title: Synthetic utilization of polynitroaromatic compounds. 3. Preparation of substituted dibenz[b,f][1,4]oxazepine-11(10H)-ones from 2,4,6-trinitrobenzoic acid via nucleophilic displacement of nitro groups.
abstract: [Reaction: see text]. 1,3-dinitrodibenz[b,f][1,4]oxazepin-11(10H)-one, prepared by intramolecular displacement of nitro group in N-(2-hydroxyphenyl)-2,4,6-trinitrobenzamide, reacts with O- and S-nucleophiles to yield the products of mono- or bis-substitution of the nitro groups. The nitro group in position 3 is displaced first. This observation is in contrast with earlier results for the nitro-substituted benzoannulated five-membered heterocycles. This difference in reactivity is likely due to the increased steric hindrance for peri-nitro group displacement in the case of the benzoannulated seven-membered heterocycle. N-Alkylation of the nitro-substituted dibenz[b,f][1,4]oxazepin-11(10H)-ones yields analogues of a known antidepressant drug Sintamil. The structure of the products is confirmed by NOE experiments and alternative synthesis.
authors.affiliation: N. D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Pr., 47 Moscow, 119991, Russia.
authors.forename: Alexander V
authors.initials: AV
authors.lastname: Samet
authors.forename: Victor N
authors.initials: VN
authors.lastname: Marshalkin
authors.forename: Konstantine A
authors.initials: KA
authors.lastname: Kislyi
authors.forename: Natalya B
authors.initials: NB
authors.lastname: Chernysheva
authors.forename: Yuri A
authors.initials: YA
authors.lastname: Strelenko
authors.forename: Victor V
authors.initials: VV
authors.lastname: Semenov
mesh_terms: D003989:Dibenzoxazepines / Q000138:chemical synthesis* / Q000737:chemistry*; D015394:Molecular Structure; D009574:Nitro Compounds / Q000737:chemistry*
chemical_list: D003989:Dibenzoxazepines; D009574:Nitro Compounds; C036433:dibenz(b,f)(1,4)oxazepine