Synthesis and spectroscopic investigation of aryloxy- and arylthioalkenes, alkynes, and allenes

Filippova, A. Kh.; Frolov, Yu. L.; Lyashenko, G. S.; Modonov, V. B.; Ivanova, N. A.; Kalikhman, I. D.; Воронков, М. Г.; Vyazankin, N. S.

doi:10.1007/bf00954612

Cited by 3 publications

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“…10 kcal/mol more preferable than that of the 2‐propenyl cation . Raman and UV spectral study of aryloxy‐ and arylthioalkenes, ‐alkynes and ‐allenes has shown that the π‐electron system in these molecules forms a united conjugation system . As to N‐allenylsulfonamides, they are poorly studied, even synthetically.…”

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

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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.

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Section: Introductionmentioning

confidence: 99%