Acid/Base properties of alcohols

Several important chemical reactions of alcohols involving the O-H bond or oxygen-hydrogen bond only and leave the carbon-oxygen bond intact. An important example is salt formation with acids and bases. Alcohols, like water, are both weak bases and weak acids. The acid ionization constant (Ka) of ethanol is about 10~18, slightly less than that of water. Ethanol can be converted to its conjugate base by the conjugate base of a weaker acid such as ammonia {Ka — 10~35), or hydrogen (Ka ~ 10-38). It is convenient to employ sodium metal or sodium hydride, which react vigorously but controllably with alcohols:

The order of acidity of various liquid alcohols generally is water > primary > secondary > tertiary ROH. By this we mean that the equilibrium position for the proton-transfer reaction (Equation 15-1) lies more on the side of ROH and OHe as R is changed from primary to secondary to tertiary; therefore, tert-butyl alcohol is considered less acidic than ethanol:

However, in the gas phase the order of acidity is reversed, and the equilibrium position for Equation 15-1 lies increasingly on the side of ROGas R is changed from primary to secondary to tertiary, terf-Butyl alcohol is therefore more acidic than ethanol in the gas phase. This seeming contradiction appears more reasonable when one considers what effect solvation (or the lack of it) has on equilibria expressed by Equation 15-1. In solution, the larger anions of alcohols, known as alkoxide ions, probably are less well solvated than the smaller ions, because fewer solvent molecules can be accommodated around the negatively charged oxygen in the larger ions:

Acidity of alcohols therefore decreases as the size of the conjugate base increases. However, “naked” gaseous ions are more stable the larger the associated R groups, probably because the larger R groups can stabilize the charge on the oxygen atom better than the smaller R groups. They do this by polarization of their bonding electrons, and the bigger the group, the more polarizable it is. (Also see Section 11-8A, which deals with the somewhat similar situation encountered with respect to the relative acidities of ethyne and water.)

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مواضيع ذات صلة

Diastereotopic protons in acyclic compounds

Spotting diastereotopic protons in the NMR spectrum

How to tell if protons are homotopic, enantiotopic, or diastereotopic

The size of the geminal coupling constant

Geminal (2J) coupling

Heteroatoms in rings have axial and equatorial lone pairs

Four-membered rings

Ring size and NMR

Baldwin’s rules and ring opening

Combatting ΔS‡—the Thorpe–Ingold effect

Thermodynamic control over ring size

Making heterocycles: ring-closing reactions