Phosphorothioate Thiophosphate Esters

FIGURE 12.20 Some applications of industrial phosphate esters. Phosphonate esters and phosphorothioate (thiophosphate) esters are also important in some of these applications. 

Several salts of dialkylphosphorodithioic acids (Chapter 9.10) have applications as anti-wear and anti-corrosion additives to lubricating oils. Zinc salts of this kind, Zn[(RO)2PSS]2, R = hexyl, for example, are made by adding zinc oxide to the acid which is itself obtained from P4S,o and the appropriate alcohol (4.104). These zinc salts are believed to react with the metal surfaces of gears and moving engine parts to give smoother surfaces which have improved wear and corrosion resistance. 

The sodium salt (Pr 0)2PSSNa is useful as an activator of thiazole accelerators used for the low-temperature vulcanisation of rubber. Other uses of [(RO)2PS2l2Ni, for example, are as anti-oxidants in plastics (Section 12.15). Sodium and ammonium dialkylphosphoro-dilhioates (R= Et or Pr) are used as flotation agents to suspend and separate metallic ores from unwantedcontaminants. Dithiophosphinic acids, R2P(S)SH, can be used to extract Am and Ln from radioactive wastes [41]. 

Antimony tris-dialkylphosphorodithioates, [(RO)2PSS]3Sb, are useful as passivating agents in petroleum refining because they prevent the poisoning of the catalyst by the contaminant metals which are present in the oil feeds. 

Dialkyl phosphorochloridothioates, important as intermediates for insecticide manufacture, are made by reaction (12.93), but care has to be taken to avoid other products (9.369). 

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The mechanism of an actual hydrolysis reaction catalyzed by this prototype phosphomonoesterase has never been studied stereochemically. This apparent omission is presumably explained by the very low catalytic efficiency of the enzyme toward phosphorothioate monoesters as compared to phosphate monoesters (75) certainly, chiral [ O, 0]phosphorothioate 0-ester substrates already exist, and methodology is available for the configurational analysis of the chiral [ 0, 0, 0]thiophosphate that would be produced if the chiral substrate were hydrolyzed in H2. In fact, the low catalytic reactivity of phosphorothioate O-esters and the high reactivity of phosphorothioate S-esters has been explained by the enzyme utilizing nucleophilic catalysis (an associate mechanism) to achieve hydrolysis of the phosphate ester bond 40). 

In boiling xylene, 0-aryl 0-methyl O-2-propynyl phosphorothioates isomerize to 0-aryl 0-methyl 5-propadienyl phosphorothioates, although with only low to moderate conversions. The anions from the conventionally-synthesized mono-thiophosphate esters (76) (R = H or Ph, = H R R = (CH2)n, n = 3 or 4) rearrange, and on subsequent alkylation or acylation (R = Me, Et, Pr, Pr , Ac, Bu CO, (PhO)2P(X), X = O, S, or Se) yield the products (77) in the (Z) configuration the latter esters undergo Diels-Alder reactions with common dienophiles (e.g. acrylonitrile, acrolein, maleic anhydride, etc.) to give the systems... 

Synonyms AI3-23284 Blitex BRN 1885571 Caswell No. 724 Dermafos Dermaphos Dimethyl trichlorophenyl thiophosphate 0,0-Dimethyl-0-2,4,5-trichlorophenyl phosphorothio-ate 0,0-Dimethyl 0-(2,4,5-trichlorophenyl)thiophosphate Dow ET 14 Dow ET 57 Ectoral EINECS 206-082-6 ENT 23284 EPA pesticide chemical code 058301 ET 14 ET 57 Etrolene Fenchlorfos Fenchlorophos Fenchchlorphos Karlan Korlan Korlane Nanchor Nanker Nankor NSC 8926 QMS 123 Phenchlorfos Phosphorothioic acid, 0,0-dimethyl 0-(2,4,5-trichlorophenyl) ester Remelt Ronne Rovan Smear, Trichlormetaphos Trichlorometafos Trolen Trolene Trolene 20L Troline Viozene. 

As noted previously, studies of the mechanisms of phosphate monoester solvolysis have been extended to the mechanisms of the analogous phosphorothioate ester solvolysis because the thiometaphosphate anion is believed to be more stable than the metaphosphate anion. Thus, a general method based upon P NMR spectroscopy for the configurational analysis of chiral thiophosphate monoesters (see Fig. 10) was described recently by Cullis and co-workers (38). 

Fenitrothion. Phosphorothioic acid 0,0-dimethyl 0-(3-methyl-4-nitrophenyl) ester O.O-dimethyl O-4-nitro-m-tolyl phosphorothioate O.O-dimethyl 0-(3-methyl-4-nitrophenyl) phosphorothioate O.O-dimethyl O-4-nitro-m-tolyl thiophosphate MEP metathion Bayer 41831 Bayer S 5660 ENT 23715 OMS 45 AC 47300 Accothion Cyten Cyfen Folithion Sumithion. C H, jNOjPS mol wt 277.25. C 38.99%, H 4.36%, N 5.05%, O 28.85%. P 11.17%, S... 

Methyl Parathion. Phosphorothioic acid 0,0-di-methyl 0-(4-nitrophenyl) ester O.O-dimethyl O-p-nltro-phenyl phosphorothioate O.O-dimethyl O-p-nitrophenyl thiophosphate dimethyl parathion parathion-methyl meta-phos E 601 ENT-17292 Dalf (obsolete) Fotidot-M Meta-cide Metron Nitrox 80 Penncap M. C,Hl(NOsPS mol wt 263.23. C 36.50%, H 3.83%, N 5.32%, O 30.39%, P lt.77%. S 12.18%. Prepn Fletcher el at., J. Am. Chem. Soc. 72, 2461 (1950). Manuf Faith, Keyes Sc Clark s Industrial Chemicals, F. A. Lowenheim, M. K. Moran, Eds. (Wiley-Intersci-ence. New York, 4th ed., 1975) pp 552-555. Toxicity data T. B. Gaines, Toxicol. Appl. Pharmacol. 14, 515 (1969). 

Diethyl 0-[4-(melhylsulfinyl)phenyl] phosphoro-thioate, AI3-24945 BAY 25141 Bayer 25141 BRN 2219515 Caswell No. 343 Chemagro 25141 Daconit Dasanit Diethyl p-methylsulfinylphenyl thiophosphate p,0-Diethyl O-p-(methylsuifinyl)phenyl thiophosphate EINECS 204-114-3 ENT 24,945 EPA Pesticide Chemical Code 032701 Fensulfothion HSDB 1580 OMS 37 0,0-Diaethyl-0-4-methylsulfinyl-phenyl-monothiophos-phat 0,0-Diathyl-0-4-methylsulfinyl-phenyl-monothio-phosphat 0,0-Diethyl 0-p-(methylsulfinyl)phenyl thiophosphate 0,0-Diethyl 0-4-methylsulphinylphehyl phosphorothioate 0,0-Diethyl 0-(p-(methylsulfinyl)-phenyl) phosphorothioate 0,0-Diethyl 0-(4-(methylsulfinyl)phenyl) phosphorothioate Phenol, p-(methylsulfinyl)-, 0-ester with 0,0-diethyl phosphoro-thioate Phosphorothioic acid, 0,0-diethyl 0-(4-(methylsulfinyl)phenyl) ester S 767 Terracur P VUAgT 96 ... 

Synonyms S-(diethylaminoethyl) C),0-di-ethyl phosphorothioate (2-diethylamino) ethylphosphorothioic acid 0,0-diethyl ester 0,0-diethyl S-(5-diethylaminoethyl) thiophosphate Citram Tetram... 

Synonyms 0,0-dimethyl 5-(ethylmercapto) ethyl thiophosphate phosphorothioic acid S-[2-(ethylthio)ethyl]- 0,0-dimethyl ester Metasystox Isometasystox Methyl isosys-tox Metasystox forte Methyl demeton thioester Demeton-S-methyl sulfide... 

Synonyms 0-(2,5-Dichloro-4-iodophenyl) 0,0-dimethyl phosphorothioate 3,4-Dichlorophenol, O-ester with 0-methyl methylphosphoramidothioate 0,0-Dimethyl-0-(2,5-dichloro-4-iodophenyl thiophosphate lodophos Jodfenphos Phenol, 3,4-dichloro-, O-ester with O-methyl methyl phosphoramidothioate Phosphorothioic acid, 0-(2,5-dichloro-4-iodophenyl) 0,0-dimethyl ester Empirical CsHsC IOsPS Properties Cryst. powd. sol. in kerosene m.w. 412.99 m.p. 76 C... 

Synonyms AAT AATP Diethyl-p-nitrophenyl monothiophosphate 0,0-Diethyl-0-4-nitrophenyl phosphorothioate 0,0-Diethyl-0-p-nitrophenyl phosphorothioate Diethyl-p-nitrophenylthionophosphate 0,0-Diethyl-p-nitrophenyl thiophosphate Diethyl parathion DNTP Ethyl parathion p-Nitrophenol, 0-ester with 0,0-diethylphosphorothioate Oleoparathion Parathion-ethyl Parathion liquid Phosphorothioic acid, 0,0-diethyl 0-(4-nitrophenyl) ester... 

Synonyms Phosphorothioic acid, tributyl ester Phosphorothioic acid, 0,0, 0"-tributyl ester Tri-n-butyl phosphorothioate Tributyl thiophosphate... 

Synonyms Phenyl phosphorothioate Phosphorothioic acid, 0,0,0-triphenyl ester TPPT Triphenyl phosphorothioate 0,0,0-Triphenyl phosphorothioate Triphenyl thiophosphate 0,0,0-Triphenyl thiophosphate Empirical CisHisOaPS Properties M.w. 342.35 Uses EP agent for lubricants adjuvant in lubricants for incidental food-contact use Regulatory FDA 21CFR 178.3570 Trade Name Synonyms Irgalube TPPT [Ciba Spec. Chems./Plastic Addit. http //WWW. cibasc. com]... 

Synonyms Bay 25141 Bayer 25141 Bayer S 161 Chemagro 25,141 Dasanit 0,0-Diethyl O-4-methylsulphinylphenyl phosphorothioate 0,0-Diethyl (9-p-methylsulphi-nylphenyl phosphorothioate 0,0-Diethyl O-p-methylsulphinylphenyl thiophosphate DMSP ENT 24945 OMS 37 Phosphorothioic acid 0,0-diethyl 0-(p-(methylsulfi-nyl)phenyl) ester Terracur P. 

Synonyms Bay 21097 Bayer 21097 Demeton-methyl sulfoxide Demeton-O-methyl sulfoxide Demeton-5 -methyl sulfoxide 0,0-Dimethyl 5 -(2-eththionylethyl) phospho-rothioate Dimethyl 5 -(2-eththionylethyl) thiophosphate 0,0-Dimethyl 5 -2-(ethylsulfi-nyl)ethyl phosphorothioate 0,0-Dimethyl S -2-(ethylsulfinyl)ethyl thiophosphate 0,0-Dimethyl iS-ethylsulphinylethyl phosphorothioate ENT 24964 dimethyl phosphorothioate Isomethylsystox sulfoxide Metaisosystox sulfoxide Metasystemox Metasystox-R Methyl demeton-O-sulfoxide Metilmercaptofosoksid Oxydemetonmethyl Phosphothioic acid 0,0-dimethyl S -2-(ethylsulfinyl)ethyl ester R 2170. 

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