Synthesis of α-Oxoketene CyclicO,S and S,S Acetals

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Synthesis and cytotoxicity of dinuclear platinum(Ⅱ) complexes of (1S, 3S)-1, 2, 3, 4-tetrahydroisoquinolines

A series of novel dinuclear platinum(Ⅱ) complexes with (1S, 3S)-1,2,3,4-tetrahydroisoquinolines as the ligands were synthesized as potential anticancer agents in several steps starting from commercially available L-DOPA. The cytotoxicities of the series of dinuclear platinum(Ⅱ) complexes of tetrahydroisoquinoline were tested against HCT-8, BEL-7402, A2780, MCF-7, Hela, A549 and BGC-823 cell lines by the MTT test. These complexes showed selective inhibition activity against cisplatin-insensitive cell line Skov3.     

Synthesis of (4R,5S)-(−)- and (4S,5S)-(+)-L-Factors and Muricatacin from D-Glucose

Abstract

In connection with our projects on the synthesis of biologically active 5-hydroxyalkan-4-olides which have a chiral 2.3-diol unit,¹ we have carried out the synthesis of (4R,5S)-(?)- and (4R,5S)-(+)-L-factors (1).² the proposed autoregulators from Streptomyees griseus, and muricatacin (2),³ a biologically active constituent from the seeds of Annona muricata L. via 2.3-dihydroxy aldehydes derived from D-glucose. Hex-3-enofuranose4 was prepared by the elimination of thetriflate derived from D-glucose.     

Synthesis of Urine Drug Metabolites: Glucuronosyl Esters of Carboxymefloquine,Indoprofen, (S)‐Naproxen,and Desmethyl (S)‐Naproxen

Abstract

A general procedure for the synthesis of 1‐O‐acyl‐β‐D‐glucuronic acids using the benzyl 1-O-trichloroacetimidoyl-2,3,4-tri-O-benzyl-D-glucopyranuronate 6 as donor is exemplified by the synthesis of the urine metabolites of (S)‐naproxen, desmethyl (S)‐naproxen, indoprofen, and carboxymefloquine. The key intermediate benzyl 2,3,4‐tri‐O‐benzyl‐D‐glucopyranuronate 5 is easily accessible in four steps (29%) from the peracetylated β-D-glucuronic acid 1.     

Direct conversion of carboxylic acids and carboxylic esters into S,S′-diphenyl acetals and phenyl sulfides with thexylphenylthioborane

Reaction of carboxylic acids with thexylphenylthioborane in methylene chloride at room temperature gives S,S′-diphenyl acetals in high yields and carboxylic esters are converted into phenyl sulfides in the presence of zinc iodide under similar conditions.     

Synthesis and structural characterization of camphanates of (−)-(2S3S,3S) and (+)-(2S,3R)-4-Phenyl-3-bromo-2-butanol diastereoisomers

The X-ray crystal structures of (–)-syn-4-phenyl-3-bromo-2-butyl camphanate (I) and (+-anti-4-phenyl-3-bromo-2-butyl camphanate (II) have been determined. Thesyn diastereoisomer of bromohydrin has the (2S,3S) absolute configuration whereas theanti diastereoisomer has the (2S,3R) absolute configuration. The crystallized derivatives I and II have been obtained by the reaction of each stereoisomer of bromohydrin, synthesized by reduction with baker's yeast, with (1S)-camphanic chloride. Crystal data: (I) C₂₀H₂₅BrO₄:M _w: 409.32; orthorhombic,P2₁2₁2₁;a=11.245(3),b=12.086(1),c=14.512(4) å; Z=4; finalR=0.053 for 1819 observed reflections. (II) C₂₀H₂₅BrO₄;M _w=409.32; monoclinic, P2₁;a=11.352(1),b=6.378(1),c=14.255(2) å,=110.38(1);Z=2; finalR=0.045 for 1672 observed reflections.     

Nitrimines: VII. Reaction of S,S′-Dimethyl-N-nitroimidodithiocarbonate with Alkali. Synthesis of S-Methyl-N-nitrothiocarbamate and Its Salts

Russian Journal of Organic Chemistry - Reaction of S,S′-dimethyl-N-nitroimidodithiocarbonate with alkali in aqueous-alcoholic solution results in salts of S-methyl-N-nitrothiocarbamate. In...     

Facile Synthesis of (S,S)‐1,2‐Diacylamides and (S,S)‐1,2‐Diamines with C 2‐Symmetry

A series of chiral vicinal tertiary diacylamides with C ₂‐symmetry was synthesized from (S)‐α‐phenylethylamine, different aromatic aldehydes, and oxalyl chloride. The diacylamides obtained were then reduced to afford chiral vicinal diamines with C ₂‐symmetry. We propose that the diacylamides existed in four stable conformational isomers in solution because of the dihedral angle between acylamide bonds.     

One-pot Synthesis and Crystal Structure of （1S,2R,3S,4R,5S）-1-Phenyl-2,4-dibenzoyl-3,5-difurylhexanol

(1S,2R,3S,4R,5S)-1-Phenyl-2,4-dibenzoyl-3,5-difurylhexanol 1 was synthesized by one-pot reaction of hypnone and furfurol in alkali H2O/EtOH solution and structurally defined to contain a chair-formed aliphatic carbocycle, on which the bulky substituents occupy the equatorial positions.     

A Convenient Synthesis of Pyrazolylpyrazoles Using α-Oxo Ketene S,S- and N,S-Acetals

Aryl-substitutedpyrazolederivativeshavealreadyattractedwideattentioninrecentdecadesbecausetheywerereportedtoshowabroadspectrum0fbi0logicalactivities.Forinstance,severalsubstitutedpyrazolyIpyrazoIesdemonstratedhighpreemergentherbicidalactivityagainstawidevarietyofbroadleafweedspecies"'.Pyraz0lyl-pyrimidinesexhibiteds0mefungicidalactivity'.Fripronil(5-amino-3-cyan0-l-(2',6,-dichloro-4'-trifluoromethylphenyisanewpyrazoleinsecticidethatprovidesexcellentc0ntrolofmanysoilandf0liarinsects0nawidevari…     

Diaminodithioether complexes of nickel(II) and palladium(II): A unique case of dealkylation of S,S′-thioether

Summary Nickel(II) and palladium(II) complexes of the 1,3-di(o-aminophenylthio) propane (H₂L¹) and 1,2-di(o-aminophenylthio)xylene (H₂L²) ligands have been prepared and characterized. The hydrobromide salt of H₂L¹ gave a 12 ligand-metal complex of Pd^II, whereas free H₂L¹ formed the usual 1:1 species. The reaction of Na₂PdCl₄ with H₂L² resulted in S,S-dealkylation of the ligand and formation of a mononuclear complex of the corresponding thiol, i.e. 2-aminobenzenethiol. NiCl₂, NiBr₂ and Ni(ClO₄)₂ did not react directly with H₂L². Ni^II is a fairly hard ion and therefore does not coordinate to the soft thioether moiety in H₂L² in the absence of soft anions which symbiotically motivate Ni^II to act as a soft acceptor. It thus does not react with H₂L² in the presence of hard ions such as Cl^–, Br^- and ClO ₄ ^– , but, the in situ reaction of the constituents produced the tetrahedral Ni^II complex, contrary to earlier reports of similar types of octahedral species.     

Ab initio quantum mechanical calculations of energy,geometry, vibrational frequencies and IR intensities of tetraphosphorus tetrasulphide, α-P4S4(D2d), and vibrational analysis of As4S4 and As4Se4

Geometry, vibrational frequencies and IR intensities are calculated for α-P₄S₄ by scaled quantum mechanical calculations at the 6-31G*/SCF and STO-3G*/SCF levels. For both basis sets the frequencies are scaled with factors close to or equal to those found for P₄S₃, and based on these results a revised assignment is proposed. The α-P₄S₄ force field is transferred to the isostructural As₄S₄ and As₄Se₄ molecules and rescaled, and based on a good fit to experimental frequencies a new assignment is also proposed for these compounds.     

Metals and semi-metals in street soils of São Paulo city,Brazil

São Paulo is the largest city in Brazil and South America with about 20 million inhabitants in the metropolitan area, more than nine million motor vehicles and intense industrial activity, which are responsible for increasing pollution in the region. Nevertheless, little is known concerning metal and semi-metal content in the soils of this metropolitan region. This type of information could be extremely useful as a fingerprint of environmental pollution. The present study determined the elements As, Ba, Co, Cr, Sb, and Zn concentrations in soils adjacent to avenues of highly dense traffic in São Paulo city to assess their levels and possible sources. The analytical technique employed was Instrumental neutron activation analysis. The results showed, except for Co, concentration levels higher than the reference values for soils of São Paulo, according to the Environmental Protection Agency of the State of São Paulo guidelines. When compared to similar studies in other cities around the world, São Paulo soils presented higher levels, probably due to its high density traffic and industrial activity. The concentrations obtained for As and Cr indicate anthropogenic origin. The high levels of the traffic-related elements Ba, Sb, and Zn in soils nearby high density traffic avenues indicate they may originate from vehicular exhausts.     

Major and trace element assessment of Tietê river sediments, São Paulo, Brazil

The objective of this study was to quantify major and trace elements present in sediments collected from the one of Brazil’s most important rivers, Tietê River. Sediments from 5 different sampling points (P₀–P₄), in 3 campaigns (2008/2009), from the headwaters to Suzano County upstream from São Paulo city were collected. X-ray fluorescence was applied for measuring total concentration of major elements and instrumental neutron activation analysis (INAA) for trace elements. The elements Cd, Hg and Pb were determined by atomic absorption spectrometry after digestion using the US EPA 3,051 procedure. These metal concentrations were compared to the PEL and TEL oriented values from CCME. The sampling sites P₃ and P₄, near industrialized areas, showed the highest concentrations for potentially bioavailable metals, mainly Pb and Hg. The results obtained by INAA were compared to upper continental crust values. A strong enrichment was found for the elements As, Br, Sb, Th, U and Zn. These results evidenced contamination by industrial effluents and sewage even relatively close to the Tietê River headwaters. The worst biological effects (acute toxicity) on benthonic organism Hyalella azteca were also observed at P₃ and P₄.     

Reactions of half-sandwich Co(III) complexes with heterocyclic thione ligands: η2-N,S coordination mode and formation of S–S bond

The reactions of Cp¹CoI₂(CO) with heterocyclic thione ligands yields a η²-N, S coordination family of cobalt complexes for adjacent N, S donor atoms, and dinuclear disulfide cobalt complexes for opposite N, S donor atoms.     

Preparation, characterization, and catalysis of mecro-catalysts

Because catalysis by metals is a surface phenomenon, many technological catalysts contain small (typically nanometre-sired) supported metal particles with a large fraction of the atoms exposed. Many reactions, such as hydrocarbon hydrogenations, are structure-insensitive, proceeding at approximately the same rates on metal particles of various sizes provided that they are larger than 1 nm and show bulk-like metallic behavior. But the catalytic properties are not known when metal particles become so small that their sizes are indium clusters consisting of several indium atoms. Here the catalytic behavior of precisely defined clusters of just four and six indium atoms on solid supports is shown. It is found that the Ir4 and Ir6 clusters differ in catalytic activity both from each other and from metallic Ir particles.     

Structure and Stability of Interstellar Molecule C_3S

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