Methyl £-tolyl sulfone

After the mixture is cooled to 75°, 200 ml. of benzene is added (Note 5). The mixture is stirred briefly, and the liquid is decanted from the solid into a 5-1. separatory funnel. The aqueous layer is separated and extracted again with 200 ml. of benzene. The aqueous layer is then returned to the separatory funnel, and the solid in the reaction flask is washed in with it by means of 2 1. of water. The mixture is shaken with 200-ml. portions of benzene until all solid has dissolved (usually three portions of benzene suffice). All the benzene extracts are combined and dried with 20 g. of anhydrous calcium chloride. The drying agent is removed by filtration and washed with two 20-ml. portions of benzene. Benzene is removed from the filtrate by distillation under reduced pressure (Note 6), and the solid which separates is dried further at about 10 mm. and room temperature to constant weight. The yield (Note 2) of methyl -tolyl sulfone is 298-317 g. (69-73%), m.p. 83-87.5°. Further purification is generally unnecessary, but, if desired, the product may be recrystallized from carbon tetrachloride or ethanol-water (1 1). The submitters state that the method may be extended to the preparation of methyl phenyl sulfone and, presumably, of methyl aryl sulfones generally (Note 7). 

Methyl />-tolyl sulfone has been prepared by oxidation of methyl 7>-tolyl sulfide with hydrogen peroxide 4 r or ruthenium tetroxide,6 by alkylation of sodium -toluenesullinate with methyl iodide 7,8 or with methyl potassium sulfate,9 by decarboxylation of -tolylsulfonylacetic acid,7 by thermal decomposition of tetramethylammonium -toluenesulfinate,10 by reaction of cw-bis-(%tolylsulfonvl)-ethene with sodium hydroxide (low yield),11 by the reaction of methanesulfonyl chloride with toluene in the presence of aluminum chloride (mixture of isomers),12 by... 

The reaction of chloro(methoxy)methyl tolyl sulfone with a base generates methoxy(4-tosyl)-carbene (carbenoid) which adds to 1,2-dimethoxyethene, straight chain and cyclic enol ethers or arylethenes to give 1-methoxy-l-tosylcyclopropanes. Concentrated (50%) aqueous potassium hydroxide with a catalytic quantity of 18-crown-6 or, in one case, butyllithium, was used as the base (see Houben-Weyl, Vol. El9b, pp 1730-1734). 

METHYL TOLYL SULFONE (Sulfone, methyl -tolyl)... 

The methylsulfonylation of toluene by reaction with methylsulfonyl chloride in the presence of aluminium chloride catalyst affords methyl tolyl sulfone (52% yield) with an ortho meta para isomer ratio of 53 14 33. Attempts have been made to obtain greater selectivity in sulfonylations a supported Lewis acid catalyst has been recommended for selective sulfonylation, but it did not give good results in the methylsulfonylation of toluene. The best pura-selectivity... 

C8Hi0O2S, Methyl p-tolyl sulfone [l-Methyl-4-(methylsulfonyl)benzene]... 

C10H10O2S, l-Methyl-4-(l-propynylsulfonyl)benzene C, 0H 0O2S, l-Methyl-4-(2-propynylsulfonyl)benzene C10H10O2S, l-Methyl-4-(l, 2-propadienylsulfonyl)benzene Ci0Hi2O2S, Allyl p-tolyl sulfone [l-Methyl-4-(2-propenylsulfonyl)benzene]... 

Ci4Hi402S, Dibenzyl sulfone c15h14o2s, cis-Styryl p-tolyl sulfone [(Z)-1 -Methyl-4-(2-phenylethenyl)sulfonylbenzene] c15HI4o2s, frans-Styryl p-tolyl sulfone [( )-l-Methyl-4-(2-phenylethenyl)sulfonylbenzene] C12H10O4S2, Diphenyl disulfone... 

Methylthiomethyl p-tolyl sulfone 257 was shown to react with various esters in the presence of excess NaH, affording compounds 263 which, upon reduction with NaBH4 and further treatment with alkali, can be converted to the corresponding aldehydes344. Oxidation of 263 with hydrogen peroxide gives S-methyl a-ketocarbothioates 264335. 

SCH2COOEt) ° and with methyl methylsulfinylmethyl sulfide (MeSCH2SOMe) or methylthiomethyl p-tolyl sulfone (MeSCH2S02C6H4Me) (to give ArCH2-SMe), in each case with a Lewis acid catalyst. 

Z)-1 -Methyl-4-(2-phenylethenyl)sulfonylbenzene] C,5Hi402S, trans-Styryl p-tolyl sulfone... 

Methyl-p-tolyl sulfide Methyl-p-tolyl sulfone S [99]... 

Enantioselective Darzens Reaction. An enantioselective Darzens reaction between ethyl methyl ketone and chloromethyl p-tolyl sulfone in the presence of a chiral ammonium salt derived from (1) and chloromethylpolystyrene affords an optically active a,p-epoxy sulfone in 23% ee. ... 

C8H10O2S methyl p-tolyl sulfone 3185-99-7 24.00 1.1508 2 14201 C8H11N30 2-amino-4,6-dimethyl-3-pyridinecarboxamide 7144-20-9 25.00 1.1509 2... 

Additions of the Michael type of nucleophiles to the carbon-carbon double bond of thiete 1,1-dioxides to give 3-substituted thietane 1,1-dioxides occur readily. The addition of hydrogen has been discussed in Section A. Nucleophiles include cyanide, the anion of nitroethane, the lithium salt of r-butyl o-tolyl sulfone, dimethylamine, cyclohexylamine, ethoxide, and hydrogen sulfide. The reaction is exemplified by the synthesis of 278. Additions to 3-chloro-2H-thiete 1,1-dioxide most likely proceed by an addition-elimination mechanism an example is shown for the addition of the anion of dimethylmalonate to give 279. The replacement of a 3-morpholinyl group by a 3-A methyl-A-phenylamino group in thiete 1,1-dioxide is another example of addition-elimination. An addition of ethoxide with elimination of p-nitrophenyl anion may occur with 268 (Ar = / -N02C6H4). " Addition of bromine via N-bromo-succinimide to the double bond of 4-phenyl-2H-thiete 1,1-dioxide occurs only in 1.5% yield. ... 

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