Nitrilimine

Nitrilimines or nitrile amides are a class of organic compounds sharing a common functional group with the general structure R-CN-NR corresponding to the conjugate base of an amine bonded to the N-terminus of a nitrile. The dominant structure for the parent compound nitrilimine is that of the propargyl-like 1 in scheme 1 with a C-N triple bond and with a formal positive charge on nitrogen and two lone pairs and a formal negative charge on the terminal nitrogen. Other structures such as hypervalent 2, allene-like 3, allylic 4 and carbene 5 are of lesser relevance.


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Nitrilimines were first observed in the thermal decomposition of 2-tetrazoles releasing nitrogen:[1]

Scheme 2. Nitrilimine formation

 

 

 

 

(6)

Nitrilimines are linear 1,3-dipoles represented by structures 1 and 3. A major use is in heterocyclic synthesis. E.g. with alkynes they generate pyrazoles in a 1,3-dipolar cycloaddition. Due to their high energy, they are usually generated in situ as a reactive intermediate.

References
  1. Communications: The Formation of Nitrile Imines in the Thermal Breakdown of 2,5-Disubstituted Tetrazoles Rolf Huisgen Michael Seidel, Juergen Sauer, James McFarland, Guenter WallbillichJ. Org. Chem.; 1959; 24(6); 892-893 Abstract
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