Glucoside of taxifolin and (+)-pinitol from Pinus sylvestris

Full text of DOI:10.1007/s10600-013-0600-6

Chemistry of Natural Compounds, Vol. 49, No. 2, May, 2013 [Russian original No. 2, March–April, 2013]
GLUCOSIDE OF TAXIFOLIN AND
(+)-PINITOL FROM Pinus sylvestris
*
G. A. Usmanova and E. Kh. Botirov
UDC 547.972
Common pine (Pinus sylvestris L.) is widely distributed in all forested regions of Siberia and comprises the principal
mass of Siberian forests [1]. Pine needles are used as an antiscorbutic agent. Pine buds are used for inhalation for inflammatory
diseases of the upper respiratory tract. Pine is rich in ascorbic acid (up to 0.3%) and contains up to 5% tanning agents and up
to 1.3% essential oil, the composition of which includes pinene, borneol, limonene, bornylacetate, cadinene, and other terpenes
in addition to sterols, terpenoids, alkylated phenols, phenolic acids, alcohols, aldehydes, ketones, stilbenes, lignans, and other
aromatic compounds [1, 2, 7–9]. Needles yielded kaempferol; quercetin; quercetin-3-O-glucoside; sylpin; derivatives of
kaempferol, quercetin, isorhamnetin, and taxifolin 3-O-glucosides acylated on the carbohydrate part; taxifolin and eriodictyol
3ꢀ-O-ꢁ-D-glucopyranosides; and other flavonoids [3–9].
We studied chemical components of P. sylvestris needles in order to discover biologically active compounds of
KMAO-Yugry plants. Dried and ground raw material was extracted at room temperature with EtOH (85%). The combined
extract was evaporated in vacuo, diluted with H O, and extracted successively with hexane, CHCl , EtOAc, and n-BuOH.
2
3
Chromatography of the EtOAc fraction over a column of silica gel using a gradient of CHCl :EtOH afforded phenolic compound
3
1; the n-BuOH fraction, 2.
20
Compound 1, slightly yellow crystals, C H O , [ꢂ] –24.6° (c 0.4, Me CO). PMR spectrum (ꢃ, ppm, J/Hz):
21 22 12
D
2
3.00–3.76 (carbohydrate protons), 4.55 (1H, d, J = 11.1, H-3), 4.71 (1H, d, J = 6.6, H-1ꢀꢀ), 5.03 (1H, d, J = 11.1, H-2), 5.88 (1H,
br.s, H-6), 5.91 (1H, br.s, H-8), 6.85 (1H, d, J = 8.2, H-5ꢀ), 7.04 (1H, br.d, J = 8.4, H-6ꢀ), 7.26 (1H, br.s, H-2ꢀ), 11.93 (1H, br.s,
5-OH).
IR, UV and PMR spectral data indicated that 1 was a glycoside of dihydroflavonol [10–12]. Acid hydrolysis produced
an aglycon of formula C H O [ꢄ
289, 325 (sh) nm] and D-glucose. The aglycon was identified as taxifolin
15 12
7
max
13
[(2R,3R)-dihydroquercetin] based on UV, PMR, and C NMR spectra and a comparison with an authentic sample [10, 11].
13
The C NMR spectrum (recorded in off-resonance mode in DMSO-d ) of 1 showed resonances for C atoms of
6
ꢁ-D-glucopyranose and taxifolin at 60.6 (C-6ꢅ), 69.7 (C-4ꢅ), 73.2 (C-2ꢅ), 75.9 (C-5ꢅ), 77.1 (C-3ꢅ), 102.1 (C-1ꢅ), 82.9 (C-2),
71.3 (C-3), 197.7 (C-4), 163.2 (C-5), 96.0 (C-6), 166.9 (C-7), 95.0 (C-8), 162.4 (C-9), 100.3 (C-10), 128.2 (C-1ꢀ), 115.5
(C-2ꢀ), 147.2 (C-3ꢀ), 144.9 (C-4ꢀ), 116.6 (C-5ꢀ), 122.8 ppm (C-6ꢀ).
The C-4ꢀ resonance underwent a strong-field shift, those of C-3ꢀ and C-5ꢀ, weak-field shifts, upon going from taxifolin
to glycoside 1 [10]. Therefore, the glucose was bonded to the hydroxyl in the 4ꢀ-position of taxifolin and 1 was taxifolin
4ꢀ-O-ꢁ-D-glucopyranoside [12].
22
Compound 2, C H O , [ꢂ] +65.63° (EtOH), did not absorb in the UV region. Its IR spectrum contained absorption
7
14
6
D
–1
bands at 3600–3250 (OH), 2300–2950 (aliphatic C–C), and 1175 cm (C–O). Acetylation of 2 produced a pentaacetyl
derivative, the mass spectrum of which showed peaks for ions with m/z 404 (3%) [M] , 345 (2), 285 (2), 243 (8), 182 (35), 150
+
(50), etc.
The PMR spectrum exhibited resonances for methoxyl protons at 3.72 ppm; five protons of a cyclohexane ring
geminal to an OH group at 4.76 (d, J = 6.5 Hz), 4.81 (d, J = 4.5 Hz), 5.02 (d, J = 2.1 Hz), 4.93 (d, J = 2.1 Hz), 4.63 (d,
J = 5.6 Hz); and one proton geminal to a OCH group at 3.31 ppm (t, J = 9.4, 9.1 Hz).
3
13
The C NMR spectrum (taken in off-resonance mode in DMSO-d ) showed resonances for six methine C atoms of
6
a cyclohexane ring bonded to an oxygen at 70.0 (C-3), 70.8 (C-1), 71.9 (C-5), 72.4 (C-2), 72.6 (C-4), 83.8 (C-6) and a
resonance for a methoxy C at 59.6 ppm.
Surgut State University, Khanty-Mansi Autonomous Okrug-Yugry (KMAO-Yugry), 628412, RF, Surgut,
Ul. Energetikov, 22, e-mail: botirov-nepi@mail.ru. Translated from Khimiya Prirodnykh Soedinenii, No. 2, March–April,
2013, pp. 291–292. Original article submitted December 14, 2012.
©
0009-3130/13/4902-0345 2013 Springer Science+Business Media New York
345

Compound 2 was identified as (+)-pinitol based on the spectral data and a comparison with an authentic sample [13,
14]. (+)-Pinitol was patented in the USA as a hypolipidemic agent [14].
Taxifolin 4ꢀ-O-ꢁ-D-glucopyranoside and (+)-pinitol were isolated from P. sylvestris for the first time.
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