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Trans Configuration (trans + configuration)

Distribution by Scientific Domains
Chemistry87%
Distribution within Chemistry
Crystallography28%

Selected Abstracts

Acute toxicity of fatty acids to the freshwater green alga Selenastrum capricornutum

ENVIRONMENTAL TOXICOLOGY, Issue 5 2003
Yasushi Kamaya
Abstract The acute toxicity of fatty acids (C14 to C18) commonly found in wood was determined by the standard algal growth inhibition test using the freshwater green alga Selenastrum capricornutum. Toxicity, quantified as IC50 values, varied depending on the number of total carbons and double bonds. Of the tested acids, oleic (cis -9-octadecenoic) acid showed the highest toxicity (72-h IC50 = 0.47 mg/L) to the alga, and triolein, a triglyceride of oleic acid, showed no apparent toxicity. Further examination of a series of C18:1 acids with a double bond at the 6, 11, or 12 position revealed that both double-bond position and cis or trans configuration affected toxicity. The 72-h IC50 data for these fatty acids and related compounds seemed to correlate well with the melting point (mp), showing two separate linear relationships: at mp < 35°C toxicity increased with increasing melting point, and at mp > 40°C toxicity decreased with melting point. © 2003 Wiley Periodicals, Inc. Environ Toxicol 18: 289,294, 2003. [source]

Divanadium(V) and Trapped Valence Linear Tetravanadium(IV,V,V,IV) Complexes

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 35 2009
Anindita Sarkar
Abstract In an acetonitrile/water mixture, reactions of the N,N,-bis(diacetyl)hydrazine (H2diah), bis(acetylacetonato)oxidovanadium(IV) [VO(acac)2] and monodentate N -coordinating heterocycles (hc) in a 1:2:2 mol ratio provide yellow divanadium(V) complexes of formula [(hc)O2V(,-diah)VO2(hc)] (1, hc = imidazole; 2, hc = pyrazole; 3, hc = 3,5-dimethyl pyrazole). On the other hand, in the same solvent mixture reactions of the same reagents in a 1:4:2 mol ratio produce green linear tetravanadium(IV,V,V,IV) complexes of formula [(acac)2OV(,-O)VO(hc)(,-diah)(hc)OV(,-O)VO(acac)2] (4, hc = imidazole; 5, hc = pyrazole; 6, hc = 3,5-dimethyl pyrazole). The complexes 1,6 have been characterized by elemental analysis, magnetic susceptibility, and various spectroscopic and electrochemical measurements. The X-ray crystal structures of 1, 3 and 6 have been determined. In all three structures, the diazine ligand diah2, is in trans configuration. Metal-centred bond parameters are consistent with the localized electronic structure of the two trans -bent {OV(,-O)VO}3+ cores present in 6. The pentavalent metal centres in 1, 3 and 6 are in a distorted trigonal-bipyramidal N2O3 coordination environment, while the terminal tetravalent metal centres in 6 are in a distorted octahedral O6 coordination sphere. The eight-line EPR spectra of the tetravanadium species (4,6) in dimethyl sulfoxide at ambient temperature indicate the rare valence localized electronic structure in the fluid phase. All the complexes are redox active and display metal-centred electron transfer processes in dimethyl sulfoxide solution. A reduction within ,0.78 to ,0.94 V (vs. Ag/AgCl) is observed for the divanadium(V) species 1,3, while a reduction and an oxidation are observed in the potential ranges ,0.82 to ,0.90 V and 0.96 to 1.12 V (vs. Ag/AgCl), respectively, for the tetravanadium species 4,6. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]

Synthesis of Tyrosine-Derived Tetrahydroisoquinolines by Lewis Acid Catalyzed Cyclization of N -(Phenylsulfonyl)alkyloxazolidinones,

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 33 2007
Stefan Tussetschläger
Abstract N -Boc-protected tyrosine esters 5a,b were converted into tetrahydroisoquinolines 13 and 14 in four steps by reduction and ring closure to oxazolidinones 9 and 10, addition of benzenesulfinic acid and aldehydes to sulfones 11 and 12 and subsequent Lewis acid catalyzed cyclization. In the case of m -tyrosine derivative 5a, selective protection with bromine prevented the formation of undesired regioisomers. Debromination of target compounds 13 was readily achieved under radical reduction conditions by using Bu3SnH/AIBN. Tetrahydroisoquinolines 13 and 14 were isolated as single diastereomers whose trans configuration was confirmed by X-ray crystal structure analysis. Partial epimerization of trans - 13i and trans - 21 to the corresponding cis diastereomers was achieved under basic conditions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

Activated ,,,-Unsaturated Aldehydes as Substrate of Dihydroxyacetone Phosphate (DHAP)-Dependent Aldolases in the Context of a Multienzyme System

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 17 2009
Israel Sánchez-Moreno
Abstract The utility for carbon-carbon bond formation of a multienzyme system composed of recombinant dihydroxyacetone kinase (DHAK) from Citrobacter freundii, the fructose bisphosphate aldolase from rabbit muscle (RAMA) and acetate kinase (AK) for adenosine triphosphate (ATP) regeneration has been studied. Several aldehydes with great structural diversity, including three ,,,-unsaturated aldehydes, have been analysed as acceptor substrates. It was found that ,,,-unsaturated aldehydes bearing an electron-withdrawing group in the , position to the double bond with a trans configuration are good acceptors for RAMA in this multienzyme system. The aldol reaction proceeds with excellent D - threo enantioselectivity and the aldol adduct is obtained in good overall yield. The L - threo and D - erythro enantiomers are also accessible from rhamnulose 1-phosphate aldolase (Rha-1PA) and fuculose 1-phosphate aldolase (Fuc-1PA) catalysed reactions, respectively. [source]

Ring transformations of heterocyclic compounds.

JOURNAL OF HETEROCYCLIC CHEMISTRY, Issue 2 2002

2,4,6-Triarylpyrylium perchlorates 1 react with methyleneindolines 3in situ generated from the corresponding methylindolium salts 2, which are spiro-fused with a cycloalkane, benzanellated cycloalkene or a heterocyclic system. These diastereoselective 2,5-[C4+C2] pyrylium ring transformations are carried out in the presence of triethylamine/acetic acid in boiling ethanol to give the dispiroindolines 4 with a trans configuration of the more bulky substituents at the cyclohexadiene ring. By the same type of transformation the dispiro compounds 7/10 with an additional fused benzene ring are obtained from the pyrylium salt 1a and 6/9, the benzo-fused analogues of 3. Spectroscopic data of the transformation products as well as their mode of formation are discussed. [source]

Structural characterization of cyclic kallidin analogues in DMSO by nuclear magnetic resonance and molecular dynamics

JOURNAL OF PEPTIDE SCIENCE, Issue 1 2005
Elisabetta Schievano
Abstract The conformational properties in DMSO of two head-to-tail cyclic analogues of kallidin ([Lys0]-bradykinin, KL) as well as those of the corresponding linear peptides were studied by NMR and molecular dynamics (MD) simulations. The modifications in the sequence were introduced at position 6, resulting in the four peptides, [Tyr6]-KL (YKL), [Trp6]-KL (WKL), cyclo-([Tyr6]-KL) (YCKL) and cyclo-([Trp6]-KL) (WCKL). The linear WKL analogue was significantly more potent than kallidin on rat duodenum preparations, whereas YKL was significantly less potent. Both cyclic peptides, YCKL and WCKL displayed similar activity, lower than that of the linear analogues and also of cyclo-KL. The two linear analogues display high conformational flexibility in DMSO. In the predominant conformer, for both peptides, all three X-Pro bonds adopt a trans configuration. Three out of four conformers present in YCKL and WCKL were completely assigned. The configurations at the X-Pro bonds are the same for the two analogues. All cyclic conformers show a cis configuration in at least one X-Pro bond and always opposite configuration for the two consecutive X-Pro bonds. The NOE-restrained MD calculations resulted in the detection of several elements of secondary structure in each of the conformers. Such elements are described and their possible relevance to biological activity is discussed. Copyright © 2004 European Peptide Society and John Wiley & Sons, Ltd. [source]

The role of specific interactions in crystalline complex formation.

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 5 2002
10-bis(4-bromophenyl)-, 10-dihydroanthracene with dimethyl sulfoxide, 10-dihydroxy-, Structural, thermochemical analysis of inclusion compounds of cis -, trans -
Abstract Referring to a crucial problem in crystal engineering and co-crystallization of host,guest complexes, whether the non-covalent supramolecular interactions existing in a pre-crystalline solution state may determine the subsequent crystal structure, the particular inclusion properties of host compounds 1, cis - and 2, trans -9,10-bis(4-bromophenyl)-9,10-dihydroxy-9,10-dihydroanthracene, with dimethyl sulfoxide (DMSO) were studied by using x-ray structure analysis and calorimetric methods. Both hosts form crystalline inclusion complexes with DMSO showing 2:3 (1·DMSO) and 1:4 (2·DMSO) host:guest composition. The crystal structure of 1·DMSO (2:3) is dominated by a strong bifurcated acceptor-type H bond interaction involving 1 and one of the DMSO molecules. Titration calorimetric investigations in solution also confirm the formation of a stable 1·DMSO (1:1) complex unit, suggesting that for crystal nuclei of 1·DMSO (2:3) the pre-formed 1:1 host,guest complex is the relevant building block while the additional molecules of DMSO fill lattice voids. In contrast, compound 2 with a trans configuration of the two hydroxy groups gives much weaker complexation with DMSO in solution, which is in agreement with single H-bond interaction, also realized in the crystal structure of the respective inclusion complex. Thermal decomposition (TG,DSC) measurements of the crystalline complexes supply supporting data for these findings. Copyright © 2002 John Wiley & Sons, Ltd. [source]

Styrene/1,3-butadiene copolymerization by C2 -symmetric group 4 metallocenes based catalysts

JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 4 2008
Mariagrazia Napoli
Abstract C2 -symmetric group 4 metallocenes based catalysts (rac -[CH2(3- tert -butyl-1-indenyl)2]ZrCl2(1), rac -[CH2(1-indenyl)2]ZrCl2(2) and rac -[CH2(3- tert -butyl-1-indenyl)2]TiCl2(3)) are able to copolymerize styrene and 1,3-butadiene, to give products with high molecular weight. In agreement with symmetry properties of metallocene precatalysts, styrene homosequences are in isotactic arrangements. Full determination of microstructure of copolymers was obtained by 13C NMR and FTIR analysis and it reveals that insertion of butadiene on styrene chain-end happens prevailingly with 1,4- trans configuration. In the butadiene homosequences, using zirconocene-based catalysts, the 1,4- trans arrangement is favored over 1,4- cis, but the latter is prevailing in the presence of titanocene (3). Diad composition analysis of the copolymers makes possible to estimate the reactivity ratios of copolymerization: zirconocenes (1) and (2) produced copolymers having r1 × r2 = 0.5 and 3.0, respectively (where 1 refers to styrene and 2 to butadiene); while titanocene (3) gave tendencially blocky styrene,butadiene copolymers (r1 × r2 = 8.5). The copolymers do not exhibit crystallinity, even when they contain a high molar fraction of styrene. Probably, comonomer homosequences are too short to crystallize (ns = 16, in the copolymer at highest styrene molar fraction). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1476,1487, 2008 [source]

Unexpected oxidation of a diphos­phine by bis­(1,3-diphenylpropane-1,3-dionato)­cobalt(II), [Co(dbm)2]

ACTA CRYSTALLOGRAPHICA SECTION C, Issue 4 2007
Phimphaka Harding
The reaction of bis­(1,3-diphenylpropane-1,3-dionato)cobalt(II), [Co(dbm)2], with bis­(diphenyl­phosphino)ethane (dppe) affords the coordination polymer catena -poly[[bis­(1,3-diphenyl­propane-1,3-dionato-,2O,O,)cobalt(II)]-,-ethyl­enebis(diphenyl­phosphine oxide)-,2O:O,], trans -[Co(C15H11O2)2(C26H24O2P2)]n, as a result of oxidation of the diphos­phine. The Co atom is octa­hedral, with a CoO6 coordination sphere, and the chelating dbm ligands adopt a trans configuration. The Co atom also lies on a centre of inversion, with a further symmetry centre bis­ecting the bridging ethyl­enebis(diphenyl­phosphine oxide) ligand. [source]

(E)-4-(4-Bromo­phenyl­diazen­yl)-2,6-dimethyl­phenyl acrylate and (E)-2,6-dimethyl-4-(4-methyl­phenyl­diazen­yl)­phenyl acrylate

ACTA CRYSTALLOGRAPHICA SECTION C, Issue 2 2007
Hasan Kocaokutgen
The crystal structures of the title compounds, C17H15BrN2O2, (I), and C18H18N2O2, (II), determined at room temperature, have a trans configuration with respect to the diazene linkage, as found for other azo (diazene) derivatives. The aromatic mean planes are nearly coplanar, with a dihedral angle between these planes of 8.31,(2)° for (I) and 3.74,(2)° for (II). In both complexes, the mean plane of the ester group is nearly perpendicular to the aromatic ring planes. In both compounds, the crystal packing involves only ,,, and ,,ring inter­actions, which combine to stabilize the extended structure. [source]

A new crystal form of Lys48-linked diubiquitin

ACTA CRYSTALLOGRAPHICA SECTION F (ELECTRONIC), Issue 9 2010
Jean-François Trempe
Lys48-linked polyubiquitin chains are recognized by the proteasome as a tag for the degradation of the attached substrates. Here, a new crystal form of Lys48-linked diubiquitin (Ub2) was obtained and the crystal structure was refined to 1.6,Å resolution. The structure reveals an ordered isopeptide bond in a trans configuration. All three molecules in the asymmetric unit were in the same closed conformation, in which the hydrophobic patches of both the distal and the proximal moieties interact with each other. Despite the different crystallization conditions and different crystal packing, the new crystal structure of Ub2 is similar to the previously published structure of diubiquitin, but differences are observed in the conformation of the flexible isopeptide linkage. [source]

Novel Phthalocyaninatobis(alkylcarboxylato)silicon(IV) Compounds: NMR Data and X-ray Structures To Study the Spacing Provided by Long Hydrocarbon Tails That Enhance Their Solubility

CHEMISTRY - A EUROPEAN JOURNAL, Issue 14 2005
Jose L. Sosa-Sánchez Dr.
Abstract The reaction between trans -PcSiCl2 (1) and the potassium salts of six fatty acids (2,a,2,f) led to the trans -PcSi[OOC(CH2)nCH3]2 compounds (3,a,3,f), which were characterised by elemental analysis, IR, UV/Vis and 1H, 13C, and 29Si NMR spectroscopy. From a detailed study of the NMR spectra, the strong anisotropic currents of the Pc macrocycle were found to have an effect on up to the sixth methylenic group. As expected, the length of the hydrocarbon tail does not affect the chemical shift of the 29Si nucleus of any of the compounds, appearing at around ,222.6. The structures of PcSi[OOC(CH2)nCH3]2, where n=7, 10, 12, 13 and 20, were determined by X-ray crystallography. All the compounds were found to be triclinic with a P space group. In all cases the observed crystallographic pseudosymmetry is Ci and the asymmetric unit consists of half a molecule. The silicon atom is at the centre of a distorted octahedron and hence its coordination number is six. The carboxylate fragments are in a trans configuration with respect to the Pc macrocycle. The supramolecular structures are discussed in detail herein. The correlation between the 1H NMR chemical shifts and the position of the corresponding carbon atoms in the hydrocarbon tail reveals that the dicarboxylate substituents exhibit a spacer-like behaviour that enhances the solubility. A detailed study of the tail variable allowed us to evaluate the loss of radial shielding along the Pc2, ligand. [source]

Indoloquinolizidine,Peptide Hybrids as Multiple Agonists for D1 and D2 Dopamine Receptors

CHEMMEDCHEM, Issue 9 2009
Marc Vendrell
Abstract Multiple-specificity ligands are considered promising pharmacological tools that may show higher efficacy in the treatment of diseases for which the modulation of a single target is therapeutically inadequate. We prepared a set of novel ligands for D1 and D2 dopamine receptors by combining two indolo[2,3- a]quinolizidine scaffolds with various tripeptide moieties. The binding and functional properties of these molecules were determined by radioligand binding studies in brain striatum membranes and by intracellular cAMP production assays in cells expressing different dopamine receptor subtypes. Some indoloquinolizidine,peptide hybrids, mainly with the trans configuration, showed dual agonist activity at both D1 and D2 dopamine receptors and may therefore be useful for testing the therapeutic potential of multivalent drugs on these targets. [source]

Identification of Chiral cis- and trans- 2-Stannyloxazolidines by Their NMR Spectra and Solid-State Structures

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 20 2004
Jean-Christophe Cintrat
Abstract The assignment of cis and trans configurations in N -protected 4-substituted 2-tributylstannyl-1,3-oxazolidines by NMR has been achieved through the use of extrapolations of Karplus,Kitching-type relationships for 3J(119Sn,C,Z,13C) to establish the shape of the oxazolidine ring. Examination of 3J(H,H) allowed the determination of torsion angles for the substituents on C4 and C5, discrimination being completed by comparison of the H2 chemical shifts, together with the 2J(Sn,C,H2) values. The validity of the method was subsequently corroborated by comparison of the results obtained for the liquid phase with those obtained from radiocrystallographic structures of triphenylstannyl analogues or DFT calculations on trimethylstannyl analogues. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source]

Characterization of reduced iso-,-acids derived from hops (Humulus lupulus) by NMR

MAGNETIC RESONANCE IN CHEMISTRY, Issue 9 2003
Lars I. Nord
Abstract Reduced forms of iso-,-acids (isohumulones), used in modern beer brewing were separated and characterized by 1H and 13C NMR spectroscopy. Components from mixtures of rho-iso-,-acids, tetrahydro-iso-,-acids, and hexahydro-iso-,-acids were isolated using high-performance liquid chromatography (HPLC) and analyzed by use of one- and two-dimensional NMR experiments. The data presented assign the identities of the main peaks in the HPLC traces for the reduced iso-,-acids. Previous tentative assignments regarding the cis and trans configurations and the structures of the acyl residues of the reduced iso-,-acids were confirmed and extensive NMR assignments were made. Furthermore, the previously unknown stereochemistry in the C-4 side-chain of the rho- and hexahydro-iso-,-acids was assigned. Copyright © 2003 John Wiley & Sons, Ltd. [source]

Modulated crystal structure of incommensurate low tridymite

ACTA CRYSTALLOGRAPHICA SECTION B, Issue 5 2009
Heribert A. Graetsch
The incommensurately modulated crystal structure of low SiO2 tridymite was refined based on single-crystal X-ray diffraction data in the superspace group Cc(,0,)0. The data set consists of 885 main reflections, 1751 first-order, 924 second-order and 119 third-order satellite reflections with I > 3,(I). The modulation is mainly made up from cooperative twistings of the rigid SiO4 tetrahedra. Two orders of displacement waves are used to describe the modulation of the Si atoms and three orders for the O atoms. The maximal amplitudes are ca 0.6,Å. O atoms bridging pairs of tetrahedra in cis and trans configurations show different positional modulation patterns. The anisotropic displacement parameters (ADPs) are also modulated. A correlation between ADP modulations and positional modulations was found. [source]