Photoisomerization of Sultams Derived from Saccharin; Part 4: [1] Generation of Cyclic Sulfine Hydroxamic Acids

Abstract

Various areno[d]annulated 3-mono- and 3,3-disubstituted 2,3-dihydro-[1,2]benzisothiazole 1,1-dioxides undergo a facile rearrangement into the corresponding 2,3-dihydro-2-hydroxy-[1,2]benzisothiazole 1-oxides upon irradiation at 254 nm in methanol. The latter represent a new, but labile functional group, i. e. the cyclic version of the sulfine hydroxamic acid. When C-3 in the starting materials is substituted by one methyl or phenyl only, that photoisomer is formed preferentially which has the sulfoxide O atom in an anti-orientation to the said substituent. 2-Alkoxymethyl substituted starting materials show the same type of formal oxygen shift. The structures of all photoproducts have been assigned largely from ¹H NMR data and unambiguously corroborated by X-ray crystal structure analyses of two photoproducts.

Key words

1,2-benzisothiazole 1,1-dioxides - 2-hydroxy-1,2-benzisothiazole 1-oxides - photoconversion - oxygen shift - X-ray crystal structure determination - absolute configuration

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Part 3: Döpp, D.; Elghamry, I.; Henkel, G.; preceding paper.

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Part 3: Döpp, D.; Elghamry, I.; Henkel, G.; preceding paper.

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All crystallographic results have been deposited at the Cambridge Crystallographic Data Centre as supplementary publication no CCDC-159468. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK.