3
3
3
H Ar); 6.92 (2H, d, J = 8.6, H Ar); 6.64 (2H, d, J = 8.3, H Ar); 6.67 (2H, d, J = 8.3, H Ar). Found,%:
C 62.99; H 5.89; N 17.04. C30H33N7Se. Calculated, %: C 63.15, H 5.83; N 17.18.
1-Ethyl-5',11'-dimethyl-8'-selenoxo-3',5',7',11'-tetraazaspiro[piperidine-4,13'-tricyclo[7.3.1.02,7]-
tridec[2]ene]-1',9'-dicarbonitrile (6b). Yield 156 mg (30%). Fine orange crystals. Mp 204-206°C. IR
spectrum, , cm-1: 2250 (2C≡N), 1645 (C=N). H NMR spectrum, δ, ppm (J, Hz): 1.06 (3H, t, J = 7.1,
NCH2CH3); 1.86-1.98 (2H, m) and 2.23-2.26 (2H, m, 3,5-CH2); 2.34 (3H, s, CH3); 2.49 (3H, s, CH3); 2.46 (2H,
q, 3J = 7.1, NCH2CH3); 2.70-2.73 (2H, m) and 2.80-2.85 (2H, m, 2,6-CH2); 2.90 (1H, d, 2J = 11.3), 2.98 (1H, d,
2J = 11.2), 3.13 (1H, d, 2J = 11.3), and 3.02 (1H, d, 2J = 11.2, 10',12'-CH2); 4.24 (1H, d, 2J = 16.6) and 4.44 (1H,
1
3
2
2
2
d, J = 16.6, 4'-CH2); 4.98 (1H, d, J = 13.0) and 5.42 (1H, d, J = 13.0, 6'-CH2). Found, %: C 52.63; H 6.35;
N 22.51. C19H27N7Se. Calculated, %: C 52.77; H 6.29; N 22.67.
1-Ethyl-5',11'-diphenyl-8'-selenoxo-3',5',7',11'-tetraazaspiro[piperidine-4,13'-tricyclo[7.3.1.02,7]-
tridec[2]ene]-1',9'-dicarbonitrile (6c). Yield 147 mg (22%). Fine orange crystals. Mp 222-224°C. IR
spectrum, , cm-1: 2250 (2C≡N), 1665 (C=N). H NMR spectrum, δ, ppm (J, Hz): 1.06 (3H, t, J = 7.2,
1
3
3
NCH2CH3); 1.77-1.93 (2H, m) and 2.24-2.38 (2H, m, 3,5-CH2); 2.45 (2H, q, J = 7.2, NCH2CH3); 2.61-2.70
(2H, m) and 2.81-2.91 (2H, m, 2,6-CH2); 3.59 (1H, d, 2J = 12.5), 3.61 (1H, d, 2J = 12.0), 3.82 (1H, d, 2J = 12.5)
2
2
2
and 3.89 (1H, d, J = 12.0, 10',12'-CH2); 4.94 (1H, d, J = 17.1) and 5.07 (1H, d, J = 17.1, 4'-CH2); 5.71 (2H,
br. s, 6'-CH2); 6.70-7.17 (10H, m, H Ph). Found, %: C 62.46; H 5.65; N 17.50. C29H31N7Se. Calculated, %:
C 62.58; H 5.61; N 17.62.
1-Ethyl-5',11'-di(4-methylphenyl)-8'-selenoxo-3',5',7',11'-tetraazaspiro[piperidine-4,13'-tricyclo-
[7.3.1.02,7]tridec[2]ene]-1',9'-dicarbonitrile (6d). Yield 232 mg (33%). Fine orange crystals. Mp 214-216°C.
1
3
IR spectrum, , cm-1: 2242 (2C≡N), 1656 (C=N). H NMR spectrum, δ, ppm (J, Hz): 1.03 (3H, t, J = 7.2,
NCH2CH3); 1.80-1.84 (2H, m) and 2.27-2.33 (2H, m, 3,5-CH2); 2.08 (3H, s, CH3); 2.24 (3H, s, CH3); 2.43 (2H,
q, 3J = 7.2, NCH2CH3); 2.62-2.66 (2H, m) and 2.78-2.83 (2H, m, 2,6-CH2); 3.47 (1H, d, 2J = 12.3, 3.56 (1H, d,
2J = 12.0), 3.76 (1H, d, 2J = 12.0), and 3.79 (1H, d, 2J = 12.0, 10',12'-CH2); 4.94 (1H, d, 2J = 17.0) and 5.02 (1H,
2
2
2
3
d, J = 17.0, 4'-CH2); 5.61 (1H, d, J = 13.4) and 5.82 (1H, d, J = 13.4, 6'-CH2); 6.56 (2H, d, J = 8.6, H Ar);
3
3
3
6.64 (2H, d, J = 8.3, H Ar); 6.68 (2H, d, J = 8.3, H Ar); 6.95 (2H, d, J = 8.6, H Ar). Found, %: C 63.54; H
6.11; N 16.64. C31H35N7Se. Calculated, %: C 63.69; H 6.03; N 16.77.
1-Benzyl-5',11'-dimethyl-8'-selenoxo-3',5',7',11'-tetraazaspiro[piperidine-4,13'-tricyclo[7.3.1.02,7]-
tridec[2]ene]-1',9'-dicarbonitrile (6e). Yield 184 mg (31%). Fine orange crystals. Mp 205-207°C. IR
spectrum, , cm-1: 2244 (2C≡N), 1650 (C=N). 1H NMR spectrum, δ, ppm (J, Hz): 1.87-1.94 (2H, m) and 2.25-
2.28 (2H, m, 3,5-CH2); 2.34 (3H, s, CH3); 2.47 (3H, s, CH3); 2.71-2.74 (2H, m), 2.83-2.92 (3H, m), 2.97 (1H, d,
2J = 11.5), 3.03 (1H, d, J = 11.5), and 3.13 (1H, d, J = 11.1, 2,6,10',12'-CH2); 3.56 (2H, br. s, CH2Ph); 4.24
(1H, d, 2J = 16.9) and 4.42 (1H, d, 2J = 16.9, 4'-CH2); 4.96 (1H, d, 2J = 13.2) and 5.39 (1H, d, 2J = 13.2, 6'-CH2);
7.16-7.31 (5H, m, H Ph). Found, %: C 58.19; H 6.02; N 19.69. C24H29N7Se. Calculated, %: C 58.29; H 5.91;
N 19.83.
2
2
1-Benzyl-5',11'-di(4-methylphenyl)-8'-selenoxo-3',5',7',11'-tetraazaspiro[piperidine-4,13'-tricyclo-
[7.3.1.02,7]tridec[2]ene]-1',9'-dicarbonitrile (6f). Yield 233 mg (30%). Fine beige crystals. Mp 181-183°C. IR
spectrum, , cm-1: 2248 (2C≡N), 1650 (C=N). 1H NMR spectrum, δ, ppm (J, Hz): 1.87-1.93 (2H, m) and 2.26-
2.31 (2H, m, 3,5-CH2); 2.06 (3H, s, CH3); 2.25 (3H, s, CH3); 2.71-2.74 (2H, m) and 2.82-2.85 (2H, m, 2,6-CH2);
3.50 (1H, d, 2J = 12.1), 3.53 (1H, d, 2J = 12.1), 3.74 (1H, d, 2J = 13.2), and 3.79 (1H, d, 2J = 13.2, 10',12'-CH2);
3.55 (2H, br. s, CH2Ph); 4.90 (1H, d, 2J = 17.2) and 4.98 (1H, d, 2J = 17.2, 4'-CH2); 5.55 (1H, d, 2J = 13.4) and
5.79 (1H, d, 2J = 13.4, 6'-CH2); 6.53 (2H, d, 3J = 8.9, H Ar); 6.61 (2H, d, 3J = 7.8, H Ar); 6.65 (2H, d, 3J = 7.8,
H Ar); 6.91 (2H, d, 3J = 8.9, H Ar); 7.17-7.30 (5H, m, H Ph). Found, %: C 66.68; H 5.86; N 15.01. C36H37N7Se.
Calculated, %: C 66.86; H 5.77; N 15.16.
X-Ray Structural Investigation of Compound 6a. Crystals of compound 6a were triclinic,
C30H33N7Se, at 298 K: a 8.6727(5), b 11.4177(5), c 13.8108(9) Å; α 89.674(5), β 83.235(5), γ 83.898(5)o;
V 1350.34(13) Å3; Mr 570.59; Z 2; space group PĪ, dcalc 1.40 g/cm3, μ(MoKα) 1.424 mm-1, F(000) 592. The
investigated crystal was a pseudomerohedric twin with two components turned by 180o along the c* axis with
476