Acylated flavonol glycosides as probing stimulants of a bean aphid, Megoura crassicauda, from Vicia angustifolia.

Article abstract of DOI:10.1016/S0031-9422(02)00226-1

A bean aphid, Megoura crassicauda, which feeds selectively on the plant genus Vicia (Fabaceae), was found to be stimulated to probe an extract solution of the host plant, narrowleaf vetch, Vicia angustifolia L., depositing characteristic stylet sheaths on a parafilm membrane. Two acylated flavonol glycosides were isolated as the specific probing stimulants from the extracts and characterized as quercetin 3-O-alpha-L-arabinopyranosyl-(1-->6)-[2"-O-(E)-p-coumaroyl]-beta-D-glucopyranoside and quercetin 3-O-alpha-L-arabinopyranosyl-(1-->6)-[2"-O-(E)-p-coumaroyl]-beta-D-galactopyranoside. A mixture of these compounds in the same equivalency strongly induced the probing response from M. crassicauda, suggesting their kairomonal roles during host recognition.

Full text of DOI:10.1016/S0031-9422(02)00226-1

Phytochemistry 61 (2002) 135–140
www.elsevier.com/locate/phytochem
Acylated flavonol glycosides as probing stimulants of a bean aphid,
Megoura crassicauda, from Vicia angustifolia
Masami Takemura, Ritsuo Nishida*, Naoki Mori, Yasumasa Kuwahara
Laboratory of Chemical Ecology, Division of Applied Life Sciences, Graduate School of Agriculture,
Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan
Received 25 April 2002; received in revised form 11 June 2002
Abstract
A bean aphid, Megoura crassicauda, which feeds selectively on the plant genus Vicia (Fabaceae), was found to be stimulated to
probe an extract solution of the host plant, narrowleaf vetch, Vicia angustifolia L., depositing characteristic stylet sheaths on a
parafilm membrane. Two acylated flavonol glycosides were isolated as the specific probing stimulants from the extracts and char-
acterized as quercetin 3-O-a-l-arabinopyranosyl-(1!6)-[200-O-(E)-p-coumaroyl]-b-d-glucopyranoside and quercetin 3-O-a-l-arabino-
pyranosyl-(1!6)-[200-O-(E)-p-coumaroyl]-b-d-galactopyranoside. A mixture of these compounds in the same equivalency strongly
induced the probing response from M. crassicauda, suggesting their kairomonal roles during host recognition. # 2002 Elsevier
Science Ltd. All rights reserved.
Keywords: Vicia angustifolia; Fabaceae; Aphid; Megoura crassicauda; Probing stimulants; Host selection; Acylated flavonol glycosides
1. Introduction
2. Results and discussion
Megoura crassicauda Mordvilko is an oligophagous
aphid which feeds selectively on Vicia plants such as
broad bean (Vicia faba L.) and narrowleaf vetch (Vicia
angustifolia L.) (Fabaceae), often causing serious
damage to the plants (Moritsu, 1983). In order to
understand the phytochemical basis of host selection in
oligophagous aphids, we investigated the chemical fac-
tors controlling the probing behaviour of the bean
aphid. Aphids in general produce proteinaceous stylet
sheaths, similar to those produced in intact plant tissues
through a stretched parafilm membrane, as a result of
probing solutions of the host plant chemicals (Miles,
1965). The formation of stylet sheaths triggered by spe-
cific phytochemical cues in plants is suggested to be
associated with the host finding behaviour of the aphids
prior to ingestion of the phloem sap of specific host
plants (Montllor, 1991). Here we report the isolation
and structural elucidation of specific probing stimulants
of M. crassicauda from V. angustifolia, one of the most
widespread host plants in Japan.
M. crassicauda actively displayed probing behaviour
toward the crude aqueous extracts of a host plant,
V. angustifolia, depositing a substantial number of thick
stylet sheaths (thickness>10 mm; length>200 mm) on a
parafilm membrane at a concentration of 1 g fresh leaf
equivalent/ml (gle/ml). The aqueous extract was sub-
jected to chromatography on an ODS column with
increasing concentrations of methanol in water frac-
tions, of which the 60% methanol eluate exhibited sig-
nificant probing activity almost equivalent to that of a
crude extract of V. angustifolia. The active eluate was
further separated by a reversed phase HPLC and two
major probing stimulants 1 and 2 ultimately being iso-
lated in small quantities (yields/g leaf: 1, 2 mg; 2, 1.6 mg).
Both compounds 1 and 2 were suggested to be closely
related flavonoid isomers with the molecular formulae
of C35H34O18, as deduced from the electro-spray ioni-
zation (ESI) mass spectra (positive m/z 743 [M+H]+;
negative m/z 741 [MꢀH]ꢀ). Alkaline hydrolysis of
compound 1 gave (E)-p-coumaric acid 3 and a quercetin
diglycoside (compound 4). Likewise, compound 2 gave
(E)-p-coumaric acid 3 and a quercetin diglycoside
(compound 5). The deacylated compounds 4 and 5 were
* Corresponding author. Fax: +81-75-753-6312.
E-mail address: ritz@kais.kyoto-u.ac.jp (R. Nishida).
0031-9422/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S0031-9422(02)00226-1

136
M. Takemura et al. / Phytochemistry 61 (2002) 135–140
found as the principal flavonol diglycosides in the crude
aqueous extracts of V. angustifolia, and were identified
as quercetin 3-O-a-l-arabinopyranosyl-(1!6)-b-d-glu-
copyranoside and quercetin 3-O-a-l-arabinopyranosyl-
(1!6)-b-d-galactopyranoside, respectively, by MS and
2D NMR spectral analyses (Tables 1 and 2), acid
hydrolyses, followed by d/l determination of sugars by
Oshima’s procedure (Oshima et al., 1982) and compar-
ison with published data (Markham et al., 1987; Yoshi-
mata et al., 1992; Ahn et al., 1996; Bylka and
Matlawska, 1999).
evidenced by their respective J1ꢀ2 values for the diaxial
00
coupling (Table 1). The anomeric signals ꢀC-1 98.6 and
00
ꢀH-1 5.59 of the glucosyl moiety indicated the direct
connection with one of the hydroxyl group of the quer-
cetin aglycone. Comparison of the carbon shifts of the
aglycone with those of published data for quercetin
(Agrawal et al., 1989) revealed an upfield shift of C-3
(Áꢀ 2.8 ppm) and downfield shift of C-4 (Áꢀ 1.3 ppm),
indicating glycosylation of C-3 of the aglycone. HMBC
spectral analysis supported further evidence for this
assignment. (E)-p-Coumaroyl ester moiety was con-
firmed to be attached to C-200 of glucose by HMBC, in
which a correlation was observed between the down-
field-shifted methine proton H-200 of glucose and car-
bonyl carbon of the coumaroyl moiety. The 13C NMR
spectrum of 1 also supported the C-200 position of acyl-
ation, since both C-100 and C-300 signals of glucose
appeared upfield by about 2.3 ppm from signals of cor-
responding compound 4. Consequently, the structure of
compound 1 was established as quercetin 3-O-a-l-ara-
binopyranosyl-(1!6)-[200-O-(E)-p-coumaroyl]-b-d-gluco-
pyranoside.
1
The H and 13C NMR spectra of compound 1 exhib-
ited very similar signals to those of compound 4, with
marked differences being on an acylated oxymethine
proton at ꢀ 4.93 (H-200) in addition to signals arising
from the p-coumaroyl moiety (Tables 1 and 2). The geo-
metry of the p-coumaroyl moiety was determined to be of
(E)-configuration from the coupling constant (J=15.9
Hz) of the olefinic protons. The linkages of the two sugars
were determined by the heteronuclear multiple bond
correlation (HMBC) spectra, where correlations from
H-1000 (ꢀ 3.96) of arabinose to the C-600 (ꢀ 67.5) of glucose,
and from H-600 (ꢀ 3.82) of glucose to the C-1000 (ꢀ 103.1) of
arabinose were observed. This indicated that arabinosyl
moiety was linked to the C-600 of glucose. The b-configur-
ation of glucose and a-configuration of arabinose were
1
The H and 13C NMR signals of compound 2 were
assigned by 2D NMR spectroscopic analysis as shown
in Tables 1 and 2. Similar to compound 1, carbon shifts
of the aglycone and the anomeric carbon, and proton
Table 1
1H NMR spectral data for compounds 1, 2, 4 and 5 (DMSO-d6, 500 MHz)a
Position
Compound 1
Compound 2
Compound 4
Compound 5
Quercetin
6
6.19 d (1.6)
6.40 d (1.6)
7.54 d (2.1)
6.89 d (8.5)
7.57 dd (2.1, 8.5)
6.20 d (1.9)
6.41 d (1.9)
7.57 d (2.2)
6.85 d (8.5)
7.65 dd (8.5, 2.2)
6.21 d (2.0)
6.41 d (2.0)
7.58 d (2.0)
6.87 d (8.3)
7.58 dd (2.0, 8.3)
6.23 d (2.0)
6.46 d (2.0)
7.60 d (2.1)
6.86 d (8.5)
7.66 dd (8.5, 2.1)
8
20
50
60
Hexosyl
glc
gal
glc
gal
5.29 d (7.7)
3.60 m
100
200
300
400
500
600
5.59 d (8.2)
4.93 dd (9.4, 8.2)
3.49 m
5.52 d (8.1)
5.22 dd (9.7, 8.1)
3.72 dm (3.2)
3.78 d (3.2)
3.70 d (3.2)
3.71 s
5.37 d (7.6)
3.25 dd (7.6, 8.6)
3.21 t (8.6)
3.10 t (8.6)
3.31 m
3.41 dd (10.4, 4.1)
3.67 d (4.1)
3.58 m
3.25 t (10.0)
3.43 dd (10.0, 7.5)
3.82 d (10.0)
3.50 dd (10.0, 7.5)
3.79 d (13.2)
3.56 dd (13.2, 7.8)
3.69 dd (10.4, 5.8)
3.46 dd (10.4, 5.8)
Arabinosyl
1000
2000
3000
4000
5000
3.96 d (7.0)
3.98 d (7.0)
3.96 d (6.8)
3.99 d (7.0)
3.17 dd (8.6, 7.0)
2.98 dd (8.6, 3.5)
3.45 br s
3.18 dd (8.7, 7.0)
3.05 dd (7.0, 3.8)
3.49 br s
3.15 dd (6.8, 9.1)
2.94 dd (9.1, 4.3)
3.41 br s
3.16 dd (7.0, 8.5)
3.03 dd (8.5, 1.6)
3.49 br s
3.52 dd (10.0, 4.0)
2.94 d (10.0)
3.57 dd (12.3, 2.9)
3.05 d (12.3)
3.49 dd (12.3, 4.0)
2.89 d (12.3)
3.55 dd (12.3, 2.3)
3.04 d (12.3)
p-Coumaroyl
2, 6
3, 5
7
7.54 d (8.5)
6.82 d (8.5)
7.59 d (15.9)
6.40 d (15.9)
7.53 d (8.5)
6.79 d (8.5)
7.58 d (15.9)
6.39 d (15.9)
8
a
Coupling constants (J in Hz) are given in parentheses.

M. Takemura et al. / Phytochemistry 61 (2002) 135–140
137
Table 2
13C NMR spectral data for compounds 1, 2, 4 and 5 (DMSO-d6, 125
MHz)
compared with that of corresponding signal (ꢀ 3.60) for
compound 5 as shown in Table 1, and both C-100 and
C-300 signals of galactose appeared upfield from signals
of corresponding compound 5 (Table 2), suggesting that
the (E)-p-coumaroyl moiety was attached at C-200 posi-
tion of galactose. The pentose and ester linkages in
2 were confirmed by HMBC, where correlations from
arabinose H-100 (ꢀ 3.98) to galactose C-600 (ꢀ 66.6); from
galactose H-600 (ꢀ 3.71) to arabinose C-100 (ꢀ 102.9); and
from galactose H-200 to the coumaroyl carbonyl carbon.
These observations indicated that the arabinose and the
(E)-p-coumaroyl moiety were linked to the C-600 and C-200
position of galactose, respectively. Thus, compound 2 was
determined to be quercetin 3-O-a-l-arabinopyranosyl-
(1!6)-[200-O-(E)-p-coumaroyl]-b-d-galactopyranoside.
A mixture of compounds 1 and 2 in a 1 gle/ml solu-
tion induced the strong probing activity equivalent to
those of the 60% methanol eluate and crude aqueous
extracts, even though each compound did not exhibit
significant activity individually at 1 gle/ml concentra-
tion. The corresponding 2 gle/ml solution of each indi-
vidual component elicited the significant response to the
level of 1+2 (1 gle/ml), suggesting that the combination
effect between 1 and 2 is ‘‘additive’’ rather than ‘‘syner-
gistic’’ (Table 3).
Position Compound 1 Compound 2 Compound 4 Compound 5
Quercetin
4
177.2
164.3
161.4
156.6
156.5
148.8
145.1
133.0
122.0
121.1
116.2
115.4
104.2
98.8
177.3
164.3
161.4
156.4
156.4
148.7
145.1
133.1
122.4
121.1
116.2
115.4
104.1
98.8
177.5
164.3
161.4
156.5
156.5
148.7
145.0
133.5
121.8
121.3
116.3
115.4
104.2
98.8
177.6
164.4
161.4
156.6
156.6
148.7
145.0
133.7
122.2
121.3
116.1
115.4
104.2
98.9
7
5
2
9
40
30
3
60
10
50
20
10
6
8
93.7
93.7
93.7
93.7
Hexosyl glc
gal
glc
gal
100
200
300
400
500
600
98.6
98.2
71.1
72.7
68.7
74.6
66.6
101.0
74.1
76.5
70.2
77.1
67.5
102.0
71.2
73.2
68.5
74.6
66.7
74.0
74.2
70.4
77.1
67.5
Arabinosyl
Both 1 and 2 appear to be newcompounds from
plants. The a-l-arabinopyranosyl-(1!6)-b-d-glucopyr-
anoside moiety in compound 1 has been known as
vicianose and was initially characterized as a structural
element of the cyanogenic glycoside vicianin contained
in V. angustifolia seeds (Bertrand, 1906; Bertrand and
Weisweiller, 1910). Although vicianoside linkages
appear in various flavonoid glycosides, and quercetin
vicianoside (4) as well as quercetin arabinosyl-(1!6)-
b-galactoside (5) are distributed in a variety of plants
(Wells and Bohm, 1988; Gil et al., 1998; Santos and
Salatino, 2000; Bomfim-Patrıcio et al., 2001), their
p-coumaroyl derivatives seem to provide a very unique
phytochemical characteristic of the host plant. In sum-
mary, these findings add to our growing knowledge of
kairomonal behaviour. Previously the effect of the chal-
cone glycoside, phlorizin, on the feeding behaviour of
Rosaceae-feeding aphids had been reported (Klingauf,
1000
2000
3000
4000
5000
103.1
70.6
72.6
67.5
65.1
102.9
70.5
72.5
67.6
65.2
102.9
70.6
72.6
67.5
65.0
102.9
70.6
72.7
67.6
65.2
p-Coumaroyl
9
165.9
165.9
160.0
145.1
130.4
125.3
115.9
114.5
4
160.0
145.1
130.4
125.3
116.0
114.5
7
2, 6
1
3, 5
8
shifts of the galactosyl moiety between 2 and 5 indicated
a direct connection of the galactosyl moiety at C-3 of
the quercetin moiety. The signal arising from H-200 of
galactose was significantly deshielded (ꢀ 5.22) when

138
M. Takemura et al. / Phytochemistry 61 (2002) 135–140
Table 3
Probing response of Megoura crassicauda to a Vicia angustifolia
extract, compounds 1 and 2
3.3. Extraction and isolation of flavonoids
Leaves and stems were extracted with 90% ethanol in
water three times. The combined ethanolic solution was
evaporated in vacuo, and the residue was dissolved in
water and defatted five times with hexane. The crude
aqueous extract (23.2 g/1000 gle) was subjected to
chromatography on a reversed-phase column (100 g of
Cosmosil 140C18-OPN, nacalai tesque, 210ꢂ35 mm
i.d.) eluted in sequence each with an H2O–MeOH gra-
dient (100:0; 90:10; 80:20; 60:40; 40:60 and 0:100%,
respectively). The H2O–MeOH (40:60) was then sub-
jected to prep. HPLC using a reversed-phase column
(nacalai tesque COSMOSIL 5C18-AR 150ꢂ4.6 mm
i.d.), eluted with MeOH:H2O containing 1% acetic acid
(1:1) at a flowrate of 1.0 ml/min. The active fraction
eluted at the retention volume of ca. 5.5–7.5 and, this
Samplea
Probing activity (points) (N)
Control
23.8 (33) a
83.8 (9) b
87.4 (9) b
37.4 (18) a
25.5 (18) a
79.8 (18) b
78.8 (9) b
66.6 (9) b
Crude aqueous ext.
60% MeOH eluate
Compound 1
Compound 2
Compounds 1+2
Compound 1 (2 gle/ml)
Compound 2 (2 gle/ml)
Fractions with the same letters are not significantly different at
P=0.05 in Kruskal–Wallis test followed by Dunn’s multiple-compari-
son test.
a
Dose: All fractions were examined at 1 gle/ml, except for com-
pounds 1 and 2 (2 gle/ml).
being further subjected to prep. HPLC using
a
1971; cf. Montgomery and Arn, 1974), and the quinol-
izidine alkaloid, sparteine, has been suggested to be s a
feeding stimulant of the broom aphid, Acyrthosiphon
spartii (Koch.), which feeds exclusively on Cytisus
scoparius (L.) (Fabaceae) (Smith, 1966). Flavonoid
glycosides have also been reported as probing stimulants
of rice planthoppers (Kim et al., 1985; Adjei-Afriyie et
al., 2000a,b). A systematic effort is thus needed to
clarify the kairomonal roles of plant secondary meta-
bolites together with the primary nutrients in the
sequential process of feeding behaviour in these phloem-
sucking insects.
reversed-phase column (YMC Pack Pro-C18, S-5 mm,
120 A 250ꢂ6.0 mm i.d.) at 40 ꢁC, eluted as above.
Compounds 1 and 2 were isolated at tR=12.8 and
13.3 min, respectively, as a yellowsolid mass. The
total yield of compounds 1 and 2 from 1000 g of the
leaves was ca. 2.0 and 1.6 mg, respectively. A portion
of H2O–MeOH (60:40) eluate was also subjected to
prep. HPLC using a reversed-phase column (YMC
Pack Pro-C18, S-5 mm, 120 A 250ꢂ10 mm i.d.), eluted
with acetonitrile:water containing 1% acetic acid
(15:85) at a flowrate of 3.0 ml/min. Compounds
4
and 5 were isolated at tR=23.3 and 21.9 min, respec-
tively, as a yellowsolid mass (contents/g leaf: 4, 12.5
mg; 5, 33.8 mg).
3. Experimental
3.4. Quercetin 3-O-ꢁ-l-arabinopyranosyl-(1!6)-[200-O-
(E)-p-coumaroyl]-ꢂ-d-glucopyranoside (1)
3.1. General
Optical rotation was measured with a Jasco DIP-370
spectropolarimeter, and UV spectra were measured with
a Beckman DU-64 spectrophotometer. The MS data were
recorded with a Shimadzu LCMS-2010A (probe voltage
4.5 kV, CDL temperature 250 ꢁC) using a reversed-phase
column (Cadenza CD-C18 75 mmꢂ3.0 mm i.d.) eluted
with 15–30% acetonitrile+0.1% acetic acid in water
(0.2 ml/min) with ESI-positive and ESI-negative
Yellowsolid. [ ꢁ]1D7 ꢀ90ꢁ (MeOH; c 0.73); UV lMmaexOH
nm (log e): 264 (4.10), 317 (4.20), 363 (3.96); LCMS
(ESI-negative) m/z (rel. int.): 742 [M]ꢀ (33), 741
[MꢀH]ꢀ (100); LCMS (ESI-positive) m/z: 765
[M+Na]+
(5),
743
[M+H]+
(23),
441
[M+Hꢀquercetin]+ (100), 303 [quercetin+H]+ (38).
For 1H and 13C NMR spectral data, see Tables 1
and 2.
1
modes. H and 13C NMR spectras were measured with
a Bruker APX 500 FT-NMR spectrometer (500 MHz)
and a Bruker AC 300 FT-NMR spectrometer (300
MHz) with TMS as an internal standard.
3.5. Quercetin 3-O-ꢁ-l-arabinopyranosyl-(1!6)-[200-O-
(E)-p-coumaroyl]-ꢂ-d-galactopyranoside (2)
Yellowsolid. [ ꢁ]1D7ꢀ46ꢁ (MeOH; c 0.44); UV lMmaexOH
nm (log e): 264 (4.04), 317 (4.12), 363 (3.92); LCMS
(ESI-negative) m/z (rel. int.): 742 [M]ꢀ (33),
741[MꢀH]ꢀ (100); LCMS (ESI-positive) m/z: 765
3.2. Plant material
Leaves and stems of V. angustifolia were collected in
Sakyo-ku, Kyoto, Japan in April 2000, and identified by
Dr. Reiichi Miura of Kyoto University. A voucher spe-
cimen is deposited at the Herbarium of Pesticide
Research Institute, Kyoto University.
[M+Na]+
(5),
743
[M+H]+
(20),
441
[M+Hꢀquercetin]+ (100), 303 [quercetin+H]+ (12).
For 1H and 13C NMR spectral data, see Tables 1
and 2.

M. Takemura et al. / Phytochemistry 61 (2002) 135–140
139
3.6. Quercetin 3-O-ꢁ-l-arabinopyranosyl-(1!6)-ꢂ-d-
glucopyranoside (4)
Polyamine II 250ꢂ4.6 mm i.d.; 70% acetonitrile/water;
1.0 ml/min). Sugars liberated from compound 4 were
identified as l-arabinose and d-glucose, from com-
pound 5 were identified as l-arabinose and d-galactose
Yellowsolid. [ ꢁ]1D7 ꢀ19ꢁ (MeOH; c 0.13); UV lMmaexOH
nm (log e): 258 (4.25), 360 (4.18); LCMS (ESI-negative)
m/z: 596 [M]ꢀ (33), 595 [MꢀH]ꢀ (100); LCMS (ESI-
positive) m/z: 597 [M+H]+ (71), 303 [quercetin+H]+
1
by comparison of H NMR spectra with those of the
standard sugars and diastereoisomeric derivatization of
each sugar component according to Oshima’s method
(Oshima et al., 1982).
1
(100). For H and 13C NMR spectral data, see Tables 1
and 2.
3.10. Bioassay
3.7. Quercetin 3-O-ꢁ-l-arabinopyranosyl-(1!6)-ꢂ-d-
galactopyranoside (5)
Five apterous adult viviparae of M. crassicauda were
starved for 2 h, and then allowed to probe a test solu-
tion (0.4 ml) of either a sample solution or distilled
water (control) through a Parafilm1 M (American Can
Co.) membrane for 24 h under laboratory conditions
Yellowsolid. [ ꢁ]1D7 ꢀ87ꢁ (MeOH; c 0.44); UV lMmaexOH
nm (log e): 258 (4.37), 360 (4.28); LCMS (ESI-negative)
m/z: 596 [M]ꢀ (37), 595 [MꢀH]ꢀ (100); LCMS (ESI-
positive) m/z: 619 [M+Na]+ (11), 597 [M+H]+ (71),
303 [quercetin+H]+ (100). For 1H and 13C NMR
spectral data, see Tables 1 and 2.
ꢁ
(25 C, 16 L:8 D). The stylet sheaths deposited on the
parafilm membrane were observed under a microscope
after being stained with a red fuchsin basic solution.
The probing sheaths were classified according to the
degree of branching, non-branching or branching,
which were assigned coefficients of 1 and 2, respectively.
The intensity of probing activity was scored as the total
points.
3.8. Alkaline hydrolysis of compounds 1 and 2
Compounds 1 and 2 (ca. 100 and 50 mg, respectively)
were dissolved in 0.1 N KOH (100 and 50 ml, respec-
tively) and kept for 1 h. The reaction mixtures were
acidified with acetic acid, and submitted to LCMS. The
deacylated compounds 1 and 2 were identified by direct
comparison of LCMS data with those of compounds 4
and 5.
Deacylated compound 1. LCMS (ESI-negative) m/z:
596 [M]ꢀ (27), 595 [MꢀH]ꢀ (100); LCMS (ESI-positive)
m/z: 619 [M+Na]+ (100), 597 [M+H]+ (77), 303
[quercetin+H]+ (77).
Acknowledgements
We thank Dr. Reiichi Miura of Kyoto University for
identification of the plant. We are grateful to Dr. John
A. Pickett for reviewing the manuscript. This work was
supported in part by a Grant-in-Aid for Scientific
Research (No. 10460049) from the Japan Society for the
Promotion of Science.
Deacylated compound 2. LCMS (ESI-negative) m/z:
596 [M]ꢀ (26), 595 [MꢀH]ꢀ (100); LCMS (ESI-positive)
m/z: 635 [M+K]+ (57), 619 [M+Na]+ (11), 597
[M+H]+ (68), 303 [quercetin+H]+ (100).
References
(E)-p-Coumaric acid 3 liberated from both 1 and 2.
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