ISSN:
0009-2940
Keywords:
3,6-Alkanooxepine-4,5-dicarboxylic esters
;
Methanohydroazulene derivatives
;
Photochemical rearrangement
;
Tricycloalkene derivatives
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Synthesis of Medium and Large Rings, XXIII. Photochemical Rearrangement of 3,6-Alkanooxepine-4,5-dicarboxylic EstersIrradiation of the 3,6-alkanooxepine-4,5-dicarboxylic esters 1a-d affords the tricyclic aldehydes 2a-d, the constitutions of which were determined by X-ray structural analysis of 2a and 2d. The disubstituted 3,6-decanooxepine 1e gives in low yield the bridged dihydrofuran 4b, whose structure was also established by X-ray analysis. Mechanistic investigations show, that the photochemical rearrangement 1 → 2 takes place via dihydrofurans 3, cyclopropane carbaldehydes 6, and cyclopentadienecarbaldehydes 7.
Notes:
Bestrahlung der 3,6-Alkanooxepin-4,5-dicarbonsäureester 1a-d liefert die tricyclischen Aldehyde 2a-d, deren Konstitutionen durch Röntgenstrukturanalyse von 2a und 2d gesichert wurden. Das analoge disubstituierte 3,6-Decanooxepin 1e führt unter anderem zum überbrückten Dihydrofuran 4b, für das ebenfalls eine Röntgenstrukturanalyse vorliegt. Mechanistische Untersuchungen zeigen, daß die Photoumlagerung 1 → 2 über Dihydrofurane 3, Cyclopropancarbaldehyde 6 und Cyclopentadiencarbaldehyde 7 verläuft.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19891220131
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