Synthesis of 2,3,4,6-tetra-O-acetyl-β-D-gluco(galacto)pyranosylcaprolactams and 2,3,4,6-tetra-O-acetyl-β-D-gluco(galacto) pyranosylpyrrolidones

A new synthesis of certain lactam-containing N-glycosides was developed. 2,3,4,6-Tetra-O-acetyl-β-D-gluco(galacto)pyranosylcaprolactams and 2,3,4,6-tetra-O-acetyl-β-D-gluco(galacto)pyranosylpyrrolidones were synthesized by condensation at room temperature of acetobromoglucose and acetobromogalactose with ɛ-caprolactams and α-pyrrolidone. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 105–106, March–April, 2006.     

Study on interaction between antibiotics and Escherichia coli DH5α by microcalorimetric method

A microcalorimetric technique based on the bacterial heat output was applied to evaluate the influence of antibiotics PIP (Piperacillin Sodium) and composite preparation of PIP and SBT (Sulbactam Sodium) on the growth of E. coli DH5α. The power–time curves of the growth metabolism of E. coli DH5α were studied using a TAM Air Isothermal Microcalorimeter at 37°C. By analyzing the power–time curves, the parameters such as growth rate constants (k), inhibitory ratio (I), the maximum heat power (P _m) and the time of the maximum heat power (t _m) were obtained. The results show that different concentrations of antibiotics affect the growth metabolism of E. coli DH5α. The PIP in the concentration range of 0–0.05 μg mL^–1 has a stimulatory effect on the E. coli DH5α growth, while the PIP of higher concentrations (0.05 –0.25 μg mL^–1) can inhibit its growth. It seems that the composite preparation composed of PIP and SBT cannot improve the inhibitory effect on E. coli DH5α as compared with the PIP.     

Conformational Analysis,Infrared, and Fluorescence Spectra of 1-Phenyl-1,2-propandione 1-oxime and Related Tautomers: Experimental and Theoretical Study

Summary. Conformational analysis and frequency calculation were achieved for 1-phenyl-1,2-propandione 1-oxime and its four tautomers: 1-nitroso-1-phenyl-1-propen-2-ol, 1-nitroso-1-phenyl-2-propanone, 2-hydroxy-1-phenyl-propenone oxime, and 3-nitroso-3-phenyl-propen-2-ol. Calculations were carried out at the Hartree–Fock (HF), Density Functional Theory (B3LYP), and the second-order M?ller–Plesset perturbation (MP2) levels of theory using 6-31G^* and 6-311G^** basis sets. Five conformers with no imaginary vibrational frequency were obtained by free rotations around three single bonds of 1-phenyl-1,2-propandione-1-oxime: Ph–C(NOH)C(O)CH₃, PhC(NOH)–C(O)CH₃, and PhC(N–OH)C(O)CH₃. Similarly, eight structures with no imaginary vibrational frequency were encountered upon rotations around three single bonds of 1-nitroso-1-phenyl-1-propen-2-ol: Ph–C(NO)C(OH)CH₃, PhC(N–O)C(OH)CH₃, and PhC(NO)C(–OH)CH₃. In the same manner, six minima were found through rotations around three single bonds of 1-nitroso-1-phenyl-2-propanone: Ph–CH(NO)C(O)CH₃, PhCH(–NO)C(O)CH₃, and PhCH(NO)–C(O)CH₃. Also, two minima were found through rotations around four single bonds of 2-hydroxy-1-phenyl-propenone oxime: Ph–C(NOH)C(OH)CH₂, PhC(N–OH)C(OH)CH₂, PhC(NOH)–C(OH)CH₂, and Ph-C(NOH)C(–OH)CH₂. Finally, two minima were found through rotations around four single bonds of 3-nitroso-3-phenyl-propen-2-ol: Ph–CH(NO)C(OH)CH₂, PhCH(–NO)C(OH)CH₂, PhCH(NO)–C(OH)CH₂, and PhCH(NO)C(–OH)CH₂. Interconversions within the above sets of conformers were probed through scanning (one and/or two dimensional), and/or QST3 techniques. The order of the stability of global minima encountered was: 1,2-propandione-1-oxime > 1-nitroso-1-phenyl-2-propanone > 1-nitroso-1-phenyl-1-propen-2-ol > 2-hydroxy-1-phenyl-propenone oxime > 3-nitroso-3-phenyl-propen-2-ol. Hydrogen bonding appears significant in tautomers of 1-nitroso-1-phenyl-1-propen-2-ol and 2-hydroxy-1-phenyl-propenone oxime. The CIS simulated λ_max for the first excited singlet state (S₁) of 1-phenyl-1,2-propandione 1-oxime is 300.4 nm, which was comparable to its experimental λ_max of 312.0 nm. The calculated IR spectra of 1-phenyl-1,2-propandione 1-oxime and its tautomers were compared to the experimental spectra.     

Study of the essential oil composition of Pinus sylvestris from Turkey

The needle oils of Pinus sylvestris L. were analyzed by GC and GC-MS. The results showed some qualitative and quantitative variations. Forty-three components were identified in the oils of P. sylvestris. All the samples of essential oils contained α-pinene, camphene, and β-pinene as major constituents. Chemical variations of P. sylvestris samples were discussed. Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 22–25, January–February, 2006.     

Sodium and silver phosphate glasses doped with chlorides of Fe,Mn and Zn

A number of samples of sodium and silver phosphate glasses doped with various compositions of some transition metals viz. iron, manganese and zinc chlorides alongwith undoped samples of sodium and silver phosphate glasses were synthesized and characterized by X-ray diffraction, IR spectral, electrical conductivity and differential scanning calorimetry (DSC). The glass transition temperature (T _g) and crystallization temperature (T _c) values obtained from DSC curves were found to increase with increasing concentration of the dopant Fe/Mn/Zn chlorides in both sodium and silver phosphate glasses and the following sequence is observed: T _g(–FeCl₃)>T _g(–MnCl₂)>T _g(–ZnCl₂) T _c(–FeCl₃)>T _c(–MnCl₂)>T _c(–ZnCl₂) The increase in T _g and T _c values indicate enhanced chemical durability of the doped glasses. The electrical conductivity values and the results of FTIR spectral studies have been correlated with the structural changes in the glass matrix by the addition of different transition metal cations as dopants.     

Minor polyphenols from <Emphasis Type="Italic">Maackia amurensis</Emphasis> wood

The rare α,4,2′,4′-tetrahydroxydihydrochalcone, flavanones liquiritigenin and naringenin, isoflavones calycosin and 5-methoxydaidzein, and reduced stilbene dihydroresveratrol were isolated for the first time from Maackia amurensis wood. The structures of the pure compounds were established using 2D NMR COSY, NOE, HMBC, and HSQC experiments. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 575–577, November–December, 2008.     

1-Acyldeoxyvasicinone salts as effective intermediate C-and N-acylating agents for alkaloids and amino acids

The reaction of deoxyvasicinone with acid chlorides of aliphatic (acetylbromide) and aromatic (benzoyl-, o-, p-methoxy-, p-nitrobenzoylchlorides) acids was studied. It was shown that 1-deoxyvasicinone salts were formed at room temperature; α-aroyloxymethylidenedeoxyvasicinones, in the presence of triethylamine at 80–85°C. It was found that acid chlorides cause 1-acyldeoxyvasicinone salts to transform into α-hydroxy-or α-aroyloxyarylidenedeoxyvasicinones, which indirectly confirmed their acylating properties. It was found that 1-acyldeoxyvasicinone salts were effective acylating agents for alkaloids (cytisine, 1,2-dihydrodeoxyvasicinone) and amino acids (glycine, β-alanine, α-aminobutyric acid) and can be used to acylate primary and secondary aliphatic and heterocyclic amines. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 585–589, November–December, 2006.     

Reaction of frangula-emodin with <Emphasis Type="Italic">α</Emphasis>-bromoalkylmethylketones

The alkylation of 1,6,8-trihydroxy-3-methylanthraquinone (frangula-emodin) by α-bromoalkylmethylketones was investigated. Hydroxyls in the 1-and 8-positions of the β-derivatives were O-acylated. The compositions and structures of the prepared compounds were confirmed by elemental analysis and UV, IR, PMR, and ¹³C NMR spectroscopy. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 324–326, July–August, 2007.     

A new triterpene from the leaves of Craibiodendron yunnanense

A new triterpene, taraxast-20(30)-en-3β,12β-diol (1), and eight known compounds were isolated from the leaves of Craibiodendron yunnanense. Their structures were established on the basis of spectral evidence. Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 35–37, January–February, 2008.     

Structure of a new xanthone from <Emphasis Type="Italic">Securidaca inappendiculata</Emphasis>

A new xanthone (1, 1,7-dihydroxy-2-methoxyxanthone), in addition to the known metabolites 1,7-dihydroxyxanthone (2), 24(R)-stigmast-7,22 (E)-dien-3α-ol (3), and 1,7-dimethoxyxanthone (4), was isolated from the roots of Securidaca inappendiculata. Compounds 1–4 were evaluated by anti-HIV assay and 1–3 showed anti-HIV-1inhibitory activity in vitro. Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 348–349, July–August, 2008.     

Two new coumarin biosides from Angelica dahurica

Two new coumarin biosides, tert-O-β-D-apiofuranosyl-(1→6)-O-β-D-glucopyranosyl-byakangelicin (1) and 2′-O-β-D-apiofuranosyl-(1→6)-β-D-glucopyranosyl-peucedanol (2), were isolated from the fresh roots of Angelica dahurica. The structures of the new compounds were elucidated on the basis of spectral analysis. Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 561–563, November–December, 2008.     

Novel <Emphasis Type="Italic">S</Emphasis>-containing lactones from monoterpene oxides

A new type of S-containing terpene lactones was produced by the reactions of limonene-1,2-oxide and β-pinene-α-oxide with mercaptoacetic acid. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 220–223, May–June, 2007.     

Synthesis of 5α-androstan-3β,17β-diol from tigogenin

5α-Androstan-3β,17β-diol (3b-adiol), a known inhibitor of prostate cancer cell growth, was synthesized from tigogenin. Its structure was confirmed by NMR and IR spectroscopy and mass spectroscopy. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 81–82, January–February, 2007.     

Synthesis of new derivatives of 3<Emphasis Type="Italic">β</Emphasis>-hydroxy18<Emphasis Type="Italic">β</Emphasis>H-olean-9,12-dien-30-oic acid

Ring A was transformed and new A-homo-4-aza- and 3-cyano-3,4-seco-olean-4-ene derivatives of 3β-hydroxy18βH-olean-9,12-dien-30-oic acid were synthesized. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 335–338, May–June, 2009.     

Quantitative HPLC Determination and Stability Studies of Pyridostemin in Extracts and Water Dispersible Granule Formulations of Stemona curtisii

A reversed-phase high-performance liquid chromatographic method has been developed and validated for the determination of pyridostemin, the major pesticidal alkaloid found in Stemona curtisii. This methodology was applied to the investigation of plant extracts and water dispersible granule formulations. Stability indicating procedures have also been carried out. The chromatographic separation was on a C₁₈ column with a mixture of acetonitrile–water–triethylamine (30:70:0.12, v/v/v), using UV detection at 300 nm. Validation procedures showed that the method was specific, accurate and precise. The response was linear over a range of 5–25 μg mL⁻¹ with recoveries in the range of 98.28–102.85%. The RSD for intra- and inter-day precision were <0.72 and <1.29%, respectively. Extraction of plant material with dichloromethane gave a significantly higher pyridostemin content in the crude extracts when compared with extractions in methanol. Partial purification of the crude extracts by silica gel column chromatography was used to concentrate the mixture about fourfold. Degradation behavior of pyridostemin in the partially purified extracts followed first-order kinetics. The main pathways for its decomposition were base hydrolysis and oxidation.     

Balanoinvolin,a new steroid derivative from <Emphasis Type="Italic">Balanophora involucrate</Emphasis>

A new compound, β-sitosterylglucoside-3′-O-linoleate, named balanoinvolin, and three known compounds coniferin, methylconiferin, and 4-O-β-D-glucopyranosylconiferyl aldehyde, were isolated from Balanophora involucrate Hook. f. and their structures were determined by MS and 1D/2D NMR spectra. Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 315–317, May–June, 2009.     

Glutinane triterpenes from the stem bark of <Emphasis Type="Italic">Euonymus hamiltonianus</Emphasis>

Three new glutinane-type triterpenes, 19α-glutin-5-en-19-ol (1), 2β,15α,21β-glutin-11-ene-2,15,21-triol (2), and 2β,19α-glutin-7,21-diene-2,19-diol (3), were isolated from the stem bark of Euonymus hamiltonianus. Their structures were determined by 1D and 2D NMR along with MS and IR. Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 321–323, May–June, 2009.     

Fatty acid composition of some Astragalus species from Turkey

In this study, the fatty acid contents of some Astragalus L. (Fabaceae) species from Turkey were determined by GC and GC-MS techniques. The seed oils of Astragalus sp. (A. echinops Aucher ex. Boiss., A. subrobustos Boriss., A. jodostachys, Boiss. & Buhse., A. falcatus Lam., A. fraxinifolius DC.) contained linolenic (between 23–41.%), linoleic (23–37%), and oleic acids (8–19%) as the major components. Fatty acid composition of the studied Astragalus taxa showed uniform fatty acid patterns. Palmitic and stearic acids were the major saturated fatty acids in the seed oils. The amounts of unsaturated fatty acids were higher than saturated fatty acids. Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 526–528, November–December, 2006.     

Synthesis of N-glycoconjugates of glycyrrhetic acid

New N-glycoconjugates that are analogs of glycyrrhizic acid were synthesized by condensation of α-L-rhamnopyranosylamine and β-D-lactosylamine with acid succinate and phthalate of glycyrrhetic acid methyl ester using N,N′-dicyclohexylcarbodiimide (DCC) or DCC-N-hydroxybenzotriazole. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 54–56, January–February, 2006.     

Triterpene glycosides from Kalopanax septemlobum. VII. Minor glycosides from stems of Kalopanax septemlobum var. maximowiczii and Kalopanax septemlobum var. typicum

Sixteen triterpene glycosides, three of which were new, hederagenin 28-O-β-D-glucuronopyranosyl ester and 28-O-β-D-gentiobiosyl ester and oleanolic acid 3-O-α-L-arabinopyranoside, were isolated from stem bark of Kalopanax septemlobum. The glycoside contents in stem bark of two varieties, maximowiczii and typicum, were compared. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 49–53, January–February, 2006.