A new naphthol from the twigs and leaves of

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SUPPLEMENTARY MATERIAL
Two new flavonol glycosides from Dimocarpus longan leaves
Yongmei Xuea,b, Wenjing Wangb, Yujiao Liua, Rui Zhana, Yegao Chena,*
a
School of Chemistry and Chemical Engineering, Yunnan Normal University,
Kunming 650500, China
b
Department of Traditional Chinese Medicine, Yunnan University of Traditional
Chinese Medicine, Kunming 650500, China
*Corresponding author. Tel: 86-871-65941089; Email: [email protected]
From the extracts of Dimocarpus longan Lour leaves, two unusual flavonol
glycosides, quercetin 3-O-(3’’-O-2’’’-methyl-2’’’-hydroxylethyl)- -D-xyloside
(1)
and
quercetin
3-O-(3’’-O-2’’’-methyl-2’’’-hydroxylethyl)--L-rhamnopyranoside (2), as well
as ten known compounds including two flavonol glycosides, afzelin (3) and
kaempferol-3-O--L-rhamnopyranoside (4), two flavans, (-)-epicatechin (5)
and proanthocyanidin A-2 (6), three triterpenoids, friedelin (7), epifriedelanol
(8)
-amyrin
and
(9),
a
peptide,
N-benzoylphenylalanyl-N-benzoylphenylalaninate (10), and
two sterols,
-sitosterol (11) and daucosterol (12) were isolated and identified by using
combination of mass spectrometry and
This
is
the
first
report
of
various 1D and 2D NMR techniques.
flavonoid
glycosides
possessing
2-methyl-2-hydroxylethoxyl group in sugar moiety from D. longan.
Keywords: Dimocarpus longan; Sapindaceae; flavonol glycoside
a
Supporting information
Spectroscopic data of the known compounds 3-12.
Figure S1. Selective HMBC (H→C) correlations for compounds 1 and 2.
Original spectra of compound 1.
HR-TOF-MS
-TOF-MS
EIMS
1
H NMR Spectrum (400 MHz, acetone-d6)
13
C NMR Spectrum (100 MHz, acetone-d6)
COSY Spectrum
HSQC Spectrum
HMBC Spectrum
Original spectra of compound 2.
HRTOFMS
-TOF-MS
EIMS
1
H NMR Spectrum (400 MHz, CD3OD)
13
C NMR Spectrum (100 MHz, CD3OD)
COSY Spectrum
HSQC Spectrum
HMBC Spectrum
Spectroscopic data of the known compounds 3-12.
afzelin (3)
Yellow powder, C21H20O11, MW: 448; 1H NMR (DMSO, 400 Hz):  12.64 (1H, s,
OH-5), 10.90 (1H, br s, OH-7), 9.75 (1H, br s, OH-4′), 9.38 (1H, br s, OH-3′), 7.28
(1H, d, J= 1.6 Hz, H-2′), 7.24 (1H, dd, J= 1.8, 8.3 Hz, H-6′), 6.85 (1H, d, J= 8.3 Hz,
H-5′), 6.38 (1H, d, J= 1.6 Hz, H-8), 6.19 (1H, d, J= 1.6 Hz, H-6), 5.24 (1H, s, H-1′′),
3.11~3.97 (4H, m), 0.80 (3H, d,J= 6.0 Hz, CH3); 13C NMR (DMSO, 100Hz):  17.59
(q, C-6′′), 70.15 (d, C-5′′), 70.42 (d, C-2′′), 70.70 (d, C-3′′), 71.24 (d, C-4′′), 93.75 (d,
C-8), 98.79 (d, C-6), 101.90 (d, C-1′′), 104.17 (s, C-10), 115.55 (d, C-2′), 115.72
(d,C-5′), 120.81 (d, C-1′), 121.24 (s, C-6′), 134.29 (s, C-3), 145.30 (s, C-3′), 148.53 (s,
C-4′), 156.55 (s, C-2), 157.43 (s, C-9), 161.38 (s, C-5), 164.29 (s, C-7), 177.84 (s,
C-4).
kaempferol-3-O--L-rhamnopyranoside (4)
Yellow powder, C21H20O10, MW: 432; 1H NMR (CD3OD, 400 Hz):  7.75 (2H, d, J=
8.8 Hz, H-2′, 6′), 6.91 (2H, d, J= 8.8 Hz, H-3′, 5′), 6.36 (1H, d, J= 2.0 Hz, H-8), 6.17
(1H, d, J= 2.0 Hz, H-6), 5.36 (1H, d, J= 1.6 Hz, H-1′′), 4.20 (1H, s, H-2′′), 0.90 (3H, d,
J= 5.5 Hz, H-6′′);
13
C NMR (CD3OD, 100Hz):  179.66 (s, C-4), 165.92 (s, C-7),
163.25 (s, C-5), 161.60 (s, C-9), 159.32 (s, C-2), 158.59 (s, C-4′), 136.25 (s, C-3),
131.92 (d, C-6′, 2′), 122.68 (d, C-1′), 116.56 (d, C-3′, 5′), 105.97 (s, C-10), 103.54 (d,
C-1′′), 99.87 (d, C-6), 94.79 (d, C-8), 73.24 (d, C-4′′), 72.18 (d, C-3′′), 72.06 (d, C-2′′),
71.95 (d, C-5′′) , 17.67 (q, C-6′′).
(-)-epicatechin (5)
Colorless powder, C15H14O6, MW: 290; 1H NMR (CD3OD, 400 Hz):  2.73 (1H, dd,
J= 2.8, 16.8 Hz, H-4b), 2.85 (1H, dd, J= 4.6, 16.7 Hz, H-4a), 3.34 (1H, br s, H-3),
4.81 (1H, s, H-2), 5.91 (1H, d, J= 2.3 Hz, H-6), 5.94 (1H, d, J= 2.2 Hz, H-8), 6.75 (1H,
d, J= 8.2 Hz, H-5′), 6.79 (1H, dd, J= 1.8, 8.2 Hz, H-6′), 6.97 (1H, d, J= 1.6 Hz, H-2′);
C NMR (CD3OD, 100Hz):  29.25 (t, C-4), 67.45 (d, C-3), 79.83 (d, C-2), 95.85 (d,
13
C-8), 96.35 (d, C-6), 100.03 (s, C-10), 115.28 (d, C-2′), 115.87 (d, C-5′), 119.38 (d,
C-6′), 132.27 (s, C-1′), 145.73 (s, C-3′), 145.89 (s, C-4′), 157.34 (s, C-9), 157.63 (s,
C-5), 157.99 (s, C-7).
proanthocyanidin A-2 (6)
Colorless powder, C30H24O12, MW: 576; 1H NMR (CD3OD, 400 Hz):  2.85 (2H, m,
H-4B), 3.30 (1H, m, H-4T), 4.06 (1H, d, J= 3.4 Hz, H-3B), 4.23 (1H, s, H-2B), 4.42
(1H, d, J= 3.4 Hz, H-3T), 6.01 (1H, d, J= 2.4 Hz, H-6T), 6.08 (1H, d, J= 2.2 Hz,
H-8T), 6.10 (1H, s, H-6B), 6.80 (1H, d, J= 1.1 Hz, H-5′T), 6.82 (1H, d, J= 0.8 Hz,
H-5′B), 7.00 (2H, dd, J=8.4, 2.0 Hz, H-6′), 7.16 (2H, dd, J=2.0, 6.0 Hz, H-2′);
13
C
NMR (CD3OD, 100Hz):  29.17 (d, C-4T), 29.84 (t, C-4B), 66.89 (d, C-3B), 67.98 (d,
C-3T), 81.66 (d, C-2B), 96.47 (s, C-6B), 96.59 (s, C-8T), 98.26 (d, C-6T), 100.12 (d,
C-2T), 102.40 (s, C-10B), 104.23 (s, C-10T), 107.15 (s, C-8B), 115.62 (d, C-5′,2′T),
115.90 (d, C-2′B), 116.02 (d, C-5′B), 119.77 (d, C-6′T), 120.37 (d, C-6′B), 131.44 (s,
C-1′B), 132.36 (s, C-1′T), 145.57 (s, C-3′T), 145.89 (s, C-3′B), 146.20 (s, C-4′B),
146.68 (s, C-4′T), 152.07 (s, C-9B), 152.20 (s, C-7B), 154.18 (s, C-9T), 156.50 (s,
C-5B), 156.91 (s, C-5T), 158.02 (s, C-7T).
friedelin (7)
Colorless neddles, C30H50O, MW: 426; 1H NMR (CDCl3, 400 Hz):  0.72 (3H, s,
H-24), 0.87 (3H, s, H-25), 0.88 (3H, s, H-23), 0.95 (3H, s, H-30), 0.99 (3H, s, H-29),
1.00 (3H, s, H-26), 1.17 (3H, s, H-27), 1.18 (3H, s, H-28), 1.36 (m, H-18), 1.54 (s,
H-10), 1.44 (m, H-8), 2.55 (m, H-4);
13
C NMR (CDCl3, 100 Hz):  22.25 (t, C-1),
41.50 (t, C-2), 213.33 (s, C-3), 58.17 (d, C-4), 42.12 (s, C-5), 41.22 (d, C-6), 18.19 (t,
C-7), 53.05 (d, C-8), 37.38 (s, C-9), 59.40 (d, C-10), 35.57 (t, C-11), 30.46 (t, C-12),
39.64 (s, C-13), 38.24 (s, C-14), 32.70 (t, C-15), 35.95 (t, C-16), 29.95 (s, C-17),
42.71 (d, C-18), 35.29 (t, C-19), 28.14 (s, C-20), 32.36 (t, C-21), 39.21 (t, C-22), 6.81
(q, C-23), 14.62 (q, C-24), 17.92 (q, C-25), 20.23 (q, C-26), 18.65 (q, C-27), 32.05 (q,
C-28), 31.75 (q, C-29), 35.00 (q, C-30).
epifriedelanol (8)
Colorless powder, C30H52O, MW: 428; 1H NMR (CD3Cl, 400 Hz):  0.86 (3H, s,
H-24), 0.93 ( 3H, s, H-25), 0.94 (3H, s, H-23), 0.96 ( 3H, s, H-30), 0.99 ( 3H, s, H-26),
1.00 (3H, s, H-29), 1.17 (3H, s, H-27), 1.17(3H, s, H-28), 3.74 (1H, brs, H-3);
13
C
NMR (CDCl3, 100 Hz):  16.34 (q, C-24), 35.12 (t, C-2), 72.72 (d, C-3), 49.10 (d,
C-4), 37.78 (s, C-5), 41.66 (t, C-6), 17.6 (t, C-7), 53.14 (d, C-8), 37.03 (s, C-9), 61.27
(d, C-10), 35.50 (t, C-11), 30.6 (t, C-12), 38.40 (s, C-13), 39.23 (s, C-14), 32.3 (t,
C-15), 36.02 (t, C-16), 30.0 (s, C-17), 42.74 (d, C-18 ), 35.29 (t, C-19) , 28.2 (s,
C-20 ), 32.74 (t, C-21), 39.62 (t, C-22), 11.60 (q, C-23), 15.73 (t, C-1), 18.2 (q, C-25),
18.6 (q, C-26), 20.09 (q, C-27), 31.75 (q, C-28), 35.00 (q, C-29 ), 32.04 (q, C-30).
-amyrin (9)
Colorless powder, mp. 141-142 oC. identified by co-TLC and comparison of UV and
IR with those of authentic samples.
N-benzoylphenylalanyl-N-benzoylphenylalaninate (10)
Colorless neddles, C32H30O4N2, MW: 492; 1H NMR (CDCl3,400 Hz):  4.91 (1H, d,
J= 6.7 Hz, H-a), 3.28 (1H, dd, J= 14.0, 6.9 Hz, H-βa), 3.22 (1H, dd, J= 13.9, 7.0 Hz,
H-βb), 4.60 (1H, m, H-a′), 3.00 (1H, dd, J= 13.7, 6.4 Hz, H-β′a), 2.89 (1H, dd, J= 13.7,
8.4 Hz, H-β′b), 4.54 (1H, dd, J= 11.3, 3.3 Hz, H-γa), 4.02 (1H, dd, J= 11.3, 4.3 Hz,
H-γb), 7.70 (2H, m, H-2, 6), 7.30 (2H, m, H-3′, 5′), 7.41 (1H, m, H-4′), 7.65 (2H, m,
H-2′, 6′), 7.37(2H, m, H-3, 5), 7.48 (1H, m, H-4), 7.28-7.20 (10H, m), 6.70 (1H, d, J=
8.4 Hz, NHb-), 6.61 (1H, d, J= 6.5 Hz, NHa-); 13C NMR (CDCl3, 100 Hz):  171.91
(s, C=0), 167.42 (s, C=O), 167.21 (s, C=O), 133.27 (s, C-1), 134.16 (s, C-1′), 127.08
(d, C-2′, 6′), 127.02 (d, C-2, 6), 128.39 (d, C-3, 5), 128.63 (d, C-3′, 5′), 131.99 (d,
C-4′), 131.36 (d, C-4), 137.13 (s, C-1′), 135.74 (s, C-1), 129.26 (d, C-2′′, 6′′), 129.13
(d, C-2′′′, 6′′′), 128.83 (d, C-3′′′, 5′′′), 128.66 (d, C-3′′, 5′′), 126.76 (d, C-4′′′) , 127.34
(d, C-4′′), 65.35 (t, C-γ), 54.47 (d, C-a), 50.25 (d, C-a′), 37.54 (t, C-β), 37.26 ( t, C-β′).
-sitosterol (11)
Colorless neddles, identified by co-TLC and comparison of 1H NMR,
13
C NMR and
EIMS with those of authentic samples.
daucosterol (12)
White powder, identified by co-TLC and comparison of 1H NMR,
EIMS with those of authentic samples.
13
C NMR and
Figure S1. Selective HMBC (H→C) correlations for compounds 1 and 2
OH
OH
OH
OH
HO
HO
O
O
O
OH
O
OH
O
O
OH
O
OH O
O
OH
OH
OH
1
OH
O
H3C
2
Original spectra of compound 1.
HR-TOF MS:
-TOF MS:
EIMS:
HNMR:
13
CNMR:
H-H COSY:
HSQC:
HMBC:
Original spectra of compound 2.
HR-TOF MS:
-TOF MS:
EIMS:
HNMR:
13
CNMR:
H-H COSY:
HSQC:
HMBC:
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