Banert Klaus, Pester Tom
Chemnitz University of Technology , Organic Chemistry , Strasse der Nationen 62 , 09111 Chemnitz , Germany.
J Org Chem. 2019 Apr 5;84(7):4033-4039. doi: 10.1021/acs.joc.9b00034. Epub 2019 Feb 25.
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.
在二氯甲烷中用叠氮化钠处理N-氯代二甲胺，并不会如五十多年来人们所想的那样生成N-叠氮基二甲胺。相反，令人惊讶的是，（叠氮甲基）二甲胺能够以良好的重现性生成。本文提出了一个合理的反应机理来解释该产物的形成。二苄基肼锂与对甲苯磺酰叠氮的反应并不会生成如之前所宣称的在室温下能用红外光谱检测到的N-叠氮基胺。将重氮基团转移至肼锂的其他实验表明，中间产物N-叠氮基胺寿命极短，或者通过两个N-N键的同步断裂直接生成1,1-重氮烯从而绕过了其形成过程。
