Generation and Reactions of Aza-ortho-xylylenes in the Injector of GC/MS System

Article abstract of DOI:10.1016/0040-4039(94)02404-Y

Nitro derivatives of 2,1-benzisothiazoline 2,2-dioxide (benzosultams) undergo thermal elimination of sulfur dioxide yielding very reactive, non-isolable aza-ortho-xylylenes.It was found that this reaction can be performed in the injector of the gas chromatograph at 300 - 350 deg C and the formed aza-ortho-xylylenes can be trapped by appropriate reagents added to the injected solution.In the preliminary experiments aza-ortho-xylylenes were reacted with dienophiles (methyl acrylate, dimethyl maleate, vinyl acetate, N-phenylmaleimide etc.) resulting in the formation of the <4+2> cycloaddition reaction products, and also with nucleophilic reagents (alcohols, amines) to give appropriate adducts.In the absence of the trapping reagent dimers of aza-ortho-xylylenes were formed.