Dithiophosphoric esters

Manufacture of dithiophosphoric ester acids from alcohol.s and diphosphorus(V) sulfide... 

Dithiophosphoric ester acids are obtained by the reaction of diphosphorus(V) oxide with alcohols or phenols ... 

Applications of Neutral Thio- and Dithiophosphoric Ester Acids... 

Applications of neutral thio- and dithiophosphoric ester acids as insecticides... 

The neutral thio- and dithiophosphoric ester acids with a reactive easily hydrolytically cleavable group, are utilized as insecticides. Their effect is based on in vivo oxidation to the corresponding phosphoric acid ester, which... 

RP(SR )NRP have thus been oxidized to the corresponding phosphorus(V) esters. The attempted oxidation of the esters 65 and 67 by elemental oxygen merely results in their isomerization to a phosphine sulphide (66) and in the second case to the thiophosphonic diester 68 . The case of 20 (X = l.p., R = SCH2Ph) is more unusual still, since such oxidation leads not only to the thiophosphonic ester (20 X = S, R = PhCH2), but also to the dithiophosphoric ester (20 X = S, R = SCH2Ph), together with other products ... 

Numerous preparative methods have been reported for these acids and their salts and ester derivatives.1 4 Dithiophosphoric acids are accessible from the reaction of phosphorus pentasulfide with alcohols or phenols (Equation 18). Dithiophosphinic acids can be prepared from thiophosphinic chlorides and sodium hydrosulfide (Equation 19), although the phenyl derivative is better prepared using a modified Friedel-Crafts reaction in which phosphorus pentasulfide is reacted with benzene in the presence of anhydrous aluminium trichloride (Equation 20). 

Dithiophosphoric acids, (RO)2PS2H, have been used for the thionation of carbonyl groups in certain aldehydes, ketones, amides, esters, thio-carboxylates and other organics.163 The mechanism for this reaction proceeds via a reversible nucleophilic attack of the thioacid on the carbonyl compound, which can then rearrange by way of a four-membered PSCO cyclic intermediate into the desired C=S containing molecule and thiophosphoric acid (Equation 81).163... 

ZDDPs are formed by the reaction of phosphorus pentasulfide (P2S5) dimer with alcohol (ROH) or phenol (dithiophosphoric acid ester formation), followed by reaction with zinc powder or zinc oxide or with zinc chloride and sodium hydroxide solutions (see below). The various types of ZDDPs differing in R-group structures are shown in Table 2.6 (SAE, 1983 Yamaguchi et al., 1966). Scheme of the formation of zinc dialkyldithiophosphate, ZDDP ... 

Dithiophosphoric acid ester Zinc dialkyldithiophosphate (monomeric)... 

Phosphorus containing additives include esters of phosphoric acids, derivatives of thiophosphoric acids, phosphites (Davey, 1950 Sakuri and Sato, 1970), and the metal salts of dithiophosphoric acid diesters, the best known of these compounds being the ZDDPs. The structure of ZDDP films, the composition of the film formed, and the mechanism of action on the molecular level are summarized in Chapter 4. 

Auch die gleichzeitige Einwirkung von Alkoholen und Ammoniak auf Dithiophosphor-saure-dichlorid-S-ester fiihrt zu Dithiophosphorsaure-amid-0,S-diestern504 (70-90%) ... 

Other successful sulfuration agents are (di)thiocarboxylic acids or dithiophosphoric acid esters (87JAP62-10081). 

Chlorination of acidic dithiophosphoric-0,0-dimethyl- or diethylesters results in the splitting off of sulfurdichloride and the formation of the ester chloride of monothiophosphoric acid ... 

Dithiophosphinic acids Dithiophosphoric acid 0,0-diesters Dithiophosphonic acid O-esters... 

Acyclic and six-membered cyclic phosphorous acids, except salicylic derivatives, exist in a form containing the P(0)H fragment and have AHn values in the gaseous phase of —70 kJ mol", and values for 1,3,2-dioxophospholanic analogues are —40 kJ mol". Calorimetric studies, in a heat-flow reaction calorimeter on the reaction of dithiophosphoric acid 0,0 -dialkyl esters, (R0)2P(S)SH, with zinc oxide, have been used to determine the reaction kinetics, "... 

Many references to kinetic measurements may have already been covered earlier with other physical methods. These include studies on pseudorotation of stereoisomers of a 10-P-5 spirophosphorane, on the formation rate of acylpho-sphonate hemiketals, on the rate of decomposition of hydroperoxides formed by the oxidation of soya phosphatidylcholine, on the kinetics of the reaction of trimethyl phosphite with benzylidene acetophenones, calorimetric studies on the reaction kinetics of dithiophosphoric acid 0,0 -dialkyl esters with zinc oxide, " and the kinetics of selective dephosphorylation of 2 -phosphorylated and 2 -thiophosphorylated dinucleotides. 

Several addition reactions of unsaturated phosphonic and phosphinic esters have been reported during the course of the year. Dithiophosphoric acids add to 2-alkoxy-vinylphosphine esters in the expected manner, and in the addition of phenyl azide to vinylphosphonates, the initial triazole (95) may be thermolysed to a C-phosphory-lated aziridine, but in the presence of triethylamine the final products are 2-anilino-vinylphosphonates. ... 

Beilstein Handbook Reference) BRN 0635993 Dimethyl phosphodithionate 0,0-Dimethyl dithiophosphate 0,0-Dimethyl dithiophosphoric acid 0,0-Dimethyl hydrogen dithiophosphate 0,0-Dimethyl phosphorodithioate EINECS 212-053-9 HSDB 5750 Kwas dwumelylo-dwutiofosfbrowy Kyselina 0,0-dimethyldithiofosforcna Methyl phosphorodithioate Phosphorodithioic acid. 0,0-dimethyl ester. 

Phosphorodithioic acid, 0,0-diisooctyl ester, zinc salt. Dithiophosphoric acid, 0,0 -diisoootyl ester, zinc sait EINECS 249-109-7 HSDB 6161 Isooctyl ZDDP Oronite Phosphorodithioic xid, 0,0-diisooctyl ester, zinc salt Zinc bis(diisooctyl dithiophosphate) Zinc, bis(0,0-diiso-octyl phosphorodithioato-S,S )- Zinc bis(0,0-diisooclyl) bis(dithiophosphate) Zinc diisooctyl dithiophosphate Zinc 0,0-diisooctyl dithiophosphate,... 

Other Studies. - The P NMR chemical shifts of alcohols, carboxylic acids and phenols phosphitylated with 2-chloro-4,4,5,5-tetramethyl-dioxaphospholane have been correlated with substituent effects of phenols. P NMR spectroscopy has also been used to study activation pathways of aryl H-phosphonate ester condensation reactions, the conversion of allenyl and divinyl phosphines to 1- and 2-phosphadienes, the reaction of tetraphosphorus decasulfide with dialkyl disulfides, the reaction of phosphine with cyclic olefins, the chemical shift tensors of powder samples of phosphole derivatives, the reactions of alcohols and mercaptans with tetraphosphorus trichalcogen diiodides, the structure of aminomethanebisphosphonic acids, and reactions of 00-di-(2-ethylhexyl)dithiophosphoric acids. ... 

N, disecbutyl p-phenylene-diamine amine borates amine guanidine derivatives esters of dithiophosphoric acid... 

SYNONYMS benzotriazine dithiophosphoric acid dimethoxy ester, S-(3,4-dihydro-4-0X0-1,2,3-benzotriazin-3-ylmethyl)-0,0-dimethyl phosphorodithio-ylmethyl phosphorodithioate, guthion , methyl azinphos. 

Salts of mono- and dithiophosphoric acid 0,0-dialkyl esters react with A -benzylidene-2,2,2-trifluoro-l-chloroethylamine at the sp carbon to give compounds (155 a-c) when X = S. these can i.somerize to (156 a,b) in the presence of triethylamine and are then rapidly transformed into (157 a,b). When R = EtO, an equilibration occurs between (157 a) and (15S a). ... 

Dithiophosphoric acid, 0,0 -isobutyl amyl ester, zinc salt See Zinc diall dithiophosphate... 

Dithiooctanoic acid. See Thioctic acid Dithiophos. See Sulfotepp Dithiophosphoric acid, 0,0 -isobutyl amyl ester, zinc salt. See Zinc dialkyl dithiophosphate Di (thiophosphoric) acid, tetraethyl ester. See Sulfotepp... 

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