Fragmentierung von α‐Aminoketoximen. V. Teil. (2‐Chinuclidinyl)‐phenyl‐ketoxim. Zur Gültigkeit der B REDT schen Regel bei energiereichen Zwischenstufen Fragmentierungsreaktionen, 18. Mitteilung

The reaction of (2‐quinuclidinyl) phenyl ketoxime tosylate ( 1 ) in aqueous ethanol or tetrahydrofuran yields 10 to 20% of benzonitrile and 4‐piperidyl‐acetaldehyde ( 6 ), the tautomer of 2‐quinuclidinol ( 5 ), besides N‐(2‐quinuclidinyl)‐benzamide ( 4 ). In phenol some 2‐phenoxyquinuclidin ( 21 ) and benzonitrile are obtained besides phenyl N‐(2‐quinuclidinyl)‐benzimidate ( 20 ). Furthermore, the α‐aminoketoximetosylate 1 reacts 2 to 4 times as fast as the homomorphous (bicyclo[2.2.2]‐2‐octyl) phenyl ketoxime tosylate ( 7 ). By contrast the latter untergoes quantitative Beckmann rearrangement to the amide 12 .