Azocines, Diazocines, and Azonines

Fully unsaturated azocines are 7r-equivalent heterocyclic analogs of cy-clooctatetraene. Addition of two electrons to the completely unsaturated azocine (34) can lead to a dianion 35 and removal of a proton from a dihy-droazocine (36) to the monoanion 37. Both the mono- and the dianions are lOTT-electron systems, corresponding to 7r-equivalent and 7r-excess analogs of cyclooctatetraenide [84CHEC-I(7)653], Aromatic dianions related to 35 have been fully characterized by and NMR (87TL2517). 

Anastassiou has summarized in two reviews the knowledge about IH-azonine (41a) [72ACR281 78AHC(23)55]. Compound 41a as well as its salts (N M ) are aromatic compounds which exist as such and not as imine polyenic forms. Tliis compound demonstrates a valence isomerism 41a/41b similar to that of l//-azepine (14a/14c see Section II,A,1) the transformation 41a 41b occurs upon irradiation. 9-Azabicyclo[6.1.0]nona-2,4,6-triene 41b displays no tendency to thermal isomerization to 41a at ambient temperature (72ACR281). 

Finally, there is a series of publications by Prinzbach and co-workers on 4,7-dihydro-l//-l,4,7-triazonine 42b (80CB3127, 80CB3161, 88CB757, 89AG1386). Tliis compound, obtained by a 3 j 3tt isomerization of 42a (ds-triaza-tris- j-homobenzene or ds-benzene triimine, its valence isomer) is a nonaromatic, nonplanar 127r-electron system, better represented as 42c. 

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