Phenyl />-tolyl sulfone

The crude, moist sulfonamide is dissolved in 1.6 1. of concentrated sulfuric acid by warming on the steam bath for 15 minutes. The sulfuric acid solution is divided into two equal parts, each of which is placed in a 4-1. beaker. The beakers are cooled in ice baths while 1.6 kg. of ice is added slowly and with stirring to the contents of each beaker. During the addition of the ice, phenyl />-tolyl sulfone separates. A total of 50 g. of Norit is added, and the solution is filtered (Notes 7 and 8). 

Phenyl />-tolyl sulfone may be isolated at this point by filtering the acid solution before using Norit, It can be purified by recrystallization from 95% ethanol m.p. 125°. 

That the base strength is decisive has also been shown by Becker.8 The replacement of potassium r-butoxide in the reaction of phenyl />-tolyl sulfone with benzalaniline by sodium methoxide resulted in the isolation of the addition product 7. This reaction is possible because the... 

Phenylpiperidine, 34, 79 Phenylsuccinic acid, 30, 83 Phenylsuccinic anhydride, 30, 85 Phenylthiourea, 31, 22 Phenyl -tolyl sulfone, 32, 10 7-Phenylvaleric acid, 36, 97... 

Tosylcarbazole is efficiently converted to carbazole with sodium iso-amyloxide in isoamyl alcohol. Phenylmagnesium bromide also brings about this change, phenyl p-tolyl sulfone being isolated as a cleavage prod-... 

The Smiles-type rearrangement of phenyl o-tolyl sulfone [222] has been shown to proceed via an addition-elimination pathway by isolation of the tricyclic intermediate. Both sites of deprotonation and addition are controlled by the sulfonyl group with contrapolarization at the second stage. 

DIENOPH1LES Acrolein. Ethynylp-tolyl sulfonc. 3-Mcthylsulfony 1-2,5-dihydro-furane. 3-Nitro-2-cyclohexenone. Phenyl vinyl sulfone. 

In 1964 it was shown by Becker8 that the condensation of phenyl p-tolyl sulfone to p-phenylsulfonyl stilbene (5) proceeded more readily and in improved yield when the reaction was carried out using benzal-aniline rather than benzaldehyde.9 This original observation was... 

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). 

Aldehydes Alkyldimesitylborane. Chloro-methyltrimethylsilane. Diethyl[(2-tetrahy-dropyranyloxy)methylphosphonate. N, N-Dimethylchloromethyleniminum chloride. Dimethyl(methylthio)sulfonium tetrafluoro-borate. Methoxy(phenylthio)methyllithium. Methylthiomethyl p-tolyl sulfone. 1-Phenyl thio- 1 -trimethylsilylethylene. Tetrakis-(triphenylphosphine)palladium. Thexyl-chloroborane-Dimethyl sulfide. 

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. ... 

Benzylbenzenesulfinic acid 4.2 To a stirred suspension of NaH (858 mg, 20 mmol) in liq. NH3 (400 mL) was added phenyl o-tolyl sulfone 3 (4.64 g, 20 mmol) and the ammonia was replaced by THF. After 7 h reflux the cooled solution was filtered to afford 2.73 g of 4 (54%) more 4 was recovered from the mother liquor to give a total yield of 70%. 

Various pyridazines, their 3-oxo or 3,6-dioxo analogs, readily undergo vicarious nucleophilic substitution (VNS) with the carbanion of chloromethyl p-tolyl sulfone. 2-Phenyl-3(2//)-pyridazinone, of a higher reactivity as an... 

Toluenesulfonyl perchlorate (which is formed from 5-10% solutions of /Koluenesulfonyl bromide and silver perchlorate in nitromethane at 0°) is the strongest sulfonylating agent known.231 For instance, it sulfonylates the relatively unreactive halobenzenes in satisfactory yield at room temperature / -bromo- and / -chloro-phenyl p-tolyl sulfone were obtained in 66.5% and 63% yield, respectively 231... 

---