ISSN:
0947-3440
Keywords:
Retrodisproportionation
;
Molecule-induced radical formation
;
Semiempirical calculations
;
Hydrogen transfer
;
Rearrangements
;
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
From the uncatalyzed transfer-hydrogenation of azulene 1 with the hydrogen donors 9,10-dihydroanthracene (4), 7H-benz[de]anthracene (5) and 9,9-diphenyl-10,10-dideuteroanthracene (6) at 340-375°C in diphenyl ether, two isomeric octahydroazulenes and, in addition, naphthalene and tetralin are obtained. From product studies, kinetics, isotopic labelling experiments and semiempirical MO calculations, a nonchain stepwise radical mechanism is proposed, which is initiated by H-atom transfer from the donor to azulene. The proposed mechanism for the formation of naphthalene and tetralin via azulene-naphthalene rearrangement under these conditions is a combination of the Scott mechanism and the Alder “walk” mechanism, which are initiated by the hydrogen-transfer step.
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/jlac.199719971008
