Reactions of

Aldehydes and ketones

 Aldehydes and ketones
unsaturated
Additions are possible
Neutral
Acid base reactions are impossible
Electron density around the carbonyl carbons is
low.
Attract nucleophiles towards the double bond.
Therefore additions are nuclephilic additions
since additions are possible,
Either oxidations or reductions are possible
Good leaving groups are absent
Substitution is difficult
No elimination reactions
 Nucleophilic addition of aldehydes and ketones

• As we discussed with the structure, due to the presence of the double

bond between C and O, these molecules favor the addition reactions.

• Because of the partial positive nature of the carbonyl carbon, attack

from a nucleophile is more favored.

• Depending on the strength of nucleophile they follow two mechanisms.

• If the nucleophile is strong, it directly attack to the carbonyl carbon
• If the nucleophile is weak, they need a support of a catalyst acid
 Nucleophilic addition of aldehydes and ketones
• Case 1: strong nucleophile

• Case 2: weak nucleophile; they follow an acid catalyzed addition mechanism

Different types of nucleophilic addition reactions of aldehydes

• Hemiacetal and acetal formation by reacting with alcohols

• Hydrates/gem diols formation by reacting with water

• Thioacetal formation by reacting with thiols

• Imine formation by reacting with primary amines

• Enamine formation by reacting with secondary amines

• Cyanohydrin formation by reacting with hydrogen cyanide

• Alkene formation by reacting with phosphorus ylides.

• Alcohol formation by reacting with organometallic reagents

 Hemiacetal and acetal formation by reacting with
alcohols
• What is a hemiacetal and a acetal?

• By reacting alcohol ROH with an aldehyde/ketone R’R”CO in the presence of an acid catalyst
hemiacetal/acetal can be synthesized.
• Alcohol act as the nucleophile
Mechanism of Hemiacetal and acetal formation by reacting
with alcohols
 Importance of acetals and ketals

• Acetals and ketals can act as protecting groups of aldehydes and

ketones.
• Acetals are stable under most conditions that do not involve acid.
• Acetals can be used to protect aldehydes and ketones from undesired
reactions in basic solutions.
• The acetal group can then be removed by acidic hydrolysis when no longer
needed.

• Eg:
 Hydrates/gem diols formation by reacting with water

• When aldehyde/ketone reacts with water instead of alcohol they

form the gem diol.

• However it is not possible to isolate most of these gem diols except

few stable gem diols.
 Thioacetal formation by reacting with thiols
• When aldehyde/ketone reacts with thiols they form thioacetals in a similar
manner to reaction of alcohols.

• They can also act as protecting groups to aldehydes/ketones.

• These thioacetals are important intermediate in the conversion of carbonyls into
hydrocarbons.
 Imine formation by reacting with primary amines
• Amine attack as a nucleophile on to the carbonyl compound.
 Enamine formation by reacting with secondary
amines
• Amine attack as a nucleophile on to the carbonyl compound.
Cyanohydrin formation by reacting with hydrogen
cyanide

• Cyanide ion act as nucleophile.

• Find out the importance of cyanohydrins.

 Alkene formation by reacting with phosphorus
ylides.
• Nucleophilic addition leads to an oxaphosphetane which spontaneously
loses triphenylphosphine oxide to give the alkene.

• This reaction is called as “Wittig reaction”

 Alcohol formation by reacting with organometallic
reagents

• RMgX, RLi, and RC≡CNa are the common organometallic reagents

which react with aldehydes and ketones to give alcohols.
 Reduction of aldehydes and ketones
• Aldehydes and ketones can reduce to corresponding alcohol using LiAlH4 or
NaBH4.
• Sodium borohydride is usually preferred over Lithium Aluminium hydride (LAH) for the reduction of
aldehydes and ketones. Sodium borohydride can be used safely and effectively in water as well as
alcohol solvents such as methanol (MeOH), whereas special precautions are required when using LAH.

• Mechanism clearly shows you that this reduction is also a result of an nucleophilic addition.
 oxidation of aldehydes and ketones to carboxylic acids
• Aldehydes can oxidized to corresponding carboxylic acids. However,
ketones cannot oxidize.
• What are the two methods you are already come across to oxidize
aldehydes to carboxylic acids.
• Jones reagent (chromic acid(H2CrO4)/ chromium trioxide (CrO3) to aqueous sulfuric
acid)
• Potassium permanganate (KMnO4)
 Oxidation of aldehydes; reaction with Tollens’
reagent and Fehlings’ reagent which are used as
identification tests
 oxidation of aldehydes and ketones to esters
• Insertion of oxygen atom between the carbonyl carbon and alkyl group using a peroxycarboxylic
acids will form an ester. This reaction is called as “Baeyer-Villger oxidation”
• Eg:
 Condensation reactions of carbonyl
compounds
• Activity : do a self study about the condensation reactions