Thiophosphoryl chloride reactions

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... 

Thiocarbonyl tetrachloride, i6, 21 Thionyl chloride, 45, 16, 98 Thiophosgene, 45, 21 Thiophosphoryl chloride, reaction with methylmagnesium bromide to yield tetramethylbiphosphine disulfide, 45,102 Toluenesulfonybromide, 46, 88 Trichloroacetyl fluoride, 46, 6 1,1,3-Trichloiio- -nonane, 46,104 Tricyclo[2.2.1.0 ]heptan-3-ol, 45,... 

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. 

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... 

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 ... 

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. 

The reaction of (-)-ephedrine (42) with thiophosphoryl chloride was reported to give 2-chloro-l,3,2-oxazaphospholidine 2-thione as the isomeric pair 101a,b, which could be separated by chromatography over silica gel [32] or recrystallization (Scheme 29) [55],... 

The reaction of 3 -amino-3 -desoxyadenosine 133 with thiophosphoryl chloride alTorded3, 5 -cyclothionophosphonate derivative 134 asamixture of P-diastereomcrs, which were separated by chromatography (Scheme 39) [70], The P-N bond cleavage,... 

Thiotraamidophosphoric acids (35) are isoelectronic with phosphoric acids and were initially reported from the reaction of phosphorus pentasulfide with primary amines at high temperatures.62 Subsequently, an improved synthesis for 35 with increased yields and milder conditions has been reported involving the room temperature reaction of thiophosphoryl chloride and primary amines (Equation 50).63 The most convenient route to the analogous selenium derivatives SeP(NHPh)3 is from the oxidation of P(NHPh)3 with elemental selenium (Equation 51).63 Also isoelectronic with phosphoric acids are dithio wamido-phosphoric acids (36), which can be prepared from the reaction of phosphorus pentasulfide with an excess of primary amine at 30°C in toluene (Equation 52).62 The selenium derivatives of 36 can be prepared in a similar reaction from phosphorus (V) selenide, although due to their increased acidity... 

The rate of reaction of phosphorus oxychloride with phenols to produce triaryl phosphates is increased by the addition of quaternary ammonium salts and the reaction temperature can be reduced without loss of overall yield [1,2]. The analogous reaction between phenoxide anions and thiophosphoryl chloride produces aryl phosphoro-dichloridothoates [3]. As with the acylation of enolizable (3-dicarbonyl compounds (3.3.12), phosphorylation leads to the predominant formation of the E-O-phos-phoryiated derivatives [4,5]. 

Although practical grade thiophosphoryl chloride obtained from Eastman Organic Chemicals will serve in this reaction, a much cleaner product is obtained if the thiophosphoryl chloride is redistilled (b.p. 122-123°). 

Tetramethylbiphosphine disulfide has been prepared by reaction of methylmagnesium halides with thiophosphoryl chloride. ... 

The activated phosphorus reagents 269 and 270 are conventionally prepared by the reaction of 2(3//)-oxazolone with the corresponding phosphorus chlorides in the presence of triethylamine. The phosphorus chlorides employed include phosphoryl chloride, thiophosphoryl chloride, mono- and dichlorophosphates, and phosphinic chloride (Fig. 5.66). 

Chloromethylphosphonothioic dichloride has been prepared by the reaction of chloromethylphosphonic dichloride with tetra-phosphorus decasulfide3-6 or with thiophosphoryl chloride under autogenous pressure3 6... 

Cyclothiophosphorylation. The diasteromers of myo-inositol-l, 2-cyclothio-phosphate (2) can be prepared by reaction of 1,4,5,6-tetraacetyl-myo-inositol (1) with thiophosphoryl chloride followed by deprotection and addition of KC1. 

Phosphorus Thiotrichloride or thiophosphoryl chloride, PSC13, has been prepared by many reactions —... 

Following phosphorylation using the Yoshikawa procedure, the reaction of pyrophosphate with the intermediate phosphorodichloridate followed by aqueous work-up provides a convenient one-pot synthesis for triphosphates. With slight modification to this procedure, thiophosphoryl chloride can be used in place of phosphoryl chloride to give 5 -( 1 -thio)triphosphates as a mixture of two diaste-reoisomers (.S p and Rp). Both procedures require the prior preparation of the DMF-soluble, bis(tri-n-butylammonium) salt of pyrophosphate. This is prepared as a 0.5 M solution, can be stored in the fridge and is converted to its terrafcis(tri-n-butylammonium) salt immediately prior to reaction. Rates of nucleoside phosphorylation vary considerably and it is necessary to monitor the formation of the phosphorodichloridate during the Yoshikawa procedure in order... 

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