Compounds with Nitrogen Chains

For sodium triimide, vide the action of sodium on hydrazine. The inclination of nitrogen to form long chains and closed rings is far less than is the case with carbon with the latter, there seems an almost unlimited number of hydrogen compounds with nitrogen, comparatively few are known, and these are usually unstable bodies, often explosive. 

Hydroxypyrroles. Pyrroles with nitrogen-substituted side chains containing hydroxyl groups are best prepared by the Paal-Knorr cyclization. Pyrroles with hydroxyl groups on carbon side chains can be made by reduction of the appropriate carbonyl compound with hydrides, by Grignard synthesis, or by iasertion of ethylene oxide or formaldehyde. For example, pyrrole plus formaldehyde gives 2-hydroxymethylpyrrole [27472-36-2] (24). The hydroxymethylpyrroles do not act as normal primary alcohols because of resonance stabilization of carbonium ions formed by loss of water. 

Diaziridines, discovered in 1958, six years after the oxaziridines, were almost immediately realized to be structural analogs of oxaziridines. Like these they showed oxidizing properties unexpected for other classes of organic nitrogen compound. Properties in common with oxaziridines include the rearrangement to open chain isomers on heating above 100 °C (for several diaziridines), and their hydrolytic behavior in acidic media, which leads to carbonyl compounds with conservation of the hetero-hetero bond. 

Cyclization of the side chain onto the nitrogen atom leads to compounds with sedative and tranquilizing activity. The lack of structural specificity, that is, the fact that both positional isomers (41,43) show the same activity, is notable. Thus, condensation of the Grignard reagent from 2-bromopyridine with ben-zophenone affords the tertiary carbinol, 40. Catalytic reduction... 

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