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CH 117 Notes 3

The document discusses carboxylic acids, including their properties, classification, nomenclature, and common reactions. Carboxylic acids contain a carboxyl group and are acidic. They can form salts, esters, amides, and undergo reduction, alkylation, and conversion to acid chlorides.

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63 views6 pages

CH 117 Notes 3

The document discusses carboxylic acids, including their properties, classification, nomenclature, and common reactions. Carboxylic acids contain a carboxyl group and are acidic. They can form salts, esters, amides, and undergo reduction, alkylation, and conversion to acid chlorides.

Uploaded by

Benson Shayo
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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CARBONYL COMPOUNDS - CARBOXYLIC ACIDS

The combination of a carbonyl group and a hydroxyl on the same carbon atom is called a carboxyl group. Compounds
containing the carboxyl group are distinctly acidic and are called carboxylic acids.

Classification according to the substituent bonded to the carboxyl group.


 Aliphatic acid has an alkyl group bonded to the carboxyl group
 Aromatic acid has an aryl group. The simplest acid is formic acid, with a proton bonded to the carboxyl group.
 Fatty acids are long-chain aliphatic acids derived from the hydrolysis of fats and oils.

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

Nomenclature of Carboxylic Acids


Names and Physical Properties of Some Carboxylic Acids

IUPAC Nomenclature
 Name of the alkane that corresponds to the longest continuous chain of carbon atoms.
 The final -e in the alkane name is replaced by the suffix -oic acid.
 The chain is numbered, starting with the carboxyl carbon atom, to give positions of substituents along the chain.
 In naming, the arboxyl group takes priority over all of the functional groups.

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 Unsaturated acids are named using the name of the corresponding alkene, with the final -e replaced by -oic acid.
o Numbered starting with the carboxyl carbon, and a number giving the location of the double bond.
o Terms cis and trans (and Z and E) are used to depict stereochemistry of the double bonds.
 Cycloalkanes with -COOH substituents are generally named as cycloalkanecarboxylic acids.

 Aliphatic dicarboxylic acids are named by adding the suffix -dioic acid to the name of the parent alkane.
o The parent alkane name is determined by using the longest continuous chain that contains both carboxyl
groups.
o The chain is numbered beginning with the carboxyl carbon atom that is closer to the substituents.

 In cyclic dicarboxylic acids the carboxyl groups are treated as substituents on the cyclic structure.

Physical Properties
Boiling Points
 Higher boiling points than do alcohols, ketones, or aldehydes of similar molecular weights

 Result from formation of a stable, hydrogen-bonded dimer containing an eight-membered ring.


o Two hydrogen bonds
o Doubling of the molecular weight of the molecules leaving the liquid phase.

Melting Points
 Acids containing more than eight carbon atoms are generally solids, unless they contain double bonds.
o The presence of double bonds (especially cis double bonds) in a long chain impedes formation of a stable
crystal lattice, resulting in a lower melting point e.g. 18 carbons stearic acid (octadecanoic acid) and
linoleic acid (cis,cis-9, 12-octadecadienoic acid)

Solubilities
 The lower molecular weight carboxylic acids (up to 4 carbons) are soluble in water due to hydrogen bonding.
 As the length of the hydrocarbon chain increases, water solubility decreases until acids with more than 1 0 carbon
atoms are essentially insoluble in water.
 Carboxylic acids are very soluble in alcohols because the acids form hydrogen bonds with alcohols.

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 Longer-chain acids are more soluble in alcohols than they are in water because alcohols are not as polar as water.

REACTIONS OF CARBOXYLIC ACIDS

1. Salts of Carboxylic acids


 A strong base completely deprotonates a carboxylic acid to a carboxylate ion and water.
o The combination of a carboxylate ion and a cation is a salt of a carboxylic acid.

 Mineral acid when added converts a carboxylic acid salt back to the original carboxylic acid.

 Like the salts of amines carboxylic acid salts are solids with little odor.
 They generally melt at high temperatures, and they often decompose before reaching their melting points.
 Carboxylate salts of the alkali metals (Li+, Na+, K+) and ammonium (NH4+) are generally soluble in water but
relatively insoluble in nonpolar organic solvents.

Identification of carboxylic acids.


 Carboxylic acids are deprotonated by the weak base sodium bicarbonate, forming the sodium salt of the acid,
carbon dioxide, and water.
o An unknown compound that is insoluble in water, but dissolves in a sodium bicarbonate solution with a
release of bubbles of carbon dioxide, is almost certainly a carboxylic acid.

Purification of carboxylic acids


Nonacidic (or weakly acidic) impurities can be removed from a carboxylic acid using acid-base extractions.
 First, the acid is dissolved in an organic solvent such as ether and shaken with water.
o The acid remains in the organic phase while any water-soluble impurities are washed out.
 Next, the acid is washed with aqueous sodium bicarbonate, forming a salt that dissolves in the aqueous phase.
o Nonacidic impurities (and weakly acidic impurities such as phenols) remain in the ether phase.
 The phases are separated
 Acidification of the aqueous phase regenerates the acid, which is insoluble in water but dissolves in a fresh portion
of ether.
 Evaporation of the final ether layer gives the purified acid.

2. Nucleophylic Acyl Substitution


Ketones and aldehydes commonly react by nucleophilic addition to the carbonyl group but carboxylic acids (and
derivatives) more commonly react by nucleophilic acyl substitution, where one nucleophile replaces another on the acyl
(C=O) carbon atom.

Example: Basic hydrolysis of ethyl benzoate

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3. Condensation of Acids with Alcohols: The Fischer Esterification
The Fisher esterification converts carboxylic acids and alcohols to esters by an acid catalyzed nucleophilic acyl
substitution. Replacement of the -OH group by the -OR group.

Example: Acid-catalyzed formation of methyl benzoate from methanol

4. Esterification Using Diazomethane


Carboxylic acids react with diazomethane to from methyl esters

5. Condensation with Amines – Formation of Amides


Carboxylic acids condense with amines to form amides. The initial acid-base reaction of a carboxylic acid with an
amine gives an ammonium carboxylate salt which on heating to above 100OC forms an amide.

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6. Reduction of Carboxylic Acids
6.1 Reduction to Primary Alcohols
Lithum aluminium hydride (LiAlH4) reduces carboxylic acids to primary alcohols.

Borane also reduces carboxylic acids to primary alcohols.

6.2 Reduction to Primary Aldehydes


Reduction of carboxylic acids to aldehydes is difficult because aldehydes are more reactive than carboxylic acids
towards most reducing agents and from primary alcohols. Reduction is done in a two step process converting the acid to
the acid chloride followed by reduction with lithium aluminium tri(t-butoxy) hydride.

Example:

7. Alkylation of Carboxylic Acids to Form Ketones


A carboxylic acid reacts with two equivalents of an organolithium reagent to form a ketone.

The first equivalent of the organolithium reagent simply deprotonates the acid. The second equivalent adds to the
carbonyl to give a stable dianion which on hydrolysis gives the hydrate of a ketone.

8. Synthesis and Use of Acid Chlorides


Carboxylic acids are converted to acid chlorides by thionyl chlorides (SOCl2) and oxalyl choloride (COCl2).

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Acid chlorides react with a wide range of nucleophiles through the addition-elimination mechanism of nucleophilic
acyl substitution.

This reaction provides an efficient two step reaction method for converting carboxylic acids to esters

Ammonia and amines react with acid chlorides to give amides. A base such as pyridine or NaOH is often added to
prevent HCl from protonating the amine.

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