Chemotaxonomy of <Emphasis Type="Italic">Ballota</Emphasis> Species

Sixteen taxa of Ballota were investigated by analyzing the contents of diterpenoid and flavonoid compositions, and the relationships were compared with their morphological properties. HPLC chromatograms of diterpenoids and flavonoids from acetone extracts of sixteen Ballota taxa revealed the presence of thirteen compounds. Isolated compounds from Ballota species were evaluated by the unweighted pair-group arithmetic average (UPGMA) clustering method. B. glandulosissima is distinct from all other taxa in the dendogram, and this species is morphologically different from other taxa by having a high number of glandular hairs. The second group is composed of B. saxatilis ssp. saxatilis and B. inaequidens; these two species are in close kinship as evidenced by their morphology (similar calyx shape). In the latter clusters at most, the affinities among taxa, as suggested by diterpenoid and flavonoid pattern, are only partially congruent with affinities based on other evidence. In general, morphologic, anatomic characters, distributions, and habitats are not concordant with the clusters. Also, no concordance was found between the sections, phylogenetic order [1], and those of the groups formed by cluster analyses.__________Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 242–244, May–June, 2005.     

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.     

Electrochemical thiocyanation of dodecahydro-7,8-dicarba-<Emphasis Type="Italic">nido</Emphasis>-undecaborate and 7,8-dimethyldecahydro-7,8-dicarba-<Emphasis Type="Italic">nido</Emphasis>-undecaborate monoanions

Electrochemical thiocyanation of the dodecahydro-7,8-dicarba-nido-undecaborate and 7,8-dimethyldecahydro-7,8-dicarba-nido-undecaborate monoanions afforded thiocyanate derivatives of these compounds, which were isolated as alkylammonium salts. The structures of the synthesized compounds were determined by the data from IR, ¹H and ¹¹B NMR, and ¹¹B-¹¹B NMR COSY spectroscopy. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1553–1556, July, 2005.     

Synthesis of isomeric 2-oxazolidinones from (1<Emphasis Type="Italic">R</Emphasis>,2<Emphasis Type="Italic">R</Emphasis>)-and (1<Emphasis Type="Italic">S</Emphasis>,2<Emphasis Type="Italic">S</Emphasis>)-2-amino-1-(4-nitrophenyl)-1,3-propanediols

A synthesis is reported for (4R,5R)-and (4S,5S)-4-hydroxymethyl-5-(4-nitrophenyl)oxazolidin-2-ones and (1′R,4R)-and (1′S,4S)-4-[hydroxy(4-nitrophenyl)methyl]oxazolidin-2-ones from (1R,2R)-and (1S,2S)-2-amino-1-(4-nitrophenyl)-1,3-propanediols. The effect of the experimental conditions on the formation of these compounds was studied. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1562–1570, October, 2007.     

Synthesis,structural and conformational study of selected <Emphasis Type="Italic">N</Emphasis>-substituted phthalimides

This paper synthesizes N-substituted phthalimides derived from nitrogen heterocycles as potential 5-HT₄ ligands by using the Mitsunobu reaction. Conformational studies of some of the new compounds have been conducted using ¹H and ¹³C-NMR spectroscopy. Proton and carbon resonances were achieved through the application of one-dimensional selective NOE, two-dimensional NMR techniques-homonuclear COSY-45, NOESY and heteronuclear ¹H-¹³C HMQC correlated spectroscopy- and double resonance experiments. The crystal structure of compound 1 was determined by X-ray diffraction.     

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.     

Chemical Composition of the Essential Oils of <Emphasis Type="Italic">Bunium elegans</Emphasis> and <Emphasis Type="Italic">Bunium caroides</Emphasis>

Analyses of the essential oils of Bunium elegans (Fenzl) Freyn and B. caroides (Boiss.) Hausskn. ex Bornm., using GC, GC/MS, and¹³ C-NMR spectroscopy resulted in identification of their chemical constituents. The oils of both species contain mainly the sesquiterpene hydrocarbons germacrene-D and E-caryophyllene, which amounted to 24.1% and 38% for B. elegans and 22.1% and 26.6% for B. caroides respectively. The oil of B. caroides contained the monoterpenes α-pinene and Z-β-ocimene in 4.1 and 5.9% respectively, while traces of monoterpenes were detected for B. elegans. On the other hand, in B. caroides the phenylpropanoid derivatives asaricin (7.5%) and dillapiole (10.2%) were among the major constituents. __________ Published in Khimiya Prirodnykh Soedinenii, No. 4, pp. 335–336, July–August, 2005.     

The chemical composition of fruits of <Emphasis Type="Italic">Pistacia atlantica</Emphasis> desf. subsp. <Emphasis Type="Italic">atlantica</Emphasis> from Algeria

The chemical composition of the fruits of the north algerian ecotype Pistacia atlantica subsp. atlantica was determined and compared to other fruits of different species in the genus growing in south Algeria and other Mediterranean regions. These fruits were analyzed for their dry matter, protein, crude oil, ash, fatty acids, and phytosterol content. The main fatty acids identified by gas chromatography were oleic (54.15%), linoleic (28.84%), and palmitic (12.21%) acids. The fruits of the north ecotype were found to be rich in protein, oil, fiber, and unsaturated fatty acids, suggesting that they may be valuable for food uses. The sterols isolated were campesterol, stigmasterol, β-sitosterol, and Δ⁵-avenasterol with β-sitosterol as the major constituent (85%±0.85). The biochemical data indicated an elevated MUFA rate (∼56%) in pistacia oil which may be important against certain pathologies for its nutritional and preventive virtues. Published in Khimiya Prirodnykh Soedinenii, No. 2, pp. 103–105, March–April, 2007.     

<Emphasis Type="Italic">O</Emphasis>- and <Emphasis Type="Italic">N</Emphasis>-Alkylation of <Emphasis Type="Italic">N</Emphasis>-halosuccinimides in ionic reactions with 1-phenyltricyclo [4.1.0.0<Superscript>2,7</Superscript>]heptane

N-Bromo and N-chlorosuccinimides add to 1-phenyltricyclo[4.1.0.0^2,7]heptane in CH₂Cl₂ with cleavage of the C(1)-C(7) bond to give isomeric 1 : 1 Markownikoff-type endo, anti-adducts of the norpinane structure in a ∼3 :7 ratio corresponding to N and O alkylation of succinimide.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No.2, pp. 457–460, February, 2005     

Separation and identification of steroidal compounds with cytotoxic activity against human gastric cancer cell lines <Emphasis Type="Italic">in vitro</Emphasis> from the rhizomes of <Emphasis Type="Italic">Paris polyphylla</Emphasis> var. <Emphasis Type="Italic">chinensis</Emphasis>

A novel steroidal saponin, along with 12 known steroidal compounds, was isolated from the rhizomes of Paris polyphylla var. chinensis. Spectral data, including two-dimensional NMR, showed that the structure of the novel saponin was 3β,21-dihydroxypregnane-5-en-20S-(22,16)-lactone-1-O-α-L-rhamnopyranosyl(1→2)-[β-D-xylopyranosyl(1→3)]-β-D-glucopyranoside. The isolated steroidal compounds were evaluated for their cytotoxic activity on human gastric cancer cell line HepG₂, SGC7901, BxPC3. Diosgenin-3-O-α-L-rhamnopyranosyl(1→2)[α-L-rabinofuranosyl(1→4)]-β-D-glucopyranoside exhibited the most potent cytotoxic activity among the isolated steroids. Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 556–560, November–December, 2007.     

Enthalpies of mixing of <Emphasis Type="Italic">o</Emphasis>- and <Emphasis Type="Italic">m</Emphasis>-isomers at 298.15 K

Excess enthalpies (H ^E) of 17 binary mixtures of o- and m-isomers of dichlorobenzene, difluorobenzene, methoxymethylbenzene, dimethylbenzene, dimethoxybenzene, aminofluorobenzene, fluoronitrobenzene, diethylbenzene, chlorofluorobenzene, fluoroiodobenzene, bromofluorobenzene, chloromethylbenzene, fluoromethylbenzene, bromomethylbenzene, iodomethylbenzene, fluoromethoxybenzene, dibromobenzene at 298.15 K were measured. All excess enthalpies measured were very small, and those of o-+m-isomers of aminofluorobenzene, dibromobenzene and iodomethylbenzene were negative but 14 other binary mixtures of isomers were positive over the whole range of mole fractions. H ^E of o-+m-isomers of dimethoxybenzene showed the largest enthalpic instability and those of aminofluorobenzene showed the largest enthalpic stability. There was a correlation between dipole–dipole interaction, dipole–induced dipole interaction or entropies of vaporization and excess partial molar enthalpies at infinite dilution.     

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.     

Synthesis of magnesium catecholate and <Emphasis Type="Italic">o</Emphasis>-semiquinone complexes by oxidation of the metal with 3,6-di-<Emphasis Type="Italic">tert</Emphasis>-butyl-<Emphasis Type="Italic">o</Emphasis>-benzoquinone

Oxidation of amalgamated magnesium metal with 3,6-di-tert-butyl-o-benzoquinone (1) in different aprotic organic solvents afforded magnesium catecholate and bis-o-semiquinolate complexes. The catecholate derivatives of magnesium CatMgL₂ (Cat is the 3,6-di-tert-butyl-o-benzoquinone dianion, L = THF or Py) were synthesized in high yields in pyridine and tetrahydrofuran, respectively. The reactions in diethyl ether or dimethoxyethane produced hexacoordinated metal bis-o-semiquinolates SQ₂MgL_n (SQ is the 3,6-di-tert-butyl-o-benzoquinone radical anion, L = Et₂O, n = 2; L = DME, n = 1). The reaction with the use of toluene as the solvent gave a magnesium bis-o-semiquinolate complex containing the coordinated unreduced o-quinone molecule. The molecular structures of the [CatMgPy₂]₂ and SQ₂Mg·DME complexes were established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 92–98, January, 2007.     

Functionalization of sterically hindered <Emphasis Type="Italic">o</Emphasis>-benzoquinones: amino-substituted 3,6-di(<Emphasis Type="Italic">tert</Emphasis>-butyl)-<Emphasis Type="Italic">o</Emphasis>-benzoquinones

New sterically hindered functionalized o-quinones were synthesized by the 1,4-nucleophilic addition of secondary cyclic amines to 3,6-di(tert-butyl)-o-benzoquinone. The ability of these o-quinones to form o-semiquinone complexes with transition and main-group metals was studied by ESR spectroscopy in solution. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1786–1793, September, 2007.     

Phenolic glycosides from <Emphasis Type="Italic">Lespedeza juncea</Emphasis>

Two new phenolic glycosides named meoside-A (1) and meoside-B (2) were isolated from Lespedeza juncea. Two compounds were characterized on the basis of 1D and 2D spectral analysis and chemical derivatization. Published in Khimiya Prirodnykh Soedinenii, No. 5, pp. 479–480, September-October, 2008.     

<Emphasis Type="Italic">N</Emphasis>-Bromoacetyl-β-<Emphasis Type="SmallCaps">D</Emphasis>-glycopyranosylamines in the synthesis of glycoconjugates of nitrogen-containing physiologically active compounds

A series of nitrogen-containing physiologically active compounds underwent smooth N-monoalkylation with N-bromoacetyl-β-glycopyranosylamines derived from N-acetyl-D-glucosamine and lactose. This reaction was demonstrated to be promising for the introduction of carbohydrate residues into heterocyclic compounds, viz., pyridine, imidazole, pyrimidinetrione, carboline, and piperazine derivatives, and into an amino acid, 5-hydroxy-L-tryptophan, which is unstable in alkaline media. Dedicated to Academician N. K. Kochetkov on the occasion of his 90th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1256–1259, May, 2005.     

Mercaptan addition to 1-<Emphasis Type="Italic">O</Emphasis>-allyl-2,3,4,6-tetra-<Emphasis Type="Italic">O</Emphasis>-acetyl-<Emphasis Type="Italic">β</Emphasis>-D-galactopyranose

Addition of ethyl-, propyl-, and n-butylmercaptans to 1-O-allyl-2,3,4,6-tetra-O-acetyl-β-D-galactopyranose in the presence of benzoyl peroxide catalyst was studied for the first time. The products were 1-O-(3-ethylthiopropyl)-2,3,4,6-tetra-O-acetyl-β-D-galactopyranose, 1-O-(3-propylthiopropyl)-2,3,4,6-tetra-O-acetyl-β-D-galactopyranose, and 1-O-(3-butylthiopropyl)-2,3,4,6-tetra-O-acetyl-β-D-galactopyranose. Deacetylation of 1-O-(3-ethylthiopropyl)-2,3,4,6-tetra-O-acetyl-β-D-galactopyranose produced 1-O-(3-ethylthiopropyl)-β-D-galactopyranose. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 209–211, May–June, 2007.     

Study on Inclusion Complex Formation of <Emphasis Type="Italic">m</Emphasis>-Aminobenzoic Acid with Native and Substituted <Emphasis Type="Italic">β</Emphasis>-Cyclodextrins

The complex formation of native and substituted β-cyclodextrins with m-aminobenzoic acid in water was characterized by calorimetry, ¹H NMR and UV spectroscopic studies. These studies showed that β-, hydroxypropyl-β- and methyl-β-cyclodextrins form 1:1 inclusion complexes with m-aminobenzoic acid. The thermodynamic properties of complex formation (K,Δ_c G ^o,Δ_c H ^o,Δ_c S ^o) were calculated. It was found that the processes of complexation are mainly favorable entropically. Introduction of hydroxypropyl- and methyl-substituents into the β-CD molecule results in negligible enhancement of stability of the complexes formed. The structure of these substituents has no influence on the stability constant values. The insertion of the carboxylic group of m-aminobenzoic acid into the cyclodextrin cavity was confirmed by ¹H NMR data.     

Norditerpene Alkaloids from <Emphasis Type="Italic">Delphinium cuneatum</Emphasis>

A mixture of two new norditerpene alkaloids consisting of two regioisomers was isolated from the total alkaloids of Delphinium cuneatum roots. Their structures were proposed as 16-demethoxydelavaine (2a and b) on the basis of PMR, ¹³C NMR, IR, and mass spectra. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 467–468, September–October, 2005.     

New glycosidic and other constituents from hulls of <Emphasis Type="Italic">Oryza sativa</Emphasis>

Three new compounds, 4-hydroxymethylene-7-(9,9,13-trimethylcyclohexyl)-heptanyl-3′,7′,7′-trimethylcyclohexa-2′,4′-dien-1′-oate (1), 1-(n-hexadec-7-enoxy)-6-(n-octadecanoxy)-β-D-glucopyranoside (2), and (Z)-12-hydroxy-9-octadecenoic acid-12-β-D-glucopyranoside (3), along with the known compound hexacosanoic acid (4), were isolated and identified from the rice hulls of Oryza sativa. Their structures were elucidated by 1D and 2D NMR spectroscopic techniques (¹H-¹H COSY, ¹H-¹³C HETCOR, DEPT) aided by EIMS, FABMS, HRFABMS, and IR spectra. Published in Khimiya Prirodnykh Soedinenii, No. 4, pp. 344–347, July–August, 2007.