Phosphorus sulfur trichloride

A number of non-routine reactions of halogenophosphines are worthy of note. The first aliphatic phosphenium cation featuring a phosphorus-sulfur bond (17) has been obtained by treatment of the chlorophosphine (18) with aluminium trichloride in dichloromethane solution. A new synthesis of acyclic chiral t-phosphines has been developed which employs selective, sequential alkylation of the chloro(amino) phosphines (19) by Grignard and organolithium reagents. The key intermediates (19) are readily prepared by the... 

Lead dioxide Aluminum carbide, hydrogen peroxide, hydrogen sulfide, hydroxylamine, ni-troalkanes, nitrogen compounds, nonmetal halides, peroxoformic acid, phosphorus, phosphorus trichloride, potassium, sulfur, sulfur dioxide, sulfides, tungsten, zirconium... 

Bischloromethyl ether has been prepared by saturation of formalin with dry hydrogen chloride by the reaction of paraformaldehyde with phosphorus trichloride or phosphorus oxychloride, by solution of paraformaldehyde in concentrated sulfuric acid and treatment with ammonium chloride or dry hydrogen chloride, and by suspension of paraformaldehyde in seventy or eighty percent sulfuric acid and treatment with chlorosulfonic acid. It is formed together with the asymmetrical isomer when methyl ether is chlorinated and when paraformaldehyde is treated with chlorosulfonic acid. The present method has been published. ... 

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. 

Powdered aluminium ignites in the vapour of arsenic trichloride or sulfur dichloride, and incandesces in phosphorus trichloride vapour [1], Above 80°C, aluminium reacts incandescently with diselenium dichloride [2], The powder ignites in contact with phosphorus pentachloride [3],... 

See Phosphorus trichloride Sulfur acids Phosphorus triiodide Sulfur acids... 

In absence of diluent or other effective control of reaction rate, the sulfoxide reacts violently or explosively with the following acetyl chloride, benzenesul-fonyl chloride, cyanuric chloride, phosphorus trichloride, phosphoryl chloride, tetrachlorosilane, sulfur dichloride, disulfur dichloride, sulfuryl chloride or thionyl chloride [1], These violent reactions are explained in terms of exothermic polymerisation of formaldehyde produced under a variety of conditions by interaction of the sulfoxide with reactive halides, acidic or basic reagents [2], Oxalyl chloride reacts explosively with DMSO at ambient temperature, but controllably in dichloromethane at -60°C [3]. 

Moller, T. et al., Inorg. Synth, 1954, 4, 72 During the preparation from phosphorus trichloride and sulfur, the quantity and quality of the aluminium chloride catalyst is critical to prevent the exothermic reaction going out of control. 

See Phosphorus tribromide Sulfur acids Phosphorus trichloride Sulfur acids See Other IODINE COMPOUNDS, HALOPHOSPHINES, NON-METAL HALIDES... 

Diselenium dichloride and seleninyl chloride both explode on addition of potassium [1,3], while the metal ignites in contact with phosphorus trichloride vapour or liquid [2], Mixtures of potassium with sulfur dichloride or sulfur dibromide, phosphorus tribromide or phosphorus trichloride, and with phosgene are shock-sensitive, usually exploding violently on impact. Potassium also explodes violently on heating with disulfur dichloride, and with sulfur dichloride or seleninyl bromide without heating [3]. 

Diphosphitylation of 2,4-0-methylene-D-glucitol (8) with phosphorus trichloride in dioxane gave 1,3 5,6-bis- 0-(chlorophosphitc) 9 (99.5%). Its amination with diethyla-mine in benzene-diethyl ether afforded the corresponding bis-amidophosphites 10. Their reaction with sulfur afforded three P-diastereomers of cyclic thiophosphate 11 in 24.8, 4.8, and 19.5% yields (Scheme 4) [19],... 

Reaction of Phosphorus Trichloride with 1,1,2-Trichloro-l-nitrosoethane in Sulfur Dioxide."... 

Nitropropane Nitrosyl fluoride Nitrosyl perchlorate Nitrourea Nitrous acid Nitryl chloride Oxalic acid See under Nitromethane chlorosulfonic acid, oleum Haloalkenes, metals, nonmetals Acetones, amines, diethyl ether, metal salts, organic materials Mercury(II) and silver salts Phosphine, phosphorus trichloride, silver nitrate, semicarbazone Ammonia, sulfur trioxide, tin(IV) bromide and iodide Furfuryl alcohol, silver, mercury, sodium chlorate, sodium chlorite, sodium hypochlorite... 

Suitable agents are chlorosulfonic acid, monohydrate, or concentrated sulfuric acid. Other methods include cyclization of phenylthioglycolic acid chlorides, which is afforded by Friedel-Crafts reaction with aluminum chloride, possibly in the presence of sulfuric acid/sodium chloride. The acid chloride is obtained from phenylthioglycolic acid with thionyl chloride or phosphorus trichloride. 

A -Unsubstituted 1,2,4-diazaphospholes (4) undergo A -alkylation by reaction with alkyl vinyl ether, sulfur ylides, and diazo compounds <95HAC403>. They react with acyl chlorides in a 2 1 molar ratio to give a mixture of the A -acylated diazaphosphole and the diazaphosphole hydrochloride. Preparative A -acyclation is achieved in presence of a tertiary amine. Sulfonyl chlorides and phosphorus trichloride also give A -substitution reactions (Scheme 2) <87TH 422-01 >. 

Chlorine readily combines with many nonmetals. Reaction with sulfur yields sulfur dichloride, SCI2 and with phosphorus the products are phosphorus trichloride, PCI3 and phosphorus pentachloride, PCI5. 

Reaction with phosphorus trichloride yields phosphorus trifluoride and with phosphoryl fluoride and sulfur trioxide, the product is phosphorus penta-fluoride ... 

Phosphorus trichloride reacts with concentrated sulfuric acid forming chlorosulfuric acid and metaphosphoric acid ... 

PCI3 + 3NH3 P(NH2)3 + 3HC1 + PCI3 Reaction with sulfur forms phosphorus trichloride sulfide ... 

Some reactions of 2,2 -bipyridine /V-oxides have been reported. The l,T-dioxide is nitrated readily to 4,4 -dinitro-2,2 -bipyridine 1,T-dioxide. ° ° °" 2,2 -Bipyridine 1-oxide is also nitrated in the 4 position. The nitro groups in 4,4 -dinitro-2,2 -bipyridine l,T-dioxide are reactive, being replaced by chlorine with concentrated hydrochloric acid," by bromine with acetyl bromide, by hydroxyl with dilute sulfuric acid, and by alkoxy groups with sodium alkoxides. Some of the dialkoxy derivatives are useful catalysts for the oxidation of aromatic compounds. The dinitro dioxide is deoxygenated to 4,4 -dinitro-2,2 -bipyridine with phosphorus trichloride in chloroform, and other substituted l,T-dioxides behave similarly, but with phosphorus trichloride alone, 4,4 -dichloro-2,2 -bipyridine results. The dinitro dioxide is reduced by iron powder in acetic acid to 4,4 -diamino-2,2 -bipyridine, whereas 4,4 -dichloro-2,2 -bipyridine l,T-dioxide is converted to its 4,4 -diamino analogs with amines. Related reactions have been described. ... 

Black powder. Potassium nitrate. Red arsenic. Sulfur, Antimony Phosphorus trichloride. Methyl disulfide. Methyl iodide. Toluene, Sodium fluoride. Isopropyl alcohol... 

Nitric acid. Sulfuric acid, N-Methylhydroxy acetamide Phosphorus oxytrichloride. Benzene, Neopentyl glycol. Pyridine, Petroleum ether. Ammonium fluoride Thiophosphorus trichloride. Benzene, Neopentyl glycol. Pyridine, Petroleum ether. Ammonium fluoride Nitric acid. Sulfuric acid. Glycerol, Magnesium sulfate Anhydrous hydrazine. Cyanogen bromide. Isopropyl alcohol. Sodium nitrite. Sodium bicarbonate. Copper nitrate trihydrate. Nitric acid. Diethyl ether... 

Manufacture. The manufacture of sulfur dichloride is similar to that of sulfur monochloride, except that the last stage of chlorination proceeds slowly and must be conducted at temperatures below 40°C. The preparation of a high assay sulfur dichloride requires special techniques, eg, continuous chlorination during distillation or distillation with traces of phosphorus trichloride or phosphorus pentasulfide [1514-80-5] (162—164). Cmde product containing 80 wt % sulfur dichloride to which is added 0.1 wt % phosphorus trichloride can be distilled to yield a 98—99 wt % pure sulfur dichloride, which can be stored for weeks at room temperature without appreciable change. 

Synthesis of sulfur tetrafluoride by fluorination of sulfur monochloride with elemental fluorine in the presence of antimony(III) chloride or phosphorus trichloride as a catalyst has also been reported 22-23 sulfur dichloride, which is formed as the byproduct, is converted back to sulfur monochloride in an absorber filled with granulated sulfur and then recycled. 

Numerous adducts of MX4 with nitrogen, phosphorus, arsenic, oxygen and sulfur donors have been obtained, mainly for niobium with X = CI or Br7 (Tables 29-33). The absence of MF4 adducts, except for [NbF4(py)2],511 may be due less to their instability than to a lack of investigations. An ill-defined fluoro trichloride complex, [NbCl3F(MeCN)2.65], has also been reported.512... 

EXERCISE 26. SULFUR MONOCHLORIDE, S2C12 PHOSPHORUS TRICHLORIDE, PClsj STANNIC CHLORIDE, SnCl4... 

The preparation of furans by acid catalyzed dehydration of 1,4-diketones followed by cyclization of the monoenol has been comprehensively reviewed (69RCR389). This method of furan preparation is useful for all 1,4-diketones which are not sterically hindered with the highly hindered l,4-bis(2,4,6-triisopropylphenyl)-l,4-butanedione no cyclization occurs (50JA5754). Although sulfuric acid is normally used for cyclization, hydrochloric acid was employed in the conversion of a 1,2-diacylethylene to a furylacrylic acid derivative (59MIP31200). Other reagents used for this purpose include polyphosphoric acid, phosphorus trichloride, zinc chloride and DMSO. Both DMSO and phosphoric esters provide neutral... 

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