transparent, colourless oil (yield 0.22 g, 35%), which after being treated with EtOH, afforded crystals (m.p. 58-61 °C; 17%). 1H NMR: • = 2.28-2.46 (m, 2 H, CH2), 3.20 (t, J = 6.4; 2 H, COCH2), 3.97-4.15 (m, 4 H, OCH2CH2O), 4.59 (dd, J = 9.2, J = 6.4, 1 H, CHCN), 5.94 (s, 1 H, CHO2), 7.34-7.38 -7.61 (m, 9 H, CHAr), 7.94 (d, J = 1.2, 1 H, CHAr), 7.96 (s, 1 H, CHAr) ppm. 13C NMR: • = 30.0, 32.1, 35.4, 65.2, 102.1, 121.3, 127.8, 128.0, 128.3, 128.4, 128.7, 130.1, 133.4, 134.6, 134.8, 136.6, 198.3 ppm. IR: • = 3060, 2224, 1644, 1596, 1444, 1300, 716 cm-1. C20H19NO3 (321.4): calcd. C 74.75, H 5.96, N 4.36; found: C 74.50, H 6.28, N 4.37.
1-Cyano-3-benzoyl-1,2-dihydronaphthalene (5a). The suspension of nitrile 15 (0.41 g, 1.32 mmol) in a mixture of acetonitrile (6 mL) and 3% HCl (16 mL) was refluxed for 2 h, then cooled and diluted with water (30 mL). The mixture was extracted with CH2Cl2 (3 x 20 mL), the combined organic phases were washed with water (2•20 mL) and dried (MgSO4). The solvents were evaporated and the crude mixture was purified by column chromatography to give the product 5a as transparent, colourless oil (yield 0.27 g, 78%). 1H NMR: • = 3.02 (part A of ABMX, JAB = 17.0, JAM = 10.4, JAX = 1.6, 1H, CH2), 3.18 (part B of ABMX, JAB = 17.0, JBM = 7.2, JBX = 0.8, 1H, CH2), 4.18 (part M of ABMX, JAM = 10.4, JBM = 7.2, 1H, CHCN), 7.23 (part X of ABMX, br.s, 1H, =CH), 7.25 (dd, JH,H = 7.2, 1.0, 1H, CHAr), 7.35-7.40 (m, 1H, CHAr), 7.41-7.46 (m, 1H, CHAr), 7.48-7.56 (m, 3H, CHAr), 7.57-7.62 (m 2H, CHAr), 7.75-7.77 (m, 1H, CHAr) ppm. 13C NMR: • = 27.0, 30.2, 119.6, 127.2, 128.6 (two C), 129.3 (three C), 129.6, 130.0, 131.0, 131.5, 132.2, 134.4, 137.4, 139.4, 196.0 ppm. IR: • = 3058, 2224, 1644, 1596, 1444, 1228, 752, 716 cm-1. C18H13NO (259.3): calcd. C 83.38, H 5.05, N 5.40; found: C 83.29, H 5.25, N 5.40.
1-Cyano-3-benzoylnaphthalene (6a). To the stirred solution of dihydronaphthalene 5a (0.27 g, 1.03 mmol) and TEBAC (0.02 g, 0.05 mmol) in benzene (15 mL), 50%aq NaOH (0.5 mL, 9.5 mmol) was added. The reaction was carried out for 2.0 h, the mixture was diluted with water (25 mL), the organic phase was separated, and the water phase was extracted with CHCl3 (3•15 mL). The combined organic phases were washed with water (20 mL) and dried (MgSO4). The solvent was evaporated, the residue was purified by column chromatography and the product 6a was obtained as transparent colourless oil, which solidified. Recrystallization from methanol afforded the product, which exhibited physical and spectral properties the same as described for 6a obtained according to the General procedure in system A, (yield 0.23 g, 85%).
References
1. Jon•czyk, A.; Zdrojewski, T.; Panasiewicz, M. Synth. Commun. 2003, 33, 4095. 2. Zdrojewski, T.; Jon•czyk, A. Tetrahedron 1995, 45, 12439. 3. Dehmlow, E. V.; Dehmlow, S. S. Phase Transfer Catalysis, 3rd Ed., Verlag Chemie: Weinheim, 1993. 4. Starks, C. M.; Liotta, C. L.; Halpern, M. Phase-Transfer Catalysis, Chapman & Hall: New York, 1994.
