A new synthetic route to aryl hydroxysulfonamides via a novel Fries-type rearrangement of aryl N,N-dialkylsulfamates

Sulfamic Acid and Its N- and O-Substituted Derivatives

“…A thia–Fries rearrangement of phenylsulfamate esters in AlCl 3 gives good yields of p - and o -arylhydroxysulfonamides, Scheme . The higher ortho/para ratios (≥1 and as high as 2.7) found at lower temperatures (90–110 °C) and shorter reaction times (5–30 min) may indicate an intramolecular mechanism for this new rearrangement.…”

Catalytic Arylation of Sulfamoyl Chlorides: A Practical Synthesis of Sulfonamides.

“…4 Electrophilic substitution reactions introducing the SO 2 NR 2 moiety directly have less precedent. Exceptions include the aluminium chloride promoted thia-Fries rearrangement 5 and sulfamoylation. 6 The use of stoichiometric Lewis acids or tin reagents is undesirable, particularly on an industrial scale, due to the serious waste problems.…”

Catalytic Arylation of Sulfamoyl Chlorides: A Practical Synthesis of Sulfonamides

“…4 Electrophilic substitution reactions introducing the SO 2 NR 2 moiety directly have less precedent. Exceptions include the aluminium chloride promoted thia-Fries rearrangement 5 and sulfamoylation. 6 The use of stoichiometric Lewis acids or tin reagents is undesirable, particularly on an industrial scale, due to the serious waste problems.…”