Nitrosation of Cyanamide: Preparation and Properties of the Elusive E‐ and Z‐N'‐Cyanodiazohydroxides

Nitrosation of cyanamide leads to unstable E/Z‐cyanodiazohydroxides that easily deprotonate to E/Z‐cyanodiazotates. Pursuing observations of E. Drechsel 145 years ago, the structure and reactivity of those products was determined, mainly in aqueous solution. Depending on the pH, three different ther...

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Published inEuropean journal of organic chemistry Vol. 2020; no. 17; pp. 2537 - 2541
Main Authors Guethner, Thomas, Huber, Evi, Sans, Juergen, Thalhammer, Franz
Format Journal Article
LanguageEnglish
Published Weinheim Wiley Subscription Services, Inc 10.05.2020
Subjects
Aqueous solutions
Cyanamide
Cyanodiazohydroxides
Diazo compounds
Nitrous oxide
Quantum mechanics
Thermal decomposition
Thermochemistry
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Summary:Nitrosation of cyanamide leads to unstable E/Z‐cyanodiazohydroxides that easily deprotonate to E/Z‐cyanodiazotates. Pursuing observations of E. Drechsel 145 years ago, the structure and reactivity of those products was determined, mainly in aqueous solution. Depending on the pH, three different thermal decomposition pathways give either N2O + HCN or N2 + HNCO. They were evaluated experimentally and by quantum mechanical calculations. The simple reaction between cyanamide and nitrous acid in aqueous solution leads to unstable azo intermediates that easily decompose into gaseous products. Principally known for 145 years, the elusive intermediates and complex reaction pathways were identified and characterized for the first time. Depending on pH conditions, either N2O + HCN or N2 + HNCO are formed by three different decomposition pathways.
ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.202000181