The alternative thermal decomposition mode of 2-oxetanone and 2-azetidinone: a DFT and PES study

Lim, CC, Xu, ZP, Huang, HH, Mok, CY and Chin, WS (2000) The alternative thermal decomposition mode of 2-oxetanone and 2-azetidinone: a DFT and PES study. Chemical Physics Letters, 325 4: 433-439. doi:10.1016/S0009-2614(00)00715-6


Author Lim, CC
Xu, ZP
Huang, HH
Mok, CY
Chin, WS
Title The alternative thermal decomposition mode of 2-oxetanone and 2-azetidinone: a DFT and PES study
Journal name Chemical Physics Letters   Check publisher's open access policy
ISSN 0009-2614
Publication date 2000-07-01
Year available 2000
Sub-type Article (original research)
DOI 10.1016/S0009-2614(00)00715-6
Open Access Status Not yet assessed
Volume 325
Issue 4
Start page 433
End page 439
Total pages 7
Place of publication AMSTERDAM
Publisher Elsevier BV
Language eng
Abstract We have found that, while 2-oxetanone undergoes thermal decarboxylation at 350 degrees C to give CO2 and ethene, 2-azetidinone proceeds in two different modes at 550 degrees C, giving isocyanic acid, ethene, ketene, hydrogen cyanide and carbon monoxide among the pyrolysis products. B3LYP/6-31G** calculations were performed to investigate the two alternative cycloreversion pathways for the two compounds. Theoretical thermodynamic data predicted that decarboxylation of 2-oxetanone has among the lowest activation barrier (159 kJ mol(-1)) and free energy (Delta G = - 183 kJ mol(-1)). While the cycloreversion to ethene can be classified as a concerted asynchronous process, natural bond orbital (NBO) analysis suggested that the cycloreversion to ketene is more asynchronous for 2-azetidinone than for 2-oxetanone. (C) 2000 Elsevier Science B.V. All rights reserved.
Keyword Ab-Initio
Beta-Propiolactone
Mechanism
Decarboxylation
Lactams
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
Collection: ResearcherID Downloads - Archived
 
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