Flavonoids from camelina sylvestris seeds

Full text of DOI:10.1007/s10600-014-1008-7

Chemistry of Natural Compounds, Vol. 50, No. 3, July, 2014 [Russian original No. 3, May–June, 2014]
FLAVONOIDS FROM Camelina sylvestris SEEDS
*
V. A. Kurkin and K. S. Pavlenko
Seeds of Camelina sylvestris L. (Brassicaceae) contain about 30–40% fatty oil that is used for food and commercial
purposes [1]. We studied earlier the fatty-acid composition of fatty oil from C. sylvestris seeds [2]. However, other compounds,
in particular flavonoids, the content of which according to our data was ~0.3% [3], are also interesting for comprehensive use
of this plant raw material.
Herein we present results for the flavonoid composition of C. sylvestris seeds cultivated in Samara Region.
We studied C. sylvestris seeds that were cultivated at Samara Tulaikov Agricultural Research Institute, RAAS
(Bezenchuk, Samara Region).
Air-dried C. sylvestris seeds (150 g) were collected in July 2013 and were extracted by EtOH (70%) first at room
temperature twice for 24 h and then with heating on a boiling-water bath for 30 min. The combined aqueous EtOH extract was
evaporated in vacuo to 50 mL, mixed with silica gel L 40/100 (30 g), and dried. The dried powder (dry extract + silica gel) was
placed on a layer of silica gel that was formed as a suspension in CHCl and eluted with CHCl and CHCl –EtOH (97:3, 95:5,
3
3
3
93:7, 90:10, 85:15, 80:20, 70:30, 60:40, and 50:50). Separation of the compounds was monitored using TLC on Sorbfil
PTSKh-AF-A-UF plates.
Fractions dominated by 1 were combined. The resulting precipitate was separated and recrystallized from EtOH to
afford 1 in 0.05% yield (of air-dried raw material mass). Fractions containing 2 were rechromatographed overWoelm polyamide
with elution by H O and aqueous EtOH (20, 40, 70, and 96%) to afford 2 (40% EtOH eluent) that was additionally purified by
2
recrystallization from aqueous EtOH.
The PMR spectrum of 1 exhibited resonances for five aromatic protons (H-2ꢀ, H-6ꢀ, H-5ꢀ, H-8, and H-6). The observation
of a 3H singlet at 3.83 ppm was indicative of a methoxy in 1 that was assigned to the C-3ꢀ position of flavonoid ring B based
on mass spectra (peak for an ion with m/z 151 corresponded to a fragment of ring B) and also UV spectra [4].
The PMR spectrum of 2 showed two 2H doublets at 7.96 (H-2ꢀ, 6ꢀ) and 6.87 (H-3ꢀ, 5ꢀ) and resonances for ring A
aromatic protons (H-8 and H-6).
Acid hydrolysis of 1 (2% HCl at 100°C) cleaved glucose, rhamnose, and the aglycon, which was identified as 3,5,7,4ꢀ-
+
tetrahydroxy-3ꢀ-methoxyflavone (isorhamnetin) based on mass spectra ([M] 316, 100%) and UV spectra [4]. Acid hydrolysis
of 2 (2% HCl at 100°C) cleaved glucose, rhamnose, and the aglycon, which was identified as 3,5,7,4ꢀ-tetrahydroxyflavone
+
(kaempferol) based on mass spectra ([M] 286, 100%) and UV spectra [4]. UV spectra indicated that the 3-OH of both
flavonoids was glycosylated. The long-wavelength band of the aglycons of 1 and 2 experienced a bathochromic shift
(+ꢁ57 nm) in the presence of AlCl [4].
3
The combined spectral data identified 1 and 2 as narcissin (3,5,7,4ꢀ-tetrahydroxy-3ꢀ-methoxyflavone 3-O-rutinoside)
and nicotiflorin (3,5,7,4ꢀ-tetrahydroxyflavone 3-O-rutinoside), respectively [5, 6].
Thus, narcissin and nicotiflorin were isolated and characterized by PMR and UV spectroscopy and mass spectrometry
for the first time from C. sylvestris seeds as a result of the study of the flavonoid composition.
PMR spectra were obtained on a Bruker AM 300 instrument (300 MHz). Mass spectra were taken on a Kratos
MS-30 mass spectrometer. UV spectra were recorded on a Specord 40 spectrophotometer (Analytik Jena).
Samara State Medical University, 443099, Samara, Ul. Chapaevskaya, 89, fax: 8 (846) 333 29 76, e-mail:
Kurkinvladimir@yandex.ru. Translated from Khimiya Prirodnykh Soedinenii, No. 3, May–June, 2014, pp. 465–466. Original
article submitted January 6, 2014.
©
0009-3130/14/5003-0539 2014 Springer Science+Business Media New York
539

3,5,7,4ꢀ-Tetrahydroxy-3ꢀ-methoxyflavone 3-O-rutinoside (1). Yellow crystals from EtOH, C H O , mp 173–
28 32 16
+
175°C (aqueous EtOH). Mass spectrum (70 eV, 200ꢂÑ, m/z, %): Ì aglycon 316 (100), 301 (70, 153 (10), 151 (9).
UV spectrum (ꢃ , nm): 257, 268 sh, 358; + NaOAc 261, 274 sh, 371; + NaOAc + H BO 261, 274 sh, 372; +AlCl 268, 276
max
3
3
3
1
sh, 403. Í NMR spectrum (300 MHz, DMSO-d , ꢄ, ppm, J/Hz): 12.53 (1H, s, 5-ÎÍ), 7.83 (1Í, d, J = 2.0, Í-2ꢀ), 7.50 (1Í, dd,
6
J = 2.0, 8.5, Í-6ꢀ), 6.87 (1Í, d, J = 8.5, Í-5ꢀ), 6.36 (1Í, d, J = 2.0, Í-8), 6.14 (1Í, d, J = 2.0, Í-6), 5.40 (d, J = 7.0, Í-1ꢀꢀ Glc),
4.41 (d, J = 2, Í-1ꢀꢀꢀ Rha), 3.83 (3Í, s, ÑÍ Î), 3.1–3.8 (10Í sugars, m), 0.99 (d, J = 6.0, ÑÍ Rha).
3
3
3,5,7,4ꢀ-Tetrahydroxyflavone 3-O-rutinoside (2). Light-yellow crystals, C H O , mp 182–186°C (aqueous EtOH).
27 30 15
+
Mass spectrum (70 eV, 200ꢂÑ, m/z, %): Ì aglycon 286 (100), 153 (25), 121 (20). UV spectrum (ꢃ , nm): 269, 355; +NaOAc
272, 304, 365; +AlCl , 274, 304, 345, 394; +AlCl + HCl 275, 304, 345, 394; + NaOMe 275, 326, 400. Í NMR spectrum
max
1
3
3
(300 MHz, DMSO-d , ꢄ, ppm, J/Hz): 12.58 (1H, s, 5-ÎÍ), 7.96 (2Í, d, J = 9, Í-2ꢀ, 6ꢀ), 6.87 (2H, d, J = 9, Í-3ꢀ, 5ꢀ), 6.33 (1Í,
6
d, J = 2.0, Í-8), 6.15 (1Í, d, J = 2.0, Í-6), 5.38 (d, J = 7.0, Í-1ꢀꢀ Glc), 4.35 (d, J = 2, Í-1ꢀꢀꢀ Rha), 3.0–4.0 (10Í sugars, m),
0.99 (d, J = 6.0, ÑÍ Rha).
3
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2.
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5.
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