Reaction of γ-dicarboxylic acids amides and imides with trifluoromethanesulfonamide and formaldehyde

Abstract

Three-component condensation of trifluoromethanesulfonamide with paraformaldehyde and succinamide depending on the reaction conditions led alongside bis(trifluoromethanesulfonamido)methane to the formation of a substitution product, bis[(trifluoromethylsulfonyl)aminomethyl]succinamide, or to a cyclization product, N-[trifluoromethylsulfonyl)aminomethyl]succinimide. The attempt to obtain the latter by the reaction of the trifluoromethanesulfonamide sodium salt CF 3 SO 2 NHNa with N-chloromethylsuccinimide unexpectedly resulted in N,N-bis(succinimidomethyl)-trifluoromethanesulfonamide. Analogously the reaction of CF 3 SO 2 NHNa with N-chloromethyl-phthalimide gave N,N-bis(phthalimidomethyl)trifluoromethanesulfonamide. The reaction of CF 3 SO 2 NHNa with succinimide and phthalimide in water and alcohol solution resulted in the ring opening and further transformation of the formed monosubstituted N-(trifluoromethylsulfonyl)amides of succinic and phthalic acids.We showed formerly that the condensation of trifluoromethanesulfonamide (triflamide) CF 3 SO 2 NH 2 with paraformaldehyde depending on the reaction conditions led to the formation of versatile linear and cyclic products [1,2]. Also the three-component reactions of triflamide with paraformaldehyde and various amides were investigated, and in some events mixed condensation products were obtained [3]. It was shown in particular that the reaction of triflamide, paraformaldehyde, and malonamide provided a spirocyclic condensation product involving both amido groups and the methylene group of the malonamide, 4,10-bis-(trifluoromethylsulfonyl)-2,4,8,10-tetraazaspiro-[5,5]undecane-1,7-dione [3]. In extension of this research the present study consists in the investigation of the reaction of succinamide, succinimide, and phthalimide with trifluoromethanesulfonamide and formaldehyde under various conditions.The investigation of the transformations in the system trifluoromethanesulfonamide-formaldehyde−succinamide (I) revealed the fundamental dependence of the reaction direction on its conditions. In the medium of concn. H 2 SO 4 alongside the unreacted triflamide and the linear product of its condensation with formaldehyde [bis(trifluoromethanesulfonamido)methane (II)] the formation was found of a product of the triple condensation at both amido groups, bis[(trifluoromethylsulfonyl)aminomethyl]-succinamide (III) that was isolated after washing the reaction product II with a mixture ether-hexane and was recrystallized from dichloromethane.The same reaction carried out in ethyl acetate in the presence of sulfuric acid alongside compound II unexpectedly furnished a cyclic amidomethylation product, N-[(trifluoromethylsulfonyl)aminomethyl]succinimide (IV) isolated analogously and recrystallized from chloroform.The structure of compound III was proved by the presence in its 1 H NMR spectrum of a singlet from CH 2 CH 2 group at 2.36 ppm, a broadened singlet of NHSO 2 , a triplrt of NHCO, and a doublet of NCH 2 N in the ratio 2:1:1:2, and of the corresponding signals in the 13 C...

Trifluoromethanesulfonamides and Related Compounds

“…93 Unexpectedly, in the reaction of the sodium salt of triflamide with Nchloromethylsuccinimide and -phthalimide, only the bis-(triflamido)-substituted derivatives were obtained, even with the equimolar ratio of the reagents, as was shown for Nchloromethylsuccinimide. 94 This was explained by a higher reactivity of the intermediate product of monosubstitution in the reaction with N-chloromethylsuccinimide. 94 Triflamide was successfully subjected to the amidoalkylation reaction with N-(2,2,2-trichloroethylidene)triflamide.…”

“…94 This was explained by a higher reactivity of the intermediate product of monosubstitution in the reaction with N-chloromethylsuccinimide. 94 Triflamide was successfully subjected to the amidoalkylation reaction with N-(2,2,2-trichloroethylidene)triflamide. (26)…”

“…Sodium salts of triflamide and N -methyltriflamide react with 1,2-dichloroperfluorocyclobutene, 1,2-dichloroperfluorocyclopentene, benzyl bromide, and cyanuric chloride (ClCN) 3 under mild conditions to give good yields of N-substituted polyfluoroalkyl and polyfluoroaryl sulfonamides Unexpectedly, in the reaction of the sodium salt of triflamide with N -chloromethylsuccinimide and -phthalimide, only the bis(triflamido)-substituted derivatives were obtained, even with the equimolar ratio of the reagents, as was shown for N -chloromethylsuccinimide This was explained by a higher reactivity of the intermediate product of monosubstitution in the reaction with N -chloromethylsuccinimide …”

Condensation of Trifluoromethanesulfonamide with Paraformaldehyde and Oxamide

“…Depending on the conditions, these reactions led to the formation of various linear and cyclic products [1][2][3][4]. In particular, the results of condensations of dicarboxylic acid amides of the general formula H 2 NCO(CH 2 ) n CONH 2 as amide component with paraformaldehyde and trifluoromethanesulfonamide were determined by the number of methylene groups in the initial amide.…”

“…In particular, the results of condensations of dicarboxylic acid amides of the general formula H 2 NCO(CH 2 ) n CONH 2 as amide component with paraformaldehyde and trifluoromethanesulfonamide were determined by the number of methylene groups in the initial amide. When n = 1, the product was spirocyclic 4,10-bis(trifluoromethylsulfonyl)-2,4,8,10-tetraazaspiro[5.5]undecane-1,7-dione [3], while amides possessing two methylene groups (n = 2) gave rise to either linear N, N-bis[(trifluoromethylsulfonyl)aminomethyl]succinamide or heterocyclization product, N-[(trifluoromethylsulfonyl)-aminomethyl]succinimide, depending on the conditions [4]. In the present work we examined the threecomponent condensation of sulfonamide I with paraformaldehyde and the simplest dicarboxylic acid amide, oxamide (II, n = 0).…”