THE MANNICH BASES OF NAPHTHALENE SERIES
991
126.9 (CH), 128.4 (CH), 128.6 (CH), 128.89 (CH),
128.95 (CH), 131.1 (C), 131.5 (C), 145.1 (C), 148.8
(C). Found, %: C 90.46; H 5.11. C27H18O. Calculated,
%: C 90.47; H 5.06.
121.8, 122.1, 122.8, 124.7, 127.3, 129.1, 129.59,
129.64, 131.1, 134.3, 147.0, 148.3, 148.9. Found, %: C
80.23; H 4.28; N 3.52. C27H17NO3. Calculated, %: C
80.38; H 4.25; N 3.47.
14-(4-Methoxyphenyl)-14H-dibenzo[a,j]xanthene
(IIb). Yield 41%, colorless crystals, mp 202–204°C
(EtOH) (mp 204–205°C [16]). IR spectrum (KBr), ν,
cm–1: 1620, 1593, 1508, 1458, 1433, 1402. 1252, 1179,
14-(2-Thienyl)-14H-dibenzo[a,j]xanthene (IIe). A
solution of 1.0 g (3.5 mmol) of 1-[(dimethylamino)(2-
thienyl)methyl]-2-naphthol Ie in 10 mL of acetic acid
was refluxed for 6 h. The reaction mixture was poured
into water, the formed precipitate was filtered off and
purified by column chromatography (eluent CHCl3)
followed by recrystallization from ethanol. Yield 0.58 g
(45%) orange crystals, mp 179–181°C. IR spectrum
(KBr), ν, cm–1: 3071 (СHAr), 1624, 1593, 1516, 1458,
1431, 1400, 1354, 1249, 1029, 960, 813, 744, 705,
609. 1Н NMR spectrum (СDCl3), δ, ppm: 6.69 d.d (1H,
1
1030, 962, 839, 824, 812, 748. Н NMR spectrum
(DMSO-d6), δ, ppm: 3.50 s (3H, CH3O), 6.62 s (1H,
H14), 6.65 d (2H, H3',5', J 8.7 Hz), 7.42 d.d.d (2H, HAr,
J 7.8, 6.9, 0.9 Hz), 7.48 d (2H, H2',6', J 8.7 Hz), 7.51 d
(2H, HAr, J 8.7 Hz), 7.59 d.d.d (2H, HAr, J 8.2, 6.9,
1.2 Hz), 7.86–7.90 m (4H, HAr), 8.63 d (2H, HAr,
J 8.5 Hz). 13С NMR spectrum (DMSO-d6), δС, ppm:
36.2 (C14H), 55.4 (CH3), 114.3 (CH), 118.2 (CH, C),
124.0 (CH), 125.0 (CH), 127.4 (CH), 129.1 (CH),
129.36 (CH), 129.45 (CH), 131.2 (C), 131.4 (C), 138.3
(C), 148.4 (C), 158.0 (C). Found, %: C 86.51; H 5.16.
C28H20O2. Calculated, %: C 86.57; H 5.19.
Hthien, J 5.0, 3.7 Hz), 6.79 d (1H, Hthien, J 3.7 Hz), 6.83
s (1Н, Н14), 6.94 d.d (1H, Hthien, J 5.0, 0.9 Hz), 7.43–
7.51 m (4H, HAr), 7.63 d.d.d (2H, HAr, J 8.2, 6.9,
0.9 Hz), 7.82 d (2H, HAr, J 9.2 Hz), 7.87 d (2H, HAr,
J 8.2 Hz), 8.39 d (2H, HAr, J 8.2 Hz). 13С NMR
spectrum (CDCl3), δС, ppm: 32.4 (C14H), 116.7 (C),
118.1 (CH), 122.7 (CH), 124.1 (CH), 124.5 (CH),
124.9 (CH), 126.4 (CH), 127.0 (CH), 128.9 (CH),
129.2 (CH), 131.1 (C), 131.3 (C), 148.5 (C), 149.1 (C).
Found, %: C 82.44; H 4.37; S 8.70. C25H16OS.
Calculated, %: C 82.39; H 4.42; S 8.80.
14-(4-Chlorophenyl)-14H-dibenzo[a,j]xanthene
(IIc). Yield 50%, pale yellow crystals, mp 287–289°C
(AcOH) (mp 290–292°C [16]). IR spectrum (KBr), ν,
cm–1: 3071 (CHAr), 1622, 1593, 1516, 1485, 1458,
1431, 1400, 1354, 1242, 1084, 1015, 961, 833, 806,
1
741, 709. Н NMR spectrum (СDCl3), δ, ppm: 6.72 s
(1H, H14), 7.17 d (2H, HAr, J 8.5 Hz), 7.43 t (2H, HAr,
J 7.4 Hz), 7.52 d (2H, HAr, J 8.9 Hz), 7.57–7.62 m
(4H, HAr), 7.90 d (4H, HAr, J 8.7 Hz), 8.63 d (2H, HAr,
J 8.5 Hz). 13С NMR spectrum (CDCl3), δС, ppm: 36.3
(C14H), 117.5 (C), 118.2 (CH), 123.9 (CH), 125.2
(CH), 127.6 (CH), 128.9 (CH), 129.2 (CH), 129.8
(CH), 130.2 (CH), 131.2 (C), 131.3 (C), 131.4 (C),
145.0 (C), 148.5 (C). Found, %: C 82.62; H 4.33.
C27H17СlO. Calculated, %: C 82.54; H 4.36.
Mass spectra were recorded on a Thermo Finnigan
Trace DSQ instrument at the direct input of the sample
into the ion source, energy of ionizing electrons 70 eV.
1H, 13C NMR and DEPT spectra were obtained on a
JEOL JNM-ECX400 spectrometer (400 and 100 MHz,
respectively) in CDCl3 or DMSO-d6, internal reference
TMS. IR spectra were recorded on a Shimadzu FTIR-
8400S spectrometer from KBr pellets. Elemental
analysis was performed on a СНNS EuroVector EA-
3000 automatic analyzer. Melting points were determined
by the capillary method on a PTP-M apparatus.
Heating of 1 g (3.2 mmol) of the Mannich base Ic
and 0.46 g (3.2 mmol) of 2-naphthol in 10 mL of
acetic acid for 6 h afforded dibenzoxanthene IIc in a
yield of 1.09 g (87%).
ACKNOWLEDGMENTS
14-(3-Nitrophenyl)-14H-dibenzo[a,j]xanthene (IId).
Yield 44%, yellow crystals, mp 212–213°C (AcOH)
(mp 213–215°C [16]). IR spectrum (KBr), ν, cm–1:
3070 (CHAr), 1619, 1590, 1525 (NO2), 1499, 1350
This work was financially supported by the
Ministry of Education and Science of Russia in the
frame of the basic part of the governmental contract
(4.1597.2014/К).
1
(NO2), 1248, 812, 750. Н NMR spectrum (СDCl3), δ,
ppm: 6.58 s (1H, H14), 7.27 d.d (1H, H5', J 8.2, 7.3 Hz),
7.43 t (2H, HAr, J 7.3 Hz), 7.50 d (2H, HAr, J 8.7 Hz),
7.61 t (2H, HAr, J 7.3 Hz), 7.78–7.89 m (6H, HAr), 8.29
d (2H, HAr, J 8.7 Hz), 8.41 s (1H, H2'). 13С NMR
spectrum (CDCl3), δС, ppm: 37.8 (C14H), 116.0, 118.2,
REFERENCES
1. Bhattacharya, A.K., Rana, K.C., Mujahid, M., Sehar, I.,
and Saxena, A.K., Bioorg. Med. Chem. Lett., 2009,
vol. 19, p. 5590. DOI: 10.1016/j.bmcl.2009.08.033.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 4 2015