Phenyl 4-nitrophenyl sulfone

Sulfinyl and sulfonyl groups were involved in early studies of the directive effects of substituents in nitration and other reactions with electrophilic reagents. Thus Twist and Smiles (in 1925) showed that nitration of phenyl methyl sulfone gave exclusively 3-nitrophenyl methyl sulfone. The results of bromination and sulfonation were analogous, so S02Me was established, like NO2, as a mefa-directing group. 

Chatterjee and Robinson ° studied the nitration of m-nitrophenyl benzyl sulfone, which occurred exclusively in the benzyl ring producing 25% ortho, 28% meta and 47% para isomer. Baldwin and Robinson " nitrated a series of phenyl alkyl sulfones PhSOjR. When R = Me, 98.5% of meta derivative was found but the amount of meta isomer fell with the chain length and branching of the alkyl group, e.g. n-Bu, 85.7% i-Pr, 80.0%. This was attributed to the electron repulsive influence of the higher alkyl groups. 

Phenacyl o-nitrophenyl sulfone hydrogenated with 10%-Pd-on-charcoal in ethyl acetate-acetic acid at room temp, and atmospheric pressure until 2 moles of hydrogen are absorbed 3-phenyl-4-hydroxy-4H-l,4-benzothiazine 1,1-dioxide. Y 11%. - Further hydrogenation leads to deoxygenation of the nitrogen. F. e. s. G. Pagani, G. 97, 1804 (1967). 

Condensation of vinyl chloride with formaldehyde and HCl (Prins reaction) yields 3,3-dichloro-l-propanol [83682-72-8] and 2,3-dichloro-l-propanol [616-23-9]. The 1,1-addition of chloroform [67-66-3] as well as the addition of other polyhalogen compounds to vinyl chloride are cataly2ed by transition-metal complexes (58). In the presence of iron pentacarbonyl [13463-40-6] both bromoform [75-25-2] CHBr, and iodoform [75-47-8] CHl, add to vinyl chloride (59,60). Other useful products of vinyl chloride addition reactions include 2,2-di luoro-4-chloro-l,3-dioxolane [162970-83-4] (61), 2-chloro-l-propanol [78-89-7] (62), 2-chloropropionaldehyde [683-50-1] (63), 4-nitrophenyl-p,p-dichloroethyl ketone [31689-13-1] (64), and p,p-dichloroethyl phenyl sulfone [3123-10-2] (65). 

Photochemical oxygen transfer reactions involving sulfoxides have also been documented. For example, a photochemical rearrangement of 2-nitrophenyl phenyl sulfoxide to 2-nitrosophenyl phenyl sulfone, and the inverse photoconversion of o-methylbenzoic acid have been reported. Finally, photochemical epimerizations of the sulfoxide centers... 

Reduced pyrazoles of type 30 react to give 4-nitrophenyl products on mononitration and then 2,4-dinitrophenyl products. Bromination and sulfonation also result in para substitution of the phenyl ring (78CHE1119). 

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. ... 

Loev and Kormendy147 first synthesized a 2,1-benzothiazine 2,2-dioxide by converting 2-(o-nitrophenyl)ethanesulfonyl chloride to the sulfonate salt 221 which was catalytically reduced to the amine 222. Treatment of 222 with phosphorus pentachloride/acetyl chloride afforded 3,4-dihydro-1//-2,1-benzothiazine 2,2-dioxide (223). They also prepared 4-phenyl-3,4-dihydro-IH-2,1-benzothiazine 2,2-dioxide (225) by treating styrene sulfonanilide (224 R = Ph) with polyphosphoric acid. However, they were unable to cyclize the ethylene sulfonamide (224 R = H) to 223 using this route.147... 

Methyl pelargonate Methyl phenyl sulfone 2-(Methylsulfonyl) ethanol p-Nitrophenol m-Nitrophenyl phenyl sulfide o-Nitrophenyi phenyl sulfide p-Nitrophenyl phenyi suifide Phenyl disulfide Phenylthioglycolic acid Phthalamide. Propargyl alcohol Propylene carbonate 3-Sulfolene 4,4 -Thiobis (6-t-butyl-o-cresol) 4,4 -Thiodibenzenethiol 4,4 -Thiodi (2,6-di-t-butylphenol) 4,4 -Thiodi (2,6-dimethylphenol) 2,2 -Thiodi (4-t-octylphenol) Thiophenol Tribromomethyl phenylsulfone... 

A soln. of 2-nitrophenyl phenyl sulfoxide in benzene irradiated with a high-pressure Hg-lamp -> 2-nitrosophenyl phenyl sulfone. Y 35%. F. e. s. R. Tanikaga, Y. Higashio, and A. Kaji, Tetrah. Let. 1970, 3273. 

In agreement with this argument, 2-(4-nitrophenyl)imidazole was chlorosulfo-nated in the imidazole ring yielding the 4-sulfonyl chloride.The phenyl nucleus is now deactivated by the presence of the electron-withdrawing nitro group, so sulfonation occurs in the imidazole ring. 

Arsono-4-nitrophenyl)-l-triazenyl phenyl azo benzene sulfonic acid. Plumbon. Plumbon S. Plumbon I RE A... 

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