ABDULAEVA et al.
390
collected. Yield 0.104 g (36%), yellow–green powder,
taneously separated, and the mixture turned violet. The
mixture was diluted with petroleum ether, and the pre-
cipitate was filtered off. Yield 0.029 g (80%), dark red
(almost black) powder, mp 259°C (decomp.). 1H NMR
spectrum (DMSO-d6), δ, ppm: 3.45 m (4H, CH2CH2),
mp 155–156°C. IR spectrum, ν, cm–1: 1677 (C=O),
1
1613, 1502. H NMR spectrum (CDCl3), δ, ppm:
3.45 m (4H, CH2CH2), 4.95 s (2H, CH2), 7.03 d (1H,
9-H, J9,8 = 7.5 Hz), 7.25 d (1H, 8-H, J8,9 = 7.5 Hz),
7.40 d (1H, 5-H, J5,4 = 7.4 Hz), 8.05 d (1H, 4-H, J4,5
=
7.02 d (1H, 9-H, J9,8 = 7.8 Hz), 7.25 d (1H, 8-H, J8,9 =
7.4 Hz). Found, %: C 80.38; H 4.56. C14H10O2. Cal-
culated, %: C 79.98; H 4.79.
7.8 Hz), 7.38 br.d (1H, 5-H, J5,4 = 7.3 Hz), 7.50–
7.70 m (3H, Ph), 8.01 d (1H, 4-H, J4,5 = 7.3 Hz), 8.36–
8.43 (2H, Ph). Found, %: C 69.25; H 3.88; F 10.60.
C21H13BF2O3. Calculated, %: C 69.65; H 3.62; F 10.49.
b. Compound IX was synthesized in a similar way
from 0.452 g (1.1 mmol) of bromomethyl ketone V.
Yield 0.038 g (16%), yellow powder, mp 156–157°C
(from ethanol).
3-Hydroxy-6,7-dihydro[6,7,1-def]chromen-2-yl-
(phenyl)methanone copper complex (XIII). A satu-
rated aqueous solution of copper(II) acetate was added
to an approximately equal volume of a saturated solu-
tion of 0.04 g (0.13 mmol) of compound X in diethyl
ether. The mixture was shaken for ~30 min, and the
dark red precipitate was filtered off and dried. Yield
0.074 g (84%), red powder, mp 210°C (decomp.). IR
spectrum, ν, cm–1: 1624, 1585, 1546, 1503, 1477,
1447, 1411, 1375. Found, %: C 73.69; H 4.07.
C42H26CuO6. Calculated, %: C 73.13; H 4.28.
3-Hydroxy-6,7-dihydro[6,7,1-def]chromen-2-yl-
(phenyl)methanone (X). A solution of 0.2 g
(0.5 mmol) of compound V in 10 ml of ethanol was
cooled with an ice bath, 2 ml of 5% potassium hydrox-
ide was added, and a dark red solid separated. After
25–30 min, the mixture was acidified with dilute (1:1)
hydrochloric acid, and the precipitate turned bright red.
It was filtered off, washed with water, and dried in air.
Yield 0.1 g (70%), red powder, mp 156–157°C. Found,
%: C 80.65; H 4.17. C21H14O3. Calculated, %: C 80.24;
H 4.49.
6,7-Dihydroindeno[6,7,1-def]chromen-3-yl
acetate (XV). A solution of 0.114 g (0.5 mmol) of
compound IX in 3 ml of acetic anhydride containing
a catalytic amount of sodium acetate was heated for
30 min under reflux. The mixture was cooled and
poured into water, and the precipitate was filtered off,
washed with water, and subjected to chromatography
on Silokhrom using chloroform as eluent. Yield
0.075 g (55%), bright yellow powder, mp 85–86°C.
IR spectrum, ν, cm–1: 1757 (C=O), 1696, 1651, 1604,
1586. UV spectrum, λmax (logε), nm: 202 (4.21), 221
(4.32), 233 (4.31), 341 (3.96), 374 (3.58). Lumines-
2-(4-Methoxybenzylidene)-6,7-dihydroindeno-
[6,7,1-def]chromene-3(2H)-one (XI). A suspension of
0.2 g (0.5 mmol) of compound V in 7 ml of methanol
was added to a solution of 0.06 ml (0.5 mmol) of
4-methoxybenzaldehyde and 0.03 g (0.6 mmol) of
sodium methoxide in 3 ml of methanol. The mixture
turned orange, and it was heated until the initial
bromomethyl ketone dissolved completely (the solu-
tion turned red). The mixture was cooled, acidified
with dilute (1:1) hydrochloric acid to weakly acidic
reaction, and diluted with water, and the red precipitate
was filtered off, washed with water, dried, and purified
by chromatography on aluminum oxide using chloro-
form as eluent. Yield 0.08 g (48%), red powder,
mp 204–205°C. IR spectrum, ν, cm–1: 1670 (C=O),
1585, 1563, 1505. 1H NMR spectrum (CDCl3), δ, ppm:
3.45 m (4H, CH2CH2), 3.88 s (3H, OCH3), 6.99 d (2H,
C6H4, J = 9.0 Hz), 7.15 s (1H, CH), 7.22 d (1H, 9-H,
J9,8 = 7.6 Hz), 7.28 d (1H, 8-H, J9,8 = 7.6 Hz), 7.45 d
(1H, 5-H, J5,4 = 7.3 Hz), 7.90 d (2H, C6H4, J = 9.0 Hz),
8.20 d (1H, 4-H, J4,5 = 7.3 Hz). Found, %: C 80.68;
H 4.67. C22H16O3. Calculated, %: C 80.47; H 4.91.
1
cence spectrum: λexcit/λmax 320/436 nm. H NMR spec-
trum (CDCl3), δ, ppm: 2.30 s (3H, CH3), 3.25 m
(4H, CH2CH2), 6.44 d (1H, 9-H, J9,8 = 7.0 Hz), 6.62 d
(1H, 4-H, J4,5 = 7.6 Hz), 6.77 s (1H, 2-H), 6.93 d (1H,
8-H, J8,9 = 7.0 Hz), 7.00 d (1H, 5-H, J = 7.6 Hz).
Found, %: C 76.47; H 4.91. C16H12O3. Calculated, %:
C 76.18; H 4.79.
Indeno[6,7,1-def]chromen-3-yl acetate (XVI).
2,3,5,6-Tetrachloro-1,4-benzoquinone, 0.068 g
(0.28 mmol), was added to a solution of 0.07 g
(0.28 mmol) of compound XIV in 2 ml of o-dichloro-
benzene. The solution turned green and was heated for
40 min under reflux. After cooling, the colorless pre-
cipitate was filtered off, the filtrate was cooled and
evaporated, and the residue was subjected to chroma-
tography on silica gel using chloroform as eluent.
Yield 0.035 g (50%), orange powder, mp 113–114°C.
IR spectrum, ν, cm–1: 1762 (C=O), 1639, 1595. UV
3-Hydroxy-6,7-dihydro[6,7,1-def]chromen-2-yl-
(phenyl)methanone complex with BF3 (XII). Boron
trifluoride–diethyl ether complex, 4–5 drops (~0.1 ml),
was added to a solution of 0.032 g (0.1 mmol) of
compound X in 2 ml of benzene, a violet solid instan-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 3 2011