N-Azidoamines and -Amides as Possible Synthons

N-azidoamines and -amides are proposed for investigation as potential new organic reagents whose carbon fragments might participate as synthons in the construction of carbon-based frameworks of molecules . The following are examples of such compounds :

When heated , the N-azido compound would decompose to the carbon fragment(s) and two nitrogen molecules . The fragments would combine with each other or with a reactive substrate to produce new carbon-carbon bonds and products .

Additions of the fragments to olefins , and cyclizations , are suggested as the principal applications of the N-azido decompositions . The safety aspect has been emphasized ; catalysis will almost certainly be required for smooth , safe , controlled decompositions of the azides .

Noting the potentially explosive nature of the N-azido compounds , several new molecules of this type have been specifically proposed for investigation as high explosive materials . Their syntheses from industrial precursors are outlined .

The preparation of the novel molecule nitrogen azide , N10 , is also discussed in this report . If it could be synthesized , this compound would be a new nitrogen allotrope :

The ebook has been recently updated to reflect new information concerning azidoamines . They were in fact investigated during the early 1960s , and were found to be very unstable , highly explosive materials . I now consider the N-azidoamines and -amides [tetrazides] to be too hazardous for any future practical utilization . Attempts were also made to prepare the compound nitrogen azide (above) , but without success , as nitrogen was the only product obtained , even at very low temperatures .

An alternate method of generating the new carbon synthons is discussed in the updated ebook , substituting the N-nitroso group for the impractical N-azide group . It might be possible to deoxygenate the N-nitroso to diimide with triphenylphosphine . The unstable diimide intermediate should expel nitrogen to produce the carbon synthons :

For example , cyclobutanone might be prepared from N-nitrosopyrrolidinone by heating with triphenylphosphine in a highly polar solvent such as propylene carbonate :

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