Springer Online Journal Archives 1860-2000
Chemistry and Pharmacology
Abstract The interaction of alcohols ROH with esters PhCOOR (R = Me,n-Bu,n-C7H15) in binary mixtures and in solutions in non-polar solvents (CCl4, cyclohexane) was studied over a wide temperature range by Fourier IR spectroscopy. Even with a great excess of alcohol (up to 3000-fold molar excess), two bands are observed in the region ofv(CO) vibrations. The low-frequency band, which is down-shifted by 15–20 cm−1 with respect to thev(CO) band in the absence of alcohol, corresponds to ester molecules bonded by hydrogen bonds of the C=O...HO type. The high-frequency band is up-shifted by 3–5 cm−1 with respect to the esterv(CO) band. The discreteness of the shift, which is confirmed by the appearance of an isobestic point, indicates that an H-complex of yet another type is formed between the alcohol and the ester. The analysis of the data available allows one to conclude that complex formation involves the alkoxyl oxygen atom of the ester. The enthalpies of formation were determined forn-BuOH H-bonds with the esters and with the transesterification catalysts, i.e., As(OBu)3, B(OBu)3, and Ti(OBu)4.
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