Copolymerizations of acrylonitrile and isoprene or butadiene were carried out in the presence of a new catalytic system containing Cr(O‐tert‐Bu)4 and AlEtCl2. It was found that the copolymer compositions have a highly alternating structure, even with varying feed ratios of monomer. The nuclear magnetic resonance spectra of the copolymers obtained with this catalytic system were observed and are discussed in terms of the alternation.
SynopsisThe complex of acrylonitrile (AN) with trimethylaluminum (AlMe3) was successfully isolated as a white needlelike crystal with a melting point of 42.5OC. In this article the preparation of the complex is described in detail. Cryoscopic and spectral investigations indicated that the complex is formed by an equimolar ratio of AN and AlMe3. From the measurement of the x-ray diffraction photograph of the crystal the repeat period was determined to be 9.47 f 0.05 A.
The pyrolyses of cyanoacetamides, 2-phenylacetanilide, 2,2-diphenylacetanilide and 2,2,2-triphenylacetanilide have been studied. The pyrolysis of cyanoacetamides gave the corresponding isocyanates and acetonitrile. On the other hand, the pyrolysis of 2-phenylacetanilide and 2,2-diphenylacetanilide gave a small amount of phenyl isocyanate, along with various byproducts. The pyrolysis of 2,2,2-triphenyl-acetanilide, however, against expectation, did not give isocyanate; only a tarry product resulted.
SynopsisThe reaction of MAN with AlMe3 was studied by the Wand 'H-NMR spectral measurement.In the presence of an excess of AlMe3, it was found that a 1:l complex of MAN and AIMe:I is initially formed and subsequently dimethyl(a-methyl isopropylidene amino)aluminum is produced by the reaction of the complex with AlMe3. The isolated product was pale yellow crystal (mp 39-40°C). The kinetics of the reaction were also examined.
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