Aldehydes, Ketones and Carboxylic Acids

By Onyancha ME

Carbonyl compounds are of utmost importance to organic chemistry. They are constituents of
fabrics, flavourings, plastics and drugs. In this Unit, we will study about the organic compounds
containing carbon-oxygen double bond (>C=O) called carbonyl group, which is one of the most
important functional groups in organic chemistry.

In aldehydes, the carbonyl group is bonded to a carbon and hydrogen while in the ketones, it is
bonded to two carbon atoms. The carbonyl compounds in which carbonyl group is bonded to
oxygen are known as carboxylic acids, and their derivatives (e.g. esters, anhydrides) while in
compounds where carbon is attached to nitrogen and to halogens are called amides and acyl
halides respectively. The general formulas of these classes of compounds are given below:

Aldehydes, ketones and carboxylic acids are widespread in plants and animal kingdom. 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.

They are used in many food products and pharmaceuticals to add flavours. Some of these families
are manufactured for use as solvents (i.e. acetone) and for preparing materials like adhesives,
paints, resins, perfumes, plastics, fabrics, etc.
Nomenclature
I. Aldehydes and ketones
Aldehydes and ketones are the simplest and most important carbonyl compounds. There are two
systems of nomenclature of aldehydes and ketones.
(a) Common names
Aldehydes and ketones are often called by their common names instead of IUPAC names. The
common names of most aldehydes are derived from the common names of the corresponding
carboxylic acids by replacing the ending –ic (-oic)of acid with -aldehyde. At the same time, the
names reflect the Latin or Greek term for the original source of the acid or aldehyde. The location
of the substituent in the carbon chain is indicated by Greek letters α, β, γ, δ, etc. The α-carbon
being the one directly linked to the aldehyde group, β- carbon the next, and so on.

The common names of ketones are derived by naming two alkyl or aryl groups bonded to the
carbonyl group. The locations of substituents are indicated by Greek letters, α α′, β β′ and so on
beginning with the carbon atoms next to the carbonyl group, indicated as αα′. Some ketones have
historical common names, the simplest dimethyl ketone is called acetone. Alkyl phenyl ketones
are usually named by adding the acyl group as prefix to phenone. For example

(b) IUPAC names

The IUPAC names of open chain aliphatic aldehydes and ketones are derived from the names of
the corresponding alkanes by replacing the ending –e with –al and –one respectively. In case of
aldehydes the longest carbon chain is numbered starting from the carbon of the aldehyde group
while in case of ketones the numbering begins from the end nearer to the carbonyl group. The
substituents are prefixed in alphabetical order along with numerals indicating their positions in the
carbon chain. The same applies to cyclic ketones, where the carbonyl carbon is numbered one.
When the aldehyde group is attached to a ring, the suffix carbaldehyde is added after the full name
of the cycloalkane. The numbering of the ring carbon atoms start from the carbon atom attached to
the aldehyde group. The name of the simplest aromatic aldehyde carrying the aldehyde group on a
benzene ring is benzenecarbaldehyde. However, the common name benzaldehyde is also accepted
by IUPAC. Other aromatic aldehydes are hence named as substituted benzaldehydes.
The common and IUPAC names of some aldehydes and ketones are given in Table 12.1.
Table 12.1: Common and IUPAC Names of Some Aldehydes and Ketones
structure Common name IUPAC name
Aldehydes
HCHO Formaldehyde Methanal
CH3CHO Acetaldehyde Ethanal
(CH3)2CHCHO Isobutyraldehyde 2-Methypropanal
3-Methylcyclohexane
γ-Methylcyclohexanal
carbaldehyde
Α-Methoxypropion
CH3CH(OCH3)CHO 2-Methoxypropanal
aldehyde
CH3CH2CH2CH2CHO Veleraldehyde Pentanal
CH2=CHCHO Acrolein Prop-2-enal

Phthaldehyde Benzene-1,2-dicarbaldehyde
 3-Bromobenzenecarbaldehyde or
m-Bromobenzaldehyde
3-Bromobenzaldehyde

Ketones
CH3COCH2CH2CH3 Methyl n-propyl ketone Pentan-2-one
(CH3)2CHCOCH(CH3)2 Diisopropyl ketone 2,4-Dimethylpentan-3-one

α-Methlycyclohexanone 2-Methylcyclohexanone

(CH2)2C=CHCOCH3 Mesityl oxide 4-Methylpent-3-en-2-one

Structure of the Carbonyl Group
The carbon-oxygen double bond is polarised due to higher electronegativity of oxygen relative to
carbon. Hence, the carbonyl carbon is an electrophilic (Lewis acid), and carbonyl oxygen, a
nucleophilic (Lewis base) centre. Carbonyl compounds have substantial dipole moments and are
polar than ethers. The high polarity of the carbonyl group is explained on the basis of resonance
involving a neutral (A) and a dipolar (B) structures as shown.

Intext Questions
Write the structures of the following compounds.
(i) α-Methoxypropionaldehyde
(ii) 3-Hydroxybutanal
(iii) 2-Hydroxycyclopentane carbaldehyde
(iv) 4-Oxopentanal
(v) di-sec.butyl ketone
(vi) 4-Fluoroacetophenone
Preparation/synthesis of Aldehydes and Ketones
1. By oxidation of alcohols
Aldehydes and ketones are generally prepared by oxidation of primary and secondary alcohols,
respectively. Oxidation of alcohols involves the formation of a carbon- oxygen double bond with
cleavage of an O-H and C-H bonds.

Such a cleavage and formation of bonds occur in oxidation reactions. Depending on the oxidizing
agent used, a primary alcohol is oxidized to an aldehyde which in turn is oxidized to a carboxylic
acid.
Strong oxidising agents such as acidified potassium permanganate are used for getting carboxylic
acids from alcohols directly. CrO3 in anhydrous medium is used as the oxidising agent for the
isolation of aldehydes.

A better reagent for oxidation of primary alcohols to aldehydes in good yield is pyridinium
chlorochromate (PCC), a complex of chromium trioxide with pyridine and HCl.

Secondary alcohols are oxidised to ketones by chromic anhyride (CrO3).

Tertiary alcohols do not undergo oxidation reaction. Under strong reaction conditions such as
strong oxidising agents (KMnO4) and elevated temperatures, cleavage of various C-C bonds takes
place and a mixture of carboxylic acids containing lesser number of carbon atoms is formed.
2. By dehydrogenation of alcohols
This method is suitable for volatile alcohols and is of industrial application. In this method alcohol
vapours are passed over heavy metal catalysts (Ag or Cu). Primary and secondary alcohols give
aldehydes and ketones, respectively

3. From hydrocarbons
(i) By ozonolysis of alkenes: As we know, ozonolysis of alkenes followed by reaction with zinc
dust and water gives aldehydes, ketones or a mixture of both depending on the substitution pattern
of the alkene.
(ii) By hydration of alkynes: Addition of water to ethyne in the presence of H2SO4 and HgSO4
gives acetaldehyde. All other alkynes give ketones in this reaction.
Preparation of Aldehydes
1. From acyl chloride (acid chloride). Acyl chloride (acid chloride) is hydrogenated over
catalyst, palladium on Barium sulphate. This reaction is called Rosenmund reduction.
2. From nitriles and esters
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.

Alternatively, nitriles are selectively reduced by diisobutylaluminium hydride, (DIBAL-H) to
imines followed by hydrolysis to aldehydes:

Similarly, esters are also reduced to aldehydes with DIBAL-H.

3. From hydrocarbons
Aromatic aldehydes (benzaldehyde and its derivatives) are prepared from aromatic hydrocarbons
by the following methods:
(i) By oxidation of methylbenzene
Strong oxidising agents oxidise toluene and its 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. The following methods are used for
this purpose.
(a) Use of chromyl chloride (CrO2Cl2): Chromyl chloride oxidises methyl group to a chromium
complex, which on hydrolysis gives corresponding benzaldehyde. This reaction is called Etard
reaction.

This reaction is called Etard reaction.

(b) Use of chromic oxide (CrO3): Toluene or substituted toluene is converted to benzylidene
diacetate on treating with chromic oxide in acetic anhydride. The benzylidene diacetate can be
hydrolysed to corresponding benzaldehyde with aqueous acid.
(ii) By side chain chlorination followed by hydrolysis.
Side chain chlorination of toluene gives benzal chloride, which on hydrolysis gives benzaldehyde.
This is a commercial method of manufacture of benzaldehyde.

(iii) By Gatterman – Koch reaction.

When benzene or its derivative is treated with carbon monoxide and hydrogen chloride in the
presence of anhydrous aluminium chloride or cuprous chloride, it gives benzaldehyde or
substituted benzaldehyde.

Preparation of Ketones
1. From acyl chlorides
Treatment of acyl chlorides with dialkylcadmium, prepared by the reaction of cadmium chloride
with Grignard reagent, gives ketones.

2. From nitriles
Treating a nitrile with Grignard reagent followed by hydrolysis yields a ketone.

3. From benzene or substituted benzenes

When benzene or substituted benzene is treated with acid chloride in the presence of anhydrous
aluminium chloride, it affords the corresponding ketone. This reaction is known as Friedel-Crafts
acylation reaction.
Sample questions
Give names of the reagents to bring about the following transformations:
(i) Hexan-1-ol to hexanal
(ii) Cyclohexanol to cyclohexanone
(iii) p-Fluorotoluene to p-fluorobenzaldehyde
(iv) Ethanenitrile to ethanal
(v) Allyl alcohol to propenal
(vi) But-2-ene to ethanal
Solution
(i) C5H5NH+CrO3Cl-(PCC)
(ii) K2Cr2O7 in acidic medium
(iii) CrO3 in the presence of acetic anhydride/ 1. CrO2Cl22. HOH
(iv) (Diisobutyl)aluminium hydride (DIBAL-H)
(v) PCC
(vi) O3/H2O-Zn dust
Intext Question
Write the structures of products of the following reactions;

Physical properties
Methanal is a gas at room temperature. Ethanal is a volatile liquid. Other aldehydes and ketones
are liquid or solid at room temperature. The boiling points of aldehydes and ketones are higher
than hydrocarbons and ethers of comparable molecular masses. It is due to weak molecular
association in aldehydes and ketones arising out of the dipole-dipole interactions. Also, their
boiling points are lower than those of alcohols of similar molecular masses due to absence of
intermolecular hydrogen bonding. The following compounds of molecular masses 58 and 60 are
ranked in order of increasing boiling points.
B.p.(K) Molecular Mass
n-Butane 273 58
Methoxyethane 281 60
Propanal 322 58
Acetone 329 58
Propan-1-ol 370 60
The lower members of aldehydes and ketones such as methanal, ethanal and propanone are
miscible with water in all proportions, because they form hydrogen bond with water.

However, the solubility of aldehydes and ketones decreases rapidly on increasing the length of
alkyl chain. All aldehydes and ketones are fairly soluble in organic solvents like benzene, ether,
methanol, chloroform, etc. The lower aldehydes have sharp pungent odours. As the size of the
molecule increases, the odour becomes less pungent and more fragrant. In fact, many naturally
occurring aldehydes and ketones are used in the blending of perfumes and flavouring agents.
Sample question
Arrange the following compounds in the increasing order of their boiling points:
CH3CH2CH2CHO, CH3CH2CH2CH2OH, H5C2-O-C2H5, CH3CH2CH2CH2CH3
Solution
The molecular masses of these compounds are in the range of 72 to 74. Since only butan-1-ol
molecules are associated due to extensive intermolecular hydrogen bonding, therefore, the boiling
point of butan-1-ol would be the highest. Butanal is more polar than ethoxyethane. Therefore, the
intermolecular dipole-dipole attraction is stronger in the former. n-Pentane molecules have only
weak van der Waals forces. Hence increasing order of boiling points of the given compounds is as
follows:
CH3CH2CH2CH2CH3 < H5C2-O-C2H5 < CH3CH2CH2CHO < CH3CH2CH2CH2OH
Intext Question
Arrange the following compounds in increasing order of their boiling points.
CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3
Chemical Reactions
Since aldehydes and ketones both possess the carbonyl functional group, they undergo similar
chemical reactions.
1. Nucleophilic addition reactions
Contrary to electrophilic addition reactions observed in alkenes, the aldehydes and ketones
undergo nucleophilic addition reactions.
(i) Mechanism of nucleophilic addition reactions
A nucleophile (electron rich entity) attacks the electrophilic carbon atom of the polar carbonyl
group from a direction approximately perpendicular to the plane of sp2 hybridised orbitals of
carbonyl carbon (Fig. 12.2). The hybridisation of carbon changes from sp2 to sp3 in this process,
and a tetrahedral alkoxide intermediate is produced. This intermediate captures a proton from the
reaction medium to give the electrically neutral product. The net result is addition of Nu− and H+
across the carbon oxygen double bond as shown in Fig. 12.2.
(ii) Reactivity
Aldehydes are generally more reactive than ketones in nucleophilic addition reactions due to steric
(bulkiness) and electronic reasons. Sterically, the presence of two relatively large substituents in
ketones hinders the approach of 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 electrophilicity of the carbonyl more effectively than in former.
Sample question
Would you expect benzaldehyde to be more reactive or less reactive in nucleophilic addition
reactions than propanal? Explain your answer.
Solution
The carbon atom of the carbonyl group of benzaldehyde is less electrophilic than carbon
atom of the carbonyl group present in propanal. The polarity of the carbonyl group is
reduced in benzaldehyde due to resonance and hence it is less reactive than propanal.
(iii) Some important examples of nucleophilic addition and nucleophilic addition-elimination
reactions:
(a) Addition of hydrogen cyanide (HCN): Aldehydes and ketones react with hydrogen cyanide
(HCN) to yield cyanohydrins. 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. Cyanohydrins are useful synthetic
intermediates.
(b) Addition of sodium hydrogensulphite: Sodium hydrogensulphite adds to aldehydes and
ketones to form the addition products. The position of the equilibrium lies largely to the right hand
side for most aldehydes and to the left for most ketones due to steric reasons. The
hydrogensulphite addition compound is water soluble and can be converted back to the original
carbonyl compound by treating it with dilute mineral acid or alkali. Therefore, these are useful for
separation and purification of aldehydes.

(c) 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
as acetal as shown in the reaction.
Ketones react with ethylene glycol under similar conditions to form cyclic products known as
ethylene glycol ketals.

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.
Acetals and ketals are hydrolysed with aqueous mineral acids to yield corresponding aldehydes
and ketones respectively.
(d) Addition of ammonia and its derivatives: Nucleophiles, such as ammonia and its derivatives
H2N-Z add to the carbonyl group of aldehydes and ketones. The reaction is reversible and
catalysed by acid. The equilibrium favours the product formation due to rapid dehydration of the
intermediate to form >C=N-Z. Z = Alkyl, aryl, OH, NH2, C6H5NH, NHCONH2, etc.

Table 12.2: Some N-Substituted Derivatives of Aldehydes and Ketones (>C=N-Z)

Z Reagent name Carbonyl derivative Product name

-H Ammonia Imine

Substituted
-R Amine
imine(Schiff’s base)

-OH Hydroxylamine Oxime

-NH2 Hydrazine Hydrazone

Phenylhydrazine Phenylhydrazone
 2,4- 2,4-
Dinitrophenylhydrazin Dinitrophenylhydrazon
e e

Semicarbazide semicarbazone

2. Reduction
(i) Reduction to alcohols: Aldehydes and ketones are reduced to primary and secondary alcohols
respectively by sodium borohydride (NaBH 4) or lithium aluminium hydride (LiAlH4) as well as
by catalytic hydrogenation. The usual catalyst is a finely divided metal such as platinum,
palladium or nickel. Aldehydes yield primary alcohols whereas ketones give secondary alcohols.

(ii) Reduction to hydrocarbons: The carbonyl group of aldehydes and ketones is reduced to CH 2
group on treatment with zinc- amalgam and concentrated hydrochloric acid [Clemmensen
reduction] or with hydrazine followed by heating with sodium or potassium hydroxide in high
boiling solvent such as ethylene glycol (Wolff-Kishner reduction).

3. Oxidation
Aldehydes differ from ketones in their oxidation reactions. 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:
(i) Tollens’ test: On warming an aldehyde with freshly prepared ammoniacal silver nitrate
solution (Tollens’ reagent), a bright silver mirror is produced due to the formation of silver metal.
The aldehydes are oxidised to corresponding carboxylate anion. The reaction occurs in alkaline
medium.

(ii) Fehling’s test: Fehling reagent comprises of two solutions, Fehling solution A and Fehling
solution B. Fehling solution A is aqueous copper sulphate and Fehling solution B is alkaline
sodium potassium tartarate (Rochelle salt). 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.

(iii) Oxidation of methyl ketones by haloform reaction:

Aldehydes and ketones having at least one methyl group linked to the carbonyl carbon atom
(methyl ketones) are oxidised by sodium hypohalite to sodium salts of corresponding carboxylic
acids having one carbon atom less than that of carbonyl compound. The methyl group is
converted to haloform. This oxidation does not affect a carbon-carbon double bond, if present in
the molecule. Iodoform reaction with sodium hypoiodite is also used for detection of CH 3CO
group or CH3CH(OH) group which produces CH3CO group on oxidation.

Sample question
An organic compound (A) with molecular formula C 8H8O forms an orange-red precipitate with
2,4-DNP reagent and gives yellow precipitate on heating with iodine in the presence of sodium
hydroxide. It neither reduces Tollens’ or Fehlings’ reagent, nor does it decolourise bromine water
or Baeyer’s reagent. On drastic oxidation with chromic acid, it gives a carboxylic acid (B) having
molecular formula C7H6O2. Identify the compounds (A) and (B) and explain the reactions
involved.
Solution
(A) forms 2,4-DNP derivative. Therefore, it is an aldehyde or a ketone. Since it does not reduce
Tollens’ or Fehling reagent, (A) must be a ketone. (A) responds to iodoform test. Therefore, it
should be a methyl ketone. The molecular formula of (A) indicates high degree of unsaturation,
yet it does not decolourise bromine water or Baeyer’s reagent. This indicates the presence of
unsaturation due to an aromatic ring.
Compound (B), being an oxidation product of a ketone should be a carboxylic acid. The molecular
formula of (B) indicates that it should be benzoic acid and compound (A) should, therefore, be a
monosubstituted aromatic methyl ketone. The molecular formula of (A) indicates that it should be
phenyl methyl ketone (acetophenone). Reactions are as follows:
4. 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. 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.

(i) Aldol condensation: Aldehydes and ketones having at least one α-hydrogen undergo a
reaction in the presence of dilute alkali as catalyst to form β-hydroxy aldehydes (aldol) or β-
hydroxy ketones (ketol), respectively. This is known as Aldol reaction.

The name aldol is derived from the names of the two functional groups, aldehyde and alcohol,
present in the products. 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.
Though ketones give ketols (compounds containing a keto and alcohol groups), the general name
aldol condensation still applies to the reactions of ketones due to their similarity with aldehydes.
(ii) Cross aldol condensation: When aldol condensation is carried out between two 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. This is illustrated below by aldol reaction of a
mixture of ethanal and propanal.

5. Other reactions
(i) Cannizzaro reaction: Aldehydes which do not have an α-hydrogen atom, undergo self-
oxidation and reduction (disproportionation) reaction on treatment with concentrated alkali. In this
reaction, one molecule of the aldehyde is reduced to alcohol while another is oxidised to
carboxylic acid salt.

(ii) Electrophilic substitution reaction: Aromatic aldehydes and ketones undergo electrophilic
substitution at the ring in which the carbonyl group acts as a deactivating and meta-directing
group.

Intext Questions
1. Arrange the following compounds in increasing order of their reactivity in nucleophilic addition
reactions.
(i) Ethanal, Propanal, Propanone, Butanone.
(ii) Benzaldehyde, p-Tolualdehyde, p-Nitrobenzaldehyde, Acetophenone.
Hint: Consider steric effect and electronic effect.
2. Predict the products of the following reactions:
Uses of Aldehydes and Ketones
In chemical industry aldehydes and ketones are used as solvents, starting materials and reagents
for the synthesis of other products. Formaldehyde is well known as formalin (40%) solution used
to preserve biological specimens and to prepare bakelite (a phenol-formaldehyde resin), urea-
formaldehyde glues and other polymeric products. Acetaldehyde is used primarily as a starting
material in the manufacture of acetic acid, ethyl acetate, vinyl acetate, polymers and drugs.
Benzaldehyde is used in perfumery and in dye industries. Acetone and ethyl methyl ketone are
common industrial solvents. Many aldehydes and ketones, e.g., butyraldehyde, vanillin,
acetophenone, camphor, etc. are well known for their odours and flavours.