ChemInform Abstract: REACTIONS OF KETONES WITH HYDROXYLAMINE‐O‐SULFONIC ACID

Abstract

Die alicyclischen Ketone bzw. Acetophenon (I) reagieren mit I‐Iydroxylamin‐O‐schwefelsäure zu den instabilen Sulfoketoximen, die mit NH3 in Form ihrer stabilen Ammoniumsalze (II) isoliert werden.

Insights into Regioselective Oxy (−O−) and Imino (−NH−) Group Insertions of 3-Nortricyclanone

“…Elusive diaziridines are sometimes accessible by the action of ammonia upon oxime- O -sulfonic acids or esters . Therefore, 3-nortricyclanone oxime- O -sulfonic acid ( 3 ) was immediately sought for this transformation because such diaziridine precursors are easily formed by the action of H 2 NOSO 2 OH, hydroxylamine- O -sulfonic acid (HOSA), upon cyclic ketones (eq 1) …”

“…Historically, oxime- O -sulfonic acids are unstable species that, on occasion, have been isolated as their potassium or ammonium salts (e.g., 4 in Scheme ) . Furthermore, a facile way to perform the Beckmann rearrangement directly upon cyclic ketones makes use of HOSA . This eliminates the need for preparing the oxime, e.g., 3-nortricyclanone oxime ( 7 ), 15d, in a separate step because the rearrangement proceeds through oxime- O -sulfonic acids …”

“…Lactam 16a likely derives from the normal Beckmann rearrangement syn- 3 → 9 . But 16a could also stem from a tandem reaction involving the abnormal Beckmann rearrangement syn- 3 → 8 , called Beckmann fragmentation, and the subsequent Ritter reaction 8 → 9 , 21b, even though intramolecular Ritter reactions are rare .…”