Toluenesulfonamide, Dichloro

Cm.OROCARBONSANDCm.OROHYDROCARBONS - RDIG-Cm.ORINATED TOLUENES] (Vol 6) N,N-Dichloro-p-toluenesulfonamide [473-34-7]... 

Dichloramine-T, A/ W-dichloro-T -toluenesulfonamide [473-34-7] is insoluble in water, but soluble in a number of organic solvents, including chlorinated paraffin. Its medical usage appears to have declined. 

Alkylation of 7V-benzyl-p-toluenesulfonamide (12a) with a threefold excess of fra j-l,4-dichloro-2-butene (ila) gives the allylic chloride 11b. which is treated with sodium acetate in DMF followed by hydrolysis to afford the allylic alcohol 10a in an overall 68% yield. 

The reaction of A/,A/-dichloro-4-toluenesulfonamide with indene was unexpectedly Irans stereoselective, compared with the addition to (L )-stilbene, which gave a mixture of anti- and. n> -adducts after bisulfite treatment14 The regioselectivity indicates that a radical mechanism is operating in this reaction. 

Nitrile imines can also be prepared conveniently by the oxidation of easily accessible hydrazones (Scheme 5.45). The oxidant generally used is chloramine-T (N-chloro-N-sodio-p-toluenesulfonamide, CAT). Other oxidants such as iodobenzene diacetate (IBD) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone have also been used. 

The N-SES group can be incorporated by treating an aldehyde with iV-sulfinyl-/3-trimethylsilylethanesulfonamide (SESNSO) (13), which can be made by treating the sulfonamide (12) with thionyl chloride and a catalytic amount of M,fV-dichloro-/7-toluenesulfonamide (eq 7) (see also fV-sulfinyl-/7-toluenesulfon-amide. The iV-sulfonyl imine can be used in situ in a number of reactions. For example, the fV-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 bicycUc lactam (16). Also, the fV-sulfonyl imine derived from isobutyraldehyde and (13) reacts with vinylmagnesium bromide to provide the allylic SES-sutfonamide (17) in 65% yield (eq 9). ... 

---