Aluminum chloride benzene-sulfur reaction

The earliest reported reference describing the synthesis of phenylene sulfide stmctures is that of Friedel and Crafts in 1888 (6). The electrophilic reactions studied were based on reactions of benzene and various sulfur sources. These electrophilic substitution reactions were characterized by low yields (50—80%) of rather poorly characterized products by the standards of 1990s. Products contained many by-products, such as thianthrene. Results of self-condensation of thiophenol, catalyzed by aluminum chloride and sulfuric acid (7), were analogous to those of Friedel and Crafts. 

Excess benzene stops the reaction at the monoalkylated stage and prevents the polymerization of propylene. The cumene is separated by distillation, boiling point 153°C. Other catalysts that have been used are aluminum chloride and sulfuric acid. 

In early work on organosulfur compounds, Duess (I) and Hil-ditch (2) reported the preparation of various aromatic disulfides by condensation reactions of thiophenol on treatment with aluminum chloride and sulfuric acid, respectively. Macallum (3) was the first to report the preparation of a phenylene sulfide polymer. His procedure involved the reaction of sulfur, sodium carbonate, and dichlorobenzene in a sealed vessel. Polymers made by this scheme generally have more than one sulfur atom between benzene rings, as indicated by the structure —( C6H4S )w-. 

Cyclohexylbenzene has been prepared by the hydrogenation of biphenyl1 and of cyclohexenylbenzene2 over nickel, by the reaction of cyclohexyl chloride3 or bromide4 with benzene in the presence of aluminum chloride, and by the addition of benzene to cyclohexene in the presence of aluminum chloride,5 sulfuric acid,6 or boron halides.7... 

The first reported assignment of the PPS stmcture to reaction products prepared from benzene and sulfur in the presence of aluminum chloride was made by Genvresse in 1897 (8). These products were oligomeric and contained too much sulfur to be pure PPS. Genvresse isolated thianthrene and an amorphous, insoluble material that melted at 295°C. These early synthetic efforts have been reviewed (9—11). 

Friedel-Grafts Reaction. Until quite recently, the manufacture of anthraquiaone ia the United States was by the Friedel-Crafts reaction benzene [71-43-2] and phthaUc anhydride [85-44-9] condense ia the preseace of anhydrous aluminum chloride to give o-benzoylbenzoic acid [85-52-9] which, on treatment with concentrated sulfuric acid, is converted iato anthraquiaoae ia high yields and purity (33). 

Reactions other than those of the nucleophilic reactivity of alkyl sulfates iavolve reactions with hydrocarbons, thermal degradation, sulfonation, halogenation of the alkyl groups, and reduction of the sulfate groups. Aromatic hydrocarbons, eg, benzene and naphthalene, react with alkyl sulfates when cataly2ed by aluminum chloride to give Fhedel-Crafts-type alkylation product mixtures (59). Isobutane is readily alkylated by a dipropyl sulfate mixture from the reaction of propylene ia propane with sulfuric acid (60). 

The principal use of the alkylation process is the production of high octane aviation and motor gasoline blending stocks by the chemical addition of C2, C3, C4, or C5 olefins or mixtures of these olefins to an iso-paraffin, usually isobutane. Alkylation of benzene with olefins to produce styrene, cumene, and detergent alkylate are petrochemical processes. The alkylation reaction can be promoted by concentrated sulfuric acid, hydrofluoric acid, aluminum chloride, or boron fluoride at low temperatures. Thermal alkylation is possible at high temperatures and very high pressures. 

Ethyl benzoylacetate has been prepared by the condensation (by means of sodium ethylate) of ethyl acetate with ethyl benzoate,1 acetophenone with ethyl carbonate,2 and acetophenone with ethyl oxalate, with subsequent heating 3 by treatment of ethyl phenylpropiolate4 or a-bromocinnamic acid 5 with concentrated sulfuric acid, and of ethyl diazoacetate with benzalde-hyde 6 by the condensation of benzene with the monoethyl ester of malonyl monoacid chloride and aluminum chloride,7 of benzoyl chloride with the product of the reaction of magnesium and ethyl chloroacetate in ether,8 of alcohol on benzoylacetimino ethyl... 

Phenylnaphthalene has been prepared by the reaction of a-halonaphthalenes with mercury diphenyl3 6 or with benzene in the presence of aluminum chloride,6 and by means of the Gri-gnard synthesis, starting with either bromobenzene, cyclohexyl chloride, and a-tetralone 7 or with a-bromonaphthalene and cyclohexanone.6 8 9 Dehydrogenation of the reduced naphthalene has been accomplished by the use of sulfur,6 bromine,8 platinum black, or selenium.7 The formation of the hydrocar-... 

Reactions involving sulfur-linked substituents have been exclusively dealkylations of S-alkyl substituents to yield a thiocarbonyl group. Debenzyl-ations under mild conditions with aluminum chloride in benzene were mentioned earlier (Section IV,A,2,a). Pyridine demethylates salts 137 selectively to give 175. ° ... 

Cyclization (Scheme 8) was accomplished using either phosphoryl chloride or aluminum chloride. A range of substituents were introduced into the benzene ring (alkyl, aryl, or CN) or the 3- or 4-position (alkyl or aryl) and selenium successfully replaced sulfur in these reactions. 

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>. 

It was mentioned earlier in this chapter that acid amides and nitrocompounds form conducting solutions in liquid ammonia and hydrazine the ionization in these cases is undoubtedly accompanied by, and is associated with, compound formation between solute and solvent. The same is true of triphenylmethyl chloride which is a fair electrolytic conductor when dissolved in liquid sulfur dioxide it also conducts to some extent in nitromethane, nitrobenzene and acetone solutions. In chloroform and benzene, however, there is no compound formation and no conductance. The electrolytic conduction of triphenylmethyl chloride in fused aluminum chloride, which is itself a poor conductor, appears to be due to the reaction... 

Dry hydrogen chloride (about 5 g.) is passed into a suspension of 200 g. (1.50 moles) of anhydrous aluminum chloride in 400 g. of benzene, and then 126 g. (1.97 moles) of dry gaseous sulfur dioxide is introduced into the mixture Hood). After standing 12 hours at room temperature, the reaction mixture is poured on crushed ice and a solution of 260 g. (6.50 moles) of sodium hydroxide in 1 1. of water is added. The resulting mixture is heated on a water bath under a reflux condenser until the yellow particles of the aluminum chloride-benzenesulfinic acid salt have disappeared. The mixture is steam-distilled to remove excess benzene (about 250 g. is collected), and carbon dioxide is passed into the reaction mixture to cause precipitation of the alumina. After filtration the filtrate is evaporated and concentrated hydrochloric acid is added to the cold solution to precipitate the benzenesulfinic acid. A yield of 170 g. (80%) of pure product melting at 83° is obtained. 

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. 

For chlorination in the liquid phase, chlorine gas is led into the liquid and is dispersed in the form of fine bubbles. In most chlorina-tions heat and a catalyst are employed. Phosphorus and its halides, sulfur and its halides, iron, aluminum chloride, antimony chloride, and iodine are among the common catalysts used for chlorinations. For laboratory use red phosphorus, iron, and thionyl chloride give good results. Aluminum chloride (or aluminum-mercury couple), although a very efficient catalyst, clogs the disperser. The use of actinic light is sometimes used to promote chlorination in the liquid phase, and is extensively used in the vapor phase. The action of the catalysts is assumed to activate a few chlorine molecules which initiate chain reactions. For example, in the chlorination of benzene the reaction begins with the dissociation of a few molecules of chlorine to atoms ... 

Diphenyl sulfide can best be prepared by reaction of benzene with sulfur mono chloride in the presence of aluminum chloride. ... 

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) ... 

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