New Compounds from Flowers of Phlojodicarpus sibiricus

Article abstract of DOI:10.1007/s10600-020-03109-9

Chromatographic separation of the MeOH extract from flowers of Phlojodicarpus sibiricus (Fisch.) Koso.-Pol. (Apiaceae) isolated 27 compounds including three new glycosides, the structures of which were established by UV, IR, and NMR spectroscopy and mass

Full text of DOI:10.1007/s10600-020-03109-9

DOI 10.1007/s10600-020-03109-9
Chemistry of Natural Compounds, Vol. 56, No. 4, July, 2020
NEW COMPOUNDS FROM FLOWERS OF Phlojodicarpus sibiricus
1*
2
D. N. Olennikov and N. K. Chirikova
Chromatographic separation of the MeOH extract from flowers of Phlojodicarpus sibiricus
(Fisch.) Koso.-Pol. (Apiaceae) isolated 27 compounds including three new glycosides, the structures of
which were established by UV, IR, and NMR spectroscopy and mass spectrometry as (R)-peucedanol -7-O-
(6″-O-β-D-apiofuranosyl)-β-D-glucopyranoside-3′-O-β-D-glucopyranoside (phlojosibiriside I, 1), diosmetin-
7-O-(6″-O-β-D-apiofuranosyl)-β-D-glucopyranoside (phlojosibiriside II, 2), and diosmetin-7-O-(2″-O-acetyl-
6″-O-β-D- apiofuranosyl)-β-D-glucopyranoside (phlojosibiriside III, 3).
Keywords: Phlojodicarpus sibiricus, Apiaceae, phlojosibiriside, peucedanol, diosmetin.
Phlojodicarpus Turcz. ex Ledeb. is a small genus of medicinal plants in the familyApiaceae, representatives of which
are distributed in Siberia, the Russian Far East, and Mongolia [1]. The species P. sibiricus (Fisch.) Koso.-Pol. is used most in
eastern Siberia to treat atherosclerosis, obesity, tuberculosis, and stomach diseases [2]. Information on the chemical composition
of P. sibiricus indicates the presence in it of simple coumarins and their glycosides, khellactone esters, hydroxycinnamates,
flavonoids, and essential oil [1, 3–5]. Only roots, herb, or seeds of P. sibiricus have been chemically analyzed because of their
wide use as medicinal raw material. Information on the compounds extracted from flowers of this species is missing, which
hinders drawing a conclusion about their possible practical value. In continuation of studies of Siberian species of Phlojodicarpus
[1, 6], the composition of phenolic compounds from flowers of P. sibiricus were studied in the present work.
Chromatographic separation of the MeOH extract from P. sibiricus flowers by column chromatography (CC) over
silica gel, polyamide, and Sephadex LH-20 and by preparative HPLC isolated three new glycosides 1–3 and 24 known
compounds (4–27) that were identified using UV, IR, and NMR spectroscopy and mass spectrometry as 3′,4′-di-O-isobutyryl-
cis-khellactone (4) [7], praeruptorin D (5) [8], dihydrosamidin (6) [9], visnadin (7) [10], hyuganin D (8) [11],
3′,4′-di-O-acetyl-cis-khellactone (9) [12], 4′-O-acetyl-cis-khellactone (10) [13], praeroside II (11) [14], praeroside VI (12)
[14], diosmetin-7-O-glucoside (13) [15], (R)-peucedanol-7-O-glucoside (14) [16], (R)-peucedanol-2′-O-glucoside (15) [16],
(R)-peucedanol-3′-O-glucoside (16) [16], skimmin (17) [17], umbelliferone-7-O-(6″-apiosyl)glucoside (18) [5],
4,5-di-O-caffeylquinic acid (19) [18], 3,5-di-O-caffeoylquinic acid (20) [19], 1,3-di-O-caffeoylquinic acid (21) [18],
5-O-caffeoylquinic acid (22) [20], 4-O-caffeoylquinic acid (23) [18], 1-O-caffeoylquinic acid (24) [18], peujaponiside (25)
[21], (R)-peucedanol-2′-O-(6″-apiosyl)glucosides (26) [22], and (R)-peucedanol-3′-O-(6″-apiosyl)glucoside (27) [23].
Compounds 5–10, 14, 16, 18, 22, and 24 were previously observed in P. sibiricus [1, 3–5]; constituents 4, 11–13, 15, 17,
19–21, 23 and 25–27 were detected for the first time for this species.
+
Compound 1 had the molecular formula C H O based on HR-ESI-MS (m/z 721.4007 [M + H] ; calcd 721.6296)
31 44 19
13
and C NMR data (Table 1). The UV spectrum was similar to those of 7-hydroxycoumarins (λ
249, 289sh, 330 nm) [21].
max
–1
The IR spectrum contained bands for carbonyl (1708 cm ) and an aromatic ring (1625) that were characteristic of coumarins
[16]. The acid-hydrolysis products of 1 included D-glucose and D-apiose in a 2:1 ratio and (R)-peucedanol, which was
identified using [α] , UV and NMR spectroscopy, and mass spectrometry as compared to the known compound and literature
D
+
data [24]. The positive-ion mass spectrum had peaks for the protonated molecule (m/z 721 [M + H] ) and adduct ions (m/z 743
[M + Na] and 759 [M + K] ) and peaks caused by loss of two glucoses (162 amu; C H O ) and one apiose (132 amu;
+
+
6
10 5
C H O ) with m/z 589, 559, 427, and 265 [1].
5
8 4
1) Institute of General and Experimental Biology, Siberian Branch, Russian Academy of Sciences, 6 Sakh′yanovoi
St., Ulan-Ude, 670047, e-mail: olennikovdn@mail.ru; 2) M. K. Ammosov North-Eastern Federal University, 58 Belinskogo
St., Yakutsk, 677000, e-mail: hofnung@mail.ru. Translated from Khimiya Prirodnykh Soedinenii, No. 4, July–August, 2020,
pp. 544–548. Original article submitted December 23, 2019.
©
628
0009-3130/20/5604-0628 2020 Springer Science+Business Media, LLC

13
TABLE 1. C NMR Spectra of 1–3 (125 MHz, MeOH-d , 298 K, δ, ppm)
4
C atom
C atom
1
2
3
1
2
3
2
3
4
5
6
7
8
9
10
1′
2′
3′
4′
5′
6′
164.5
114.1
146.9
131.6
128.3
160.4
104.4
155.8
114.9
32.9
78.8
82.1
–
164.4
103.2
182.2
161.2
100.3
163.1
95.1
157.8
105.2
122.0
110.6
146.3
150.7
114.7
120.2
–
164.2
103.4
182.4
160.8
100.1
163.4
95.3
157.7
105.7
121.7
111.9
146.5
150.5
114.4
119.8
–
75.2
77.9
71.7
78.3
69.8
–
74.8
77.6
71.6
78.5
70.1
–
76.5
75.4
71.5
78.2
69.8
21.4
171.2
110.4
76.8
80.2
75.2
65.3
–
2′′
3′′
4′′
5′′
6′′
2′′-CH3CO
2′′-CH3CO
1′′′
–
–
110.5
76.9
80.5
75.7
65.2
100.4
74.8
77.5
71.4
78.0
62.1
110.2
76.7
80.6
75.4
65.4
–
–
–
–
–
2′′′
3′′′
4′′′
5′′′
1′′′′
2′′′′
3′′′′
4′′′′
–
–
–
–
–
–
23.2, 23.7
–
102.5
3′,3′-(CH3)2
4′-OCH3
1′′
59.1
102.1
58.7
100.2
5′′′′
6′′′′
–
–
OH
6''''
HO
HO
OH
4'''O
HO
O
1'''
OCH
3
4'
O
5'''
3'
HO
O
1''''
O
O
6''
O
O
1''
1'
3'
4''' O
HO OH
HO
HO
5'''
10
9
7
1'''
7
OH
O
O
6
O
O
HO
O
R
O
6''
HO OH
HO
OH
2, 3
2: R = H; 3: R = Ac
OH 1''
1
HO
Fig. 1. Structures and HMBC correlations of 1–3.
13
The positions of resonances in PMR and C NMR spectra were close to those of the known glycoside (R)-peucedanol-
3′-O-(6″-apiosylfuranosyl)glucopyranoside (26) [23] besides additional resonances due to the additional glucose residue.
The PMR spectrum had two doublets at δ 6.31 and 7.81 (J = 9.2 Hz, H-3 and H-4) and two singlets for aromatic protons
at δ 7.43 and 6.94 (H-5 and H-8), which were typical for 7-hydroxy-6-substituted coumarins [21]. Two paired doublets
at δ 2.48 and 3.02 (H-1′ and H-1′ ) and two 3H singlets at δ 1.22 and 1.25 (H-3′) were attributed to the 3,4-dihydroxyisopentyl
a
b
side chain on C-6 of (R)-peucedanol [16]. The SSCCs for the anomeric proton resonances of glucopyranoses (δ 4.96/4.69)
and apiofuranoses of 1 and 2 (δ 5.63) of 7.1/7.6 and 2.5 Hz, respectively, were consistent with their β-configurations [16].
HMBC spectral data (Fig. 1) allowed the attachment sites of the carbohydrates to the aglycon to be found. Several key
correlations were observed between resonances for glucopyranose H-1″ of 1 (δ 4.96) and aglycon C-7 (δ 160.4); apiofuranose
H-1″′ (δ 5.63) and glucopyranose C-6″ of 1 (δ 69.8); glucopyranose H-1″″ of 2 (δ 4.69) and side-chain C-3′ (δ 82.1). Thus,
the 6″-O-β-D-apiofuranosyl-β-D-glucopyranose was bonded to C-7 of (R)-peucedanol; β-D-glucopyranose, to side-chain
C-3′. The studies established the structure of 1 as (R)-peucedanol-7-O-(6″-O-β-D-apiofuranosyl)-β-D-glucopyranoside-3′-O-
β-D-glucopyranoside, which was called phlojosibiriside I. Several monoglycosides of (R)-peucedanol are known and include
the 7-O-, 2′-O-, and 3′-O-monoglucosides from Seseli montanum L. [16] and the 3′-O-(6″-apiosyl)glucoside from Peucedanum
japonicum Thunb. [21], Phlojodicarpus villosus (Turcz. ex Fisch. & C. A. Mey.) Turcz. ex Ledeb., and P. sibiricus [23].
The (R)-peucedanol diglycoside was observed for the first time in nature.
629

–
Compound 2 had the molecular formula C H O according to HR-ESI-MS (m/z 593.6384 [M – H] ; calcd 593.4704)
27 30 15
13
and C NMR spectroscopy. The UV spectrum showed bands typical of flavones (λ
255, 270, 344 nm) [25]. Hydrolysis
max
of 2 produced D-glucose and D-apiose 1:1) and diosmetin [26]. The negative-ion mass spectrum contained peaks for the
–
deprotonated molecule with m/z 593 [M – H] and ions with m/z 461 and 299 due to sequential loss of apiose and glucose,
13
respectively. The positions of resonances in PMR and C NMR spectra were close to those of diosmetin-7-O-β-D-
glucopyranoside (13) [15] although with additional resonances for apiofuranose at δ 5.59 (H-1″′), 3.79 (H-2″′), 3.70, 4.30
(H-4″′), and 3.67 (H-5″′) in the PMR spectrum and at δ 110.2 (C-1″′), 76.7 (C-2″′), 80.6 (C-3″′), 75.4 (C-4″′), and 65.4 (C-5″′)
13
in the C NMR spectrum. The SSCCs for resonances of the glucopyranose (J = 7.4 Hz) and apiofuranose anomeric protons
(J = 2.2 Hz) were consistent with their β-configurations. The weak-field shift of the glucopyranose C-6″ resonance
(δ 61.5→70.1) relative to 13 indicated the presence of a substituent that was an apiofuranose according to the HMBC
C
spectrum (Fig. 1) because correlations were found between apiose H-1″′ (δ 5.59) and glucose C-6″ (δ 70.1). The results
indicated that 2 was diosmetin-7-O-(6″-O-β-apiofuranosyl)-β-D-glucopyranoside and was called phlojosibiriside II.
–
The molecular mass of 3 was 42 amu greater (C H O , m/z 635.3718 [M – H] ) than that of 2. Its spectral
29 32 16
–
–
characteristics were similar to those of 2. Results from mass spectrometry {m/z 635 [M – H] , 593 [(M – H) – C H O] } and
2
2
13
PMR (δ 1.90, 3H, s) and C NMR spectroscopy [δ 21.4 (CH CO), 171.2 (CH CO)] indicated that an additional acetyl was
3
3
present in 3 [27, 28]. The acetyl was confirmed to be located on C-2″ because the glucopyranose C-2″ resonance was shifted
to weak field (δ 74.8→76.5) as compared to 2 and correlations were observed between the acetyl protons (δ 1.90) and
C
H
glucopyranose C-2″ (δ 76.5) in the HMBC spectrum. These results allowed 3 to be described as an acetyl derivative of
C
phlojosibiriside II or diosmetin-7-O-(2″-O-acetyl-6″-O-β-D-apiofuranosyl)-β-D-glucopyranoside, which was called
phlojosibiriside III.
Information on diosmetin apioglycosides is scant. The only known compound is diosmetin-7-O-(2″-O-apiosyl-6″-O-
acetyl)glucoside from Paullinia pinnata L. (Sapindaceae) [28], an isomer of which is phlojosibiriside III. It was shown earlier
that 6″-O-apiosylglucose could be incorporated in phenolic compounds observed in Phlojodicarpus species. In particular,
umbelliferone 6″-O-apiosylglucoside (18) was also found in P. villosus and P. turczaninovii Sipliv. [Ferulopsis hystrix (Bunge)
Pimenov] [1, 5]. The incorporation of apiose into phenolic glycosides is probably a chemical signature of the genus
Phlojodicarpus.
In general, the research showed that the composition of phenolic compounds from P. sibiricus was similar to that of
other organs (roots, herb, seeds) [1, 5] but differed by a larger structural variety of coumarin and flavonoid glycosides, which
allowed flowers of P. sibiricus to be considered medicinal raw material.
EXPERIMENTAL
General comments were published [1, 32]. Flowers of P. sibiricus were collected in Barguzinsky District
(Republic of Buryatia, Russia; July 26, 2016; 53°59′26.3″ N, 108°89′17.2″ E). A specimen of the raw material is preserved at
the herbarium of the IGEB, SB, RAS (No. CRo/an-03/23-25/0716). The species was determined by Dr. T. A. Aseeva (IGEB,
SB, RAS). Raw material was dried in a convection oven (50°C) to moisture <5% and ground (1–2 mm).
Isolation of 1–26. Plant raw material (860 g) was extracted (3×) with MeOH (1:12, 50°C) in an ultrasonic bath
(100 W, 35 Hz). The extract was concentrated to dryness and suspended in H O (1:5). The resulting suspension was extracted
2
with hexane, EtOAc, and BuOH to give fractions P-1 (34.4 g), P-2 (80.8), and P-3 (120.4), respectively. Fraction P-1 (30 g)
was chromatographed over SiO (CC, 50 × 5 cm, eluent hexane–EtOAc, 100:0→50:50), RP-SiO (CC, 40 × 2 cm, eluent
2
2
H O–MeCN, 50:50→0:100), and Sephadex LH-20 (CC, 50 × 1 cm, eluent MeCN–Me CO, 100:0→80:20) and by preparative
2
2
(prep.) HPLC [isocratic (% MeCN): 0–90 min, 80%] to afford 3′,4′-di-O-isobutyryl-cis-khellactone (14 mg, 4) [7],
3′,4′-di-O-angeloyl-cis-khellactone (praeruptorin D, 19 mg, 5) [8], 3′-O-isovaleryl-4′-O-acetyl-cis-khellactone (dihydrosamidin,
821 mg, 6) [8, 9], 3′-O-(2′′-methylbutyryl)-4′-O-acetyl-cis-khellactone (visnadin, 15 mg, 7) [10], 3′-O-acetyl-4′-O-isobutyryl-
cis-khellactone (hyuganin D, 215 mg, 8) [11], 3′,4′-di-O-acetyl-cis-khellactone (11 mg, 9) [12], and 4′-O-acetyl-cis-khellactone
(20 mg, 10) [13].
Fraction P-2 (75 g) was separated by CC over polyamide (30 × 6 cm, eluent H O–EtOH, 100:0→10:90), SiO (CC,
2
2
20 × 3 cm, eluent hexane–EtOAc, 100:0→70:30), RP-SiO (CC, 40 × 2 cm, eluent H O-–MeCN, 100:0→30:70), and Sephadex
2
2
LH-20 (CC, 50 × 1 cm, eluent EtOH–H O, 90:10→30:70) and by prep. HPLC [gradient mode (% MeCN): 0–70 min, 5–50%,
2
50–90 min, 50–80%] to isolate 1 (27 mg), cis-khellactone-3′-O-glucoside (praeroside II, 38 mg, 11) [14], cis-khellactone-3′-
630

O-(6″-apioside)glucoside (praeroside VI, 26 mg, 12) [14], diosmetin-7-O-glucoside (41 mg, 13) [15], (R)-peucedanol-7-O-
glucoside (21 mg, 14) [16], (R)-peucedanol-2′-O-glucoside (11 mg, 15) [16], (R)-peucedanol-3′-O-glucoside (9 mg, 16) [16],
umbelliferone-7-O-glucoside (skimmin, 57 mg, 17) [17], umbelliferone-7-O-(6″-apiosyl)glucoside (43 mg, 18) [5], 4,5-di-O-
caffeoylquinic acid (37 mg, 19) [18], 3,5-di-O-caffeoylquinic acid (42 mg, 20) [19], 1,3-di-O-caffeoylquinic acid (51 mg, 21)
[18], 5-O-caffeoylquinic acid (308 mg, 22) [20], 4-O-caffeoylquinic acid (9 mg, 23) [18], and 1-O-caffeoylquinic acid
(5 mg, 24) [18].
Chromatographic separation of fraction P-3 (95 g) over polyamide (50 × 6 cm, eluent H O–EtOH, 100:0→10:90)
2
and Sephadex LH-20 (CC, 50 × 1 cm, eluent EtOH–H O, 90:10→10:90) and by prep. HPLC [gradient mode (% MeCN):
2
0–50 min, 5–30%, 50–70 min, 30–40%, 70–90 min, 40–65%] to afford 2 (31 mg), 3 (18 mg), (R)-peucedanol-7-O-(6″-
apiosyl)glucoside (peujaponiside, 24 mg, 25) [21], (R)-peucedanol-2′-O-(6″-apiosyl)glucoside (10 mg, 26) [22], and
(R)-peucedanol-3′-O-(6″-apiosyl)glucoside (14 mg, 27) [23].
–1
Phlojosibiriside I (1). C H O . UV spectrum (50% EtOH, λ , nm): 249, 289 sh, 330. IR spectrum (ν, cm ):
31 44 19
max
+
+
+
1625, 1708. HR-ESI-MS, m/z 721.4007 [M + H] (calcd 721.6296); (+)ESI-MS, m/z: 721 [M + H] , 743 [M + Na] , 759
[M + K] ; 721→559 [(M + H) – C H O ] , 589 [(M + H) – C H O ] ; 559→427 [(M + H) – C H O – C H O ] , 265
[(M + H) – 2 × C H O – C H O ] ; (–)ESI-MS, m/z: 719 [M – H] , 263 [(M – H) – 2 × C H O – C H O ] . Í NMR
+
+
+
+
6
10
5
5
8
4
6
10
5
5
8
4
+
–
– 1
6
10
5
5
8
4
6
10
5
5 8 4
spectrum (500 MHz, MeOH-d , 298 K, δ, ppm, J/Hz): aglycon – 7.81 (1Í, d, J = 9.2, H-4), 7.43 (1Í, s, H-5), 6.94 (1Í, s,
4
H-8), 6.31 (1Í, d, J = 9.2, H-3), 4.06 (1Í, dd, J = 9.8, 1.7, H-2′), 3.02 (1Í, dd, J = 14.0, 1.7, H-1′ ), 2.48 (1Í, dd, J = 14.0,
b
10.1, H-1′ ), 1.22, 1.25 (2 × 3H, s, 3′,3′-(CH ) ); 7-Î-β-D-glucopyranose – 4.96 (1Í, d, J = 7.1, H-1′′), 4.15 (1Í, m, H-6′′ ),
a
3 2
a
3.60 (1Í, m, H-6′′ ), 3.10–3.58 (8Í, m, H-2′′–5′′, H-2′′′′–5′′′′); 6′′-Î-β-D-apiofuranose – 5.63 (1Í, d, J = 2.5, H-1′′′), 4.29
b
(1Í, m, H-4′′′ ), 4.01 (1Í, m, H-6′′′′ ), 3.78 (1Í, m, H-2′′′), 3.72 (1Í, m, H-4′′′ ), 3.65 (2Í, m, H-5′′′); 3′-Î-β-D-glucopyranose
b
a
a
13
– 4.69 (1Í, d, J = 7.6, H-1′′′′), 3.70 (1Í, m, H-6′′′′ ), 3.10–3.58 (8Í, m, H-2′′–5′′, H-2′′′′–5′′′′). C NMR spectrum
b
(125 MHz, MeOH-d , 298 K, δ, ppm) is given in Table 1.
4
20
23
(R)-Peucedanol. C H O . [α] +48.9° (c 1.0, EtOH) {lit.: [α] +43.3° (c 1.2, EtOH) [21]}. UV spectrum (50%
14 16
5
D
D
+
EtOH, λ , nm): 248, 258, 290 sh, 333. HR-ESI-MS, m/z: 265.4711 [M + H] (calcd 265.2620); (+)ESI-MS, m/z: 265
max
+
+
+
– 1
[M + H] , 287 [M + Na] , 303 [M + K] ; (–)ESI-MS, m/z: 263 [M – H] . Í NMR spectrum (500 MHz, MeOH-d , 298 K, δ,
4
ppm, J/Hz): 7.86 (1Í, d, J = 9.1, H-4), 7.45 (1Í, s, H-5), 6.90 (1Í, s, H-8), 6.30 (1Í, d, J = 9.1, H-3), 3.67 (1Í, dd, J = 10.1,
13
2.0, H-2′), 2.94 (1Í, dd, J = 14.1, 2.0, H-1′ ), 2.33 (1Í, dd, J = 14.1, 10.0, H-1′ ), 1.21, 1.23 (2 × 3H, s, 3′,3′-(CH ) ). C NMR
b
a
3 2
spectrum (125 MHz, MeOH-d , 298 K, δ, ppm): 164.3 (C-2), 112.0 (C-3), 147.2 (C-4), 131.9 (C-5), 126.9 (C-6), 161.7 (C-7),
4
103.1 (C-8), 156.1 (C-9), 112.9 (C-10), 32.8 (C-1′), 79.2 (C-2′), 74.3 (C-3′), 25.5, 26.1 {3′,3′-(CH ) }.
3 2
Phlojosibiriside II (2). C H O . UV spectrum (50% EtOH, λ , nm): 255, 270, 344. HR-ESI-MS, m/z: 593.6384
27 30 15
max
–
+
–
–
[M – H] (calcd 593.4704). (+)ESI-MS, m/z: 595 [M+H] ; (–)ESI-MS, m/z: 593 [M – H] ; 593→461 [(M – H) – C H O ] , 299
5
8 4
–
– 1
[(M – H) – C H O – C H O ] ; 299→285 [(M – H) – C H O – C H O – CH ] . Í NMR spectrum (500 MHz,
5
8
4
6
10
5
5
8
4
6
10
5
2
MeOH-d /DMSO-d *, 298 K, δ, ppm, J/Hz): aglycon – 13.04* (1Í, br.s, 5-OH), 9.84* (1Í, br.s, 3′-OH), 7.76 (1Í, dd, J = 2.0,
4
6
8.0, H-6′), 7.50 (1Í, d, J = 2.2, H-2′), 7.04 (1Í, d, J = 8.0, H-5′), 6.87 (1Í, s, H-3), 6.78 (1Í, d, J = 2.1, H-8), 6.43 (1Í, d,
J = 2.1, H-6), 3.82 (3Í, s, 4′-OCH ); 7-Î-β-D-glucopyranose – 5.03 (1Í, d, J = 7.4, H-1′′), 4.07 (1Í, m, H-6′′ ), 3.64 (1Í, m,
3
a
H-6′′ ), 3.37 (1Í, m, H-2′′), 3.07–3.31 (3Í, m, H-3′′–5′′); 6′′-Î-β-D-apiofuranose – 5.59 (1Í, d, J = 2.2, H-1′′′), 4.30 (1Í,
b
13
m, H-4′′′ ), 3.79 (1Í, m, H-2′′′), 3.70 (1Í, m, H-4′′′ ), 3.67 (2Í, m, H-5′′′). C NMR spectrum (125 MHz, MeOH-d ,
b
a
4
298 K, δ, ppm) is given in Table 1.
–1
Phlojosibiriside III (3). C H O . UV spectrum (50% EtOH, λ , nm): 254, 270, 343. IR spectrum (ν, cm ):
29 32 16
max
–
+
1638, 1720. HR-ESI-MS, m/z 635.3718 [M – H] (calcd 635.5042); (+)ESI-MS, m/z 637 [M + H] ; (–)ESI-MS, m/z: 635
–
–
–
[M – H] ; 635→593 [(M – H) – C H O] ; 593→461 [(M – H) – C H O – C H O ] , 299 [(M – H) – C H O – C H O –
2
2
2
2
5
8
4
2
2
5 8 4
–
– 1
C H O ] ; 299→285 [(M – H) – C H O – C H O – C H O – CH ] . Í NMR spectrum (500 MHz, MeOH-d /DMSO-d *,
6
10
5
2
2
5
8
4
6
10
5
2
4
6
298 K, δ, ppm, J/Hz): aglycon – 13.01* (1Í, br.s, 5-OH), 9.89* (1Í, br.s, 3′-OH), 7.69 (1Í, dd, J = 2.0, 8.3, H-6′), 7.43 (1Í,
d, J = 2.0, H-2′), 7.01 (1Í, d, J = 8.3, H-5′), 6.75 (1Í, s, H-3), 6.70 (1Í, d, J = 2.0, H-8), 6.42 (1Í, d, J = 2.0, H-6), 3.83 (3Í,
s, 4′-OCH ); 7-Î-β-D-glucopyranose – 4.98 (1Í, d, J = 7.2, H-1′′), 4.11 (1Í, m, H-6′′ ), 3.62 (1Í, m, H-6′′ ), 3.49 (1Í, m,
3
a
b
H-2′′), 3.02–3.29 (3Í, m, H-3′′–5′′), 1.90 (3Í, s, 2′′-CH CO); 6′′-Î-β-D-apiofuranose – 5.46 (1Í, d, J = 2.1, H-1′′′), 4.25 (1Í, m,
3
13
H-4′′′ ), 3.82 (1Í, m, H-2′′′), 3.74 (1Í, m, H-4′′′ ), 3.69 (2Í, m, H-5′′′). C NMR spectrum (125 MHz, MeOH-d , 298 K,
b
a
4
δ, ppm) is given in Table 1.
Acid Hydrolysis. The compound (5–7 mg) and TFA (5%) in Me CO (70%, 3 mL) was heated at 110°C (60 min).
2
The hydrolysate was concentrated to dryness under vacuum. The dry residue was dissolved in EtOH (50%, 5 mL).
631

The resulting solution was placed on polyamide (10 g) and eluted by H O (50 mL, eluate I) and MeOH (70%, 100 mL, eluate II).
2
The monosaccharide composition in eluate I and their assignment as D- and L-types were determined by HPLC-UV after
reaction with 3-methyl-1-phenyl-2-pyrazolin-5-one [29] and L-tryptophan [30], respectively. The aglycons were analyzed by
HPLC-MS [31] using retention times and UV and mass spectra and comparisons with known compounds and literature data.
Eluate I of 1 contained D-glucose and D-apiose (2:1); 2 and 3, D-glucose and D-apiose (1:1). Eluate II of 1 contained
(R)-peucedanol [16]; 2 and 3, diosmetin [26].
ACKNOWLEDGMENT
The studies were supported by FASO Russia (AAAA-AA17-117011810037-0 and FSRG-2020-0019).
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