Acid-Catalyzed Cleavage of 1,4-Dimethyl-1,4-dihydronaphthalene 1,4-Endoperoxide. Reactivity of the Resulting Hydroperoxy Carbocation with Nucleophiles

✍ Scribed by Charles W. Jefford; Jean-Claude Rossier; Shigeo Kohmoto; John Boukouvalas

• Book ID: 102858128
• Publisher: John Wiley and Sons
• Year: 1985
• Tongue: German
• Weight: 653 KB
• Volume: 68
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.19850680635

✦ Synopsis

In the presence of acids, 1,4-dimethyl-l,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 Hocktype cleavage and dimerization giving 2,3-dihydro-1 -benzoxepins, 4-methyl-1-naphthol, and a 1,2,5,6-tetraoxocane as by-products.

'1 Preliminary communication, see [I].