GEIN et al.
88
a fragment of a colorless plate crystal using
CrysAlisPro software package [15]. Monoclinic crystal
system, space group P21/n; C25H23N3O3S; unit cell
parameters: a = 20.986(3), b = 18.1649(17), c =
25.727(3) Å; β = 110.099(15)°; V = 9210(2) Å3;
M 445.52; dcalc = 1.285 g/cm3; Z = 16. Total of 69535
reflection intensities were measured, including 22602
independent reflections and 12265 reflections with
I > 2σ(I). A correction for absorption was applied
empirically by the SCALE3 ABSPACK algorithm
[15]. The structure was solved by the direct method
and was refined by the full-matrix least-squares
method in anisotropic approximation for all non-hy-
drogen atoms. Hydrogen atoms of the NH groups were
localized from the difference Fourier maps, and their
positions were refined independently in isotropic
approximation. The other hydrogens were refined
according to the riding model in isotropic approxima-
tion. All calculations were performed using SHELXL
[16] and OLEX2 [17]. Final divergence factors: R1 =
0.0688, wR2 = 0.1492 [reflections with I > 2σ(I)]; R1 =
0.1395, wR2 = 0.1942 (all independent reflections);
goodness of fit S = 1.028.
C 69.80, 70.02; H 5.31, 5.50; N 9.66, 9.91.
C25H23N3O2S. Calculated, %: C 69.91; H 5.40; N 9.78.
N-(2,4-Dimethylphenyl)-2-methyl-3-phenyl-4-
sulfanylidene-3,4,5,6-tetrahydro-2H-2,6-methano-
1,3,5-benzoxadiazocine-11-carboxamide (1c). Yield
3.50 g (79%), mp 230–232°C. IR spectrum, ν, cm–1:
1
3272, 3150 (NH), 1664 (C=O), 1592 (C=C). H NMR
spectrum, δ, ppm: 1.42 s (3H, 2-CH3), 2.21 s and
2.25 s (3H each, Me2C6H3), 3.50 m (1H, 11-H),
4.70 d.d (1H, 6-H, J = 1.8, 1.0 Hz), 6.87–7.23 m
(12H, Harom), 9.29 d (1H, 5-H, J = 2.8 Hz), 9.42 s
(1H, CONH). Found, %: C 70.29, 70.52; H 5.60, 5.77;
N 9.36, 9.60. C26H25N3O2S. Calculated, %: C 70.40;
H 5.68; N 9.47.
N-(2-Methoxyphenyl)-2-methyl-3-phenyl-4-sul-
fanylidene-3,4,5,6-tetrahydro-2H-2,6-methano-
1,3,5-benzoxadiazocine-11-carboxamide (1d). Yield
3.38 g (76%), mp 214–215°C. IR spectrum, ν, cm–1:
1
3392, 3200 (NH), 1680 (C=O), 1600 (C=C). H NMR
spectrum, δ, ppm: 1.39 s (3H, 2-CH3), 3.79 s (3H,
CH3O), 3.74 m (1H, 11-H), 4.65 d.d (1H, 6-H, J = 2.8,
1.8 Hz), 6.83–8.05 m (13H, Harom), 9.28 d (1H, 5-H,
J = 4.6 Hz), 9.56 s (1H, CONH). Found, %: C 67.29,
67.52; H 5.12, 5.29; N 9.31, 9.56. C25H23N3O3S. Cal-
culated, %: C 67.40; H 5.20; N 9.43.
Compounds 1a–1f (general procedure). A mixture
of 10 mmol of acetoacetamide, 10 mmol of salicyl-
aldehyde, and 15 mmol of N-phenylthiourea in 15 mL
of ethanol containing 8 mmol of sodium hydrogen
sulfate was heated for 1 h under reflux. After cooling,
the precipitate was filtered off and recrystallized from
ethanol.
N-(2-Chlorophenyl)-2-methyl-3-phenyl-4-sul-
fanylidene-3,4,5,6-tetrahydro-2H-2,6-methano-
1,3,5-benzoxadiazocine-11-carboxamide (1e). Yield
4.00 g (89%), mp 225–227°C. IR spectrum, ν, cm–1:
1
3384, 3190 (NH), 1680 (C=O), 1588 (C=C). H NMR
2-Methyl-N,3-diphenyl-4-sulfanylidene-3,4,5,6-
tetrahydro-2H-2,6-methano-1,3,5-benzoxadiazo-
cine-11-carboxamide (1a). Yield 3.49 g (84%),
mp 210–212°C. IR spectrum, ν, cm–1: 3304, 3200
(NH), 1672 (C=O), 1596 (C=C). 1H NMR spectrum, δ,
ppm: 1.41 s (3H, 2-CH3), 3.71 m (1H, 11-H), 4.66 d.d
(1H, 6-H, J = 1.8, 3.8 Hz), 6.89–8.08 m (14H, Harom),
9.32 d (1H, 5-H, J = 5.6 Hz), 9.59 s (1H, CONH).
Found, %: C 69.25, 69.50; H 5.00, 5.17; N 10.00,
10.24. C24H21N3O2S. Calculated, %: C 69.38; H 5.09;
N 10.11.
spectrum, δ, ppm: 1.43 s (3H, 2-CH3), 3.64 m (1H,
11-H), 4.74 d.d (1H, 6-H, J = 2.7, 1.9 Hz), 6.82–
7.77 m (13H, Harom), 9.35 d (1H, 5-H, J = 4.6 Hz),
9.85 s (1H, CONH). Found, %: C 63.95, 64.18;
H 4.38, 4.57; N 9.22, 9.47. C24H20ClN3O2S. Calculat-
ed, %: C 64.06; H 4.48; N 9.34.
N,N-Diethyl-2-methyl-3-phenyl-4-sulfanylidene-
3,4,5,6-tetrahydro-2H-2,6-methano-1,3,5-benzoxa-
diazocine-11-carboxamide (1f). Yield 2.46 g (62%),
1
mp 196–198°C. H NMR spectrum, δ, ppm: 1.11 m
(6H, CH3CH2), 3.41 m (4H, CH3CH2), 1.35 s (3H,
2-CH3), 3.59 m (1H, 11-H), 4.42 d.d (1H, 6-H, J = 1.7,
2.1 Hz), 6.87–7.27 m (9H, Harom), 9.13 d (1H, 5-H,
J = 3.8 Hz). Found, %: C 66.36, 66.59; H 6.77, 6.94;
N 10.46, 10.70. C22H27N3O2S. Calculated, %: C 66.47;
H 6.85; N 10.57.
2-Methyl-N-(2-methylphenyl)-3-phenyl-4-sul-
fanylidene-3,4,5,6-tetrahydro-2H-2,6-methano-
1,3,5-benzoxadiazocine-11-carboxamide (1b). Yield
3.48 g (81%), mp 226–228°C. IR spectrum, ν, cm–1:
1
3328, 3240 (NH), 1680 (C=O), 1592 (C=C). H NMR
spectrum, δ, ppm: 1.45 s (3H, 2-CH3), 2.25 s (3H,
CH3C6H4), 3.55 m (1H, 11-H), 4.75 d.d (1H, 6-H, J =
2.7, 2.8 Hz), 6.82–7.47 m (13H, Harom), 9.37 d (1H,
5-H, J = 5.5 Hz), 9.54 s (1H, CONH). Found, %:
This study was performed under financial support
by the Russian Science Foundation (project no. 15-13-
10029).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 1 2017