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Synthesis and Photolysis of 1,4-Dialkyl-1,4-dihydro-5H-tetrazol-5-ones and -thiones. A Novel Approach to Diaziridinones and Carbodiimides
Quast, Helmut,Bieber, Lothar
, p. 3253 - 3272 (2007/10/02)
The regioselective alkylation of the 1-tert-butyl-1,4-dihydro-5H-tetrazol-5-one (7) produced the 1,4-dialkyltetrazolones 8b and c.The electron impact induced decomposition of the known, most simple tetrazolone 8a proceeded via a cycloelimination into methyl azide and methyl isocyanate.On photolysis in acetonitrile or pentane, the tetrazolones 8 lost nitrogen and formed 1,2-dialkyldiaziridinones 24, of which 24c was isolated in pure form.Very reactive alkylating reagents, e.g. methyl fluorosulfonate, trimethyloxonium tetrafluoroborate, or tert-butyl alcohol/tetrafluoroboric acid in ether, preferentially alkylated N-3 of 1-methyl-5-(methylthio)-1H-tetrazole (9a); dimethyl sulfate reacted almost equally at N-3 or N-4.In the mixture of the salts 10a and 11a obtained in this way, only 11a was demethylated at the sulfur atom by triethylamine in acetonitrile affording the easily separable tetrazolethione 5a.Diazomethane methylated 1-tert-butyl-1,4-dihydro-5H-tetrazole-5-thione (18b) predominantly at the sulfur atom.In contrast, 2-diazopropane gave approximately equal fractions of S-alkylation and N-4-alkylation producing the tetrazolethione 5c.Besides fragment ions resulting from cycloelimination products, in the electron impact induced decomposition of the most simple tetrazolethione 5a, ions were observed which correspond to loss of nitrogen from the molecular ion.On photolysis in alkanes or acetonitrile in the temperature range between +20 and -40 deg C the tetrazolethiones lost nitrogen furnishing high yields of sulfur and the carbodiimides 30.
