TETRAZOLES: XLVI.
1527
7-Ethoxy-2,5-diphenyl-3H-1,3,4-benzotriazepine
(Ia). A solution of 0.01 mol N-(p-ethoxyphenyl)-
benzimidoyl chloride in 10 ml of chloroform was
added dropwise over a period of 30 min to a mixture
of 0.01 mol of 5-phenyltetrazole, 0.001 mol of tetra-
butylammonium bromide, 10 ml of a 10% aqueous
solution of sodium hydroxide, and 30 ml of chloro-
form under stirring at 20 C. The mixture was stirred
for 4 h at 20 C, and the organic phase was separated,
washed with a 1% aqueous solution of NaOH and
with water (2 10 ml), and dried over magnesium
sulfate. The solvent was removed under reduced pres-
sure, 20 ml of toluene was added to the residue, the
mixture was heated for 3 h at 110 C, and the solvent
was distilled off under reduced pressure. Yield 2.29 g
(70%), mp 243 245 C (from acetonitrile). IR spec-
1365, 1395, 1435, 1450, 1490, 1505, 1545, 1565,
1570, 1595, 1625, 2865, 2935, 3040, 3070, 3345.
1H NMR spectrum (DMSO-d6), , ppm: 2.25 s (3H,
CH3), 7.05 7.95 m (12H, Harom), 8.1 s (1H, NH).
Found, %: C 64.63; H 4.22; N 10.90. C21H16BrN3.
Calculated, %: C 64.63; H 4.13; Br 20.47; N 10.77.
5-(2-Pyridyl)-2-phenyl-3H-1,3,4-benzotriazepine
(Ie). Yield 61%, mp 248 249 C (from acetonitrile).
1
IR spectrum, , cm : 905, 920, 935, 955, 965, 990,
1000, 1005, 1035, 1050, 1080, 1095, 1120, 1165,
1185, 1230, 1250, 1290, 1300, 1305, 1335, 1415,
1435, 1460, 1475, 1500, 1565, 1570, 1600, 1615,
2865, 2935, 3070, 3345. 1H NMR spectrum
(DMSO-d6), , ppm: 7.02 8.57 m (13H, Harom, 1H,
NH). Found, %: C 76.50; H 4.73; N 18.76. C19H14N4.
Calculated, %: C 76.49; H 4.73; N 18.78.
1
trum, , cm : 905, 925, 940, 950, 960, 995, 1005,
1-Methyl-2,5-diphenyl-1H-1,3,4-benzotriazepine
(IIIa). Potassium tert-butoxide, 2 mmol, was added
to a solution of 1.7 mmol of 2,5-diphenyl-3H-1,3,4-
benzotriazepine in 30 ml of anhydrous tetrahydro-
furan. The mixture was stirred for 30 min at 20 C,
2.5 mmol of methyl iodide was added, and the mix-
ture was stirred for 2 h at 20 C and diluted with
150 ml of water. The precipitate was filtered off.
Yield 0.42 g (80%), mp 173 175 C (from aqueous
1035, 1050, 1080, 1095, 1115, 1165, 1185, 1215,
1245, 1265, 1295, 1325, 1400, 1415, 1450, 1460,
1480, 1500, 1510, 1565, 1570, 1585, 1595, 1630,
2865, 2895, 2910, 2935, 2945, 2990, 3035, 3070,
1
3300. H NMR spectrum (DMSO-d6), , ppm: 1.31 t
(3H, CH3), 3.91 q (2H, CH2), 6.45 7.96 m (13H,
Harom, and 1H, NH). Found, %: C 77.38; H 5.61;
N 12.30. C22H19N3O. Calculated, %: C 77.40; H 5.61;
N 12.31.
1
DMF). IR spectrum, , cm : 930, 945, 965, 975, 990,
5-(4-Methoxyphenyl)-2-phenyl-3H-1,3,4-benzo-
triazepine (Ib). Yield 47%, mp 238 239 C (from
1005, 1025, 1045, 1080, 1090, 1130, 1160, 1170,
1195, 1270, 1280, 1300, 1320, 1325, 1355, 1425,
1450, 1470, 1490, 1520, 1550, 1565, 1590, 1605,
1645, 2820, 2865, 2890, 2930, 2965, 3005, 3030,
1
butyl acetate). IR spectrum, , cm : 920, 935, 950,
965, 985, 1010, 1040, 1080, 1090, 1115, 1175, 1185,
1235, 1270, 1285, 1300, 1320, 1330, 1420, 1455,
1510, 1520, 1555, 1580, 1600, 1615, 1685, 2840,
2860, 2905, 2940, 2965, 3010, 3070, 3085, 3335.
1H NMR spectrum (DMSO-d6), , ppm: 3.81 s (3H,
OCH3), 6.9 8.2 m (13H, Harom), 9.2 s (1H, NH).
Found, %: C 77.05; H 5.23; N 12.72. C21H17N3O.
Calculated, %: C 77.04; H 5.23; N 12.84.
1
3070. H NMR spectrum (CDCl3), , ppm: 3.06 s
(3H, CH3), 7.09 7.42 m (14H, Harom). Found, %:
C 81.18; H 5.7; N 13.48. C21H17N3. Calculated, %:
C 81.03; H 5.47; N 13.50.
1-Ethyl-2,5-diphenyl-1H-1,3,4-benzotriazepine
(IIIb). Yield 57%, mp 204 206 C (from aqueous
1
DMF). IR spectrum, , cm : 925, 950, 965, 975, 990,
2-(4-Bromophenyl)-7-chloro-5-phenyl-3H-1,3,4-
benzotriazepine (Ic). Yield 72%, mp 224 225 C
1005, 1030, 1055, 1080, 1100, 1105, 1135, 1160,
1180, 1250, 1285, 1325, 1365, 1385, 1410, 1445,
1475, 1495, 1545, 1565, 1590, 1605, 1640, 2860,
1
(from DMF ethanol, 1:1). IR spectrum, , cm : 900,
935, 945, 990, 1015, 1035, 1080, 1105, 1130, 1175,
1190, 1225, 1240, 1260, 1270, 1285, 1300, 1325,
1390, 1400, 1445, 1495, 1550, 1560, 1590, 1615,
1
2895, 2935, 2945, 2990, 3040, 3075. H NMR spec-
trum (DMSO-d6), , ppm: 1.05 t (3H, CH3), 3.35 m
(1H, NCH2), 3.70 m (1H, NCH2), 7.32 7.62 m
(14H, Harom). Found, %: C 81.13; H 5.98; N 12.98.
C22H19N3. Calculated, %: C 81.23; H 5.85; N 12.92.
1
2865, 2935, 3040, 3065, 3315. H NMR spectrum
(DMSO-d6), , ppm: 6.8 8.3 m (12H, Harom). Found,
%: C 58.45; H 3.15; N 10.25. C20H13BrClN3. Calcu-
lated, %: C 58.49; H 3.19; Br 19.46; Cl 8.63; N 10.23.
1-Butyl-2,5-diphenyl-1H-1,3,4-benzotriazepine
(IIIc). Yield 48%, mp 77 80 C (from petroleum
5-(4-Bromophenyl)-7-methyl-2-phenyl-3H-1,3,4-
benzotriazepine (Id). Yield 65%, mp 252 253 C
1
ether). IR spectrum, , cm : 925, 950, 975, 990,
1
1005, 1030, 1070, 1085, 1110, 1140, 1175, 1230,
1260, 1280, 1305, 1330, 1350, 1375, 1450, 1470,
1490, 1545, 1595, 1605, 2885, 2940, 2965, 3045,
(from DMF 2-propanol, 1:1). IR spectrum, , cm :
905, 925, 940, 955, 975, 990, 1015, 1035, 1075,
1090, 1115, 1135, 1160, 1185, 1225, 1235, 1330,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 10 2003