9
6
E.A. Porter et al. / Phytochemistry 81 (2012) 90–96
3
00 °C at 6 °C/min, injection temp. 350 °C, and helium as the carrier
Acknowledgements
gas at 1 ml/min. The acid hydrolysates of 4 and 10 each gave L-
rhamnose and
D
-galactose at t
R
= 10.2 and 12.2 min, respectively
The authors thank Boots the Chemist (Nottingham) for the ini-
tial supply of leaf material and financial support, the Medical Re-
search Council Biomedical NMR Centre, National Institute for
Medical Research, Mill Hill, London, for access to high-field NMR
facilities, Mr. Jonathon Reichl and Miss. Lauren Gooch for technical
assistance, and staff at the Herbarium, Royal Botanic Gardens, Kew,
for guidance in the sampling of herbarium material.
(
identical to authentic standards).
3.6. Quercetin 3-O-
a-
L-rhamnopyranosyl-(1 ? 2)-[6-O-(3-hydroxy-3-
methylglutaryl)-b-
D-galactopyranoside] (4)
UV (LC-PDA) kmax nm: 256, 292 (sh), 356; 1H NMR (DMSO-
Appendix A. Supplementary data
0
d
6
+D
2
O): d 7.51 (1H, dd, J = 8.4, 2.1 Hz, H-6 ), 7.44 (1H, d,
0
0
J = 2.1 Hz, H-2 ), 6.78 (1H, d, J = 8.5 Hz, H-5 ), 6.11 (1H, br s, H-8),
.92 (1H, br s, H-6); b-Gal (primary): 5.38 (1H, d, J = 7.8 Hz, Gal
H-1), 3.71 (1H, dd, J = 9.6, 7.7 Hz, Gal H-2), 3.55 (1H, dd, J = 9.7,
.4 Hz, Gal H-3), 3.65 (1H, br d, J = 3.6 Hz, Gal H-4), 3.56 (1H, m,
Gal H-5), 3.94 (1H, dd, J = 11.3, 7.8 Hz, Gal H-6a), 3.87 (1H, dd,
J = 11.3, 5.0 Hz, Gal H-6b); -Rha (terminal): 4.97 (1H, d,
J = 1.6 Hz, Rha H-1), 3.77 (1H, dd, J = 3.4, 1.7 Hz, Rha H-2), 3.53
1H, dd, J = 9.6, 3.4 Hz, Rha H-3), 3.15 (1H, t, J = 9.6 Hz, Rha H-4),
.81 (1H, dd, J = 9.6, 6.2 Hz, Rha H-5), 0.83 (3H, d, J = 6.2 Hz, Rha
H-6); HMG: 2.16 (1H, d, J = 13.3 Hz, H-2a), 2.09 (1H, d,
J = 13.3 Hz, H-2b), 0.87 (3H, s, 3-CH ), 2.06 (1H, d, J = 15.4 Hz, H-
5
3
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(
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H
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20 , 753.1884); LC–ESI–MS/MS (ion trap) of [MꢀH] , m/z
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rel. int.): 691 (3), 651 (5), 609 [(MꢀH)ꢀHMG] (100); LC–ESI–
3
MS (m/z 753 ? 609), m/z (rel. int.): 489 (13), 445 (loss of rham-
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H-3 /5 ), 6.41 (1H, d, J = 2.1 Hz, H-8), 6.17 (1H, d, J = 2.1 Hz, H-6);
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3
.65 (1H, br d, J = 3.5 Hz, Gal H-4), 3.57 (1H, m, Gal H-5), 4.00
1H, dd, J = 11.5, 8.0 Hz, Gal H-6a), 3.85 (1H, dd, J = 11.5, 4.1 Hz,
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s, 3-CH ), 2.03 (1H, d, J = 15.4 Hz, H-4a), 1.86 (1H, d, J = 15.4 Hz,
(
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29, 205–211.
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0
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0
5
), 99.6 (C-6), 94.7 (C-8); b-Gal (primary): 99.3 (Gal C-1), 76.1
(
Gal C-2), 73.9 (Gal C-3), 69.1 (Gal C-4), 73.3 (Gal C-5), 63.6 (Gal
C-6); -Rha (terminal): 101.3 (Rha C-1), 70.9 (Rha C-2), 71.0 (Rha
C-3), 72.4 (Rha C-4), 68.9 (Rha C-5), 17.5 (Rha C-6); HMG: 171.5
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3
);
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LC-HRESIMS (orbitrap) m/z: 737.1931 [MꢀH]
(calc. for
ꢀ
C
33
H
37
O
19 , 737.1935);
ꢀ
LC–ESI–MS/MS (ion trap) of [MꢀH] , m/z (rel. int.): 675 (13),
ꢀ
3
6
7
3
2
35 (18), 593 [(MꢀH)–HMG]
(100); LC–ESI–MS
(m/z
37 ? 593), m/z (rel. int.): 473 (7), 429 (loss of rhamnose) (43),
–
93 (10), 327 (9), 285 [kaempferol–H] (97), 284 [kaempferol–
dꢀ
H] (100), 255 (26).