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Too Short-Lived or Not Existing Species: N‑Azidoamines Reinvestigated

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journal contribution
posted on 19.02.2019, 00:00 by Klaus Banert, Tom Pester
Treatment of N-chlorodimethylamine with sodium azide in dichloromethane does not lead to N-azidodimethylamine, as thought for more than 50 years. Instead, surprisingly, (azidomethyl)­dimethylamine is generated with good reproducibility. A plausible reaction mechanism to explain the formation of this product is presented. The reaction of lithium dibenzylhydrazide with tosyl azide does not result in the creation of an N-azidoamine, which can be detected by IR spectroscopy at ambient temperature, as it was claimed previously. Additional experiments with diazo group transfer to lithium hydrazides show that intermediate N-azidoamines are very short-lived or their formation is bypassed by direct generation of 1,1-diazenes via synchronous cleavage of two N–N bonds.