Benzenesulfinamides

Of great importance was the discovery by Johnson et al. (185) of the stereospecific synthesis of optically active sulfonimidoyl chlorides, which are key substrates for making new types of sulfonimidoyl compounds. The method involves chlorination of readily available chiral sulfinamides with chlorine or A/-chlorobenzotriazole. Scheme 12 summarizes the synthesis of (-)-(/ )-A/-methylphenylsulfonimidoyl chloride 163 from (+HS>N-methyl benzenesulfinamide 164 and its reactions with sodium phenoxide and dimethylamine. 

SULFINIMINES (THIOOXIMINE S-OXIDES) ASYMMETRIC SYNTHESIS OF METHYL (R)-(+)- 3-PHENYLALANATE FROM (S)-(+)-N-(BENZYLIDENE)-p-TOLUENESULFIN AMIDE (Benzenepropanoic acid, p-amino-, (R)-, methyl ester from Benzenesulfinamide, 4-methyl-N-(phenylmethylene)- [S-(E)]-)... 

The ortholithiation of benzenesulfinamides 256 is of use in the regioselective synthesis of m ta-substituted compounds 257 the sulfinamide group is used to set up two ortho... 

Condensation of benzenesulfinamide (58) with reactive carbonyl compounds such as hexafluoroacetone (59) gave hemiaminal 60 in 74% yield.44 Subsequent treatment with trifluoroacetic anhydride and pyridine afforded 62 in 42% yield. Elimination of TfOH in 61 was proposed to account for this. 

Amines also react with 62 to give the corresponding amine adducts in good yield.44 However, with 123 n-butylamine gave the corresponding n-butyl imine 125 in 85% yield.30 Apparently, the initially formed amine adduct 124 eliminates benzenesulfinamide (58) with the formation of 125. On the other hand, 123 reacts with phenylhydrazine in ethanol at 50 °C to give the stable hydrazine adduct in 60% yield (124, n-Bu = PhNH).30... 

Benzenesulfinamides 716 717 Benzenesulfinyl chloride is dissolved in five times the amount of ether and treated with 2 moles of amine at 0°. The precipitate is collected, washed with water, dissolved in ethanol, and reprecipitated by addition of a little water. Thus were obtained benzenesulfinamide, m.p. 121°, and its jV,jV-dimethyl derivative (readily soluble in ether), b.p. 90°/2-3 mm, benzenesulfinanilide, m.p. 112-114°, and l-(benzenesulfinyl)piperidine, m.p. 83°. 

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