Methyl 4-nitrophenyl sulfide

An alternative method for asymmetric and metal-free sulfoxidation was explored by Kita et al. [133], In their approach, iodosylbenzene (Ph-I02) was used as oxidant in reversed micelles formed by cetyltrimethylammonium bromide (CTAB) in toluene. From the numerous chiral inductors tested, tartaric acid derivatives proved best. In the presence of 10 mol% bis(2-methoxybenzoyl)tartaric acid, methyl (4-nitrophenyl)sulfide was converted into the sulfoxide in 91% yield and with 72% enantiomeric excess [133],... 

Asymmetric imidations of aryl alkyl sulfides with [(tosylimino)iodo]ben-zene, catalyzed by various chiral (salen)manganese(III) complexes, have been investigated in some detail [31,32]. The influence of catalyst structure, solvent, temperature, 3°-amine AT-oxides, and the presence of molecular sieves on product yields and the enantioselectivity of imidation with 17 was evaluated. Enan-tioselectivities as high as 90 % ee and 97 % ee with methyl 2-nitrophenyl sulfide and methyl 2,4-dinitrophenyl sulfide, respectively, were achieved. 

Orthanilic acid was first made by the reduction of nitro-benzenesulfonic acid by ammonium sulfide.2 This reduction has also been carried out electrolyticallv, and by the use of iron or zinc.3 The acid has also been made by the rearrangement of phenylsulfamic acid,4 by the action of sodium hypobromite upon potassium o-carbaminebenzenesulfonate,5 by the reduction of the mixed nitrobenzenesulfonic acids followed by separation of the isomers,6 by the action of methyl alcohol upon o-nitro-phenylsulfurchloride,7 by the action of acid upon diacetyl diphenylsulfamide,8 by the debromination of />-bromoaniline-e-sulfonic acid,9 by the reduction of 1,2,6-aminothiophenolsulfonic acid,10 and by the hydrolysis and reduction of e-nitrobenzene-sulfonyl chloride, which was obtained from di-o-nitrophenyl-disulfide.11... 

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. ... 

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... 

More recently, Katsuki et al. [109] prepared the Salen manganese complex (50) (Figure 1.6), which is efficient in the oxidation of alkyl aryl sulfide with iodosobenzene as oxidant. With 1 mol% of catalyst, they obtained the 2-nitrophenyl methyl sulfoxide in 1 h at -20°C in acetonitrile solution with 90% ee and 88% yield. This is currently one of the best results for catalytic asymmetric sulfoxidation. 

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