Issue 7, 1994

Photochemical nitration by tetranitromethane. Part XVIII. The regiochemistry of nitrito/trinitromethyl and nitro/trinitromethyl addition to 2,3-dimethylnaphthalene: thermal 1,3-dipolar additions of nitro groups to alkenes

Abstract

The photolysis of the 2,3-dimethylnaphthalene–tetranitromethane charge-transfer complex gives 2,3-dimethyl-1-nitronaphthalene, 2,3-dimethyl-5-nitronaphthalene and adducts: epimeric pairs of 6,7-dimethyl-1-nitro-4-trinitromethyl-1,4-dihydronaphthalene 7 and 8, 1-hydroxy-6,7-dimethyl-4-tri-nitromethyl-1,4-dihydronaphthalene 11 and 12, 2,3-dimethyl-1-nitro-4-trinitromethyl-1,4-dihydro-naphthalene 13 and 14, and the structurally similar trans-6,7-dimethyl-2-nitro-1-trinitromethyl-1,2-dihydronaphthalene 9 and trans-2-hydroxy-6,7-dimethyl-1-trinitromethyl-1,2-dihydronaphthalene 10. At +20 °C in either dichloromethane or acetonitrile the adducts 714 comprise some 70% of the product mixture, but at –20 °C in either solvent the total adduct yield is reduced to ca. 31%. In adduct formation trinitromethanide ion reacts preferentially at C-5 in the 2,3-dimethylnaphthalene radical cation. Adducts 9 and 10 undergo thermal cycloaddition in (2H)chloroform at 22 °C to give the nitro cycloadduct 16 and hydroxy cycloadduct 15, respectively. An X-ray crystal structure is reported for hydroxy cycloadduct 15, as are preliminary results of a single crystal X-ray analysis of adduct 7.

Article information

Article type
Paper

J. Chem. Soc., Perkin Trans. 2, 1994, 1485-1490

Photochemical nitration by tetranitromethane. Part XVIII. The regiochemistry of nitrito/trinitromethyl and nitro/trinitromethyl addition to 2,3-dimethylnaphthalene: thermal 1,3-dipolar additions of nitro groups to alkenes

C. P. Butts, J. L. Calvert, L. Eberson, M. P. Hartshorn, F. Radner and W. T. Robinson, J. Chem. Soc., Perkin Trans. 2, 1994, 1485 DOI: 10.1039/P29940001485

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