SHORT COMMUNICATIONSAcrylamide and N-substituted acrylamides are used in both fine organic synthesis and industry as intermediate products for the preparation of carbo-and heterochain polymers and copolymers and polyfunctional acyclic and heterocyclic compounds. While performing our systematic studies on the synthetic potential of halogen-containing N-sulfonyl imines, which have become readily accessible as a result of development of methods for their synthesis from N,N-dichlorosulfonamides, polyhaloethenes, and phenylacetylene [1], we examined reactions of N-(2,2,2-trichloroethylidene)trifluoromethane-and -arenesulfonamides Ia-Ic and N-(2-phenyl-2,2-dichloroethylidene)-4-chlorobenzenesulfonamide (Id) with acrylamides.We previously showed that carboxamides, ureas, and sulfonamides add to N-sulfonyl imines derived from polychlorinated aldehydes to give the corresponding symmetric and asymmetric 1,1-bis(acylamino)polychloroalkanes [1].In the present work we found for the first time that Schiff bases Ia-Id obtained from the corresponding N,N-dichloro sulfonamides, trichloroethylene, and phenylacetylene readily take up acrylamide (within 2-3 h) to give N-(1-sulfonylamino-2-polychloroethyl)-acrylamides IIa-IId. Heating of the reaction mixture to 40-50°C accelerates the process. We observed no formation of poly(acrylamide), though acrylamide is known to readily undergo polymerization in the presence of radical initiators.The structure of acrylamide derivatives IIa-IId was proved by spectral data and elemental analyses. The IR spectra of IIa-IId contained absorption bands due to stretching vibrations of the amide NH, carbonyl, and sulfonyl groups. Amides IIa-IId showed in the 1 H NMR spectra signals corresponding to protons in the aromatic rings, NH-CH-NH fragment, and vinyl group. The latter appeared as an ABX spin system. In the 13 C NMR spectra of IIa-IId we observed signals from carbon atoms in the polyhaloethyl fragment and carbonyl group; the CF 3 signal in the spectrum of IIa was split into a quartet due to coupling with fluorine nuclei.Compounds IIa-IId are colorless crystalline substances which are insoluble in water, poorly soluble in nonpolar organic solvents, and readily soluble in acetone, DMSO, and aqueous alkali. The presence of proton-donor and proton-acceptor substituents, polyhalomethyl fragments, and a double bond in molecules IIa-IId makes these compounds potential ligands for complex formation with metals and promising intermediate products for fine organic synthesis, specifically for the preparation of nitrogen-containing acyclic and heterocyclic compounds and carbo-and heterochain polymers and copolymers having labile hydrogen atoms. Structural features of amides IIa-IId could give rise to formation of strong intra-and intermolecular hydrogen bonds; therefore, these compounds may X = Cl, R = CF 3 (a), Ph (b), 4-ClC 6 H 4 (c); X = Ph, R = 4-ClC 6 H 4 (d). RSO 2 NH CH HN CCl 2 X C HC O CH 2

SHORT COMMUNICATIONSThere are only a few published data on N-alkenylsubstituted sulfonamides of the general formula R 1 SO 2 N(R 2 )-C(R 3 )=CR 4 R 5 . Hydrostannylation of N-tosyl-substituted ynamines TsN(Bzl)C≡CSiMe 3 [1] and TsN(Bzl)C≡CH [2] led to the corresponding N-tosyl enamines TsN(Bzl)C(SnBu 3 )=CHSiMe 3 [1] and TsN(Bzl)C(SnBu 3 )=CH 2 , and coupling of the latter with various organic halogen compounds RX afforded N-benzyl-N-(1-R-vinyl)-p-toluenesulfonamides TsN(Bzl)C(R)=CH 2 ; N-alkenylsultams were synthesized from N-alkynyl precursors [3]. Unsaturated derivatives of trifluoromethanesulfonamide containing a CF 3 SO 2 N(R)CH=CHR′ fragment were not reported so far. With a view to obtain N-(2-phenylethenyl)-trifluoromethanesulfonamide CF 3 SO 2 NHCH=CHPh we previously synthesized N-(2-phenylethyl)trifluoromethanesulfonamide whose bromination gave N-(2-bromo-2-phenylethyl)trifluoromethanesulfonamide, and the latter was subjected to dehydrobromination by the action of triethylamine [4]. Unexpectedly, the product of this reaction was 2,5-diphenyl-1,4-bis(trifluoromethylsulfonyl)piperazine (Scheme 1); its 1 H and 13 C NMR spectra and melting point were identical to those of a sample synthesized by us previously from styrene and trifluoromethanesulfonamide (its structure was proved by X-ray analysis [5]). initial trifluoromethanesulfonamide contains an NH proton. To rule out this possibility N-(2-phenylethyl)-trifluoromethanesulfonamide (I) was preliminarily subjected to methylation with methyl iodide. N-Methyl-N-(2-phenylethyl)trifluoromethanesulfonamide (II) thus formed was brominated to N-(2-bromo-2-phenylethyl)-N-methyltrifluoromethanesulfonamide (III), and dehydrobromination of the latter with alcoholic alkali afforded N-methyl-N-[(E)-2-phenylethenyl]trifluoromethanesulfonamide (IV) (Scheme 2) as the first representative of N-alkenyl-substituted trifluoromethanesulfonamide derivatives.

Configurational assignment of seven synthesized N-arylsulfonylimines of alpha-polychloroaldehydes has been carried out by means of experimental measurements and high-level ab initio calculations of their (13)C--(13)C, (13)C--(1)H and (15)N--(1)H spin-spin coupling constants. The title compounds were shown to exist in solution solely in the form of E isomers, in line with thermodynamic reasoning.

No abstract

No abstract