R. Glaser, and R. Kent Murmann, C. Barnes
Feb 9, 1996
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0
Influential Citations
32
Citations
Journal
Journal of Organic Chemistry
Abstract
NOCl addition to 2-methyl-2-butene produces a white crystalline solid which was shown by low-temperature X-ray diffraction to contain trans-dimers 2 of 2-chloro-2-methyl-3-nitrosobutane (1n): C10H20N2O2Cl2, Mr = 271.18, monoclinic, I2/a, a = 11.982(4), b = 7.1297(7), c = 15.735(5) A, β = 90.20(2)°, V = 1344.2(6) A3, Z = 4, Dx = 1.340(2) g cm-3, (Mo Kα) = 0.70930 A, μ = 4.7 cm-1, F(000) = 1152, T = 173 K, R = 0.030, Rw = 0.032 for 791 observed reflections of 898 unique data. Diazene dioxide 2 also is the dominant species in solution although some spectroscopic and chemical observations indicate the presence of monomeric nitroso compound 1n and of the tautomeric oxime 1o at least in small quantities. In conjunction with the experimental study, conformational and configurational equilibrium structure preferences and the bonding in diazene dioxides R(O)NN(O)R‘ (3: R = R‘ = H, 4: R = H, R‘ = Me, 5: R = R‘ = Me) were studied at the MP2(full)/6-31G* level. The 1A‘ and 3A‘‘ states of HNO and MeNO and the oxim...