March 2014
A New Method for the Facile Synthesis of Hydroxylated Flavones by Using Allyl Protection
297
ion); Anal. Calcd. for C18H14Cl2O3: C, 61.91; H, 4.04%. Found: C,
61.78; H, 3.98%.
120.54, 120.26, 118.45, 116.37, 111.35, 71.84, 56.23, 25.21;
MS(m/z): 416 (M+ ion); Anal. Calcd. for C26H24O5: C, 74.98;
H, 5.81%. Found: C, 74.75; H, 5.96%.
1-(2′-Hydroxy-5′-methyl-phenyl)-3-(3-methoxy-4-allyloxyphenyl)-
prop-2-enÀ1-one (5d). Yellow solid; mp 78ꢀC; IR (KBr): 2930,
2869, 1887, 1627, 1558, 1467, 1342, 1292, 1288, 1242, 1179,
1-(2′-Hydroxy-4′-benzyloxy-phenyl)-3-(3-allyloxy-4-
methoxyphenyl)-prop-2-enÀ1-one (5i).
124ꢀC; IR (KBr): 2933, 2869, 1886, 1632, 1557, 1469, 1344,
1298, 1281, 1243, 1175, 1133, 1005, 949, 816, 752, 673 cmÀ1
Yellow solid; mp
1130, 1002, 947, 815, 751, 678 cmÀ1 1H NMR (300 MHz,
;
CDCl3): d 7.87 (d, J = 15.3Hz, 1H), 7.66 (s, 1H), 7.51 (d,
J = 15Hz, 1H), 7.39 (m, 2H), 7.16(d, J = 2.1 Hz, 1H), 6.93 (dd,
J = 3.9,4.5 Hz, 2H), 6.12 (m, 1H), 5.45 (dd, J = 18.3, 11.7Hz, 2H),
4.68(d, J = 5.7 Hz, 2H), 3.96(s, 3H), 2.32 (s, 3H); 13C NMR
(300MHz, CDCl3): d 182.20, 158.30, 150.88, 149.60, 147.12,
136.30, 132.82, 128.43, 127.23, 123.78, 123.26, 121.60, 120.63,
120.15, 118.22, 116.62, 111.23, 71.80, 56.15, 24.71; MS(m/z):
324 (M+ ion); Anal. Calcd. for C20H20O4: C, 74.06; H, 6.21%.
Found: C, 74.13; H, 6.26%.
;
1H NMR (300MHz, CDCl3): d 7.82 (dd, J = 7.2, 4.7 Hz, 2H),
7.61 (m, 5H), 7.35 (m, 2H), 6.93 (dd, J = 8.7, 8.2 Hz, 2H), 6.77
(m, 2H), 6.12 (m, 1H), 5.44 (dd, J = 17.4, 10.1 Hz, 2H), 5.11 (d,
J = 2.7Hz, 2H), 4.69 (m, 2H), 3.93 (s, 3H); 13C NMR (300MHz,
CDCl3): d 182.27, 157.56, 151.21, 149.13, 147.32, 135.58,
132.30, 128.47, 127.23, 123.71, 123.08, 121.18, 120.35, 120.62,
118.76, 116.28, 111.42, 71.19, 56.25, 24.78; MS(m/z): 416
(M+ ion); Anal. Calcd. for C26H24O5: C, 74.98; H, 5.81%.
Found: C, 74.73; H, 5.95%.
1-(2′-Hydroxy-5′-methyl-phenyl)-3-(2-allyloxyphenyl)-prop-
2-enÀ1-one (5e).
2864, 1899, 1633, 1560, 1488, 1446, 1346, 1290, 1247, 1180,
1128, 1008, 945, 817, 748, 675 cmÀ1 1H NMR (300 MHz,
Yellow solid; mp 73ꢀC; IR (KBr): 2922,
1-(2′-Hydroxy-4′-benzyloxy-phenyl)-3-(2-allyloxyphenyl)-
prop-2-enÀ1-one (5j). Yellow solid; mp 118ꢀC; IR (KBr): 2928,
2862, 1881, 1630, 1552, 1464, 1345, 1293, 1284, 1245, 1176,
;
CDCl3): d 8.19 (d, J = 15.3Hz, 1H), 7.88 (d, J = 15.6Hz, 1H),
7.66 (m, 2H), 7.38 (m, 2H), 7.03 (m, 3H), 6.19 (m, 1H), 5.52
(dd, J = 17.1, 10.5Hz, 2H), 4.66 (d, J = 5.4Hz, 2H), 2.33 (s, 3H);
13C NMR (300 MHz, CDCl3): d 189.82, 158.51, 156.78, 144.99,
136.81, 133.58, 132.85, 128.52, 127.28, 123.88, 120.56, 121.15,
118.22, 116.85, 114.22, 112.48, 110.56, 72.68. 23.92; MS(m/z):
294 (M+ ion); Anal. Calcd. for C19H18O3: C, 77.53; H, 6.16%.
Found: C, 77.39; H, 6.25%.
1137, 1007, 945, 818, 751, 670 cmÀ1 1H NMR (300 MHz,
;
CDCl3): d 7.81 (dd, J = 7.4, 4.8 Hz, 2H), 7.62 (m, 5H), 7.33 (m,
2H), 6.92 (dd, J = 8.7, 8.1 Hz, 2H), 6.76 (m, 3H), 6.09 (m, 1H),
5.45 (dd, J = 17.2, 10.3 Hz, 2H), 5.13 (d, J = 2.7 Hz, 2H), 4.68
(m, 2H); 13C NMR (300 MHz, CDCl3): d 189. 17, 158.45,
151.39, 149.29, 147.45, 135.61, 132.35, 128.48, 127.47,
123.36, 123.13, 121.24, 120.52, 120.28, 118.71, 116.68,
111.39, 71.28, 56.28, 24.72; MS(m/z): 386 (M+ ion); Anal.
Calcd. for C25H22O4: C, 77.70; H, 5.74%. Found: C, 77.87; H,
5.59%.
1-(2′-Hydroxy-phenyl)-3-(3-allyloxy-4-methoxyphenyl)-prop-
2-enÀ1-one (5f). Yellow solid; mp 73ꢀC; IR (KBr): 2928, 2863,
1884, 1625, 1553, 1464, 1346, 1295, 1286, 1247, 1181, 1132,
1-(2′-Hydroxy-4′-allyloxyphenyl)-3-(3-allyloxy-4-methoxyphenyl)-
prop-2-enÀ1-one (5k). Yellow solid; mp 89ꢀC; IR (KBr): 2931,
2858, 1882, 1623, 1555, 1466, 1346, 1291, 1284, 1249, 1179,
1
1005, 949, 812, 749, 675 cmÀ1; H NMR (300MHz, CDCl3): d
7.89 (d, J = 15.4 Hz, 1H), 7.62 (s, 1H), 7.49 (d, J = 15.3 Hz, 1H),
7.35 (m, 2H), 7.14 (m, 1H), 6.78 (m, 3H), 6.11 (m, 1H), 5.43
(dd, J = 18.4, 11.8Hz, 2H), 4.65 (d, J = 5.8 Hz, 2H), 3.95 (s, 3H);
13C NMR (300 MHz, CDCl3): d 181.19, 157.32, 151.56, 149.61,
147.23, 136.32, 132.75, 128.37, 127.28, 124.15, 123.23, 121.55,
120.48, 120.16, 118.31, 116.49, 111.28, 71.85, 56.14, 23.89; MS
(m/z): 310 (M+ ion); Anal. Calcd. for C19H18O4: C, 73.53; H,
5.85%. Found: C, 73.46; H, 5.94%.
1135, 1001, 946, 814, 747, 678cmÀ1 1H NMR (300MHz,
;
CDCl3): d 7.90 (d, J = 15.2 Hz, 1H), 7.56 (s, 1H), 7.48 (m, 1H),
6.84 (m, 2H), 6.58 (m, 3H), 6.09 (m, 2H), 5.42 (dd, J = 18.2,
11.4Hz, 4H), 4.45 (d, J = 5.7 Hz, 4H), 3.93 (s, 3H); 13C NMR
(300 MHz, CDCl3): d 190.23, 158.32, 151.67, 149.63, 147.25,
136.72, 132.87, 128.42, 127.19, 124.18, 123.34, 121.65, 120.26,
120.13, 118.27, 116.61, 111.82, 72.66, 56.14, 24.89; MS(m/z):
366 (M+ ion); Anal. Calcd. for C22H22O5: C, 72.12; H, 6.05%.
Found: C, 72.34; H, 5.92%.
1-(2′-Hydroxy-5′-chloro-phenyl)-3-(3-allyloxy-4-methoxyphenyl)-
prop-2-enÀ1-one (5g). Yellow solid; mp 84ꢀC; IR (KBr): 2924,
2866, 1883, 1629, 1555, 1462, 1347, 1298, 1285, 1246, 1183,
1-(2′,4′-Diallyloxyphenyl)-3-(3-allyloxy-4-methoxyphenyl)-
1135, 1002, 953, 818, 747, 674 cmÀ1
;
1H NMR (300 MHz,
prop-2-enÀ1-one (5l).
1005, 945, 815, 746, 676 cmÀ1; H NMR (300 MHz, CDCl3):
Thick oil; IR (KBr): 2935, 2852,
CDCl3): d 7.91 (d, J = 15.3 Hz, 1H), 7.70 (s, 1H), 7.54 (d,
J = 15.5 Hz, 1H), 7.38 (m, 1H), 7.22 (m, 2H), 6.59 (m, 2H),
6.13 (m, 1H), 5.48 (dd, J = 18.2, 12.1 Hz, 2H), 4.64 (d,
J = 5.7 Hz, 2H), 3.93 (s, 3H); 13C NMR (300 MHz, CDCl3):
d 182.53, 156.44, 151.52, 149.38, 147.72, 136.29, 132.63,
127.85, 127.23, 124.26, 123.17, 121.47, 120.61, 120.19,
118.41, 116.56, 111.14, 71.52, 56.19, 24.55; MS(m/z): 344
(M+ ion); Anal. Calcd. for C19H17ClO4: C, 66.19; H, 4.97%.
Found: C, 66.27; H, 4.88%.
1884, 1625, 1558, 1464, 1345, 1292, 1288, 1250, 1182, 1137,
1
d 7.91 (d, J = 15.2 Hz, 1H), 7.58 (s, 1H), 7.46 (m, 1H), 6.82
(m, 2H), 6.57 (m, 3H), 6.07 (m, 3H), 5.44 (dd, J = 18.6,
11.2 Hz, 6H), 4.47 (d, J = 5.6 Hz, 6H), 3.93 (s, 3H); 13C NMR
(300 MHz, CDCl3): d 190.09, 159.12, 151.42, 149.17, 149.09,
133.91, 132.87, 128.42, 127.19, 119.34, 119.65, 118.26,
118.13, 116.34, 113.61, 106.82, 72.66, 72.12, 56.14; MS(m/z):
406 (M+ ion); Anal. Calcd. for C25H26O5: C, 73.87; H, 6.45%.
Found: C, 73.99; H, 6.29%.
1-(2′-Hydroxy-4′-benzyloxy-phenyl)-3-(3-methoxy-4-
allyloxyphenyl)-prop-2-enÀ1-one (5h).
Yellow solid; mp
1-(2′-Hydroxy-5′-chloro-phenyl)-2-methyl-3-(2-allyloxyphenyl)-
prop-2-enÀ1-one (5m). Yellow solid; mp 84ꢀC; IR (KBr): 2936,
2872, 1909, 1695, 1636, 1562, 1414, 1351, 1284, 1248, 1178, 1003,
127ꢀC; IR (KBr): 2939, 2870, 1889, 1631, 1556, 1466, 1345,
1294, 1286, 1245, 1177, 1132, 1007, 951, 818, 753, 675cmÀ1
;
1H NMR (300 MHz, CDCl3): d 7.84 (dd, J = 7.2, 4.8 Hz, 2H),
7.63 (m, 5H), 7.33 (m, 2H), 6.96 (dd, J = 8.7, 8.1 Hz, 2H), 6.78
(m, 2H), 6.13 (m, 1H), 5.44 (dd, J = 17.4, 9.9 Hz, 2H), 5.10 (d,
J = 2.7 Hz, 2H), 4.70 (m, 2H), 3.94 (s, 3H); 13C NMR
(300 MHz, CDCl3): d 182.36, 157.27, 150.82, 149.43, 147.26,
135.44, 132.76, 128.59, 127.34, 123.76, 123.19, 121.23,
956, 855, 746, 642 cmÀ1 1H NMR (300 MHz, CDCl3): d 7.85
;
(m, 1H), 7.67 (d, J= 2.1 Hz, 3H), 7.56 (m, 3H), 7.23 (m, 1H), 6.09
(m, 1H), 5.48 (dd, J= 17.1, 11.1 Hz, 2H), 4.67 (dd, J= 4.5, 5.1 Hz,
2H), 3.38 (s, 3H); 13C NMR (300 MHz, CDCl3): d 190.51, 156.78,
135.61, 133.28, 132.48, 131.43, 129.81, 128.43, 127.63, 127.40,
124.02, 123.30, 120.21, 118.06, 117.78, 116.50, 115.12, 69.15,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet