1,3-diallyl-5-[ω-(diphenylphosphino)alkyl] isocyanurates in reactions of complex formation with palladium(ii) dichloride

The reactions of phosphine derivatives of diallyl isocyanurates with palladium(ii) dichloride lead to the formation of complexes, whose structure, composition, and stability depend on the length of the methylene chain between the isocyanurate and diphenylphosphine fragments in the ligand. 1,3-Diallyl-5-[5′-(diphenylphosphino)pentyl and 10′-(diphenyl-phosphino)decyl] isocyanurates with PdCl₂ form monomeric L₂PdCl₂ trans-complexes in which P atoms of the ligands participate in coordination with the metal. 1,3-Diallyl-5-[2′-(diphenylphosphino)ethyl] isocyanurate with PdCl₂ forms a dimeric (LPdCl₂)₂ complex, which decomposes in a solution to the monomer including solvent molecule into the coordination sphere of the metal. The reactions of 1,3-diallyl-5-[4′-(diphenylphosphino)butyl] isocyanurate and 1,3-diallyl-5-[6′-(diphenylphosphino)hexyl] isocyanurate with PdCl₂ give monomeric chelate LPdCl₂ complexes in which one of the allyl groups of the isocyanurate cycle participates in coordination with the central ion along with the phosphorus atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1859–1865, September, 1998.     

1,3-Dipolar cycloaddition of diazomethane and diazocyclopropane to 2-fluoro-3-methylbutadiene and thermal transformations of fluorine-containing vinylpyrazolines and vinylcyclopropanes

Reactions of 2-fluoro-3-methylbuta-1,3-diene with diazomethane in ether at 15 °C and with diazocyclopropane generated in situ by decomposition of N-cyclopropyl-N-nitrosourea in the presence of K₂CO₃ in CH₂Cl₂ at –10 °C selectively involve the double bond at the methyl group to give 3-(1-fluorovinyl)-3-methylpyrazolines. Thermal dediazotization of the latter at 250 °C yields 1-(1-fluorovinyl)-1-methylcyclopropane and -spiropentane 5, which are capable of isomerizing, under more severe conditions (400—600 °C), into 1-fluoro-2-methylcyclopent-1-ene and 5-fluoro-4-methylspiro[2.4]hept-4-ene (7), respectively. Spiropentane derivative 5 partially isomerizes into 1-fluoro-2-methyl-3-methylidenecyclohex-1-ene. In a similar way, thermolysis of 6-(2,3,3-trifluorocyclobut-1-enyl)-4,5-diazaspiro[2.4]hept-4-ene at 400 °C gives a mixture of 1-(spiropentyl)-2,3,3-trifluorocyclobut-1-ene and 2,3,3-trifluoro-1-(2-methylidenecyclobutyl)cyclobut-1-ene. Thermolysis of 1-cyclopropyl-2,3,3-trifluorocyclobut-1-ene at 550—620 °C affords a mixture of 1-(trifluorovinyl)cyclopentene and 2,3-difluorotoluene.     

Flavonoid glycosides fromThalictrum squarrosum St. ex Willd. andThalictrum minus L.

Two flavonoid allose diglycosides were found in the terrestrial part ofThalictrum squarrosum St. ex Willd. andT. minus L. (Ranunculaceae). 7,4′-Di-O-β-allopyranosylapigenin was isolated fromT. minus. InT. squarrosum, its monoacetate was also found and characterized as 7-O-(6-O-acetyl-β-allopyranosyl)-4′-O-(β-allopyranosyl)apigenin. The sites of attachment of the carbohydrate residues were determined by HMBC; the location of the acetate group was identified by ROESY. Both substances were isolated from these plants for the first time. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 392–394, February, 1999.     

PMR and <Superscript>13</Superscript>C NMR spectra of biologically active compounds. XIII.* Structure and stereochemistry of a new phenylpropanoid glycoside isolated from <Emphasis Type="Italic">Onopordum acanthium</Emphasis> seeds

The structure of a new compound was determined using PMR and ¹³C NMR spectroscopy (HHCOSY, HSBC, HMBC, ROESY) as 2-[3′-methoxy,4-O-β-D-galactopyranos-1-yl)benzyl]-3-(3″,4″-dimethoxybenzyl)-4hydroxybutyric acid, which was isolated for the first time from seeds of Scotch thistle Onopordum acanthium L. *For No. XII, see [1]. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 53–55, January–February, 2009.     

Structure of lipid A from the marine gram-negative bacterium <Emphasis Type="Italic">Pseudoalteromonas nigrifaciens</Emphasis> IAM 13010<Superscript>T</Superscript>

The structure of lipid A from the marine γ-proteobacterium Pseudoalteromonas nigrifaciens IAM 13010^T that was prepared by hydrolysis of the corresponding lipopolysaccharide by acetic acid (1%) was determined by chemical analysis, ¹³C NMR spectroscopy, and MALDI/TOF and LSIMS mass spectrometry. It was shown that lipid A is a β-1,6-bonded disaccharide of glucosamine that is substituted by two phosphoric acids (in the C1 and C4′ positions), two (R)-3-hydroxyalkanoic (normal and branched) acids with ester bonding (at the C3 and C3′-positions), and (R)-3-hydroxydodecanoic and (R)-3-dodecanoyloxydodecanoic acids (both with amide bonding at C2′ and C2, respectively). It was hypothesized that this type of structure is typical of lipid A from bacteria of the genus Pseudoalteromonas in general. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 425–429, September–October, 2007.     

Determination of protonation constants of some fluorinated polyamines by means of <Superscript>13</Superscript>C NMR data processed by the new computer program HypNMR2000. Protonation sequence in polyamines

The pK_a values of 6-fluoro-4,8-diazadodecane-1,12-diamine (6-fluorospermine) (1), 6,6-difluoro-4,8-diazadodecane-1,12-diamine (6,6-difluorospermine) (2), 6-fluoro-4-azaoctane-1,8-diamine (6-fluorospermidine) (3) and 6,6-difluoro-4-azaoctane-1,8-diamine (6,6-difluorospermidine) (4) in D₂O solution have been determined at 40 °C from ¹³C NMR chemical shifts data using the new computer program HypNMR2000. The enthalpies of protonation of compounds 1–4 and the parent amines spermine (5) and spermidine (6) have been determined from microcalorimetric titration data. The values of H° were used to derive basicity constants relative to 25 °C. The NMR data have been analysed by two different methods to obtain information on the protonation sequence in the polyamines 1–5. The protonation sequence for spermine is related to its biological activity.Abbreviations PKC Protein kinase C - PS Phosphatidylserine - VB Microsoft Visual BasicPresented at the Spanish-Italian Congress on the Thermodynamics of Metal Complexes, Santiago de Compostela, Spain, June 2–6, 2002     

Two new isomeric lignans from <Emphasis Type="Italic">Eusideroxylon zwageri</Emphasis>

Two new lignans were isolated with two other known compounds, eusiderin A and eusiderin I, from Eusideroxylon zwageri (billian). The two new lignans have isomeric structure. The structures of the new lignans were determined to be (2R,3R,4S)-2,3-dimethyl-6,7-dimethoxy-4-ethoxy (3′,4′,5′-trimethoxybenzene)-1,5-dihydroxytetralin and (2R,3S,4S)-2,3-dimethyl-6,7-dimethoxy-4-ethoxy(3′,4′,5′-trimethoxybenzene)-1,5-dihydroxytetralin. Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 303–305, May–June, 2009.     

Synthesis ofN-substituted 4-benzoyl-2-iminothiazolium bromides

Substituted thioureas react with 1-bromo-2-benzoylacetylene in various solvents at 20°C to give the correspondingN-substituted 4-benzoyl-2-(R-imino)-3-R′-thiazolium bromides. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 199–200, January, 1997.     

121,123Sb NQR study of solid phases formed in systems (MF)1−x −(M′F) x −SbF3−H2O (M, M′=Na, K, Rb, Cs, and NH4)

Crystalline substances formed in the (MF)_1−x −(M′F) _x −SbF₃−H₂O systems (M, M′=Na, K, Rb, Cs, and NH₄;x=0 to 1) were investigated by^121,123Sb NQR spectroscopy at 77 K. The formation of individual Sb^III complexes NaCs₃Sb₄F₁₆·H₂O and NaKSbF₅·1.5H₂O, and statistically disordered mixed crystals M_1−x −M′ _x −SbF₄ (M, M′=K, Rb, Cs, and NH₄) was established. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 109–112, January, 1999.     

Structural and physicochemical characteristics of chelate nickel(II) compounds based on 1,2,3-triketone (hydrazone)imines

The crystal structures of the chelates Ni^IIL (L²⁻ are the N,N′-(o-phenylene)-bis[4-(4-methylphenyl)hydrazono-3-oxo-1,1,2,2-tetrafluorononane-5-iminate], N,N′-ethylene-bis[3-(4-methylphenyl)hydrazono-4-oxo-5,5,6,6,7,7,8,8-octafluorooctane-2-iminate], or N,N′-ethylene-bis(4-hydroxy-5,5,6,6,7,7,8,8-octafluoro-3-octene-2-iminate) anions) were studied by X-ray diffraction. Magnetic measurements and ESR spectroscopic studies revealed the appearance of paramagnetism due to a tetrahedral distortion of the coordination unit and also the unusual behavior of the effective magnetic moment at low temperatures. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 103–109, January, 2007.     

Asymmetric trimethylsilylcyanation of aldehydes catalyzed by chiral salen TiIV complexes with theC 1 symmetry

Asymmetric trimethylsilylcyanation of a number of aromatic and aliphatic aldehydes catalyzed by chiral Ti^IV complexes preparedin situ from Ti(OPrⁱ)₄ and (1S)-[N,N′-bis(2′-hydroxy-3′-tert-butylbenzylidene)]-1,2-diaminoalkanes gives products with (S)-absolute configurations. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2040–2042, November, 1997.     

Study of isomorphism in fluorine-containing antimony(III) complexes

The mutual influence of the atoms on the composition of solid fluorine-containing antimony(iii) complexes formed in aqueous solutions in the (MF) _x −(M′F) _n−x −SbF₃ (M, M′=Na, K, Rb, Cs, and NH₄;n=1, 2;x=0 to 2), (KNO₂) _n −(KY) _n −SbF₃ (Y=F, Cl, SO₄;n=0.5, 1), and K₂SbF₅−K₂SbCl₅ systems was investigated by elemental, X-ray, and thermogravimetric analyses and by IR and^121,123Sb NQR spectroscopy. The isomorphism conditions for fluorine-containing antimony(iii) compounds resulting in the formation of complexes NaM′SbF₅·1.5H₂O (M′=K and Rb), K₂SbF₅·1.5H₂O, NaCs₃Sb₄F₁₆·H₂O, KsbF₃Cl, K₂SbF₂Cl₃ with constant compositions, continuous M _x M′_2−x SbF₅ (0<x<2) and limited M _x M′_1−x SbF₄ (0.25<x<0.75; M, M′=K, Rb, Cs, and NH₄) solid solutions or LiF+MSbF₄ (M=Na, K, Rb, and Cs), M₂SbF₅+Cs₂SbF₅ (M=Na and K) and MSbF₄+NaSbF₄ (M=Rb and NH₄) mechanical mixtures were determined. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 103–108, January, 1999.     

Characterization and quantification of anthocyanins in selected artichoke (Cynara scolymus L.) cultivars by HPLC–DAD–ESI–MS n

The anthocyanin pattern of artichoke heads (Cynara scolymus L.) has been investigated by high-performance liquid chromatography–electrospray ionization mass spectrometry. For this purpose a suitable extraction and liquid chromatographic method was developed. Besides the main anthocyanins—cyanidin 3,5-diglucoside, cyanidin 3-glucoside, cyanidin 3,5-malonyldiglucoside, cyanidin 3-(3′′-malonyl)glucoside, and cyanidin 3-(6′′-malonyl)glucoside—several minor compounds were identified. Among these, two peonidin derivatives and one delphinidin derivative were characterized on the basis of their fragmentation patterns. To the best of our knowledge this is the first report on anthocyanins in artichoke heads consisting of aglycones other than those of cyanidin. Quantification of individual compounds was performed by external calibration. Cyanidin 3-(6′′-malonyl)glucoside was found to be the major anthocyanin in all the samples analyzed. Total anthocyanin content ranged from 8.4 to 1,705.4 mg kg⁻¹ dry mass.      

Reaction of 2-(4,5-dihydrofur-3-yl)-1,3-diphenyl-1,3-diaza-2-2λ3-phospholidine withC,N-diphenylnitriliminewithC,N-diphenylnitrilimine

The reaction of 2-(4,5-dihydrofur-3-yl)-1,3-diphenyl-1,3-diaza-2λ³-phospholidine withC,N-diphenylnitrilimine is a multistage process, in the course of which the 1,2,4-diazaphosphorine ring is formed and both rings of the initial organophosphorus compound are cleaved. 5-(2-Chloroethyl)-4-(N,N′-diphenylethylenediamino)-1,3-diphenyl-1,4-dihydro-1, 2,4λ⁵-diazaphosphorine was obtained as the final product. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 125–128, January, 2000.     

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.     

Benzo-1,2,3,4-tetrazine 1,3-dioxides annulated with tetraazapentalenes

New heterocyclic system, viz., 8,12-dehydro-8H,12H-[1,2,3]triazolo[2′,1′:1,2][1,2,3]triazolo-[4,5-f][1,2,3,4]benzotetrazine 2,4-dioxide, has been synthesized by thermolysis of 5-azido-6-(1,2,3-triazol-2-yl)benzotetrazine 1,3-dioxide, and its thermal stability and spectral properties have been studied. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 186–188, January, 2008.     

Synthesis of N-(4′-Benzo[15-crown-5])thiophenoxyphenylaminoglyoxime and its complexes with some transition metals

4-(Chloroacetyl)diphenyl thioether (1) was synthesized from chloroacetyl chloride and diphenyl thioether in the presence of AlCl₃ as catalyst in a Friedel-Crafts reaction. Subsequently, its keto oxime (2) and glyoxime (3) derivatives were prepared. N-(4′-Benzo[15-crown-5]thiophenoxyphenylaminoglyoxime (H₂L) and its sodium chloride complex (H₂L · NaCl) were prepared from 4-(thiophenoxy)chlorophenylglyoxime (3), 4′-aminobenzo[15-crown-5] and sodium bicarbonate or sodium bicarbonate and sodium chloride. Ni(II), Co(II) and Cu(II) complexes of H₂L and H₂L · NaCl have a metal–ligand ratio of 1:2 and the ligand coordinates through the two N atoms, as do most of the vic-dioximes. The BF₂-capped Ni(II) mononuclear complex of the vic-dioxime was prepared. The macrocyclic ligands and their transition metal complexes were characterized on the basis of FT-IR, ¹H NMR, ¹³C NMR spectroscopy and elemental analyses data.     

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.     

Products and kinetics of the thermal decomposition of (l-(−)-menthyl)[2,2′-methylene-bis-(4-methyl-6-tert-butylphenyl)] phosphite ozonide

Two conformers (chair, boat) of [l-(–)-menthyl)]-[2,2-methylene-bis-(4-methyl-6-tert-butylphenyl)] phosphite ozonide have been obtained by the low temperature ozonization (–80 °C) of [l-(–)-menthyl)]-[2,2-methylene-bis-(4-methyl-6-tert-butylphenyl)] phosphite. It was determined that decomposition of the ozonide is first order with the rate constant logk ₀ = (10.92±1.10)–(14.02±1.25)/gq ( = 2.303RT, kcal mol^–1), leading to [l-(–)-menthyl)]-[2,2-methylene-bis-(4-methyl-6-tert-butylphenyl)] phosphate and oxygen (including singlet oxygen). Conformational transitions (chair-boat) for [l-(–)-menthyl)]-[2,2-methylene-bis-(4-methyl-6-tert-butylphenyl)] phosphate have been registered by³¹P NMR spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1758–1761, October, 1994.This work was supported by Russian Foundation for Basic Research (Project No. 93-03-532l).