Chemical Composition of Essential Oil from Dionysia hissarica

The genus Dionysia Fenzl (Primulaceae) numbers 49 species that are broadly distributed in Afghanistan, Central Asia, and Iran. Five species occur in Central Asia; only one, D. hissarica, in the flora of Uzbekistan [[1] ].

D. hissarica Lipsky from the Khursang River valley of Sangardak basin (1,200-1,600 m above sea level) was first described in 1901. The plant is a very rare endemic and is currently listed in the Red Book of Uzbekistan as a threatened species [[2] ]. D. hissarica is a very aromatic plant with a specific aroma. Its chemical composition has not been studied until now. Herein, essential oil from the aerial part of D. hissarica was analyzed using GC-MS.

The aerial part of D. hissarica was collected in summer 2011 in the Machai Baisun-Tau River valley at 1,600 m above sea level (Hissar Mountains, Kashkadarya District, Uzbekistan). Taxonomic identification was made at the Botany Institute, AS, RU. A specimen of the collected D. hissarica is preserved in the herbarium collection under code No. 0251, 9.VII 2011.

Essential oils were produced according to the protocol published in our previous articles [[3] , [4] ]. For this, aerial part of D. hissarica (50 g) was placed into a 500-mL working flask and treated with distilled H2O (~200 mL). Distillate was collected for 2 h using a Clevenger apparatus and extracted with CH2Cl2. The extract of essential oil was dried over anhydrous Na2SO4. The resulting oil (yield ~0.7%) was stored in a refrigerator at -4°C until use.

Essential-oil constituents were analyzed by GC-MS on an Agilent 7890B gas chromatograph with a 5977A quadrupole mass spectrometer as the detector, an autosampler, VF-Wax ms quartz column (30 m, 100% polyethylene glycol) with inner diameter 0.25 μm (Agilent Technologies, Netherlands), and He carrier gas at constant flow rate 0.9 mL/min. The vaporizer temperature was 280°C, ion-source temperature 230°C, GC-MS interface temperature 280°C. Electron-impact ionization at 70 eV was used. Data were collected in the mass range 45-950 amu.

Essential oil dissolved in CH2Cl2 (0.5 μL) was injected automatically with flow division 1:20 into the vaporizer. The column temperature was maintained at 50°C for 5 min, raised from 50 to 280°C at 5°C/min, and held at 280°C for 15 min at the end. The injector temperature was 250°C; detector temperature, 270°C. Enhanced ChemStation version MSD F.01.01.2317 software (Agilent Technologies) was used to record and integrate chromatograms. Quantitative contents of essential-oil constituents were calculated from peak areas. Qualitative analysis was based on comparing retention indices (RI) and total mass spectra with the corresponding data for standard oil constituents and pure compounds and with GC-MS libraries and the Wiley Registry of Mass Spectral Data (9th Ed.), NIST Mass Spectral Library (2011), and catalogs [[5] , [6] ].

Table 1 lists the essential-oil composition of D. hissarica. A total of 74 constituents were found in the essential oil. The total content of identified constituents was 93.9%. The main constituents were 2′-hydroxy-5′-methoxyacetophenone (9.7%), myrtenol (6.9%), globulol (6.4%), eudesm-6-en-4-α-ol (6.0%), 2′-hydroxy-4′-methoxyacetophenone (5.8%), δ-cadinene (4.3%), α-cadinol (3.4%), and benzaldehyde dimethyl acetal (3.3%).

Qualitative Composition and Quantitative Content of Essential Oil Constituents from Dionysia hissarica

Compound	RI	Peak area, %	Compound	RI	Peak area, %
γ-Terpinene	1242	Tr.	Phenol	1991	0.2
Cymol	1267	Tr.	Methyl tetradecanoate	2005	Tr.
3-Hexen-1-ol	1379	Tr.	α-Humulene oxide	2030	1.0
1,1-Dimethoxynonane	1466	Tr.	Humulene epoxide	2047	0.4
α-Copaene	1484	Tr.	Epiglobulol	2056	1.2
Benzaldehyde	1513	1.1	Globulol	2090	6.4
α-Gurjunene	1522	Tr.	Viridiflorol	2096	1.0
Benzaldehyde dimethyl acetal	1532	3.3	cis-3-Hexenyl benzoate	2115	1.1
Linalool	1543	0.7	Hexahydrofarnesyl acetone	2123	1.1
Endo-bornyl acetate	1572	Tr.	epi-α-Cadinol	2163	2.1
(Z)-Caryophyllene	1588	1.4	Eudesm-6-en-4-α-ol	2167	6.0
4-Terpineol	1595	2.9	t-Muurolol	2180	1.7
(E)-Caryophyllene	1604	0.2	2′-Hydroxy-5′-methoxyacetophenone*	2188	9.7
Alloaromadendrene	1636	0.5	α-Eudesmol	2207	1.4
Acetophenone	1641	2.6	Methyl hexadecanoate	2212	0.6
α-Humulene	1659	Tr.	α-Cadinol	2222	3.4
2-Hydroxybenzaldehyde	1667	1.9	5-epi-Neointermedeol	2227	1.7
γ-Murolene	1681	0.6	2′-Hydroxy-4′-methoxyacetophenone*	2258	5.8
α-Terpineol	1688	0.4	Decanoic acid	2265	0.2
β-Selinene	1708	0.2	Caryophylla-4(12),8(13)-dien-5-α-ol	2278	1.0
α-Murolene	1717	1.5	Caryophylla-4(12),8(13)-dien-5-β-ol	2285	2.7
δ-Cadinene	1752	4.3	Dihydroactinidiolide	2322	1.6
β-Citronellol	1759	Tr.	p-Vinylphenol	2380	0.7
Methyl salicylate	1764	0.4	Methyl oleate	2439	0.5
Neryl propionate	1773	1.2	Dodecanoic acid	2475	0.2
Myrtenol	1792	6.9	Methyl linoleate	2484	Tr.
β-Damascenone	1811	0.2	trans-Nuciferol*	2508	0.2
Geranyl propionate	1818	0.2	Methyl linolenate	2552	0.4
Isopiperitone	1830	Tr.	Vanillin	2562	1.4
trans-Carveol	1834	0.3	(E)-5-Octadecene	2576	0.7
Guaiacol	1849	0.5	Phytol	2603	0.3
Neryl (S)-2-methylbutanoate	1853	0.5	Acetovanillone	2619	Tr.
trans-β-Ionone	1923	0.7	Tetradecanoic acid	2689	0.3
2,6-Dimethylocta-3,7-diene-2,6-diol	1934	Tr.	Benzylacetophenone*	2766	0.8
1-Dodecanol	1963	1.0	Hexadecanoic acid	2899	1.1
trans-Caryophyllene oxide	1967	0.5	2′-Hydroxy-3-phenylpropiophenone*	2927	1.5
2-Methoxyacetophenone	1977	0.9	Total		93.9
cis-Caryophyllene oxide	1985	0.7

Translated from Khimiya Prirodnykh Soedinenii, No. 3, May-June, 2018, pp. 503-504.

Acknowledgment

N. Z. Mamadalieva thanks the Erasmus Mundus TIMUR project and the Department of Chemistry of Renewable Resources, BOKU, Vienna, Austria, for financial support of the research.

References Citations

1 Tozhibaev KS, Turginov OT, Bot. Zh., 2012, 97, 966

• 2 Red Book of the Republic of Uzbekistan. Rare and Threatened Plant and Animal Species [in Russian], Chinor ENK, Tashkent, Uzbekistan, 2009, pp. 168-169.
• 3 Mamadalieva NZ, Sharopov FS, Satyal P, Azimova SS, Wink M, Nat. Prod. Res., 2017, 31, 1172, 10.1080/14786419.2016.1222383
• 4 Mamadalieva NZ, Sharopov FS, Satyal P, Azimova SS, Wink M, Nat. Prod. Commun., 2016, 11, 1891
• 5 R. P. Adams, Identification of Essential Oil Components by Gas Chromatography/Mass Spectrometry, Allured Publishing Corporation, Carol Stream, Illinois, US, 2007, 804 pp.
• 6 Babushok VI, Linstrom PJ, Zenkevich IG, J. Phys. Chem. Ref. Data, 2011, 40, 1, 10.1063/1.3653552

By N. Z. Mamadalieva; O. T. Turginov; T. Rosenau; M. Fakhrutdinova; Sh. S. Azimova; K. Sh. Tozhibaev and S. Bohmdorfer