Carboxylic acid

Solubility

Carboxylic acid dimers

Carboxylic acids are polar. Because they are both hydrogen-bond acceptors (the carbonyl –C=O) and hydrogen-bond donors (the hydroxyl –OH), they also participate in hydrogen bonding. Together the hydroxyl and carbonyl group forms the functional group carboxyl. Carboxylic acids usually exist as dimeric pairs in nonpolar media due to their tendency to "self-associate." Smaller carboxylic acids (1 to 5 carbons) are soluble in water, whereas higher carboxylic acids are less soluble due to the increasing hydrophobic nature of the alkyl chain. These longer chain acids tend to be rather soluble in less-polar solvents such as ethers and alcohols.^[5]

Boiling points

Carboxylic acids tend to have higher boiling points than water, not only because of their increased surface area, but also because of their tendency to form stabilised dimers. Carboxylic acids tend to evaporate or boil as these dimers. For boiling to occur, either the dimer bonds must be broken or the entire dimer arrangement must be vaporised, both of which increase the enthalpy of vaporization requirements significantly.

Acidity

Carboxylic acids are Brønsted–Lowry acids because they are proton (H⁺) donors. They are the most common type of organic acid.

Carboxylic acids are typically weak acids, meaning that they only partially dissociate into H⁺ cations and RCOO⁻ anions in neutral aqueous solution. For example, at room temperature, in a 1-molar solution of acetic acid, only 0.4% of the acid molecules are dissociated. Electronegative substituents give stronger acids.

Deprotonation of carboxylic acids gives carboxylate anions; these are resonance stabilized, because the negative charge is delocalized over the two oxygen atoms, increasing the stability of the anion. Each of the carbon–oxygen bonds in the carboxylate anion has a partial double-bond character.

Odor

Carboxylic acids often have strong odors, especially the volatile derivatives. Most common are acetic acid (vinegar) and butyric acid (human vomit). Conversely esters of carboxylic acids tend to have pleasant odors and many are used in perfume.

Industrial routes

In general, industrial routes to carboxylic acids differ from those used on smaller scale because they require specialized equipment.

• Oxidation of aldehydes with air using cobalt and manganese catalysts. The required aldehydes are readily obtained from alkenes by hydroformylation.
• Oxidation of hydrocarbons using air. For simple alkanes, this method is inexpensive but not selective enough to be useful. Allylic and benzylic compounds undergo more selective oxidations. Alkyl groups on a benzene ring are oxidized to the carboxylic acid, regardless of its chain length. Benzoic acid from toluene, terephthalic acid from para-xylene, and phthalic acid from ortho-xylene are illustrative large-scale conversions. Acrylic acid is generated from propene.^[7]
• Base-catalyzed dehydrogenation of alcohols.
• Carbonylation is versatile method when coupled to the addition of water. This method is effective for alkenes that generate secondary and tertiary carbocations, e.g. isobutylene to pivalic acid. In the Koch reaction, the addition of water and carbon monoxide to alkenes is catalyzed by strong acids. Acetic acid and formic acid are produced by the carbonylation of methanol, conducted with iodide and alkoxide promoters, respectively, and often with high pressures of carbon monoxide, usually involving additional hydrolytic steps. Hydrocarboxylations involve the simultaneous addition of water and CO. Such reactions are sometimes called "Reppe chemistry":

HCCH + CO + H₂O → CH₂=CHCO₂H

• Some long-chain carboxylic acids are obtained by the hydrolysis of triglycerides obtained from plant or animal oils; these methods are related to soap making.
• fermentation of ethanol is used in the production of vinegar.

Laboratory methods

Preparative methods for small scale reactions for research or for production of fine chemicals often employ expensive consumable reagents.

• oxidation of primary alcohols or aldehydes with strong oxidants such as potassium dichromate, Jones reagent, potassium permanganate, or sodium chlorite. The method is amenable to laboratory conditions compared to the industrial use of air, which is "greener", since it yields less inorganic side products such as chromium or manganese oxides.
• Oxidative cleavage of olefins by ozonolysis, potassium permanganate, or potassium dichromate.
• Carboxylic acids can also be obtained by the hydrolysis of nitriles, esters, or amides, in general with acid- or base-catalysis.
• Carbonation of a Grignard and organolithium reagents:

RLi + CO₂ → RCO₂Li

RCO₂Li + HCl → RCO₂H + LiCl

• Halogenation followed by hydrolysis of methyl ketones in the haloform reaction
• The Kolbe–Schmitt reaction provides a route to salicylic acid, precursor to aspirin.
• Base-catalyzed cleavage of non-enolizable ketones, especially aryl ketones:^[8]

RC(O)Ar + H₂O → RCO₂H + ArH

Less-common reactions

Many reactions afford carboxylic acids but are used only in specific cases or are mainly of academic interest:

• Disproportionation of an aldehyde in the Cannizzaro reaction
• Rearrangement of diketones in the benzilic acid rearrangement involving the generation of benzoic acids are the von Richter reaction from nitrobenzenes and the Kolbe–Schmitt reaction from phenols.

Specialized reactions

• As with all carbonyl compounds, the protons on the α-carbon are labile due to keto–enol tautomerization. Thus, the α-carbon is easily halogenated in the Hell–Volhard–Zelinsky halogenation.
• The Schmidt reaction converts carboxylic acids to amines.
• Carboxylic acids are decarboxylated in the Hunsdiecker reaction.
• The Dakin–West reaction converts an amino acid to the corresponding amino ketone.
• In the Barbier–Wieland degradation, an carboxylic acid on an aliphatic chain having a simple the methylene bridge at the alpha position can have the chain shortened by one carbon. The inverse procedure is the Arndt–Eistert synthesis, where an acid is converted into acyl halide, which is then reacted with diazomethane to give one additional methylene in the aliphatic chain.
• Many acids undergo oxidative decarboxylation. Enzymes that catalyze these reactions are known as carboxylases (EC 6.4.1) and decarboxylases (EC 4.1.1).
• Carboxylic acids are reduced to aldehydes via the ester and DIBAL, via the acid chloride in the Rosenmund reduction and via the thioester in the Fukuyama reduction.
• In ketonic decarboxylation carboxylic acids are converted to ketones.
• Organolithium reagents (>2 equiv) react with carboxylic acids to give a dilithium 1,1-diolate, a stable tetrahedral intermediate which decomposes to give a ketone upon acidic workup.
• The Kolbe electrolysis is an electrolytic, decarboxylative dimerization reaction. In other words, it gets rid of the carboxyl groups of two acid molecules, and joins the remaining fragments together.