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CHAPTER 20: CARBOXYLIC ACIDS

A carboxylic acid donates protons by heterolytic cleavage of the acidic O H bond to give a proton and a carboxylate ion.

Nomenclature
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Common names: the positions of substituents are named using Greek letters.
IUPAC Names: The final -e in the alkane name is replaced by the suffix -oic acid.
IUPAC Names: The chain is numbered, starting with the carboxyl carbon atom, to give positions of substituents along the chain.
IUPAC Names: The stereochemical terms cis and trans (and Z and E) are used as they are with other alkenes.
IUPAC Names: Cycloalkanes with -COOH substituents are generally named as cycloalkanecarboxylic acids.
Aromatic acids in the form Ar-COOH are named as derivatives of benzoic acid.
Dicarboxylic acids: Substituted dicarboxylic acids are given common names using Greek letters, as with the simple carboxylic acids. Greek letters are assigned beginning with the
carbon atom next to the carboxyl group that is closer to the substituents.
Benzoic acids with two carboxylic acids are called phthalic acids. (phthalic, isophthalic, terephthalic)
For naming of dicarboxylic acids using IUPAC add the suffix -dioic

Structure are physical Properties

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Carboxyl group: The entire molecule isapproximately planar, with nearly trigonal bond angles.
Boiling points: Carboxylic acids boil at considerably higher temperatures than do alcohols, ketones, or aldehydes of similar molecular weights.
The high boiling points of carboxylic acids result from formation of a stable, hydrogen- bonded dimer.

Melting points: More than 8 carbon atoms

solids. Double bonds prevent the formation of a stable crystal lattice resulting to a lower melting point.
Dicarboxylic acids have relatively high melting points.
Solubility: Carboxylic acids form hydrogen bonds with water, and the lower- molecular-weight acids (up through four carbon atoms) are miscible with water.
Carboxylic acids are very soluble in alcohols because the acids form hydrogen bonds with alcohols.

Acidity of Carboxylic acids

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Ka: acid dissociation constant

Dissociation of either an acid or an alcohol involves breaking an O H bond, but dissociation of a carboxylic acid gives a carboxylate ion with the negative charge spread out
equally over two oxygen atoms (charge dissociation makes it more stable than the alcoxide ion).

Effects of substituents on Acidity:

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Any substituent that stabilizes the negatively charged carboxylate ion promotes dissociation and results in a stronger acid.
Electronegative atoms lead to greater acidity because of the inductive effect.
The magnitude of a substituent effect depends on its distance from the carboxyl group.
Substituents on the alpha carbon atom are most effective in increasing acid strength. More distant substituents have smaller effects on acidity, showing that inductive effects
decrease rapidly with distance.

Salts of Carboxylic Acids:

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The combination of a carboxylate ion and a cation is a salt of a carboxylic acid. It is caused by deprotonation by a strong base.
Carboxylic acid salts have very different properties from the acids
Carboxylic acid salts end in ate when named

Properties of carboxylic acid salts

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Melt in high temperatures

Decomposition prior to reaching the melting temperature
Soluble in water but nonsoluble in polar organic solvents
NaHCO3 is a weak base that can deprotonate

Infrared Spectroscopy of Carboxylic Acids

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In a saturated acid, this vibration occurs around 1710 cm-1, often broadened by hydrogen bonding involving the carbonyl group.
In conjugated acids, the carbonyl stretching frequency is lowered to about 1690 cm-1.
The O - H stretching vibration of a carboxylic acid absorbs in a broad band around
2500 3500 cm-1, which is lower compared to alcohols.
The broad hydroxyl band appears right on top of the C - H stretching region (making it broad)
Some spikes are found at 2500-2700 cm-1

NMR Spectroscopy of Carboxylic Acids

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Most deshielded protons absorbing between 10 and 13

Always unsplit because of proton exchange
The protons on the alpha carbon atom absorb between d 2.0 and d 2.5
For C-NMR: The carbonyl carbon atom absorbs around 170 to 180 ppm and the alpha carbon atom absorbs around 30 to 40 ppm.

Mass Spectroscopy of Carboxylic Acids

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The molecular ion peak of a carboxylic acid is usually small because favorable modes of fragmentation are available.
The most common fragmentation is loss of a molecule of an alkene (McLafferty rearrangement)

Synthesis of Carboxylic Acids

1.
2.
3.

From primary alcohols or aldehydes by H2CrO4 formed from Na2Cr2O7 and H2SO4 or NaOCl
Alkenes with warm and concentrated KMnO4 (glycol intermediate). Ketone formation also possible.
Alkynes with concentrated KMnO 4 or ozonolysis.

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4.

Carboxylation of a Gringnard reagend.

5.

Formation and hydrolysis of Nitriled: good for primary and unhindered.

Reactions of Carboxylic acids and derivatives; Nucleophilic Acyl Substitution

Condensation of COOH with alcohols: Fischer Esterification (Acid catalyzed)

Fischer esterification is an equilibrium (small eqm constants)

Esterification Using Diazomethane:

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Carboxylic acids are converted to their methyl esters very simply by adding an ether solution of diazomethane.
By product is nitrogen gas

Condensation of Acids with Amines: Direct synthesis of Amides

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Reduction of Carboxylic Acids
1.

Reduction to primary alcohols by LAH, H3O+

Borane also reduces carboxylic acids to primary alcohols. (BH3,THF, H3O+)

2.
Reduction to aldehydes
Reduction of carboxylic acids to aldehydes is difficult because aldehydes are more reactive than carboxylic acids toward most reducing agents.

Alkylation of Carboxylic Acids to form ketones

Synthesis of Acid Chlorides

Reaction with alcohols to form esters

Reaction with amines to form amides