Cyclization reaction of amines with dialkyl carbonates to yield 1,3-oxazinan-2-ones

McElroy, C. Robert; Aricò, Fabio; Benetollo, Franco; Tundo, Pietro

doi:10.1351/PAC-CON-11-07-18

Pure Appl. Chem., 2012, Vol. 84, No. 3, pp. 707-719

http://dx.doi.org/10.1351/PAC-CON-11-07-18

Published online 2011-11-23

Cyclization reaction of amines with dialkyl carbonates to yield 1,3-oxazinan-2-ones*

C. Robert McElroy¹, Fabio Aricò¹, Franco Benetollo² and Pietro Tundo¹*

¹ Università Ca’ Foscari di Venezia, Dipartimento di Scienze Ambientali, Informatica e Statistica, Dorsoduro 2137, 30123, Venice, Italy
² ICIS-CNR, Corso Stati Uniti 4, 35127 Padova, Italy

Abstract: A number of six-membered cyclic carbamates (oxazinanones) were synthesized from the reaction of a primary amine or hydrazine with a dicarbonate derivative of 1,3-diols in a one-pot reaction, in good yield, short time span, and in the absence of a solvent. The reaction proceeds in two steps: an intermolecular reaction to give a linear intermediate and an intramolecular cyclization to yield the cyclic carbamate. This is the first example of a carbonate reacting selectively and sequentially, firstly at the carbonyl center to form a linear carbamate and then as a leaving group to yield a cyclic carbamate.

*Pure Appl. Chem. 84, 411–860 (2012). A collection of invited papers for the IUPAC project 2008-016-1-300 “Chlorine-free Synthesis for Green Chemistry”.