ISSN:
0009-2940
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Radical Pair Mechanism in the Aromatic Rearrangement of O-Alkylsulfinyl-N-phenylhydroxylaminesO-Alkylsulfinyl-N-benzoyl-N-phenylhydroxylamines (3) rearrange at - 70°C to give sulfonamides 4, o-sulfones 5, p-sulfones 6, and o-sulfonates 7. These reactions proceed intramolecularly via the radical pair 13 by [1,2]-, [2,3]- and [2,5]-shifts in both radicals as proved both by experiments with 18O-indicated N-benzoyl-N-phenylhydroxylamine (1) and by strong 13C-CIDNP effects. The third oxigen in the o-sulfonate 7 is donated by a second molecule of the educt 1.
Notes:
O-Alkylsulfinyl-N-benzoyl-N-phenylhydroxylamine (3) lagern sich schon bei ca. - 70°C um in Sulfonamide 4, o- und p-Sulfone 5 und 6 sowie in o-Sulfonate 7. Alle Reaktionen verlaufen intramolekular über das Radikalpaar 13 unter [1,2]-, [2,3]- und [2,5]-Verschiebungen in den Radikalen. Dies zeigen Versuche an 18O-indiziertem N-Benzoyl-N-phenylhydroxylamin (1) sowie die starken 13C-CIDNP-Effekte. Der zur Bildung des o-Sulfonats 7 benötigte Sauerstoff entstammt einem zweiten Molekül des Edukts 1.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19801130116
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