Advanced

Selective, Green Synthesis of Six-Membered Cyclic Carbonates by Lipase-Catalyzed Chemospecific Transesterification of Diols with Dimethyl Carbonate

Pyo, Sang-Hyun LU and Hatti-Kaul, Rajni LU (2012) In Advanced Synthesis & Catalysis 354(5). p.797-802
Abstract
A facile and green synthesis of six-membered cyclic carbonates, the potential monomers for isocyanate-free polyurethanes and polycarbonates, was achieved by transesterification of diols with dimethyl carbonate catalyzed by immobilized Candida antarctica lipase B, Novozym (R) 435, followed by thermal cyclization in a solvent-free medium. The difference in the chemospecificity of the lipase for the primary, secondary and tertiary alcohols as acyl acceptors was utilized to obtain a highly chemoselective synthesis of the cyclic carbonate in high yield. In the lipase-catalyzed reaction with diols, the product contained almost equal proportions of mono- and di-carbonates with 1,3-propanediol having two primary alcohols, a higher proportion of... (More)
A facile and green synthesis of six-membered cyclic carbonates, the potential monomers for isocyanate-free polyurethanes and polycarbonates, was achieved by transesterification of diols with dimethyl carbonate catalyzed by immobilized Candida antarctica lipase B, Novozym (R) 435, followed by thermal cyclization in a solvent-free medium. The difference in the chemospecificity of the lipase for the primary, secondary and tertiary alcohols as acyl acceptors was utilized to obtain a highly chemoselective synthesis of the cyclic carbonate in high yield. In the lipase-catalyzed reaction with diols, the product contained almost equal proportions of mono- and di-carbonates with 1,3-propanediol having two primary alcohols, a higher proportion of mono-carbonate with 1,3-butanediol having a primary and a secondary alcohol, and mainly mono-carbonate with 3-methyl-1,3-butanediol having a primary and a tertiary alcohol. The chemospecificity of cyclic carbonates formed by thermal treatment at 90 degrees C was closely related to the proportion of mono-carbonate. The yield of cyclic carbonate was 99.3% with 3-methyl-1,3-butanediol, 85.5% with 1,3-butanediol, and 43.2% with 1,3-propanediol. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
3-propanediol, transesterification, 3-methyl-1, chemoselectivity, 1, 3-butanediol, thermal cyclization
in
Advanced Synthesis & Catalysis
volume
354
issue
5
pages
797 - 802
publisher
John Wiley & Sons
external identifiers
  • wos:000301777500006
  • scopus:84858766266
ISSN
1615-4150
DOI
10.1002/adsc.201100822
language
English
LU publication?
yes
id
92d5652c-1be5-44a2-9317-28c2d6f035c4 (old id 2591313)
date added to LUP
2012-05-30 14:41:53
date last changed
2017-07-02 04:04:30
@article{92d5652c-1be5-44a2-9317-28c2d6f035c4,
  abstract     = {A facile and green synthesis of six-membered cyclic carbonates, the potential monomers for isocyanate-free polyurethanes and polycarbonates, was achieved by transesterification of diols with dimethyl carbonate catalyzed by immobilized Candida antarctica lipase B, Novozym (R) 435, followed by thermal cyclization in a solvent-free medium. The difference in the chemospecificity of the lipase for the primary, secondary and tertiary alcohols as acyl acceptors was utilized to obtain a highly chemoselective synthesis of the cyclic carbonate in high yield. In the lipase-catalyzed reaction with diols, the product contained almost equal proportions of mono- and di-carbonates with 1,3-propanediol having two primary alcohols, a higher proportion of mono-carbonate with 1,3-butanediol having a primary and a secondary alcohol, and mainly mono-carbonate with 3-methyl-1,3-butanediol having a primary and a tertiary alcohol. The chemospecificity of cyclic carbonates formed by thermal treatment at 90 degrees C was closely related to the proportion of mono-carbonate. The yield of cyclic carbonate was 99.3% with 3-methyl-1,3-butanediol, 85.5% with 1,3-butanediol, and 43.2% with 1,3-propanediol.},
  author       = {Pyo, Sang-Hyun and Hatti-Kaul, Rajni},
  issn         = {1615-4150},
  keyword      = {3-propanediol,transesterification,3-methyl-1,chemoselectivity,1,3-butanediol,thermal cyclization},
  language     = {eng},
  number       = {5},
  pages        = {797--802},
  publisher    = {John Wiley & Sons},
  series       = {Advanced Synthesis & Catalysis},
  title        = {Selective, Green Synthesis of Six-Membered Cyclic Carbonates by Lipase-Catalyzed Chemospecific Transesterification of Diols with Dimethyl Carbonate},
  url          = {http://dx.doi.org/10.1002/adsc.201100822},
  volume       = {354},
  year         = {2012},
}