Bromination-dehydrobromination/debromination of N-Methyl-N-(2-phenylethenyl)trifluoromethanesulfonamide

Ushakova, I. V.; Shainyan, B. А.

doi:10.1134/s1070428013060213

Cited by 12 publications

(6 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We noticed a number of the desired elimination were accomplished by the reaction with alcoholic alkali . Therefore, the reaction mixture after oxidative bromination was confronted with the basic triethylamine (Et 3 N) in ethanol (EtOH) at 70 °C for 6 h under nitrogen atmosphere (Figure.…”

Section: Resultsmentioning

confidence: 99%

Solvent effect on the debromination/dehydrobromination of bromo‐damascone

Cheng

Ren

et al. 2016

Flavour & Fragrance J

View full text Add to dashboard Cite

The dehydrogenative synthesis of β‐damascenone from β‐damascone via the related allyl bromide intermediate was studied in depth. The requisite dehydrobromination thereof was found strongly solvent system dependent. Under respective conditions, the product was identified as dehydrogenation‐derived a, 4‐alkoxy‐derived b and 4‐oxo‐derived c, accordingly. In addition, the conversion from b to a was successfully accomplished, thereby offering an alternative access (with one step more) to reach β‐damascenone. Copyright © 2016 John Wiley & Sons, Ltd.

show abstract

Section: Resultsmentioning

confidence: 99%

Solvent effect on the debromination/dehydrobromination of bromo‐damascone

Cheng

Ren

et al. 2016

Flavour & Fragrance J

View full text Add to dashboard Cite

show abstract

“…Unsaturated derivatives of trifluoromethanesulfonamide (triflamide) belong to a rare class of compounds which are of interest from both synthetic and theoretical point of view. Except for the first N‐alkenyl derivative, N‐methyl‐N‐[( E )‐2‐phenylethenyl]triflamide, reported in the recent review on triflamides, there are only a few recent papers on linear and cyclic N‐alkenyl triflamides . Even less is known about the reactivity of the double bond in these compounds; we only had to mention that it does not add alcohols or amines, although is readily brominated by elemental bromine .…”

Section: Introductionmentioning

confidence: 99%

The structure and proton affinity of N‐benzyl‐N‐(allenyl)trifluoromethanesulfonamide: FT‐IR, DFT and ab initio study, NBO analysis

Shainyan

Chípanina

Oznobikhina

et al. 2013

J of Physical Organic Chem

Self Cite

View full text Add to dashboard Cite

The first N-allenyl derivative of trifluoromethanesulfonamide, N-benzyl-N-(allenyl)trifluoromethanesulfonamide (1), was studied experimentally by the FT-IR spectroscopy and theoretically at the DFT and MP2 levels of theory. The intramolecular interaction of the nitrogen atom with the triflyl and the allenyl group was studied in comparison with the analogously substituted vinyl derivatives. Compound 1 in heptane solution at 295-183 K exists as an equilibrium mixture of conformational isomers. Protonation at different basic sites in a series of reference molecules is studied theoretically. The central C 2 atom of the allenyl group in 1 has the highest proton affinity, which is 16 kcal/mol higher than in the N-vinyl analogues. The relative ability of the allenyl and vinyl groups to conjugation with an electron-rich and electron-deficient nitrogen atom lone electron pair is discussed. From the NBO analysis, the conjugation of the nitrogen lone electron pair with the allenyl group is much stronger than with the vinyl group.

show abstract

“…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].…”

mentioning

confidence: 99%

mentioning

confidence: 99%

Highly unsaturated trifluoromethanesulfonamide derivatives

Shainyan

Danilevich

2015

Russ J Org Chem

Self Cite

View full text Add to dashboard Cite

Reactions of N-propargyltriflamide TfNHCH 2 C≡CH (Tf = CF 3 SO 2 ) with allyl bromide or propargyl bromide in DMSO afforded highly unsaturated triflamide derivatives: N-allyl-N-propargyltriflamide TfN· (CH 2 CH=CH 2 )(CH 2 C≡CH), N-allenyl-N-allyltriflamide TfN(CH 2 CH=CH 2 )(CH=C=CH 2 ), and N-allenyl-Npropargyltriflamide TfN(CH=C=CH 2 )(CH 2 C≡CH). By the reaction of triflamide with propargyl bromide in DMSO N,N-dipropargyltriflamide TfN(CH 2 C≡CH) 2 was obtained, which under the treatment with t-BuOK in DMSO underwent isomerization giving an equilibrium mixture with N-allenyl-N-propargyltriflamide TfN (CH 2 C≡CH)(CH=C=CH 2 ) in a ratio 85 : 15. Unsaturated derivatives of trifluoromethanesulfonamide were unknown till recently. Moreover, scanty publications appeared on N-alkenyl-substituted nonfluorinated sulfonamides RSO 2 N(R)-C(R')=C<. The only published data concerned the hydrostannylation of N-tosyl-substituted ynamines TsN(Bn)C≡CSiMe 3 [1] and TsN(Bn)C≡CH [2] resulting in N-tosylsubstituted enamines TsN(Bn)C(SnBu 3 )=CHSiMe 3 [1]and TsN(Bn)C(SnBu 3 )=CH 2 respectively, the coupling of the latter with diverse organyl halides RX afforded N-benzyl-N-(1-R-vinyl)tosylamides TsN(Bn)C(R) =CH 2 , and also the formation of N-alkenylsultams from their N-alkynyl precursors was described [3]. Recently, we have prepared by dehydrobromination of N-(2-bromo-2-phenylethyl)-N-(methyl)-trifluoromethane-sulfonamide CF 3 SO 2 N(Me)CH 2 CHBrPh the first representative of N-alkenyl-substituted trifluoromethanesulfonamides containing a double bond at the nitrogen atom: N-methyl-N-[(E)-2-phenylethenyl]trifluoromethanesulfonamide CF 3 SO 2 N(Me)CH=CHPh [4]. We failed to obtain its NH-analog by a similar procedure: Dehydrobromination of N-(2-bromo-2-phenylethyl)-trifluoromethanesulfonamide with trimethylamine yielded the product of cyclodimerization, 2,5-diphenyl-1,4-bis(trifluoromethyl-sulfonyl)-piperazine [5].Other attempts to prepare unsaturated triflamide derivatives by reacting triflamide or its sodium salt with vinyl bromide or chloroacetylene in DMSO, or by a direct vinylation with acetylene under various conditions (in DMSO with KOH and with t-BuOK, with CdO or CuCl additive, with potassium metal in dioxane, at 100-200°C, for 2-5 h) were unsuccessful, always unreacted triflamide was recovered. Apparently, the failure was due both to the extremely low nucleophilicity of the nitrogen atom in the triflamide and to the low reactivity of the non-activated vinyl halides.Considering that N-sulfinyltriflamide CF 3 SO 2 N=S=O readily reacted with aldehydes [6-8] we regarded as an interesting approach the ketene synthesis which after isomerization might lead to the formation of the simplest acetylenic triflamide.However passing the ketene flow obtained by acetone thermal decomposition through a solution of CF 3 SO 2 NSO in THF also failed to provide the target product; only the initial triflamide was isolated.Later we prepared other N-vinyl- [9] and N-allylsubstituted triflamides [10,11] containing one double bond, i.e., possessing t...

show abstract

Bromination-dehydrobromination/debromination of N-Methyl-N-(2-phenylethenyl)trifluoromethanesulfonamide

Cited by 12 publications

References 1 publication

Solvent effect on the debromination/dehydrobromination of bromo‐damascone

Solvent effect on the debromination/dehydrobromination of bromo‐damascone

The structure and proton affinity of N‐benzyl‐N‐(allenyl)trifluoromethanesulfonamide: FT‐IR, DFT and ab initio study, NBO analysis

Highly unsaturated trifluoromethanesulfonamide derivatives

Contact Info

Product

Resources

About