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Vibrational spectra of 2-methylpropanal: Assignments, self-associations and solvent effects

✍ Scribed by A. Piart-Goypiron; M.H. Baron; J. Belloc; M.J. Coulange; H. Zine


Book ID
103907569
Publisher
Elsevier Science
Year
1991
Tongue
English
Weight
892 KB
Volume
47
Category
Article
ISSN
1386-1425

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✦ Synopsis


Raman

and infrared spectra of 2-methylpropanal (CH,),CHCHO, (CH,),CDCHO and (CH&CHCDO in different physical states (liquid, solid and solution) have been investigated between 4000 and 40cm-'. A complete assignment is carried out on the basis of one predominant conformer (anticlinal) in equilibrium with another less stable one (synperiplanar). Some vibrational modes of the synperiplanar form are identified. The CO stretching region is carefully examined. The complex structure of this band as a function of the physical state of the pure aldehyde and the polarity of the solvent for solutions is discussed. The structure can-be explained by Fermi resonances between combinations and the fundamental vC0 mode. In the pure liquid, as well as in solution, the broadness of the band can be due to random dipolar interactions. In polar basic solvents (CH3CN and DMSO), these interactions implicate both aldehyde and solvent. When the solvent is slightly acidic (HCCI,). weak hydrogen bonds between the aldehydic group and the solvent may occur. Moving from the liquid to the solid state, in addition to the fact that the less stable conformer disappears, molecular association between the CO groups by charge transfer may account for the observed changes. water, the solution was dried with Na2S04 and finally distilled. Despite a careful preparation of the three derivatives, small amounts of undesirable compounds may be observed in the spectra, for instance, traces of 2-methylpropanoic acid, gem-diol (CH&--CH-CH(OH)? and methylene chloride (in MPC'D).


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