Thiophosphate compounds

Thus the condensation of dichloroether or chloroacetone fails to give the parent compound, 2-hydroxythiazole (158a), Rj = R2 = R3 = H (221). However, 2-hydroxythiazole can be obtained in 12% yield from chloro-acetaldehyde (386). The condensation of ammonium thiocarbamate with cf-chloroketones gives the corresponding 2-hydroxy derivatives in 25 to 70% yields (76, 221, 304, 412) (Table 11-24). These compounds condensed with ClP(S)(OEt)2 give the corresponding 2-thiazolyl-thiophosphates (791). 

The reaction of thioethers with ethyleneimine in the presence of acid yields sulfonium compounds. The reaction is reversible under alkaline conditions (125). Compounds in which double-bonded sulfur can exist in tautomerism with a form having a free SH group, such as thiourea (126,127), thiocarboxyhc acids (128), and thiophosphates (129), react to give aminoaLkylated products. The P-aminoethyl thiocarboxylate rearranges to give the amide. 

Titanium(III) chloride (particularly in slightly alkaline medium) reduces the p-nitro groups of the thiophosphate insecticides to amino groups, which are then reacted with nitrite in acid mediiun in a second step to yield a diazonium compound as intermediate. This is then coupled to N-(l-naphthyl)-ethylenediamine dihydrochloride to yield an azo dye [3]. In the case of benzodiazepines the first reaction step includes an additional acid hydrolysis to the corresponding benzophenone derivative [2]. 

Tetrabromophthalein ethyl ester potassium salt is a pH indicator that changa from blue to yellow in the pH range 4.2-3. It is known that proteins and alkaloids fordli blue-colored salt-like adsorption compounds with this indicator that are not destroyeti by weak acids [3]. Thiophosphate pesticides and triazines possibly form similar conhi pounds. 

The widespread commercial use of DDT [l,l,l-trichloro-2,2-bis-(p-chlorophenyl)-ethane] and the potentialities of the more recently developed parathion (0,0-diethyl O-p-nitrophenyl thiophosphate) have placed emphasis on such investigations concerning these compounds. 

It has been reported that the compound resulting from Equation 26 may be hazardous to distill 12). However, the compound resulting from Equation 27 has been prepared and attempts have been made to add sulfur to this phosphite in order to obtain the desired thiophosphate. Similar reactions have been reported in the literature (2). A very vigorous reaction takes place. Another method is shown in Equations 29 and 30. 

In Formula 33 is pictured a completely mixed ester of a thiophosphate in which all groups are different. The thiophosphoryl chloride method was used for preparing such compounds. It was of interest to see whether or not other compounds could be prepared by the condensation of a dialkyl chlorothiophosphate with a phenol to give products such as shown in Formulas 34 to 36. 

In compounds (333) and (336) the amines substitute one of the dithiophosphate ligands to form a NiN4S2 core with the second dithiophosphate ligand serving as a counterion. Coordination number 5 is rare, but is found for complex (345) where one of thiophosphates switched to a monodentate coordination,879 and in compound (346) where only one additional phosphine adduct coordinates to Ni.880... 

Although no extensive data are available for evaluating the toxicity of phosphine selenides, these compounds are similar to organophosphates and -thiophosphates, many of which are insecticides and related to the so-called nerve gases. 3 A high toxicity for mammals has been noted in (RO)2P(Se)X compounds 3 Consequently, the phosphine selenides should be handled carefully. 

Hydroperoxide decomposing antioxidants. These are compounds that react with hydroperoxides without forming free radicals sulfides, phosphites, arsenites, thiophosphates, carbamates, and some metal complexes. Reactions with hydroperoxides can be either stoichiometric (typical of, for example, sulfides and phosphites) or catalytic (typical of chelate metal complexes). 

A combined addition of a chain-breaking inhibitor and a hydroperoxide-breaking substance is widely used to induce a more efficient inhibition of oxidative processes in polyalkenes, rubbers, lubricants, and other materials [3 8]. Kennerly and Patterson [12] were the first to study the combined action of a mixture, phenol (aromatic amine) + zinc dithiophosphate, on the oxidation of mineral oil. Various phenols and aromatic amines can well serve as peroxyl radical scavengers (see Chapter 15), while arylphosphites, thiopropionic ethers, dialkylthio-propionates, zinc and nickel thiophosphates, and other compounds are used to break down hydroperoxide (see Chapter 17). Efficient inhibitory blends are usually prepared empirically, by choosing such blend compositions that induce maximal inhibitory periods [13],... 

Synonyms AAT AATP AC 3422 ACC 3422 AI3-15108 Alkron Aileron American Cyanamide 3422 Aphamite Aralo B 404 Bay E-605 Bayer E-605 Bladan Bladan F BRN 2059093 C-06604 Caswell No. 637 CCRIS 493 Compound 3422 Corothion Corthion Corthione Danthion DDF 0,0-Diethyl-0-4-nitrophenyl phosphorothioate 0,0-Diethyl 0-p-nitrophenyl phosphorothioate Diethyl-4-nitrophenyl phosphorothionate Diethyl-p-nitrophenyl thionophosphate 0,0-Di-ethyl-0-4-nitrophenyl thionophosphate 0,0-Diethyl-O-p-nitrophenyl thionophosphate Diethyl-p-nitrophenyl thiophosphate 0,0-Diethyl-O-p-nitrophenyl... 

The author hopes that this chapter has convinced the readers of the value of homogeneous catalysis for the synthesis of organophosphorus compounds and for organo-heteroatom compounds in a broader sense. Hydrosilylation and hydroboration are indispensable modern synthetic reactions in this category. The H-P addition reactions herein described joins them as a third member. Although this chapter does not cover, the addition reactions of the S-P and Se-P bonds in thiophosphates [39] and selenophosphates [40] to alkynes also proceed in the presence of transition metal catalysts. In view of the wide use of phosphorus compounds, the new procedures will find practical applications. 

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