Ritter Reactions. V. Further Investigation of the 3-Azatricyclo[5.3.1.0^4,9]undec-2-ene System

Abstract

2,6-Dimethylenebicyclo[3.3.1] nonane (1) and acetonitrile react under Ritter reaction conditions to produce exo-ll-acetamido-2,4,endo-ll-trimethyl-3-azatricyclo[5.3.1.0^4,9 ]undec-2-ene (2)monohydrate whose crystal structure [C₁₅H₂₄N₂O.H₂O, P 2₁, a 8.21 3(3), b lO.84l(l),c 8.234(2) Å, β 95. 57(2)º, Z 2] was determined with a final R 0.036. The diene (1) reacts similarly with benzonitrile to produce the phenyl-substituted analogue (3). In contrast, the reaction of (1) and benzyl cyanide yields a different type of product, 2-benzoyl-4,endo11-dimethyl-exo-11-phenylacetamido-3-azatricyco[5.3.1.0^4,9]undec-2-ene (5a), where one of the two nitrile -derived groups has undergone spontaneous oxidation during the one-flask preparation. p- Bromo - and p- chloro-benzyl cyanides behave in a similar manner yielding the adducts (5b,c) respectively.