Metal-organic frameworks as efficient catalytic systems for the synthesis of 1,5-benzodiazepines from 1,2-phenylenediamine and ketones

• Published in: Journal of catalysis 2017-10, Vol.354, p.128-137
• Main Authors: Timofeeva, M.N., Panchenko, V.N., Prikhod'ko, S.A., Ayupov, A.B., Larichev, Yu.V., Khan, Nazmul Abedin, Jhung, Sung Hwa
• Format: Article
• Language: English
• Subjects: 1,2-Phenylenediamine; 1,5-Benzodiazepine; Acidity; Ketones; Metal-organic framework; MIL-100
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/j.jcat.2017.08.009

[Display omitted] •Synthesis of 1,5-benzodiazepines over MIL-100(M), MIL-110 and MIL-96 was studied.•Effect of Brønsted and Lewis acidity on MIL’s performance was investigated.•Lewis acidity of MIL-100(Fe, Cr, Al, V) was studied by EPR spectroscopy.•The type of M3+(Al, Fe, Cr, V) and structure of MILs affect the yield of product.•MIL-100(M) samples perform well in compared with zeolites. Benzodiazepines and their derivatives are a very important class of nitrogen-containing heterocyclic compounds with biological activity that are widely used in medicine. In this study, we demonstrated synthesis of 1,5-benzodiazepines from 1,2-phenylenediamine and ketones (acetone, cyclohexanone, acetophenone, methyl ethyl ketone) in the presence of isostructural porous metal-benzenetricarboxylates of the families MIL-100(M) (M: V3+, Al3+, Fe3+ and Cr3+) and three porous aluminium trimesates Al-BTCs (MIL-96(Al), MIL-100(Al) and MIL-110(Al)). A combination of catalytic, theoretical and physicochemical methods showed that reaction rates and yields of 1,5-benzodiazepines were adjusted by the type of metal ions and accessibility of active sites. The yield of 1,5-benzodiazepines in the presence of MIL-100(M) was comparable with zeolites, such as HY, H-ZSM−5, β-zeolite and heulandite.