Two novel solid reagents—1‐sulfonimidoyl‐ and 1‐sulfamimidoyl‐3‐methylimidazolium derivatives—for the synthesis of sulfonimidamides and imidosulfuric diamides, respectively, were developed. It is shown that these reagents are very effective in substitution reactions with various N‐ and O‐nucleophiles; therefore, they significantly extend the accessibility to the chemical space covered by organosulfur(VI) compounds with S=N bonds. In addition, previously unknown imidosulfuric diamides with free imino nitrogen groups were prepared, and their physical and chemical properties were characterized (including molecular geometry, pKa, Log P, microsomal stability, and reactivity towards typical electrophiles). Similar to other organosulfur(VI) derivatives with S=N bonds, these compounds can be considered as promising bioisosteres of amides, ureas, or sulfonamides.

The tetramethyl ester of (hydroxy)(phenyl)methylenebis-(phosphonic acid) reacts with morpholinosulfur trifluoride (MOST) to provide, along with the expected product of the substitution of a hydroxy group by fluorine, the adduct of (morpholino)(phenyl)carbene with PF 5 , compound 3a. Fluorination of dimethyl α-aroylphosphonates with MOST yields adducts of (amino)(aryl)carbene with PF 5 (p-XC 6 H 4 )(Morph)-C:ǞPF 5 [3a-f, where Morph is morpholyl, X = H (a), Me (b), Results and DiscussionWe have elaborated a new approach to the synthesis of α-fluoromethylenebis(phosphonic acid)s by nucleophilic [a] Scheme 3. Fluorination of methyl esters of α-aroylphosphonic acids (yields are given for isolated products).