Benzodiazepinone과 1,5-Benzodiazepine 유도체의 합성 연구 = Syntheses of Benzodiazepinone and 1,5-Benzodiazepine derivatives

다국어 초록 (Multilingual Abstract)

The reaction of o-phenylenediamine 5 with acrylic acid 11 in the presencce of P₂O5+H₃PO₄afforded benzodiazepinone 13 and pyridobenzodiazepinono 17.
The reactions of o-phenylenediamine 5 with acrylic acid 11 in the presence of PPA or SiO₂afforded only benzodiazepinone 13.
But the reaction of O-phenylenediamine 5 with acrylic acid 11 in the presence of acetonedicarboxylic acid 18 or acetonedicarboxylic acid 18 and PPA or acetonedicarboxylic acid 18 and SiO₂was respectively synthesized 2,4,4,-trimethyI-3H-5-hydro-1.5-benzodi-azepine 23 as new cyclic imine compound.
We propose that formation of 2-(2`-imine)propyI-N-isopropylidene aniline proceed though 2-amino, N-isopropylidene aniline intermediate C and 2-(N-a-methylethyI) amino, N-isopropylidene aniline intermediate G.
The reaction of o-phenylenediamine 5 with acetonedicarboxylic acid 18 in the presence of PPA or SiO₂or HCI gave
2,4,4-trimethyI-3H-5-hydro-1,5-benzodiazepine 23.
Using acetone 19 instead of acetonedicarboxylic acid 18, the reaction of o-phenylenediamine 5 in the presence of PPA or SiO₂or acrylic acid 11 was synthesized 2,4,4-trimethyI-3H-5-hydro-1,5-benzodiazepine 23 as same product.
And also the reaction of o-phenylenediamine 5 with acetone 19 and acrylic 11 in the presence of PPA or SiO₂was obtained 2,4,4-trimethyI-3H-5-hydro-1,5-benzodiazepine 23.
In case of acetophenone 21 in stead of acceton 19, the reaction of o-phenylenediamine 5 in presence of PPA or SiO₂at 40~45℃ were obtained 2,4-diphenyI-4methyI-3H-5-hydro-1,5-benzodiazepine 24.
The reaction of o-phenylenediamine 5 with crotonic acid 25 in the presence of PPA or P₂O5+H₃PO₄or SiO₂at 100~110℃ afforded respectively 4-methybenzodiazepinone 26 as 1:1 cycloadduct.