Abstract
Detailed structures of methacrolein dimer (MAD) were analyzed by nuclear magnetic resonance (NMR) and theoretical calculations. Two dimensional 1H and 13C NMR peaks were assigned. Relative stability of conformations and interconversion barrier height were studied by semi-empirical MNDO and ab initio DFT calculations. Barrier height between pseudoaxial and pseudoequatorial half-chair conformers was 5.8 kcal mol−1. Separations of chemical shifts of two protons bonded to the same methylene carbons became larger as measurement temperature decreased, due to reduced mobility of the ring framework.
Similar content being viewed by others
Article PDF
References
Y. Kitahama, H. Ohama, and H. Kobayashi, J. Polym. Sci., B, 5, 1019 (1967).
Y. Kitahama, J. Polym. Sci., A-1, 6, 2309 (1968).
J. Maslinska-Solich, A. Macionga, and R. Turczyn, Polish J. Appl. Chem., 39, 467 (1995).
J. Maslinska-Solich, A. Macionga, and R. Turczyn, Reactive & Functional Polymers, 26, 35 (1995).
C. H. Bushweller and J. W. O’Neil, Tetrahedron Lett., 53, 4713 (1969).
E. L. Eliel, M. Manoharan, K. M. Pietrusiewicz, and K. D. Hargrave, Org. Magn. Reson., 21, 94 (1983).
SpecInfo(R) 3.1.6.0, Chemical Concepts GmbH, 1996.
UniChem(R) chemistry codes, APG-5505 3.0, Cray Research, Inc., 1995.
A. D. Becke, J. Chem. Phys., 84, 4524 (1986).
J. P. Perdew, Phys. Rev., 33, 8822 (1986).
F. A. I. Anet, in “The Comformational Analysis of Cyclohexenes, Cyclohexadienes, and Related Hydroaromatic Compounds,” P. W. Rabideau, Ed., VCH Publishers, New York, N.Y., 1989, Chapter 1.
M. M. J. Tecklenburg and J. Laane, J. Am. Chem. Soc., 111, 6920 (1989).
F. A. L. Anet, D. I. Freedberg, J. W. Storer, and K. N. Houk, J. Am. Chem. Soc., 114, 10969 (1992).
C. W. Andrews, B. Fraser-Reid, and J. P. Bowen, J. Am. Chem. Soc., 113, 8293 (1991).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Sofue, S., Yamasaki, T., Morita, H. et al. NMR and Theoretical Study on Conformation of Methacrolein Dimer, 2,5-Dimethyl-3,4-dihydro-2H-pyran-2-carboxyaldehyde. Polym J 30, 891–896 (1998). https://doi.org/10.1295/polymj.30.891
Issue Date:
DOI: https://doi.org/10.1295/polymj.30.891