Oxidation reactions of azines: XIII. Synthesis, molecular structure, and oxidation reactions of 3-methyl-3,3′,4,4′,5,6-hexahydro-1′H,2H-spiro[benzo[f]isoquinoline-1,2′-naphthalen]-1′-one

• Published in: Russian journal of organic chemistry 2014-12, Vol.50 (12), p.1797-1803
• Main Authors: Malkova, A. V., Kotsyuba, V. E., Soldatenkov, A. T., Soldatova, S. A., Polyanskii, K. B., Kolyadina, N. M., Khrustalev, V. N.
• Format: Article
• Language: English
• Subjects: Chemistry; Chemistry and Materials Science; Organic Chemistry; Review
• ISSN: 1070-4280; 1608-3393
• DOI: 10.1134/S1070428014120148

The condensation of 3,4-dihydronaphthalen-1(2 H )-one with methylamine and formaldehyde in acid medium gave N , N -bis(1-oxo-1,2,3,4-tetrahydronaphthalen-2-ylmethyl)methanamine hydrochloride which was converted into 3-methyl-3,3′,4,4′,5,6-hexahydro-1′ H ,2 H -spiro[benzo[ f ]isoquinoline-1,2′-naphthalen]-1′-one by heating in 48% aqueous HBr or 50% H 2 SO 4 . Oxidation of the spiro compound with KMnO 4 initially involved the methylene group of the allylamine fragment with formation of the corresponding lactam which then underwent cis -dihydroxylation at C 4a and C 10b . Oxidation of the same compound with KMnO 4 in the presence of some CH acids (trifluoroacetone and 4-bromoacetophenone) or aromatic amines (4-fluoroaniline and 2-bromo-4-nitroaniline) afforded, respectively, 4-acylmethylidene or 4-arylimino derivatives via C-C or C-N cross-coupling at the 4-position.