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Interaction of Acetonitrile with Olefins and Alcohols in Zeolite H‐ZSM‐5: In situ Solid‐state NMR Characterization of the Reaction Products
Author(s) -
Stepanov Alexander G.,
Luzgin Mikhail V.
Publication year - 1997
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.19970030109
Subject(s) - chemistry , zeolite , acetonitrile , catalysis , alcohol , ritter reaction , inorganic chemistry , organic chemistry , photochemistry , medicinal chemistry
The reaction products and intermediates from the interaction of acetonitrile with olefins (oct‐1‐ene) or alcohols ( tert ‐butyl alcohol) in zeolite H‐ZSM‐5 at 296 K have been characterized with 13 C and 15 N solid‐state NMR. It has been shown that coadsorption of acetonitrile and olefin on H‐ZSM‐5 gives rise to the intermediate N ‐alkylnitrilium cation represents a persistent species inside a zeolite under anhydrous conditions. Upon admittance of water to the pores of the zeolite, the N ‐alkylnitrilium cation slowly converts into N ‐alkylamide in accordance with the classic Ritter reaction. In the case of acetonitrile and alcohol, just after coadsorption both the intermediate N ‐alkylnitrilium cation and the final N ‐alkyl‐amide are identified simultaneously; the former slowly disappears over a few days. Thus, 1) it has been shown that the Ritter reaction can occur not only in liquid acidic media but also on a solid acid catalyst, zeolite H‐ZSM‐5; 2) N ‐alkylnitrilium cations have been detected and characterized with solid‐state NMR as persistent intermediates in the Ritter reaction for the first time while the reaction proceeds.