Fe-containing mesoporous mesophase silica materials as effective catalysts for synthesis of 1,5-benzodiazepine form o-phenylenediamine and acetone | Vestnik Tomskogo gosudarstvennogo universiteta. Chimia – Tomsk State University Journal of Chemistry. 2017. № 7. DOI: 10.17223/24135542/7/6

Fe-containing mesoporous mesophase silica materials as effective catalysts for synthesis of 1,5-benzodiazepine form o-phenylenediamine and acetone

Fe-MMM-2 possesses a hexagonal structure with uniform mesopores (a diameter of 3.75-3.85 nm and silicate wall thickness of 1.3-1.4 nm) and does not have micropores. This material also has high internal and low external surface areas (900- 950 m/g). According to IR spectroscopy using pyridine as the probe molecule, Fe-MMM-2 materials have acid sites (proton affinity (PA) 1175-1188 kJ/mol) and therefore can have potential in acid-type reactions. Reaction was carried out at 50°C, with aceton/(I) mol/mol ratio of 2.5 in methanol as the major reaction medium. It was found that in the presence of Fe-MMM-2, the main product was 1.5 benzadiazepine with 68-88% yield. The maximum yield of (III) was 85-88% in presence of 1.7% Fe-MMM for 180 min. Fe content affected the performance of Fe-MMM-2. The yield of 1.5 benzadiazepine increases linearly with the increase of Fe content. At the same time, correlation between conversion of (I) and Fe content in Fe-MMM-2 is dome-shaped, with maximum conversion at 2-3 wt% of Fe. This phenomenon was related to effects of the Fe oligomeric state and surface acidity, which vary with Fe content. The high reaction rate and yield of 1.5 benzodiazepine are achieved with isolated iron sites in framework of Fe-MMM-2. The maximum yield of 1.5 benzodiazepine was 86-88% under the condition investigated in the presence of 1.7% Fe-MMM-2. The catalytic performance of the most active Fe-MMM-2 sample with 1.7 wt% was compared with that of H-ZSM-5, zeolite-fi, and zeolites under solvent-free conditions, with a 4/1 molar ratio of acetone/(I) at 50 C. In the presence of 1.7% Fe-MMM, an 86% yield of (III) was observed after 5 h. Activity of 1.7% Fe-MMM-2 was comparable to that of zeolites such as zeolite HY (Si/Al 2.5, framework type FAU) and zeolite Heulandite (Si/Al 5, framework type HEU). At the same time, zeolites such as zeolite H-ZSM-5 (Si/Al 28, framework type MFI) and в -Zeolite (Si/Al 30, framework type BEA) show lower activity than 1.7% Fe-MMM-2 that can be explained by the difference in surface acidity.

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Keywords

1,5-Бензодиазепин, о-Фенилендиамин, ацетон, железосодержащие мезопористые мезофазные силикатные материалы, кислотный катализ

Authors

Name	Organization	E-mail
Makarova Kristina N.	Novosibirsk State Technical University	kristina-kristi-makarova@mail.ru
Malushev Mikhail E.	Boreskov Institute of Catalysis SB RAS	mem@catalysis.ru
Panchenko Valentina N.	Novosibirsk State Technical University; Boreskov Institute of Catalysis SB RAS	panchenko@catalysis.ru
Ayupov Artem B.	Boreskov Institute of Catalysis SB RAS	artem@catalysis.ru
Timofeeva Maria N.	Novosibirsk State Technical University; Institute of Catalysis SB RAS	timofeeva@catalysis.ru

Всего: 5

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