Abstract
The alkylation of 5-(β-dimethylaminoethyl)tetrazole (1) with dimethyl sulfate afforded 5-(β-dimethylaminoethyl)-1-methyltetrazole (2) and 5-(β-dimethylaminoethyl)-2-methyltetrazole (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 sulfates. 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.
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2082—2088, October, 2009.
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Ostrovskii, V.A., Podkameneva, M.E., Poplavskii, V.S. et al. Kinetics and mechanism of formation of isomeric 1-methyl- and 2-methyl-5-vinyltetrazoles. Russ Chem Bull 58, 2147–2153 (2009). https://doi.org/10.1007/s11172-009-0293-y
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DOI: https://doi.org/10.1007/s11172-009-0293-y