Synthesis and Properties of Alkylene (Dialkyl) Dithiophosphate Derivatives of Thionyl Chloride

Alkylene (dialkyl) dithiophosphate derivatives of thionyl chloride of the general formula (S)SS(O)Cl and (RO)₂(S)SS(O)Cl where G = ─ CH₂(CH₃)₂CCH₂─, ─ CH₂CH₂CH(CH₃)─, ─ C(CH₃)₂CH₂CH(CH₃)─ and R = i-C₃H₇, have been synthesized by reacting thionyl chloride with alkylene/dialkyl dithiophosphates in a 1:1 molar ratio in refluxing benzene. A similar reaction in a 1:2 molar ratio yields the corresponding products of the type (S₂)₂S═O and [(RO))₂PS₂]₂S═O. It is interesting to note here that the sulfur atom of the thionyl chloride has been retained in the product, which is evidenced by sulfur analysis. The products thus obtained are light yellow colored semi solid (1:1 products) and orange colored liquids (1:2 products); and are soluble in common organic solvents. These new compounds have been characterized by elemental analysis, molecular weight measurements, and spectroscopic [IR and NMR (¹H and ³¹P)] studies. These compounds are found to be biologically active against bacteria S.aureus and E.coli.     

Syntheses and spectroscopic studies of diphenylphosphinato derivatives of boron

Summary 2-Diphenylphosphinato-1,3,2-dioxaborolanes and -borinanes of the type (whereG = -CH₂CHMe-, -CH₂CH₂CH₂-, -CH₂CH₂CHMe-,-CMe₂CMe₂-, -CMe₂CH₂CHMe-,-CH₂CMe₂CH₂-, -CH₂CEt₂CH₂-, and -C₆H₄-) are obtained by the reaction of diphenylphosphinic acid with the corresponding 2,2-oxo-bis-1,3,2-dioxaborolanes and-borinanes. The products are white crystalline solids, which have sharp melting points and are hydrolytically stable. They have been characterized by elemental analysis, IR and multinuclear NMR (¹¹B,³¹P, and¹¹⁹Sn) studies. The data suggest structures with monodentate phosphinato moieties and 3-coordinated boron atoms.

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Synthesen und spektroskopische Untersuchungen von Diphenylphosphinatoderivaten von Bor

Zusammenfassung 2-Diphenylphosphinato-1,3,2-dioxaborolane und -borinane des Typs (mitG = -CH₂CHMe-, -CH₂CH₂CH₂-,-CH₂CH₂CHMe-, -CMe₂CMe₂-,-CMe₂CH₂CHMe-, -CH₂CMe₂CH₂-, -CH₂CEt₂CH₂- und C₆H₄) erhält man durch Reaktion von Diphenylphosphinsäure mit den entsprechenden 2,2-Oxo-bis-1,3,2-dioxaborolanen und -borinanen. Die Produkte sind weiße, kristalline, hydrolyseunempfindliche Festkörper. Sie wurden mittels Elementaranalyse, IR-Spektroskopie und multinuklearer NMR-Spektroskopie (¹¹B,³¹P und¹¹⁹Sn) charakterisiert. Die Resultate legen Strukturen mit monodentaten Phosphinatoeinheiten und dreifach koordinierten Boratomen nahe.

     

MIXED HALIDE DIALKYL AND ALKYLENEDITHIOPHOSPHATE DERIVATIVES OF RUTHENIUM (III)

Abstract

Mixed chloride dialkyl and alkylenedithiophosphates of ruthenium (III). RuC1_3-n|(S₂P(OR)₂|n (R = Prⁿ, and Ph) and RuCl_3-n,[S₂ POGO]n G =-CMe₂CMe₂,- CH₂CMe₂CH₂-, -CH₂CEt₂CH₂-. and -CMe₂CH₂CHMe-, n = 1,2 have been synthesized for the first time by the reactions of ruthenium trichloride with ammonium dialkyl and alkylenedithiophosphate or alternatively by disproportionation reactions of ruthenium trichloride with ruthenium tris(dialkyl and alkylenedithiophosphates) in different stoichiometric ratios in benzene.

These new complexes have been characterized by elemental analysis, molecular weight determinations, as well as IR and NMR (¹H and ³¹P) data. Chelated structures with bidentate dialkyl and alkylenedithiophosphates groups have been proposed for all these derivatives.     

DIALKYL(ARYL) PHOSPHORYL DERIVATIVES OF ALKYLENE DITHIOPHOSPHATES

Dialkyl(aryl) phosphoryl derivatives of alkylene dithiophosphates of general formula (S)SP(O)(OR) ₂ : R = Pr ⁱ , Ph and G = ═CMe ₂ CMe ₂ ═, ═CH ₂ CH ₂ CHMe═, ═CH ₂ CH ₂ CH ₂ CH ₂ ═, ═CMe ₂ CH ₂ CHMe═, and ═CH ₂ CMe ₂ CH ₂ ═; have been synthesized by reacting dialkyl and diaryl phosphoryl chloride with ammonium salts of alkylene dithiophosphates in 1:1 molar ratio in refluxing benzene. The products formed are yellow-colored viscous liquids and white-colored waxy solids; they are soluble in common organic solvents and are nonvolatile, even under reduced pressure. The new compounds have been characterized by elemental analysis, molecular weight measurements and spectroscopic (IR, ¹ H NMR, and ³¹ P NMR)] data.     

Synthesis and Characterization of Tris(Triphenylphosphine) Ruthenium (II) Alkylene Dithiophosphate and Their Halide Derivatives

Abstract

Reactions of (Ph₃P)₃RuCl₂ with the ammonium salt of alkylene dithiophosphoric acids in 1:1 and 1:2 stoichiometry gave complexes of the type (Ph₃P)₃Ru(Cl)[S₂POGO](A) and (Ph₃P)₃ Ru[S₂ POGO]₂(B), G= -CMe₂CMe₂-,-CH₂CMe₂CH₂-, -CH₂CEt₂CH₂- and -CMe₂CH₂CHMe-. Molecular weight determinations and IR and NMR (¹H and ³¹P) spectral data indicate a hexacoordinated octahedral structure. The dithioligand in (B) complexes show monodentate and bidentare chelating.     

The Synthesis and Characterization of 2-Amino-3-methylpyridinium Dihydrogenmonophosphate: (C6H9N2)H2PO4

A new crystal of 2-amino-3-methylpyridinium dihydrogenmonophosphate has been prepared and characterized by X-ray crystallography, thermal analysis, and impedance and NMR spectroscopies. This compound crystallizes in the triclinic space group P with a = 7.343(2) Å, b = 7.987(2) Å, c = 8.116(4) Å, α = 77,62(3)°, β = 77,74(3)°, γ = 87,03(2)°, V = 454.3 (3)ų, and Z = 2. The crystal structure was solved and refined to R = 0.030 with 1602 independent reflections. The atomic arrangement can be described as (H₂PO₄ ^?)_n polymeric chains anchoring the 2-amino-3-methylpyridinium cations through short hydrogen bonds. All ring atoms of the organic entity are coplanar. The exocyclic N atom is an electron receiving center, which is consistent with features of imino resonance evidenced by bond lengths and angles. Solid state ³¹P, ¹³C, and ¹⁵N CP-MAS-NMR spectroscopies are in agreement with the X-ray structure. Ab initio calculations allow the attribution of carbons and nitrogen to the independent crystallographic sites.     

Synthesis and Properties of 2-Alkylene/Dialkyl Dithiophosphato-2-oxo-1,3,2-dioxaphosphorinanes

Reactions of 2-chloro-2-oxo-1,3,2-dioxaphosphorinanes with ammonium alkylene/dialkyl dithiophosphates in a 1:1 molar ratio in refluxing benzene solution yields nonvolatile, yellow viscous liquids of the type (S)S(O) and (RO)₂ P(S)S(O) , respectively. [G = ? CH₂CH₂CHCH₃?,. ? C(CH₃)₂CH₂CHCH₃?,. ? CH₂C(CH₃)₂CH₂; R = i-C₃H₇, C₂H₅].

These compounds are hygroscopic and monomeric in nature. The newly synthesized derivatives have been characterized by physicochemical and spectroscopic techniques (IR, NMR [¹H&³¹P], and M.W).