Phosphorus sulfochloride

Phosphorus sulfochloride, 79 42 Phosphorus sulfohalides, physical properties of, 79 43t Phosphorus-sulfur bonds, 79 26-27 Phosphorus tetroxide, 79 52 Phosphorus tribromide, physical properties of, 4 325... 

Phosphorus pentasulfide bensulide, fonofos, tebuthiuron, tetrapropyl dithiopyrophosphate, thiazopyr, see DEPA, DEPCT, DMPA, DMPCT Phosphorus pentoxide chlorotalonil, TEPP Phosphorus sulfochloride see Thiophosphorylchloride... 

Phosphorus(V) oxybromide, 2 151 Phosphorus(V) sulfobromide, 2 153 Phdsphorus(V) sulfobromodifluo-ride, formation of, from phosphorus (V) sulfobromide, 2 154 Phosphorus (V) sulfochloride, 4 71 from phosphorus (III) chloride, aluminum chloride, and sulfur, 4 71... 

Several procedures have been reported for the synthesis of phosphorus (V) sulfochloride. These include the reaction of phosphorus(V) chloride with hydrogen sulfide,1,2 of phosphorus (III) chloride with sulfur,3 4 of carbon tetrachloride with phosphorus(V) sulfide,5 and of phosphorus(V) chloride with phosphorus(V) sulfide.5 The second and fourth methods form the bases for the two syntheses presented here. 

The older literature reports the synthesis of phosphorus-(V) sulfochloride by reaction of phosphorus (V) chloride with phosphorus (V) sulfide in a sealed tube at 120°. Experience has shown that pressures as great as 700 p.s.i. may result under these conditions, indicating that an autoclave or bomb should be used. In the absence of these, the reactor shown in Fig. 8 is suitable. It consists of an oil bath containing a lecture bottle fitted with a pipe plug (iron pipe size, % in.), a thermometer, and a knife type of immersion heater. Although no difficulty has been experienced in the use of this reactor, it is well to keep it behind a barricade during the reaction. 

Phosphorus(V) sulfochloride is a colorless, fuming liquid with boiling point 125° and specific gravity 1.635. The alpha form solidifies at —40.8°, while the beta form solidifies at —36.2°.7 The compound hydrolyzes slowly in water and rapidly in alkaline solution. In water, the hydrolysis products are orthophosphoric acid, hydrochloric acid, and hydrogen sulfide. Phosphorus (Y) sulfochloride is soluble in benzene, carbon tetrachloride, carbon disulfide, and chloroform. It reacts with ethanol, yielding O-ethyl dichlorothiophosphate8 (synthesis 25). 

Fia. 8. Apparatus for the preparation of phosphorus (V) sulfochloride from phosphorus(V) sulfide and phosphorus (V) chloride. 

Phosphorus (V) sulfochloride, synthesis 24 0-Ethyl dichlorothiophosphate, synthesis 25... 

Applications In 1994 about half of the Phosphorus(III) chloride consumed in the USA was utilized in the manufacture of the intermediate phosphorous acid, a further 19.4% to phosphorus(V) oxychloride. Di and trialkylphosphonates, triarylphosphonate, pho.sphorus(V) sulfochloride and phosphorus(V) chloride are also manufactured directly from pho.sphorus(III) chloride. Broken down according to the field of application of the end products, the consumption of phosphorus(IIl) chloride is the USA in 1994 53.6% was utilized for pesticide production (mainly for glyphosphate), 18% for the manufacture of water treatment chemicals (phosphonic acids) and tensides (acid chlorides of fatty acids and secondary products), 17.1% in the manufacture of polymer additives (flame retardants, stabilizers etc.) as well as small quantities for the production of hydraulic fluids, lubricants and additives for lubricating oils. 

Phosphorus(V) sulfochloride can either be manufactured from phosphorus(lll) chloride and sulfur at 180°C in an autoclave or by passing phosphorus(III) chloride vapor through molten sulfur ... 

Catalysts such as e.g. aluminum chloride reduce the reaction temperature to such a degree that the reaction can be carried out in phosphorus(V) sulfochloride. Purification is by distillation. 

Application, Phosphorus(V) sulfochloride is mainly utilized in the manufacture of ester chlorides of thiophosphoric acids (precursors for pesticides). 

Alternatively the ester chloride can be produced from phosphorus(V) sulfochloride and an alcohol. 

Carbon suboxide, 52 Carbonylation, 148, 149, 216 Carbonyl chlorofluoride, 48, 54 Carbonyl cyanide, 60-61 N,N -Carbonyldiimidazole, 61 1,1-Carbonyldi-l,2,4-triazole, 61 N-Carbonylsulfamic acid chloride (N-Carbonylsulfamyl chloride), 61 Carboxamides, 270 Carboxamine-N-sulfochlorides, 70 p-Carboxybenzenediazonium chloride, 62 p-Carboxybenzenesulfonazide, 62 Carboxylation, 15, 16 Carboxylic acid anhydrides, 133 Carboxylic acid N,N-dimethylamines, 153 Carboxylic anhydrides, 409-410 p-Carboxyphenylhydrazones, 62 Cardenolides, 130, 131 (S-Carotene, 19 /-Carvone, 451, 452 i//-Caryophyllene, 149, 150 Catechol, 65, 233 Catechol amines, 159 Catechyl phosphorus tribromide, 63 Catechyl phosphorus trichloride, 63 Cis-Cecropia juvenile hormone, 261 Cedrene, 234, 235 a-Cedrene, 349 /3-Cedrene, 349 Cendranoxide, 234, 235 Cephalosporin C, 48 Ceric ammonium nitrate, 63-65 Ceric sulfate. 65 Cesium fluoride, 346 trans-Chalcone oxide, 422 Chalcone phenylhydrazones, 257, 258 Chalcones, 406 Chloramine, 65-66, 69 Chloranil, 66-67, 113, 116, 401,454... 

Three hundred milliliters of a cool aqueous solution containing 40 g. of sodium hydroxide (1 mol) is added to 17.5 ml. of phosphorus(V) sulfochloride (0.17 mol)6 in a 1-1. three-necked round-bottomed flask equipped with a reflux condenser, a thermometer, and a motor-driven stirrer. The mixture is heated at 103 to 109° for 15 to 20 minutes, until the phosphorus (V) sulfochloride layer has disappeared. The solid hydrated sodium monothio-... 

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