IV-sulfinyl-p-toluenesulfonamide

If iV-sulfinyl-p-toluenesulfonamide is prepared from p-tohienesulfonamide by using SOCl2 only, the yield turns out to be low even after heating the reaction mixture (refluxing benzene) for five days. By method B, however, the yield is high after only one hour at 20 °C in dichloromethane. 

Mock and Nugent investigated the mechanism of the [4 + 2] cycloaddition of iV-sulfinyl-p-toluenesulfonamide (9) and the isomeric 2,4-hex-adienes 10,11, and 12 in detail (Scheme l-II).11 These workers determined the relative stereochemistry of the resulting adducts and proposed a stepwise dipolar mechanism based primarily on the difference in sulfur stereochemistry between adducts produced from dienes 11 and 12. 

Hofmann s classical synthesis of 3,5-disubstituted 1,2,4-thiadiazoles by the oxidation of thioamides (1869)3 continues to be further exemplified. The oxidants employed include iodine,9-11 bromine,12 chlorine,13 and nitrous acid,14 as well as /V-chlorobenzamidine (which is recovered as benzamidine)15 and IV-sulfinyl-p-toluenesulfonamide (which evolves sulfur dioxide in the process).16 Irradiation with UV light in the presence of oxygen effects the same reaction, but has not been used on a preparative scale.17... 

Kresze and Wagner examined the regioselectivity of the cycloaddition of IV-sulfinyl-p-toluenesulfonamide (9) with several unsymmetrical dienes [Eq. (9)]. ... 

The A -SES group can be incorporated by treating an aldehyde with (V-sulfinyl-p-trimethylsilylethanesulfonamide (SESNSO) (13), which can be made by treating the sulfonamide (12) with Thionyl Chloride and a catalytic amount of N,N-dichloro-p-toluenesulfonamide (eq 7) (see also N-Sulfinyl-p-toluenesulfonamide). The )V-sulfonyl imine can be used in situ in a number of reactions. For example, the A(-sulfonyl imine from aldehyde (14) reacts with 2,3-dimethylbutadiene (eq 8) to give the Diels-Alder adduct (15). Treatment of (15) with fluoride ion affords the bicyclic lactam (16). Also, the IV-sulfonyl imine derived from isobutyraldehyde and (13) reacts with Vinylmagne-sium Bromide to provide the allylic SES-sulfonamide (17) in 65% yield (eq 9). ... 

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