On the Aminolysis of Bis‐Imidoylchlorides of Oxalic Acid. II. Reaction with Aliphatic Diamines and Aminoalcohols
The aminolysis of bis‐imidoylchloride 1 derived from oxalic acid with several diamines and aminoalcohols was investigated. At room temperature diamines 2 as well as aminoalcohols 7 give mainly the cyclic amidines 3 and mixed amidine‐imidates 8 in moderately up to good yields. While cis‐1,2‐diaminocyclohexane yields at room temperature the bicyclic amidine 3a, the trans isomer reacts to 3b only when heated for several hours. Depending on the conditions, the racemic 1,2‐diaminopropane 2h gives derivatives of pyrazine 3h or the open‐chain amidine 5 resulting from an oxidative aromatization and subsequent hydrolysis. Histamine 2i and 1,8‐diamino‐3,6‐dioxaoctane 2p react selectively with 1 to seven‐ respectively twelve‐membered heterocycles 3i and 3p. The mixed aliphatic and aromatic diamines 2n, o show an anomalous behaviour leading to 2,2′‐bis‐chinazolines 3n, o.
In comparison with acyclic oxalic amidines the new cyclic derivatives show less molecular dynamic in their nmr spectra. In some cases, a s‐trans‐arrangement of the amidine substructure was observed.
The reaction of pyrido[1,2‐a]pyrazines 1 with nitroso compounds 2 provides pyridyl substituted 1,2,4‐triazinones 4 via a domino reaction which involves a cycloaddition and a ring transformation reaction. The intermediate and regioselective formed oxadiazines 4′ were trapped by complexation yielding the (CO)4Mo‐complex 5. Derivatives of diazene such as N‐phenyltriazolindione 6a, phthalazinedione 6b or esters of azodicarboxylic acid 6c‐6f reacted with 1 to give different derivatives of 1,2,4‐triazine 7a‐f. The use of oxygen gave oxadiazinones 8.
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