H. P. S. Chauhan

SYNTHESIS AND CHARACTERIZATION OF 2-MERCAPTO-2-THIONO-1,3,2-DIOXAPHOSPHOLANES AND DIOXAPHOSPHORINANES

Abstract 2-Mercapto-2-thiono-1,3,2-dioxaphospholanes and dioxaphosphorinanes, have been synthesized by the reactions of phosphorus pentasulphide with some 1,2-diols (viz., butane-2,3-diol and 2,3-dimethylbutane-2,3-diol) and 1,3-diols (viz., 2-methylpentane-2,4-diol, 2,2-dimethylpropane-1,3-diol and 2,2-diethylpropane-1,3-diol) in 1:2 molar ratio in dry benzene. These volatile compounds have been purified by distillation under reduced pressure. The 2-methylpentane-2,4-diol derivative, however, decomposed during attempted distillations. These new compounds have been characterized by elemental analysis, molecular weight determinations, measurement of pK a values and IR as well as NMR spectroscopic studies. The ammonium and sodium salts of some of these acids have also been characterized.

Mixed halide dialkyldithiophosphate derivatives of arsenic(III) and antimony(III)

Abstract Mixed chloride dialkyldithiophosphates of arsenic(III) and antimony(III), [(RO) 2 PSS] n MCl 3−n (M = As, Sb; n = 1, 2; R = C 2 H 5 , n -C 3 H 7 , i -C 3 H 7 and i -C 4 H 9 ) have been synthesized for the first time by the reac metal chlorides with sodium dialkyldithiophosphates or alternatively by co-disproportionation reactions of metal chlorides with metal tris (dialkyldithiophosphates) in different stoichiometric ratios. Mixed halide dialkyl-dithiophosphates of antimony(III) have also been prepared by the cleavage reactions of antimony tris (diisopropyldithiophosphate) with bromine or iodine. Hydrolysis reactions of a few of these compounds have also been studied. The new compounds have been characterized by elemental analyses, molecular weight determinations (cryoscopic) as well as IR and NMR ( 1 H, 31 P) data; chelated structures with bidentate dialkyldithiophosphate groups are proposed.

Alkylenedithiophosphate derivatives of arsenic(III), antimony(III) and bismuth(III)

Abstract Tris(alkylenedithiophosphates) of arsenic(III), antimony(III) and bismuth(III), have been synthesized by the reactions of alkylenedithiophosphoric acids with metal oxides and chlorides and of their ammonium salts with metal chlorides in suitable solvents. Mixed chloride alkylenedithiophosphates of arsenic(III) and antimony(III), have been obtained by the reactions of metal chlorides with ammonium alkylenedithiophosphates at 1 : 1 and 1 : 2 molar ratios or alternatively by the co-disproportionations reactions of metal chlorides with metal tris(alkylenedithiophosphates) at different (2 : 1 and 1 : 2) molar ratios. These new compounds have been characterized by elemental analyses, molecular weight measurements and spectroscopic (IR, and 1H and 31P NMR) data. Chelated structures with bidentate alkylenedithiophosphate groups have been proposed for all these derivatives.

SYNTHESIS AND REACTIONS OF MIXED HALIDE DIALKYLDITHIOPHOSPHATE DERIVATIVES OF BISMUTH(III)

Abstract Mixed chloride dialkyldithiophosphates of bismuth(III), [(RO)2PS2] n BiCl3-n (n = 1, 2; R [dbnd] Et, Pr n , Pr i and Bu i ) have been synthesized for the first time by the reactions of bismuth trichloride with sodium diisopropyldithiophosphate or alternatively by co-disproportionation reactions of bismuth trichloride with bismuth tris(dialkyldithiophosphates) in different stoichiometric ratios in suitable organic solvents. Monohalobismuth bis(diisopropyldithiophosphates) have also been synthesized by the cleavage reactions of bismuth tris(dialkyldithiophosphates) with bromine or iodine in 2:1 molar ratio. These new derivatives have been characterized by elemental analysis, molecular weight determinations (both cryoscopic and ebullioscopic) as well as spectroscopic (IR, 1H NMR and 31P NMR) studies. On the basis of these data chelated structures with bidentate dialkyldithiophosphate groups have been proposed for these monomeric derivatives. Hydrolysis reactions of some of these compounds have also ...

Synthlsis and Characterization of Dialkyldithiophoate Derivatives of Arsenic(III)

Abstract Compounds of the type G-O-O-AsS2P(OR)2 (G = -CH2CH2-, -(CH3)CHCh2, -(CH3 -(CH3)2CC(GH3)2- and -CH2CH[dbnd]CHCH2 - and R [dbnd] C2H5, n-C3H7, i-C3H7, sec.-C4H9 and C6H5 have been synthesized by the reactions of 2-chloro-1,3,2-diox-arsolanes and -arsenanes with sodium, lead and ammonium salts of dialkyldithio-phosphoric acids in stoichiometric ratios. These new derivatives have been characterized by elemental analyses and molecular weight determinations. Attempts have been made to elucidate the structure of these compounds by their IR and NMR spectra.

CRYSTAL AND MOLECULAR STRUCTURE OF BISMUTH TRIS(2,2-DIETHYLTRIMETHYLENE DITHIOPHOSPHATE),BI[SP(S)OCH2CEt2CH2O]3

Abstract Bismuth tris(2,2-diethyltrimethylene dithiophosphate), M = 884.8, monoclinic, P2,/c, a = 9.591(3), b = 10.059(1), c = 36.170(5) A, β = 90.51(2)°, V = 3489.5 A3, Z = 4, Dc = 1.68 g cm−3, (MoKα) = 0.71069 A, μ = 55.5 cm−1, F(000) = 880, T = 295 K. Final R = 0.122 for 3183 reflections. The coordination geometry around bismuth is slightly distorted octahedral with three short and three long Bi[sbnd]S bonds (average lengths, 2.74 and 2.85 A, respectively); 1,3,2Dioxaphosphorinane rings are present in chair form. Preliminary data have also been obtained for bismuth tris(2,3-butylene dithiophosphate), M = 758.6, monoclinic, C2/c, a = 16.684(8), b = 13.682(6), c = 11.930(6) A, β = 98.45(2), V = 2693.8 A3, Z = 4, T = 295 K, Dc = 1.87 g cm−3,μ = 69.1 cm−1 and R = 0.052 for 1073 reflections. The chelation is symmetrical in this compound with Bi-S bond lengths of 2.76 and 2.79 A.

Synthesis and Characterization of Tetraphenylhosphonium and—Arsonium Dialkldithiophosphates

Abstract Compounds of the type [Ph4M]+[S2P(OR)2]− (M = P, As; R = CH3, C2H5, n-C3K7 i-C3H7 and i-C4H9) have been synthesized by the reactions of tetraphenylphosphonium bromide and -arsonium chloride with sodium dialkyldithiophosphates in stoichiometric ratios in parent alcohols. The white crystalline products can be recrystallized from aqueous alcohols and show sharp melting points. The derivatives have been characterized as ionic salts by spectroscopic (IR, PMR and 31P NMR) and conductance studies.