3624.     WEGHOFER, H.  [Addition of N2O4 to Olefinic Double Bonds.]  Erdöl u. Kohle, vol. 4, 1951, pp. 1-3; Brennstoff-Chem., vol. 30, 1949, p. 440.

        Addition of N2O4 to 2-methylbutene-2 was investigated to clarify the structure of the reaction products.  In connection therewith, Fischer-Tropsch olefins were converted, and the composition of the reaction products as well as several of the reactions were described.  By adding N2O4 to olefins, such as 2-methylbutene-2, there are formed, besides crystallized nitrosonitrate, an oily fraction, which, like the nitrous ester of 3-nitro-2-methylbutanol-2, is changed by treatment with NaOH into 3-nitro-2-methylbutanol-2 (nitronitrite).  In performing the reaction, saponification with NaOH takes place at once, the nitrosonitrate yielding oximes and the nitronitrite nitroalcohols.  The % division of the reaction products depends largely upon the reaction temperature, furthermore a very definite effect of peroxide addition exists.  For example, the division at 0° without peroxide gives 73% oxime and 27% nitroalcohol; with 1% benzoyl-peroxide, 40% oxime and 60% nitroalcohol.  The addition of N2O4 to a Fischer-Tropsch heptene in butanol solution yields, among other compounds, a dioxynitro compound.  There are, thus, 3 reaction products available:  A nitrosonitrate, a nitronitrite and a dinitro compound, the proportion of each depending upon the chosen reaction conditions (temperature and additives), the solvent agents, and the structure of the olefins.