Azines Chichibabin amination

H.C. van der Plas u. M. Wozniak, Croat. Chem. Acta 59, 33-49 (1968) . .Potassium Permanganate in Liquid Ammonia. An Effective Reagent in the Chichibabin Amination of Azines". 

Van der, P. H. C. Potassium permanganate in liquid ammonia. An effective reagent in the Chichibabin amination of azines (review). Khim. Geterotsiki. Soedin. 1987,1011-1027. 

An evaluation of the effect of benzo annelation on the ease of the Chichibabin reaction in the azine and azole series was made by Doron kin et al. (79CHE218). They related the dependence on time of the total amount of gas evolved as a measure of the activity of the compound. For azine compounds aminated in o-xylene with sodium amide, the activity decreased in... 

The Chichibabin amination reaction, first reported by Chichibabin and Zeide in 1914, is simply a reaction for the introduction of an amino group to azines. This is one of the first examples of nucleophilic hydrogen substitution (SnH) reactions and is considered one of the most influential reactions in heterocyclic chemistry transformations of pyridines and azines in the 20th century. " ... 

The Chichibabin reaction138 and other aminations of nitrogen heterocycles139 have been reviewed. Accounts of the introduction of an amino group into azines and nitroaromatic... 

The examples shown are illustrative of the many easy nucleophilic additions to the polyaza-azines both 3-phenyl-l,2,4,5-tetrazine and 1,3,5-triazine itself add ammonia and simple amines (contrast the requirement for hot sodamide (Chichibabin reaction) for pyridine (8.3.1.2)) and thus amino and alkyamino derivatives can be obtained via oxidative trapping with permanganate. 

The examples shown below are illustrative of the many easy nucleophilic additions to the polyaza-azines the reaction of 1,2,4,5-tetrazine with simple amines can be contrasted with the requirement for sodamide (Chichibabin reaction) for the diazines and pyridine. The easy addition at C-5 of 1,2,4-tri-azines is shown by the VNS reaction of the 3-methylthio-derivatives in the absence of activating groups the ready displacement of methylthio from the same compound is also indicative. ... 

The most common nncleophiles that are resistant toward oxidation are ammonia and hydroxide anion. Indeed, such strong oxidant as KMnO is soluble in liquid ammonia and forms solutions that are stable even at room temperature (under pressure). These solutions are efficient agents for amination of electron-deficient nitroarenes and azines that proceeds via addition of ammonia to the ring, followed by oxidation of the o -adducts with KMnO. This amination process of azines is often referred to as the oxidative Chichibabin reaction [7]. For instance, the reaction... 

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