Selective N-15-Labeling and Analysis of C-13-N-15 J Couplings as an Effective Tool for Studying the Structure and Azide-Tetrazole Equilibrium in a Series of Tetrazolo{[}1,5-b]{[}1,2,4]triazines and Tetrazolo{[}1,5-a]pyrimidines / Deev Sergey L.,Shenkarev Zakhar O.,Shestakova Tatyana S.,Chupakhin Oleg N.,Rusinov Vladimir L.,Arseniev Alexander S. // JOURNAL OF ORGANIC CHEMISTRY. - 2010. - V. 75, l. 24. - P. 8487-8497.

ISSN/EISSN:

0022-3263 / нет данных

Type:

Article

Abstract:

Two general methods for the selective incorporation of an N-15-label in the azole ring of tetrazolo{[}1,5-b]{[}1,2,4]triazines and tetrazolo{[}1,5-a]pyrimidines were developed. The first approach included treatment of azinylhydrazides with N-15-labeled nitrous acid, and the second approach was based on fusion of the azine ring to {[}2-N-15]-5-aminotetrazole. The synthesized compounds were studied by H-1, C-13, and N-15 NMR spectroscopy in both DMSO and TFA solution, in which the azide-tetrazole equilibrium is shifted to tetrazole and azide forms, respectively. Incorporation of the N-15-label led to the appearance of C-13-N-15 J coupling constants (J(CN)), which can be measured easily using either 1D C-13 spectra with selective N-15 decoupling or with amplitude modulated 1D C-13 spin-echo experiments with selective inversion of the N-15 nuclei. The observed J(CN) patterns permit unambiguous determination of the type of fusion between the azole and azine rings in tetrazolo{[}1,5-b]{[}1,2,4]triazine derivatives. Joint analysis of J(CN) patterns and N-15 chemical shifts was found to be the most efficient way to study the azido-tetrazole equilibrium.

Author keywords:

NUCLEAR MAGNETIC-RESONANCE; STRUCTURE ELUCIDATION; DERIVATIVES; TAUTOMERISM; PYRIMIDINE; PRODUCTS; NMR; TRANSFORMATIONS; SPECTROSCOPY; HETEROCYCLES

DOI:

10.1021/jo1017876

Web of Science ID:

ISI:000285081100019

Соавторы в МНС:

Другие поля

Поле	Значение
Month	DEC 17
Publisher	AMER CHEMICAL SOC
Address	1155 16TH ST, NW, WASHINGTON, DC 20036 USA
Language	English
Keywords-Plus	NUCLEAR MAGNETIC-RESONANCE; STRUCTURE ELUCIDATION; DERIVATIVES; TAUTOMERISM; PYRIMIDINE; PRODUCTS; NMR; TRANSFORMATIONS; SPECTROSCOPY; HETEROCYCLES
Research-Areas	Chemistry
Web-of-Science-Categories	Chemistry, Organic
Author-Email	deevsl@yandex.ru chupakhin@ios.uran.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{''} {[}P2444]; Russian Foundation for Basic Research {[}10-03-01007]; Russian Federation {[}Nsh-65261.2010.3]
Funding-Text	This work was supported by the Federal Target Program ``Scientific and Science-Educational Personnel of Innovative Russia{''} (State contract P2444), Russian Foundation for Basic Research (project no. 10-03-01007), and President's of Russian Federation grant (Grant for Leading Scientific Schools Nsh-65261.2010.3).
Number-of-Cited-References	65
Usage-Count-Since-2013	13
Journal-ISO	J. Org. Chem.
Doc-Delivery-Number	691LK