Study of the Beckmann rearrangement of acetophenone oxime over porous solids by means of solid state NMR spectroscopy
作者： Ana Belen Fernandez , Ines Lezcano-Gonzalez , Mercedes Boronat , Teresa Blasco , Avelino Corma
DOI: 10.1039/B816276J
关键词: Catalysis 、 Acetanilide 、 Amide 、 Chemistry 、 Beckmann rearrangement 、 Acetophenone 、 Organic chemistry 、 Zeolite 、 Oxime 、 Hydrogen bond 、 Polymer chemistry 、 Physical and Theoretical Chemistry 、 General Physics and Astronomy
摘要: The Beckmann rearrangement of acetophenone oxime using zeolite H-beta and silicalite-N as catalysts has been investigated by means 15N 13C solid state NMR spectroscopy in combination with theoretical calculations. results obtained show that the is N-protonated at room temperature on acid sites H-beta. At reaction temperatures 423 K or above, two isomeric amides, acetanilide N-methyl benzamide (NMB) are formed, interact Bronsted through hydrogen bonds. presence residual water hydrolyzes while larger amounts inhibit formation NMB cause total hydrolysis acetanilide. Over siliceous silicalite-N, containing silanol nests active sites, adsorbed bonds only formed above. In water, starts 473 K, still being very selective up to 573 amide partially hydrolyzed above this .
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sci-hub.se 参考文章(27)
E. Gutierrez, A.J. Aznar, E. Ruiz-Hitzky, Beckmann Rearrangement Reactions on Acidic Solids Studies in Surface Science and Catalysis. ,vol. 59, pp. 539- 547 ,(1991) , 10.1016/S0167-2991(08)61163-5
G.P. Heitmann, G. Dahlhoff, W.F. Hölderich, Catalytically Active Sites for the Beckmann Rearrangement of Cyclohexanone Oxime to ε-Caprolactam Journal of Catalysis. ,vol. 186, pp. 12- 19 ,(1999) , 10.1006/JCAT.1999.2552
M. Hunger, S. Ernst, S. Steuernagel, J. Weitkamp, High-field 1H MAS NMR investigations of acidic and non-acidic hydroxyl groups in zeolites H-Beta, H-ZSM-5, H-ZSM-58 and H-MCM-22 Microporous Materials. ,vol. 6, pp. 349- 353 ,(1996) , 10.1016/0927-6513(96)00043-0
V REDDYMARTHALA, S RABL, J HUANG, S REZAI, B THOMAS, M HUNGER, In situ solid-state NMR investigations of the vapor-phase Beckmann rearrangement of 15N-cyclohexanone oxime on MFI-type zeolites and mesoporous SBA-15 materials in the absence and presence of the additive 13C-methanol Journal of Catalysis. ,vol. 257, pp. 134- 141 ,(2008) , 10.1016/J.JCAT.2008.04.014
Gerd Dahlhoff, John P. M. Niederer, Wolfgang F. Hoelderich, ϵ-Caprolactam: new by-product free synthesis routes Catalysis Reviews-science and Engineering. ,vol. 43, pp. 381- 441 ,(2001) , 10.1081/CR-120001808
J. Hafner, L. Benco, T. Bucko, Active Sites for the Vapor Phase Beckmann Rearrangement over Mordenite: An ab Initio Study Journal of Physical Chemistry A. ,vol. 108, pp. 11388- 11397 ,(2004) , 10.1021/JP0471103
A FERNANDEZ, I LEZCANOGONZALEZ, M BORONAT, T BLASCO, A CORMA, NMR spectroscopy and theoretical calculations demonstrate the nature and location of active sites for the Beckmann rearrangement reaction in microporous materials Journal of Catalysis. ,vol. 249, pp. 116- 119 ,(2007) , 10.1016/J.JCAT.2007.03.030
G Heitmann, Modified Beta zeolites as catalysts for the Beckmann rearrangement of cyclohexanone oxime Applied Catalysis A-general. ,vol. 185, pp. 99- 108 ,(1999) , 10.1016/S0926-860X(99)00126-X
P LANDIS, Organic reactions catalyzed by crystalline aluminosilicates: IV. Beckmann rearrangement of ketoximes to amides Journal of Catalysis. ,vol. 6, pp. 245- 252 ,(1966) , 10.1016/0021-9517(66)90055-8
A FERNANDEZ, A MARINAS, T BLASCO, V FORNES, A CORMA, Insight into the active sites for the Beckmann rearrangement on porous solids by in situ infrared spectroscopy Journal of Catalysis. ,vol. 243, pp. 270- 277 ,(2006) , 10.1016/J.JCAT.2006.06.029