The Reaction of Carbonyldiimidazole with Alcohols to Form Carbamates and N-Alkylimidazoles

Yuanqing Tang; Yuxiang Dong; Jonathan L. Vennerstrom

doi:10.1055/s-2004-831215

PAPER

The Reaction of Carbonyldiimidazole with Alcohols to Form Carbamates and N-Alkylimidazoles

Yuanqing Tang, Yuxiang Dong, Jonathan L. Vennerstrom*
College of Pharmacy, University of Nebraska Medical Center, 986025 Nebraska Medical Center, Omaha, NE 68198-6025, USA
Fax: +1(402)5599543; e-Mail: jvenners@unmc.edu;

Abstract

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Abstract

The reactions of non-benzylic primary and secondary aliphatic alcohols with carbonyldiimidazole (CDI) afford the corresponding carbamates but not N-alkylimidazoles. For benzylic primary alcohols, formation of N-alkylimidazoles proceeds reasonably at 170 °C in several different solvents and occurs by way of the initially formed carbamate. However, under these rather forcing conditions, or even at lower reaction temperatures, elimination is a significant side reaction for benzylic secondary alcohols with β-hydrogen atoms. With one exception, reactions of six N,N-disubstituted β-aminoalcohols with CDI to form N-alkylimidazoles proceed under relatively mild conditions and may occur by way of an aziridinium intermediate.

Keywords

alcohols - alkylations - carbonyldiimidazole (CDI) - carbamates - N-alkylimidazoles

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