Unusual Temperature-Sensitive Protonation Behaviour of 4-(Dimethylamino)pyridine Научная публикация
| Журнал |
Organic and Biomolecular Chemistry
ISSN: 1477-0520 , E-ISSN: 1477-0539 |
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| Вых. Данные | Год: 2021, Том: 19, Номер: 4, Страницы: 866-872 Страниц : 7 DOI: 10.1039/d0ob01893g | ||||||
| Ключевые слова | Positive ions; Pyridine | ||||||
| Авторы |
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| Организации |
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Информация о финансировании (2)
| 1 | Федеральное агентство научных организаций России | 0303-2016-0006 (V.44.1.6) |
| 2 | Федеральное агентство научных организаций России | 0302-2018-0007 (АААА-А18-118020290191-2) |
Реферат:
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.
Библиографическая ссылка:
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 CAPlusCA 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 CAPlusCA PMID OpenAlex
Даты:
| Поступила в редакцию: | 14 сент. 2020 г. |
| Принята к публикации: | 17 дек. 2020 г. |
| Опубликована online: | 18 дек. 2020 г. |
| Опубликована в печати: | 28 янв. 2021 г. |
Идентификаторы БД:
| Web of science: | WOS:000614577400017 |
| Scopus: | 2-s2.0-85100392285 |
| РИНЦ: | 44957999 |
| Chemical Abstracts: | 2020:2624195 |
| Chemical Abstracts (print): | 174:364413 |
| PMID (PubMed): | 33409515 |
| OpenAlex: | W3111586764 |