3H-naphtho[2,3-e]-1,2,4-triazepines

Full text of DOI:10.1007/s11178-005-0087-0

Russian Journal of Organic Chemistry, Vol. 40, No. 11, 2004, pp. 1707-1708. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 11,
004, pp. 1751-1752.
2
Original Russian Text Copyright Ó 2004 by Nikulin, Artamonova, Koldobskii.
SHORT
COMMUNICATIONS
3H-Naphtho[2,3-e]-1,2,4-triazepines
V.V. Nikulin, T.V.Artamonova, and G.I. Koldobskii
St. Petersburg State Technological Institute, St. Petersburg, 190013 Russia
e-mail: koldobsk@tu.spb.ru
Received May 18, 2004
The thermal transformation of N-imidoyltetrazoles
unknown 3H-naphtho[2,3-e]-1,2,4-triazepines. It should
be noted that the reaction occurred 110–115°C and was
accompanied with tarring resulting in decreased yield of
the reaction product.
generated from 5-substituted tetrazoles and N-
aryl(hetaryl)benzimidoyl chlorides may be regarded as
one of the most promising ways of building up complex
heterocyclic systems including one or several triazepine
rings [1-8].
Unlike 3H-1,3,4-benzo- and 3H-pyrido[6,7-e]-1,2,4-
triazepines that are readily hydrolyzed in water solutions
of mineral acids to the corresponding aminobenzo-
phenones [2, 8], 3H-naphtho-[2,3-e]-1,2.4-triazepines
under the same conditions undergo more complicated
transformations resulting in 3-arylbenzo-[f]indazoles.
In extension of the study on the thermal transformation
of disubstituted tetrazoles we found that the heating of
N-imidoyltetrazoles prepared from 5-aryltetrazoles and
N-(2-naphthyl)benzimidoyl chlorides under conditions of
the phase-transfer catalysis gave rise to previously
+
1
+
5
& +
,D
1
1
& 5& + 5ꢀ
&O
1
+
ꢀ
1
1
1
&
+ 5ꢀ
5
& +
2
,5-Diphenyl-3H-naphtho-[2,3-e]-1,2,4-tri-
&
+&O ꢁꢁꢁDTXHRXVꢁ1D2+ꢂꢁ
1
1
ꢃꢄꢁYROꢅ
azepine (Ia). To a mixture of 0.01 mol 5-phenyltetrazole,
0.001 mol of tetrabutylammonium bromide, 10 ml of 10%
water solution of NaOH, and 30 ml of chloroform at 20°C
while stirring was added within 30 min 0.01 mol of N-(2-
naphthyl)benzimidoyl chloride in 10 ml of chloroform. The
reaction mixture was stirred for 4 h at 20°C, the phases
were separated, the organic layer was washed with 1%
aqueous NaOH, with water (2´10 ml), and dried with
magnesium sulfate. The chloroform was removed in a
vacuum, to the solid residue 20 ml of toluene was added,
the mixture was heated for 2 h at 110°C, cooled, the
precipitate was filtered off and dried in air. Yield 0.714
1
1
%X 1%U
1
&
+ 5ꢀ
1
'
1+
1
1
5
& +
B
,
DꢁꢁꢁH
–
R = R' = H (a); R = H (b, c), R' = Me (b), 4-NO2 (c); R =
-MeO, R' = H(d); R = 4-Cl, R' = H (e).
g(36%), mp 300–302°C (from DMF). IR spectrum, Cm
1: 920, 940, 949, 959, 977, 993, 1026, 1075, 1101, 1144,
4
1070-4280/04/4011-1705Ó2004 MAIK “Nauka/Interperiodica”

1708
NIKULIN et al.
1154, 1170, 1179, 1210, 1227, 1256, 1287, 1303, 1313, 1339,
Acid hydrolysis of 2,5-diphenyl-3H-naphtho-[2,3-
1
1
3
378, 1395, 1418, 1438, 1445, 1449, 1473, 1495, 1508,
560, 1578, 1600, 1624, 2853, 2925, 3023, 3049, 3080,
313. H NMR spectrum, d, ppm: 7.05– 8.08 m
e]-1,2,4-triazepine (Ia). A mixture of 5 mmol of
triazepine Ia and 30 ml of concn. HCl was heated for 5 h
at 100°C, then cooled to 20°C, the separated precipitate
was filtered off and stirred with 50 ml of 10% water
solution of K CO for 30 min at 50°C, then cooled to
1
(16Harom), 8.50 s (1H, NH). Found, %: C 83.05; H 4.98;
N 12.07. C H N . Calculated, %: C 83.00; H 4.90;
2
4
17
3
2
3
N 12.10.
Likewise were prepared and purified compounds
Ib–e.
-(4-Tolyl)-5-phenyl-3H-naphtho[2,3-e]-1,2,4-
triazepine (Ib). Yield 0.235 g (17%), mp 283–286°C
20°C, the separated precipitate was filtered off and dried
in air. We obtained 1.044 g (86%) of 3-phenylbenzo-
[
f]indazole, mp 195–196°C (from ethanol) [9]. IR
–
1
spectrum, cm : 921, 971, 1001, 1029, 1049, 1071, 1089,
130, 1159, 1177, 1204, 1259, 1270, 1286, 1325, 1367, 1418,
2
1
1
2
3
7
436, 1445, 1451, 1468, 1485, 1510, 1544, 1601, 1621,
754, 2849, 2913, 2944, 2992, 3042, 3117, 3139, 3174,
–
1
(
from toluene). IR spectrum, cm : 921, 936, 960, 997,
1
1
1
028, 1075, 1097, 1155, 1187, 1213, 1228, 1254, 1301,
1
193, 3197. H NMR spectrum (acetone-d ), d, ppm:
6
313, 1378, 1420, 1439, 1474, 1511, 1556, 1577, 1602,
.42–8.20 m (11Harom), 12.76 s (1H, NH).
1
624, 2854, 2921, 2954, 3028, 3057, 3317. H NMR
IR spectra were recorded on a spectrometer
spectrum, d, ppm: 2.36 s (3H, CH ), 7.05–8.07 m
3
1
Shimadzu FTIR-8400S from KBr pellets, H NMR
spectra were registered on a Bruker AC-200 instrument
(15Harom), 8.45 s (1H, NH). Found, %: C 83.25; H 5.29;
N 11.67. C H N . Calculated, %: C 83.10; H 5.26;
2
5
19
3
in DMSO-d . The purity and homogeneity of compounds
N 11.64.
-(4-Nitrophenyl)-5-phenyl-3H-naphtho[2,3-e]-
,2,4-triazepine (Ic). Yield 0.635 g (27%), mp 294-
6
obtained was checked by TLC on Silufol UV-254 plates,
eluent chloroform–petroleum ether–ethyl acetate,
2
1
2
1
0:15:3.
-
1
96°C (from toluene). IR spectrum, cm : 922, 937, 959,
The study was carried out under financial support of
the Ministry of Education of the Russian Federation
993, 1014, 1030, 1076, 1096, 1211, 1222, 1253, 1286, 1298,
1
1
318, 1344, 1349, 1372, 1418, 1438, 1506, 1515, 1524,
549, 1567, 1581, 1599, 1625, 2853, 2922, 3075, 3319.
(federal purposeful program “Integration”, grant no. 667).
1
H NMR spectrum, d, ppm: 7.06–8.36 m (15Harom),
8
.73 s (1H, NH). Found, %: C 73.45; H 4.09; N 14.37.
REFERENCES
C H N O . Calculated, %: C 73.47; H 4.08; N 14.29.
2
4
16
4
2
5
-(4-Methoxyphenyl)-2-phenyl-3H-naphtho[2,3-
1. Koldobskii, G. I., Nikonova, I. V., Zhivich, A. B., Ostrov-
skii, V. A., and Poplavskii, V. S., Zh. Obshch Khim., 1992,
vol. 62, p. 194.
2. Ivanova, S. E. and Koldobskii, G. I., Khim. Geterotsikl. Soed.,
1993, p. 907.
3. Koldobskii, G., Ivanova, S., Nikonova, I., Zhivich, A., and
Ostrovskii, V., Acta Chem. Scand., 1994, vol. 48, p. 596.
4. Koldobskii, G. I. and Ivanova, S. E., Zh. Org. Khim., 1995,
vol. 31, p. 1601.
e]-1,2,4-triazepine (Id). Yield 0.651 g (31%), mp 296–
–
1
2
1
1
2
98°C (from toluene). IR spectrum, cm : 918, 935, 959,
034, 1095, 1167, 1174, 1222, 1253, 1300, 1312, 1377,
416, 1440, 1447, 1494, 1508, 1548, 1579, 1606, 1625,
834, 2901, 2931, 2956, 3006, 3058, 3319. H NMR
spectrum, d, ppm: 3.75 s (3H, CH ), 6.85–8.07 m
1
3
(
15Harom), 8.46 s (1H, NH). Found, %: C 79.66; H 5.16;
N 11.14. C H N O. Calculated, %: C 79.58; H 5.04;
2
5
19
3
N 11.14.
-Phenyl-5-(4-chlorophenyl)-3H-naphtho[2,3-e]-
,2,4-triazepine (Ie). Yield 0.597 g (28%), mp 299–
5. Artamonova, T. V. and Koldobskii, G. I., Zh. Org. Khim.,
1997, vol. 33, p. 1850.
2
6
. Artamonova, T. V. and Koldobskii, G. I., Zh. Org. Khim.,
2000, vol. 36, p. 1749.
1
3
1
1
3
–
1
01°C (from toluene). IR spectrum, cm : 937, 959, 1013,
078, 1094, 1154, 1225, 1258, 1285, 1303, 1377, 1449,
478, 1484, 1548, 1562, 1573, 1593, 1622, 2853, 2922,
7
8
. Morgenstern, O., Pharmazie, 2000, vol. 55, p. 871.
. Nikulin, V. V., Artamonova, T. V., and Koldobskii, G. I., Zh.
Org. Khim., 2003, vol. 39, p. 647.
1
067, 3315. H NMR spectrum, d, ppm: 7.04–8.09 m
15Harom), 8.56 s (1H, NH). Found, %: C 75.59; H 4.23;
9
. Adger, B. M., Bradbury, S., Keating, M., Rees, C. W.,
Storr, R. C., and Williams, M. T., JCS Perkin Trans, 1, 1975,
p. 31.
(
N 11.04. C H N Cl. Calculated, %: C 75.49; H 4.19;
2
4
16
3
N 11.01.
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 11 2004