Production of Benzoic Acid

• The compounds can be produced from the oxidation of alkylbenzenes

• The alkyl side-chain in alkylbenzenes, such as methylbenzene, can be
oxidised to a carboxylic acid
• The alkylbenzene is heated under reflux with a solution of hot alkaline
KMnO4 (this is the oxidising agent)
• The purple colour of the Mn7+ ions disappears as they are reduced to Mn4+ ions
• A brown precipitate of MnO2 is formed
• The mixture is then acidified with dilute acid (such as hydrochloric acid)
to protonate the organic product and form and produce a benzoic acid
Reactions of Carboxylic Acids to Produce Acyl Chlorides

• Acyl chlorides are compounds with the functional group -COCl

• They look similar in structure to carboxylic acids but have a Cl atom
instead of an -OH group attached to the carbonyl (C=O)
• Acyl chlorides are more reactive than their corresponding carboxylic
acids and are therefore often used as starting materials in the
production of organic compounds such as esters
• They can be prepared from the reaction of carboxylic acids with:
• Solid phosphorus(V) chloride (PCl5)
• Liquid phosphorus(III) chloride (PCl3) and heat
• Liquid sulfur dichloride oxide (SOCl2)
• For example, the acyl chloride ethanoyl chloride can be formed
from ethanoic acid in the above reactions
Further Oxidation of Carboxylic Acids

Methanoic acid
• Methanoic acid is a strong reducing agent and gets further
oxidised to carbon dioxide (CO2)
• The oxidation of methanoic acid can occur by:
• Warming methanoic acid with mild oxidising agents such
as Fehling’s or Tollens’ reagent
• In a Fehling’s solution, the Cu2+ ion is reduced to Cu+ ion which precipitates as red Cu2O
• With Tollens’ reagent, the Ag+ is reduced to Ag
• Using stronger oxidising agents such as acidified KMnO4 or acidified K2Cr2O7
• The purple KMnO4 solution turns colourless as Mn7+ ions are reduced to Mn2+ ions
• The orange K2Cr2O7 solution turns green as the Cr6+ ions are reduced to Cr3+ ions
Ethanedioic acid
• Another carboxylic acid that can get further oxidised is ethanedioic
acid
• A strong oxidising agent such as warm acidified KMnO4 is required
for the oxidation of ethanedioic acid to carbon dioxide
Relative Acidities of Carboxylic Acids, Phenols & Alcohols

• Carboxylic acids are compounds with a -COOH functional group

• They can act as acids and lose a proton (H+ ion) in an aqueous solution
to form carboxylate salts and water
• However, carboxylic acids are only weak acids as the position of
equilibrium lies well over to the left-hand side
• The pKa values of carboxylic acids, phenols, and alcohols suggest that
carboxylic acids are stronger acids than alcohols and phenols
• The smaller the pKa value, the stronger the acid
Relative acidity of ethanol, phenol & carboxylic acids table
Strength of O-H bond

• In carboxylic acids, the electrons in the O-H bond are drawn towards
the C-O bond
• The electrons in the C-O bond are drawn towards the C=O bond
• Overall, the O-H bond is weakened due to the carbonyl (C=O) group
removing electron density from it and drawing it towards itself
• Carboxylic acids can therefore more easily lose a proton compared to
phenols and alcohols which lack this electron-withdrawing carbonyl
group
Production of Esters by Reacting Alcohols With Acyl Chlorides

• Esters are organic compounds with an -COR functional group

• They have characteristic smells and are used in perfumes, cosmetics and as
solvents
• Esters can be prepared from the condensation reaction between alcohols and
carboxylic acids
• This is also called an esterification reaction
• A more effective way of preparing esters is from the condensation reaction
between alcohols and acyl chlorides instead
• Unlike the reactions with carboxylic acids, acyl chlorides are more reactive (so the
reactions happen faster) and their reactions go to completion (so no equilibrium
mixture is formed and the yield of the ester is maximum)
• Examples of esterification reactions include:
• Formation of ethyl ethanoate from ethanol and ethanoyl chloride
• Formation of phenyl benzoate from phenol and benzoyl chloride
Reactions of Acyl Chlorides

• Acyl chlorides are reactive organic compounds that undergo many

reactions such as addition-elimination reactions
• In addition-elimination reactions, the addition of a small molecule
across the C=O bond takes place followed by elimination of a small
molecule
• Examples of these addition-elimination reactions include:
• Hydrolysis
• Reaction with alcohols and phenols to form esters
• Reaction with ammonia and amines to form amides
Hydrolysis
• The hydrolysis of acyl chlorides results in the formation of
a carboxylic acid and HCl molecule
• This is an addition-elimination reaction
• A water molecule adds across the C=O bond
• A hydrochloric acid (HCl) molecule is eliminated
• An example is the hydrolysis of propanoyl chloride to form propanoic
acid and HCl
Formation of esters

• The esterification of acyl chlorides is also an addition-

elimination reaction
• The alcohol or phenol adds across the C=O bond
• A HCl molecule is eliminated
Formation of amides

• Acyl chlorides can form amides from their condensation

reaction with amines and ammonia
• This is also an example of an addition-elimination reaction as
• The amine or ammonia molecule adds across the C=O bond
• A HCl molecule is eliminated
Hydrolysis of Acyl Chlorides, Alkyl Chlorides
& Halogenoarenes

• Hydrolysis is the breakdown of a compound using water

• The ease of hydrolysis for different organic compounds may differ
• For example, the ease of hydrolysis, starting with the compounds
most readily broken down, is: acyl chloride > alkyl chloride > aryl
chloride
• This trend can be explained by looking at the strength of the C-Cl
Strength of C-Cl bond in acyl chlorides

• Acyl chlorides are hydrolysed most readily at room temperature

• This is because the carbon bonded to the chlorine atom is also
attached to an oxygen atom
• There are two strong electronegative atoms pulling electrons away
from the carbonyl carbon, leaving it very δ+
• The C-Cl bond is therefore weakened and nucleophilic attack of the
carbonyl carbon is much more rapid
Strength of C-Cl bond in alkyl chlorides

• The carbonyl carbon in alkyl chlorides is only attached to one

electronegative atom which pulls electrons away from it
• This carbon atom is therefore not very δ+ and the C-Cl bond is
stronger than the C-Cl bond in acyl chlorides
• The hydrolysis of alkyl chlorides, therefore, requires a strong
alkali (such as OH-) to be refluxed with it
• An OH- ion will hydrolyse the alkyl chloride as it is a stronger
nucleophile than H2O
Strength of C-Cl bond in aryl chlorides

• In aryl chlorides, the C-Cl bond, therefore, has some double-bond

character causing it to become stronger
• As a result, the C-Cl bond is difficult to break and hydrolysis will not
occur