Please use this identifier to cite or link to this item:
https://hdl.handle.net/10316/17954
Title: | In situ direct photoproduction of ketenes from substituted coumarins isolated in solid argon: The case of N-(2-oxo-2H-chromen-3-yl)acetamide | Authors: | Kuş, N. Breda, S. Fausto, R. |
Issue Date: | Oct-2008 | Publisher: | Elsevier | Serial title, monograph or event: | Journal of Molecular Structure | Volume: | 924-926 | Abstract: | In this study, the infrared spectrum of N-(2-oxo-2H-chromen-3-yl)acetamide (3-acetamidocoumarin; 3AC) isolated in solid argon, at 10 K, was obtained and assigned. In consonance with the relative energies of the three conformers predicted theoretically, only the most stable form was observed experimentally. This conformer is stabilized by two intramolecular hydrogen bonds and is similar to the structural unit of 3AC found in crystalline phase. Upon in situ UV (λ > 215 nm) irradiation of the matrix-isolated compound, the characteristic IR intense band due to the antisymmetric stretching vibration of the ketene (CCO) group was observed, indicating occurrence of the ring-opening isomerization reaction to the open-ring ketene isomeric of 3AC. In consonance with the theoretical structural predictions for the most stable isomers of this photoproduct, the experimental data indicates that it is produced in the E arrangement of the (O)CCCC(CO) fragment. There were also experimental indications pointing to occurrence of a second photoreaction channel, corresponding to decarbonylation. On the other hand, contrarily to what is generally observed for α-pyrones derivatives, including unsubstituted coumarin, no photochemical production of Dewar isomer of 3AC was observed. This last result, follows the trend observed for 2-pyrone-3-carboxylate, and seems to be a quite general rule for matrix-isolated α-pyrones bearing relatively volumous substituents at the position 3, as a consequence of the unfavorable relaxation of the matrix around the guest molecule that would be required to accommodate the Dewar isomers of these compounds, whose structure deviates strongly from planarity, thus mismatching the primarily occupied matrix sites. | URI: | https://hdl.handle.net/10316/17954 | DOI: | 10.1016/j.molstruc.2008.10.013 | Rights: | openAccess |
Appears in Collections: | FCTUC Química - Artigos em Revistas Internacionais |
Files in This Item:
File | Description | Size | Format | |
---|---|---|---|---|
Journal of Molecular Structure, 924-926 (2009) 81.pdf | 845.46 kB | Adobe PDF | View/Open |
SCOPUSTM
Citations
4
checked on May 1, 2023
WEB OF SCIENCETM
Citations
10
4
checked on May 2, 2023
Page view(s) 50
501
checked on Sep 4, 2024
Download(s)
338
checked on Sep 4, 2024
Google ScholarTM
Check
Altmetric
Altmetric
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.