4-(Dimethylamino)Pyridinium Azide in Protic Ionic Liquid Media as a Stable Equivalent of Hydrazoic Acid

We report a procedure for the multigram synthesis of 4-(dimethylamino)pyridinium azide, a stable, non-explosive, low-hygroscopic source of azide ion soluble in both protic and aprotic organic solvents. In protic ionic liquid media this reagent was shown to serve as a safer equivalent of toxic and unstable hydrazoic acid. The synthetic utility of this system was demonstrated using donor-acceptor cyclopropane ring opening as a model process. General procedures furnishing a variety of dialkyl (2-azido-2-arylethyl)malonates or 4-azido-4-arylbutyrates, depending on the protic ionic liquid applied, were elaborated. The conversion times for studied donor-acceptor cyclopropanes were established providing the relative reactivity sequence. The application of 4-(dimethylamino)pyridinium azide for a conventional nucleophilic substitution, oxirane ring opening, (3+2)-cycloaddition to (thio)cyano group as well as their combinations realized as telescopic synthesis was also demonstrated. © 2022 Wiley-VCH GmbH.

Andreev I.A.1 , Boichenko M.A.2 , Ratmanova N.K.1 , Ivanova O.A. 2 , Levina I.I.3 , Khrustalev V.N. 4, 5 , Sedov I.A.6 , Trushkov I.V. 1, 4
Wiley-VCH Verlag
  • 1 Dmitry Rogachev National Medical Research Center of Pediatric Hematology, Oncology and Immunology, Samory Mashela st. 1, Moscow, 117997, Russian Federation
  • 2 M. V. Lomonosov Moscow State University, Department of Chemistry, Leninskie Gory 1–3, Moscow, 119991, Russian Federation
  • 3 N. M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Kosygina st. 4, Moscow, 119334, Russian Federation
  • 4 N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky pr. 47, Moscow, 119334, Russian Federation
  • 5 RUDN University, Faculty of Science, Miklukho-Maklaya st. 6, Moscow, 117198, Russian Federation
  • 6 Chemical Institute, Kazan Federal University, Kremlevskaya st. 18, Kazan, 420008, Russian Federation
Ключевые слова
Azides; Donor-acceptor cyclopropanes; Ionic liquids; Nitrogen heterocycles; Small ring systems
Дата создания
Дата изменения
Постоянная ссылка

Другие записи