Photo-on-Demand Base-Catalyzed Phosgenation Reactions with Chloroform: Synthesis of Arylcarbonate and Halocarbonate Esters

J Org Chem. 2021 Jul 16;86(14):9811-9819. doi: 10.1021/acs.joc.1c01210. Epub 2021 Jun 28.

Abstract

Carbonate esters are utilized as solvents and reagents for C1 building blocks in organic synthesis. This study reports a novel photo-on-demand in situ synthesis of carbonate esters with CHCl3 solutions containing a mixture of an aromatic or haloalkyl alcohol having relatively high acidity, and an organic base. We found that the acid-base interaction of the alcohol and base in the CHCl3 solution plays a key role in enabling the photochemical reaction. This reaction allows practical syntheses of diphenyl carbonate derivatives, haloalkyl carbonates, and polycarbonates, which are important chemicals and materials in industry.