Dithiophosphonic Acids Research Articles

Lawesson’s reagent in the synthesis of a malic ester of dithiophosphonate salts with antifungal activity

Lawesson’s reagent reacted with racemic diethyl malate to yield O-(1,2-bis(ethylcarboxylate)ethyl-1 4-methoxyphenyl dithiophosphonic acid. The acid formed pyridinium dithiophosphonate salts with 3-(hydroxymethyl)pyridine, pyridoxine, and (S)-(–)-nicotine. The salts revealed antifungal activity against Candida albicans.

A ternary composite nanofibrous photocatalyst: FcLR-gC3N4/polyisothianaphthene/polyacrylonitrile for degradation of organic dyes

BackgroundWater pollution by organic dyes is one of the important environmental issues. When substances such as organic dyes are discharged into water, they can severely pollute the water and harm the life of living organisms. MethodsA new ternary composite nanofibrous photocatalyst, FcLR-gC3N4/PITN/PAN, was produced through 1) synthesis of a graphitic carbon nitride (g-C3N4)-based ferrocenyl dithiophosphonic acid, FcLR-gC3N4, by the attachment of Ferrocenyl Lawesson's Reagent (FcLR) to g-C3N4 nanosheets, 2) incorporation of the FcLR-gC3N4 into the polymeric matrix of as-prepared polyisothianaphthene (PITN) blending with polyacrylonitrile (PAN), and 3) fabrication of electrospun nanofibers (NFs) through electrospinning. Significant findingsThe degradation of methyl orange (MO) and methylene blue (MB) was more efficient on FcLR-gC3N4 compared to g-C3N4 alone, and on FcLR-gC3N4/PITN/PAN compared to FcLR-gC3N4, confirming the effective role of both FcLR and PITN/PAN matrix in the degradation of the dyes. The ternary composite nanofiber degraded 92% of MB and 29% of MO. The MB mineralization percentages of 65% (TOC), 60% (COD), and 55% (BOD) were achieved after 2 h and 30 min. Radical trapping experiments consistent with the Tauc plots and Mott-Schottky plots distinguished O2•- as the primary species in the degradation mechanism of MB. The MB degradation pathway was determined through LC-MS-MS. The electrochemical impedance spectrum (EIS) and photocurrent measurements confirmed the higher photocatalytic activity of FcLR-gC3N4 compared to g-C3N4 alone by studying the charge carrier's separation and recombination. A high recyclability was found for FcLR-gC3N4. The recycling stability of FcLR-gC3N4 increased after its embedding into the nanofibrous matrix of PITN/PAN.

Chiral Salts of Dithiophosphonic Acids on the Basis of Monoterpenyl Alcohols and Cinchona Alkaloids

Chiral Salts of Dithiophosphonic Acids on the Basis of Monoterpenyl Alcohols and Cinchona Alkaloids

Diphasic Sheeting Device with Cyanex-301 for Dislodging Feature of Divalent Cadmium from Industrial Effluent.

A novel diphasic sheeting device (DSD) including complemental feeding stage and complemental disintegrating stage for dislodging features of Cd(II), was investigated. The complemental feeding stage included feeding liquor and Bis(2,4,4 trimethylamyl) dithiophosphonic acid (Cyanex-301) as the carrier in petroleum, and the complemental disintegrating stage included Cyanex-301 as the carrier in petroleum and hydrochloric acid as the disintegrating reagent. The impacts of volumetric ratio of sheeting liquor and feeding liquor(S/F), initial molarity of Cd(II) and ion intensity of the feeding liquor, pH, volumetric ratio of sheeting liquor and disintegrating reagent (S/D), molarity of hydrochloric acid liquor, Cyanex-301 molarity in the complemental disintegrating stage on dislodging of Cd(II), the virtues of DSD compared to the traditional sheeting device, the constancy of system, the reuse of sheeting liquor, and the retention of the sheeting stage were also investigated. Experimental results illustrated that the optimum dislodging conditions of Cd(II) were achieved as hydrochloric acid molarity was 4.00 mol/L, Cyanex-301 molarity was 0.150 mol/L, and S/D was 1:1 in the complemental disintegrating stage, S/F was 1:10, and pH was 5.00 in the complemental feeding stage. The ion intensity of the complemental feeding stage had no distinct impact on the dislodging feature of Cd(II). When initial Cd(II) molarity was 3.20 × 10−4 mol/L, the Cd(II) dislodging percentage was up to 92.9% in 210 min. The dynamic formula was inferred on the basis of the theorem of mass transferring and the interfacial chemistry.

2,4-Bis(2,4-dimethoxyphenyl)-1,3-dithia-2,4-diphosphetane 2,4-disulfide and its derivatives: Syntheses, structural characterizations, anticancer activities, and theoretical studies on some dithiophosphonato Ni(II) complex

New 2,4-bis(2,4-dimethoxyphenyl)-1,3-dithia-2,4-diphosphetane 2,4-disulfide, (SAV-A2), was synthesized from the reaction P4S10 and 1,3-dimethoxybenzene. SAV-A2 was reacted with alcohols to form dithiophosphonic acid monoesters (HLn, HS2P((2,4-CH3O)2C6H3)(ORn); n=1–3, R1=2‑butyl‑; R2=n-pentyl-; R3=4‑tert‑but-benzyl-). The acids were converted to the ammonium salts ([NH4Ln]) to serve as the source of the ligands (Ln), to obtain Ni(II) complexes, ([Ni(Ln)2]). [Ni(L2)2] crystal structure was elucidated by single-crystal X-ray diffraction analysis. In addition, Density Functional Theory (DFT) calculations of [Ni(L2)2] was performed. The molecular docking studies of the complex with liver cancer protein, PDB ID: 3WZE and colon cancer antigen proteins, ID 2HQ6 were done compare with experimental and theoretical results. All compounds were tested on liver- and colon cancer cell lines. Among the complexes tested, [Ni(L3)2] showed an activity closer to that of cisplatin against the colon cancer cell line. The other compounds were found to be have less active.

The Syntheses and Characterization of New Dithiophosphonates derived from Novel 2,4-Bis(methoxytolyl)-1,3-dithia-2,4-diphosphetane 2,4- disulfides and Their Ni(II) Complexes

Two new perthiophosphonic acid anhydrides, 2,4-bis(Rx,y)-1,3-dithia-2,4-diphosphetane 2,4-disulfide (Rx=3-methoxytolyle, SAV-B1 and Ry=2-methoxytolyle, SAV-B2) were synthesized. From the reaction of these dimers, (Rx,y‐P(S)S)2, with alcohols and then dry ammonia gas, ammonium salts of the dithiophosphonic acids ((Rx,y)(RnO)PS2H), Rn, R1= ethyl-, R2= 2-propyl-), namely, four new compounds of the type [NH4][S2P(Rx,y)(ORn)] were obtained. The ammonium salts were further reacted with NiCl2.6H2O to prepare four new dithiophosphonato nickel(II) complexes, [Ni(S2P(Rx,y)(ORn))]. The ligands and the complexes were characterized by mass-(ESI), 1H-, 13C-, 31P-NMR, IR-spectroscopy, HSQC techniques and elemental analyses. Complementary structural information was provided by the HSQC spectra of the [NH4][S2P(Rx,y)(OR2)]. The structure of the perthiophosphonic acid anhydrides were deduced from the structures of dithiophosphonates thereof.

New Homodinuclear Alkyl and Aryl Dithiophosphonato Cd(II) and Hg(II) complexes: Syntheses and Characterizations

New Cd(II) and Hg(II) complexes of previously known five dithiophosphonic acids ((p-MeO-C6H4)PS(SH)(OR), HLn, (n= 1-5); R= 3-pentyl-, HL1; R=1-phenyl-1-propyl-, HL2; R= 4-tert-butyl benzyl-, HL3; R= diphenylmethyl-, HL4; R= 4-tert- butyl cyclohexyl-, HL5) were prepared and characterized. To do this, the dithiophosphonic acids involved were treated with stoichiometric amount of the corresponding metal salts in methyl alcohol. The complexes came of as powdery crystals and were recrystallized from chloroform. The pure complexes were characterized by using elemental analyses as well as mas-(ESI), FTIR-, Raman-, NMR- (1H, 13C, 31P) spectroscopies.

Investigation of spectroscopic studies and DFT calculations on glucofuranose derivatives of dithiophosphonates

2,4-Bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide (Lawesson’s reagent: LR) was reacted with 1,2:5,6-di-O-cyclohexylidene-α-D-glucofuranose and 1,2:5,6-di-O-isopropylidene-α-D-glucofuranose in toluene and gave rise to crude dithiophosphonic acids. The crude dithiophosphonic acids were treated with excess triethylamine and the triethylammonium salts of dithiophosphonic acids (1) and (2) were isolated by crystallization method. Compounds 1 and 2 were characterized by elemental analysis, IR, and NMR (1H-, 13C- and 31P-) spectroscopies and mass spectrometry. In addition, NMR spectra, the electronic properties (the electronic chemical potential, electronegativity, chemical hardness and the global electrophilicity index) and NBO analysis of compound 2 have been calculated by using the Gaussian 16 W program. The electronic properties were calculated using Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) energies by density functional method (DFT/B3LYP) at 6-31G(d,p) level. The HOMO and LUMO energies are −5.9 and −0.72 eV, respectively. The HOMO–LUMO energy difference is 5.18 eV and this value shows that compound 2 has a high stability and low reactivity.

Cinchona Alkaloids in the Synthesis of Chiral Salts of Phosphorus Dithioacids on the Basis of 1,2:3,4‐Di‐O‐isopropylidene‐α‐D‐galactopyranose

AbstractOptically active dithiophosphoric and dithiophosphonic acids were obtained by the reactions of 1,2:3,4‐di‐O‐isopropylidene‐α‐D‐galactopyranose with tetraphosphorus decasulfide or Lawesson's reagent respectively. The reactions of dithiophosphoric and dithiophosphonic acids with 8 S,9R‐quinine, 8R,9 S‐quinidine, 8 S,9R‐cinchonidine, 8R,9 S‐cinchonine, and 8R,9 S‐hydroquinidine result in chiral salts of dithiophosphoric and dithiophosphonic acids. Antimicrobial activity of products obtained was tested.

Chiral S‐stannyl dithiophosphates and dithiophosphonates on the basis of monoterpenols

Chiral S‐tributylstannyl dithiophosphates and dithiophosphonates were obtained by the reactions of optically active dithiophosphoric and dithiophosphonic acids containing (S)‐(–)‐menthyl and (R)‐(+)‐menthyl substituents with gaseous ammonia and tributyl chlorostannane. The reactions of chiral ammonium dithiophosphate containing (1R)‐endo‐(+)‐fenchyl substituent with tributyl chlorostannane or tetrachlorostannane result in corresponding S‐tributylstannyl dithiophosphate or tetrakis(dithiophosphato)stannane. Molecular structure of ammonium O,O‐di‐(–)‐menthyldithiophosphate was studied by X‐ray single crystal diffraction. Bactericidal activity of S‐tributylstannyl dithiophosphates was tested.

Solvent-free mechanochemical synthesis of dithiophosphonic acids and corresponding nickel(II) complexes

GRAPHICAL ABSTRACT

Syntheses, characterization of and studies on the electrochemical behaviour of ferrocenyl dithiophosphonates and 4-methoxyphenyl dithiophosphonates

GRAPHICAL ABSTRACT

2,4-Diorganyl 1,3,2,4-dithiadiphosphetane-2,4-disulfides, their structure and S-silyl dithiophosphonic derivatives

GRAPHICAL ABSTRACT

Structural studies on some dithiophosphonato complexes of Ni(II), Cd(II), Hg(II) and theoretical studies on a dithiophosphonato Ni(II) complex using density functional theory

In this study, three dithiophosphonic acid complexes, namely, trans-bis-[O-3-methylbutyl (4-methoxyphenyl)dithiophosphonato]nickel(II), Ni(L)2; bis-{bis-[O-3-phenylpropyl (4-methoxyphenyl)dithiophosphonato]cadmium(II)}, [Cd(L)2]2 and bis-{bis-[O-3-methylbutyl (4-methoxyphenyl)dithiophosphonato]mercury(II)}, [Hg(L)2]2 were prepared. The compounds were characterized by elemental analysis; MS; FTIR and Raman spectroscopies and were also investigated by 1H-, 13C- and 31P- NMR. The Ni(L)2 complex was elucidated by X-ray crystallography, molecular characterization and density functional modelling studies. The molecular structure obtained from X-ray single-crystal analysis of the Ni(L)2 complex in the ground state has been compared using density functional theory (DFT), B3LYP functional with 6-311G(d,p) basis set. In addition to the optimized geometrical structures, atomic charges and nonlinear optical (NLO) effects have been investigated by using DFT. The experimental (spectroscopic) and calculated vibrational frequencies (using DFT) of the Ni(L)2 have been compared. There exists a good correlation between experimental and theoretical data for the Ni(L)2 complex.

C/O/P/S cycles derived from oxidative intramolecular disulfide (–S–S–) coupling of ferrocenyl dithiophosphonates

The symmetrical 2,4-diferrocenyl-1,3-dithiadiphosphetane disulfide dimer, [FcP(μ-S)S]2 (Fc = ferrocenyl), reacts with ethanediol (molar ratio 1:1), trans-1,2-cyclohexanediol (molar ratio 1:1) and pentaerythritol (molar ratio 2:1) at 70 °C to form the respective dithiophosphonic acids in high yield. The acids were readily deprotonated by anhydrous ammonia to yield the corresponding ammonium salts (NH4)2[S2P(Fc)OCH2CH2O(Fc)PS2] (1), (NH4)2[(S2PFc)2(trans-1,2-O,O′-C6H10)] (2) and (NH4)4[C{CH2OPS2(Fc)}4] (3). The salts undergo facile intramolecular oxidation with the mild oxidant iodine in a I2/MeOH mixture resulting in new ferrocene-based disulfides of the type [{-CH2OP(S)(Fc)S-}2] (4), [(S2P-Fc)2(trans-1,2-O,O′-C6H10)] (5) and [C{CH2OP(S)(Fc)S}4] (6). The compounds 1–6 were characterized by 1H and 31P NMR and bulk purity were confirmed by either ESI-MS or elemental analysis. Compounds 4–6 were additionally characterized by single crystal X-ray analyses and 4 and 6 subjected to electrochemical investigations. Compounds 4–6 represent the first examples of structurally characterized intramolecular S–S coupled products derived from ferrocene-based dithiophosphonates.

Synthesis, crystal structure and ab initio/DFT calculations of a derivative of dithiophosphonates

The compound 2 has been synthesized from the reaction of 2,4-Bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide and (R)-1-[3,5-Bis(trifloromethyl)phenyl]ethanol in toluene. The obtained crude dithiophosphonic acid 1 has been treated with the excess of N(C2H5)3 to give rise to 2, [(+HN(C2H5)3][(O–CH3CH–C6H3(CF3)2)(CH3OC6H4)PS2-]. The compound 2 has been characterized by using the spectroscopic methods such as IR, 1H, 13C, 31P NMR and structural analysing method such as X-ray crystallography. It crystallizes in the orthorhombic system, whose space group is P212121. It consists of a dithiophosphonate bridged methoxyphenyl and bis(triflorophenylethyl) groups and a triethylammonium moiety linked by NH⋯S and CH⋯F hydrogen bonds. In the crystal structure, the C17H14F6O2PS2 molecule is elongated along the b-axis and stacked along the a-axis. The triethylammonium, N(CH2CH3)3, molecule fill in the cavities between the C17H14F6O2PS2 molecule. Moreover, ab initio methods based on Hartree–Fock (HF) and Density Functional Theory (DFT) calculations with the basis set of 6-31G(d) are also carried out to determine the molecular structural properties and to calculate FT-IR and NMR spectrum of the compound 2. The experimental results and theoretical calculations have been compared, and they are found to be in good agreement.

Dithiophosphoric and Dithiophosphonic Acids and Their Derivatives on the Basis of Thymol: Synthesis and Antimicrobial Activity

Biologically active dithiophosphoric and dithiophosphonic acids, their ammonium salts as well as S-silyl and S-plumbyl derivatives were prepared by the reaction of thymol with tetraphosphorus decasulfide and 2,4-diaryl 1,3,2,4-dithiadiphosphetane-2,4-disulfides.

Synthesis and Properties of Organogermanium and Organotin Dithiophosphonate Complexes; Crystal Structures of (C6H5)2Sn(Cl)[(p-MeOC6H4)(EtO)PS2−S, S′], Me2Sn[(p-MeOC6H4)(MeO)PS2-S]2, Me2Sn[(p-MeOC6H4)( i PrO)PS2-S]2, and Me2Ge{[(C6H5)3SiO](p-MeOC6H4)PS2-S}2

2,4–Bis-(4-methoxyphenyl)-1,3,2λ5,4λ5-dithiadiphosphetane-2,4-disulfide (Lawesson's reagent) reacts with a variety of alcohols and silanols to form dithiophosphonic acids in a facile manner. Their lithium salts react with organotin- and organogermanium chlorides to produce organometallic dithiophosphonate complexes of the type A R3“M[S(S)P(R)(OR′)] (M = Ge, Sn; R = 4-MeOC6H4; R′ = Me, SiPh3, GePh3, SnPh3; R″ = Me, Ph) and B R2”M[S(S)P(R)(OR′)]2 (M = Ge, Sn; R = 4-MeOC6H4; R′ = Me, Et, i Pr, tBu, SiPh3; R″ = Me, Ph). The ligands in the new organometallic compounds are bound in an asymmetric fashion as revealed by four X-ray structure determinations, containing one representative example of type A and three examples of type B . All new compounds are fully characterized by analytical and spectroscopic methods.

2D hydrogen bond networks in the crystals of [(NH 4 · H 2O) 2][(RO)(Fc)P(S) 2] 2 (R = 3-(BzO)-Bz, 4-( n-Bu)-Bz, Bz = benzyl)

Herein we report on the preparation of hydrated ammonium salts of the dithiophosphonic acids (RO)(Fc)P(S)(SH) (R = derivative of benzyl) featuring [(NH 4 · H 2O) 2] 2+ cations formed by N–H⋯O hydrogen bonds. Interaction of these cations with the PS 2 − units gives rise to unprecedented 2D networks, formed solely by hydrogen bonds. These unique networks containing two- and three centered hydrogen bonds are valuable examples of the acceptor properties of sulfur atoms.

The synthesis of a new dithiophosphonic acid and its coordination properties toward Ni(II): A combined NMR and X-ray diffraction study

In order to investigate the coordination properties of the new, dianionic, S-donor ligand 4-methoxophenyldithiophosphonate (L), a dithiophosphonate salt of L(H 2pz) 2 formula was prepared (Hpz = pyrazole), characterized by multinuclear solution and solid state NMR, and subsequently employed in the synthesis of two Ni(II) metal complexes of [NiL 2](H 2pz) 2 and [NiL 2](HNEt 3) 2 formula. The latter species were fully characterized by a combined NMR and X-ray diffraction study, allowing to disclose interesting structural features, such as subtle deformations of the ligand (and their influence on the magnetic resonance properties of the 31P nuclei), imposed by distinct hydrogen-bond patterns.