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Liquid Phase Oxidation of 1, 4 and 1, 2‐Dihydronaphthalene
Author(s) -
Martan M.,
Manassen J.,
Vofsi D.
Publication year - 1969
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.196900100
Subject(s) - chemistry , autoxidation , dehydrogenation , catalysis , naphthalene , photochemistry , epoxide , olefin fiber , chain propagation , double bond , hydrogen atom abstraction , cobalt , medicinal chemistry , hydrogen , organic chemistry , polymerization , polymer
The two isomeric olefins, 1,2 and 1,4‐dihydronaphthalene, were subjected to autoxidation. Although rates as well as product patterns were entirely different for both olefins, it could be shown that an α‐peroxy radical is a common intermediate with both substrates. The difference in behaviour is caused by the fact that with the 1,4‐isomer chain propagation takes place by hydrogen abstraction, while addition to the reactive double bond occurs with the 1,2‐isomer. By cooxidation experiments of the two olefins a high conversion into an epoxide could be obtained, which was shown to be a reaction intermediate in the formation of β‐tetralone from the 1,2‐isomer. The products obtained on cobalt ion catalyzed oxidation were in agreement with the accepted mechanism for this reaction. The fact that attack by oxygen with both isomers occurs only at the α‐position is contrary to what could be expected on the basis of the thermodynamic stability of the products, but is in agreement with the recently proposed principle of least motion. With base catalysis almost exclusively the dehydrogenation product naphthalene was obtained.