Cyclisation of alpha-diazonitriles to 5-halo-1,2,3-triazoles: A computational study / Fabian Walter M. F.,Bakulev Vasiliy A.,Janoschek Rudolf // JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM. - 2007. - V. 821, l. 1-3. - P. 89-94.

ISSN/EISSN:

0166-1280 / нет данных

Type:

Article

Abstract:

Density functional theory {[}3LYP/6-31G(d) with inclusion of solvent effects by the Onsager SCRF approximation] is used to investigate the mechanism of the hydrogen halide induced cyclisation of alpha-diazonitriles to 5-halo-1,2,3-triazoles. The reaction occurs stepwise. The first step, addition of the hydrogen halide onto the nitrile group to form diazo imidoyl halides, is rate determining. Barriers are calculated to be in the range 20-30 kcal mol(-1). The largest ones were found for 2-diazornalononitrile and 2-trifluoroacetyl-2-diazoacetonitrile. The second step, cyclisation of these intermediates to the triazoles, has a significantly lower barrier, < 15 kcal mol(-1). (c) 2007 Elsevier B.V. All rights reserved.

Author keywords:

density functional theory; {[}2+2]; {[}4+2] cycloaddition; cyclisation; transition states; substituent effects REACTION FIELD MODEL; ENERGY DERIVATIVES; AB-INITIO; 5-SUBSTITUTED 4-CHLORO-1,2,3-TRIAZOLES; DISTRIBUTED MULTIPOLES; HYDROGEN HALIDES; HALOGEN ACIDS; DENSITY; 1,2,3-TRIAZOLES; REACTIVITY

DOI:

10.1016/j.theochem.2007.06.028

Web of Science ID:

ISI:000250652300011

Соавторы в МНС:

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Другие поля

Поле	Значение
Month	NOV 1
Publisher	ELSEVIER SCIENCE BV
Address	PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS
Language	English
Keywords-Plus	REACTION FIELD MODEL; ENERGY DERIVATIVES; AB-INITIO; 5-SUBSTITUTED 4-CHLORO-1,2,3-TRIAZOLES; DISTRIBUTED MULTIPOLES; HYDROGEN HALIDES; HALOGEN ACIDS; DENSITY; 1,2,3-TRIAZOLES; REACTIVITY
Research-Areas	Chemistry
Web-of-Science-Categories	Chemistry, Physical
Author-Email	walter.fabian@uni-graz.at
Number-of-Cited-References	42
Usage-Count-Last-180-days	1
Usage-Count-Since-2013	2
Journal-ISO	Theochem-J. Mol. Struct.
Doc-Delivery-Number	227JF