Long-Range H-1-N-15 J Couplings Providing a Method for Direct Studies of the Structure and Azide-Tetrazole Equilibrium in a Series of Azido-1,2,4-triazines and Azidopyrimidines / Shestakova Tatyana S.,Shenkarev Zalchar O.,Deev Sergey L.,Chupakhin Oleg N.,Khalymbadzha Igor A.,Rusinov Vladimir L.,Arseniev Alexander S. // JOURNAL OF ORGANIC CHEMISTRY. - 2013. - V. 78, l. 14. - P. 6975-6982.

ISSN/EISSN:

0022-3263 / нет данных

Type:

Article

Abstract:

The selectively N-15 labeled azido-1,2,4-triazine 2{*}A and azidopyrimidine 4{*}A were synthesized by treating hydrazinoazines with N-15-labeled nitrous acid. The synthesized compounds were studied by H-1, C-13, and N-15 NMR spectroscopy in DMSO, TFA, and DMSO/TFA solutions, where the azide-tetrazole equilibrium could lead to the formation of two tetrazoles (T, T') and one azide (A) isomer for each compound. The incorporation of the N-15 label led to the appearance of long-range H-1-N-15 coupling constants (J(HN)), which can be measured easily by using amplitude-modulated 1D H-1 spin echo experiments with selective inversion of the N-15 nuclei. The observed J(HN) patterns enable the unambiguous determination of the mode of fusion between the azole and azine rings in the two groups of tetrazole isomers (2{*}T', 4{*}T' and 2{*}T, 4{*}T), even for minor isoforms with a low concentration in solution. However, the azide isomers (2{*}A and 4{*}A) are characterized by the absence of detectable J(HN) coupling. The analysis of the J(HN) couplings in N-15-labeled compounds provides a simple and efficient method for direct NMR studies of the azide tetrazole equilibrium in solution.

Author keywords:

NUCLEAR-MAGNETIC-RESONANCE; STRUCTURE ELUCIDATION; ALKYNE CYCLOADDITION; NMR; NUCLEOSIDES; ANALOGS; SYSTEMS

DOI:

10.1021/jo4008207

Web of Science ID:

ISI:000322210700013

Соавторы в МНС:

Другие поля

Поле	Значение
Month	JUL 19
Publisher	AMER CHEMICAL SOC
Address	1155 16TH ST, NW, WASHINGTON, DC 20036 USA
Language	English
Keywords-Plus	NUCLEAR-MAGNETIC-RESONANCE; STRUCTURE ELUCIDATION; ALKYNE CYCLOADDITION; NMR; NUCLEOSIDES; ANALOGS; SYSTEMS
Research-Areas	Chemistry
Web-of-Science-Categories	Chemistry, Organic
Author-Email	deevsl@yandex.ru
ResearcherID-Numbers	Shenkarev, Zakhar/P-1808-2015
ORCID-Numbers	Shenkarev, Zakhar/0000-0003-1383-3522 Deyev, Sergey/0000-0002-3952-0631
Funding-Acknowledgement	Federal Target Program ``Scientific and Science-Educational Personnel of Innovative Russia{''} {[}14.A18.21.0806]; Russian Foundation for Basic Research {[}10-03-01007, 12-03-31476]
Funding-Text	This work was supported by the Federal Target Program ``Scientific and Science-Educational Personnel of Innovative Russia{''} (State Contract No. 14.A18.21.0806) and the Russian Foundation for Basic Research (Project Nos. 10-03-01007 and 12-03-31476).
Number-of-Cited-References	42
Usage-Count-Last-180-days	5
Usage-Count-Since-2013	37
Journal-ISO	J. Org. Chem.
Doc-Delivery-Number	188RG