Sulfur monochloride, reaction with benzene

One route to thianthrene (70 Z, Z = S) involves reaction of sulfur monochloride with benzene over aluminum chloride (66HC(21-2)1155). 

A general route to phenoxathiins 85 (Z = O, Z = S) utilizes the reaction of diphenyl ethers with sulfur. One route to thianthrene 85 (Z, Z = S) involves reaction of sulfur monochloride with benzene over aluminum chloride. Likewise, tf-methoxyphenol reacts with sulfur dichloride to give, depending on the rate of addition of the reactant, 2,8-dihydroxy-3,7-dimethoxythianthrene 89 or l,6-dichloro-2,7-dihydroxy-3,8-dimethoxythianthrene 90 <1997JCM272>. 

Cyclopropyl ketones and lactams as well as amides of cyclopropanecarboxylic acids were converted to the corresponding thiocarbonyl compounds on reaction with 2,4-bis(4-methoxyphenyl)-l,3,2,4-dithiadiphosphetane-2,4-dithione (Lawesson s reagent) in benzene or toluene the yields were good. For example, reaction of lactam 1 to give thione 2. Thiones were also formed when hydrazones were treated with sulfur monochloride. ... 

TP here are very few examples in the literature of poly (arylene polysulfides). Perhaps the first such preparation was that of Fried el and Crafts (I), in which benzene reacted with sulfur in the presence of aluminum chloride. Within the last 15 years, several poly(arylene polysulfides) have been prepared by related reactions in which various aromatic compounds reacted with sulfur monochloride in the presence of Friedel-Crafts catalysts (2, 3, 4). A variation of this reaction has also been reported using a bifiunctional sulfenyl chloride (5) ... 

Summary Sulfur monochloride is readily prepared by reacting dry chlorine gas with powdered sulfur. The reaction is carried out in an inert solvent such as methylene chloride or benzene. After the reaction is complete, the reaction mixture is quickly filtered, and then distilled to remove the methylene chloride or benzene solvent. 

A mixture of 120 g. (0.89 mole) of sulfur monochloride and 200 g. (2.56 moles) of benzene is heated on a water bath with stirring while 100 g. (0.75 mole) of anhydrous aluminum chloride is added slowly in small portions. The reaction mixture is heated for 2 hours longer, then cooled, and a mixture of crushed ice and hydrochloric acid is added slowly. The mixture is steam-distilled for 3 hours. The solid residue in the flask is triturated with ether, and the remaining solid is recrystallized two times from methyl ethyl ketone to give thian-threne melting at 154° in 25-30% yield. 

ESTANO (Spanish) (7440-31-5) Finely divided material is combustible and forms explosive mixture with air. Contact with moisture in air forms tin dioxide. Violent reaction with strong acids, strong oxidizers, ammonium perchlorate, ammonium nitrate, bis-o-azido benzoyl peroxide, bromates, bromine, bromine pentafluoride, bromine trifluoride, bromine azide, cadmium, carbon tetrachloride, chlorine, chlorine monofluoride, chlorine nitrate, chlorine pentafluoride, chlorites, copper(II) nitrate, fluorine, hydriodic acid, dimethylarsinic acid, ni-trosyl fluoride, oxygen difluoride, perchlorates, perchloroethylene, potassium dioxide, phosphorus pentoxide, sulfur, sulfur dichloride. Reacts with alkalis, forming flammable hydrogen gas. Incompatible with arsenic compounds, azochloramide, benzene diazonium-4-sulfonate, benzyl chloride, chloric acid, cobalt chloride, copper oxide, 3,3 -dichloro-4,4 -diamin-odiphenylmethane, hexafluorobenzene, hydrazinium nitrate, glicidol, iodine heptafluoride, iodine monochloride, iodine pentafluoride, lead monoxide, mercuric oxide, nitryl fluoride, peroxyformic acid, phosphorus, phosphorus trichloride, tellurium, turpentine, sodium acetylide, sodium peroxide, titanium dioxide. Contact with acetaldehyde may cause polymerization. May form explosive compounds with hexachloroethane, pentachloroethane, picric acid, potassium iodate, potassium peroxide, 2,4,6-trinitrobenzene-1,3,5-triol. 

---