Document Detail

Ring-opening polymerization of ε-caprolactone catalyzed by sulfonic acids: computational evidence for bifunctional activation.
MedLine Citation:
PMID:  20799719     Owner:  NLM     Status:  MEDLINE    
The mechanism of ring-opening of ε-caprolactone by methanol catalyzed by trifluoromethane and methane sulfonic acids has been studied computationally at the DFT level of theory. For both elementary steps, the sulfonic acid was predicted to behave as a bifunctional catalyst. The nucleophilic addition proceeds via activation of both the monomer and the alcohol. The ring-opening involves the cleavage of the endo C-O bond of the tetrahedral intermediate with concomitant proton transfer. In both cases, the sulfonic acid acts as a proton shuttle via its acidic hydrogen atom and basic oxygen atoms. The computed activation barriers are consistent with the relatively fast polymerizations observed experimentally at room temperature with both catalysts.
Nicolas Susperregui; Damien Delcroix; Blanca Martin-Vaca; Didier Bourissou; Laurent Maron
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Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't    
Journal Detail:
Title:  The Journal of organic chemistry     Volume:  75     ISSN:  1520-6904     ISO Abbreviation:  J. Org. Chem.     Publication Date:  2010 Oct 
Date Detail:
Created Date:  2010-09-24     Completed Date:  2011-01-04     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  2985193R     Medline TA:  J Org Chem     Country:  United States    
Other Details:
Languages:  eng     Pagination:  6581-7     Citation Subset:  IM    
University of Toulouse, INSA, UPS, LPCNO, 135 Avenue de Rangueil, F-31077 Toulouse, France.
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MeSH Terms
Chlorofluorocarbons, Methane / chemistry
Computer Simulation*
Hydrogen Bonding
Methanol / chemistry
Molecular Structure
Polyesters / chemical synthesis*,  chemistry
Sulfonic Acids / chemistry*
Reg. No./Substance:
0/Chlorofluorocarbons, Methane; 0/Polyesters; 0/Sulfonic Acids; 24980-41-4/polycaprolactone; 67-56-1/Methanol; 75-46-7/fluoroform

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine

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