Azidiniumsalze. 22. Mitteilung. über 3‐äthyl‐2‐tetrazo‐6‐X‐benzo[d]thiazoline und ihre Reaktivität: Ein Beitrag zur Chemie nucleophiler Carbene

Abstract

Professor Edgar Heilbronner zum 60. Geburtstag gewidmet (27.1.81) 3-Ethyl-2-tetrazo-6-X-benzo [dthiazolines and Their Reactivity: A Contribution to the Chemistry of Nucleophilic Carbenes SummaryThe synthesis of 3-ethyl-2-tetrazo-6-X-benzo [d]thiazolines 3 -a new class of azohomologous diazo compounds -by addition of azide ions to azidinium salts 4 is described, their structure and some of their reactions are discussed. The thermolysis of 3 at ca. 270 K in DMFA or THF generates nucleophilic carbenes 1, whose trapping by electrophilic compounds such as 3 , 4, diazonium salts, diazo compounds, methanol, sulfur and tetracyanoethylene could be studied. Direct dimerisation of 1 to 2 (without acid/base catalysis) could not be found, as demonstrated by the behavior of 1 e.

Nucleophilic Attack of Azide at Electrophilic Azides: Formation of N6 Units in Hexazene and Aminopentazole Derivatives

“…Moreover, we assume that the decay of 7 and 17 will offer an access to dimethylaminomethylidene, a rarely studied carbene . This expectation is based on the known decomposition reaction of 13 , which led to the corresponding short‐lived benzothiazol‐2‐ylidene …”

Nucleophiler Angriff von Azid auf elektrophile Azide: Bildung von N6‐Einheiten in Hexazen‐ und Aminopentazolderivaten

“…Außerdem vermuten wir, dass der Zerfall von 7 und 17 einen Zugang zu Dimethylaminomethyliden, einem nur sehr selten untersuchten Carben, eröffnen wird. Diese Annahme beruht auf der bekannten Zersetzungsreaktion von 13 , die zum entsprechenden kurzlebigen Benzothiazol‐2‐yliden führt …”

Color Chemistry as Reflected in Helvetica Chimica Acta

“…of N,, generates nucleophilic carbenes, whose trapping by electrophilic compounds, e.g. with the starting material (3A-3B) or with arenediazonium ions, provides evidence of their nucleophilicity [50].…”