A new method for the halogenation of olefinic bonds without the utilization of molecular halogens is described. This synthetic technique is based on the reaction of olefins with copper(II) halides in the presence of strong coordinating agents. Simple olefins are converted to vicinal dihaloalkanes in good to excellent yields. Conjugated diolefins experienced predominately 1,4 addition. Complexed copper(II) halides in combination with different halide donors afforded an in situ synthesis of pseudohalogen compounds, which yielded ultimately chloroiodoand chlorobromoalkanes. The general scope of these reactions has been demonstrated for a variety

second fraction (bp 134-136°) was better than 95% monchloride (3.2 g, 80%). It could be used as such for further reaction. On vpc examination (Silicone oil column 20 ft, or Ucon-550 column 6 ft, or diisodecyl phthalate column 6 ft) the material was found to consist of three monochlorides which were in the ratio 2.5:95.0:2.5. The major component was separated by chromatography, The minor components were not identified. The purified monochloride, «25d 1.4725, had strong infrared absorptions (µ, neat liquid) at 3.35, 7.78, 10.85, and 14.10; mol wt 116, 118 (mass spectrometry). (For the nmr spectrum, see Results.

±0.002) Á, b = 17.509 (±0.002) Á, c = 8.833 (±0.001) Á, 0 -102.78 (±0.03)°, space group, P2i/c, molecules/unit cell, 4, density (caled) = 1.289 g/cm3, and density (measured by flotation) = 1.32 g/cm8.Intensity data were collected by the stationary counterstationary crystal technique using balanced filters for Cu Ka radiation.14 The intensities (maximum two -100°) were converted to structure factor amplitudes by applying appropriate corrections for absorption, ai-at splitting, and Lorentz-polarization effects. These data were scaled by Wilson statistics15 and converted to their respective normalized structure factors.The phases of the 159 largest normalized structure factors were derived by the application of the Sayre relationships.16 Electron density and least squares calculations using all the data enabled the atomic coordinates of atoms and the thermal parameters (hydrogens isotropically and others anisotropically) to be refined. The final R index for the observed data was 0.038. A table of ( 14) T. F. Furnas and D.

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