Search results for "Thioether"
showing 10 items of 36 documents
Synthesis, reactivity and structural studies of carboranyl thioethers and disulfides.
2005
The equimolar reaction of 1-SH-2-R-1,2-closo-C2B10H10 (R = Me, H, Ph) with KOH in ethanol produces the thiolate species [1-S-2-R-1,2-closo-C2B10H10]−. These react with iodine to give the disulfide bridged dicluster (1-S-2-R-1,2-closo-C2B10H10)2 (R = H, Me, Ph) compounds as analytically pure, white and air-stable solids in high yield. Synthesis of monothioether bridged species is synthetically more difficult. In fact three procedures have been tested to obtain the thioether bridged dicluster compounds (2-R-1,2-closo-C2B10H10)2S (R = Me, H, Ph) but only (2-Me-1,2-closo-C2B10H10)2S was successfully synthesized and characterized. Attempts to produce mixed compounds (1-R-1,2-closo-C2B10H10)S(1-R…
Field desorption mass spectrometric characterization of thiol conjugates related to the oxidative metabolism of the anticancer drug 4′-(9-acridinylam…
1983
Conjugation products with glutathione (GSH) and other endogenous thiol derivatives related to the oxidative metabolism of the anticancer drug, 4′-(9-acridinlyamino) methanesulfon-m-anisidide (m-AMSA) were synthesized and characterized by field desorption mass spectrometry. The primary microsomal oxidation product of m-AMSA, m-AQDI, was prepared by MnO2 oxidation of the parent drug and reacted with equimolar GSH, cysteine, N-acetylcysteine and N-acetylcysteine methyl ester to form m-AMSA-(5′)-thiol conjugates linkedat the aniline ring, as major products. Field desorption mass spectra of the conjugates provided abundant [MH]plus; ions, and characteristic fragment ions by cleavage at the thioe…
Identification of conjugation and cleavage products in the thiolytic metabolism of the anticancer drug 4'-(9-acridinylamino)methanesulfon-m-anisidide.
1981
Conjugation and cleavage products in the thiolytic metabolism of the anticancer drug 4′ -(9-acridinyl amino)methanesulfon-m-anisidide were identified primarily by high-pressure liquid chromatography in combination with field desorption mass spectrometry. The spontaneous metabolic pathway of the drug, as related to its susceptibility to nucleophilic attack by endogenous thiols at the 9-carbon atom of the acridine moiety, has been studied. Among the metabolite fraction of 4′-(9-acridinylamino)methanesulfon-m-anisidide excreted in rat bile after administration of a therapeutic dose, a conjugate was identified as the 9-acridinyl thioether of glutathione. This conjugation product and the corresp…
Selective and Efficient Removal of Mercury from Aqueous Media with the Highly Flexible Arms of a BioMOF
2016
A robust and water-stable metal-organic framework (MOF), featuring hexagonal channels decorated with methionine residues (1), selectively captures toxic species such as CH3 Hg(+) and Hg(2+) from water. 1 exhibits the largest Hg(2+) uptake capacity ever reported for a MOF, decreasing the [Hg(2+) ] and [CH3 Hg(+) ] concentrations in potable water from highly hazardous 10 ppm to the much safer values of 6 and 27 ppb, respectively. Just like with biological systems, the high-performance metal capture also involves a molecular recognition process. Both CH3 Hg(+) and Hg(2+) are efficiently immobilized by specific conformations adopted by the flexible thioether "claws" decorating the pores of 1. T…
Coordination properties of some nickel(II) monophosphono dipeptides species in aqueous solution: The role of phosphonic oxygen in complex stabilizati…
2008
Abstract Equilibrium studies on the nickel(II) complexes of oxygen and nitrogen donor ligand (monophosphono dipeptides: 1- (N- l -leucylamino)methylphosphonic acid – Leu-Gly(P), and a thioether sulfur donor ligands (monophosphono dipeptides: 1-N-(glycyloamino)-2-(S-benzylthio)ethanephosphonic acid – Gly-(Bz)Cys(P), d (−) and Gly-(Bz)Cys(P), d (+) were performed by potentiometric titration and NIR–Vis spectroscopy. Additionally, the ligand-field parameters (CFM/AOM) were estimated and discussed in the tetragonal distortion framework. The lowest tetragonal distortion was observed in the case of the [NiHL] species, whereas the strongest in the case of [NiL2] species. In the latter species the …
1,3-Dipolar cycloaddition of diaryldiazomethanes across N-ethoxy-carbonyl-N-(2,2,2-trichloroethylidene)amine and reactivity of the resulting 2-azabut…
2016
Abstract 1,3-dipolar cycloaddition of diaryldiazomethanes Ar2C N2 across Cl3C–CH N–CO2Et 1 yields Δ3-1,2,4-triazolines 2. Thermolysis of 2 leads, via transient azomethine ylides 3, to diaryldichloroazabutadienes [Ar(Ar')C N–CH CCl2] 4. Treatment of 4a (Ar = Ar' = C6H5) and 4c (Ar = Ar' = p-ClC6H4) with NaSR in DMF yields 2-azabutadienes [Ar2C N–C(H) C(SR)2] 5. In contrast, nucleophilic attack of NaStBu on 4 affords azadienic dithioethers [Ar2C N–C(StBu) C(H)(StBu)] (7a Ar = C6H5; 7b Ar' = p-ClC6H4). The reaction of 4a with NaSEt conducted in neat EtSH produces [Ph2C N–C(H)(SEt)–CCl2H] 8, which after dehydrochloration by NaOMe and subsequent addition of NaSEt is converted to [Ph2C N–C(SEt) C…
Versatility and dynamics of the copper(I) coordination sphere in sterically hindering tris(pyrazolyl)methane-incorporating macrobicycles
2009
Two arene-capped macrobicycles (1 and 2) incorporating the tris(pyrazolyl)methane (Tpm) chelate have been prepared from a benzylthiol-functionalized Tpm precursor (3). Reaction of either macrobicycle with Cu(CH3CN)4+ leads to tetrahedral or trigonal-planar, fluxional complexes incorporating the Cu(CH3CN)+ subunit ([Cu(1)(CH3CN)]+ and [Cu(2)(CH3CN)]+). The acetonitrile ancillary ligand does not fit inside the macrobicycle cavity and can be removed by heating under vacuum, which produces the [Cu(1)]+ and [Cu(2)]+ species probably involving intramolecular thioether coordination. The [Cu(1)(CH3CN)]+ complex was shown to convert slowly in wet acetone into a helical coordination polymer, which is…
Complexation behaviour of hexadentate ligands possessing N2O4and N2O2S2cores: differential reactivity towards Co(ii), Ni(ii) and Zn(ii) salts and str…
2004
Reactions of divalent metal salts of Co, Ni and Zn with 1,2-di(salicylaldimino-o-phenylthio) ethane (H2L1) and 1,2-di(naphthaldimino-o-phenylthio) ethane (H2L2), having N2O2S2 cores, and 1,2-di(O-salicylaldimino-o-hydroxyphenyl) ethane (H2L3), having a N2O4 core, have been explored. Out of the three ligands and the nine products obtained from the corresponding reactions, two ligands and seven products were crystallographically characterized. However, all the ligands and the products were characterized by analytical and spectral methods. Reaction of H2L1 and H2L2 with Co(II) salts results in oxidative cleavage of the C-S bond to produce a Co(III) product bound to two dissimilar tridentate li…
Structural, vibrational, thermal and magnetic investigation of novel Co(II), Cu(II), Zn(II) and Hg(II) crystalline metal complexes with 2-amino-5-ben…
2005
Abstract The 2-amino-5-benzylmercapto-1,3,4-thiadiazole (C9H9N3S2) is a low weight model of a protonated copolymer resin used as a metal uptake agent. New monomeric crystalline metal complexes of C9H9N3S2 with Co(II), Cu(II), Zn(II) and Hg(II) were synthesized and investigated in order to facilitate the interpretation of the metal/resin binding mode. These materials have been studied by single crystal X-ray Diffraction and FTIR Spectroscopy at room temperature. Crystal data for these triclinic phases are reported. All frameworks consist of discrete monomeric units that provide crystalline stability through a network of hydrogen bond interactions. The Co(II), Zn(II) and Hg(II) ions are surro…
Synthesis, properties and crystal structure of bis(metiamide)bis(isothiocyanato)nickel(II)
1991
Abstract The crystal structure of Ni(metiamide)2(NCS)2 was determined by X-ray diffraction methods. Unlike cimetidine, which is a tridentate ligand, metiamide (C9H16N4S2): N-Methyl-N-[2-{(5-methylimidazol-4-yl)methylthio}ethyl]thiourea (which also possesses three potential donor sites) is bidentate, coordinated to the nickel atom through N(imidazole) and S(thioether) atoms. The S(thiourea) atom does not take part in the coordination; instead, the isothiocyanate ion is coordinated through nitrogen to the metal atom. The nickel atom lies on a centre of symmetry in an elongated octahedral environment: the nitrogen atoms occupy equatorial positions (NiN = 2.04 and 2.06 A) and S(thioether) atom…