Pivalic acid is a carboxylic acid with a molecular formula of (CH3)3CCO2H. This colourless, odoriferous organic compound is solid at room temperature. Two abbreviations for pivalic acid are t-BuC(O)OH and PivOH. The pivalyl or pivaloyl group is abbreviated t-BuC(O).
Pivalic acid is an isomer of valeric acid, the other two isomers of it are 2-methylbutanoic acid and 3-methylbutanoic acid.
Preparation
Pivalic acid is prepared on a commercial scale by hydrocarboxylation of
isobutene via the
Koch reaction:
- (CH3)2C=CH2 + CO + H2O → (CH3)3CCO2H
Such reactions require an acid
catalyst such as hydrogen fluoride.
tert-Butyl alcohol and
isobutyl alcohol can also be used in place of isobutene. Globally, several million kilograms are produced annually.
Pivalic acid is also economically recovered as a byproduct from the production of semisynthetic penicillins like
ampicillin and
amoxycillin.
It was originally prepared by the oxidation of pinacolone with chromic acid:
An alternative oxidative route uses aqueous bromine and proceeds by oxidation of pinacolone.
The hydrolysis of
Pivalonitrile has also been described.
[Butlerow, Ann. 165, 322 (1873).] Another laboratory route involves carbonation of the
Grignard reagent formed from
tert-butyl chloride
Applications
Relative to esters of most carboxylic acids,
of pivalic acid are unusually resistant to hydrolysis. Some applications result from this thermal stability. Polymers derived from pivalate esters of
vinyl alcohol are highly reflective lacquers.
Use in the laboratory
Pivalic acid is sometimes used as an internal chemical shift standard for
NMR spectra of aqueous solutions. While DSS is more commonly used for this purpose, the minor peaks from protons on the three methylene bridges in DSS can be problematic. The
1H NMR spectrum at 25 °C and neutral pH is a singlet at 1.08 ppm.
Pivalic acid is employed as co-catalyst in some palladium-catalyzed C-H functionalization reactions.
Alcohol protection
The pivaloyl (abbreviated Piv or Pv) group is a
protective group for alcohols in organic synthesis. Common protection methods include treatment of the alcohol with pivaloyl chloride (PvCl) in the presence of
pyridine.
Alternatively, the esters can be prepared using pivaloic anhydride in the presence of Lewis acids such as scandium triflate (Sc(OTf)3).
Common deprotection methods involve hydrolysis with a base or other nucleophiles.
See also
