Nitrates heterolytic fission

Investigations by Honeyman [3] have shown that two modes of heterolytic fission of 2,3-nitrate groups can occur under the action of sodium methoxide in methanol on 4,6-O-benzylidene-a-D-glucoside 2,3-nitrate. 

Propargyl cations may also be generated by heterolytic fission of the C—X bond of allenyl derivatives (178). Early attempts to solvolyse chloride 178 (R = H R = Me) in alcoholic solution, even in the presence of silver nitrate, did not furnish reliable conclusions concerning the possibility of unimolecular solvolysis through the propargyl cation (Pudovik, 1951 Hennion and Maloney, 1951). The apparently slow... 

The reaction of piperidine with N2O4 yields both the N-nitroso- and N-nitroamines. The yield of nitrosamine increases with increasing [piperidine] but levels off at ca 50 %, whereas the nitroamine yield increases almost linearly. The two products are believed to arise from the two isomers of N2O4 (Scheme 17), the nitroamine resulting from homolytic fission of the N—N bond, whilst the nitroso product is formed by initial heterolytic fission of the N—O bond in the nitroso nitrate form (Challis and Kyrtopoulos, 1978). 

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