以碱Y沸石为催化剂的DMC在N上的甲基化反应.pdf

TETRAHEDRON LETTERS Pergamon Tetrahedron Letters 44 (2003) 8139–8142 Selective N -methylation of primary aliphatic amines with dimethyl carbonate in the presence of alkali cation exchanged Y-faujasites Maurizio Selva* and Pietro Tundo Dipartimento di Scienze Ambientali dell ’Universita` Ca’ Foscari, Calle Larga S. Marta 2137, 30123 Venezia, Italy Received 17 July 2003; revised 18 August 2003; accepted 3 September 2003 Abstract—The N -methylation of aliphatic amines [XC H (CH ) NH ; n =1, X=H (1a), o -MeO (1b), p -MeO (1c); n =2, X =H 6 4 2 n 2 (2a), o -MeO (2b); 1d: PhCH(Me)NH2] with dimethyl carbonate (DMC) is efficiently catalysed by NaY faujasite: on condition that CO (a co-product of the reaction) is carefully removed, N -methyl- and N,N -dimethyl-amines (RNHMe and RNMe ) are 2 2 obtained in good overall yields (70–90%). Otherwise, in the presence of CO , carbamates (RNHCO Me) form competitively to a 2 2 large extent. The reaction probably proceeds through a BAl2 displacement of the amine on DMC. © 2003 Elsevier Ltd. All rights reserved. In the presence of alkali cation