115.9, 122.0, 122.7; 126.5, 126.6, 127.0, and 128.1 (C-1,2,3,4,5,6,11); 129.3, 129.6, 130.3, 130.5, 131.1, 132.1,
and 133.2 (C-4a,6a,7,7a,10a,11a,11b). Found, %: Cl 10.62; N 4.29. C21H24ClNO. Calculated, %: Cl 10.37;
N 4.10.
7-Hydroxymethyl-9,9-dipropylnaphtho[1,2-f]isoquinolinium Chloride (3b). Yield 1.66 g (65%),
glassy material. IR spectrum, , cm-1: 3200-3500 (OH), 3040, 1600 (aromatic ring), 1080, 1050 (OH), 870, 810,
760, 740 (penta-, 1,2,3,4-tetra-, 1,2-disubstituted ring respectively). Found, %: Cl 9.29; N 4.16. C23H28ClNO.
Calculated, %: Cl 9.58; N 3.79.
7-Hydroxymethyl-9,9-tetramethylenenaphtho[1,2-f]isoindolinium Chloride (3c). Yield 1.36 g
(67%); mp 232-233ºC (H2O). IR spectrum, , cm-1: 3250-3500, 1060, 1030 (OH), 1580 (aromatic ring), 870,
1
810, 760, 730 (penta-, 1,2,3,4-tetra- and 1,2- disubstituted benzene ring respectively). H NMR spectrum, ,
ppm (J, Hz): 2.32 (4H, m, 2NCH2CH2); 3.86 (4H, m, 2NCH2CH2); 5.03 (2H, br. s, OCH2); 5.17 (2H, s) and 5.39
(2H, s, 8,10-CH2); 5.80 (1H, br. s, OH); 7.63 (1H, m) and 7.68 (1H, m, H-2,3); 7.86 (1H, d, J = 9.2) and 8.09
(1H, d, J = 9.2, H-5,6); 7.95 (1H, dd, J = 7.7, J = 1.9) and 8.75 (1H, dd, J = 8.2, J = 1.3, H-1,4); 8.76 (1H, s,
H-11). 13C NMR spectrum, , ppm: 21.4 (NCH2CH2); 58.5 (OCH2); 62.7 (NCH2CH2); 66.0 and 66.5 (C-8,10);
116.3, 122.1, 122.7, 126.5, 126.6, 127.0, and 128.1 (C-1,2,3,4,5,6,11); 129.4, 129.7, 130.2, 130.7, 131.1, 132.2,
and 133.7 (C-4a,6a,7,7a,10a,11a,11b). Found, %: Cl 10.71; N 4.23. C21H22ClNO. Calculated, %: Cl 10.43;
N 4.12.
Cyclization of Salts 1a-e and 2a,b with Subsequent Recyclization of the Formed Products 3a-e and
5a,b Respectively (General Method). After cyclization by the method reported above for salts 1a-e, 2a,b, the
cooled reaction mixture was treated with KOH dissolved in water (1 ml, overall molar ratio of base to salt 2:1) and
the obtained mixture was held for 1 h at 80-85ºC. The cooled reaction product was extracted with ether (salts
1a-c) or dichloromethane (salts 1d,e and 2a,b) (330 ml). After washing with water, titration with 0.1 N H2SO4
revealed the presence of 73-75% of the amine. The extract was washed with water, dried over MgSO4,
evaporated, and the residue was recrystallized to give the recyclization products 4a-e, 6a,b.
11-Diethylaminomethyl-1,3-dihydrophenanthro[1,2-c]furan (4a). Yield 1.52 g (72%); mp 63-64ºC
(EtOH). IR spectrum, , cm-1: 3030, 1600 (aromatic ring), 1100, 1060 (C–O–C in ring), 870, 810, 730 (penta-,
1
1,2,3,4-tetra-, 1,2-disubstituted ring respectively). H NMR spectrum, , ppm (J, Hz): 1.08 (6H, t, J = 7.1,
2CH3); 2.55 (4H, q, J = 7.1, 2CH2CH3); 3.73 (2H, s, NCH2); 5.28 (2H, t, J = 2.8, 1-CH2); 5.44 (2H, t, J = 2.8,
3-CH2); 7.50 (1Н, d, J = 8.9) and 7.74 (1Н, d, J = 8.9, H-4,5); 7.56 (1Н, m) and 7.63 (1Н, m, H-7,8); 7.88 (1Н,
dd, J = 7.8 and 1.7) and 8.69 (1Н, d, J = 8.2, Н-6,9); 8.50 (1Н, s, Н-10). 13C NMR spectrum, , ppm: 11.4
(CH3); 46.2 (CH2CH3); 56.8 (NCH2); 72.2 and 73.3 (C-1,3); 121.3, 122.0, 122.4, 124.3, 125.7, 126.1, and 126.5
(C-4,5,6,7,8,9,10); 128.1, 129.1, 129.8, 131.1, 132.3, 135.6, and 136.5 (C-3а,3b,5а,9а,9b,11,11а). Found, %:
C 82.23; H 7.80; N 4.25. C21H23NO. Calculated, %: C 82.58; H 7.59; N 4.59. Mp of picrate 195-196ºC (EtOH);
mp of hydrochloride 200-202ºC (EtOH).
11-Dipropylaminomethyl-1,3-dihydrophenanthro[1,2-c]furan (4b). Yield 1.63 g (70%); mp 50-52ºC
(EtOH). IR spectrum, , cm-1: 3060, 1600 (aromatic ring), 1080, 1040 (C–O–C in ring), 870, 810, 770, 730
(penta-, 1,2,3,4-tetra-, 1,2-disubstituted benzene ring respectively). 1H NMR spectrum, , ppm (J, Hz): 0.88 (6H, t,
J = 7.3, 2CH3); 1.52 (4H, m, 2CH2CH2); 2.42 (4H, m, 2NCH2CH2); 3.72 (2H, s, NCH2); 5.27 (2H, t, J = 2.8,
1-CH2); 5.44 (2H, t, J = 2.8, 3-CH2); 7.50 (1Н, d, J = 8.9) and 7.74 (1Н, d, J = 8.9, H-4,5); 7.56 (1Н, m) and
7.63 (1Н, m, H-7,8); 7.88 (1Н, dd, J = 7.8, J = 1.6) and 8.67 (1Н, d, J = 8.2, Н-6,9); 8.51 (1Н, s, Н-10). 13C NMR
spectrum, , ppm: 11.5 (CH3); 19.6 (CH2CH3); 55.5 (NCH2CH2); 57.8 (NCH2); 72.3 and 73.3 (C-1,3); 121.4,
122.0, 123.3, 124.3, 125.6, 126.1, and 126.5 (C-4,5,6,7,8,9,10); 128.1, 129.1, 129.9, 131.1, 132.2, 135.6, and
136.4 (C-3а,3b,5а,9а,9b,11,11а). Found, %: C 82.52; H 8.32; N 4.39. C23H27NO. Calculated, %: C 82.84;
H 8.16; N 4.20. Mp of picrate 192-193ºC (EtOH); mp of hydrochloride 205-207ºC (EtOH).
1-(1,3-Dihydrophenanthro[1,2-c]furan-11-ylmethyl)pyrrolidine (4c). Yield 1.3 g (71%); mp 82-83ºC
(EtOH). IR spectrum, , cm-1: 3060, 1600 (aromatic ring), 1080, 1040 (C–O–C in ring), 870, 810, 770, 730
1
(penta-, 1,2,3,4-tetra- and 1,2-disubstituted ring respectively). H NMR spectrum, , ppm (J, Hz): 1.81 (4H, m,
2NCH2CH2); 2.54 (4H, m, 2NCH2CH2); 3.79 (2H, br. s, NCH2); 5.28 (2H, t, J = 2.8, 1-CH2); 5.45 (2H, t, J = 2.8,
1095