with a coupling constant of 16 Hz. The signal of the phenyl protons ortho to the imino nitrogen atom is a multiplet centered at 7 = 2.4 (relative intensity 2); and that of the remaining aromatic protons is a multiplet centered at T ~ 2.8 (relative intensity 8). Analogous substances provide an indication of the shift of signals of the CH2 protons on the four-membered ring to lower field owing to the neighboring nitrogen atom. Further, we also derive structure ( I ) from the mass spectrum, specifically from the appearance of the ion M-42 and of a fragment at m ' e 42 (H~C-N-CHZ). The compound is found to have molecular weight 234. The UV spectrum (in alcohol) includes a n absorption band at 244 nm (E = 12200). In the I R spectrum (KBr) the C = N absorption is at 6.2 pm and, remarkably, three absorption bands occur between 9.98 p n and 10.16 pm. It is tempting t o ascribe the formation of ( I ) to addition of ketene phenyl imine t o phenylazirine. According t o Smolinsk y 111, phenylazirine and ketene phenylimine coexist after pyrolysis of c/.-azidostyrene. The characteristic ketene imine absorption[ll at 5 pm in the IR spectrum of our reaction mixture after photolysis can be explained by presence of a small amount of ketene phenyl imine. However, no trace of ( I ) is t o be found in the gas chromatogram after pyrolysis of a-azidostyrene at 350 "C. Nor is any trace of ( I ) t o be found in the mixture obtained o n addition of azidostyrene t o boiling phenylazirine (ca. 180 "C). From our results, together with the observation that ( I ) is also formed on photolysis of phenylazirine, we conclude that it is formed by photochemical and not by thermal activation. This is thus the first case of intermolecular photocycloaddition t o a carbonnitrogen double bond. [3] Mercury high-pressure lamp: Philips HPK 125 W. 141 The NMR spectra were measured with a Varian A-60 apparatus for CC14 solutions with tetramethylsilane as internal standard. The synthesis of Ru~C15[P(n-C4H9)3]4 has been described recently and the results of chemical investigations suggest 111 the structure ( I ) . The complex has a magnetic moment of 0.75 B.M. per ruthenium atornI21 corresponding to one unpaired electron in the molecule. The dark red crystals are monoclinic, space group P21,'c with a = 13.866, b = 16.003, c = 30.545 A, p = 110.0". There are four molecules in the unit cell and the observed density gives a molecular weight of 1170.7 (theoretical 1188.8). The intensities were measured on a linear diffractometer [31 and the structure was determined by Patterson and Fourier methods.A least squares refinement of 3776 planes gives a current R-factor of 0.083. The standard deviations of the Ru-CI and Ru-P bond lengths are 0.0052 and 0.0054 8, respectively.+ 2 333 1 2 3 2 6The X-ray analysis confirms the structure ( I ) and the Ru-CI and Ru-P distances are shown in the figure. The coordination round the ruthenium atoms is approximately octahedral (the largest angular distortion is 12.4 ") and the environments of these atoms are very similar. The Ru....R...
The pyrrolidine (6) obtained in experiment 2 could be prepared, in 90% yield, also by treatment of one mol of the azomethine N-benzylidenebenzylamine in THF at 20°C with one mol of 2-methylbutadiene and a catalytic amount (0.05 mol) of lithium pyrrolidide. Apparently the lithium pyrrolidide formed in the addition process is able to metalate the azomethine smoothly. This base-catalyzed union of an azomethine (10) and an alkene, which is presumably not restricted to the special system discussed here, may lead to an industrially interesting process. Z
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