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.
[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.
Samet
Alexander V
AV
N. D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Pr., 47 Moscow, 119991, Russia.
Marshalkin
Victor N
VN
Kislyi
Konstantine A
KA
Chernysheva
Natalya B
NB
Strelenko
Yuri A
YA
Semenov
Victor V
VV
D003989:Dibenzoxazepines / Q000138:chemical synthesis* / Q000737:chemistry*; D015394:Molecular Structure; D009574:Nitro Compounds / Q000737:chemistry*
D003989:Dibenzoxazepines; D009574:Nitro Compounds; C036433:dibenz(b,f)(1,4)oxazepine