Regioselective alkylation of amino- and mercapto-1,2,4-triazoles with t-BuOH–HClO4

Войтехович, Сергей В.; Lyakhov, Alexander S.; Ivashkevich, Ludmila S.; Матулис, Вадим Э.; Grigoriev, Yury V.; Гапоник, П. Н.; Ивашкевич, Олег А.

doi:10.1016/j.tet.2012.04.063

Cited by 18 publications

(6 citation statements)

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“…Selective N 1 ‐alkylation can be explained by the complete protonation of initial triazole with formation of 4 H ‐[1,2,4]triazol‐1‐ium cation 3 , in which only N 1 atom is accessible for electrophilic attack with tert ‐butyl cation generated by t BuOH–HClO 4 system. This mechanism is proposed by analogy with that of N 1 ‐ tert ‐butylation of 5‐amino‐1,2,4‐triazole . It should be noted that during the alkylation, precipitate of perchlorate 4 was initially formed.…”

Section: Resultsmentioning

confidence: 89%

Copper(II) Halide Complexes with 1‐tert‐Butyl‐1H‐1,2,4‐triazole and 1‐tert‐Butyl‐1H‐tetrazole

Войтехович

Degtyarik

Lyakhov

et al. 2017

Zeitschrift anorg allge chemie

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1-tert-Butyl-1H-1,2,4-triazole (tbtr) was found to react with copper(II) chloride or bromide to give the complexes [Cu(tbtr) 2 X 2 ] n and [Cu(tbtr) 4 X 2 ] (X = Cl, Br). 1-tert-Butyl-1H-tetrazole (tbtt) reacts with copper(II) bromide resulting in the formation of the complex [Cu 3 (tbtt) 6 Br 6 ]. The obtained crystalline complexes as well as free ligand tbtr were characterized by elemental analysis, IR spectroscopy, thermal and X-ray analyses. For free ligand tbtr, 1 H NMR and 13 C NMR spectra were also recorded. In all the complexes, tbtr and tbtt act as monodentate ligands coordinated by Cu II cations via the * Dr. S. V. Voitekhovich Fax: +375172264696 E-Mail: azole@tut.by [a] 100 heteroring N 4 atoms. The triazole complexes [Cu(tbtr) 2 Cl 2 ] n and [Cu(tbtr) 2 Br 2 ] n are isotypic, being 1D coordination polymers, formed at the expense of single halide bridges between neighboring copper(II) cations. The isotypic complexes [Cu(tbtr) 4 Cl 2 ] and [Cu(tbtr) 4 Br 2 ] reveal mononuclear centrosymmetric structure, with octahedral coordination of Cu II cations. The tetrazole compound [Cu 3 (tbtt) 6 Br 6 ] is a linear trinuclear complex, in which neighboring copper(II) cations are linked by single bromide bridges. Scheme 1. 1-R-Tetrazoles and structural motifs of their copper(II) halide complexes.dentate coordination (Scheme 2). It should be noted that complexes of type A are of interest since they undergo ferromagnetic transition at temperatures lower than 10 K. [10] Scheme 2. The N 4 coordination mode of 1-R-tetrazoles and 1-R-1,2,4triazoles, realized in their copper(II) halide complexes.

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Section: Resultsmentioning

confidence: 89%

Copper(II) Halide Complexes with 1‐tert‐Butyl‐1H‐1,2,4‐triazole and 1‐tert‐Butyl‐1H‐tetrazole

Войтехович

Degtyarik

Lyakhov

et al. 2017

Zeitschrift anorg allge chemie

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“…A suitable starting point for our work was provided by the recent report that the commercially available 3-amino-1,2,4-triazole is readily di- tert -butylated under mild conditions on a multigram scale by a mixture of tert -butanol and 65% aqueous perchloric acid to furnish 1- tert -butyl-3- tert -butylamino-1,2,4-triazol-4-ium perchlorate, whose subsequent reaction with dilute aqueous sodium hydroxide cleanly affords 1- tert -butyl-3- tert -butylamino-1,2,4-triazole ( 5 ) [ 58 ]. The methylation of this compound with trimethyloxonium tetrafluoroborate in dichloromethane occurred exclusively at N 4 ( Scheme 1 ); 1- tert -butyl-3- tert -butylamino-4-methyl-1,2,4-triazol-4-ium tetrafluoroborate ( 6 H[BF 4 ]) was obtained almost quantitatively.…”

Section: Resultsmentioning

confidence: 99%

“…Gold and silver compounds were handled with exclusion of light. 1- tert -Butyl-3- tert -butylamino-1,2,4-triazole ( 5 ) [ 58 ] and [AuCl(THT)] (THT = tetrahydrothiophene) [ 111 ] were synthesized by adapted versions of published procedures. A Hettich ROTINA 46 RS centrifuge suitable for Schlenk tubes was used to separate precipitates, which could not easily be removed by filtration.…”

Section: Methodsmentioning

confidence: 99%

Coinage Metal Complexes of the Carbenic Tautomer of a Conjugated Mesomeric Betaine Akin to Nitron

et al. 2017

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This study was motivated by our recent observation that the analytical reagent Nitron (2) is an “instant carbene”, whose reaction with coinage metal salts MX afforded complexes of its carbenic tautomer 1,4-diphenyl-3-phenylamino-1,2,4-triazol-5-ylidene (2′). Our aim was to establish an alkyl homologue of 2 in order to achieve a carbenic tautomer of higher donicity. For this purpose 1-tert-butyl-4-methyl-1,2,4-triazol-4-ium-3-tert-butylaminide (6) was synthesized. Its reactions with MX afforded complexes of the carbenic tautomer 1-tert-butyl-3-tert-butylamino-4-methyl-1,2,4-triazol-5-ylidene (6′). With a stoichiometric ratio of 1:1 complexes of the type [MX(6′)] were obtained. A ratio of 2:1 furnished complexes of the type [MX(6′)2] or [M(6′)2]X. 6′ is a better σ-donor and less electrophilic than 2′ according to NMR spectroscopic data of 6H[BF4] and 6′ = Se, respectively, and IR spectroscopic data of [RhCl(6′)(CO)2] confirm that its net electron donor capacity is superior to that of 2′. A comparison of the complexes of 2′ and 6′ reveals two pronounced structural differences. [CuX(6′)2] (X = Cl, Br) exhibit more acute C–Cu–C bond angles than [CuX(2′)2]. In contrast to [CuCl(2′)], [CuCl(6′)] aggregates through Cu···Cu contacts of ca. 2.87 Å, compatible with cuprophilic interactions. These differences may be explained by the complementary steric requirements of the t-Bu and the Me substituent of 6′.

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“…Particularly, the 1 H NMR spectra of 2 and 3 lack the signal of the C( 5)H proton that is observed at 9.74 ppm in the spectrum of the triazolium salt 1. 7 The formation of the metalcarbon also leads to a significant (up to 38 ppm) downfield shift of C( 5) resonances in comparison with the spectrum of the precursor salt (145.3 ppm). The 13 C NMR spectrum of 3 displays a singlet resonance at 183.2 ppm, whereas in the spectrum of silverĲI) complex 2 the carbene carbon appears as a doublet of doublets due to fully resolved coupling to both silver isotopes ĳ 1 JĲ 13 C-107 Ag) = 190.3 Hz; 1 JĲ 13 C-109 Ag) = 219.5 Hz], which can be quite rarely observed experimentally.…”

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confidence: 99%

“…The 1,2,4-triazolium perchlorate 1 was synthesized by excessive tert-butylation of 4-amino-1,2,4-triazole in acidic media according to a previously reported method. 7 NHC complexes 2 and 3 were obtained using a modified silverĲI) oxide procedure proposed by Wang and Lin 8 (see Scheme 1).…”

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confidence: 99%

A novel aminotriazole-based NHC complex for the design of gold(i) anti-cancer agents: synthesis and biological evaluation

2015

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Regioselective alkylation of amino- and mercapto-1,2,4-triazoles with t-BuOH–HClO4

Cited by 18 publications

References 30 publications

Copper(II) Halide Complexes with 1‐tert‐Butyl‐1H‐1,2,4‐triazole and 1‐tert‐Butyl‐1H‐tetrazole

Copper(II) Halide Complexes with 1‐tert‐Butyl‐1H‐1,2,4‐triazole and 1‐tert‐Butyl‐1H‐tetrazole

Coinage Metal Complexes of the Carbenic Tautomer of a Conjugated Mesomeric Betaine Akin to Nitron

A novel aminotriazole-based NHC complex for the design of gold(i) anti-cancer agents: synthesis and biological evaluation

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