Dibenzoazepine derivatives

Meanwhile, Catellani, Derat and their co-workers developed the synthesis of dihydrodibenzoazepine and dibenzoazepine derivatives from 2-bromoanilines and aryl iodides. The process was based on the sequential reaction of three components, an aryl iodide, a bromoaniline, and either norbornene or norbornadiene in the presence of palladium as the catalyst (Scheme 4.13c). Whereas the use of norbornene leads to dihydrodibenzoazepine derivatives, norbornadiene allows an additional step consisting of a retro-Diels-Alder reaction, thus leading to the parent dibenzoazepines. 

The Ugi-4-component reaction has also been used to directly access diverse dibenzoazepine derivatives from suitably substituted biaryl derivatives (Scheme 7) [42]. In comparison to conventional heating, use of MW led to much reduction in the reaction time with significant improvement of the yield. This method should be particularly suited for library s5mthesis of such type of compounds. 

Fig 2 Chromatogram of dibenzoazepine and phenothiazine derivatives after staining with F( REST reagent 1 = fluphenazine, 2 = periciazine, 3 = promethazine, 4 = alimemazine, 5 = mixtur of substances 1 to 4, 6 = mixture of substances 7 to 12, 7 = dibutil, 8 = levomepromaziMi 9 = chlorpromazine, 10 = verophene, 11 - dixjrazine, 12 = perphenazine. 

Both acridone and dibenzo[6,/]azepine produce unexpected products (Scheme 7.39) when reacted with dimethylvinylidene carbene (7.1.18.A). Acridone reacts initially at the nitrogen atom to produce the 10-(3,3-dimethylallenyl) derivative (13%) and a pyrroloacridone (10%) which, if the structure is correct, could be derived from the allene by sigmatropic shifts [16]. The dibenzoazepine reacts as expected to produce a cyclopropyl derivative but, under the reaction conditions, the adduct rearranges spontaneously to yield a 1,6-methanodibenzo[b,/]cyclo-prop [J]azepine, the structure of which was confirmed by X-ray crystallography [17]. 

This method has been used for the synthesis of 1-aryl and polycyclic isatins derived from phenoxazine, phenothiazine and dibenzoazepine as well as indoline. In the case of dimethoxyanilines, spontaneous cyclization to yield dimethoxyisatins in the absence of a Lewis acid has been observed, as exemplified in the synthesis of melosatin A, albeit in very low yield (Scheme 8). 

Dibenzoazepines and their dihydro derivatives are components of a series of psychopharmaceuticals (antidepressants and antiepileptics) such as carbamazepine 31 and desipramine 33. 

D.W. Jones You showed a computer drawing derived from a dipole-type program for the structure of a dibenzoazepine-based drug complexed with a ring-containing molecule. In some ways, is not the extent of structural detail slightly spurious in that the number of observables is insufficient to determine independently (as distinct from showing consistency with) the main structural framework. 

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