Phenyl p-tolyl sulfone

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-... 

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... 

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... 

K-ferf-butoxide added to a soln. of p-anisylideneaniline and phenyl p-tolyl sulfone in dimethylformamide, and kept 15 min. under Ng p-phenylsulfonyl-p -methoxystilbene. Y 98%. F. e. s. H.-D. Becker, J. Org. Ghem. 29, 2891 (1964). 

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. 

DIENOPHILES Acrolein. Ethynyl p-tolyl sulfone. 3-Methylsulfonyl-2,5-dihydro-furane. 3-Nitro-2-cyclohexenone. Phenyl vinyl sulfone. 

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... 

Sttlfone sjmthesh. The reaction of phenyl tosylate with n-butyllithium gives n-butyl p-tolyl sulfone in 85% yield. This synthesis is general for sulfonate esters, and any oiganolithium compound can be used. ... 

Benzene ring from cyclopentadienones. Allyl phenyl sulfone and tetraphenylcyclo-pentadienone heated at 180° in polyethyleneglycol 200 under N2 for 15 min 1,2,3,4-tetraphenylbenzene. Y 62%. F.e. and with cinnamyl p-tolyl sulfone as dienophile s. P. Raja Kumar, J. Chem. Soc. Chem. Commun. 1989, 509-10. 

Ohta and coworkers used a bacterium, Corynebacterium equi IFO 3730, rather than a fungus, to oxidize eight alkyl phenyl and p-tolyl sulfides to their respective sulfoxides (119, 120) of configuration R. Virtually all of the sulfur compounds were accounted for as the sum of uncreacted sulfide, sulfoxide and sulfone. The enantiomeric purities of the sulfoxides obtained were quite good and are shown below in parentheses. The formation of the allyl sulfoxides in high optical purity is noteworthy. The authors believe that the sulfoxides were formed by enantioselective oxidation of the sulfides rather than by enantioselective oxidation of racemic sulfoxides, since the yield of sulfoxides was greater than 50% in five of the ten oxidations reported (see also Reference 34). 

Other common intermediates for azo pigment production are 2,4-dinitro-aniline, acetoacet-o-chloroanilide, acetoacet-o-toluidide, phenyl- and p-tolyl-methylpyrazolone, 2-hydroxy-3-naphthoic acid, Naphtol AS and its derivatives, and 2-chloro-4-aminotoluene-5-sulfonic acid. 

RuCyaq. Na(lO )/CH3CN-CCiy0°C (D-mannitol-1,2 5,6-diacetonide-2,3-cyclic sulfite (6 g) to the sulfate) [116], and stoich. RuOyCCl (ca. 5 g methyl-p-tolyl, meth-ylbenzyl and triphenyl-methyl phenyl and diphenyl sulfides to the sulfones) [99,122],... 

A further catalytic method for asymmetric sulfoxidation of aryl alkyl sulfides was reported by Adam s group, who utilized secondary hydroperoxides 16a, 161 and 191b as oxidants and asymmetric inductors (Scheme 114) . This titanium-catalyzed oxidation reaction by (S)-l-phenylethyl hydroperoxide 16a at —20°C in CCI4 afforded good to high enantiomeric excesses for methyl phenyl and p-tolyl alkyl sulfides ee up to 80%). Detailed mechanistic studies showed that the enantioselectivity of the sulfide oxidation results from a combination of a rather low asymmetric induction in the sulfoxidation ee <20%) followed by a kinetic resolution of the sulfoxide by further oxidation to the sulfone... 

It was reported earher that the oxidation of a sulfoxide to a sulfone involves either an initial nucleophihc attack of the nucleophilic oxidant or an electrophihc attack by an electrophilic oxidant. It is noteworthy that the oxidation of p-tolyl methyl, phenyl methyl and p-chlorophenyl methyl sulfoxides to the sulfones using the sulfonylperoxy intermediate 51 appears to be electrophihc, namely the relative reactivity order was p-tolyl methyl > phenyl methyl > p-chlorophenyl methyl sulfoxide based on competitive oxidations. 

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°. 

When it was found by Becker8 that p-phenylsulfonylstilbene could readily be obtained by condensation of phenyl-p-tolylsulfone with benzalaniline, it was considered that this was a result of the stabilization of the p-tolyl anion by the mesomeric effect of the sulfone group. 

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