2495-32-1Relevant articles and documents
Highly Substituted 1,3-Dienes, IV. An Experimental and Theoretical Study of the Stereochemical Properties of 2-tert-Butyl-1,3-butadiene and 2,3-Di-tert-butyl-1,3-butadiene
Traetteberg, Marit,Hopf, Henning,Lipka, Helmut,Haenel, Ralf
, p. 1459 - 1468 (2007/10/02)
The molecular structure and conformation of 2-tert-butyl-1,3-butadiene (1) and of 2,3-di-tert-butyl-1,3-butadiene (2) have been studied by the gas electron diffraction method.The monosubstituted compound is observed to have a gauche orientation (φ = 32 deg) of the conjugated C=C bonds.The forces determining the preferred conformation of this molecule (syn or gauche) appear to be similar to those operative in the case of the high-energy conformer of unsubstituted 1,3-butadiene.The disubstituted compound has an approximately perpendicular orientation of the C=C-C=C system (φ = 101.5 deg), and in this case the preferred orientation is described as a result of minimalization of the nonbonded interactions. - Theoretical calculations of the structure and conformation of the two molecules have been carried out by molecular mechanics (MM3) and by ab initio (HF/3-21G) methods.The results from both sets of calculations are in good agreement with the observed structures of the two compounds. - Key Words: Dienes, conjugated / Conformation / Butadienes, orthogonal, gauche / Gas electron diffraction