Flavonoids from Stachys annua Growing in Azerbaijan

Article abstract of DOI:10.1007/s10600-018-2318-y

The new acylated flavonoid bioside 4′-O-methylisoscutellarein-7-O-[4-O-acetyl]allopyranosyl-(1→2)-glucopyranoside (1) was isolated from the aerial parts of Stachys annua L. (Lamiaceae). Subterranean organs yielded for the first time 4′-O-methylisoscutella

Full text of DOI:10.1007/s10600-018-2318-y

DOI 10.1007/s10600-018-2318-y
Chemistry of Natural Compounds, Vol. 54, No. 2, March, 2018
FLAVONOIDS FROM Stachys annua GROWING IN AZERBAIJAN
1
1*
2
2
I. S. Movsumov, E. A. Garayev, B. Baghdikian, F. Mabrouki,
3
2
1
1,2
G. Herbette, E. Ollivier, T. A. Suleimanov, and E. E. Garayev
The new acylated flavonoid bioside 4ꢀ-O-methylisoscutellarein-7-O-[4ꢀꢀꢀ-O-acetyl]allopyranosyl-(1ꢁ2)-
glucopyranoside (1) was isolated from the aerial parts of Stachys annua L. (Lamiaceae). Subterranean
organs yielded for the first time 4ꢀ-O-methylisoscutellarein (2) and 4ꢀ-O-methylisoscutellarein-7-O-[6ꢀꢀ-O-
acetyl]allopyranosyl-(1ꢁ2)-glucopyranoside (3). Chemical structures of the isolated compounds were
elucidated using NMR spectroscopy.
Keywords: Stachys annua, Lamiaceae, new acylated bioside, annuoside.
In continuation of the search for potential new sources of biologically active compounds [1], we studied the aerial and
subterranean organs of Stachys annua L. from the flora of Azerbaijan.
Previously, several Stachys species including S. annua from Ukraine, Azerbaijan, and European countries
were incompletely studied [2]. Earlier, we isolated from the aerial parts of S. annua ꢂ-sitosterol, ursolic acid, and
4
ꢀ-O-methylisoscutellarein-7-O-[6ꢀꢃ-O-acetyl]allopyranosyl-(1ꢁ2)-glucopyranoside [3].
Herein, data are presented for the new acylated bioside 4ꢀ-O-methylisoscutellarein-7-O-[4ꢀꢃ-O-acetyl]allopyranosyl-
(
1ꢁ2)-glucopyranoside (annuoside, 1) from the aerial part and 4ꢀ-O-methylisoscutellarein (2) and 4ꢀ-O-methylisoscutellarein-
7
-O-(6ꢀꢃ-O-acetyl)allopyranosyl-(1ꢁ2)-glucopyranoside (3) from the subterranean organs of S. annua.
OH
4' OCH
3
6
''
OH
O
HO
HO
O
9
O
O
1'
7
6'
O 1''
3
''
3
O
OH
10
5
6'''
O
OH
O
1'''
3
'''
OH
HO
1
Acid hydrolysis of 1 produced the aglycon, acetic acid, D-glucose, and D-allose.
PMR spectra showed resonances for aromatic-ring protons at ꢄ 8.2–6.0 ppm. Correlations were observed in the
COSY spectrum between H-1ꢃ–H-2ꢃ–H-3ꢃ–H-4ꢃ–H-5ꢃ and H-1ꢀꢃ–H-2ꢀꢃ–H-3ꢀꢃ–H-4ꢀꢃ–H-5ꢀꢃ and corresponded to ring protons
of the two sugars.
Resonances for anomeric protons could be seen in the HMBC spectrum. A correlation between H-1ꢃ (ꢄ 5.17 ppm)
and C-7 (ꢄ 151.0) confirmed that the first sugar was bonded to C-7. Two correlations between H-2ꢃ (ꢄ 3.63) and C-1ꢀꢃ (ꢄ 101.4)
in addition to H-1ꢀꢃ (ꢄ 4.97) and C-2ꢃ (ꢄ 81.7) confirmed that the second sugar was bonded to the first at C-2ꢃ. The HMBC
spectrum established that the OCH group (ꢄ 3.87) was situated on C-4ꢀ (ꢄ 162.3); the CH (ꢄ 1.99), to –COO (ꢄ 169.4); the
3
3
methyl ester –COOCH , to C-4ꢀꢃ (ꢄ 4.53).
3
1
) Azerbaijan Medical University, 21 A. Bakikhanov St., Baku, AZ 1000, Azerbaijan, e-mail: eldargar@mail.ru;
2
) Aix-Marseille Univ. IMBE, Laboratoire de Pharmacognosie et Ethnopharmacologie, Faculte de Pharmacie, 27 Boulevard
Jean Moulin, CS30064, 13385 Marseille Cedex 5, France; 3) Spectropole, FR1739, Aix-Marseille Universite, Campus Scientique
Saint Jerome, Service 511, 13397 Marseille Cedex 20, France, e-mail: gaetan.herbette@univ-amu.fr. Translated from Khimiya
Prirodnykh Soedinenii, No. 2, March–April, 2018, pp. 217–218. Original article submitted July 13, 2017.
0
009-3130/18/5402-0261 ©2018 Springer Science+Business Media, LLC
261

The aglycon had the formula C H O , mp 272–274°C (EtOH), and R 0.81. The physicochemical and chemical
1
6
12
6
f
properties and chromatographic and spectroscopic data for the aglycon of annuoside identified it as 4ꢀ-O-methylisoscutellarein.
EXPERIMENTAL
General Comments. Chromatography used Filtrak FN5 paper and solvent system n-BuOH–HOAc–H O (4:1:5, 1).
2
UV spectra were recorded on an Agilent Technologies Cary 60 UV-Vis instrument; NMR spectra, on a Bruker AM-600
spectrometer; melting points, on a CMP 20 apparatus.
Isolation of Glavonoids from the Aerial Part of S. Annua. Raw material was collected in June 2015 in the vicinity
of Shamakhi, Republic of Azerbaijan. Air-dried and ground aerial plant parts (1.0 kg) were extracted (3ꢅ) with EtOH (80%)
at room temperature. The extracts were combined and evaporated in vacuo to a watery residue that was worked up sequentially
with hexane, CHCl , and EtOAc.
3
Recrystallization from aqueous EtOH of the EtOAc extract afforded 4ꢀ-O-methylisoscutellarein-7-O-(6ꢀꢃ-O-
acetyl)allopyranosyl-(1ꢁ2)-glucopyranoside [3] and compound 1, which was called annuoside [3].
Annuoside (1), C H O , greenish-yellow crystals; soluble in aqueous EtOH, DMF, and Py; poorly soluble in
3
0 34 17
1
EtOH and H O; insoluble in CHCl and EtOAc; mp 176–178°C (H O), R 0.59. Í NMR spectrum (600 MHz, DMSO-d , ꢄ,
2
3
2
f
6
ppm, J/Hz): 8.11 (2Í, d, J = 8.8, Í-2ꢀ, 6ꢀ), 7.14 (2Í, d, J = 8.8, Í-3ꢀ, 5ꢀ), 6.92 (1Í, s, Í-3), 6.64 (1Í, s, Í-6), 5.17 (1Í, d,
J = 7.7, Í-1ꢀꢀ), 4.97 (1Í, d, J = 7.7, Í-1ꢀꢀꢀ), 4.53 (1Í, dd, J = 10.2, 2.5, Í-4ꢀꢀꢀ), 4.09 (1Í, br.t, J = 2.8, Í-3ꢀꢀꢀ), 3.87 (3Í, s,
ÎÑÍ ), 3.86 (1Í, m, Í-5ꢀꢀꢀ), 3.73 (1Í, m, Í-6ꢀꢀ), 3.63 (1Í, dd, J = 9.0, 7.7, Í-2ꢀꢀ), 3.51 (1Í, m, Í-3ꢀꢀ), 3.48 (1Í, m, Í-6ꢀꢀ),
3
3
.46 (1Í, m, Í-5ꢀꢀ), 3.27 (1Í, m, Í-6ꢀꢀꢀ), 3.25 (1Í, m, Í-4ꢀꢀ), 3.22 (1Í, m, Í-2ꢀꢀꢀ), 3.23 (1Í, m, Í-6ꢀꢀꢀ), 1.99 (s, OÀñ).
1
3
C NMR spectrum (150 MHz, DMSO-d , ꢄ, ppm): 163.5 (Ñ-2), 103.4 (Ñ-3), 182.2 (Ñ-4), 152.3 (Ñ-5), 98.1 (Ñ-6), 151.0
6
(
(
(
Ñ-7), 126.8 (Ñ-8), 144.1 (Ñ-9), 104.8 (Ñ-10), 122.8 (Ñ-1ꢀ), 128.3 (Ñ-2ꢀ, 6ꢀ), 114.4 (Ñ-3ꢀ, 5ꢀ), 162.3 (Ñ-4ꢀ), 55.4 (ÎÑÍ ), 98.9
Ñ-1ꢀꢀ), 81.7 (Ñ-2ꢀꢀ), 75.4 (Ñ-3ꢀꢀ), 69.0 (Ñ-4ꢀꢀ), 76.7 (Ñ-5ꢀꢀ), 60.3 (Ñ-6ꢀꢀ), 101.4 (Ñ-1ꢀꢀꢀ), 70.9 (Ñ-2ꢀꢀꢀ), 67.6 (Ñ-3ꢀꢀꢀ), 69.0
Ñ-4ꢀꢀꢀ), 71.6 (Ñ-5ꢀꢀꢀ), 59.6 (Ñ-6ꢀꢀꢀ), 20.8, 169.4 (OÀñ) [3].
3
Isolation of Flavonoids from Subterranean Organs of S. Annua L. Ground and air-dried subterranean organs
0.8 kg) were extracted (3ꢅ) with EtOH (80%) at room temperature. The combined extracts were evaporated in vacuo to an
(
aqueous residue that was worked up sequentially with hexane, CHCl , hexane–EtOAc, and EtOAc.
3
Recrystallization of the hexane–EtOAc extract from aqueous EtOH produced 2 (4ꢀ-methoxyisoscutellarein), C H O ,
16 12 6
mp 270–272°C, R 0.81. Alkaline hydrolysis of 2 formed 4-methoxybenzoic acid [4].
f
Recrystallization of the EtOAc extract from EtOH produced 3, acid hydrolysis (5% H SO , 5 h) of which cleaved 3
2
4
into the aglycon, AcOH, D-glucose, and D-allose. Aglycon, C H O , mp 270–272°C (EtOH), R 0.81. Compound 3 was
1
6
12
6
f
isolated earlier from the subterranean organs of S. annua [5].
REFERENCES
1
2
.
.
Flora of Azerbaijan [in Russian], Vol. VI, Baku, 1957, 646 pp.
Plant Resources. Flowering Plants, Their Chemical Compositions, and Use. Families Hippuridaceae-Lobeliaceae
in Russian], Nauka, St. Petersburg, 1991, 197 pp.
[
3
4
.
.
D. C. Albach, R. J. Grayer, S. R. Jensen, F. Ozgokce, and N. C. Veitch, Phytochemistry, 64 (7), 1295 (2003).
N. F. Komissarenko, A. I. Derkach, I. P. Sheremet, I. P. Kovalev, and V. G. Gordienko, Chem. Nat. Compd.,
14, 445 (1979).
5.
I. S. Movsumov, D. Yu. Yusifova, T. A. Suleimanov, V. Mahiou-Leddet, G. Herbette, B. Baghdikian, E. E. Garayev,
E. Ollivier, and E. A. Garayev, Chem. Nat. Compd., 52, 324 (2016).
262