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.     

Synthesis of 2,3-<Emphasis Type="Italic">cis</Emphasis> Stereomeric Emetamines <Emphasis Type="Italic">via Reissert</Emphasis> Compounds

Summary. Alkylation of Reissert compounds with certain benzoquinolizinone derivatives followed by hydrolytic cleavage afforded the core of the title compounds in a two step sequence. Finally, the lactam intermediates were reduced with DIBAH giving the target compounds, the structural and stereochemical assignments of which were achieved by ¹³C NMR spectroscopy. Part of PhD thesis, LMU München, D     

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.     

Synthesis of 4<Emphasis Type="Italic">E</Emphasis>,7<Emphasis Type="Italic">Z</Emphasis>-tridecadien-1-ylacetate,a component of the <Emphasis Type="Italic">Phthorimaea opercucella</Emphasis> sex pheromone

A new synthetic approach to 4E,7Z-tridecadien-1-ylacetate, a component of the Phthorimaea opercucella (Zeller) potato moth sex pheromone, was developed using a highly stereoselective Claisen rearrangement and Wittig reaction. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 235–236, May–June, 2007.     

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.     

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.     

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.     

Reaction sites of <Emphasis Type="Italic">N,N′</Emphasis>-substituted <Emphasis Type="Italic">p</Emphasis>-phenylenediamine antioxidants

The geometries of N,N′-diphenylbenzene-1,4-diamine (DPPD), N-phenyl-N′-(1-phenylethyl)benzene-1,4-diamine (SPPD), N-(4-methylpentan-2-yl)-N′-phenylbenzene-1,4-diamine (6PPD), N-propan-2-yl-N′-phenylbenzene-1,4-diamine (IPPD), N-(2-methoxybenzyl)-N′-phenylbenzene-1,4-diamine (MBPPD), and N-phenyl-N′-(2-phenylpropan-2-yl)benzene-1,4-diamine (CPPD) as well as of their dehydrogenation products were optimized by the semiempirical AM1 method. The results support the idea of stable N_B=C_X structures formation during the consecutive dehydrogenation of SPPD, 6PPD, IPPD, and MBPPD antioxidants. The biradicals formed during the second step of dehydrogenation of substituted phenylenediamines might be important for their antioxidant effectiveness. Dedicated to Professor Vladimír Kvasnička, DrSc., in honour of his 65th birthday     

<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     

<Emphasis Type="Italic">Ab initio</Emphasis> study of aniline and <Emphasis Type="Italic">n</Emphasis>-propylamine associates with nitrobenzene and <Emphasis Type="Italic">m</Emphasis>-cresol

An ab initio (6-31G**) study of binary associates of aniline and n-propylamine with nitrobenzene and m-cresol has been carried out. The structures corresponding to the total energy minimum of the system have been found for the associates, and their geometrical and energy characteristics have been determined. Basic types of intermolecular interactions have been established, and their effects on the reactivity of the amino group have been investigated.Original Russian Text Copyright © 2004 by I. A. Novakov, V. V. Korolkov, A. I. Pavlyuchko, B. S. Orlinson, and L. A. GribovTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 595–601, July–August, 2004.This revised version was published online in April 2005 with a corrected cover date.     

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.     

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.     

Influence of inhibitory compounds and minor sugars on xylitol production by Debaryomyces hansenii

To obtain in-depth information on the overall metabolic behavior of the new good xylitol producer Debaryomyces hansenii UFV-170, batch bioconversions were carried out using semisynthetic media with compositions simulating those of typical acidic hemicellulose hydrolysates of sugarcane bagasse. For this purpose, we used media containing glucose (4.3-6.5 g/L), xylose (60.1-92.1 g/L), or arabinose (5.9-9.2 g/L), or binary or ternary mixtures of them in either the presence or absence of typical inhibitors of acidic hydrolysates, such as furfural (1.0-5.0 g/L), hydroxymethylfurfural (0.01- 0.30 g/L), acetic acid (0.5-3.0 g/L), and vanillin (0.5-3.0 g/L). D. hansenii exhibited a good tolerance to high sugar concentrations as well as to the presence of inhibiting compounds in the fermentation media. It was able to produce xylitol only from xylose, arabitol from arabinose, and no glucitol from glucose. Arabinose metabolization was incomplete, while ethanol was mainly produced from glucose and, to a lesser less extent, from xylose and arabinose. The results suggest potential application of this strain in xyloseto- xylitol bioconversion from complex xylose media from lignocellulosic materials.     

Structure and photochromism of 2-(<Emphasis Type="Italic">N</Emphasis>-acyl-<Emphasis Type="Italic">N</Emphasis>-arylaminomethylene)benzo[<Emphasis Type="Italic">b</Emphasis>]thiophen-3(2<Emphasis Type="Italic">H</Emphasis>)-ones

It was shown by electron absorption spectroscopy and X-ray diffraction analysis that steric strains in photochromic 2-(N-acyl-N-arylaminomethylene) benzo[b]thiophen-3(2H)-one molecules ortho-substituted in the N-phenyl ring increase the quantum yield of the N→O photoinduced rearrangement in accord with an increase in the steric constant of the ortho-substituent.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2151–2155, October, 2004.     

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.     

<Emphasis Type="Italic">tert</Emphasis>-Butyl (2<Emphasis Type="Italic">S</Emphasis>)-(<Emphasis Type="Italic">p</Emphasis>-tolylsulfonyloxy)propionate — a suitable reagent for the direct alkylation of indole derivatives

A new method is proposed for the synthesis of indole derivatives containing a chiral substituent at the nitrogen atom, which includes the direct alkylation of indole derivatives with tert-butyl (2S)-(p-tolylsulfonyloxy)propionate, obtained from commercial ethyl (S)-lactate with subsequent conversion to the corresponding p-toluenesulfonyloxy derivative by hydrolysis, and esterification. Dedicated to Academician B. A. Trofimov on his 70^th birthday. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, 1391–1398, September, 2008.     

Two new compounds from <Emphasis Type="Italic">Phyllanthus niruri</Emphasis>

Three compounds were isolated from Phyllanthus niruri Linn. One effective method, improved dry column liquid chromatography for isolating these compounds, was applied on a silica gel column. It is a combination of conventional dry column chromatographic and flash chromatographic techniques. Structures of those obtained compounds were elucidated by means of spectral techniques including IR, MS, and 1D NMR and 2D NMR. Compound 1 was elucidated as 2,3,5,6-tetrahydroxybenzyl acetate. Compound 2 , 2,4,5-trihydroxy-3-(4,6,7-trihydroxy-3-oxo-1,3-dihydroisobenzofuran-5-yl)-benzoic acid methyl ester, was given the name phyllangin, and compound 3 was named corilagin. Compounds 1 and 2 are new compounds.Published in Khimiya Prirodnykh Soedinenii, No. 5, pp. 380–382, September–October, 2004.     

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.     

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.