The Synthesis of 4a-Aminoalkyl-1,2,3,4,4a,9-Hexahydrophenanthrenes. Versatile Intermediates for Potential CNS Drugs. I

Abstract

The synthesis of 1-aminoalkyl-1-hydroxy-2,2-tetramethylene-1,2,3,4-tetrahydronaphthalenes and their Wagner–Meerwein rearrangements into 4a-aminoalkyl-1,2,3,4,4a,9-hexahydrophen-anthrenes are described.

Cyclization of ylidenemalononitriles. 9. Rearrangement of 2-cyano-3-(1-methylcyclopentyl)indenone to 4a-methyl-9-oxo-10-cyano-1,2,3,4,4a,9-hexahydrophenanthrene

“…The ether layers were washed with water and brine, dried, and evaporated. Recrystallization of the residue with cyclohexane and a little chloroform resulted in a gummy oil that deposited on cooling, which on addition of a few drops of chloroform with stirring gave 4.61 g (90%) of a fine white powder, mp 162.0-163.5 °C; IR (KBr) 3.1 brd, 3.45, 4.55 s, 5.91 w, 6.15 s, 6.40, 6.77 µ ; NMR (CDCI3) 1.5-2.5 (m, 11H, alkyl), 4.67 (s, 0.5 , H adjacent to C=0), 5.35 (low and rounded, 0.5 H, enolic), 7.5-8.5 (m, 4 H, aryl).…”

“…The ether was washed with brine, dried, and evaporated. Distillation of the residue gave 3.18 g (80%) of 13 as a colorless oil, which crystallized when scratched after standing in the refrigerator overnight, bp 140 °C sharp (1.3 mm) [lit.17 bp 147 °C (2 mm)]; mp 32-34 °C; IR 3.40, 6.00, 6.13, 6.24, 6.76 Mm; NMR (CDCI3) 2.00 (s, 8 H, cyclopentyl), 6.19 (d, 1 H, J = 10 Hz, vinyl), 6.90 (d, l H, J = 10 Hz, vinyl), 7.41 (m, 3 H, aryl), 8.10 (broadened d, 1 H, J = 7 Hz, peri-).…”

“…5 °C; IR (KBr)3.40,4.50,6.25,6.70 Mm; NMR (CDClg) 1.7-2.5 (m, 8 H, cyclopentyl), 3.35 (s, 2 H, benzyl), 3.85 (s, 3 H, MeO), 6.43 (d, 2 H, J = 8 Hz, aryl ortho to MeO),6.88 (d, 2 H, J = 8 Hz, aryl ortho to C=C), 7.5-8.0 (m, 5 H, aryl).Anal. Caled for C23H22N20: C, 80.67; H, 6.47; N, 8.18; MW 342.…”