Dithiophosphoric Acid Research Articles

Synthesis, structure and characterization of new stibocanes substituted with dithiophosphate ligands

Four new stibocanes substituted with cyclic dithiophosphate ligands O(CH2CH2S)2SbS2P(OCH2)2CEt2 (1), O(CH2CH2S)2SbS2P(OCH2)2C(Me)Pr (2), S(CH2CH2S)2SbS2P(OCH2)2CEt2 (3) and S(CH2CH2S)2SbS2P(OCH2)2C(Me)Pr (4) were prepared from the corresponding chloro oxa- and thia-stibocanes and the sodium salt of the dithiophosphoric acids 5,5-diethyl-(2-mercapto-2-thiono-1,3,2-dioxaphosphinane) and 5-methyl-5-propyl-(2-mercapto-2-thiono-1,3,2-dioxaphosphinane) in ethanol. The compounds obtained were characterized by IR, EI-MS and multinuclear NMR (1H, 13C, 31P) spectroscopies. The single-crystal structures of 1 and 2 were determined which show the presence of three types of secondary bonding: i.e. strong Sb---O transannular interactions of 2.607(4) and 2.600(4)Å, respectively, anisobidentate coordination of the ligand (exocyclic chelation) average Sb---S distance 3.355Å and intermolecular interactions that lead to supramolecular associations. The coordination geometry around antimony atom in both 1 and 2 can be described as Ψ tricapped trigonal bipyramidal AB4CD2E. The eight membered ring presents a boat-chair conformation in both compounds and the 1,3,2-dioxaphosphinane ring has the chair conformation, with the stibocane in the axial position.

Biodegradation Mechanism of Aniline Aerofloat by <i>Bacillus vallismortis</i> Isolated from SBR System

Aniline aerofloat [dianilino dithiophosphoric acid (C6H5NH)2PSSH], is an organic flotation reagent used frequently in lead sulfide mineral (PbS) flotation. It’s a refractory organics in floatation wastewater for it’s hard to be degraded and remains for long. Chemical and physical methods are widely used for treating aniline aerofloat, but that will bring high cost and secondary pollution. In this paper, an aniline aerofloat–degrading bacterium which used aniline aerofloat as sole carbon and energy source was isolated from SBR (sequencing batch reactor) system and the biodegradation pathway of aniline aerofloat was inferred based on the biodegradation mechanism of aniline with physicochemical phenomena of medium.

Modeling Purification of Phosphoric Acid Contaminated with Cadmium by Liquid-liquid Extraction

Phosphoric acid production is considered as second worldwide after that of sulphuric acid. It is an important and necessary intermediate chemical compound in sensitive industrial fields such as the fertilizers, detergents, food, pharmaceutical industries. Its main production is through the wet process which is responsible for the presence of various impurities like metallic cations such as Pb2 +, Cd2 +, Mg2 +, etc, initially contained in the phosphate rocks. Indeed many techniques for the purification of phosphoric acid have been developed. In this work the modeling of the purification of phosphoric acid by liquid-liquid extraction was considered. The model was tested on Cd2 + as contaminant and di (2ethylhexyl) dithiophosphoric acid diluted in dodecane as complexing agent. The results obtained from a parametric study investigating the effect of the initial concentrations of phosphoric acid and that of the complexing agent, are reported.

Di-(2-ethylhexyl) dithiophosphoric acid surface protected gold nanoparticles: micellar synthesis, stabilization, isolation, and properties

Gold nanoparticles (AuNPs) were synthesized in the organic solution by means of the reduction of HAuCl4 by hydrazine in reverse micelles of oxyethylated surfactant Triton N-42, with decane as the dispersion medium. To isolate the powder of particles, the micelles were destroyed with chloroform in the presence of di-(2-ethylhexyl) dithiophosphoric acid as a surface protecting agent. According to the results of several experiments, the yield is within the limits of 90–98%, calculated for gold. The obtained preparations are dark blue hydrophobic powders containing aggregated but not agglomerated gold nanoparticles, as well as microcrystals (∼0.08–0.2 μm) of NaCl. The powders get re-dispersed in weakly polar organic solvents with the formation of colloidal solutions. The shape of the nanoparticles is spherical. Their nuclei are gold single crystals with a narrow size distribution; their diameter (d Au) is about two times as large as the diameter of the aqueous nucleus (d c) of initial micelles: d Au = 7.7 ± 1.4 nm (d c = 3.6 nm) and 8.8 ± 1.5 nm (4.6 nm). The preparations were studied by means of dynamic light scattering, atomic force microscopy, transmission electron microscopy, UV–vis spectroscopy, IR spectroscopy, X-ray powder diffraction, and thermogravimetric and elemental analyses. In the case of the particles with d Au = 8.8 nm, the product is a mixture of AuNPs and the salt with the molar ratio Au/NaCl ≈ 1:4.54, while the gross composition of AuNPs per one gold atom is estimated as Au(C16H34O2PS2Na∙2N2H4)0.16 with the number of gold atoms in one particle ∼21,000.

Asymmetric Brønsted Acid Catalysis Enabling Hydroaminations of Dienes and Allenes

Acid treatment: Toste et al. recently unveiled a new pathway for asymmetric Brønsted acid catalysis of reactions involving dienes or allenes, and achieved highly efficient intramolecular hydroamination and hydroarylation reactions (see scheme). The PS bond proved necessary for reactivity, and dithiophosphoric acids emerged as efficient catalysts. The association/displacement sequence led to chiral pyrrolidines and isoxazolidines in excellent yields and ee values.

Synthesis and antimicrobial studies of bis(O,O′‐dialkyl and alkylene dithiophosphoric acid) adducts of diphenyl diselenide

AbstractDialkyl and alkylene dithiophoshoric acids react with diphenyl diselenide in a 1:2 molar ratio in refluxing benzene to yield Ph2Se2·2HS2P(OR)2 (R = Et, Pr‐n, Pr‐i, Bu‐i and Ph) and , where G = ‐CH2CMe2CH2‐, ‐CH2CEt2CH2‐ and ‐CMe2CMe2‐. The complexes are yellow solids (in the cyclic chain) and yellow sticky solids (in the open chain), are soluble in common organic solvents and are monomeric in nature. They were characterized on the basis of elemental analyses, molecular weight determinations, IR and NMR (1H, 13C and 31P). The spectral data revealed addition of dithiophosphate moieties to the diselenide. Studies were conducted to assess the growth‐inhibiting potential of some of the synthesized complexes against various bacterial strains. Copyright © 2011 John Wiley & Sons, Ltd.

Dithiophosphoric Acid Catalyzed Hydro-amination of Dienes

Toste and co-workers report the highly enantioselective hydroamination of 1,2- and 1,3-dienes catalyzed by dithiophosphoric acids 1. The reaction is proposed to be initiated by protonation of the diene and subsequent addition of the catalyst in syn fashion. This adduct is cleaved again through an intramolecular SN2′ reaction, in which the internal nitrogen nucleophile replaces the dithiophosphate. This activation mode, involving covalent binding of the catalyst to the substrate, is supported by mechanistic studies. Furthermore, the authors extended successfully their catalytic system to hydroarylation reactions.

Phosphorylation and Thiophosphorylation of Oligomeric Polyesterpolyols of Boltorn H20, H30, and H40

Dialkyl phosphate derivatives of Boltorn H20, H30, and H40 were prepared by the use of ultrasound irradiation in the substitution reactions of the polyesterpolyols with dialkyl chlorophosphates. Unsaturated polyacrylates were obtained by the reactions of Boltorn H20, H30, and H40 with acryloyl and methacryloyl chlorides. The reactions of these polyacrylate esters with O,O-dialkyl dithiophosphoric acids in the presence of Lewis acid catalysts have brought about the formation of the corresponding dithiophosphates.

Terpene Analogues of Dithiophospate Pesticides

New optically active O,O-diterpenyl dithiophosphoric and O-terpenyl aryldithiophosphonic acids were prepared when chiral terpenols such as (1R)-endo-(+)-fenchyl alcohol, (1S)-endo-(−)-borneol, (1R)-(−)-nopol, and (1R,2S,3S,5R)-(+)-isopinocampheol were involved in reactions with tetraphosphorus decasulfide and 2,4-diaryl 1,3,2,4-dithiadiphosphetane-2,4-disulfides.

Synthesis and Characterization of Chlorobis(cyclopentadienyl) Titanium(IV) and Zirconium(IV) O,O’-Dialkyl and Alkylene Dithiophosphates

Reactions of O,O′-dialkyl and alkylene dithiophosphoric acids with bis (cyclopentadienyl) titanium(IV) and zirconium (IV) dichloride in a 1:1 molar ratio in refluxing benzene proceeds with elimination of HCl and formation of the substituted derivatives, Cp2MCl[S2P(OR)2] (where R = Et, Pr-n, Pr-i, Bu-i and Ph), Cp2MCl[S2POGO] (where G = ‒CH2CMe2CH2‒, ‒CH2CEt2CH2‒ and ‒CMe2CMe2‒), (M = Ti and Zr). The complexes are dark red and yellow solids, soluble in common organic solvents and monomeric in nature. These have been characterized on the basis of elemental analyses, molecular weight determinations, IR, and NMR (1H, 13C, and 31P). GRAPHICAL ABSTRACT

Asymmetric additions to dienes catalysed by a dithiophosphoric acid

Chiral Brønsted acids have become an invaluable tool for achieving a variety of asymmetric chemical transformations under catalytic conditions while avoiding the use of toxic and expensive metals1–8. While the catalysts developed so far are remarkably effective at activating polarized functional groups, chemists have not yet been able to use organic Brønsted acids to catalyze highly enantioselective transformations of unactivated carbon-carbon multiple bonds. This deficiency persists despite the fact that racemic acid-catalyzed “Markovnikov” additions to olefins are a well-established part of the chemist’s toolbox. Here we show that chiral dithiophosphoric acids catalyze the intramolecular hydroamination and hydroarylation of dienes and allenes to generate heterocyclic products in exceptional yield and enantiomeric excess. To help rationalize the unique success of this catalytic system, we present a mechanistic hypothesis that involves the addition of the acid catalyst to the diene followed by SN2′ displacement of the resulting dithiophosphate intermediate. Mass spectrometry and deuterium labelling studies are presented in support of the proposed mechanism. The catalysts and concepts revealed in this study should prove applicable to other asymmetric functionalizations of unsaturated systems.

Metals are not the only catalysts

A long-standing problem in chemistry has been to find catalysts that allow molecules to distinguish between the two faces of reaction intermediates called carbocations. A way around the problem has been found. See Letter p.245 Previous work on nucleophilic additions catalysed by chiral Bronsted acids has been restricted to polarized heteroatom-containing functionalities such as imines, aziridines and carbonyls. This limitation has yet to be overcome despite the fact that acid-catalysed 'Markovnikov' additions to olefins have been known for more than a century. Here the authors show that chiral dithiophosphoric acids can catalyse the intramolecular hydroamination and hydroarylation of dienes and allenes to generate heterocyclic products in exceptional yield and enantiomeric excess. They present a mechanistic hypothesis that involves the addition of the acid catalyst to the diene, followed by SN2′ displacement of the resulting dithiophosphate intermediate. The proposed mechanism is supported by mass spectroscopy and deuterium labelling studies.

ChemInform Abstract: Metal and Organometal Complexes of Oxy- and Thiophosphorus Acids. Part 8. Reactions of O,O-Diisopropyl and O,O-Alkylene Dithiophosphoric Acids with Titanium and Tin Tetrachloride.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Reactions of Monobutyltin Oxide with Dialkyl and Alkylene Dithiophosphoric Acids: Synthesis and Spectral Studies.

Abstract Monobutyltin(IV) dialkyl and alkylene dithiophosphates, [OSnBuS2P(OR)2]2, HOSnBu[S2P(OR)2]2, (R = Prn, Pri, Bui and Ph), [OSnBuS2POCH2CMe2CH2O]n HOSnBu[S2POCH2CMe2CH2O]2, BuSn[S2P(OR)2]3 (R = Ph and Bui) and BuSn[S2POCH2CH2CH(Me)O]3 have been synthesized by the reactions of monobutyltin oxide with dialkyl and alkylene dithiophosphoric acids, in 1:1, 1:2 and 1:3 molar ratios in refluxing benzene. These products have been characterized by molecular weight determinations, NMR (1H, 13C, 31P and 119Sn), IR and elemental analyses. Plausible structures have been suggested.

Monoterpenoids dithiophosphates. Synthesis and biological activity

O,O-Dialkyldithiophosphoric acids adds at the double bond of the racemic camphene and (+)- limonene in the presence of Lewis acids in accordance with the Markownikoff rule with the formation of Sterpenyl esters of dithiophosphoric acids. The reaction with camphene is accompanied by the rearrangement of camphane structure to that of bornane. Addition of dithiophosphoric acid to (+)-limonene proceeds with the participation of the exocyclic double bond. Toxic and genotoxic properties of the monoterpenoid dithiophosphates were studied.

Surfactant dithiophosphates lubricating oil additives

This paper presents a research on the tribological properties and the action mechanisms of surfactant lubricating oil additives, polyalkoxy glycol ammonium salts and O,O,S-triesters of polyalkoxy glycol dithiophosphoric acid. To understand the physicochemical properties of surfactants, polyalkoxy glycol dithiophosphoric acid behaviour both in solution and at metal surfaces are identified and discussed. The STM adsorption on steel surface, four-ball and ball disc tests of friction of water, synthetic and mineral oil solutions studies of these additives are presented. Friction and wear properties are dependent on tribological parameters, chemical structure of the additives and their surface active behaviour in tribological systems. The relationships are presented on the example of additives with different molecular structures and masses.

Study of a novel anti‐wear additive used in ashless anti‐wear hydraulic fluid

PurposeThe purpose of this paper is to develop novel ashless additives and to meet the need for formulating ashless anti‐wear (AW) hydraulic fluid or other industrial lubricating oils. This paper also aims to investigate the tribological behaviours and mechanism of an acrylate of dialkyl dithiophosphoric acid (ADDP), as an additive in some group I/II base oils compared with some traditional s‐p containing AW additives.Design/methodology/approachADDP is synthesized in the laboratory. The chemical composition and structure of the lubricating additive are analyzed by means of infrared spectroscopy. Its extreme pressure (EP), AW and friction reduction properties as additive in base oils, compared with some traditional s‐p containing AW additives, are investigated using a four‐ball machine according to relative testing standards. The tribological mechanism is discussed according to the scanning electron microscope (SEM) analytical data.FindingsThe results indicate that the four‐ball PB value of the prepared ADDP in HVIWH650 is better than that of the IRGLUBE 353; the thermal stability of ADDP is equivalent to the zinc dialkyl dithiophosphate (ZDDP) and the SEM data show that the prepared ADDP additive could form a layer of uniform film on the worn surface serving as lubricant and protective film. This may be the chief reason why the prepared ADDP possesses better AW property than ZDDP.Research limitations/implicationsHowever, more experimental studies such as the synergic effect with other additives should be performed, from which it could be learned whether the novel AW additive would be applicable in industrial oils.Practical implicationsThe results may be useful for the researchers to formulate some ashless industrial oils.Originality/valueA novel additive was synthesized in the laboratory; it would find a promising industrial application as an ashless AW additive.

Extraction of Am(III) and lanthanides(III) with organo dithiophosphinic acids

AbstractExtraction of Am(III) and Ln(III) from NaClO4medium has been investigated with di(2-ethylhexyl) dithiophosphoric acid, di(2-ethylhexyl) monothiophosphoric acid, di(2-ethylhexyl) monothiophosphinic acid, octylphenyl dithiophosphinic acid and 11 kinds of dialkyl dithiophosphinic acids (alkyl = hexyl, heptyl, octyl, nonyl, 2-ethylhexyl, 1-methylheptyl, phenyl, chlorophenyl, methylphenyl, 2,5-dimethylphenyl, and 3,5-dichloro-4-methylphenyl) in xylene. The effect of chemical structures of those extractants on separation capability has been studied. The relationship between the slope value of the lgD−pH and extraction conditions can be described as: lgS=alg(CHA/CMS/4)+b. In the presence of macro amounts of Eu(ClO4)3, the formula, lg SFAm/Eu=B−2lg(CHL−DEu/(DEu+1)CEu), can well describe the relationship between separation factor and the extraction condition. A high separation factor (SFAm/Eu=2500) is obtained by solvent extraction from 1 mol/L NaNO3solution with 0.5 mol/L di(2-ethylhexyl) dithiophosphinic acid in toluene.

P-NITROPHENYL AND p-NITROBENZOYL DERIVATIVES OF 0,0' - ALKYLENE DITHIOPHOSPHATE

ABSTRACT p-Nitrophenyl and p-nitrobenzoyl derivatives of O,O’–alkylene dithiophosphate, OGOP(S)SC 6 H 4 NO 2 and OGOP(S)SCOC 6 H 4 NO 2 (Where G = -CMe 2 CMe 2 -, -CH 2 CMe 2 CH 2 -, -CMe 2 CH 2 CHMe-, -CH 2 CH 2 CHMe-) have been synthesized by the reactions of p-bromo nitrobenzene / p-nitrobenzoyl chloride with ammonium salt of alkylene dithiophosphoric acids. These derivatives are yellow and red coloured solids, respectively and are soluble in common organic solvents. These are characterized by elemental analysis, IR and NMR ( 1 H and 31 P) spectral studies. In contrast to the bi-dentate chelating behaviour of the ligand in the metal and organometal derivatives of alkylene dithiophosphates, the behaviour of dithiophosphato moiety in these derivatives is found to be mono-dentate in nature.Keywords :- p-Bromo nitrobenzene, p-nitrobenzoyl chloride, ammonium salt of alkylene dithiophosphoric acids. INTRODUCTION Alkylene dithiophosphoric acids are known as cyclic analogous of dialkyl dithiophosphoric acid (open chain)

Extraction of Cadmium from Phosphoric Acid Media by Di(2‐ethylhexyl) Dithiophosphoric Acid

Di(2‐ethylhexyl) dithiophosphoric acid (D2EHDTPA) was examined for cadmium removal from phosphoric acid solutions. High extraction performance was achieved. By means of slope and saturation methods, the stoichiometry of the complex was postulated. Both methods indicated the presence of anhydrous CdR2 as being the metallic extracted complex, HR denoting the D2EHDTPA molecule. The stripping of cadmium from the organic phase was ensured by aqueous solutions of HCl; quantitative stripping was achieved with either HCl (4 M) or an HCl‐NaCl mixture.