Anti-Bredt Molecules. 3. 3-Oxa-1-azabicyclononan-2-one and 6-Oxa-1-azabicyclooctan-7-one, Two Atom-Bridged Bicyclic Urethanes Possessing Bridgehead Nitrogen

Article abstract of DOI:10.1021/jo01314a022

The first atom-bridged bicyclic urethanes possessing bridgehead nitrogen have been synthesized and their properties examined briefly. 3-Oxa-1-azabicyclo<3.3.1>nonan-2-one was synthesized from 3-(hydroxymethyl)-piperidine and phosgene by using two alternate reaction schemes. 6-Oxa-1-azabicyclo<3.2.1>octan-7-one was synthesized similarly from 3-hydroxypiperidine.Both compounds were stable, white, crystalline solids with normal infrared spectra.They were rather stable to acids and bases, but phosphoric acid initiated ring-opening polymerization demonstrated strain in the system.A novel O -> N rearrangement of two aminochloroformates to hydroxy N-carbamoyl chlorides was demonstrated.