Azocine, 2-methoxy-, synthesis

Azocine, dihydromethoxydimethyl-synthesis, 7, 661 Azocine, methoxy-reactions, 7, 664 Azocine, 2-methoxy-synthesis, 7, 663 Azocine, octahydro-drugs, 7, 655... 

By far the most thoroughly investigated azocines are the 2-methoxy derivatives prepared and studied by Paquette and coworkers (7lAG(E)ll). The synthesis involves addition of chlorosulfonyl isocyanate to a cyclohexadiene, conversion to the imidate and introduction of another double bond by allylic bromination and dehydrohalogenation. Valence isomerization then ensues and 2-methoxyazocine (98) or alkyl homologs are isolated from this sequence in multigram quantities as stable yellow oils. NMR data (see 98) clearly indicate the monocyclic azocine structure the spectra are invariant from -70 to 180 °C and indicate less than 2% of the bicyclic valence isomers. 

---