Selective, Green Synthesis of Six-Membered Cyclic Carbonates by Lipase-Catalyzed Chemospecific Transesterification of Diols with Dimethyl Carbonate
(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:
https://lup.lub.lu.se/record/2591313
- author
- Pyo, Sang-Hyun LU and Hatti-Kaul, Rajni LU
- organization
- publishing date
- 2012
- 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 Inc.
- 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
- 2016-04-01 14:12:35
- date last changed
- 2022-04-22 02:01:35
@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}},
keywords = {{3-propanediol; transesterification; 3-methyl-1; chemoselectivity; 1; 3-butanediol; thermal cyclization}},
language = {{eng}},
number = {{5}},
pages = {{797--802}},
publisher = {{John Wiley & Sons Inc.}},
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}},
doi = {{10.1002/adsc.201100822}},
volume = {{354}},
year = {{2012}},
}