A fragmentation pattern is suggested for 1-nitropropane by comparing its mass spectrum with that of its a-, p-and y-deuterated analogues.As part of an investigation on the behaviour of nitro compounds upon electron impact, we have studied the mass spectrum of 1-nitropropane. With electrons of 70 eV no peak corresponding with the molecular ion (m/e = 89) is found, but a small peak at m/e = 90 was detected. This agrees with the work of Collin who found it impossible to determine ionisation potentials for nitroethane and 1-nitropropane.Nevertheless, we shall represent the molecular fragmentations as arising from the decomposition of (unstable) molecular ions which probably result by loss of an electron from one of the oxygen atoms.By comparison of the ordinary spectrum with those of the a-, B-and y-deuterated derivatives, we can assume that the molecular ion decomposes in different ways (see Figs. 1 to 4).
Intramolecular hydrogen transfer and water eliminationIn the mass spectra of 1-nitropropane and its B-deuterated analogue a small peak is found at m/e = 61. In the spectra of the a-and y-deuterated compounds, this peak is shifted to m/e = 63 and 62, respectively [scheme I, sequence (a) to (d)].The peak at m/e = 72 in the mass spectrum of the undeuterated compound shifts to m/e = 74 for the three deuterated nitropropanes [scheme I, sequence (a) to (e)].This can all be explained by a hydrogen transfer from the y-C atom to one of the oxygen atoms from the nitro group. The "rearranged" ion can decompose in two ways. The sequence leading to the ion (d) at m/e = 61 resembles the elimination of an olefin from alkyl ketones and esters, con-J . Collin, Bull. Soc. Roy. Sci. Likge 23, 194 (1954).
to this compound is again based largely on its NMR spectrum (see Figure), in which the signals for the ring-and bridge protons exhibit the expected large shifts to lower (0.4-1.7 7 ) and higher fields (10.3 and 11.8 T, J = 10 cps),respectively,reIative to the signals in the spectrum of (2). Compound (2) and the salt ( 3 ) must have the same carbon skeleton, for on catalytic hydrogenation both give the same saturated hydrocarbon C12H~2, which we consider to be bicyclo [5,4, Ildodecane. The N M R and ultraviolet spectra of (3) resemble those of the benzotropylium cation 151.
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