1070
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 6, June, 2006
Ostrovskaya et al.
PriOH afforded a precipitate as small dark aggregates insoluble
in Me2CO and PriOH but soluble in DMF and DMSO with
red coloration. Found (%): C, 69.02; H, 4.01; N, 11.65.
t.decomp. 185 °C. A solution of compound 4 in a mixture of
equal volumes of EtOH, DMF, water, and Me2CO is orangeꢀ
red. UV, λmax/nm (εmax): 506.2 (28800). Found (%): C, 55.51;
H, 4.69; N, 10.03; S, 7.61. C19H17N3O4S•2H2O. Calculated (%):
C, 54.40; H, 5.01; N, 10.02; S, 7.61. IR, ν/cm–1: 3400 (O—H);
3230 (N—H bond.); 3190—2980 (O—H of water, C—H aliph.,
C—H arom.); 1600, 1548, 1484 (C=C arom.); 1460 (N=Ntrans);
1410 (C aliph.—N); 1360 (C arom.—N); 1316, 1280 (C—S);
1260, 1120 (C—C arom.); 1090 (C—C, C—O); 1028, 1004,
1000 (C—S); 980 (C—N—C); 836, 760 (C—H arom.); 724, 664,
620 (C—H). After drying at 100 °C (100 Torr), the weight loss
was 8.01% (2 H2O). T.decomp. 205—214 °C. Found (%):
C, 58.91; H, 4.53; N, 10.70; S, 8.26. C19H17N3O4S. Calcuꢀ
lated (%): C, 59.52; H, 4.49; N, 10.96; S, 8.36.
Xꢀray diffraction study of 3. Xꢀray diffraction study was carꢀ
ried out in the Xꢀray Structural Center (A. N. Nesmeyanov
Institute of Organoelement Compounds of the Russian Acadꢀ
emy of Sciences) according to standard procedures7 on a Bruker
AXS SMART 1000 diffractometer equipped with a CCD detecꢀ
tor (λ(Mo), graphite monochromator, ω scanning technique
with a step of 0.3°, the exposure time per frame was 10 s,
C
20H17N3O3. Calculated (%): C, 69.15; H, 4.93; N, 12.10. IR,
ν/cm–1: 3400 (O—H); 3270 (N—H bond.); 3070 (C—H aliph.);
2850—2950, 2300—2600 (C—H aliph., H—O bond.); 1692
(C=O); 1600, 1544, 1480 (C=C arom.); 1456, 1436 (N=Ntrans);
1412 (C aliph.—N); 1364 (C arom.—N); 1308, 1264 (C—C);
1244 (C—O); 1164, 1128 (C—C arom.); 1112, 1060 (C—OCOH);
1040 (C—C, C—O); 1012 (C—O); 960 (C—N—C); 856, 816,
772, 688, 616 (C—H arom.).
6ꢀ[(2ꢀCarboxyphenyl)azo]ꢀ3ꢀhydroxyꢀ7,8ꢀbenzoꢀ1,2,3,4ꢀ
tetrahydroquinoline (3). A diazo solution consisting of 2ꢀamiꢀ
nobenzoic (anthranilic) acid (0.42 g, 3 mmol), 10% AcOH
(7.5 mL, 12.5 mmol), a 1 M HCl solution (2.3 mL, 2.3 mmol),
and a 10% NaNO2 solution (2.1 mL, 3 mmol) was added
dropwise with vigorous stirring to a mixture of compound 1
(0.585 g, 3 mmol) in water (40 mL), DMF (20 mL), and EtOH
(20 mL) at 0—3 °C for 1 h. The reaction mixture was kept in a
refrigerator for 48 h. The darkꢀviolet precipitate that formed was
filtered off, successively washed with water (150 mL) and EtOH
(20 mL), and dried. The yield was 0.9 g (79%), t.decomp.
185 °C. A violet solution in EtOH was obtained. UV (EtOH),
2θ
= 52°). For compound 3•0.5EtOH: C21H20N3O3.5,
max
M = 370.4, space group Pccn, a = 19.065(8) Å, b = 21.619(8) Å,
c = 9.770(4) Å, V = 4027(3) Å3, 120 K, Z = 8, 10263 reflections
were measured of which 3551 reflections were with F 2 > 2σ(I ),
dcalc = 1.222 g cm–3, µ = 0.085 cm–1, R1 = 0.0657, wR2 = 0.1264.
The molecular structure of 3 is shown in Figs 2 and 3.
λ
max/nm (εmax): 572.0 (27600). Found (%): C, 62.67; H, 5.70;
N, 10.94. C20H17N3O3•2H2O. Calculated (%): C, 62.65;
H, 5.53; N, 10.96. A portion of the product was dissolved in
boiling EtOH. The hot solution was filtered through a glass
sinter into a thermally insulated vessel and kept at ~20 °C for
two weeks. The prismatic single crystals that formed were sepaꢀ
rated from the solution by decantation and dried in air at ~20 °C.
Xꢀray diffraction data for the molecules of composition
References
20H17N3O3•0.5EtOH are presented in Figs 2 and 3. IR, ν/cm–1
:
1. V. M. Ostrovskaya, O. A. Zaporozhets, G. K. Budnikov, and
N. M. Chernavskaya, Voda. Indikatornye sistemy [Water. Inꢀ
dicator Systems], Izdꢀvo FGUP VTII, Moscow, 2004, 59 (in
Russian).
2. V. M. Ostrovskaya, Pat. RF 2009486; Byul. izobret. [Invention
Bull.], 1994, 5 (in Russian).
C
2400—3400 br (O—H bond., N—H bond., O—H, C—H aliph.);
1672 (C=O); 1604, 1588, 1528, 1484 (C=C arom.); 1452
(N=Ntrans); 1400—1200 br; 1160 (C—C); 1128 (C—C arom.);
1088, 1068, 1040 (C—O); 980 (C—N—C); 852, 752, 708, 684,
652 (C—H arom.).
3. V. M. Ostrovskaya, 26th Int. Symp. on Environmental Anal.
Chem. (Vienna, April 9—12, 1996), Book of Abstrs, Vienna,
1996, FR 15.
4. V. M. Ostrovskaya, O. A. Prokopenko, S. E. Nefedov, and
Yu. L. Shishkin, Pat. RF 2265828; Byul. izobret. [Invention
Bull.], 2005, 34 (in Russian).
5. N. N. Vorozhtsov and S. I. Kutkevichus, Zh. Obshch. Khim.,
1957, 27, 2521 [J. Gen. Chem. USSR, 1957, 27 (Engl. Transl.)].
6. J. R. Merchant and S. S. Salgar, J. Ind. Chem. Soc.,
1963, 40, 23.
7. SMART (Control) and SAINT (Integration) Software, Verꢀ
sion 5.0, Bruker AXS Inc., Madison, WI, 1997.
3ꢀHydroxyꢀ6ꢀ[(4ꢀsulfophenyl)azo]ꢀ7,8ꢀbenzoꢀ1,2,3,4ꢀtetraꢀ
hydroquinoline (4). A 10% NaNO2 solution (1.4 mL, 2 mmol)
was added with stirring to a mixture of sulfanilic acid (0.346 g,
2 mmol), 10% AcOH (6 mL, 10 mmol), and a 1 M HCl solution
(2 mL, 2 mmol) at 0—1 °C. After 1 h, the resulting suspension
was added dropwise to a solution of compound 1 (0.39 g, 2 mmol)
in EtOH (43 mL), heating of the reaction mixture being preꢀ
vented. Then the mixture was stirred for 1 h. The brownꢀviolet
precipitate that formed was filtered off, successively washed with
water (100 mL), DMF (20 mL), and EtOH (20 mL), and
dried. Reprecipitation was performed from DMF with an
Me2CO—hexane mixture (1 : 1, v/v), t.decomp. 158—164 °C.
Then the reaction product was reprecipitated from a 10% NaOH
solution with a fourfold volume of 5% AcOH, washed with a
twofold volume of 1 M HCl, then with water to neutral pH, and,
finally, with Me2CO and hexane. The yield was 0.9 g (79%),
Received November 3, 2005;
in revised form May 4, 2006