0,0 -Diethyl dithiophosphate, and

Bum, AJ. Phosphoms-31 nuclear magnetic resonance study of the mechanism and kinetics of the hydrolysis of zinc(II) 0,0-diethyl dithiophosphate and some related compoimds. Journal of the Chemical Society Perkin Transaction, 1990,2, 753-758. 

Salts of the ester 0,0 -diethyl dithiophosphate have been prepared by two different methods. One involves the reaction of (C2H50)2P(S)C1 with potassium hydrogen sulfide.1 The other is the reaction of phosphorus (V) sulfide with ethanol followed by the addition of metal halide.1-3 The second method is the basis for this preparation, although the chromium(III) compound has not previously been reported. Salts of cobalt(III), nickel(II), and lead(II) can be prepared by analogous reactions using cobalt (III) fluoride, nickel(II) chloride 6-hydrate, and lead(I) oxide, respectively. 

Caution. The apparatus should be set up in a hood, since hydrogen sulfide and hydrogen chloride are liberated during the reactions. The preparation of 0,0 -diethyl dithiophosphate is done in a nitrogen atmosphere because of the reactivity of the acid toward air and water. 

Chromium(III) (0,0 -diethyl dithiophosphate) forms beautiful flakes which are purple by reflected fight and di-chroic by transmitted fight they are purple at one angle and green at another. The salt is soluble in organic solvents but insoluble in water. It is stable toward air and water, but decomposes at temperatures above its melting point. 

Examples of this reaction type are the addition of 0,0-diethyl dithiophosphate at the endocyclic double bond of 1,3,2-dioxathiole 2-oxide (73) (62USP3053852) and the addition of bromine or sulfur trioxide at the vinyl group of the cyclic sulfate (31) (79IZV118). 

Tellurium Bis[0,0-diethyl dithiophosphate]2 1.6 g(10 mmol) of tellurium dioxide are dissolved in 5 ml of hot, concentrated hydrochloric acid, the solution is cooled to 20°, 15 m/of water arc added, the mixture is stirred, and 8.3 g (40 mmol) of sodium diethyl dithiophosphate dissolved in 20 ml of water are added slowly. The resultant solution is decanted from the yellow solid formed, the solid is washed with cold ethanol, and recrystallized from ethanol or benzene yield 3.8 g (76%) m.p. 66° (dec.). 

Phenyl tellurium Bis[diethyldithiocarbamate] 0,0-Diethyl Dithiophosphate To a solution of 1.91 g (4.0 mmol) of phenyl tellurium bis[diethyldithiocarbamale] chloride in dichloromethane are added 0.90 g (4.0 mmol) of potassium 0,0-diethyl dithiophosphate. The mixture is stirred for 2 h and then filtered. The filtrate is taken to dryness. The yellow residue is recrystallized from dichloromethane/hexane by slow evaporation m.p. 149-151° (dec.). 

X-ray structural investigations of diphenyl tellurium bis[0,0 -diethyl dithiophosphate] revealed the two dithiophosphates to be monodentate and located at the two apical positions of the trigonal bipyramidal molecule . ... 

The [4+2] cycloaddition of acylisocyanates to isocyanates to give 2,4-dioxo-2,4-2/-l,3 5-oxadiazines is well established <1981BSF28, 1970ZNB1180>. Thus, the water-sensitive 1,3,5-oxadiazine 61, formed from acylisocyanate 284 and phenyl isocyanate, reacts with 0,0-diethyl dithiophosphate to afford the oxadiazine 92 (Scheme 59) <1996SC783>. However, these oxadiazines are difficult to isolate as they undergo rapid decomposition. 

P-Laheled compounds. A mixture of P2S3, abs. ethanol, and benzene refluxed 3 hrs., more ethanol added, then refluxed further 2 hrs. until all the solids have dissolved 0,0-diethyl dithiophosphate- P (radio-Y 85%), 30.5 g. ice-cooled, treated with a soln. of Na in ethanol (prepared under N2) until the pH reaches 8-9.3, part of the ethanol distilled off in vacuo, methylene bromide added, refluxed 3 hrs. with stirring, cooled, again brought to pH 9.3 with Na-ethoxide soln., more methylene bromide added, and refluxed 2 hrs. 27.5 g. 0,0,0, 0 -tetraethyl S,S -methylene bisphosphorodithioate- p (radio-Y 87% purity 89.5%). S. F. Forman and B. L. Gilbert, J. Agr. Food Chem. 9, 260 (1961). 

Proton donators can heterolytically split hexamethyldisilazane and trimethyl-methylaminosilane.—E 0,0-diethyl dithiophosphate in ether added slowly to a soln. of hexamethyldisilazane in ether 0,0 -diethyl S-trimethylsilyl dithiophosphate. Y 90-95%. F. e. s. M. Becke-Goehring and G. Wunsch, B. 93, 326 (1960). 

Tellurium bis[0.0-dimethyl dithiophosphate] (m.p. 91 °) was prepared in 80% yield as described for the diethyl compound but using methanol to wash and recrystallize the compound2. 

DIMETHYL DITHIOPHOSPHATE of DIETHYL MERCAPTOSUCCINATE (121-75-5) Combustible liquid (flash point >325°F/>163°C). Incompatible with strong oxidizers, magnesium, perchloric acid, alkaline pesticides. Attacks metals, some plastics, rubber, and coatings. 

The OH group in 3-hydroxymethyl-3,4-dihydro-l,2,3-benzotriazin-4-one is replaced by chlorine under treatment with thionyl chloride in chloroform <1956USP2758115> and by bromine under treatment with phosphorus tribromide in acetonitrile <1955DEP927270>. 3-Chloromethyl-3,4-dihydro-l,2,3-benzotriazin -one is used for the manufacture of Azinphos methyl by exchange of the chlorine with O,0 -diethyl-dithiophosphate in the presence of sodium bicarbonate in acetone <1955DEP927270>. 

Figure 6. Cyclic voltammograms for a chalcocite electrode in 0.05 mol dm sodium tetraborate (pH 9.2) (—) and in the same solution containing 10" mol dm" diethyl dithiophosphate (—). Scans at 50 mV s" taken to different upper potential limits. (From Buckley and Woods. )...

Metal dialkyl dithiocarbamates inhibit the oxidation of hydrocarbons and polymers [25,28,30,76 79]. Like metal dithiophosphates, they are reactive toward hydroperoxides. At room temperature, the reactions of metal dialkyl dithiocarbamates with hydroperoxides occur with an induction period, during which the reaction products are formed that catalyze the breakdown of hydroperoxide [78]. At higher temperatures, the reaction is bimolecular and occurs with the rate v = k[ROOH][inhibitor]. The reaction of hydroperoxide with dialkyl dithiocarbamate is accompanied by the formation of radicals [30,76,78]. The bulk yield of radicals in the reaction of nickel diethyl dithiocarbamate with cumyl hydroperoxide is 0.2 at... 

---