Vinyltetrazoles: synthesis and properties

Kizhnyaev, V. N.; Vereshchagin, L. I.

doi:10.1070/rc2003v072n02abeh000731

Cited by 64 publications

(27 citation statements)

References 46 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…458 Salt 7 shows a clear-cut polyelectrolyte activity toward an aseptic inflammatory process, which may be used to accelerate healing of wounds and to suppress scar formation. 459 Trialkylstannyl derivatives of 5-aryl-and -hetaryltetrazoles 103 were patented as herbicides and animal parasite control means. 460 Gadolinium(III) complexes 50 and 51 71 and the complexes GdL 3 (H 2 O) n and Na[GdL(H 2 O)] obtained from ligands 226 71 and 227, 461 respectively, are promising for the use in medicine as contrasting agents for magnetic resonance diagnostics.…”

Section: Applications Of Metal Tetrazole Derivativesmentioning

confidence: 99%

Metal derivatives of tetrazoles

Гапоник¹,

2006

View full text Add to dashboard Cite

Published data on the synthesis, structure, properties Published data on the synthesis, structure, properties and applications of metal derivatives of tetrazoles are generalised and applications of metal derivatives of tetrazoles are generalised and described systematically. Compounds based on the anionic and described systematically. Compounds based on the anionic and neutral tetrazole forms, and neutral tetrazole forms, C C-and -and N N-mono-and -mono-and C C, ,N N-disubsti--disubstituted tetrazoles are considered. The bibliography includes 464 tuted tetrazoles are considered. The bibliography includes 464 references references. . ReceivedDepending on the reaction conditions, meta-and para-5,5 Hphenyleneditetrazoles 25 react with Cd, Zn and Mn(II) salts to give essentially different, as regards both composition and structure, complexes 26, 27, 44 28, 45 29. 46 The structures of compounds 26 ± 29 were determined by X-ray diffraction. Compounds 26 ± 28 in which the doubly charged anions derived from tetrazole 25 function as bridges are two-and three-dimensional coordination polymers. Conversely, compound 29 is a mononuclear aqua complex containing no metal ± tetrazole coordination bond. In the structure of complex 28, one-dimensional channels were found which occupy up to 35% of the void volume and encapsulate tetrameric cyclic water clusters and DMF molecules. On heating to 150 8C, water and DMF are removed from the channels, which accounts for the interest of researchers in this type of compound for the preparation of inclusion compounds and sorbents. A coordination polymer with a composition similar to complex K + 7

show abstract

Section: Applications Of Metal Tetrazole Derivativesmentioning

confidence: 99%

Metal derivatives of tetrazoles

Гапоник¹,

2006

View full text Add to dashboard Cite

show abstract

“…1 Beginning from the 1960s chemists are searching for efficient methods of syn thesis of N alkyl 5 vinyltetrazoles. 2 This search is imped ed by numerous quantitative studies of key chemical pro cesses resulting in 5 vinyltetrazole derivatives. The results on studying the kinetics of alkylation of NH unsubstituted 5 vinyltetrazole with methyl iodide in an acetonitrile me dium in the presence of triethylamine have recently 3 been published.…”

mentioning

confidence: 99%

Kinetics and mechanism of formation of isomeric 1-methyl- and 2-methyl-5-vinyltetrazoles

et al. 2009

View full text Add to dashboard Cite

The alkylation of 5 (β dimethylaminoethyl)tetrazole (1) with dimethyl sulfate afforded 5 (β dimethylaminoethyl) 1 methyltetrazole (2) and 5 (β dimethylaminoethyl) 2 methyltetr azole (3). The exhaustive alkylation of compounds 2 and 3 at the terminal dimethylamino group gave 1 methyl (4) and 2 methyl 5 (β trimethylammonioethyl)tetrazole (5) methyl sul fates. The proton elimination from the α methylene (with respect to the tetrazole cycle) groups of the quaternary ammonium cations of salts 4 and 5 by the action of a base leads to the corresponding zwitterions 4 ± and 5 ± , which in the rate determining step undergo the cleavage of the nitrogen-carbon bond with the formation of 1 methyl 5 vinyl (6) and 2 methyl 5 vinyltetrazole (7). The true constant of the transformation of zwitterion 4 ± into tetrazole 6 is 21 times higher than that for the transformation of zwitterion 5 ± into tetrazole 7.Key words: 1 methyl 5 vinyltetrazole, 2 methyl 5 vinyltetrazole, kinetics of formation, deamination mechanism.Isomeric N alkyl 5 vinyltetrazoles are initial mono mers in the synthesis of the corresponding poly(vinyl tetrazoles), which are promising high energy polymers with a series of unique properties. 1 Beginning from the 1960s chemists are searching for efficient methods of syn thesis of N alkyl 5 vinyltetrazoles. 2 This search is imped ed by numerous quantitative studies of key chemical pro cesses resulting in 5 vinyltetrazole derivatives. The results on studying the kinetics of alkylation of NH unsubstituted 5 vinyltetrazole with methyl iodide in an acetonitrile me dium in the presence of triethylamine have recently 3 been published. The hypothetical mechanism was formulated 3 and the boundaries for changing the reaction conditions, which allow one to control the rate and selectivity of alky lation in certain limits, were determined. However, since the initial substrate is NH unsubstituted 5 vinyltetrazole is a hardly accessible compound yet, the patented method for the preparation of N alkyl 5 vinyltetrazoles based on the synthesis and subsequent alkylation of 5 (β dimethyl aminoethyl)tetrazole with dimethyl sulfate in an aqueous medium in the presence of alkaline metal hydroxide seems more promising. 4,5 The variants of this method described in the cited patents are almost identical and only differ by the nature of the base used: NaOH (see Ref. 4) and KOH (see Ref. 5), respectively. Let us consider the hypothetical sequence of the synthesis of isomeric N methyl 5 vinyltetr azoles postulated in the patents 4,5 (Scheme 1).Isomeric vinyltetrazoles 6 and 7 are formed due to the deamination of intermediate quaternary ammonium salts Scheme 1

show abstract

“…Vinyltetrazoles and their derivatives are promising substrates in the synthesis of various tetrazolecontaining polymers with valuable properties utilized in medicine and engineering [1]. Synthesis of some derivatives of vinyltetrazoles, in particular, of styryltetrazoles, is poorly understood.…”

Section: Short Communicationsmentioning

confidence: 99%

“…

In a series of publications [2, 3] the synthesis of styryltetrazoles, containing substituents with strong electron-acceptor properties (F, NO 2 , CN, CO 2 H) in the aryl fragment based on cross-coupling of С-, Nvinyltetrazole with halobenzenes by Heck reaction is described.

…”

mentioning

confidence: 99%

Heck reaction of 2-methyl-5-vinyl-2H-tetrazole with iodoarenes

et al. 2015

View full text Add to dashboard Cite

SHORT COMMUNICATIONSVinyltetrazoles and their derivatives are promising substrates in the synthesis of various tetrazolecontaining polymers with valuable properties utilized in medicine and engineering [1]. Synthesis of some derivatives of vinyltetrazoles, in particular, of styryltetrazoles, is poorly understood.In a series of publications [2, 3] the synthesis of styryltetrazoles, containing substituents with strong electron-acceptor properties (F, NO 2 , CN, CO 2 H) in the aryl fragment based on cross-coupling of С-, Nvinyltetrazole with halobenzenes by Heck reaction is described. However no information exists on the synthesis of similar compounds containing electrondonor substituents. The electronic effect of the substituent in the aromatic fragment may significantly affect the efficiency of this reaction. The nature of the halogen present in the haloarene and the composition of the catalytic system are also of fundamental importance [4][5][6][7].In this study we synthesized styryltetrazoles 3a-3d, containing in the para-position of the aromatic fragment donor (Me, t-Bu, MeO) and weakly acceptor (Cl) substituents. In the reaction with 2-methyl-5-vinyl-2Н-tetrazole iodoarenes 2a-2d were used applying as a catalyst Pd(OAc) 2 . The reaction was carried out in the presence of K 2 CO 3 in DMF at heating.In all cases the reaction proceeded with high yields (73-80%). The cross-coupling occurs stereoselectively affording exclusively Е-2-methyl-5-styryltetrazoles 3a-3d, as show the large values of the spin-spin coupling constants ( 3 J 16.5 Hz).Hence, 2-methyl-5-vinyl-2H-tetrazole enters in Heck reaction with iodoarenes containing not only electron-acceptor (as has been shown in [2,3]), but also electron-donor substituents at the use as a catalytic system Pd(OAc) 2 in the presence of K 2 CO 3 in DMF. (3a-3d). General procedure. Pd(OAc) 2 (4 mol %) was added to a solution of 45 mmol of iodoarene 2a-2d in 5 mL of DMF under an argon atmosphere. The reaction mixture 2-Methyl-5-styryl-2H-tetrazoles

show abstract

Vinyltetrazoles: synthesis and properties

Cited by 64 publications

References 46 publications

Metal derivatives of tetrazoles

Metal derivatives of tetrazoles

Kinetics and mechanism of formation of isomeric 1-methyl- and 2-methyl-5-vinyltetrazoles

Heck reaction of 2-methyl-5-vinyl-2H-tetrazole with iodoarenes

Contact Info

Product

Resources

About