Components of <Emphasis Type="Italic">Artemisia pontica</Emphasis>

Chemical components from the aerial part of the Kazakhstan population of Artemisia pontica, from which the rarely encountered flavonoids 7-O-methyl- and 4′,7-di-O-methyl-esters of apigenin were isolated for the first time, were identified. The complete chemical composition of the essential oil was established using GC-MS.__________Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 143–145, March–April, 2005.     

RP‐HPLC determination of phenylalkanoids and monoterpenoids in Rhodiola rosea and identification by LC‐ESI‐TOF

An HPLC method permitting the simultaneous determination of fourteen analytes (phenylalkanoids and monoterpenoids) from the roots of Rhodiola rosea was developed. A separation was achieved within 35 min using C₁₈ column material and a water–acetonitrile mobile phase, both containing a 0.05% phosphoric acid gradient system and a temperature of 53°C. The method was validated for linearity, repeatability, limits of detection and limits of quantification. The limits of detection and limits of quantification of 14 phenylalkanoids and monoterpenoids were found to be 0.20–1.0 and 0.5–3.5 µg/mL, respectively. The wavelengths used for quantification of phenylalkanoids and monoterpenoids with a diode array detector were 205, 220 and 251 nm. The method was used to analyze the roots of two species of Rhodiola and commercial extracts of R. rosea and provides preliminary evidence of phytochemical differences between North American and Eurasian populations of R. rosea. LC–mass spectrometry coupled with electrospray ionization (ESI) interface method is described for the identification of phenylalkanoids and monoterpenoids in various Rhodiola samples. This method involved the use of the [M + H]⁺, [M + NH₄]⁺ and [M + Na]⁺ ions in the positive ion mode with extractive ion monitoring (EIM). Copyright © 2009 John Wiley & Sons, Ltd.     

Natural cyclic α, β-enone monoterpenoids in nucleophilic addition reactions

The literature on transformations of natural cyclic α,β-enone monoterpenoids into compounds of more complicated structure via 1,2-and 1,4-addition reactions was reviewed. The data were systematized according to the effects of the conditions and nature of the starting substrates on the selectivity of the 1,2-and 1,4-addition reactions. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 303–316, July–August, 2006.     

Novel Bispidine-Monoterpene Conjugates—Synthesis and Application as Ligands for the Catalytic Ethylation of Chalcones

A number of new chiral bispidines containing monoterpenoid fragments have been obtained. The bispidines were studied as ligands for Ni-catalyzed addition of diethylzinc to chalcones. The conditions for chromatographic analysis by HPLC-UV were developed, in which the peaks of the enantiomers of all synthesized chiral products were separated, which made it possible to determine the enantiomeric excess of the resulting mixture. It was demonstrated that bispidine-monoterpenoid conjugates can be used as the ligands for diethylzinc addition to chalcone C=C double bond but not as inducers of chirality. Besides products of ethylation, formation of products of formal hydrogenation of the chalcone C=C double bond was observed in all cases. Note, that this formation of hydrogenation products in significant amounts in the presence of such catalytic systems was found for the first time. A tentative scheme explaining the formation of all products was proposed.     

Composition of Essential Oils from Roots and Aerial Parts of Carpesium cernuum and Their Antibacterial and Cytotoxic Activities

Carpesium cernuum L., one of the two Carpesium species occurring in Europe, in the Far East and India, found use as a vegetable and a traditional medicinal remedy for several ailments. In the present study, compositions of essential oils distilled from roots and shoots of C. cernuum plants, cultivated in the open field, have been studied by GC-MS-FID supported by NMR spectroscopy. The analyses led to the identification of 120 compounds in total, of which 115 were found in aerial parts and 37 in roots of the plants. The major constituents found in the oil from shoots were: α-pinene (35%) and 2,5-dimethoxy-p-cymene (thymohydroquinone dimethyl ether, 12%), whereas 2,5-dimethoxy-p-cymene (55%), thymyl isobutyrate (9%) and thymol methyl ether (8%) predominated in the essential oil obtained from the roots. Antibacterial and cytotoxic activities of the essential oils distilled from C. cernuum were also tested. The essential oil from aerial parts of the plant demonstrated good inhibitory activity against Staphylococcus aureus ATCC 29213 and Escherichia coli ATCC 25922 (MIC: 15.6 μL/mL).     

Insect Pheromones Synthesized by Oxidative Transformations of Natural Monoterpenoids

The literature on oxidative transformations of natural monoterpenoids to synthesize insect pheromones was reviewed. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 509–522, November–December, 2005.     

Synthesis of certain monoterpenoid glucosides

The monoterpenols borneol, verbenol, 4-(1-hydroxyethyl)carene-2, and myrtenol were glucosylated using acetobromoglucose. The structures of the prepared derivatives were established using PMR and ¹³C NMR spectroscopy. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 348–349, July–August, 2006.     

Sulfuric acid-promoted rearrangement of 3-(<Emphasis Type="Italic">N</Emphasis>-acylamino)-substituted caran-4-one oximes

The rearrangement of 3-(N-acylamino)-substituted caran-4-one oximes in the presence of sulfuric acid affords 2-oxa-4-azabicyclo[3.3.1]non-3-en-6-one derivatives. 3-Aminocaran-4-one oximes, in which the amino group contains such substituents as acetyl, propionyl, chloroacetyl, 1-adamantylcarbonyl, benzoyl, 2-thienylcarbonyl, or anilinocarbonyl, undergo this reaction. N-Acyl derivatives of higher fatty (heptanoic and nonadecanoic) acids do not undergo this reaction. The reaction with D₂SO₄ leads to the replacement of all hydrogen atoms of the isopropyl group by deuterium. The mechanism of this rearrangement is proposed. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1837–1844, August, 2005.     

Synthesis of α-amino oximes and bis-α-amino oximes from the monoterpene hydrocarbons 3-carene and α-pinene and α,ω-diamines

The reaction of nitroso chlorides of natural monoterpene hydrocarbons, 3-carene and -pinene, with simple ,-diamines (1,2-diaminoethane, 1,3-diaminopropane, piperazine, 1,6-diaminohexane, diethylenetriamine) results in the formation of -amino oximes and bis--amino oximes. The product structures were proved by spectroscopy. The procedures of separation and purification of diamino oximes and diamino dioximes are described. Detailed analysis of the ¹H and ¹³C NMR spectra of the new chiral nitrogen-containing derivatives was carried out.     

Essential Oil Compositions of Pinus Species (P. contorta Subsp. contorta,P. ponderosa var. ponderosa,and P. flexilis); Enantiomeric Distribution of Terpenoids in Pinus Species

Pinus species are important in traditional medicine throughout their ranges, and pine essential oils are of interest in aromatherapy and as topical treatments. In this work, the leaf (needle) essential oils of Pinus ponderosa var. ponderosa and Pinus contorta subsp. contorta from Oregon and Pinus flexilis growing in Idaho, have been obtained by hydrodistillation and analyzed by gas chromatographic techniques. The leaf essential oil of P. ponderosa was dominated by β-pinene (21.5–55.3%), methyl chavicol (8.5–41.5%), α-pinene (3.6–9.6%), δ-3-carene (3.6–6.2%), and α-terpineol (1.4–5.3%). The major components of P. contorta essential oil were β-phellandrene (23.8%), terpinen-4-ol (11.0%). The essential oil of P. flexilis was dominated by α-pinene (37.1%), β-pinene (21.9%), bornyl acetate (12.8%), and camphene (8.5%). Chiral gas chromatography revealed the enantiomeric ratios of α-pinene and limonene to be variable, but (−)-β-pinene predominated in Pinus essential oils.