1734
Vol. 56, No. 12
6,6ꢀ-Methylene-bis-[3-(2-anilinoacetyl)-4-hydroxycoumarin] (6) To a
stirred solution of 5 (0.01 mol) in ethanol (20 ml) was added arylamine
3.99 (4H, d), 4.03 (2H, s), 6.17 (4H, d, Jꢂ7.8 Hz), 6.98 (4H, d, Jꢂ8.2 Hz),
7.18 (2H, d, Jꢂ8.3 Hz), 7.23 (2H, d, Jꢂ7.8 Hz), 7.56 (2H, s), 8.99 (2H, t),
(0.02 mol) and the mixture was refluxed for 2 h. After completion of the re- 11.41 (2H, s). 13C-NMR d: 19.5, 43.4, 47.4, 100.1, 115.2, 115.8, 117.2,
action (monitored by TLC), the reaction mixture was poured into ice-cold 118.2, 127.6, 130.6, 131.4, 136.3, 148.0, 148.1, 156.8, 179.0, 182.3. MS
water. The crude product formed as solid was filtered, dried and subjected to m/z: 630 (Mꢃ).
coloumn chromatography over silica gel using 30% EtOAc in hexane as elu-
6,6ꢀ-Methylene-bis-[3-(4-methoxy-2-anilinoacetyl)-4-hydroxy-
ent to obtain pure product 6. A similar procedure was used to prepare the coumarin] (6f) Yellow solid, yield 87%, mp 132—134 °C. IR (KBr) cmꢁ1
:
1
other compounds 6b—f.
3450—3360, 2870, 1720, 1565, 1465, 1223, 1175. H-NMR (DMSO-d6) d:
5,5ꢀ-Methylene-bis-salicylic acid (2) White solid, yield 87%, mp 3.99 (4H, d), 3.82 (6H, s), 4.03 (2H, s), 6.21 (4H, d, Jꢂ7.8 Hz), 6.95 (4H, d,
1
238—240 °C (dec.). IR (KBr) cmꢁ1: 3410, 3062, 1702. H-NMR (DMSO- Jꢂ8.2 Hz), 7.16 (2H, d, Jꢂ8.2 Hz), 7.25 (2H, d, Jꢂ7.7 Hz), 7.57 (2H, s),
d6) d: 3.99 (2H, s), 6.92 (2H, d, Jꢂ9.1 Hz), 7.38 (2H, d, Jꢂ9.1 Hz), 7.42
8.97 (2H, t), 11.40 (2H, s). 13C-NMR d: 19.6, 43.4, 47.4, 100.1, 115.2,
(2H, s), 9.87 (2H, s), 10.90 (2H, s). 13C-NMR d: 44.7, 111.2, 123.8, 132.6, 115.9, 117.4, 118.2, 127.7, 130.6, 131.4, 136.3, 148.1, 148.2, 156.7, 179.1,
133.9, 137.9, 161.3, 176.7. MS m/z: 288 (Mꢃ).
182.4. MS m/z: 662 (Mꢃ).
5,5ꢀ-Methylene-bis-ethylsalicylate (3) Pink solid, yield 84%, mp
220—222 °C (dec.). IR (KBr) cmꢁ1: 3367, 3062, 1718, 1220. 1H-NMR
(DMSO-d6) d: 1.41 (6H, t, Jꢂ7.2 Hz), 3.94 (2H, s), 4.30 (4H, q, Jꢂ7.2 Hz),
7.10—7.76 (6H, m), 11.20 (2H, s). 13C-NMR d: 16.0, 43.8, 60.3, 113.4,
119.7, 128.3, 130.1, 131.9, 154.1, 170.2. MS m/z: 344 (Mꢃ).
Acknowledgement The authors thank the Director, Indian Institute of
Chemical Technology, Hyderabad, India for providing the spectral data.
References
6,6ꢀ-Methylene-bis-[(3-acetyl)-4-hydroxycoumarin] (4) Pink solid,
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yield 88%, mp 118—120 °C. IR (KBr) cmꢁ1: 3438, 3062, 1730, 1685, 1561,
1
1174. H-NMR (DMSO-d6) d: 2.32 (6H, s), 4.00 (2H, s), 7.22—7.70 (6H,
m), 11.60 (2H, s). 13C-NMR d: 20.9, 43.6, 101.2, 117.3, 119.1, 121.9, 130.7,
136.2, 149.8, 159.7, 178.3, 184.2. MS m/z: 420 (Mꢃ).
6,6ꢀ-Methylene-bis-[3-(2-bromoacetyl)-4-hydroxycoumarin] (5) Red
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1
1180, 586. H-NMR ( DMSO-d6) d: 3.92 (2H, s), 4.21 (4H, s), 7.14 (2H, d,
Jꢂ8.6 Hz), 7.18 (2H, d, Jꢂ8.6 Hz), 7.50 (2H, s), 15.07 (2H, s). 13C-NMR d:
31.9, 43.5, 101.0, 115.8, 118.2, 119.6, 131.4, 136.3, 149.2, 157.6, 182.1,
185.2. MS m/z: 578 (Mꢃ).
6,6ꢀ-Methylene-bis-[3-(2-anilinoacetyl)-4-hydroxycoumarin] (6a)
Brown solid, yield 88%, mp 168—170 °C. IR (KBr) cmꢁ1: 3451—3359,
1721, 1592, 1468, 1173. 1H-NMR (DMSO-d6) d: 3.95 (4H, d), 4.03 (2H, s),
6.73 (4H, d, Jꢂ8.3 Hz), 6.83 (6H, m), 7.18 (2H, d, Jꢂ8.6 Hz), 7.28 (2H, d,
Jꢂ8.3 Hz), 7.61 (2H, s), 8.89 (2H, t), 11.29 (2H, s). 13C-NMR d: 43.5, 47.4,
100.1, 114.0, 115.8, 116.8, 117.2, 118.2, 127.1, 131.4, 136.3, 147.8, 148.0,
156.8, 179.0, 182.3. MS m/z: 602 (Mꢃ).
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6,6ꢀ-Methylene-bis-[3-(3-nitro-2-anilinoacetyl)-4-hydroxycoumarin] 10) Pechmann V. H., Duisberg C., Chem. Ber., 17, 929—979 (1884).
(6b) Yellow solid, yield 87%, mp 138—140 °C. IR (KBr) cmꢁ1: 3450— 11) Perkin W. H., Henry W. Sr., J. Chem. Soc., 28, 10—11 (1875).
1
3354, 1719, 1590, 1518, 1470, 1171. H-NMR (DMSO-d6) d: 3.95 (4H, d)
4.03 (2H, s), 6.79 (2H, s), 7.09 (2H, m), 7.18 (2H, d, Jꢂ8.6 Hz), 7.26 (2H, d
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Jꢂ8.3 Hz), 7.31 (2H, d, Jꢂ7.2 Hz), 7.58 (2H, s), 7.73 (2H, d, Jꢂ7.1 Hz), 14) Cairns N., Harwood L. M., Astles D. P., J. Chem. Soc., Perkin Trans. I,
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115.8, 117.2, 118.2, 128.1, 131.4, 136.3, 146.4, 148.0, 153.4, 156.8, 179.0, 15) Mali R. S., Tilve S. A., Synth. Commun., 20, 1781—1791 (1990).
182.3. MS m/z: 716 (Mꢃ).
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(6c) Yellow solid, yield 84%, mp 180—181 °C. IR (KBr) cmꢁ1: 3455— 17) Cartwright G. A., McNab H., J. Chem. Res. (S), 1997, 296—300
1
3358, 1720, 1593, 1522, 1468, 1168. H-NMR (DMSO-d6) d: 3.99 (4H, d),
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4.03 (2H, s), 6.75 (4H, d, Jꢂ7.2 Hz), 7.18 (2H, d, Jꢂ8.3 Hz), 7.23 (2H, d, 18) Sanjeeva Reddy Ch., Nagaraj A., J. Heterocycl. Chem., 44, 1357—
Jꢂ7.7 Hz), 7.56 (2H, s), 7.94 (4H, d, Jꢂ7.1 Hz), 8.99 (2H, t), 11.41 (2H, s).
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139.1, 148.0, 151.7, 156.8, 179.0, 182.3. MS m/z: 716 (Mꢃ).
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(6d) Yellow solid, yield 89%, mp 184—186 °C. IR (KBr) cmꢁ1: 3460—
3350, 1724, 1560, 1465, 1172. H-NMR (DMSO-d6) d: 3.99 (4H, d), 4.03 21) Clemenson H., J. Am. Chem. Soc., 33, 737—741 (1911).
(2H, s), 6.47 (4H, d, Jꢂ8.1 Hz), 7.09 (4H, d, Jꢂ8.7 Hz), 7.18 (2H, d, 22) Bigi F., Chesini L., Maggi R., Sartori C., J. Org. Chem., 64, 1033—
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1
Jꢂ8.3 Hz), 7.23 (2H, d, Jꢂ7.7 Hz), 7.56 (2H, s), 8.99 (2H, t), 11.41 (2H, s).
13C-NMR d: 43.4, 47.4, 100.1, 115.9, 117.2, 118.2, 119.6, 124.1, 127.8,
131.4, 136.3, 147.5, 148.1, 156.8, 179.1, 182.3. MS m/z: 671 (Mꢃ).
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(6e) Yellow solid, yield 90%, mp 148—150 °C. IR (KBr) cmꢁ1: 3458—
3352, 2872, 1721, 1562, 1464, 1170. H-NMR (DMSO-d6) d: 2.00 (6H, s),
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1