424 JOURNAL OF CHEMICAL RESEARCH 2015
O
O
H
_
H2O
O
O
2 + 3
H
O
Ar
O
N
O
O
O
5
_
_
O
+
4
N
_
CO2
H
_
Ar
H
H
O
H
O
HN
7
1
6
Scheme 2
1
Experimental
71.62; H, 4.01; N, 4.22%. MS (m/z, %): 319 (10). H NMR (400 MHz,
CDCl3): δ 2.92 (1H, d, J 16 Hz, CH), 3.28 (1H, dd, 2JHH 16.0 Hz, 3JHH 7.2
Elemental analyses were performed using a Heraeus CHN–O–Rapid
analyser. Mass spectra were recorded on a Finnigan-Mat 8430 mass
spectrometer operating at an ionisation potential of 70 eV. IR spectra were
recorded on a Shimadzu IR-470 spectrometer. 1H and 13C NMR spectra
were recorded on Bruker DRX-400 Avance spectrometer at solution in
CDCl3 using TMS as internal standard. The chemicals used in this work
were purchased from Fluka (Buchs, Switzerland) and were used without
further purification.
3
Hz, CH), 5.63 (1H, d, JHH 6.0 Hz, CH), 7.15–8.11 (10H, m, aromatic)
ppm. 13C NMR (100.6 MHz, CDCl3): δ 42.10 (CH), 45.89 (CH2), 118.53,
120.78, 122.30, 122.95, 124.36, 126.41, 128.53, 128.72, 129.03, 130.12,
133.62, 145.27, 152.97, 153.09 and 168.97 ppm.
1-(3-Methoxyphenyl)-1,2-dihydro-3H-naphtho[2,1-b]pyran-3-ones
(4e): Yellow oil, IR (KBr) (νmax cm-1): 1763, 1605, 1524, 1452, 1301,
1267, 1170, 1100, 1025. Anal. calcd for C20H16O3: C, 78.93; H, 5.30%;
found: C, 79.08; H, 5.46%. MS (m/z, %): 304 (5). 1H NMR (400 MHz,
CDCl3): δ 2.83 (1H, d, J 16 Hz, CH), 3.45 (1H, dd, 2JHH 16.0 Hz, 3JHH
7.2 Hz, CH), 3.78 (3H, s, OCH3), 4.52 (1H, d, 3JHH 6.0 Hz, CH), 6.95–7.84
(10H, m, aromatic) ppm.13C NMR (100.6 MHz, CDCl3): δ 42.08 (CH),
45.78 (CH2), 56.57 (OCH3), 111.55, 113.63, 119.12, 119.27, 119.74, 123.35,
124.05, 127.38, 129.20, 129.42, 129.98, 130.18, 133.25, 145.38, 154.10,
159.82 and 169.05 ppm.
1-(4-Methoxyphenyl)-1,2-dihydro-3H-naphtho[2,1-b]pyran-3-ones
(4f): Yellow oil, IR (KBr) (νmax cm-1): 1770, 1603, 1511, 1459, 1306, 1254,
1171, 1103, 1031. Anal. calcd for C20H16O3: C, 78.93; H, 5.30%; found: C,
79.09; H, 5.50%. MS (m/z, %): 304 (7). 1H NMR (400 MHz, CDCl3): δ
3.01 (1H, d, J 16 Hz, CH), 3.39 (1H, dd, 2JHH 16.0 Hz, 3JHH 7.2 Hz, CH),
General procedure
β-Naphthol (1 mmol, 0.144 g) under reflux conditions was added to a
stirred solution of the Meldrum’s acid (1 mmol, 0.144 g) and aryl aldehyde
(1 mmol) in methanol (10 mL), in the presence of basic catalytic amount
of piperidine (three drops),. The reaction progress was controlled by TLC
(n-hexane/ethyl acetate, 1:1). After 3 h, the reaction was complete and the
solvent was removed under reduced pressure to afford the product.
1-Phenyl-1,2-dihydro-3H-naphtho[2,1-b]pyran-3-ones (4a): Yellow
oil, IR (KBr) (νmax cm-1): 1775, 1599, 1512, 1452, 1254, 1171, 1137, 1025.
Anal. calcd for C19H14O2: C, 83.19; H, 5.14%; found: C, 83.31; H, 5.23%.
MS (m/z, %): 274 (4). 1H NMR (400 MHz, CDCl3): δ 2.73 (1H, d, J 16
Hz, CH), 3.24 (1H, dd, 2JHH 16.0 Hz, 3JHH 7.2 Hz, CH), 4.95 (1H, d, 3JHH
6.0 Hz, CH), 7.14–7.82 (11H, m, aromatic) ppm. 13C NMR (100.6 MHz,
CDCl3): δ 41.63 (CH), 45.56 (CH2), 118.87, 119.76, 124.21, 124.31,
126.52, 127.38, 128.78, 129.40, 129.70, 130.14, 133.19, 141.79, 150.93,
156.07 and 168.82 ppm.
1-(2-Chlorophenyl)-1,2-dihydro-3H-naphtho[2,1-b]pyran-3-ones
(4b): Yellow oil, IR (KBr) (νmax cm-1): 1771, 1608, 1511, 1493, 1270,
1176, 1129, 1019. Anal. calcd for C19H13ClO2: C, 73.91; H, 4.24%;
found: C, 74.00; H, 4.39%. MS (m/z, %): 308 (7). 1H NMR (400 MHz,
CDCl3): δ 2.84 (1H, d, J 16 Hz, CH), 3.35 (1H, dd, JHH 16.0 Hz, JHH
7.2 Hz, CH), 5.06 (1H, d, 3JHH 6.0 Hz, CH), 7.14–8.03 (10H, m, aromatic)
ppm. 13C NMR (100.6 MHz, CDCl3): δ 42.31 (CH), 45.84 (CH2), 118.25,
119.75, 123.40, 124.55, 125.92, 127.10, 127.81, 129.17, 130.07, 130.66,
131.05, 133.54, 140.36, 142.02, 150. 47, 155.74 and 169.80 ppm.
3
3.62 (3H, s, OCH3), 4.22 (1H, d, JHH 6.0 Hz, CH), 7.11–7.72 (10H, m,
aromatic) ppm. 13C NMR (100.6 MHz, CDCl3): δ 42.23 (CH), 45.70
(CH2), 56.49 (OCH3), 119.28, 123.45, 124.26, 126.35, 127.40, 128.59,
129.47, 129.85, 130.02, 130.62, 133.7, 145.6, 154.22, 159.38 and 168.73
ppm.
1-(4-Methylphenyl)-1,2-dihydro-3H-naphtho[2,1-b]pyran-3-ones
(4g). Yellow oil, IR (KBr) (νmax cm-1): 1734, 1593, 1512, 1455, 1375, 1299,
1217, 1165, 1023. Anal. calcd for C20H16O2: C, 83.31; H, 5.59%; found:
C, 83.49; H, 5.74%. MS (m/z, %): 288 (6). 1H NMR (400 MHz, CDCl3):
δ 2.31 (3H, s, CH3), 2.73 (1H, d, J 16 Hz, CH), 3.34 (1H, dd, 2JHH 16.0
Hz, 3JHH 7.2 Hz, CH), 4.92 (1H, d, 3JHH 6.0 Hz, CH), 7.31–7.82 (10H, m,
aromatic) ppm. 13C NMR (100.6 MHz, CDCl3): δ 23.70 (CH3), 42.36
(CH), 45.55 (CH2), 110.49, 119.22, 120.38, 124.07, 127.32, 127.39, 128.83,
129.54, 129.45, 130.64, 136.07, 141.30, 143.84, 156.19 and 171.72 ppm.
2
3
1-(4-Bromophenyl)-1,2-dihydro-3H-naphtho[2,1-b]pyran-3-ones
(4c): Yellow oil, IR (KBr) (νmax cm-1): 1775, 1595, 1513, 1485, 1263,
1178, 1136, 1010. Anal. calcd for C19H13BrO2: C, 64.61; H, 3.71%;
found: C, 64.44; H, 3.50%. MS (m/z, %): 353 (5). 1H NMR (400 MHz,
15 June 2015; accepted 26 June 2015
Published online: 9 July 2015
CDCl3): δ 2.87 (1H, d, J 16 Hz, CH), 3.26 (1H, dd, JHH 16.0 Hz, 3JHH
2
7.2 Hz, CH), 4.92 (1H, d, 3JHH 6.0 Hz, CH), 6.99–7.88 (10H, m, aromatic)
ppm. 13C NMR (100.6 MHz, CDCl3): δ 38.36 (CH), 45.55 (CH2), 118.65,
120.42, 122.66, 124.09, 126.68, 127.39, 127.50, 129.97, 130.28, 130.69,
132.27, 140.88, 150.91, 154.94, 168.31 ppm.
References
1
2
I. Yavari, and A. Ramazani, Synth. Commun., 1997, 27, 1385.
I. Ugi, Angew. Chem. Int Ed Engl., 1982, 21, 810.
A. Dömling and I. Ugi, Angew. Chem. Int Ed., 2000, 39, 3169.
A. Dömling, Chem. Rev., 2006, 106, 17.
1-(4-Nitrophenyl)-1,2-dihydro-3H-naphtho[2,1-b]pyran-3-ones (4d):
Yellow oil, IR (KBr) (νmax cm-1): 1709, 1612, 1513, 1465, 1347, 1269, 1136,
1072. Anal. calcd for C19H13NO4: C, 71.47; H, 4.10; N, 4.39%; found: C,
3
4
5