# Flavonoids from Stachys annua Growing in Azerbaijan

I.S S Movsumov, E.A. A Garayev, Beatrice Baghdikian, Fathi Mabrouki, Gaëtan Herbette, Evelyne Ollivier, T.A. A Suleimanov, E.E. Garayev

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I.S S Movsumov, E.A. A Garayev, Beatrice Baghdikian, Fathi Mabrouki, Gaëtan Herbette, et al. Flavonoids from Stachys annua Growing in Azerbaijan. Chemistry of Natural Compounds, 2018, 54 (2), pp.261-262. 10.1007/s10600-018-2318-y. hal-01802785

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Distributed under a Creative Commons Attribution 4.0 International License
FLAVONOIDS FROM *Stachys annua* GROWING IN AZERBAIJAN

I. S. Movsumov,<fnref n="1" /> E. A. Garayev,<fnref n="1" />* B. Baghdikian,<fnref n="2" /> F. Mabrouki,<fnref n="2" /> G. Herbette,<fnref n="3" /> E. Ollivier,<fnref n="2" /> T. A. Suleimanov,<fnref n="1" /> and E. E. Garayev<fnref n="1" />,<fnref n="2" />

Translated from *Khimiya Prirodnykh Soedinenii*, No. 2, March-April, 2018, pp. 217-218. Original article submitted July 13, 2017.

*The new acylated flavonoid bioside 4'-O-methylisoscutellarein-7-O-[4'''-O-acetyl]alpyranosyl-(1→2)-glucopyranoside (1) was isolated from the aerial parts of Stachys annua L. (Lamiaceae). Subterranean organs yielded for the first time 4'-O-methylisoscutellarein (2) and 4'-O-methylisoscutellarein-7-O-[6''-O-acetyl]alpyranosyl-(1→2)-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* β-sitosterol, ursolic acid, and 4'-*O*-methylisoscutellarein-7-*O*-[6'''-*O*-acetyl]alpyranosyl-(1→2)-glucopyranoside [3].

Herein, data are presented for the new acylated bioside 4'-*O*-methylisoscutellarein-7-*O*-[4'''-*O*-acetyl]alpyranosyl-(1→2)-glucopyranoside (annuoside, 1) from the aerial part and 4'-*O*-methylisoscutellarein (2) and 4'-*O*-methylisoscutellarein-7-*O*- (6'''-*O*-acetyl)alpyranosyl-(1→2)-glucopyranoside (3) from the subterranean organs of *S. annua*.

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Acid hydrolysis of **1** produced the aglycon, acetic acid, D-glucose, and D-allose.

PMR spectra showed resonances for aromatic-ring protons at δ 8.2-6.0 ppm. Correlations were observed in the COSY spectrum between H-1"-H-2"-H-3"-H-4"-H-5" and H-1'''-H-2'''-H-3'''-H-4'''-H-5''' and corresponded to ring protons of the two sugars.

Resonances for anomeric protons could be seen in the HMBC spectrum. A correlation between H-1" (δ 5.17 ppm) and C-7 (δ 151.0) confirmed that the first sugar was bonded to C-7. Two correlations between H-2" (δ 3.63) and C-1''' (δ 101.4) in addition to H-1''' (δ 4.97) and C-2" (δ 81.7) confirmed that the second sugar was bonded to the first at C-2". The HMBC spectrum established that the OCH₃ group (δ 3.87) was situated on C-4' (δ 162.3); the CH₃ (δ 1.99), to -COO (δ 169.4); the methyl ester -COOCH₃, to C-4''' (δ 4.53).

<footnote n="1">1) Azerbaijan Medical University, 21 A. Bakikhanov St., Baku, AZ 1000, Azerbaijan, e-mail: eldargar@mail.ru;</footnote>

<footnote n="2">2) Aix-Marseille Univ. IMBE, Laboratoire de Pharmacognosie et Ethnopharmacologie, Faculte de Pharmacie, 27 Boulevard Jean Moulin, CS30064, 13385 Marseille Cedex 5, France;</footnote>

<footnote n="3">3) Spectropole, FR1739, Aix-Marseille Universite, Campus Scientique Saint Jerome, Service 511, 13397 Marseille Cedex 20, France, e-mail: gaetan.herbette@univ-amu.fr.</footnote>
The aglycon had the formula $C_{16}H_{12}O_6$, mp 272–274°C (EtOH), and $R_f$ 0.81. The physicochemical and chemical properties and chromatographic and spectroscopic data for the aglycon of annuoside identified it as 4'-*O*-methylisoscutellarein.

## EXPERIMENTAL

**General Comments.** Chromatography used Filtrak FN5 paper and solvent system *n*-BuOH–HOAc–$H_2O$ (4:1:5, 1). 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 (3×) 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, $CHCl_3$, and EtOAc.

Recrystallization from aqueous EtOH of the EtOAc extract afforded 4'-*O*-methylisoscutellarein-7-*O*-((6'''-*O*-acetyl)alpyranosyl-(1→2)-glucopyranoside [3] and compound 1, which was called annuoside [3].

**Annuoside (1)**, $C_{30}H_{34}O_{17}$, greenish-yellow crystals; soluble in aqueous EtOH, DMF, and Py; poorly soluble in EtOH and $H_2O$; insoluble in $CHCl_3$ and EtOAc; mp 176–178°C ($H_2O$), $R_f$ 0.59. $^1$H NMR spectrum (600 MHz, DMSO-d$_6$, $\delta$, ppm, J/Hz): 8.11 (2H, d, J = 8.8, H-2', 6'), 7.14 (2H, d, J = 8.8, H-3', 5'), 6.92 (1H, s, H-3), 6.64 (1H, s, H-6), 5.17 (1H, d, J = 7.7, H-1''), 4.97 (1H, d, J = 7.7, H-1'''), 4.53 (1H, dd, J = 10.2, 2.5, H-4'''), 4.09 (1H, br.t, J = 2.8, H-3'''), 3.87 (3H, s, $OCH_3$), 3.86 (1H, m, H-5'''), 3.73 (1H, m, H-6''), 3.63 (1H, dd, J = 9.0, 7.7, H-2''), 3.51 (1H, m, H-3''), 3.48 (1H, m, H-6''), 3.46 (1H, m, H-5''), 3.27 (1H, m, H-6'''), 3.25 (1H, m, H-4''), 3.22 (1H, m, H-2'''), 3.23 (1H, m, H-6'''), 1.99 (s, OAc). $^{13}$C NMR spectrum (150 MHz, DMSO-d$_6$, $\delta$, ppm): 163.5 (C-2), 103.4 (C-3), 182.2 (C-4), 152.3 (C-5), 98.1 (C-6), 151.0 (C-7), 126.8 (C-8), 144.1 (C-9), 104.8 (C-10), 122.8 (C-1'), 128.3 (C-2', 6'), 114.4 (C-3', 5'), 162.3 (C-4'), 55.4 ($OCH_3$), 98.9 (C-1''), 81.7 (C-2''), 75.4 (C-3''), 69.0 (C-4''), 76.7 (C-5''), 60.3 (C-6''), 101.4 (C-1'''), 70.9 (C-2'''), 67.6 (C-3'''), 69.0 (C-4'''), 71.6 (C-5'''), 59.6 (C-6'''), 20.8, 169.4 (OAc) [3].

**Isolation of Flavonoids from Subterranean Organs of *S. Annua* L.** Ground and air-dried subterranean organs (0.8 kg) were extracted (3×) with EtOH (80%) at room temperature. The combined extracts were evaporated in vacuo to an aqueous residue that was worked up sequentially with hexane, $CHCl_3$, hexane–EtOAc, and EtOAc.

Recrystallization of the hexane–EtOAc extract from aqueous EtOH produced **2** (4'-methoxyisoscutellarein), $C_{16}H_{12}O_6$, mp 270–272°C, $R_f$ 0.81. Alkaline hydrolysis of **2** formed 4-methoxybenzoic acid [4].

Recrystallization of the EtOAc extract from EtOH produced **3**, acid hydrolysis (5% $H_2SO_4$, 5 h) of which cleaved **3** into the aglycon, AcOH, D-glucose, and D-allose. Aglycon, $C_{16}H_{12}O_6$, mp 270–272°C (EtOH), $R_f$ 0.81. Compound **3** was isolated earlier from the subterranean organs of *S. annua* [5].

## REFERENCES

1. *Flora of Azerbaijan* [in Russian], Vol. VI, Baku, 1957, 646 pp.

2. *Plant Resources. Flowering Plants, Their Chemical Compositions, and Use. Families Hippuridaceae-Lobeliaceae* [in Russian], Nauka, St. Petersburg, 1991, 197 pp.

3. D. C. Albach, R. J. Grayer, S. R. Jensen, F. Ozgokce, and N. C. Veitch, *Phytochemistry*, **64** (7), 1295 (2003).

4. 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).