SNAr REACTION OF 1,3-DICHLORO-4,6-DINITROBENZENE
947
trum, δ, ppm: 6.30 s (1H, 3-H), 7.15 m (6H, m-H,
p-H), 7.23 d.d (4H, o-H, J = 15.8, 8.2 Hz), 8.66 s (1H,
6-H). Found: m/z 353.0758 [M + H]+. C18H13N2O6.
Calculated: [M + H] 353.0774.
IR spectrum (KBr), δ, cm–1: 3060 (C–Harom), 1568
(C=Carom), 1470 (C=Carom), 813, 740. H NMR
spectrum, δ, ppm: 7.25–7.60 m (18H). Found:
m/z 648.9077 [M + H]+. C30H19Cl4S4. Calculated:
[M + H] 648.9095.
1
4,6-Dinitro-N,N′-diphenylbenzene-1,3-diamine
(3c). Yield 1.34 g (91%), mp 179–181°C; published
data [19]: mp 185°C. IR spectrum (KBr), ν, cm–1: 3317
(NH), 3085 (C–Harom), 1618 (C=Carom), 1581
The melting points were measured with a Poly
Therm A melting point apparatus at a heating rate of
1
3 deg/min and were not corrected. The H NMR
1
(C=Carom), 1517 (NO2), 1322 (NO2), 742. H NMR
spectra were recorded at 25°C on a Bruker DRX500
spectrometer at 500 MHz using DMSO-d6 as solvent
and tetramethylsilane as internal standard. The high-
resolution mass spectra (electrospray ionization) were
obtained on a Bruker micrOTOF II instrument. The IR
spectra were recorded on a Perkin Elmer Spectrum 65
spectrometer equipped with a universal ATR sampling
accessory (resolution 4 cm–1; number of scans 32).
spectrum, δ, ppm: 6.36 s (1H, 2-H), 7.17 t (2H, p-H,
J = 7.0 Hz), 7.27 d (4H, o-H, J = 7.5 Hz), 7.36 t (4H,
m-H, J = 7.7 Hz), 9.04 s (1H, 5-H), 9.73 s (2H, NH).
Found: m/z 351.1090 [M + H]+. C18H15N4O4. Calculat-
ed: [M + H] 351.1094.
Compounds 4a, 4b, 5a, and 5b (general proce-
dure). Benzenethiol 2a or 2d, 12.7 (in the synthesis of
4a and 4b) or 17.0 mmol (in the synthesis of 5a and
5b), was dissolved in 20 mL of DMF, and 3.50 g
(25.32 mmol) of anhydrous potassium carbonate and
1.00 g (4.22 mmol) of compound 1 were added. The
mixture was stirred for 4 h at 140°C, cooled, and
poured into water, and the precipitate was filtered off,
washed several times with water, and recrystallized
from propan-2-ol–DMF.
REFERENCES
1. Zotova, N.V., Kushakova, P.M., Kuznetsov, V.A.,
Rodin, A.A., and Garabadzhiu, A.V., Russ. J. Org.
Chem., 2005, vol. 41, p. 214.
2. Senger, N.A., Bo, B., Cheng, Q., Keeffe, J.R.,
Gronert, S., and Wu, W., J. Org. Chem., 2012, vol. 77,
p. 9535.
5-Nitro-1,2,4-tris(phenylsulfanyl)benzene (4a).
Yield 1.49 g (79%), mp 112–115°C. IR spectrum
(KBr), ν, cm–1: 3050 (C–Harom), 1572 (C=Carom), 1531
(NO2), 1485 (C=Carom), 1438 (C=Carom), 1320 (NO2),
747, 689. 1H NMR spectrum, δ, ppm: 6.18 s (1H, 3-H),
7.21–7.31 m (8H), 7.40–7.48 m (7H), 8.03 s (1H,
6-H). Found: m/z 448.0487 [M + H]+. C24H18NO2S3.
Calculated: [M + H] 448.0500.
3. Senskey, M.D., Bradshaw, J.D., Tessier, C.A., and
Youngs, W.J., Tetrahedron Lett., 1995, vol. 36, p. 6217.
4. Menezes, F.G., Ricardo, J., Dias, R., Bortoluzzi, A.J.,
and Zucco, C., Quim. Nova, 2007, vol. 30, p. 356.
5. Blasko, A., Bunton, C.A., Gillitt, N.D., Bacaloglu, R.,
Yunes, S.F., and Zucco, C., J. Braz. Chem. Soc., 2013,
vol. 24, p. 1146.
6. Zotova, N.V., Kushakova, P.M., Kuznetsov, V.A.,
Rodin, A.A., and Garabadzhiu, A.V., Russ. J. Org.
Chem., 2004, vol. 40, p. 1473.
5-Nitro-1,2,4-tris[(4-chlorophenyl)sulfanyl]ben-
zene (4b). Yield 1.87 g (81%), mp 209–211°C. IR
spectrum (KBr), ν, cm–1: 3084 (C–Harom), 1570
(C=Carom), 1527 (NO2), 1477 (C=Carom), 1317 (NO2),
7. Vlasov, V.M., Russ. Chem. Rev., 2003, vol. 72, p. 681.
8. Rusanov, A.L., Komarova, L.G., Sheveleva, T.S.,
Prigozhina, M.P., Shevelev, S.A., Dutov, M.D.,
Vatsadze, I.A., and Serushkina, O.V., React. Funct.
Polym., 1996, vol. 30, p. 279.
1
1090, 817. H NMR spectrum, δ, ppm: 6.13 s (1H,
3-H), 7.29 d (2H, J = 8.5 Hz), 7.36–7.41 m (8H),
7.47 d (2H, J = 8.5 Hz), 8.18 s (1H, 6-H). Found:
m/z 549.9315 [M + H]+. C24H15Cl3NO2S3. Calculated:
[M + H] 549.9331.
9. Rusanov, A.L., Tartakovskiy, V.A., Shevelev, S.A.,
Dutov, M.D., Vatsadse, I.A., Serushkina, O.V.,
Komarova, L.G., Prigozhina, M.P., Bulycheva, E.G., and
Elshina, L.B., Polymer, 2000, vol. 41, p. 5021.
1,2,4,5-Tetrakis(phenylsulfanyl)benzene (5a).
Yield 1.76 g (82%), mp 135.5–137.5°C. IR spectrum
(KBr), ν, cm–1: 3053 (C–Harom), 1571 (C=Carom), 1484
10. Sapozhnikov, O.Yu., Dutov, M.D., Kachala, V.V., and
Shevelev, S.A., Mendeleev Commun., 2002, vol. 12,
p. 231.
1
(C=Carom), 1438 (C=Carom), 746, 688. H NMR spec-
trum, δ, ppm: 6.70 s (2H, 3-H, 6-H), 7.20–7.25 m
(8H), 7.30–7.32 m (12H). Found: m/z 511.0669
[M + H]+. C30H23S4. Calculated: [M + H] 511.0683.
11. Shevelev, S.A., Dutov, M.D., Vatsadze, I.A., Koro-
lev, M.A., and Rusanov, A.L., Mendeleev Commun.,
1996, vol. 6, p. 155.
1,2,4,5-Tetrakis[(4-chlorophenyl)sulfanyl]ben-
12. Bartoli, G. and Todesco, E., Acc. Chem. Res., 1977,
zene (5b). Yield 2.30 g (84%), mp 263.5–266.5°C.
vol. 10, p. 125.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 6 2018