Author:
Fu Nanyan,Allen Annette D,Chan Winnie,Kobayashi Shinjiro,Tidwell Thomas T,Tahmassebi Daryoush,Aguilar Angelica,Cabrera Eduardo Peña,Godoy Jazmin
Abstract
2- and 3-Furylketenes (18 and 20), 2- and 3-thienylketenes (19 and 21), and bis(2,5-ketenyl)thiophene (24) have been generated as observable reactive intermediates by photochemical Wolff rearrangements. Stabilization energies of the monoketenes 18–21 have been determined by DFT computations of isodesmic energy changes, and these ketenes are predicted to be modestly destabilized relative to phenylketene. Rate constants for reaction of 18–21 with H2O and with n-BuNH2 have been measured and are similar to those of the 2-, 3-, and 4-pyridylketenes (1). The product of reaction of 2-furylketene (18) with H2O is calculated to be stable as an acid enol, and reaction of 18 with the stable free radical TEMPO forms a stable ester enol, consistent with stabilization by intramolecular H-bonding to the furyl oxygen. Bis(thienyl)-1,2-bisketenes 26 and 28 have been generated by photochemical cyclobutenedione ring opening and are highly reactive in ring closure. This is attributed to destabilization of the ketenes and stabilization of the cyclobutenediones by the electron donating aryl groups.Key words: ketenes, furans, thiophenes, reactive intermediates, photolysis, mechanisms.
Publisher
Canadian Science Publishing
Subject
Organic Chemistry,General Chemistry,Catalysis
Cited by
9 articles.
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