Jul-Aug 2001
A Library of Pyranocoumarin Derivatives
969
H-9), 5.30 (dd, 1H, J = 2.6, 6.0 Hz, H-2), 4.23 (m, 1H, H-4), 2.67
OCH b), 2.46 (m, 1H, H-3a), 2.31 (m, 1H, H-3b), 1.12 (t, 3H, J =
2
13
13
(m, 1H, H-3a), 2.30 (m, 1H, H-3b); C nmr (CDCl ): δ 161.85 (C-
6.6 Hz, CH ); C nmr (CDCl ): δ 161.5 (C-5), 158.9 (C-10b),
3
3
3
5), 161.2 (C-10b), 152.9 (C-6a), 143.25 (C-1''), 139.0 (C-1'), 131.7
(C-8), 128.8 (C-3', C-2''), 128.7 (C-2'), 126.8 (C-3''), 126.6 (C-4'),
126.0 (C-4''), 123.75 (C-9), 122.9 (C-10), 116.6 (C-7), 115.7 (C-
10a), 104.9 (C-4a), 79.65 (C-2), 41.5 (C-4), 39.1 (C-3).
152.9 (C-6a), 142.95 (C-1'), 131.7 (C-8), 128.1 (C-2'), 127.45 (C-
3'), 126.2 (C-4'), 123.8 (C-9), 122.7 (C-10), 116.6 (C-7), 115.7
(C-10a), 103.8 (C-4a), 100.1 (C-2), 65.1 (OCH ), 35.8 (C-3),
2
35.1 (C-4), 15.0 (CH ).
3
Anal. Calcd for C
H
O : C, 81.34; H, 5.12. Found: C, 81.30;
Anal. Calcd for C H O : C, 75.41; H, 6.33. Found: C, 75.56;
24 18
3
22 22 4
H, 5.10.
H, 6.49.
2,3,4,5-Tetrahydro-2-[3'-(+)-menthyloxy]-4-phenylpyrano[3.2-c]-
benzopyran-5-one (6).
2,3,4,5-Tetrahydro-2-tert-butyloxy-4-phenylpyrano[3,2-c]ben-
zopyran-5-one (4).
The two diastereomers, after MPLC purification (petroleum
The two diastereomers, after CC purification (petroleum
ether/EtOAc 19:1), were colorless oils. R (hexane-EtOAc 8:2) =
ether/EtOAc 19:1), were colorless solids. R (hexane/EtOAc
f
f
8:2) = 0.54 (cis), 0.46 (trans); ir (KBr) 1713, 1626, 1493, 1088,
0.32 (cis), 0.29 (trans); ir (liquid film) 1815, 1690, 1410, 1299,
-1
+
-1
+
941, 758 cm ; ms: m/z 350(M ), 294, 265, 251, 175, 121; CI:
870, 750 cm ; ms: m/z 432 (M ), 294, 265, 251, 121; CI: 433
+
+
351 (MH ).
(MH ).
1
1
The trans-isomer has mp 162 °C; H nmr (CDCl ): δ 7.81 (d,
The trans-isomer has H nmr (CDCl ): δ 7.85 (d, 1H, J = 7.0
3
3
1H, J = 8.1 Hz, H-10), 7.53 (t, 1H, J = 7.7 Hz, H-8), 7.33 (m, 1H,
H-7), 7.29 (m, 1H, H-9), 7.27-7.24 (m, 5H, Ph), 5.51 (dd, 1H, J =
2.5, 8.0 Hz, H-2), 4.25 (dd, 1H, J = 5.8, 4.7 Hz, H-4), 2.33 (m,
Hz, H-10), 7.53 (t, 1H, J = 7.7 Hz, H-8), 7.33-7.27 (m, 2H, H-7,
H-9), 7.21-7.18 (m, 5H, Ph), 5.56 (dd, 1H, J = 3.0, 7.7 Hz, H-2),
4.18, (dd, 1H, J = 6.4 Hz, H-4), 3.63 (m, 1H, H-3'), 2.46 (m, 1H,
H-3a), 2.33 (m, 1H, H-3b), 2.27 (m, 1H, H-2'a), 1.62-1.60, (m,
4H, H-5'a, H-6'a,b, H-8'), 1.40 (m, 1H, H-1'), 1.33 (m, 1H, H-4')
0.93 (m, 1H, H-5'b), 0.89 (m, 3H, H-7'), 0.80 (m, 4H, H-2'b,
13
1H, H-3b), 2.12 (m, 1H, H-3a), 1.29 (s, 9H, t-But); C nmr
(CDCl ): δ 161.5 (C-5), 159.4 (C-10b), 152.9 (C-6a), 140.15
3
(C-1'), 131.6 (C-8), 128.7 (C-2'), 127.3 (C-3'), 126.7 (C-4'), 123.7
(C-9), 122.8 (C-10), 116.6 (C-7), 115.8 (C-10a), 102.3 (C-4a),
94.0 (C-2), 76.2 (C-t-But), 37.0 (C-3), 35.5 (C-4), 28.6 (t-But).
13
H-9'), 0.69 (br d, 3H, H-10'); C nmr (CDCl ): δ 161.7 (C-5),
3
159.3 (C-10b), 152.8 (C-6a), 142.8 (C-1''), 131.7 (C-8), 128.0
(C-3''), 127.3 (C-2''), 126.0 (C-4''), 123.87(C-9), 122.8 (C-10),
116.6 (C-7), 115.8 (C-10a), 103.5 (C-4a), 97.6 (C-2), 77.8 (C-3'),
47.3 (C-4'), 40.2 (C-2'), 36.8 (C-4), 35.4 (C-6'), 34.0 (C-3), 31.4
(C-1'), 25.0 (C-8'), 23.0 (C-5'), 22.2 (C-7'), 20.9 (C-9'), 15.9
(C-10').
Anal. Calcd for C
H
O : C, 75.41; H, 6.33. Found: C, 75.63;
22 22
4
H, 6.44.
1
The cis-isomer has mp 162 °C; H nmr (CDCl ): δ 7.81 (d, 1H,
3
J = 8.2 Hz, H-10), 7.53 (t, 1H, J = 7.8 Hz, H-8), 7.33 (m, 1H,
H-7), 7.29 (m, 1H, H-9), 7.27-7.24 (m, 5H, Ph), 5.67 (dd, 1H, J =
2.5, 5.5 Hz, H-2), 4.16 (m, 1H, H-4), 2.4 (m, 1H, H-3b), 2.27 (m,
Anal. Calcd for C
H
O : C, 77.75; H, 7.46. Found: C, 77.70;
28 32
4
13
1H, H-3a), 1.22 (s, 9H, t-But); C nmr (CDCl ): δ 161.5 (C-5),
H, 7.96.
3
1
159.35 (C-10b), 152.9 (C-6a), 140.1 (C-1'), 131.6 (C-8), 128.0
(C-2'), 126.2 (C-3'), 126.1 (C-4'), 123.7 (C-9), 122.8 (C-10),
116.6 (C-7), 115.9 (C-10a), 103.6 (C-4a), 95.1 (C-2), 76.2 (C-t-
But), 37.3 (C-3), 35.5 (C-4), 28.3 (t-But).
The cis-isomer has H nmr (CDCl ): δ 7.83 (d, 1H, J = 7.1 Hz,
3
H-10), 7.53 (t, 1H, J = 7.5 Hz, H-8), 7.33 (m, 1H, H-7), 7.27 (m,
1H, H-9), 7.21-7.18 (m, 5H, Ph), 5.47 (dd, 1H, J = 2.5, 4.6 Hz,
H-2), 4.08, (dd, 1H, J = 6.0 Hz, H-4), 3.38 (m, 1H, H-3'), 2.46 (m,
1H, H-3a), 2.33 (m, 1H, H-3b), 2.27 (m, 1H, H-2'a), 1.62-1.60,
(m, 4H, H-5'a, H-6'a,b, H-8'), 1.40 (m, 1H, H-1'), 1.33 (m, 1H,
H-4') 0.93 (m, 1H, H-5'b), 0.89 (m, 3H, H-7'), 0.80 (m, 1H, H-
Anal. Calcd for C
H O : C, 75.41; H, 6.33. Found: C, 75.33;
22 22 4
H, 6.34.
2,3,4,5-Tetrahydro-2-ethoxy-4-phenylpyrano[3,2-c]benzopyran-
5-one (5).
13
2'b), 0.68 (br d, 3H, H-9'), 0.62 (br d, 3H, H-10'); C nmr
(CDCl ): δ 161.7 (C-5), 159.2 (C-10b), 152.8 (C-6a), 143.0
3
The two diastereomers, after CC purification (petroleum
(C-1''), 131.7 (C-8), 128.0 (C-3''), 127.3 (C-2''), 126.0 (C-4''),
123.8(C-9), 122.7 (C-10), 116.7 (C-7), 115.8 (C-10a), 103.5
(C-4a), 101.5 (C-2), 82.4 (C-3'), 48.0 (C-4'), 43.2 (C-2'), 36.0
(C-4), 35.0 (C-6'), 34.0 (C-3), 31.6 (C-1'), 25.2 (C-8'), 23.0
(C-5'), 22.3 (C-7'), 20.9 (C-9'), 15.9 (C-10').
ether/EtOAc 19:1), were colorless solids. R (hexane/EtOAc 8:2) =
f
0.45 (cis), 0.36 (trans); ir (KBr) 1713, 1626, 1493, 1084, 849, 758
-1
+
+
cm ; ms: m/z 322(M ), 293, 265, 249, 121; CI 323 (MH ).
1
The trans-isomer has mp 142 °C; H nmr (CDCl ): δ 7.87 (br
d, 1H, J = 7.2 Hz, H-10), 7.53 (t, 1H, J = 7.8 Hz, H-8), 7.33 (m,
7H, H-7, Ph, H-9), 5.27 (dd, 1H, J = 3.0, 7.7 Hz, H-2), 4.25 (dd,
3
Anal. Calcd for C
H O : C, 77.75; H, 7.46. Found: C, 77.66;
28 32 4
H, 7.60.
1H, J = 6.0 Hz, H-4), 4.08 (m, 1H, OCH a), 3.69 (m, 1H,
2
2,3,4,5-Tetrahydro-2-methyl-2-methoxy-4-phenylpyrano[3,2-c]-
benzopyran-5-one (7).
OCH b), 2.30-2.28 (m, 2H, H-3a, H-3b), 1.28 (t, 3H, J = 6.6 Hz,
2
13
CH ); C nmr (CDCl ): δ 161.5 (C-5), 158.9 (C-10b), 152.9 (C-
3
3
6a), 142.95 (C-1'), 131.7 (C-8), 128.7 (C-2'), 127.45 (C-3'), 126.2
(C-4'), 123.8 (C-9), 122.7 (C-10), 116.6 (C-7), 115.7 (C-10a),
The two diastereomers, after CC purification (petroleum
ether/EtOAc 19:1), were white powders. R (hexane / EtOAc
f
105.0 (C-4a), 99.3 (C-2), 65.6 (OCH ), 35.8 (C-3), 35.4 (C-4),
8:2) = 0.43 (cis), 0.34 (trans); ir (KBr) 1709, 1626, 1493, 1068,
2
-1
+
15.2 (CH ).
978, 752 cm ; ms: m/z 322(M ), 275, 265, 249, 148, 121; CI:
3
+
Anal. Calcd for C
H
O : C, 75.41; H, 6.33. Found: C, 75.63;
323 (MH ).
22 22
4
1
H, 6.44.
The trans -isomer has mp 170 °C; H nmr (CDCl ): δ 7.90 (d,
1H, J = 7.6 Hz, H-10), 7.57 (br t, 1H, J = 7.2 Hz, H-8), 7.33-7,23
(m, 7H, H-9, Ph, H-7), 4.13 (dd, 1H, J = 7.0, 4.0 Hz, H-4), 4.08
3
1
The cis -Isomer has mp 144 °C; H nmr (CDCl ): δ 7.87 (br d,
1H, J = 7.1 Hz H-10), 7.53 (t, 1H, J = 7.8 Hz, H-8), 7.32-7.23 (m,
7H, H-7, Ph, H-9), 5.44 (dd, 1H, J = 2.5, 4.6 Hz, H-2), 4.15 (dd,
3
(s, 3H, OCH ), 2.48 (m, 1H, H-3a), 2.33 (m, 1H, H-3b), 1.63 (s,
3
13
1H, J = 6.0 Hz, H-4), 3.95 (m, 1H, OCH a), 3.62 (m, 1H,
3H, CH ); C nmr (CDCl ): δ 161.5 (C-5), 158.9 (C-10b), 152.8
2
3
3