Thiophosphorylations thiophosphoryl chloride

Thiophosphorylation. Thiophosphoryl chloride will thio-phosphorylate amines, alcohols," amino alcohols, diols, and diamines. The rate of reaction decreases as each chlorine atom in replaced thus it is possible to replace each chlorine atom with a different substituent under controlled reaction conditions. Thiophosphoryl derivatives of chiral amino alcohols have been studied extensively as stereochemical probes for the stepwise hydrolyses and alcoholysis of thiophosphates (eq 2), which can lead to the... 

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... 

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... 

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. 

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... 

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. 

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. 

Weber (8) states that the intermediate thiophosphoryl chloride can be obtained from phosphorus pentachloride, as shown in Equation 10. 

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. 

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]. 

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,... 

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. ... 

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