M. G. Bogdanov et al.
FULL PAPER
lated, which gave, after recrystallisation, colourless crystals con-
taining 1 equiv. CH3OH. Yield: 1.402 g (70%); m.p. 239–241 °C.
(؎)-trans-11-(4-Nitrophenyl)-6-oxo-11,12-dihydro-6H-dibenzo[c,h]-
chromene-12-carboxylic Acid (5d): From the reaction of homoph-
thalic anhydride (1.973 g, 12.168 mmol) and 4-nitrobenzaldehyde
(0.611 g, 4.043 mmol) in pyridine (10 mL), an oil (1.216 g, 72%)
was isolated, which gave, after recrystallisation, colourless crystals.
Yield: 1.101 g (65 %); m.p. 237–239 °C. 1H NMR (600 MHz,
3
1H NMR (600 MHz, CDCl3, 20 °C, TMS): δ = 8.34 (dd, JH,H
=
=
=
4
3
4
7.9, JH,H = 0.9 Hz, 1 H, ArH), 8.01 (dd, JH,H = 7.8, JH,H
3
3
4
1.0 Hz, 1 H, ArH), 7.63 (ddd, JH,H = 8.3, JH,H = 7.3, JH,H
3
1.4 Hz, 1 H, ArH), 7.52 (d, JH,H = 8.1 Hz, 1 H, ArH), 7.45 (dt,
3JH,H = 7.2, JH,H = 1.1 Hz, 1 H, ArH), 7.42 (ddd, JH,H = 7.7,
CDCl3, 20 °C, TMS): δ = 8.35 (dd, JH,H = 7.8, JH,H = 0.7 Hz, 1
4
3
3
4
3JH,H = 7.6, 4JH,H = 1.2 Hz, 1 H, ArH), 7.31 (dt, 3JH,H = 7.5, 4JH,H
H, ArH), 8.05 (d, JH,H = 8.8 Hz, 2 H, CH11-Ph), 8.01 (d, JH,H
=
=
3
3
3
3
= 1.3 Hz, 1 H, ArH), 7.22 (d, JH,H = 7.1 Hz, 1 H, ArH), 7.20–
7.5 Hz, 1 H, ArH), 7.68–7.65 (m, 1 H, ArH), 7.48 (t, JH,H
7.13 (m, 5 H, CH11-Ph), 5.07 (s, 1 H, 11-H), 3.95 (s, 1 H, 12-H) 7.5 Hz, 1 H, ArH), 7.45–7.43 (m, 2 H, ArH), 7.36–7.32 (m, 3 H,
ppm. 13C NMR (150 MHz, CDCl3, 20 °C, TMS): δ = 173.6 (CO-
COOH), 161.9 (COlactone), 148.3, 140.1, 136.7, 134.9 (CHAr), 131.4,
ArH), 7.23 (d, 3JH,H = 7.4 Hz, 1 H, ArH), 5.20 (s, 1 H, 11-H), 3.93
(s, 1 H, 12-H) ppm. 13C NMR (150 MHz, CDCl3, 20 °C, TMS): δ
130.5 (CHAr), 129.9 (CHAr), 129.6 (CHAr), 128.8 (CHAr), 128.2 = 172.7 (COCOOH), 161.4 (COlactone), 148.6, 147.6, 146.9, 136.0,
(CHAr), 128.0, 127.7 (CHAr), 127.2 (CHAr), 122.8 (CHAr), 122.7 135.0 (CHAr), 130.6, 130.5 (CHAr), 130.1 (CHAr), 129.9 (CHAr),
(CHAr), 121.1, 110.3, 52.1 (C-12), 40.4 (C-11) ppm. IR (Nujol): ν
128.5 (CHAr), 128.2 (CHAr), 128.0 (CHAr), 127.5, 124.0 (CHAr),
˜
= 1710 (C=O), 1700 (C=O), 1630 (C=C) cm–1. C24H16O4·CH3OH 122.8 (CHAr), 122.2 (CHAr), 121.0, 109.2, 51.6 (C-12), 40.0 (C-11)
(400.42): calcd. C 74.99, H 5.03, O 19.98; found C 75.39, H 5.14,
O 19.47.
ppm. IR (Nujol): ν = 1720 (C=O), 1680 (C=O) cm–1. C H NO
˜
24 15 6
(413.38): calcd. C 69.73, H 3.66, N 3.39, O 23.22; found C 69.71,
H 3.91, N 3.45, O 22.93.
(؎)-trans-11-(4-Methoxyphenyl)-6-oxo-11,12-dihydro-6H-dibenzo-
[c,h]chromene-12-carboxylic Acid (5b): From the reaction of
homophthalic anhydride (2.027 g, 12.501 mmol) and 4-methoxy-
benzaldehyde (0.568 g, 0.51 mL, 4.171 mmol) in pyridine (10 mL),
an oil (1.323 g, 80%) was isolated, which gave, after recrystalli-
sation, colourless crystals containing 0.5 equiv. CH3OH. Yield:
1.253 g (75 %); m.p. 158–160 °C. 1H NMR (600 MHz, CDCl3,
20 °C, TMS): δ = 8.34 (dd, 3JH,H = 7.9, 4JH,H = 1.0 Hz, 1 H, ArH),
(؎)-trans-11-(2,4-Dimethoxyphenyl)-6-oxo-11,12-dihydro-6H-di-
benzo[c,h]chromene-12-carboxylic Acid (5e): From the reaction of
homophthalic anhydride (0.568 g, 3.501 mmol) and 2,4-dimeth-
oxybenzaldehyde (0.194 g, 1.167 mmol), an oil (0.248 g, 50%) was
isolated. This compound was obtained as colourless crystals con-
taining 0.5 equiv. CH3OH. Yield: 0.166 g (33%); m.p. 144–146 °C.
3
1H NMR (600 MHz, CDCl3, 20 °C, TMS): δ = 8.32 (dd, JH,H
=
3
8.00 (d, JH,H = 7.7 Hz, 1 H, ArH), 7.65–7.62 (m, 1 H, ArH), 7.52
7.9, 4JH,H = 0.9 Hz, 1 H, ArH), 7.97 (d, 3JH,H = 7.7 Hz, 1 H, ArH),
3
4
(d, JH,H = 8.0 Hz, 1 H, ArH), 7.46–7.43 (m, JH,H = 1.1 Hz, 1 H,
3
7.61–7.58 (m, 1 H, ArH), 7.42 (t, JH,H = 7.2 Hz, 1 H, ArH), 7.39
3
4
ArH), 7.41 (dt, JH,H = 7.7, JH,H = 1.1 Hz, 1 H, ArH), 7.32–7.30
(m, 1 H, ArH), 7.22 (d, JH,H = 7.4 Hz, 1 H, ArH), 7.05 (d, JH,H
= 8.8 Hz, 2 H, CH11-Ph), 6.71 (d, JH,H = 8.8 Hz, 2 H, CH11-Ph),
(dt, 3JH,H = 7.7, 4JH,H = 1.0 Hz, 1 H, ArH), 7.36 (d, 3JH,H = 8.0 Hz,
1 H, ArH), 7.27–7.25 (m, 1 H, ArH), 7.16 (d, 3JH,H = 7.4 Hz, 1 H,
3
3
3
3
4
ArH), 6.49 (d, JH,H = 9.0 Hz, 1 H, CH11-Ph), 6.48 (d, JH,H
=
5.01 (s, 1 H, 11-H), 3.92 (s, 1 H, 12-H), 3.69 (s, 3 H, OCH3) ppm.
13C NMR (150 MHz, CDCl3, 20 °C, TMS): δ = 173.7 (COCOOH),
161.9 (COlactone), 158.6, 148.1, 136.7, 134.9 (CHAr), 132.0, 131.5,
130.6 (CHAr), 130.0 (CHAr), 129.6 (CHAr), 128.3 (CH11-Ph), 128.2,
128.0, 127.7 (CHAr), 122.9 (CHAr), 122.7 (CHAr), 121.2, 114.1
(CH11-Ph), 110.7, 55.0 (OCH3), 52.3 (C-12), 39.7 (C-11) ppm. IR
3
4
2.8 Hz, 1 H, CH11-Ph), 6.07 (dd, JH,H = 8.6, JH,H = 2.4 Hz, 1 H,
CH11-Ph), 5.33 (s, 1 H, 11-H), 3.95 (s, 3 H, OCH3), 3.93 (s, 1 H,
12-H), 3.65 (s, 3 H, OCH3) ppm. 13C NMR (150 MHz, CDCl3,
20 °C, TMS): δ = 177.7 (COCOOH), 162.0 (COlactone), 160.1, 157.1,
148.4, 136.7, 135.1 (CHAr), 130.8, 130.7 (CHAr), 130.1 (CHAr),
129.7 (CHAr), 128.6 (CHAr), 128.4 (CHAr), 128.2 (CHAr), 127.9,
123.0 (CHAr), 122.8 (CHAr), 121.3, 118.9, 110.5, 103.8 (CHAr), 98.8
(CHAr), 55.6 (OCH3), 55.2 (OCH3), 49.5 (C-12), 32.2 (C-11) ppm.
(Nujol): ν = 1690 (C=O), 1640 (C=C) cm–1. C H O ·0.5CH OH
˜
25 18
5
3
(414.43): calcd. C 73.90, H 4.86, O 21.23; found C 74.16, H 4.76,
O 21.08.
IR (CHCl ): ν = 1690 (C=O) cm–1. C H O ·0.5CH OH (444.45):
˜
3
26 20
6
3
(؎)-trans-11-(Benzo[d][1,3]dioxol-5-yl)-6-oxo-11,12-dihydro-6H-
dibenzo[c,h]chromene-12-carboxylic Acid (5c): From the reaction of
homophthalic anhydride (0.534 g, 3.293 mmol) and benzo[d][1,3]-
dioxol-5-carbaldehyde (0.165 g, 1.099 mmol) in pyridine (3 mL), an
oil (0.296 g, 65%) was isolated, which gave, after recrystallisation,
colourless crystals. Yield: 0.252 g (56 %); m.p. 246–248 °C. 1H
calcd. C 71.61, H 4.99, O 23.40; found C 71.78, H 4.65, O 23.57.
(؎)-trans-11-(3,4-Dimethoxyphenyl)-6-oxo-11,12-dihydro-6H-di-
benzo[c,h]chromene-12-carboxylic Acid (5f): From the reaction of
homophthalic anhydride (0.568 g, 3.501 mmol) and 3,4-dimeth-
oxybenzaldehyde (0.194 g, 1.167 mmol), an oil (0.373 g, 75%) was
isolated. The compound was obtained as colourless crystals con-
3
NMR (600 MHz, CDCl3, 20 °C, TMS): δ = 8.34 (dd, JH,H = 7.9,
3
1
4JH,H = 1.0 Hz, 1 H, ArH), 7.99 (d, JH,H = 7.7 Hz, 1 H, ArH),
taining 1.5 equiv. H2O. Yield: 0.236 g (47%); m.p. 157–159 °C. H
3
3
7.67–7.64 (m, 1 H, ArH), 7.52 (d, JH,H = 8.1 Hz, 1 H, ArH), 7.45
NMR (600 MHz, CDCl3, 20 °C, TMS): δ = 8.34 (dd, JH,H = 7.9,
3
3
3
4
(t, JH,H = 7.5 Hz, 1 H, ArH), 7.41 (t, JH,H = 7.6 Hz, 1 H, ArH), 4JH,H = 1.0 Hz, 1 H, ArH), 7.99 (dd, JH,H = 7.8, JH,H = 1.0 Hz,
3
3
4
7.31 (ddd, JH,H = 7.4, JH,H = 7.3, JH,H = 0.8 Hz, 1 H, ArH),
1 H, ArH), 7.65–7.63 (m, 1 H, ArH), 7.49 (d, 3JH,H = 8.0 Hz, 1 H,
3
3
4
3
4
7.24 (d, JH,H = 7.4 Hz, 1 H, ArH), 6.66 (dd, JH,H = 8.1, JH,H
=
ArH), 7.47–7.44 (m, 1 H, ArH), 7.42 (dt, JH,H = 7.7, JH,H =
1.5 Hz, 1 H, CH11-Ph), 6.62 (d, 3JH,H = 8.1 Hz, 1 H, CH11-Ph), 6.56 1.2 Hz, 1 H, ArH), 7.30 (dt, 3JH,H = 7.5, 4JH,H = 1.2 Hz 1 H, ArH),
4
3
3
(d, JH,H = 1.5 Hz, 1 H, CH11-Ph), 5.85 (d, JH,H = 3.1 Hz, 2 H,
CH11-Ph), 4.98 (s, 1 H, 11-H), 3.92 (s, 1 H, 12-H) ppm. 13C NMR
(150 MHz, CDCl3, 20 °C, TMS): δ = 173.5 (COCOOH), 161.7
7.18 (d, JH,H = 7.4 Hz, 1 H, ArH), 6.63–6.59 (m, 3 H, CH11-Ph),
4.89 (s, 1 H, 11-H), 3.94 (s, 1 H, 12-H), 3.74 (s, 1 H, OCH3), 3.65
(s, 3 H, OCH3) ppm. 13C NMR (150 MHz, CDCl3, 20 °C, TMS):
(COlactone), 148.1, 147.7, 146.5, 136.6, 134.8 (CHAr), 133.9, 131.3, δ = 176.9 (COCOOH), 161.9 (COlactone), 149.1, 148.3, 148.0, 136.5,
130.5 (CHAr), 129.9 (CHAr), 129.6 (CHAr), 128.2 (CHAr), 127.8, 135.1 (CHAr), 131.8, 130.6 (CHAr), 130.3, 130.3 (CHAr), 129.9
127.7 (CHAr), 122.8 (CHAr), 122.7 (CHAr), 121.1, 120.3 (CHAr), (CHAr), 128.8 (CHAr), 128.2, 128.1 (CHAr), 123.0 (CHAr), 122.7
110.4, 108.4 (CHAr), 107.4 (CHAr), 100.8 (CH2), 52.2 (C-12), 40.0 (CHAr), 121.3, 119.3 (CHAr), 111.2 (CHAr), 110.6, 110.1 (CHAr),
(C-11) ppm. IR (Nujol): ν = 1730 (C=O), 1680 (C=O), 1650 (C=C)
55.7 (OCH3), 55.7 (OCH3), 52.0 (C-12), 40.0 (C-11) ppm. IR
˜
cm–1. C25H16O6 (412.39): calcd. C 72.81, H 3.91, O 23.28; found C
72.92, H 4.19, O 22.89.
(CHCl ): ν = 1690 (C=O) cm–1. C H O ·1.5H O (455.46): calcd.
˜
3
26 20
6
2
C 68.56, H 5.09, O 26.35; found C 68.22, H 4.76, O 27.02.
382
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Eur. J. Org. Chem. 2011, 377–384