Unusual Temperature-Sensitive Protonation Behaviour of 4-(Dimethylamino)pyridine Full article
| Journal |
Organic and Biomolecular Chemistry
ISSN: 1477-0520 , E-ISSN: 1477-0539 |
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| Output data | Year: 2021, Volume: 19, Number: 4, Pages: 866-872 Pages count : 7 DOI: 10.1039/d0ob01893g | ||||||
| Tags | Positive ions; Pyridine | ||||||
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| Affiliations |
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Funding (2)
| 1 | Federal Agency for Scientific Organizations | 0303-2016-0006 (V.44.1.6) |
| 2 | Federal Agency for Scientific Organizations | 0302-2018-0007 (АААА-А18-118020290191-2) |
Abstract:
Stimuli-responsive and, in particular, temperature-responsive smart materials have recently gained much attention in a variety of applications. On the other hand, 4-(dimethylamino)pyridine (DMAP) and related structures are widely used as nucleophilic catalysts and also as specific parts of rationally designed molecules, where reversible reactions of the pyridinic nitrogen with electrophiles are involved. In our study, we have found an unexpectedly significant impact of temperature on the protonation degree of DMAP derivatives, especially in the case of protonation of the 4-(dimethylamino)-1-(2,3,5,6-tetrafluoropyridin-4-yl)pyridinium cation, derived from the reaction of DMAP with pentafluoropyridine. Thus, when dissolved in the TfOH-SO2ClF-CD2Cl2acid system at 30 °C, this cation underwent a slight (<7%) protonation on the dimethylamino group, while the temperature decrease to −70 °C resulted in its complete protonation. Notably, such a scale of this phenomenon has never been observed before for other weak nucleophiles, being many times lower at the same change of temperature. The mechanistic aspects of these intriguing results are discussed. © The Royal Society of Chemistry 2021.
Cite:
Genaev A.M.
, Salnikov G.E.
, Koltunov K.Y.
Unusual Temperature-Sensitive Protonation Behaviour of 4-(Dimethylamino)pyridine
Organic and Biomolecular Chemistry. 2021. V.19. N4. P.866-872. DOI: 10.1039/d0ob01893g WOS Scopus РИНЦ ANCAN PMID OpenAlex
Unusual Temperature-Sensitive Protonation Behaviour of 4-(Dimethylamino)pyridine
Organic and Biomolecular Chemistry. 2021. V.19. N4. P.866-872. DOI: 10.1039/d0ob01893g WOS Scopus РИНЦ ANCAN PMID OpenAlex
Dates:
| Submitted: | Sep 14, 2020 |
| Accepted: | Dec 17, 2020 |
| Published online: | Dec 18, 2020 |
| Published print: | Jan 28, 2021 |
Identifiers:
| Web of science: | WOS:000614577400017 |
| Scopus: | 2-s2.0-85100392285 |
| Elibrary: | 44957999 |
| Chemical Abstracts: | 2020:2624195 |
| Chemical Abstracts (print): | 174:364413 |
| PMID: | 33409515 |
| OpenAlex: | W3111586764 |