A new megastigmane glucoside and three new flavonoid glycosides from spiraea prunifolia var. simpliciflora

Article abstract of DOI:10.1002/hlca.201300402

A new megastigmane glucoside, simplicifloranoside (1), and three new flavonol glycosides, prunifolianosides A-C (2-4, resp.), were isolated from the aerial parts of Spiraea prunifolia var. simpliciflora. In addition, fifteen known compounds, including five phenolic acids, three lignans, four flavonoids, one eugenol glycoside, and two alkyl-primeverosides, were also identified. Their structures were elucidated on the basis of detailed spectroscopic analyses and acid hydrolysis. Copyright

Full text of DOI:10.1002/hlca.201300402

Helvetica Chimica Acta – Vol. 97 (2014)
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A New Megastigmane Glucoside and Three New Flavonoid Glycosides from
Spiraea prunifolia var. simpliciflora
by Min Hye Yean, Ju Sun Kim, Sam Sik Kang, and Yeong Shik Kim*
Natural Products Research Institute and College of Pharmacy, Seoul National University, Seoul 151-742,
Korea (phone: þ 82-2-8802479; fax: þ 82-2-7654768; e-mail: kims@snu.ac.kr)
A new megastigmane glucoside, simplicifloranoside (1), and three new flavonol glycosides,
prunifolianosides A – C (2 – 4, resp.), were isolated from the aerial parts of Spiraea prunifolia var.
simpliciflora. In addition, fifteen known compounds, including five phenolic acids, three lignans, four
flavonoids, one eugenol glycoside, and two alkyl-primeverosides, were also identified. Their structures
were elucidated on the basis of detailed spectroscopic analyses and acid hydrolysis.
Introduction. – The genus Spiraea (Rosaceae) comprises over 90 species growing as
shrubs in temperate regions of the northern hemisphere and in Eastern Asia. Sixteen
species of this genus have been identified in Korea [1][2]. Spiraea prunifolia Sieb.,
which is a widespread ornamental plant originally from China, has been used as a hedge
or garden plant in Japan [3]. S. prunifolia var. simpliciflora Nakai, the only variety of S.
prunifolia, is a deciduous shrub endemic to Korea that can be found in most parts of the
country [4 – 6]. Various species of Spiraea have been used traditionally for the
treatment of malaria, fever, and emetic conditions [1][4 – 6]. Phytochemical and
biological investigations of S. prunifolia have led to the discovery of novel biologically
active compounds, most notably tuliposides from the leaves [3][7]. Pharmacological
studies revealed that the extract of the roots of S. prunifolia var. simpliciflora possesses
antioxidant and anti-inflammatory activities [8 – 11]. Phytochemical studies of S.
prunifolia var. simpliciflora have been focused on the roots, which resulted in the
isolation of sterols, triterpenoids, and a monoterpene lactone glycoside [4 – 6][9].
Consequently, we investigated the chemical composition of the aerial parts of S.
prunifolia var. simpliciflora, and we isolated a new megastigmane glucoside (1), and
three new flavonol glycosides, 2 – 4, along with 15 known compounds. Their structures
were elucidated by spectroscopic methods and acid hydrolysis.
Results and Discussion. – The aerial parts of S. prunifolia var. simpliciflora were
extracted with MeOH, and the extract was partitioned using hexane, CH2Cl2, AcOEt,
BuOH, and H2O. The AcOEt and BuOH extracts were subjected to sequential column
chromatography over silica gel and RP-18 gel to yield the new megastigmane glucoside,
1, and three new flavonol glycosides, 2 – 4 (Fig. 1), together with 15 known compounds.
Compound 1 was obtained as amorphous powder, and its molecular formula was
determined as C19H32O7 by HR-FAB-MS, indicating four degrees of unsaturation. The
1H- and 13C-NMR data confirmed the presence of 19 C-atoms (Table 1). Analysis of the
ꢀ 2014 Verlag Helvetica Chimica Acta AG, Zꢁrich

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Fig. 1. The structures of compounds 1 – 4
1H- and 13C-NMR, and HMQC data revealed, in addition to one sugar moiety, that
there were two tertiary Me, two secondary Me, two CH2, three CH (one O-bearing),
1
groups, and one quaternary, two olefinic, and one C¼O C-atoms. The H,1H-COSY
data of
1
indicated two isolated H-atom spin-systems corresponding to
CH2(4)ꢀCH(5)ꢀCH(6)ꢀCH(7)¼CH(8)ꢀCH(9)ꢀMe(10), where C(9) was an O-bear-
ing C-atom, and the spin system of the sugar moiety. The remaining connections were
Table 1. 1H- and 13C-NMR Data of 1. d in ppm, J in Hza).
Position
1
d(H)b)
d(C)c)
1
2
3
4
5
6
7
8
9
10
11
12
13
39.4
56.6
214.5
49.9
34.8
57.8
131.7
137.5
78.1
21.7
2.03 (dd, J ¼ 2.4, 13.2), 2.42 (br. d, J ¼ 13.2)
2.16 (ddd, J ¼ 0.8, 11.2, 12.8), 2.30 (ddd, J ¼ 2.4, 4.6, 13.9)
1.82 – 1.90 (m)
1.96 (t, J ¼ 9.4)
5.43 (ddd, J ¼ 0.8, 8.6, 15.4)
5.68 (dd, J ¼ 6.9, 15.4)
4.39 (br. dd, J ¼ 6.3, 12.7)
1.30 (d, J ¼ 6.4)
0.81 (s)
1.00 (s)
21.4
31.2
21.4
0.93 (d, J ¼ 6.2)
Glc
1’
2’
3’
4’
5’
6’
4.37 (d, J ¼ 7.8)
102.4
75.3
77.8
71.4
77.9
62.5
3.18 (dd, J ¼ 8.0, 9.2)
3.35 (t, J ¼ 9.1)
3.33 (t, J ¼ 8.2)
3.17 – 3.23 (overlapping)
3.67 (dd, J ¼ 5.0, 11.9), 3.80 (dd, J ¼ 2.4, 11.9)
a) The assignments were based on 1H,1H-COSY, DEPT, HMQC, and HMBC experiments. b) Recorded
at 400 MHz in CD3OD. c) Recorded at 100 MHz in CD3OD.

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established by analysis of HMBCs (Fig. 2). The HMBCs Me(11)/C(1), C(2), and C(6),
and Me(12)/C(1), C(2), and C(6) indicated that C(11), C(12), C(2), and C(6) were all
connected with C(1), whereas HMBCs CH2(2)/C(3) and C(6); and CH2(4)/C(5), C(6),
and C(13) led to the connections C(3) with C(2) and C(4). The cross-peaks Me(13)/
C(4), C(5), and C(6) in the HMBC spectrum evidenced that C(5) was connected with
C(4), C(6), and C(13), completing a cyclohexanone moiety. The 3-hydroxybut-1-enyl
group connected to C(6) of the cyclohexanone ring in 1 was identified by 1H,1H-COSY
correlations, which revealed that 1 possessed a 3-oxomegastigm-7-ene-9-ol moiety (4,5-
dihydro-3-oxo-a-ionol). Acid hydrolysis of 1 afforded d-glucose, which was identified
by GC analysis and comparison with authentic samples [12]. The J value of the
anomeric H-atom established the sugar unit in 1 as b-d-glucopyranosyl (J ¼ 7.8 ) . The
HMBC from HꢀC(1’) to C(9) established that the glucopyranosyl moiety was
connected to C(9) of the aglycon. The relative configuration at C(5) and C(6) was
determined through extensive analyses of the coupling patterns of the H-atoms bonded
to a cyclohexanone ring and NOE correlations in the NOESY experiment. The large
coupling constant of the signal at d(H) 1.96 (t, J ¼ 9.4, HꢀC(6)) indicated for axial
orientations HꢀC(5) and HꢀC(6). Me(13) and the side chain at C(6) were equatorially
oriented, as evidenced by NOE correlations HꢀC(6)/HaxꢀC(2), Me(12) and Me(13)
(Fig. 3). The large coupling constant (J ¼ 15.4) between HꢀC(7) and HꢀC(8) indicated
the (E) configuration of the C(7)¼C(8) bond. The absolute configuration of 1 was
determined by analysis of its CD spectrum and comparison of its 13C-NMR data with
those of (9R)- and (9S)-analogs. The CD spectrum of 1 showed a positive Cotton effect
at 240 nm (De þ 13.23), which was similar to that in the spectrum of (6R)-3-oxo-a-ionol
glucoside, indicating the (6R)-configuration [13 – 15]. It was reported that the chemical
shifts of C(9) and C(10) were indicative (d(C) 77.3 – 79.1 (C(9)) and 21.2 – 21.8 (C(10))
and d(C) 74.7 – 76.3 (C(9)) and 22.3 – 22.6 (C(10)) for (R)- and (S)-configurations,
respectively, for 7,8-didehydro-9-hydroxymegastmane 9-O-b-d-glucopyranosides [13 –
16]. Thus, the absolute configuration at C(9) was assigned as (R) on the basis of the
diagnostic chemical shifts of d(C) 78.1 (C(9)) and 21.7 (C(10)) in the 13C-NMR
spectrum. Therefore, the structure of 1 was elucidated as 9-O-b-d-glucopyranonsyl
(5R,6R,9R,7E)-9-hydroxymegastigm-7-en-3-one and named simplicifloranoside. 4,5-
Dihydro-3-oxo-a-ionyl b-d-glucopyranoside has been isolated from Stenochlaena
palustris [17] and Vitis vinifera [18], but the configuration of the aglycone moiety
had not been established. Unfortunately, NMR data are only available for the
peracetate derivative so that a direct comparison with 1 was is not possible. The
occurrence of cyclohexanone derivatives without a C¼C bond in the cyclohexanone
moiety is not common in megastigmanes. This is the first report of this compound class
in the Spiraea genus.
Compound (2) was isolated as yellow powder, and its molecular formula was
deduced as C28H30O17 from HR-FAB-MS (m/z 639.1586 ([M þ H]þ, C28H31O1þ7 ; calc.
639.1561). The IR spectrum showed typical absorption bands for OH (3408 cmꢀ1),
C¼O (1727 cmꢀ1), a,b-unsaturated C¼O (1655 cmꢀ1), aromatic C¼C (1607 and
1509 cmꢀ1), and glycosidic CꢀO (1070 cmꢀ1) groups. The UV spectrum exhibited
absorption bands at 256, 264, and 354 nm, suggesting a flavonol skeleton. The 1H- and
13C-NMR spectra displayed signals characteristic of 5,7,3’,4’-tetrasubstitued flavonol
glycosides with an Ac group (d(H) 2.03 (s); d(C) 21.1, 169.7), and two sugar moieties

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Fig. 2. Important 1H,1H-COSY (—) and HMB (H ! C)
correlations of 1
Fig. 3. Key NOESY (H $ H) correlations of 1
(cyclohexanone part)
evidenced by signals of two anomeric C-atoms (d(C) 102.7 (C(1’’’)), 99.3 (C(1’’)) and
the corresponding anomeric H-atoms (d(H) 3.95 (d, J ¼ 6.6, HꢀC(1’’’)), 5.39 (d, J ¼ 8.0,
HꢀC(1’’)) (Table 2). Acid hydrolysis of 2 yielded quercetin identified by direct
comparison with an authentic sample and two sugars. The sugars were identified as d-
galactose and l-arabinose by GC analysis [12]. The glycosidic linkage was established
by the HMBCs between the signals at d(H) 5.39 (HꢀC(1’’)) and d(C) 133.2 (C(3)), and
between those at d(H) 3.95 (HꢀC(1’’’)) and d(C) 66.4 (C(6’’)), indicating that the
galactose unit was located at C(3) of aglycon, and the arabinose unit was attached to
C(6) of galactose (Fig. 4). The remaining Ac group was placed at C(2’’) of galactose
evidenced by three-bond correlation between the signals at d(H) 5.10 (HꢀC(2’’)) and
d(C) 169.7 (ester C¼O). Thus, 2 was characterized unambiguously as quercetin 3-O-a-
l-arabinopyranosyl-(1 ! 6)-(2’’-O-acetyl-b-d-galactopyranoside), and it was named
prunifolianoside A.
The molecular formulae of compounds 3 and 4 were deduced as C28H30O16 and
1
C29H32O17, respectively, from HR-FAB-MS. The H- and 13C-NMR spectra of 3 and 4
Fig. 4. Key HMBCs (H ! C) of 2, 3, and 4 (R ¼
OH, H, and MeO, resp.)

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were similar to those of 2 (Table 2), except for the presence of kaempferol and
isorhamnetin, respectively, as the aglycon rather than quercetin, as confirmed by the
acid hydrolysis experiments. Acid hydrolysis and coupling patterns of anomeric H-
atoms of 3 and 4 confirmed the presence of d-galactose and l-arabinose [12], and their
positions, as determined by HMBC, were the same as in 2. Consequently, compounds 3
and 4 were characterized as kaempferol 3-O-a-l-arabinopyranosyl-(1 ! 6)-(2’’-O-
acetyl-b-d-galactopyranoside) (prunifolianoside B) and isorhamnetin 3-O-a-l-arabi-
nopyranosyl-(1 ! 6)-(2’’-O-acetyl-b-d-galactopyranoside) (prunifolianoside C), re-
spectively.
In addition, the known compounds were identified as caffeic acid (5)1) [19], 1-O-
cinnamoyl-b-d-glucopyranose (6) [20], 1-O-p-coumaroyl-b-d-glucopyranose (7) [21],
1-O-caffeoyl-b-d-glucopyranose (8) [19], 1,2-O-dicaffeoyl-b-d-glucopyranose (9) [22],
pinoresinol 4’-O-glucopyranoside (10) [23], 8-hydroxypinoresinol 4’-O-b-d-glucopyr-
anoside (11) [24], (ꢀ)-nortracheloside (12) [25], trifolin (13) [26], astragalin (14) [26],
hyperin (15) [26], quercetin 3-O-(2’’’-O-caffeoyl-a-l-arabinopyranosyl)-(1 ! 6)-b-d-
galactopyranoside (16) [27], hexyl-b-primeveroside (17) [28], (Z)-hex-3-enyl-b-
primeveroside (18) [29], and eugenol 4-O-b-primeveroside (19) [30] by comparison
of the spectral data with those reported in the literature. To the best of our knowledge,
this is the first report on the isolation of constituents from aerial parts of S. prunifolia
var. simpliciflora. Compounds 10 – 12 and 16 – 19 were isolated from the genus Spiraea
for the first time, and compounds 5 – 9 and 13 – 15 were obtained from this plant for the
first time.
This study was financially supported by the Second Phase of the Brain Korea 21 Program in 2010. The
authors are grateful to Em. Prof. KiHwan Bae, College of Pharmacy Chungnam National University, for
the identification of the plant materials.
Experimental Part
General. TLC: Silica gel 60 F254 (Merck) and RP-18254S (Merck); visualization by UV light, staining
with I2 vapor, or spraying with 20% H2SO4, followed by heating. Column chromatography (CC): silica gel
(SiO2; 230 – 400 mesh; Merck, Germany), LiChroprep RP18 (40 – 63 mm, Merck), and Sephadex LH-20
(Amersham Biosciences AB). Optical rotations: JASCO P-1020 polarimeter. UV/VIS Spectra: Hitachi
JP/U3010 spectrometer; lmax (log e) in nm. CD Spectra: JASCO J-715 ORD/CD spectrophotometer; De
in nm. IR Spectra: JASCO FT/IR-5300 spectrometer; ˜n in cmꢀ1. NMR Spectra: Bruker Avance 400
(400 MHz) or a Bruker Avance 500 (500 MHz); CD3OD or (D6)DMSO; d in ppm rel. to Me4Si as
internal standard, J in Hz. EI-MS: Hewlett Packard 5989B spectrometer; in m/z. FAB-MS and HR-FAB-
MS (positive-ion mode and negative-ion mode, resp.; 3-nitrobenzyl alcohol matrix): JEOL JMS-700
MStation spectrometer; in m/z. ESI-MS and HR-ESI-MS (positive-ion mode): Agilent Technologies Q-
TOF 6530 mass spectrometer; in m/z.
Plant Material. The aerial parts of S. prunifolia var. simpliciflora were collected at Dang-jin,
Chungnam Province, Korea, in May, 2011. The botanical identification was accomplished by Em. Prof.
KiHwan Bae. A voucher specimen (KSS201105) was deposited with the Natural Products Research
Institute, College of Pharmacy, Seoul National University.
Extraction and Isolation. The crushed aerial parts of S. prunifolia var. simpliciflora (5.8 kg) were
extracted four times with MeOH (10 l) under reflux (70 – 808, each 3 h) to give an extract (613 g). The
MeOH extract was suspended in H2O (8 l) and successively partitioned with hexane (3 ꢁ 5 l), CH2Cl2
1
)
Formulae not shown for compounds 5 – 19 (see, therefore, the corresponding references).

Helvetica Chimica Acta – Vol. 97 (2014)
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(3 ꢁ 5 l), AcOEt (4 ꢁ 5 l), and BuOH (5 ꢁ 5 l) to yield 133.0, 17.1, 106.4, and 253.6 g, resp. A portion of
the AcOEt fraction (100 g) was subjected to CC (SiO2; CH2Cl2/MeOH 100 :1, 100 :3, 100 :5) to yield
seven fractions, Frs. E-01 – E-07. Fr. E-04 (16 g) was submitted to CC (SiO2; hexane/AcOEt 10 :1, 10 :3,
10 :5) to yield 20 fractions, Frs. E-04-01 – E-04-20. Fr. E-04-01 (6.0 g) was purified by repeated CC (SiO2;
CH2Cl2/MeOH 100 :1, 100 :3, 100 :5; then SiO2; hexane/AcOEt 100 :1, 100 :3, 100 :5). Fr. E-04-01-23
(150 mg) was further purified by repeated CC (SiO2; CH2Cl2/MeOH 100 :0.5; then RP-18; 60% MeOH)
to afford 5 (5 mg). Fr. E-04-04 (3.0 g) was purified by CC (SiO2; CH2Cl2/MeOH 100 :1, 100 :3, 100 :5).
Fr. E-04-04-02 (2.7 g) was purified by repeated CC (SiO2; hexane/AcOEt 100 :3, 100 :5, 100 :7; then
SiO2; CH2Cl2/MeOH 100 :1, 100 :3, 100 :5) to afford 6 (30 mg). Fr. E-05 (3.0 g) was submitted to CC
(SiO2; hexane/AcOEt (100 :3, 100 :5, 100 :7) to yield seven fractions, Frs. E-05-01 – E-05-07. Fr. E-05-02
(1.1 g) was purified by repeated CC (SiO2; CH2Cl2/MeOH 100 :1, 100 :3, 100 :5; then RP-18; 60%
MeOH) to afford 7 (8 mg). Fr. E-05-02-04 (1.0 g) was further purified by repeated CC (SiO2; CH2Cl2/
MeOH 100 :1, 100 :3, 100 :5; then RP-18; 40% MeOH) to afford 8 (9 mg). Fr. E-05-07 (37 mg) was
subjected to repeated CC (SiO2; hexane/acetone 100 :1, 100 :3, 100 :5; then RP-18; 60% MeOH) to yield
9 (6 mg). Fr. E-06 (5.0 g) was purified by CC (SiO2; hexane/AcOEt 10 :5, 10 :7, 0 :10) to yield eight
fractions, Frs. E-06-01 – E-06-08. Fr. E-06 – 02 (17 mg) was separated by CC (RP-18; 60% MeOH) to
afford 10 (10 mg). Fr. E-06 – 03 (2 g) was purified by repeated CC (SiO2; hexane/AcOEt 10 :5, 10 :7,
0 :10; then SiO2; CH2Cl2/MeOH 100 :3, 100 :7, 100 :10) to afford 11 (2 mg) and 12 (40 mg). Fr. E-06-05
(21 mg) was subjected to CC (RP-18; 40% MeOH) to afford 13 (9 mg). A portion of the BuOH fraction
(200 g) was subjected to CC (SiO2; CH2Cl2/MeOH 100 :3, 100 :10, 100 :20) to furnish ten fractions,
Frs. B-01 – B-10. Fr. B-02 (8.0 g) was purified by CC (SiO2; hexane/AcOEt 100 :1, 100 :2, 100 :5) to yield
six fractions, Frs. B-02-01 – B-02-06. Fr. B-02-01 (67 mg) was purified by repeated CC (SiO2; hexane/
AcOEt 100 :50, 100 :65, 100 :85; then SiO2; CH2Cl2/MeOH 100 :10, 100 :30, 100 :70) to afford 14
(22 mg). Fr. B-02-03 (19 mg) was further purified by CC (SiO2; CH2Cl2/MeOH 10 :1, 10 :3, 10 :7) to
afford 15 (10 mg). Fr. B-03 (10 mg) was submitted to CC (SiO2; hexane/AcOEt 100 :50, 100 :65, 100 :85)
to yield nine fractions, Frs. B-03-01 – B-03-09. Fr. B-03-02 was purified by CC (RP-18; 50% MeOH) to
afford 16 (2 mg). Fr. B-05 (13 g) was separated by CC (SiO2; CH2Cl2/MeOH 10 :1, 10 :3, 10 :7) to yield
nine fractions, Frs. B-05-01 – B-05-09. Fr. B-05-02 (3.1 g) was purified by CC (SiO2; hexane/AcOEt
100 :50, 100 :65, 100 :85). Fr. B-05-02-03 (1.3 g) was further submitted to repeated CC (SiO2; CH2Cl2/
MeOH 10 :1, 10 :3, 10 :7; then RP-18; 50% MeOH) to afford 1 (2 mg), and 17 (18 mg). Fr. B-05-03
(1.9 g) was purified by repeated CC (SiO2; CH2Cl2/MeOH 10 :1, 10 :3, 10 :7; then SiO2; CH2Cl2/MeOH
10 :1, 10 :3, 10 :7) to afford 18 (2 mg), 19 (2 mg), 3 (5 mg), and 4 (5 mg). Fr. B-05-04 (1.3 g) was
separated by repeated CC (SiO2; CH2Cl2/MeOH 10 :1, 10 :3, 10 :7; then RP-18; 60% MeOH) to afford 2
(34 mg).
Acid Hydrolysis. Compounds 1 – 4 (each 2 mg) were refluxed with 5% HCl in 60% aq. dioxane
(5 ml) for 1 h. The mixture was concentrated, added to crushed ice, and extracted with CHCl3. The aq.
layer was neutralized with Ag2CO3 and filtered, and the filtrate was concentrated under reduced
pressure. The dried sugars were treated with pyridine (0.1 ml), and then the soln. was added to a pyridine
soln. (0.1 ml) of l-cysteine methyl ester hydrochloride (2 mg) and warmed at 608 for 1 h. The solvent was
evaporated under N2 and dried in vacuo. The residue was trimethylsilylated with TMS-HT (0.1 ml) at 608
for 30 min. After the addition of hexane and H2O, the hexane layer was removed and checked by GC
analysis; HP5 column (30 m ꢁ 0.32 mm ꢁ 0.25 mm); injector and detector temp., 2008; GC oven temp.;
2308: from 1: tR 11.67 min; from 2 – 4: tR 6.80 and 12.69 min; l-arabinose, tR 6.80 min; d-arabinose, tR
7.29 min; d-glucose, tR 11.67 min; l-glucose, tR 12.18 min; d-galactose, tR 12.69 min; l-galactose, tR
13.45 min.
Simplicifloranoside (¼(5R,6R,9R,7E)-9-Hydroxy-3-oxomegastigm-7-ene 9-O-b-d-Glucopyra-
noside ¼ (2R,3E)-4-[(1R,6R)-2,2,6-Trimethyl-4-oxocyclohexyl]but-3-en-2-yl b-d-Glucopyranoside; 1).
Amorphous white powder. [a]1D8 ¼ ꢀ29.5 (c ¼ 0.25, MeOH). UV (MeOH): 285 (4.61). CD (MeOH):
240 (þ13.23), 288 (þ4.96), 322 (ꢀ0.96). IR (KBr): 3402 (OH), 1719 (C¼O), 1656 (C¼C), 1076
(glycosidic CꢀO), 932 ((E)-C¼C). 1H- and 13C-NMR: see Table 1. FAB-MS: 371 ([M ꢀ H]ꢀ). HR-FAB-
MS: 371.2065 ([M ꢀ H]ꢀ, C19H31O7ꢀ ; calc. 371.2069).
Prunifolianoside
A
(¼Quercetin 3-O-a-l-Arabinopyranosyl-(1 ! 6)-(2’’-O-acetyl-b-d-gal-
actopyranoside) ¼ 2-(3,4-Dihydroxyphenyl)-5,7-dihydroxy-4-oxo-4H-1-benzopyran-3-yl 4-O-Acetyl-6-

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O-a-l-arabinopyranosyl-b-d-galactopyranoside; 2). Yellow powder. [a]2D0 ¼ ꢀ22.7 (c ¼ 0.50, MeOH).
UV (MeOH): 354 (4.16), 298 (sh, 3.94), 264 (sh, 4.18), 256 (4.23), 207 (4.53). UV (MeONa): 406 (4.26),
332 (sh, 3.95), 271 (4.31), 210 (4.75). UV (AlCl3): 427 (4.11), 307 (sh, 3.95), 247 (4.29), 208 (4.54). UV
(AlCl3/HCl): 400 (4.04), 359 (sh, 4.00), 307 (sh, 3.95), 270 (4.23), 207 (4.51). UV (AcONa): 382 (4.09),
324 (sh, 3.99), 273 (4.28), 213 (4.79). UV (AcONa/H3BO3): 376 (4.19), 261 (4.30), 3.25 (4.78). IR (KBr):
3408 (OH), 1727 (C¼O), 1655 (a,b-unsat. C¼O), 1607, 1509 (arom. C¼C), 1070 (glycosidic CꢀO). 1H-
and 13C-NMR: see Table 2. FAB-MS: 639 ([M þ H]þ). HR-FAB-MS: 639.1586 ([M þ H]þ, C28H31Oþ17
;
calc. 639.1561).
Prunifolianoside
B
(¼ Kaempferol 3-O-a-l-Arabinopyranosyl-(1 ! 6)-(2’’-O-acetyl-b-d-gal-
actopyranoside) ¼ 5,7-Dihydroxy-2-(4-hydroxyphenyl)-4-oxo-4H-1-benzopyran-3-yl 4-O-Acetyl-6-O-a-
l-arabinopyranosyl-b-d-galactopyranoside; 3). Yellow powder. [a]1D8 ¼ ꢀ10.6 (c ¼ 0.50, MeOH). UV
(MeOH): 343 (3.16), 294 (sh, 3.18), 267 (3.30), 203 (3.66). UV (MeONa): 408 (3.24), 325 (sh, 3.24), 283
(3.40), 206 (4.18). UV (AlCl3): 3.93 (3.25), 339 (sh, 3.34), 303 (3.40), 274 (3.55), 203 (3.93). UV (AlCl3/
HCl): 387 (3.06), 347 (3.14), 305 (3.16), 274 (3.33), 203 (3.68). UV (AcONa): 357 (3.10), 301 (sh, 3.18),
273 (3.34), 213 (4.29). UV (AcONa/H3BO3): 347 (3.17), 267 (3.31), 211 (4.30). IR (KBr): 3139 (OH),
1737 (C¼O), 1626 (C¼C), 1071 (glycosidic CꢀO). 1H- and 13C-NMR: see Table 2. FAB-MS: 623 ([M þ
H]þ). HR-FAB-MS: 623.1634 ([M þ H]þ, C28H31O1þ6 ; calc. 623.1612).
Prunifolianoside C (¼ Isorhamnetin 3-O-a-l-Arabinopyranosyl-(1 ! 6)-(2’’-O-acetyl-b-d-gal-
actopyranoside) ¼ 5,7-Dihydroxy-2-(4-hydroxy-3-methoxyphenyl)-4-oxo-4H-1-benzopyran-3-yl 4-O-
Acetyl-6-O-a-l-arabinopyranosyl-b-d-galactopyranoside; 4). Yellow powder. [a]1D8 ¼ ꢀ15.3 (c ¼ 0.50,
MeOH). UV (MeOH): 347 (3.27), 303 (sh, 3.31), 263 (sh, 3.44), 254 (3.46), 203 (3.96). UV (MeONa):
414 (3.30), 313 (sh, 3.32), 303 (sh, 3.31), 280 (3.52), 206 (4.29). UV (AlCl3): 391 (3.21), 297 (sh, 3.31), 271
(3.50), 203 (3.99). UV (AlCl3/HCl): 393 (3.16), 297 (sh, 3.28), 271 (3.46), 204 (3.93). UV (AcONa): 367
(sh, 3.17), 311 (3.34), 273 (3.50), 213 (4.30). UV (AcONa/H3BO3): 349 (3.27), 307 (sh, 3.33), 265 (3.47),
256 (3.47), 213 (4.31). IR (KBr): 3418 (OH), 1736 (C¼O), 1654 (a,b-unsat. C¼O), 1604, 1511 (arom.
1
C¼C), 1072 (glycosidic CꢀO). H- and 13C-NMR: see Table 2. FAB-MS: 675 ([M þ Na]þ) 653 ([M þ
H]þ), 307 ([isorhamnetin þ H]þ). HR-FAB-MS: 653.1524 ([M þ H]þ, C29H33O1þ7 ; calc. 653.1512).
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Received November 11, 2013