The Reactions of Nitrogen Tetroxide with Organic Compounds.

Some organic syntheses with clay-supported reagents

“…N204 is known to effect nitrations (Ross et al, 1980;Riebsomer, 1945). Moreover, there is a constant interest in the chemistry of nitrogen oxides as substitutes for highly corrosive reagents such as hot mixtures of nitric and sulphuric acids, as used in industry.…”

Some Studies of the Oxides of Nitrogen

“…1, at pressures up to 7000 pounds per square inch (psi) in the temperature interval between 40° and 34Ö J F. The desired quantities of nitrogen dioxide or mixtures of this compound with nitric oxide were added to the vessel and the equilibrium pressure was determined at a series of temperatures. The oxides of nitrogen are interesting inorganic chemical compounds and have been studied extensively (1,2). In the case of nitrogen dioxide, an increase in pressure favors the formation of a dimeric molecule (nitrogen tetroxide) from two molecules of nitrogen dioxide.…”

“…Neither nitrogen dioxide nor nitric oxide undergoes significant decomposition when stored in mild steel containers. The nitrogen dioxide and its mixtures with nitric oxide are relatively active oxidants and apparently play an important part in the nitration of many organic compounds (2,9). For this reason they should be considered as useful additions to the series of compounds which may be employed as the oxidant in binary liquid fuel systems despite their toxicity.…”

Development of Nitrolactonization Mediated by Iron(III) Nitrate Nonahydrate

“…Lower equivalent of Fe(NO 3 ) 3 would not be enough to undergo NO 2 addition reaction but lead to decomposition of 5a probably due to the equilibrium mixture between NO 2 and its various reactive isomers of N 2 O 4 (entry 5). [40][41][42][43] Higher equivalent of Fe(NO 3 ) 3 would generate a high concentration of HNO 3 , which lead to proto-lactonization rather than radical addition of NO 2 (entry 6). To investigate the assumption that the heating-up time and reaction temperature would affect the reaction progress and yield, the reaction mixture was quickly heated (entries 7-9).…”

“…It was assumed that cleavage of the O-NO bond of E took place in the reaction media or by addition of water during the workup stage. The ambident property of NO 2 might produce nitrite intermediate C. It had been reported not only that partial pressure of oxygen influenced the production of nitrite adducts in the reaction of isobutylene and N 2 O 4 which has been regarded as an equilibrium mixture with NO 2 , [40][41][42][43]45) but also that oxidative cleavage of a tetrasubstituted olefin catalyzed by Fe(NO 3 ) 3 would proceed via a dinitrite intermediate in the presence of molecular oxygen. 37) We speculated that production of 6a might be related to the amount of dissolved oxygen in the reaction media, however the detailed effect of the dissolved oxygen on the production of 6a was unclear.…”