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Acid‐Catalyzed Cleavage of 1,4‐Dimethyl‐1,4‐dihydronaphthalene 1,4‐Endoperoxide. Reactivity of the Resulting Hydroperoxy Carbocation with Nucleophiles
Author(s) -
Jefford Charles W.,
Rossier JeanClaude,
Kohmoto Shigeo,
Boukouvalas John
Publication year - 1985
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19850680635
Subject(s) - chemistry , carbocation , nucleophile , aromatization , regioselectivity , cleavage (geology) , reactivity (psychology) , medicinal chemistry , ring (chemistry) , catalysis , stereochemistry , organic chemistry , medicine , alternative medicine , geotechnical engineering , pathology , fracture (geology) , engineering
In the presence of acids, 1,4‐dimethyl‐1,4‐dihydronaphthalene 1,4‐endoperoxide readily reacts with nucleophiles to produce methyl‐ and ring‐substituted naphthalenes in high yields. The regioselectivity observed depends on the nucleophile. The key intermediate is shown to be the corresponding hydroperoxy carbocation which could be intercepted in certain cases prior to aromatization. The hydroperoxide also undergoes Hock ‐type cleavage and dimerization giving 2,3‐dihydro‐1‐benzoxepins, 4‐methyl‐1‐naphthol, and a 1,2,5,6‐tetraoxocane as by‐products.