ISSN:
0947-6539
Keywords:
alcohols
;
nitriles
;
NMR spectroscopy
;
olefins
;
zeolites
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
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 13C and 15N 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.
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/chem.19970030109
Permalink