<Emphasis Type="Italic">Ferula gummosa</Emphasis> Fruits: An Aromatic Antimicrobial Agent

Ferula gummosa Boiss. (Apiaceae) fruit volatile oil was analyzed by GC/MS. Seventy-three components (96.89%) were identified, and the major components were β-pinene (43.78%), α-pinene (27.27%), and myrcene (3.37%). The antimicrobial activity of the oil was tested on three strains of Gram positive bacteria (Staphylococcus aureus, S. epidermis, and Bacillus subtilis), three strains of Gram negative bacteria (Escherichia coli, Salmonella typhi, and Pseudomonas aeruginosa), and two strains of fungi (Candida albicans and C. kefyr). The essential oil remarkably inhibited the growth of the tested microorganisms. The results indicate that the fruits have potential for use as an aromatic antimicrobial agent.__________Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 252–254, May–June, 2005.     

Composition and Antimicrobial Activity of <Emphasis Type="Italic">Helichrysum italicum</Emphasis> Essential Oil and Its Terpene and Terpenoid Fractions

The essential oil of Helichrysum italicum (Roth) G. Don from Croatia has been fractionated into terpene and terpenoid fractions and analyzed using GC/MS. Fifty-two compounds were identified. The main hydrocarbons of the oil were α-pinene (10.2%), α-cedrene (9.6%) aromadendrene (4.4%), β-caryophyllene (4.2%), and limonene (3.8%), while the main oxygen-containing compounds were neryl acetate (11.5%), 2-methylcyclohexyl pentanoate (8.3%), 2-methylcyclohexyl octanoate (4.8%), and geranyl acetate (4.7%). The essential oil and its terpene and terpenoid fractions were evaluated for antibacterial and antifungal activities. The screening of antimicrobial activity was conducted by a disc diffusion test and the minimum inhibitory concentration was determined against Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, and Candida albicans. The essential oil and its terpenoid fraction exhibited higher antimicrobial activity with respect to the terpene fraction. The antimicrobial activities of the oil and its terpenoid fraction were more pronounced against Staphylococcus aureus and Candida albicans.__________Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 29–32, January–February, 2005.     

Chemical Composition of the Essential Oil of <Emphasis Type="Italic">Salvia macilenta</Emphasis> from Iran

The hydrodistilled essential oil composition from the aerial parts of Salvia macilenta (Lamiaceae) from Iran was analyzed by GC and GC-MS. The oil analysis confirmed the characterization of thirty-one compounds, accounting for 99.4% of the total oil. Analysis of the oil showed that the oil of S. macilenta was rich in monoterpene hydrocarbons with a-pinene (60%) as the main component followed by γ-elemene (6.1%), thymol (5.2%), elemol (4.7%), and β-caryophyllene (4.1%).__________Published in Khimiya Prirodnykh Soedinenii, No. 2, pp. 136–137, March–April, 2005.     

Triterpene Glycosides from <Emphasis Type="Italic">Kalopanax septemlobum</Emphasis>. II. Glycosides E,K, and L from Leaves of <Emphasis Type="Italic">Kalopanax septemlobum</Emphasis> var. <Emphasis Type="Italic">maximowiczii</Emphasis> Introduced to Crimea

The known hederagenin 3-O-β-D-glucopyranosyl-(1→4)-O-β-D-xylopyranosyl-(1→ 3)-O-α-L-rhamnopyranosyl-(1→2)-O-α-L-arabinopyranoside (sapindoside C) and its 28-O-α-L-rhamnopyranosyl-(1→4)-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl and 28-O-α-L-rhamnopyranosyl-(1→4)-O-6-O-acetyl-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl esters, new triterpene glycosides, were isolated from leaves of Kalopanax septemlobum var. maximowiczii introduced to Crimea. The structures of these compounds were established using chemical methods and two-dimensional NMR spectroscopy.__________Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 260–262, May–June, 2005.     

Fatty Acids from the Sponge <Emphasis Type="Italic">Tedania dirhaphis</Emphasis>

The fatty acid (FA) composition of total lipids from the marine sponge Tedania dirhaphis from the Sea of Okhotsk was studied. GC and GC-MS identified 50 acids, particular attention being paid to components with 14–22 C atoms. Acids 16-Me-19:0, 10,14-Me₂-15:1(Δ6), 18:1(Δ6), 18:1(Δ8), and 22:1(Δ16) were observed and identified for the first time in sponges. The main FA in lipids from T. dirhaphis was 28:3(Δ5,9,21), the relative content of which reached 63.3%.__________Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 233–236, May–June, 2005.     

Thermal analysis and gas chromatography coupled mass spectrometry analyses of hydroxypropyl-β-cyclodextrin inclusion complex containing Lippia gracilis essential oil

Inclusion complexation with cyclodextrins is an effective way to improve stability and turn liquid materials into re-dispersible and easy-to-handle powders. In the present work, the complexation of L. gracilis essential oil, already recognized as a potent larvicide material, with hydroxylpropyl-β-cyclodextrin was performed using slurry and paste procedures and the complexes obtained were evaluated. The gas chromatography coupled to mass spectrometry (GC/MS) analysis showed a total volatile content of 99.24% in the L. gracilis oil. The characterization of the complex involved the analysis of the original essential oil, the surface, and the total extracted oils. The major components in L. gracilis essential oil were identified as carvacrol (23.52%), p-cymene (15.82%), γ-terpinene (14.17%), and thymol (7.27%). GC/MS results showed significant differences between the original oil, the slurry, and paste complexation. Thermal characterization indicates the occurrence of complexation, mainly in paste complexes, which presents a TG–DTA peak at 230–275 °C, probably related to oil loss.     

Essential Oil Composition and Antibacterial Activity of the Leaves of <Emphasis Type="Italic">Stachys schtschegleevii</Emphasis> from Iran

The composition of the essential oil obtained by hydrodistillation from the leaves of Stachys schtschegleevii Sosn. before the flowering stage was analyzed by GC and GC-MS. Forty-five compounds representing 98.7% of the total oil were identified, of which α-pinene (36.4%), germacrene-D (18.6%), limonene (8.2%), and piperitone (6.2%) were the major constituents. Furthermore, antibacterial activity of the entire oil and its two main monoterpenes was evaluated against six Gram-positive and Gram-negative bacteria. The oil exhibited moderate activity against the tested bacteria.__________Published in Khimiya Prirodnykh Soedinenii, No. 2, pp. 138–140, March–April, 2005.     

Terpenes,Coumarins, and Flavones from <Emphasis Type="Italic">Acacia pennatula</Emphasis>

The chemical analysis of the acetone extract of the dried leaves from Acacia pennatula yielded triacontanol, β-sitosterol palmitate, β-sitosterol, squalene, nonaprenol, norphytane, lupenone, lupeol, daphnetin and catechin, while from the methanol extract were isolated catechin, epigallocatechin, eriodictyol, β-sitosteryl-β-D-glucopyranoside, and stigmasteryl-β-D-glucopyranoside. The structures of all these natural products were established based on their IR, ¹H, and ¹³C NMR and MS data.__________Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 240–241, May–June, 2005.     

Chemical Composition of the Needles Oil of <Emphasis Type="Italic">Pinus canariensis</Emphasis> from Algeria

The essential oil of the needles of Pinus canariensis, cultivated in the Algiers region (Algeria), was obtained by hydrodistillation in a yield of 0.3% and analyzed by capillary GC and GC/MS. More than 46 compounds were identified amounting to ca 92.6% of the total oil. The more important constituents were β-selinene (63.7%), β-caryophyllene (9.9%), and limonene (3.5%).__________Published in Khimiya Prirodnykh Soedinenii, No. 2, pp. 134–135, March–April, 2005.     

Arjunolic Acid Derivative Glycoside from the Stems of <Emphasis Type="Italic">Hedera colchica</Emphasis>

Five triterpenoid saponins were isolated from the stems of Hedera colchica K. Koch (Araliaceae). Two of them are new natural substances. HCS-A (1): 3-O-α-L-arabinopyranoside, 28-O-α-L-rhamnopyranosyl-(1→ 4)-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl-arjunolic acid. HCSt-B (2):3-O-β-D-xylopyranoside, 28-O-α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl-hederagenin. A derivative of arjunolic acid is described for the first time in the Araliaceae family. The chemical structures of isolated compounds were established on the basis of chemical and 1D and 2D NMR experiments.__________Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 39–41, January–February, 2005.     

Lithiated γ-O-functionalized propyl phenyl sulfides and sulfones of the type Li[CH(SOxPh)CH2CH2OR] (x = 0, 2). [Li{CH(SPh)CH2CH2Ot-Bu}(tmeda)] – A structurally characterized organolithium inner complex

Lithiation of O-functionalized alkyl phenyl sulfides PhSCH₂CH₂CH₂OR (R = Me, 1a; i-Pr, 1b; t-Bu, 1c; CPh₃, 1d) with n-BuLi/tmeda in n-pentane resulted in the formation of α- and ortho-lithiated compounds [Li{CH(SPh)CH₂CH₂OR}(tmeda)] (α-2a–d) and [Li{o-C₆H₄SCH₂CH₂CH₂OR)(tmeda)] (o-2a–d), respectively, which has been proved by subsequent reaction with n-Bu₃SnCl yielding the requisite stannylated γ-OR-functionalized propyl phenyl sulfides n-Bu₃SnCH(SPh)CH₂CH₂OR (α-3a–d) and n-Bu₃Sn(o-C₆H₄SCH₂CH₂CH₂OR) (o-3a–d). The α/ortho ratios were found to be dependent on the sterical demand of the substituent R. Stannylated alkyl phenyl sulfides α-3a–c were found to react with n-BuLi/tmeda and n-BuLi yielding the pure α-lithiated compounds α-2a–c and [Li{CH(SPh)CH₂CH₂OR}] (α-4a–b), respectively, as white to yellowish powders. Single-crystal X-ray diffraction analysis of [Li{CH(SPh)CH₂CH₂Ot-Bu}(tmeda)] (α-2c) exhibited a distorted tetrahedral coordination of lithium having a chelating tmeda ligand and a C,O coordinated organyl ligand. Thus, α-2c is a typical organolithium inner complex.Lithiation of O-functionalized alkyl phenyl sulfones PhSO₂CH₂CH₂CH₂OR (R = Me, 5a; i-Pr, 5b; CPh₃, 5c) with n-BuLi resulted in the exclusive formation of the α-lithiated products Li[CH(SO₂Ph)CH₂CH₂OR] (6a–c) that were found to react with n-Bu₃SnCl yielding the requisite α-stannylated compounds n-Bu₃SnCH(SO₂Ph)CH₂CH₂OR (7a–c). The identities of all lithium and tin compounds have been unambiguously proved by NMR spectroscopy (¹H, ¹³C, ¹¹⁹Sn).     

Aryltetralin Lignans from <Emphasis Type="Italic">Linum mucronatum</Emphasis> Bertol. ssp. <Emphasis Type="Italic">mucronatum</Emphasis>

The dried and aerial part of Linum mucronatum ssp. mucronatum was analyzed by gas chromatography-mass spectrometry (GC-MS). Two aryltetralin lignans, podophylloyoxin, 6-methoxypodophylloyoxin, and β-peltatin, were identified. This is the first report of the analysis of L. mucronatum ssp. mucronatum.__________Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 24–25, January–February, 2005.     

Triterpene Glycosides from Kalopanax septemlobum. 1. Glycosides A, B, C, F, G1, G2, I2, H, and J from Leaves of Kalopanax septemlobum var. Maximowichii Introduced to Crimea

Eight known glycosides of hederagenin and the new triterpene glycoside 3-O-β-D-xylopyranosyl-(1→3)-O-α-L-rhamnopyranosyl-(1→2)-O-α-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl-(1→4)-O-6-O-acetyl-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl ester of hederagenin were isolated by chromatographic methods from leaves of Kalopanax septemlobum var. maximowichii introduced to Crimea. The known 3-O-α-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl-(1→4)-O-6-O-acetyl-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl ester of hederagenin was observed for the first time in Kalopanax septemlobum.__________Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 156–159, March–April, 2005.     

On Chloralose-Cyclodextrin Complexes by <Emphasis Type="Italic">ESI</Emphasis>-Mass Spectrometry

α-Chloralose is a useful mild anaesthetic, providing stable but not deep anaesthesia. Host–guest complexes of α-chloralose with α-, β- and γ-cyclodextrin (CD) were studied using electrospray ionisation (ESI-MS) mass spectrometry and molecular modelling (MD). As it is currently administered, chloralose is transported in a convenient water-soluble complex, and released to react on a physiological level with the reactor sites. It is believed that the chloraloses (α and its isomer β) are encapsulated within the CD cavity. However, the ESI spectra did not reveal such the presence of inclusion compounds. Searching of alternative mechanisms of transportation of these anaesthetic agents, we found that outer-cavity complexes of inserted chloraloses, as found from MD calculations, do have a reasonable stability.This revised version was published online in July 2005 with a corrected issue number.     

Substoichiometric TiCl4-mediated vicinal difunctionalization of α,β-acetylenic ketones for the synthesis of β-halo Baylis–Hillman olefins

A substoichiometric amount of titanium tetrachloride was found to be effective to promote and participate in the tandem α-hydroxyalkylation/β-chlorination of α,β-acetylenic ketones in the presence of (n-Bu)₄NI. This method provides the concise synthesis of (E)-β-halo Baylis–Hillman adducts. No β-iodo products were detected when using this combination of halogen sources. The reaction process involves 1,4-addition of chloro anion released from TiCl₄ onto α,β-acetylenic ketones to give TiCl₃–allenolate intermediates followed by the titanium Lewis acid-promoted carbonyl addition. Modest to good yields (53–77%) and excellent E/Z stereoselectivity (>95%) have been obtained for 10 examples.     

Deracemisation of aryl substituted α-hydroxy esters using Candida parapsilosis ATCC 7330: effect of substrate structure and mechanism

Candida parapsilosis ATCC 7330 was found to be an efficient biocatalyst for the deracemisation of aryl α-hydroxy esters (65–85% yield and 90–99% ee). A variety of aryl and aryl substituted α-hydroxy esters were synthesized to reflect steric and electronic effects on biocatalytic deracemisation. The mechanism of this biocatalytic deracemisation was found to be stereoinversion.     

Synthesis of novel dibenzo-2,6,9-triazabicyclo[3.3.1]nonanes from <Emphasis Type="Italic">o</Emphasis>-tosylamino- and <Emphasis Type="Italic">o</Emphasis>-mesylaminobenzaldehydes

Condensation of o-tosylaminobenzaldehyde with γ-aminobutyric, 4-aminophenylthioacetic, and p-aminobenzoic acids and β-alanine gave 6,12-epimino-5,11-ditosyl-5,6,11,12-tetrahydrodibenzo[b, f]-1,5-diazocines with carboxyl-containing substituents at the bridging N atoms. The structures of three products were examined by X-ray diffraction analysis. Condensation of o-mesylaminobenzaldehyde (prepared by the McFadyen-Stevens reaction) with NH₄OAc and primary amines afforded 6,12-epimino-5,11-dimesyl-5,6,11,12-tetrahydrodibenzo[b, f]-1,5-diazocine derivatives.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2165–2171, October, 2004.     

Triterpene Glycosides from Kalopanax septemlobum. III. Glycosides D2, I1, and K1 from Leaves of Kalopanax septemlobum var. maximowiczii Introduced in Crimea

The new caffeylated triterpene glycosides hederagenin 3-O-(6-O-caffeyl-β-D-glucopyranosyl)-(1→4)-O-β-D-xylopyranosyl-(1→3)-O-α-L-rhamnopyranosyl-(1→2)-O-β-L-arabinopyranoside and its 28-O-α-L-rhamnopyranosyl-(1→4)-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl and 28-O-α-L-rhamnopyranosyl-(1→4)-O-6-O-acetyl-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl esters were isolated from leaves of Kalopanax septemlobum var. maximowiczii introduced in Crimea. The structures of these compounds were established using chemical methods and NMR spectroscopy.__________Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 263–267, May–June, 2005.     

Structure of Galactomannans from <Emphasis Type="Italic">Gleditsia delavayi</Emphasis> and <Emphasis Type="Italic">G. aquatica</Emphasis> by <Superscript>1</Superscript>H and <Superscript>13</Superscript>C NMR Spectroscopy

The structure of galactomannans isolated from seeds of G. delavayi and G. aquatica was studied by ¹H and ¹³C NMR spectroscopy. It was found that the galactomannans consisted mainly of β-1-4-bound mannopyranoses, a part of which was substituted on the C-6 hydroxyl by terminal units of α-galactopyranose.__________Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 12–13, January–February, 2005.     

Volumetric and transport properties of binary liquid mixtures of N-methylacetamide with lactones at temperatures (303.15 to 318.15) K

The values of density (ρ), viscosity (η) and speed of sound (u) have been measured for binary liquid mixtures of γ-butyrolactone (GBL), δ-valerolactone (DVL), and ε-caprolactone (ECL) with N-methylacetamide (NMA) over the whole composition range at T = (303.15 to 318.15) K and atmospheric pressure. From these data, excess molar volume (V^E), deviation in viscosity (Δη), and deviation in isentropic compressibility (Δκ_s), are calculated. The results are fitted to a Redlich–Kister type polynomial equation to derive binary coefficients and standard deviations.