115.8, 100.2, 83.6, 42.1, 27.9, 26.0, 22.9, 18.0; IR (neat) 3061,
2971, 2922, 1718, 1642, 1608, 1565, 1451, 1365, 1279, 1178,
1111, 1034, 986, 910, 758, 726 cm-1; HRMS m/z (M+) calcd for
C19H20O3: 296.1412. Found: 296.1413.
J = 7.3 Hz), 8.07 (d, 1H, J = 8.1 Hz), 7.97 (d, 1H, J = 8.1 Hz),
7.67 (dd, 1H, J = 8.1, 7.3 Hz), 7.57 (dd, 1H, J = 8.1, 7.3 Hz), 6.51
(s, 1H), 5.17 (dd, 1H, J = 11.1, 5.1 Hz), 2.51–1.34 (m, 8H); 13
C
NMR (300 MHz, CDCl3) d 180.7, 158.3, 133.7, 133.6, 131.6,
131.3, 129.3, 128.1, 126.3, 126.0, 125.9, 125.6, 123.5, 111.1,
109.9, 79.1, 35.1, 33.0, 26.8, 24.4; IR (neat) 3060, 2933, 2857,
1632, 1577, 1422, 1383, 1296, 1198, 1026, 941, 861 cm-1; HRMS
m/z (M+) calcd for C20H16O2: 288.1150. Found: 288.1147.
2,9-Dimethyl-2-(4-methyl-pent-3-enyl)-2H-pyrano[3,2-c]chro-
men-5-one (27). Reaction of 4-hydroxy-6-methylcoumarin (7)
(176 mg, 1.0 mmol) with citral (305 mg, 2.0 mmol) afforded 27
(208 mg, 67%) as a liquid: 1H NMR (300 MHz, CDCl3) d 7.53
(s, 1H), 7.30 (d, 1H, J = 7.8 Hz), 7.16 (d, 1H, J = 7.8 Hz), 6.56 (d,
1H, J = 9.9 Hz), 5.44 (d, 1H, J = 9.9 Hz), 5.07 (t, 1H, J = 6.6 Hz),
2.39 (s, 3H), 2.15–2.08 (m, 2H), 1.92–1.82 (m, 1H), 1.77–1.67 (m,
1H), 1.59 (s, 3H), 1.53 (s, 3H), 1.49 (s, 3H); 13C NMR (75 MHz,
CDCl3) d 160.9, 158.9, 151.2, 133.5, 132.9, 132.0, 124.8, 123.3,
122.1, 117.7, 116.3, 114.9, 99.7, 82.9, 41.6, 27.4, 25.4, 22.4, 20.7,
17.5; IR (neat) 3056, 2969, 2922, 2860, 1715, 1642, 1571, 1496,
1448, 1421, 1358, 1316, 1276, 1210, 1162, 1120, 1040, 1017, 919,
817, 725 cm-1; HRMS m/z (M+) calcd for C20H22O3: 310.1569.
Found: 310.1566.
Ferprenin (34)24. Reaction of 4-hydroxycoumarin (6)
(162 mg, 1.0 mmol) with trans,trans-farnesal (440 mg, 2.0 mmol)
1
afforded 34 (222 mg, 61%) as a liquid: H NMR (300 MHz,
CDCl3) d 7.73 (d, 1H, J = 7.8 Hz), 7.45 (t, 1H, J = 7.8 Hz),
7.24–7.18 (m, 2H), 6.51 (d, 1H, J = 9.9 Hz), 5.41 (d, 1H, J =
9.9 Hz), 5.06–4.96 (m, 2H), 2.12–2.04 (m, 2H), 1.98–1.91 (m,
2H), 1.87–1.77 (m, 2H), 1.74–1.63 (m, 2H), 1.59 (s, 3H), 1.50
(s, 3H), 1.48 (s, 3H), 1.45 (s, 3H); 13C NMR (75 MHz, CDCl3)
d 160.8, 158.9, 153.0, 135.8, 131.9, 131.2, 125.0, 124.1, 123.8,
123.4, 123.0, 122.5, 117.1, 116.6, 115.3, 99.8, 83.0, 41.6, 39.5,
27.4, 26.5, 25.5, 22.3, 17.5, 15.8; IR(neat) 2955, 2919, 1719, 1625,
1564 1489, 1444, 1371, 1283, 1178, 1107, 1033, 909, 751 cm-1.
2-(4,8-Dimethyl-nona-3,7-direnyl)-2,7,7-trimethyl-2,6,7,8-
tetrahydro-chromen-5-one (28). Reaction of 5,5-dimethyl-1,3-
cyclohexanedione (2) (140 mg, 1.0 mmol) with trans,trans-
farnesal (440 mg, 2.0 mmol) afforded 28 (205 mg, 60%) as a
liquid: 1H NMR (300 MHz, CDCl3) d 6.42 (d, 1H, J = 9.9 Hz),
5.15 (d, 1H, J = 9.9 Hz), 5.09–5.05 (m, 2H), 2.24 (s, 2H), 2.22 (s,
2H), 2.04–1.91 (m, 6H), 1.77–1.50 (m, 2H), 1.65 (s, 3H), 1.57 (s,
3H), 1.55 (s, 3H), 1.34 (s, 3H), 1.04 (s, 6H); 13C NMR (75 MHz,
CDCl3) d 194.4, 170.4, 135.6, 131.4, 124.2, 123.5, 121.4, 116.3,
109.1, 82.4, 50.4, 42.4, 41.7, 39.6, 32.2, 28.6, 28.3, 27.5, 26.6,
25.6, 22.4, 17.7, 15.9; IR (neat) 2936, 1648, 1425, 1357, 1228,
1140, 1056, 888, 831, 743, 670 cm-1; HRMS m/z (M+) calcd for
C23H34O2: 342.2559. Found: 342.2558.
2-(4,8-Dimethyl-nona-3,7-dienyl)-2,9-dimethyl-2H-pyrano-
[3,2-c]chromen-5-one (35). Reaction of 4-hydroxy-6-methyl-
coumarin (7) (176 mg, 1.0 mmol) with trans,trans-farnesal
1
(440 mg, 2.0 mmol) afforded 35 (246 mg, 65%) as a liquid: H
NMR (300 MHz, CDCl3) d 7.54 (s, 1H), 7.30 (d, 1H, J = 8.1 Hz),
7.16 (d, 1H, J = 8.1 Hz), 6.55 (d, 1H, J = 9.9 Hz), 5.50 (d, 1H,
J = 9.9 Hz), 5.11–5.01 (m, 2H), 2.39 (s, 3H), 2.16–2.08 (m, 2H),
2.03–1.96 (m, 2H), 1.92–1.83 (m, 2H), 1.77–1.17 (m, 2H), 1.64 (s,
3H), 1.55 (s, 3H), 1.53 (s, 3H), 1.49 (s, 3H); 13C NMR (75 MHz,
CDCl3) d 161.0, 159.9, 151.3, 135.8, 133.6, 133.0, 131.3, 124.8,
124.1, 123.1, 122.2, 117.3, 116.4, 115.0, 99.8, 83.0, 41.7, 19.5,
27.4, 26.5, 25.6, 22.4, 20.8, 17.6, 15.9; IR(neat) 2920, 1714, 1637,
1435, 1367, 1205, 1124, 1027, 912, 821, 730 cm-1; HRMS m/z
(M+) calcd for C25H30O3: 378.2195. Found: 378.2195.
2,3,4,5,6,7,8,10a-Octahydro-xanthen-1-one (29). Reaction
of 1,3-cyclohexanedione (1) (112 mg, 1.0 mmol) with 1-
cylohexene-1-carboxaldehyde (220 mg, 2.0 mmol) afforded 29
(125 mg, 61%) as a liquid: 1H NMR (300 MHz, CDCl3) d 6.05
(s, 1H), 4.91 (dd, 1H, J = 10.9, 4.9 Hz), 2.35–2.30 (m, 6H), 1.95–
1.24 (m, 8H); 13C NMR (75 MHz, CDCl3) d 194.8, 171.5, 141.3,
122.9, 115.8, 79.7, 36.6, 36.4, 33.3, 31.0, 28.6, 28.4, 20.6; IR
(neat) 2942, 1645, 1518, 1404, 1171, 1073, 1019, 939, 869 cm-1;
HRMS m/z (M+) calcd for C13H16O2: 204.1150. Found: 204.1150
Flindersine (36)27. Reaction of 4-hydroxy-2(1H)-quinolone
(8) (161 mg, 1.0 mmol) with 3-methyl-2-butenal (168 mg,
2.0 mmol) afforded 36 (159 mg, 70%) as a solid: mp 195 ◦C;
1H NMR (300 MHz, CDCl3) d 11.5 (s,1H), 7.87 (d, 1H, J =
8.1 Hz), 7.46 (dd, 1H, J = 8.2, 7.4 Hz), 7.31 (d, 1H, J = 8.2 Hz),
7.17 (dd, 1H, J = 8.1, 7.4 Hz), 6.75 (d, 1H, J = 9.9 Hz), 5.54
(d, 1H, J = 9.9 Hz), 1.53 (s, 6H); 13C NMR (75 MHz, CDCl3)
d 162.6, 157.5, 137.9, 130.9, 126.2, 122.5, 122.2, 117.0, 116.2,
115.3,105.5, 79.2, 28.3; IR (KBr) 3152, 2975, 1651, 1630, 1599,
1499, 1433, 1411, 1361, 1278, 1132, 872 cm-1.
3,3-Dimethyl-2,3,4,5,6,7,8,10a-octahydro-xanthen-1-one (30).
Reaction of 5,5-dimethyl-1,3-cyclohexanedione (2) (140 mg,
1.0 mmol) with 1-cylohexene-1-carboxaldehyde (220 mg,
1
2.0 mmol) afforded 30 (179 mg, 77%) as a liquid: H NMR
(300 MHz, CDCl3) d 6.05 (s, 1H), 4.92 (dd, 1H, J = 10.9,
4.9 Hz), 2.37–2.05 (m, 6H), 1.95–1.20 (m, 6H), 1.04 (s, 3H),
1.03 (s, 3H); 13C NMR (75 MHz, CDCl3) d 194.5, 170.1, 122.7,
115.8, 109.6, 79.8, 50.4, 42.5, 35,1, 33.0, 32.2, 28.3, 26.8, 24.3;
IR (neat) 2955, 1644, 1630, 1617, 1404, 1258, 1231, 1146, 1074,
1041, 1008, 945 cm-1; HRMS m/z (M+) calcd for C15H20O2:
232.1463. Found: 232.1464.
N-Methylflindersine (37)28. Reaction of 4-hydroxy-1-
methyl-2(1H)-quinolone (9) (175 mg, 1.0 mmol) with
3-methyl-2-butenal (168 mg, 2.0 mmol) afforded 37 (154 mg,
◦
1
64%) as a solid: mp 80–81 C; H NMR (300 MHz, CDCl3) d
7.93 (d, 1H, J = 8.0 Hz), d 7.51 (dd, 1H, J = 8.3, 7.3 Hz), 7.28
(d, 1H, J = 8.3 Hz), d 7.19 (dd, 1H, J = 8.0, 7.3 Hz), 6.73 (d,
1H, J = 10.0 Hz), 5.51 (d, 1H, J = 10.0 Hz), 3.67 (s, 3H), 1.49 (s,
6H); IR (KBr) 2976, 1645, 1505, 1464, 1418, 1360, 1325, 1211,
1154, 1123, 1092, 1044, 1005, 987, 895 cm-1.
10,11,12,12a-Tetrahydro-9H -13-oxa-benzo[de]naphthacen-
7-one (31). Reaction of 3-hydoxy-1H-phenalen-1-one (5)
(196 mg, 1.0 mmol) with 1-cylohexene-1-carboxaldehyde
Haplamine (38). Reaction of 6-methoxyl-1H-quinoline-2,4-
dione (10) (190 mg, 1.0 mmol) with 3-methyl-2-butenal (168 mg,
2.0 mmol) afforded 38 (159 mg, 62%) as a solid: mp 202–203 ◦C;
1
(220 mg, 2.0 mmol) afforded 31 (202 mg, 70%) as a liquid: H
NMR (300 MHz, CDCl3) d 8.55 (d, 1H, J = 7.3 Hz), 8.13 (d, 1H,
2008 | Green Chem., 2010, 12, 2003–2011
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