N-Phenyltrifluoromemanesulfonamide reacted with N,N′-dicyclohexylcarbodiimide in methylene chloride to give exchange products, N-cyclohexyltrifluoromethanesulfonamide and N-cyclohexyl-N′-phenylcarbodiimide. Reaction of the latter with trifluoromethanesulfonamide afforded N-cyclohexyl-N′-phenyl-N″-(trifluoromethanesulfonyl)guanidine. In the reaction of N-phenyltrifluoromethanesulfonamide with N,N′-dicyclohexylcarbodiimide in acetonitrile, substituent exchange was a minor process, whereas the major one was dimerization of N,N′-dicyclohexylcarbodiimide catalyzed by N-phenyltrifluoromethanesulfonamide as NH acid.

N-Allyl- and N-propargyltrifluoromethanesulfonimides were synthesized by reaction of trifluoromethanesulfonic anhydride with allylamine and propargylamine. Some reactions of the resulting unsaturated derivatives were studied, in particular bromination, dehydrobromination of the bromination product, and nucleophilic substitution of bromine.

Reaction of N-phenyltriflamide with 1,2-dibromoethane under basic conditions in DMSO unexpectedly results in N-methyl-N-phenyltriflamide and 1,3-diphenylurea. The presumed reaction mechanism includes the formation of unstable intermediate disubstitution product TfN(Ph)CH2CH2N(Ph)Tf that suffers the the С–С bond cleavage resulting in TfN(Me)Ph and N,N′-methanediylbis(N-phenyltriflamide). The latter reacts with K2CO3 releasing two molecules of potassium triflinate and after hydrolysis of diphenylcarbodiimide PhN=C=NPh gives 1,3-diphenylurea. With propargyl bromide, N-phenyltriflamide affords N-propargyl-Nphenyltriflamide in high yield. The bromination of the latter results in a mixture of Z,E-isomers of N-(2,3-dibromoprop-2-en-1-yl)-N-phenyltriflamide which undergo dehydrobromination giving first N-(3-bromopropanedienyl)-N-phenyltriflamide and then the products of the C–N bond cleavage: N-phenyltriflamide and 3,3-dimethoxyprop-1-yne.

The reaction of triflluoromethanesulfonamide with allyl bromide in dimethyl sulfoxide gave N,N-diallyltrifluoromethanesulfonamide which was subjected to bromination with 1 and 2 equiv of bromine. The product of bromine addition to both allyl groups, CF3SO2N(CH2CHBrCH2Br)2, was found to exist as a mixture of two diastereoisomers at a ratio of 9: 11. Its dehydrobromination by the action of sodium methoxide was chemoselective with successive elimination of one, two, and three hydrogen bromide molecules to afford N-(2-bromoprop-2-en-1-yl)-N-(2,3-dibromopropyl)trifluoromethanesulfonamide, N,N-bis(2-bromoprop-2-en-1-yl)trifluoromethanesulfonamide, and N-(2-bromoprop-2-en-1-yl)-N-(propadienyl)trifluoromethanesulfonamide, respectively.

Reactions of N-propargyltriflamide TfNHCH2C≡CH (Tf = CF3SO2) with allyl bromide or propargyl bromide in DMSO afforded highly unsaturated triflamide derivatives: N-allyl-N-propargyltriflamide TfN·(CH2CH=CH2)(CH2C≡CH), N-allenyl-N-allyltriflamide TfN(CH2CH=CH2)(CH=C=CH2), and N-allenyl-N-propargyltriflamide TfN(CH=C=CH2)(CH2C≡CH). By the reaction of triflamide with propargyl bromide in DMSO N,N-dipropargyltriflamide TfN(CH2C≡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 (CH2C≡CH)(CH=C=CH2) in a ratio 85: 15.

The bromination of trifluoro- N -(prop-2-yn-1-yl)methanesulfonamide with molecular bromine gives a mixture of Z - and E -isomeric N -(2,3-dibromoprop-2-en-1-yl)trifluoromethanesulfonamides, regardless of the reaction conditions. Bromine adds to both triple bonds of trifluoro- N , N -bis(prop-2-yn-1-yl)methanesulfonamide, yielding a mixture of N -(2,3-dibromprop-2-en-1-yl)trifluoro- N -(prop-2-yn-1-yl)methanesulfonamide, N , N -bis(2,3-dibromoprop-2-en-1-yl)trifluoromethanesulfonamide, and trifluoro- N , N -bis(2,2,3,3-tetrabromopropyl) methanesulfonamide. Diacetylenic trifluoromethanesulfonamide derivative, N , N ′-hexa-2,4-diyne-1,6-diylbis( trifluoromethanesulfonamide), reacts with bromine to afford N , N ′-[(2 E ,4 E )-2,3,4,5-tetrabromohexa-2,4-diene-1,6-diyl]bis(trifluoromethanesulfonamide) and isomeric N -(2,3-dibromoprop-2-en-1-yl)trifluoromethanesulfonamides resulting from reductive cleavage of the central C–C bond in the former.

Abstractsynthesis and spectroscopic characterization of the first N‐allenyl‐substituted triflamide (IV)

First N-allenyl-substitued triflamides CF 3 SO 2 N(Bn)CH=C=CH 2 were synthesized from N-allyltriflamides by sucessive reactions of bromination, N-alkylation, and dehydrobromination. Isomeric N-propargyltriflamide CF 3 SO 2 N(Bn)CH 2 C≡CH is present in the reaction products as a minor admixture.

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 C2 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. Copyright © 2013 John Wiley & Sons, Ltd.

ChemInformVolume 44, Issue 49 Preparative Organic Chemistry ChemInform Abstract: Synthesis and Properties of N-(Allyl)trifluoromethanesulfonamide. B. A. Shainyan, B. A. Shainyan A. E. Favorsky Inst. Chem., Sib. Branch, Russ. Acad. Sci., Irkutsk 664033, RussiaSearch for more papers by this authorYu. S. Danilevich, Yu. S. Danilevich A. E. Favorsky Inst. Chem., Sib. Branch, Russ. Acad. Sci., Irkutsk 664033, RussiaSearch for more papers by this author B. A. Shainyan, B. A. Shainyan A. E. Favorsky Inst. Chem., Sib. Branch, Russ. Acad. Sci., Irkutsk 664033, RussiaSearch for more papers by this authorYu. S. Danilevich, Yu. S. Danilevich A. E. Favorsky Inst. Chem., Sib. Branch, Russ. Acad. Sci., Irkutsk 664033, RussiaSearch for more papers by this author First published: 14 November 2013 https://doi.org/10.1002/chin.201349059Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume44, Issue49December 3, 2013 RelatedInformation

A novel energy-economic and environmentally benign technological procedure for chlorination of niobium and tantalum oxides as well as their low-grade ore concentrates was elaborated. The process is based on using carbon tetrachloride or silicon tetrachloride as a chlorinating agent under pressure. It proceeds at moderate temperatures and is free from the shortcomings of conventional carbochlorination processes such as the use of chlorine gas at very high temperatures and formation of toxic products and ozone depleting agents (phosgene, carbon monoxide, chlorohydrocarbons).

Two- and three-component condensations of paraformaldehyde with trifluoromethanesulfonamide, acetamide, trifluoroacetamide, 1H-benzotriazole, methanesulfonamide, and malonamide were studied. N-Hydroxymethyl derivatives of trifluoroacetamide and 1H-benzotriazole reacted with trifluoromethanesulfonamide to give N-(trifluoroacetylaminomethyl)- and N-(1H-benzotriazol-1-ylmethyl)-substituted derivatives of tri-fluoromethanesulfonamide, as well as N,N′-methylenebis(trifluoromethylsulfonamide) and N-(trifluoromethyl-sulfonylaminomethyl)trifluoroacetamide as transamination products. Three-component condensation of trifluoromethanesulfonamide with paraformaldehyde and methanesulfonamide led to the formation of 1-methylsulfonyl-3,5-bis(trifluoromethylsulfonyl)hexahydro-1,3,5-triazine, and the reaction of trifluoromethanesulfonamide with paraformaldehyde and malonamide gave 4,10-bis(trifluoromethylsulfonyl)-2,4,8,10-tetraazaspiro-[5.5]undecane-1,7-dione whose structure was proved by X-ray analysis.

Electrochemical fluorination of anisole furnished 2-and 4-fluoroanisoles in a 3:1 ratio, guaiacol, and 4,4′-dimethoxydiphenyl ether. Phenylacetonitrile alongside the fluorination in the ring suffered the transformation of the cyano group into a trifluoromethyl. 4-Bromobenzamide was fluorinated to a high conversion mostly in the ring to afford predominantly 4-bromo-3,3,6,6-tetrafluoro-1,4-cyclohexadienecarboxamide. 4-Bromonitrobenzene in a low yield gave 4-bromofluoronitrobenzene and 3,4-dibromofluoronitrobenzene. 3-Bromo-nitrobenzene and 1,4-dichlorobenzene lid not undergo fluorination. In the course of the electrolysis of the 4-bromobenzamide and 4-bromonitrobenzene in anhydrous HF apart the fluorination occurred also the bromination of the substrates.

We succeeded to observe at low temperature in reactions of trifluoromethanesulfonic anhydride and trifluoromethanesulfonyl chloride with hydrazine, phenyl hydrazine, and 1,1-dimethylhydrazine a formation of the corresponding trifluoromethanesulfonic hydrazides that at heating to room temperature decomposed liberating nitrogen and affording trifluoromethanesulfinic acid. 2-Phenyl-2 H -1,2,3-triazole-4-carboxylic hydrazide reacted with trifluoromethanesulfonic anhydride to furnish trifluoro-N'-(2-phenyl-2 H -1,2,3-triazol-4-ylcarbonyl)methane-sulfonic hydrazide that decomposed at heating with elimination of trifluoromethanesulfinic acid and nitrogen yielding 2-phenyl-2 H -1,2,3-triazole-4-carbaldehyde.

A labile equilibrium between monomeric trifluoromethanesulfonamide and its trimer and cyclic dimers in the gas phase at 385-485 K was determined by IR spectroscopy and quantum-chemical calculations (B3LYP/6-31G*).

Electrochemical fluorination of acetofenone and benzophenone was studied in anhydrous HF and in solutions. The electrochemical fluorination of acetophenone in HF occurred exclusively in the ring and furnished ortho- and meta-isomers of fluoroacetophenone, 2,5-difluoroacetophenone, and 1-(3,3,6,6-tetrafluoro-1,4-cyclohexadienyl)-1-ethanone. The fluorination of benzophenone in anhydrous HF furnished predominantly m-fluorobenzophenone, whereas in the presence of chloroform only chlorination products were obtained. The electrochemical fluorination of acetophenone in acetonitrile gave rise only to mono- and difluorinated products. The reasons for readily occurring oxidative fluorination of aromatic compounds into polyfluoro-1,4-cyclohexadienes were discussed, and the decomposition paths of fluorinated products under electron impact were considered.

Electrochemical fluorination of benzamide in anhydrous hydrogen fluoride does not involve the amide group but occurs exclusively at the aromatic ring, yielding isomeric fluoro- and difluorobenzamides and 3,3,6,6-tetrafluoro-1,4-cyclohexadienecarboxamide. Electrochemical fluorination of benzamide in acetonitrile as solvent gives the same products, as well as benzonitrile and its fluorinated derivatives and products of hydrolysis and fluorination of acetonitrile. Electrochemical fluorination of acetanilide in anhydrous HF leads to complete tarring of the reaction mixture, while its fluorination in acetonitrile results in selective formation of m-fluoroacetanilide.