NITRATION AGENTS AND METHODS MORE RARELY USED 101Phenylacetylene reacted with N 2 O 3 to yield phenylfuroxane:
(25)Petrov and Bulygina [6] found that under the conditions they used, transfer
of the double bond into the β− position with reference to the nitro group occurred,
similar to the transfer occurring in chlorination reactions, according to the mecha-
nisms proposed by Lvov [83] and by Tishchenko [84]. For example, octene- ∆^1
gave 1-nitrooctene- ∆^2 under the action of dinitrogen tetroxide:
CH 2 =CH(CH 2 ) 5 CH 3 ->NO 2 CH 2 CH = CH(CH 2 ) 4 H 3 (26)The action of dinitrogen tetroxide on aldoximes has several interesting features.
N 2 O 4This reaction has been studied by Scholl [85], Potio [35] (benzaldoxime), Mills
[86] (isonitrosoacetone), and recently by Boyer and Alul [87].
The last authors investigated the reaction with acetaldoxime, propionaldoximeand benzaldoxime. They came to the conclusion that dinitrogen tetroxide both
nitrates and oxidizes aldoximes. The nitration is more pronounced with increase
of temperature whereas oxidation is most effective at 0°C and below.
Boyer and Alul suggest the following scheme for the reactions: