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Unit 12
Aldehydes, Ketones and Carboxylic
(Concepts, Questions & Exceptions)

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Organic compounds containing carbon-oxygen double bond (>C=O) called carbonyl group

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Derivatives of carboxylic acid

(e.g. esters, anhydrides)

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They play an important role in biochemical processes of life. They add fragrance and flavour to
nature, for example, vanillin (from vanilla beans), salicylaldehyde (from meadow sweet) and
cinnamaldehyde (from cinnamon) have very pleasant fragrances
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Common names of aldehydes and ketones:

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 The IUPAC names:

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Q. Write the structures of the following compounds

(i) α-Methoxypropionaldehyde
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(ii) 3-Hydroxybutanal

(iii) 2-Hydroxycyclopentane carbaldehyde

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(iv) 4-Oxopentanal

(v) Di-sec. butyl ketone

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(vi) 4-Fluoroacetophenone

Structure of the Carbonyl Group:

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1. The bond angles are approximately 120° as expected of a trigonal coplanar structure
2. Carbonyl carbon atom is sp2 hybridized
 3. The carbon-oxygen double bond is polarised due to higher electronegativity of oxygen
relative to carbon. the carbonyl carbon is an electrophilic (Lewis acid), and carbonyl
oxygen, a nucleophilic (Lewis base) centre

Preparation of Aldehydes and Ketones:

1. Preparation of Aldehydes and Ketones both:

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a) By oxidation of alcohols
b) By dehydrogenation of alcohols (Metal with high temperature)
c) From hydrocarbons:

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1. By ozonolysis of alkenes
2. By hydration of alkynes

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A) Preparation of Aldehydes:

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1. From acyl chloride (acid chloride): Acyl chloride (acid chloride) is hydrogenated
over catalyst, palladium on barium sulphate.
This reaction is called Rosenmund reduction.

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Q. The catalyst used in Rosenmund's reduction is

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2. From nitriles: Nitriles are reduced to corresponding imine with stannous chloride in the
presence of hydrochloric acid, which on hydrolysis give corresponding aldehyde. This reaction
is called Stephen reaction.
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Q.
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 3. From esters:

4. From hydrocarbons: Aromatic aldehydes (benzaldehyde and its derivatives) are prepared

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from aromatic hydrocarbons by the following methods:

A) By oxidation of methylbenzene: Strong oxidising agents oxidise toluene and its

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derivatives to benzoic acids. However, it is possible to stop the oxidation at the
aldehyde stage with suitable reagents that convert the methyl group to an intermediate
that is difficult to oxidise further.

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(a) Use of chromyl chloride (𝐂𝐫𝐎𝟐 𝐂𝐥𝟐 ): This reaction is called Etard reaction

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(b) Use of chromic oxide (𝐂𝐫𝐎𝟑 ): The benzylidene diacetate can be hydrolysed to
corresponding benzaldehyde with aqueous acid.
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B) By side chain chlorination followed by hydrolysis:

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C) By Gatterman – Koch reaction:

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Q, Find out B in the given reactions

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 Preparation of Ketones:
1. From acyl chlorides:

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2. From Nitrile:

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3. From benzene or substituted benzenes: Friedel-Crafts acylation reaction

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Q. Write the structures of products of the following reactions;

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 Physical Properties:
1. Boiling points:
a) Methanal is a gas at room temperature and Ethanal is a volatile liquid.
b) The boiling points of aldehydes and ketones are higher than hydrocarbons and ethers of
comparable molecular masses.

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c) It is due to weak molecular association in aldehydes and ketones arising out of the dipole-
dipole interactions
d) Their boiling points are lower than those of alcohols of similar molecular masses due to

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absence of intermolecular hydrogen bonding

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2. Water solubility:
1. Methanal, ethanal and propanone are miscible with water in all proportions, because they
form hydrogen bond with water
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2. The solubility of aldehydes and ketones decreases rapidly on increasing the length of alkyl
chain.
3. All aldehydes and ketones are fairly soluble in organic solvents (benzene, ether, methanol,
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chloroform)
4. The lower aldehydes have sharp pungent odours.
5. As the size of the molecule increases, the odour becomes less pungent and more fragrant.
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Q. Arrange the following compounds in increasing order of their boiling points.

CH� CHO, CH� CH� OH, CH� OCH� , CH� CH� CH�
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 Chemical Reactions:
1. Nucleophilic addition reactions:
i) Mechanism of nucleophilic addition reactions

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Planar Tetrahedral Intermediate Adduct product

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(ii) Reactivity:
Aldehydes are generally more reactive than ketones in nucleophilic addition reactions due to steric
and electronic reasons.

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Sterically, the presence of two relatively large substituents in ketones hinders the approach of
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nucleophile to carbonyl carbon than in aldehydes having only one such substituent.
Electronically, aldehydes are more reactive than ketones because two alkyl groups reduce the
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electrophilicity of the carbonyl more effectively than in former.
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Q. Arrange the following compounds in increasing order of their reactivity in nucleophilic addition
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reactions.
(i) Ethanal, Propanal, Propanone, Butanone
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(ii) Benzaldehyde, p-Tolualdehyde, p-Nitrobenzaldehyde, Acetophenone

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Q. Arrange the following compounds in increasing order of their property as indicated:

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Acetaldehyde, Acetone, Di-tert-butyl ketone, Methyl tert-butyl ketone (reactivity towards HCN)
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 Examples of nucleophilic reactions:
a) Addition of hydrogen cyanide (HCN): This reaction occurs very slowly with pure
HCN. Therefore, it is catalysed by a base and the generated cyanide ion (CN− ) being a stronger
nucleophile readily adds to carbonyl compounds to yield corresponding cyanohydrin.

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b) Addition of sodium hydrogensulphite (𝐍𝐚𝐇𝐒𝐎𝟑 ):

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1. The hydrogensulphite addition compound is water soluble and can be converted back
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to the original carbonyl compound by treating it with dilute mineral acid or alkali.
2. Therefore, these are useful for separation and purification of aldehydes
3. Acetophenone do not react with sodium hydrogensulphite
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c) Addition of Grignard reagents: Explained in unit 10

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d) Addition of alcohols: Aldehydes react with one equivalent of monohydric alcohol in the
presence of dry hydrogen chloride to yield alkoxyalcohol intermediate, known as hemiacetals,
which further react with one more molecule of alcohol to give a gem-dialkoxy compound known
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as acetal as shown in the reaction

Dry hydrogen chloride protonates the oxygen of the carbonyl compounds and therefore, increases
the electrophilicity of the carbonyl carbon facilitating the nucleophilic attack of ethylene glycol.
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Ketones react with ethylene glycol under similar conditions to form cyclic products known as
ethylene glycol ketals
Acetals and ketals are hydrolysed with aqueous mineral acids to yield corresponding aldehydes
and ketones respectively.
 2. Nucleophilic addition-elimination reactions: Reaction with ammonia

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and its derivatives:
1. Nucleophiles, such as ammonia and its derivatives H� N-Z add to the carbonyl group of
aldehydes and ketones.

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2. The reaction is reversible and catalysed by acid.
3. The equilibrium favours the product formation due to rapid dehydration of the
intermediate to form >C=N-Z

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 Q. Predict the products of the following reactions

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3. Reduction

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(i) Reduction to alcohols: Aldehydes and ketones are reduced to primary and secondary alcohols
respectively by sodium borohydride (NaBH� ) or lithium aluminium hydride (LiAlH� ) as well as
by catalytic hydrogenation
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(ii) Reduction to hydrocarbons: The carbonyl group of aldehydes and ketones is reduced to
−CH� group
Clemmensen reduction: Zn-Hg + Con. HCl (zinc-amalgam and concentrated hydrochloric acid)
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Wolff-Kishner reduction: 𝐍𝐇𝟐 − 𝐍𝐇𝟐 + KOH/ (𝐂𝐇𝟐 -OH)𝟐 (hydrazine followed by heating
with sodium or potassium hydroxide in high boiling solvent such as ethylene glycol
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Q. Phenylmethyl ketone can be converted into ethylbenzene in one step by which of the following
reagents?
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4.Oxidation:
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Aldehydes are easily oxidised to carboxylic acids on treatment with common oxidising agents like
nitric acid, potassium permanganate, potassium dichromate, etc. Even mild oxidising agents,
mainly Tollens’ reagent and Fehlings’ reagent also oxidise aldehydes.
 Ketones are generally oxidised under vigorous conditions, i.e., strong oxidising agents and at
elevated temperatures. Their oxidation involves carbon-carbon bond cleavage to afford a mixture
of carboxylic acids having lesser number of carbon atoms than the parent ketone.
The mild oxidising agents given below are used to distinguish aldehydes from ketones

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(i) Tollens’ test or Silver Mirror Test: Tollen’s Reagent: (Ammoniacal silver nitrate
solution)

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A bright silver mirror is produced due to the formation of silver metal. The aldehydes are

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oxidised to corresponding carboxylate anion. The reaction occurs in alkaline medium
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(ii) Fehling’s test:
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Fehling solution A: is aqueous copper sulphate

Fehling solution B: Alkaline sodium potassium tartarate (Rochelle salt).
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These two solutions are mixed in equal amounts before test. On heating an aldehyde with
Fehling’s reagent, a reddish brown precipitate is obtained. Aldehydes are oxidised to
corresponding carboxylate anion. Aromatic aldehydes do not respond to this test.
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(iii) Haloform reaction or Iodoform Reaction:

1. Aldehydes and ketones having at least one methyl group linked to the carbonyl carbon
(methyl ketones)
2. NaOH and I� / NaOI
3. This is used for detection of CH� CO group or CH� CH(OH) group which produces
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CH� CO group on oxidation.

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4. The methyl group is converted to haloform (CHX� ).

5. Sodium salts of corresponding carboxylic acids having one carbon atom less than that
of carbonyl compound are produced.
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6. This oxidation does not affect a carbon-carbon double bond, if present in the molecule
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Q. Iodoform test is not given by

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(a) 2-Pentanone (b) Ethanol (c) Ethanal (d) 3-Pentanone

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Q. The reagent which does not react with both, acetone and benzaldehyde.
(a) Sodium hydrogensulphite (b) Phenyl hydrazine (c) Fehling’s solution (d) Grignard reagent
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5. Reactions due to α-hydrogen: Acidity of α-hydrogens of aldehydes and ketones:

The aldehydes and ketones undergo a number of reactions due to the acidic nature of α-hydrogen.
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The acidity of α-hydrogen atoms of carbonyl compounds is due to the strong electron withdrawing
effect of the carbonyl group and resonance stabilisation of the conjugate base.
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(A) Aldol condensation:

1. Aldehydes and ketones having at least one α-hydrogen undergo a reaction
2. Presence of dilute alkali (10% NaOH/KOH) as catalyst
3. To form β-hydroxy aldehydes (aldol) or β-hydroxy ketones (ketol), respectively. This
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is known as Aldol reaction.

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4. The aldol and ketol readily lose water to give α,β-unsaturated carbonyl compounds
which are aldol condensation products and the reaction is called Aldol condensation.
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(i) Cross aldol condensation: When aldol condensation is carried out between two

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different aldehydes and / or ketones, it is called cross aldol condensation. If both of
them contain α-hydrogen atoms, it gives a mixture of four products.

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Ketones can also be used as one component in the cross aldol reactions
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(B). Cannizzaro reaction:

1. Aldehydes which do not have an α-hydrogen atom, give this reaction
2. Reactants undergo self oxidation and reduction (disproportionation) reaction
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3. Requirement of concentrated alkali 50% (NaOH/KOH)

4. In this reaction, one molecule of the aldehyde is reduced to alcohol while another is
oxidised to carboxylic acid salt.
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Q. Which of the following compounds would undergo aldol condensation, which the Cannizzaro
reaction and which neither?

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(i) Methanal (ii) 2-Methylpentanal (iii) Benzaldehyde

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(iv) Benzophenone (v) Cyclohexanone (vi) 1-Phenylpropanone

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(vii) Phenylacetaldehyde
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Q. Cannizzaro reaction is given by

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(1) Aldehydes containing α-hydrogen atoms

(2) Aldehydes as well as ketones containing α-hydrogen atoms
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(3) Aldehydes not containing α-hydrogen atoms

(4) Aldehydes containing β-hydrogen atoms
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6. Electrophilic substitution reaction: The carbonyl group acts as a deactivating and meta-
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directing group
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Uses of Aldehydes and Ketones:

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1. As solvents, starting materials and reagents for the synthesis of other products.
2. Formaldehyde is well known as formalin (40%) solution used to preserve biological
specimens
3. To prepare bakelite (a phenol-formaldehyde resin), urea-formaldehyde glues and other
polymeric products.
 4. Acetaldehyde is used primarily as a starting material in the manufacture of acetic acid,
ethyl acetate, vinyl acetate, polymers and drugs.
5. Benzaldehyde is used in perfumery and in dye industries.
6. Acetone and ethyl methyl ketone are common industrial solvents.
7. Many aldehydes and ketones, e.g., butyraldehyde, vanillin, acetophenone, camphor, etc.
Are well known for their odours and flavours

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Carboxylic Acids

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1. Carbon compounds containing a carboxyl functional group, –COOH are called carboxylic
acids

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2. Carboxylic acids are found in nature as fatty acids (C�� − C�� ) in natural fats as esters of
glycerol.

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3. Carboxylic acids serve as starting material for several other important organic compounds
such as anhydrides, esters, acid chlorides, amides

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Nomenclature (Common name)

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 Structure of Carboxyl Group:
In carboxylic acids, the bonds to the carboxyl carbon lie in one plane and are separated by about
120°. The carboxylic carbon is less electrophilic than carbonyl carbon because of the possible
resonance.

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Methods Preparation of Carboxylic:
1. From primary alcohols and aldehydes: Oxidation by oxidising agents

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a) Potassium permanganate (KMnO� ) in neutral, acidic or alkaline media

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b) Potassium dichromate (K � Cr� O� ) in acidic media
c) Chromium trioxide (CrO� ) in acidic media
d) Carboxylic acids are also prepared from aldehydes by the use of mild oxidising agents

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2. From alkylbenzenes:
a) Oxidation with chromic acid or acidic or alkaline potassium permanganate
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b) The entire side chain is oxidised to the carboxyl group irrespective of length of the side
chain.
c) Primary and secondary alkyl groups are oxidised in this manner while tertiary group is
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not affected. Suitably substituted alkenes are also oxidised to carboxylic acids with
these oxidising reagents
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Q. Which of the following can not be oxidised to give carboxylic acid?

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 3. From nitriles and amides:
a) Nitriles are hydrolysed to amides and then to acids in the presence of acid/base as
catalyst.
b) Mild reaction conditions are used to stop the reaction at the amide stage

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4. From Grignard reagents:
a) Grignard reagents react with carbon dioxide (dry ice) to form salts of carboxylic

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acids which in turn give corresponding carboxylic acids after acidification with

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mineral acid.
b) Converting alkyl halides into corresponding carboxylic acids having one carbon
atom more than that present in alkyl halides
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5. From acyl halides and anhydrides: Hydrolysis

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6. From esters: Acidic hydrolysis of esters gives directly carboxylic acids while basic
hydrolysis gives carboxylates, which on acidification give corresponding carboxylic acids.
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 Q. Show how each of the following compounds can be converted to benzoic acid.
(i) Ethylbenzene

(ii) Acetophenone

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(iii) Bromobenzene

(iv) Phenylethene (Styrene)

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Physical Properties:

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1. Carboxylic acids are higher boiling liquids than aldehydes, ketones and even alcohols

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of comparable molecular masses. This is due to intermolecular hydrogen bonding
2. Most carboxylic acids exist as dimer in the vapour phase or in the aprotic solvents.
3. Simple aliphatic carboxylic acids having upto four carbon atoms are miscible in water

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due to the formation of hydrogen bonds with water.
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4. The solubility decreases with increasing number of carbon atoms.
5. Higher carboxylic acids are practically insoluble in water due to the increased
hydrophobic interaction of hydrocarbon part.
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6. Benzoic acid, the simplest aromatic carboxylic acid is nearly insoluble in cold water.
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7. Carboxylic acids are also soluble in less polar organic solvents like benzene, ether,
alcohol, chloroform
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Chemical Reactions:
1. Reactions Involving Cleavage of O–H Bond:
Acidity Reactions with metals and alkalies:
a) They react with weaker bases such as carbonates and hydrogencarbonates to evolve
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carbon dioxide (Phenol do not react)

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b) This reaction is used to detect the presence of carboxyl group in an organic

compound
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 Carboxylic acids dissociate in water to give resonance stabilised carboxylate anions and
hydronium ion.

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For convenience, the strength of an acid is generally indicated by its pKa value rather than its Ka

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value.
pKa = – log Ka

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Smaller the pKa, the stronger the acid (the better it is as a proton donor).

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Strong acids have pKa values < 1, the acids with pKa values between 1 and 5 are considered to be
moderately strong acids, weak acids have pKa values between 5 and 15, and extremely weak acids
have pKa values >15.
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Carboxylic acids are weaker than mineral acids, but they are stronger acids than alcohols and many
simple phenols
Why phenols are more acidic than alcohols:
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The conjugate base of carboxylic acid, a carboxylate ion, is stabilised by two equivalent resonance
structures in which the negative charge is at the more electronegative oxygen atom. The conjugate
base of phenol, a phenoxide ion, has non-equivalent resonance structures in which the negative
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charge is at the less electronegative carbon atom. Therefore, resonance in phenoxide ion is not as
important as it is in carboxylate ion.
Thus, the carboxylate ion is more stabilised than phenoxide ion, so carboxylic acids are more acidic
than phenols
 Effect of substituents on the acidity of carboxylic acids:

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The effect of the following groups in increasing acidity order is

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Ph < I < Br < Cl < F < CN < NO2 < CF3

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Direct attachment of groups such as phenyl or vinyl to the carboxylic acid, increases the acidity of
corresponding carboxylic acid. This is because of greater electronegativity of sp 2 hybridised
carbon to which carboxyl carbon is attached.
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The presence of electron withdrawing group on the phenyl of aromatic carboxylic acid increases
their acidity while electron donating groups decrease their acidity
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Q. Which acid of each pair shown here would you expect to be stronger?
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 Q. Arrange the following compounds in increasing order of their property as indicated:
(ii) CH� CH� CH(Br)COOH, CH� CH(Br) CH� COOH, (CH� )�CHCOOH, CH� CH� CH� COOH (acid
strength)

(iii) Benzoic acid, 4-Nitrobenzoic acid, 3,4-Dinitrobenzoic acid, 4-Methoxybenzoic acid (acid

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strength)

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Reactions Involving Cleavage of C–OH Bond:
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1. Formation of anhydride: 𝐇𝟐 𝐒𝐎𝟒 or with 𝐏𝟐 𝐎𝟓

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2. Esterification: Concentrated H� SO� or HCl gas as a catalyst

Mechanism of esterification of carboxylic acids:

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 3. Reactions with 𝐏𝐂𝐥𝟓 , 𝐏𝐂𝐥𝟑 and 𝐒𝐎𝐂𝐥𝟐

4. Reaction with ammonia

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Strong Heat
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Reactions Involving –COOH Group:
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1. Reduction: Diborane does not easily reduce functional groups such as ester, nitro, halo,
etc. Sodium borohydride does not reduce the carboxyl group.
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2. Decarboxylation: Carboxylic acids lose carbon dioxide to form hydrocarbons when

their sodium salts are heated with sodalime (NaOH and CaO in the ratio of 3 : 1).
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Substitution Reactions in the Hydrocarbon Part:

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1. Halogenation:
a) Carboxylic acids having an α-hydrogen are halogenated at the α-position
b) Treatment with chlorine or bromine in the presence of small amount of red phosphorus
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c) To give α-halocarboxylic acids

d) The reaction is known as Hell-Volhard-Zelinsky reaction
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2. Ring substitution:
a) Carboxyl group acts as a deactivating and meta-directing group.
b) They however, do not undergo Friedel-Crafts reaction (because the carboxyl group

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is deactivating and the catalyst aluminium chloride (Lewis acid) gets bonded to the
carboxyl group).

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Uses of Carboxylic Acids:
1. Methanoic acid is used in rubber, textile, dyeing, leather and electroplating industries.
2. Ethanoic acid is used as solvent and as vinegar in food industry.
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3. Hexanedioic acid is used in the manufacture of nylon-6, 6.
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4. Esters of benzoic acid are used in perfumery.

5. Sodium benzoate is used as a food preservative.
6. Higher fatty acids are used for the manufacture of soaps and detergents.
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Q. Give simple chemical tests to distinguish between the following pairs of compounds.
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(i) Propanal and Propanone

(ii) Acetophenone and Benzophenone

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(iii) Phenol and Benzoic acid

(iv) Benzoic acid and Ethyl benzoate

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(v) Pentan-2-one and Pentan-3-one

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(vi) Benzaldehyde and Acetophenone

(vii) Ethanal and Propanal

 Q. Complete each synthesis by giving missing starting material, reagent or products

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 Note: Do all Intex Questions, Back Exercise Questions, Solved Examples

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