N-Propargyltrifluoromethanesulfonamide

Highly unsaturated trifluoromethanesulfonamide derivatives

“…Its structure was proved by the presence in the IR spectrum of absorption bands ν(C≡C) at 2123 and ν(C=C) at 1646 cm -1 , of the signals of the propargyl and allyl groups in the Under more stringent conditions (110°C) a mixture of compound 2 with its isomer N-allenyl-N-allyltriflamide 3 formed with a slight excess of the latter as showed the data of 19 The formation of isomers 2, 3, and probably 4 distinguishes these compounds from their precursor Npropargyltriflamide 1 which does not provide any isomerization products even at heating at 150°C in DMSO in the presence of potassium tert-butoxide. The reaction mixture suffered only a strong tarring [13]. Evidently it is caused by the presence of a free NH group in compound 1 in contrast to 2-4.…”

“…On adding catalytic amounts of potassium tert-butoxide the solution turned blue, and in the 1 H, 13 C, and 19 F NMR spectra the signals appeared of the isomerization product, N-allenyl-N-propargyl-triflamide CF 3 SO 2 N(CH 2 C≡CH)(CH=C=CH 2 ) 6. According to 19 F NMR data, the ratio 5-6 was 85 : 15.…”

“…Later we prepared other N-vinyl- [9] and N-allylsubstituted triflamides [10,11] containing one double bond, i.e., possessing the summary oxidation degree of the substituents at the nitrogen atom equal +1, and also higher unsaturated derivatives with the oxidation degree +2 containing a cumulated double bond C=C [CF 3 SO 2 N(Bn)CH=C=CH 2 ] [12] or a triple bond C≡C (CF 3 SO 2 NHCH 2 C≡CH) [13], the first N-allenyl and Npropargyl triflamide derivatives. The isomeric nonfluorinated N-propargyl-and N-allenylsulfonamides are prepared by reactions of propargylamines with sulfonyl chlorides [14], or of tosylamide salts with propargyl carbonate [15], or by InCl 3 -catalyzed nucleophilic substitution of the acetate group in propargyl acetete with the tosylamide residue [16].…”

Bromination of highly unsaturated trifluoromethanesulfonamide derivatives

“…While carrying out studies in this field, we have synthesized trifluoromethanesulfonamide derivatives containing an allenyl [1], one [2] or two propargyl [3], and allyl and allenyl (or propargyl) fragments [3], as well as a diacetylene derivative, N,N′-hexa-2,4-diyne-1,6-diylbis(trifluoromethanesulfonamide) [4]. The synthesis of some of them [1] and study of their chemical properties involved bromination/dehydrobromination/debromination of several substrates [5].…”

“…The synthesis of some of them [1] and study of their chemical properties involved bromination/dehydrobromination/debromination of several substrates [5]. In continuation of these studies, in the present work we examined the bromination of trifluoro-N-(prop-2-yn-1-yl)methanesulfonamide (1), trifluoro-N,N-bis(prop-2-yn-1-yl)methanesulfonamide (2), and N,N′-hexa-2,4-diyne-1,6-diylbis(trifluoromethanesulfonamide) (3) under different conditions. The bromination of numerous terminal acetylenes and diacetylenes with various substituents has been studied in detail [6,7]; however, there are no published data on the bromination of acetylenic sulfonamide derivatives.…”