Nitrodesilylation with

Nitrodesilylation with nitronium tetrahuoroborate is also a mild and efficient way to prepare aiiphatic nitrocompounds from readily available alkylsilanes. Olah and Rochin have studied [151] the scope of the reaction, Tetramethylsilane reacts readily with NOJBFJ in sulfolane solution to give nitromethane in 80% yield. 

Although alkylsilanes, as discussed, undergo nitrodesilylation with NO2 BF4, organostannanes in preference undergo one-electron oxidation with nitronium salts. 

A decrease in the nitric acid concentration caused R to decrease as it did during a particular run (in which the acid concentration would decrease with time). Thus nitrodesilylation would seem to be of higher order than nitrodeprotonation. 

Olah and co-workers reported the synthesis of nitroalkanes and nitroalkenes from the nitrodesilylation of alkylsilanes and allylsilanes, respectively, with nitronium salts. 

Nitroacetylenes are generally unstable and very explosive and so they have been little studied. Schmitt and co-workers used the nitrodesilylation of trialkylsilylacetylenes with both nitronium salts and nitryl fluoride to obtain nitroacetylenes. Dinitrogen pentoxide has also been used for the nitrodesilylation of trialkylsilylacetylenes. Nitrodestannylation of allylsilanes has also been reported. " ... 

Millar and Philbin have explored the nitrodesilylation of silylamines with dinitrogen pen-toxide for the synthesis of nitramines and their derivatives. These reactions, which involve nitra-tive Si-N heteroatom cleavage, are conducted in methylene chloride at subambient temperature. Trimethylsilylamines give high yields of nitramine product and reactions are clean (Table 5.8). 

Synthesis of nitramines, nitramides and nitroureas via the nitrodesilylation of A/-trimethyisilyl compounds with dinitrogen pentoxide (ref. 122)... 

Olah and Narang [148] found that reaction of nitronium tetrafluorobo-rate with phenyltrimethylsilane gives only limited (10%) nitrodesilylation besides intact (predominantly para) ring nitration. 

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