding methoxyamine 1‐methoxy‐2,2,6,6‐tetramethylpiperidine ( 5 ) is produced in ≥98% yield, both in air and under N 2 , and in the absence or presence of a hydrocarbon (adamantane). Kinetic experiments show that aminoxyl 2 triggers the radical decomposition of the dioxirane, in addition to scavenging methyl radicals derived therefrom. The reactions of an aminoxyl less prone to oxidation, namely 1,2‐dihydro‐2‐methyl‐2‐phenyl‐3 H ‐indol‐3‐one‐1‐oxyl ( 4 ), with dioxiranes 1a and 1b in acetone have also been studied. In these cases, not only is the corresponding methoxyamine 8a produced (yield 12−16%), but quinoneimine‐ N ‐oxides 10 (yield 12−21%) and 11 (yield 18−19%) are also formed. Furthermore, significant amounts (8−14%) of the amine 9 (the product of deoxygenation of 4 ) can be isolated. These observations provide useful information concerning the free‐radical mechanism that follows the initial attack by the aminoxyl at the dioxirane.