A NEW NATURAL COMPOUND OF THE FURANOCOUMARIN CLASS FROM Symphyoloma graveolens C.A.Mey

ABSTRACT

The article is devoted to the phytochemical study of the species Symphyoloma graveolens. The Symphyoloma genus belongs to the Umbelliferae family. In this study, phytochemical compounds of the plant were isolated, and their structures were determined. The roots of Symphyoloma graveolens were extracted using acetone as a solvent. Then, individual components were isolated through chromatographic separation on a glass column filled with aluminum oxide (Al₂O₃). From the underground part of the plant, pimpinellin, isopimpinellin, isobergapten, oxyepoxypeucedanin hydrate, osthol, sakuranetin, xanthotoxin, and a new natural monomethoxyfuranocoumarin were isolated and identified. The chemical composition of the Symphyoloma graveolens plant (coumarin derivatives) has been determined for the first time.

АННОТАЦИЯ

Статья посвящена фитохимическому изучению вида Symphyoloma graveolens. Род Symphyoloma относится к семейству зонтичных. В этом исследовании были изолированы фитохимические вещества растения, и их структуры были установлены. Корни Symphyoloma graveolens подверглись экстракции с использованием ацетона в качестве растворителя. Затем отдельные компоненты были изолированы с помощью хроматографического разделения на стеклянной колонке, заполненной алюминием (Al₂O₃). Из подземной части были изолированы и идентифицированы пимпинеллин, изопимпинеллин, изобергаптен, оксипеуденанин-гидрат, остхол, сакуранетин, ксантофиксин и новый природный монометоксифурокумарин. Впервые определен химический состав растения Symphyoloma graveolens (производные кумарина).

Keywords: Apiaceae Lindl, furocoumarin, Symphyoloma graveolens C.A.Mey., chemical shift.

Ключевые слова: Apiaceae Lindl., фурокумарин, S. graveolens C.A.Mey., химический сдвиг.

Introduction 

Symphyoloma graveolens C.A.Mey. It is an endemic species of the Caucasus [1, 2, 10]. Fragments are observed in the flora of the Greater Caucasus [3]. There has been no research about phytochemistry of Symphyoloma graveolens present.  S.graveolens species belonging to the genus Symphyoloma was collected  from the territory of Gadabay region of the Republic of Azerbaijan and the underground part was studied [4]. Total extracted substances obtained by extraction of the underground parts with acetone were separated over a column of Al₂O₃ with elution by hexane, hexane: benzene in various ratios, benzene, benzene: CHCl₃, and pure CHCl₃. The isolated coumarin-type compounds: C₁₁H₆O₄, mp 286,0-289,5°C (1, ν_max 219, 250, 265, 300); C₁₂H₈O₄, mp 172–174°C (2, ν_max 1731,1631, 1600); C₁₂H₈O₄, mp 223–224°C (3, ν_max 1752, 1631, 1610 cm–1); C₁₃H₁₀O₅, mp 149–151°C (4, ν_max 1754, 1733, 1600, 1557); C₁₅H₁₆O₃, mp 84–85°C (5, ν_max 1730, 1622, 1564); C₁₆H₁₆O_6, mp 137,0-138,0°C (6, ν_max 1736,1624, 1587, 1550); C₁₆H₁₄O_5, mp141,0-143°C (7, ν_max 220, 249,265, 306)  and C₁₃H₁₀O₅, mp 117–119°C (8, ν_max 1745, 1630, 1584, 1546).

Compounds 1 and 3–5 were identified by direct comparison of IR spectra as isobergapten, pimpinellin, isopimpinellin, and osthole, respectively [5]. The ¹HMR spectrum of 2 had a 3H singlet at 4.00 ppm (CH₃O) and 1H doublets at 6.33 ppm (J = 9.8 Hz, H-3), 7.97 (J = 9.8 Hz, H-4), 7.10 (1H, s), 7.17 (1H, d, J = 2.3 Hz), and 7.95 (1H, d, J = 2.3 Hz) that belonged to protons of a methoxy furocoumarin. The ¹³C NMR spectrum taken with full spin–spin decoupling showed 12 resonances corresponding to ¹²C atoms of the studied molecule. The ¹³C DEPT-135 spectrum had six resonances (54.0, 103.0, 104.0, 112.0, 145.0, 147.0 ppm) for protonated C atoms, of which five according to ¹³C DEPT-90 NMR (104.0, 105.0, 114.0, 145.5, 147.5 ppm) belonged to olefinic (CH=) C atoms.

Thus, a study of these ¹³C NMR and ¹³C DEPT-135 and DEPT-90 spectra found easily that 2 was a methoxy furocoumarin. The known methoxy furocoumarin bergaptol (1), oxypeucedanin hydate (6), sakuranetin (7), isopimpinellin (8), and oxypeucedanin (9) (obtained during the synthesis of bergapten) (given below) differ in the placement of the methoxyl and the furan ring.  ¹HNMR spectra of monomethoxyfurocoumarins 2,6,7,8 (ppm,J/Hz) [5-9], (Table 1).

Table 1.

 ¹H NMR spectra of monomethoxy furocoumarins 2,6,7,8 (ppm, J/Hz) [5, 6, 7]

7-methoxy-8H-furo [2, 3-h]-1-benzopyran-2-one [5] and 8-methoxy-8H-furo [2,3-h]-1-benzopyran-2-one. The latter structure is preferred.

Materials and methods

Symphyoloma graveolens (300 g) were extracted with acetone (3×, each time for 3 d). The extracts were filtered and evaporated to afford total extracted dark-brown substances (32, 3 g, 10.76% yield).

The purity of compounds was established on Silufol UV-254 chromatographic plates. ¹HMR and ¹³C NMR spectra were taken in deuterated acetone on a Bruker 300 spectrometer at operating frequency 300 MHz for ¹H and 75 MHz for ¹³C. IR spectra were recorded in mineral oil on a UR-20 spectrophotometer. Chemical shifts were determined on the -scale relative to TMS internal standard.

Discussion

Total extracted substances (30 g) were chromatographed over a column of Al₂O₃ (neutral, III-IV activity) (h = 100, d = 3.5 cm) with elution by hexane, hexane+benzene, benzene, benzene+CHCl₃ and CHCl₃, CHCl₃ + ethanol. The volume of each fraction was 100 mL. Infrared absorption spectra were recorded on an FTIR Spectrometer Agilent Cary 630. ¹H NMR and ¹³C NMR were measured on a Bruker 300 spectrometer with a resonance frequency of 300 MHz for ¹H and 75 MHz for ¹³C. The solvent used was CDCl₃. Chemical shifts are given on the δ scale. The internal standard is TMS. The individuality of the substance was determined on Silufol UV 254 plates, and the melting point was determined using a ‘Vika’ apparatus.

Conclusion

The chemical composition of Symphyoloma graveolens plant (coumarin derivatives) was determined by us for the first time. The ¹H NMR spectrum (Table 1) shows the presence of a methoxy group (–OCH3) in the molecule, and a new natural monomethoxyfurocoumarin was isolated from this species. Bergapten, which is a coumarin derivative, ammifurin, which is a mixture of isopimpinellin and bergapten, beroxan, which is a mixture of bergapten and xantotoxin, and meladin, which contains xanthotoxin and imperatorin, are widely used in the treatment of vitiligo. Coumarin derivatives of Symphyoloma graveolens plant are expected to be used in medicine.

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