Thiophosphorylations

Radicals analogous to the above containing other chalcogens in place of oxygen are named by adding the prefixes thio-, seleno-, and so on for example, PS, thiophosphoryl CS, thiocarbonyl. 

Properties and Reactions. Phosphoms sulfochloride [3982-91-0] (thiophosphoryl chloride), PSCI3, is a colorless fuming Hquid andis made by the reaction of phosphoms trichloride with sulfur and by the reaction of PCI3 with P2S3. Phosphoms sulfochloride is dimorphic in the soHd state. It reacts with water, forming either phosphoric acid or dichlorothiophosphoric acid [14500-94-8] depending on the reaction conditions. 

Starch in aqueous suspension may react to form diesters with phosphoms oxychloride, phosphoms pentachloride, and thiophosphoryl chloride... 

DIMETHYL CHLOROTHIOPHOSPHATE sea DIMETHYL THIOPHOSPHORYL-DIMETHYL DICHLOROSILANE DIMETHYL ETHER... 

DBU, A,0-bis(trimethylsilyl)acetamide." Thiophosphorylated derivatives are cleaved more rapidly than the phosphorylated counterpart. 

Table 12.4 Some phosphoryl and thiophosphoryl halides and pseudohalides...

Most of the phosphoryl and thiophosphoryl compounds are colourless gases or volatile liquids though PSBt3 forms yellow crystals, mp 37.8°, POI3 is dark violet, mp 53°, and PSI3 is red-brown, mp 48°. All are monomeric tetrahedral (C y) or pseudotetrahedral. Some physical properties are in Table 12.4. The P-O interatomic... 

In addition to the monophosphorus phosphoryl and thiophosphoryl compounds discussed above, several poly-phosphoryl and -thiophosphoryl halides have been characterized. Pyrophos-phoryl fluoride, 0=PP2—O—P(=0)p2 (mp —0.1°, bp 72° extrap) and the white crystalline cyclic tetramer [0=P(F)—0)4 were... 

A solution of 30.3 parts of triethylamine and 12.9 parts of ethylenimine in 180 parts of dry benzene is treated with a solution of 16.9 parts of thiophosphoryl chloride in 90 parts of dry benzene at 5°C to 10°C. Triethylamine hydrochloride is filtered off. The benzene solvent is distilled from the filtrate under reduced pressure and the resulting crude product is recrystallized from petroleum ether. The N,N, N"-triethylenethiophosphoramide had a melting point of 51.5°C. 

Methylene 2 hexanone, 47, 87 5 Methyl 5 hexen 2-one, 47, 87 Methyl hvdrazine, 46, 85 Methyl isocyanide, 46, 7S Methy lmagnesium bromide, reaction with bis(10,9 borazarophenan-thryl) ether, 46, 67 reaction w ith thiophosphoryl chloride, 45,102... 

Thiocarbonyl tetrachloride, 46, 21 m Thiocresol (Warning), 47, 107 Thionyl chloride, 46, 16 98 Thiophosgene 46, 21 Thiophosphoryl chloride, reaction with methylmagnesium bromide to i lelci tetramethylbiphosphine disulhdc 46,102... 

CCI2S 463-71-8) see Tizanidine Tolnaftate thiophosphoryl chloride (Cl,PS 3982-91-0) see Thiotepa thiosalicylic acid... 

Naskar, M., Debnath, S.C., and Basu, D.K. Effect of Bis (Diisopropyl) Thiophosphoryl Disulfide on the Co-Vulcanization of Carboxyhc Acrylonitrile Butadiene Rubber and Ethylene Propylene Diene Rubber Blends. Rubber Chem. Technol. 75(3), 309-322, July/August 2002. 

CA-isoprene rubber cured with bis(dusopropyl)thiophosphoryl disulfide (DIPDIS) shows results at 160°C, producing a predominantly monosulfidic network structure [14]. Similar work on heat-resistant network structures has been carried out on other synthetic rubbers. For example, a sulfur-less system using 1 phr TBBS, 2.0 phr DTDM, and 0.4 phr TMTD in SBR gives the best aging resistance [15]. 

A"-Ray structure determinations (see Chapter 11 for details) have been reported for triphenylphosphine oxide, tri-o-tolylphosphine oxide, sulphide, and selenide, and for cw-2,2,3,4,4-pentamethyl-l-phenylphos-phetan-1-oxide (5). Electron spectroscopic studies of phosphorus oxychloride and thiophosphoryl chloride in the gaseous state, and n.m.r., i.r., and u.v. spectra of phosphine sulphides have appeared. Dipole moments have been used to define the stereochemistry of 2-cyanoethylphosphine oxides, such as (6), which is shown in its preferred conformation. 

Grignard reactions have been used in the preparation of l-(dialkyl-phosphinyl)- ,3-dienes, e.g. (11), which are intermediates in the synthesis of antiflame polymers. Double-resonance n.m.r. techniques have been applied to the study of the reactions between thiophosphoryl halides and Grignard reagents. For example, the reaction between methylmag-nesium iodide and t-butyldibromophosphine sulphide gave the mixed... 

Thiophosphoryl chloride and phenylphosphonothioic dichloride give adducts with a,a -bipyridyl and ethylenediamine, the stoicheiometry... 

Irradiation of thiophosphoryl chloride in alkanes at 260 nm leads to the formation of phosphonothionic dichlorides (63a), probably via initial P— Cl... 

Reactions of the same halogenophosphazenes with ammonia were also described, in which halide-ion displacement took place at the phosphazenyl group rather than at the thiophosphoryl group ... 

With phosphorus trichloride, a rather complex reaction results partly in the formation of [PhaP N uPPha PPhCl]+ Cl. The reactivity of the phosphorus(iii) atom is also demonstrated by its ability to desulphurize thiophosphoryl chloride, and its ready reactions with Group VI elements, diborane, and carbon disulphide ... 

The ligands N-[bis(isopropoxy)thiophosphoryI]thiobenzamide and N-[bis(isopro-poxy)thiophosphoryl]-N -phenylthiourea can be deprotonated with the acetylacetonate gold(III) derivative [Au(C6F5)2(acac)] [26] giving the corresponding pentafluorophenyl complexes with the ligand acting as a chelate one [192]. 

There have apparently been no recent developments in reagents for desulphurizing sulphoxides that use pentavalent phosphorus compounds. Reagents that were reviewed in 1984 include phosphorus pentasulphide, thiophosphoryl bromide, Lawesson s reagent (1), and phosphorus pentachloride in the presence of a trap for CD ions. The traps used included an enamine or an N, JV-dialkylaniline. Presumably, the net effect of this reaction is to generate phosphorus trichloride in situ. The three thiophosphorus reagents obviously function because the P=S bond is some 150 kJ moD weaker than the P=0 bond . 

Change in the way a reaction occurs because of inappropriate temperatures. At 20 C nitric acid converts mesitylene into 3,5-dimethylbenzoic acid without danger, but at 115°C the explosive 1,3,5-tris(nitromethyl)benzene is formed. Excessive heating of thiophosphoryl trichloride with pentaerythritol at 160°C leads to the formation of phosphine, which combusts spontaneously. 

Equations 2, 3, and 4 summarize the method proposed by the Germans for preparing parathion (compound E-605). Schrader 13) has reported that thiophosphoryl chloride was synthesized from phosphorus trichloride and sulfur by heating at 130° in a lead-lined autoclave. Woodstock and Adler 14) carried out a similar reaction at 150° to 160° C. 

In Equation 6, a method is shown by which, Woodstock and McDonald (IS) report, thiophosphoryl chloride can be obtained. Equation 7 shows a related method (16) for the preparation of this intermediate. 

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