P. N. Nagar

SYNTHESES AND SPECTROSCOPIC STUDIES OF 2-ALKYLENE DITHIOPHOSPHATO-1,3,2- DIOXARSOLANES AND -ARSENANES

Abstract Compounds of the type [where G = [sbnd]CMe2CMe2[sbnd],[sbnd]CH2CMe2CH2, G = [sbnd]CMe2CMe2[sbnd]CH2CMe2,CH2 [sbnd],[sbnd]CH2CH2CHMe[sbnd], and [sbnd]CMe2CH2,CHMe[sbnd]] have been synthesized by the reactions of ammonium salts of alkylene dithiophosphates with 2-chloro-1,3,2-dioxarsolanes and -arsenanes. The new derivatives are yellow crystalline solids, soluble in common organic solvents, monomeric in nature, and are characterized by elemental analyses, molecular weight measurements, IR and multinuclear NMR (1H, 13C, and 31 P) spectroscopic data.

Cleavage Reactions of Triphenylantimony with Dialkyl (or Alkylenyl) Dithiophosphoric Acids a

Abstract Triphenylantimony reacts with dialkyl (or alkylenyl) dithiophosphoric acids in 1:1 and 1:2 molar ratio to form complexes of the types Ph3-h Sb(S2P(OR)2]n and Ph3-n sb[S2 ]n (R = Pr-n, Pr-i, Bu-i; G = -CMe2CMe2, -CH2CMe2CH2-, - CMe2CH2CHMe-, n = 1,2) by the cleavage of antimony-carbon bonds. The complexes are colourless powdery solids, soluble in common organic solvents, monomeric in nature and have been characterized by various physico-chemical and spectroscopic [IR, NMR (1H, 13C, 31P)] techniques. a This article is dedicated to the late Prof. G. Srivastava, Department of Chemistry, University of Rajasthan, Jaipur, India.

METAL AND ORGANOMETALLOIDAL PHOSPHITES AND PHOSPHONATES

Abstract Dialkyl phosphonates are versatile chemical reagents in which existence of phosphonate and phosphite equilibrium makes them an interesting series of ambidentate ligands. The mode of chemical bonding in their metal and organometal derivatives offers interesting possibilities. Phosphorus-31 NMR spectroscopy provides convincing evidence regarding the chemical bonding modes. The present review article describes the reactions of metal and organometal halides with dialkyl phosphonates (e.g., Li, Na, K, Ag, Ca, Zn, Cd, Co, Ti, Zr, V, Nb, Ta, Ru, Ir, W, Ni, Pd, Pt, B, Al, Si, Ge, Sn, Pb, P, As, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Yb, etc.)

SYNTHESES AND PROPERTIES OF MIXED LIGAND COMPLEXES OF DIORGANOTIN(IV): PART I. β-DIKETONATO DIORGANOTIN DIALKYL (OR ARYL) DITHIOPHOSPHATES AND 1-β-DIKETONATO-3-DIALKYL DITHIOPHOSPHATO TETRABUTYL DISTANNOXANES

Abstract The mixed ligand complexes of the type R2′Sn[R″COCHCOR″] [S2P(OR‴)2] and [(R‴O)2S2P] R2′SnOSn R2′ [R″COCHCOR″] have been prepared by the reaction of diorganotin oxide (R′ = Bu, Ph) or chloride (R′ = Me) with β-diketones and dialkyl (or aryl) dithiophosphoric acids in 1:1:1 and 2:1:1 molar ratios is refluxing benzene. The products formed are monomeric, non volatile, yellow colored viscous liquids or sticky solids, soluble is common organic solvents and exhibit high sensitivity towards atmospheric moisture. These complexes have been characterized by elemental analyses, molecular weight measurements, IR and NMR (1H, 31p and 119Sn) spectral data. On the basis of 119Sn NMR studies, it was postulated that there might be disproportionation which led to the formation of mixture with fast exchange between Sn—S and Sn—O linkages.

Organic Derivatives of Alkylene Dithiophosphates, Part IV: Synthesis and Properties of Phenyl Acetyl and p-Methyl Benzoyl Derivatives of Alkylene Dithiophosphates

Reactions of phenyl acetyl chloride and p-methylbenzoyl chloride with ammonium salt of alkylene dithiophosphates in a 1:1 molar ratio in refluxing benzene solution yields nonvolatile dark yellow- or brown-colored viscous liquids of the type S 2 R (R = ─OCCH 2 C 6 H 5 , ─OCC 6 H 4 CH 3 , G = ─CMe 2 CMe 2 ─, ─CH 2 CH 2 CHMe─, ─CH 2 (CH 2 ) 2 CH 2 ─, and ─CMe 2 CH 2 CHMe─). The compounds thus obtained are hygroscopic and monomeric in nature. The newly synthesized compounds have been characterized by physicochemical and spectroscopic techniques (MW, IR, NMR [ 1 H & 31 P]).

SYNTHESES AND SPECTROSCOPIC STUDIES OF DIORGANOTIN BIS-O-ALKYL PHOSPHONATES

Abstract Diorganotin bis-O-alkyl phosphonates, R2Sn[O2P(H)OR′]2 (R = Me, Et; R′ = Me, Et, Bu, Ph) have been obtained in quantitative yield by reacting sodium salts of O-alkyl phosphonate with diorganotin dichloride. The derivatives are white colored, hydrolytically stable powdery solids, soluble in methanol (when freshly prepared) and are characterized by various physico-chemical as well as spectroscopic IR, NMR (1H, 31P and 119Sn) studies which are consistent with 6-coordinated tin atom.

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).

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.

ORGANIC DERIVATIVES OF ALKYLENE DITHIOPHOSPHATES. PART II: SYNTHESIS AND PROPERTIES OF 2- ACETANILIDE (BENZANILIDE) DERIVATIVES OF ALKYLENE DITHIOPHOSPHATES

Abstract Reactions of p- bromoacetanilide (benzanilide) with ammonium salt of alkylene dithiophosphates NH4 +; G =-CMe2CMe2-, -CH2CMe2CH2-, -CMe2CH2CHMe-, CH2CH2CHMe-) in 1:1 molar ratio in refluxing benzene solution yields; acetanilide (benzanilide) derivatives of alkylene dithiophosphates, OGOP(S)S C6H4NH COR (R = Me or Ph). The newly synthesized derivatives have been characterized by elemental analysis, molecular weight determination, IR, NMR (1H & 31P) spectral studies. In contrast to bidentate behavior in metal and organometal derivatives of alkylene dithiophosphate (adttp), the behavior of the dithiophosphato moiety in these derivatives is found to be monodentate. On the basis of above studies the formation of P(S)S-C linkage have been established.

Organic Derivatives of Alkylene Dithiophosphates Part III: Synthesis and Properties of 2-( p -nitrophenyl) and 2-( p -nitrobenzoyl) Derivatives of Alkylene Dithiophosphates

Reactions of p -bromonitrobenzene and p -nitrobenzoyl chloride with ammonium salt of alkylene dithiophosphates {\kern10pt}\raise7pt\hbox{{\vrule height2pt width.5pt}{\raise1.5pt\hbox{\vrule height.5pt width20pt}}{\vrule height2pt width.5pt}}{\kern-32pt} (OGOPS