Triphenylarsine Sulfide Research Articles

Computational Study of Sulfur Atom-Transfer Reactions from Thiiranes to ER3(E = As, P; R = CH3, Ph)

Computational estimates have been made for the P=S and As=S bond strengths in triphenylphosphine sulfide and triphenylarsine sulfide, on the basis of G3 calculations for the methyl analogues and isodesmic-exchange reactions. Also, with the performance of the G3 method level for related compounds taken into consideration, the best estimates are 82 and 68 kcal/mol, respectively. While the value for triphenylarsine sulfide is within 2 kcal/mol of the single experimental estimate, that for triphenylphosphine sulfide is lower by 6 kcal/mol. (Capps, K. B.; Wixmerten, B.; Bauer, A.; Hoff, C. D. Inorg. Chem. 1998, 37, 2861-2864.) Despite virtually identical electronegativities of P and As, it is found that there is greater charge separation in the P=S bond. It is found that S atom transfer from thiiranes to arsines is exothermic.

Direct measurement of lipid-soluble arsenic species in biological samples with HPLC-ICPMS

Lipid-soluble arsenicals (arsenolipids) occur in a wide range of biological samples where they may play a key role in the biosynthesis of organoarsenic compounds from inorganic arsenic. The study of these compounds has been hindered, however, by the lack of a suitable analytical technique able to separate and measure the various lipid species. As a source of arsenolipids, we used 10 crude fish oils from various regions of the world. Total arsenic analyses on the fish oils, performed with ICPMS following acid digestion with microwave-assisted heating, gave concentrations from 4.3 to 10.5 mg As kg(-1). All of the arsenic was soluble in non-polar solvents such as hexane. Analysis of the fish oils for arsenolipids was performed by normal phase HPLC-ICPMS with various mixtures of organic solvents as mobile phases. Inherent problems of instability associated with the introduction of organic solvents to the plasma were overcome by the use of reduced column flow, a chilled spray chamber, and the addition of oxygen directly to the plasma. All ten fish oils appeared to contain the same 4-6 major arsenolipids, but in varying amounts depending on the origin of the fish. Further chromatography with both normal phase and reversed-phase conditions on some of the oils indicated the presence of many more minor arsenolipids. Quantification was achieved by external calibration against triphenylarsine oxide or triphenylarsine sulfide, and the sum of species following HPLC of the oils matched well the total arsenic results (92-107%). The method was applied to samples of food supplements (fish oil capsules) and a packaged food product (cod liver) whereby arsenolipids were measured and found to be significant arsenic constituents. This study represents the first attempt to directly measure intact arsenolipids and, with appropriate sample preparation, may be suitable for quantitative measurement of these arsenicals in a range of biological samples, including foodstuffs.

Synthesis, Structure, and Reactivity of (Triphenylarsoranylidene)methylcyclohepta‐2,4,6‐trienone Derivatives: Reactions with Heterocumulenes and an Activated Acetylene.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Synthesis, structure, and reactivity of (triphenylarsoranylidene)methylcyclohepta-2,4,6-trienone derivatives: reactions with heterocumulenes and an activated acetylene

Stable arsonium ylide derivatives 7a,b bearing cyclohepta-2,4,6-trienyl and electron-withdrawing CO2Et and CN groups, respectively, have been prepared for the first time through a reaction of 2-chlorocyclohepta-2,4,6-trienone with the corresponding arsonium methylide derivatives in the presence of ButOK. Compounds 7a,b are isolated as stable crystalline compounds, which do not undergo hydrolysis even in acidic conditions. The X-ray crystal analysis revealed that their As–O bond distances (2.31 Å for 7a, 2.39 Å for 7b) lie below the sum of the van der Waals radii (3.37 Å), and thus, there is appreciable bonding interaction between the arsenic and the oxygen elements. With a view to constructing a series of cyclohepta-annulated heterocycles and in order to gain a better understanding of a series of arsonium ylides, 7a,b were allowed to react with heterocumulenes such as carbon disulfide, phenyl isothiocyanate, diphenylcarbodiimido, and phenyl isocyanate, in a Wittig type reaction followed by electrocyclization or a formal [8 + 2]-type cycloaddition eliminating triphenylarsine sulfide or oxide to give 2H-cyclohepta[b]furan-2-thione, its imine, 2-phenylimino-2H-cyclohepta[b]pyrrole, and 2H-cyclohepta[b]furan-2-one. On the other hand, the reactions of 7a,b with dimethyl acetylenedicarboxylate (DMAD) give azulene derivatives.

Synthesis of Some Newtris[(m-Triarylarsimido)-Phenyl] Phosphine Oxides and Their Reactions

Abstract Synthesis of some new phosphorus containing organoarsimides of the type (m-Ar3As=NPh)3 P=O have been carried out in excellent yields (>90%) via the reaction of tris(m-aminophenyl)phosphine oxide with triarylarsine dichloride (Ar=C6H5-, p-CH3C6H4-, p-ClC6H4-, p-FC6H4-, m-FC6H4-, and C6F5-) in presence of triethylamine. The reaction of tris[(m-triphenylarsimido)phenyl]phosphine oxide (1) with carbon disulphide and carbonyl sulphide yielded tris(m-isothiocyanatophenyl)phosphine oxide and triphenylarsine sulphide or -oxide respectively. The products have been characterized by usual physico-chemical techniques viz; elemental analysis, IR, H and 19F NMR.

THE REACTION OF TETRACHLORO-o-BENZOQUINONE WITH THE SULFIDES OF TRIPHENYLARSINE AND TRIPHENYLSTIBINE

Abstract The reaction of tetrachloro-o-benzoquinone (1) with triphenylarsine sulfide gives a hydrogen-bonded complex of the corresponding hydroquinone and triphenylarsine oxide (5). The same quinone reacts with triphenylstibine sulfide yielding the cyclic adduct (9). In both cases, elemental sulfur is the other product. Possible reaction mechanisms are considered and the structural assignments are based on analytical, chemical and spectroscopic results.

The structure of triphenylarsine sulfide

The structure of triphenylarsine sulfide

Reactions of triphenylphosphine sulphide, triphenylphosphine selenide and triphenylarsine sulphide with palladium(II) and platinum(II) thiocyanates

Reactions of triphenylphosphine sulphide, triphenylphosphine selenide and triphenylarsine sulphide with palladium(II) and platinum(II) thiocyanates

Reactions of triarylphosphines, triphenylarsine, and triphenylstibine with thionyl chloride and sulphur dichloride

Triarylphosphines react with thionyl chloride by oxygen transfer to give the triarylphosphine oxide and sulphur dichloride. Further reaction with sulphur dichloride gives the triarylphosphine dichloride and triarylphosphine sulphide and/or sulphur, depending on the phosphine and the mole ratio. Triphenylarsine and triphenylstibine react with thionyl chloride by chlorine transfer to give the dichloride, sulphur dioxide, and sulphur, or with sulphur dichloride to give the dichloride and sulphur. Further reaction of triphenylarsine (but not triphenylstibine) with sulphur gives triphenylarsine sulphide.

Formation of Triphenylphosphine Sulfide, Triphenylarsine Sulfide, Triphenylstibine Sulfide, and Attempts to Obtain Nitrogen Complexes from 5-Alkoxy-1,2,3,4-thiatriazoles.

Formation of Triphenylphosphine Sulfide, Triphenylarsine Sulfide, Triphenylstibine Sulfide, and Attempts to Obtain Nitrogen Complexes from 5-Alkoxy-1,2,3,4-thiatriazoles.

Metal halide complexes of triphenylphosphine sulphide and some related ligands

Triphenylphosphine sulphide forms stable complexes with halides of PdII, PtII, PtIV, AuIII, AuI, and HgII. Triphenylphosphine selenide and triphenylarsine sulphide are generally similar but decompose with AuIII and PtIV, and triphenylstibine sulphide gives identifiable adducts only with copper(I) iodide and mercury(II) iodide. Ph3AsS extracts PtII from aqueous solution approximately seven times as fast as Ph3PSe, and sixteen times as fast as Ph3PS. The 1 : 1 adducts of HgCl2 with Ph3PS, Ph3PSe, and Ph3AsS are isomorphous with one another but not with dimeric (HgCl2,Ph3AsO)2. The P–S stretching frequency in Ph3PS falls by 40–50 cm.–1 on co-ordination, and the P–Se stretching frequency in Ph3PSe by about 20 cm.–1.

A New Synthesis of Aromatic Arsenic Compounds

IN the course of a systematic study of reactions between aryl diazonium chlorides and chemical elements, it has been found that aromatic arsenic compounds may be prepared by warming a diazonium chloride under acetone with arsenic powder and chalk. With benzene-diazonium chloride there is obtained a water-soluble product from which triphenylarsine sulphide has been obtained by precipitation with hydrogen sulphide.