AISSCE -19

Chemistry Project

 Topic – Aldehydes and Ketones

 Roll Number –
 Class – XII (PCM)

Submitted by – Priyanshu Patel

Submitted to – Sir Kamal Singh
 Certificate

This is to certify that _________________of class XII PCM

has successfully completed the investigatory project on the
topic ____________________ under my guidance during the
year 2018-2019 in the partial fulfillment of the chemistry
practical examination conducted by CBSE

Teachers signature Examiner’s signature

 Acknowledgement

I would like to sincerely and profusely thank my chemistry

teacher Mr. Kamal Singh, for his able guidance and support in
completing my project.

I would also like to extend my gratitude to the principal for

providing me with all the facility that was required
Last but not the least, I would extend my gratitude towards all
teaching and non-teaching staff of St. Anthony’s senior
secondary school and towards my friends who has supported
me to complete this project.
 I n d e x

S. no Title Page
 Aldehydes and Ketones

 What are aldehydes?

An aldehyde is a common functional group in organic chemistry.
Aldehydes can be found in perfume fragrances as well as natural and
synthetic hormones. In an aldehyde, a carbonyl group is single-
bonded to a hydrogen atom. A carbonyl is a carbon that is double
bonded to an oxygen atom. The carbonyl carbon is also bonded to
another hydrogen atom or a carbon/hydrogen chain, typically known
as an R group. The general formula of aldehyde is

 What are ketones?

Ketones are Compounds in which a carbonyl group is bonded to two
carbon atoms. The general formula of ketone is

Where R maybe H, alkyl or aryl group. If R and R are same, the

ketone is called simple ketone and if R and R are different then the
ketone is called mixed ketone.
 Nomenclature of aldehyde and ketones

a) Aldehyde
Common system

In the common system, aldehydes are named according to the name

of the corresponding carboxylic acid which they form on oxidation.
The suffix –ic acid of the name of the acid is replaced by aldehyde.
For example, CH3CHO derived from acetic acid (CH3COOH) is
named as acetaldehyde.

We use letters such as α, β, γ, and δ, and so on to indicate the

location of the substituent present in the carbon chain. The α-carbon
is the one to which the aldehyde group is attached. β- Carbon is the
carbon next to the α-carbon, and so on.

β-Bromobutyraldehyde
α-Methylpropionaldehyde

IUPAC System

In the IUPAC system, the aldehydes are known as alkanals. The

name of aldehyde is derived by replacing the terminal –e of the name
of corresponding alkane by al. For example,
 The branched chain aldehydes are named by the following rules:

 The longest chain containing the –CHO group is considered as the

parent chain and the name is derived by replacing the terminal –e
of the name of the corresponding alkane by the suffix –al.
 In case of substituted aldehydes, the parent chain is numbered in
such a way that the aldehydic group (–CHO) gets lowest number
i.e., 1.
 The positions of the other substituents are indicated by numbers.
 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 starts from the carbon atom
attached to the aldehyde group. For example,

OHCCH2CH2CH2CHO

4-Bromo-3-Methylheptanal Pentanedial

C6H5CH2CH2CHO

3-Phenylpropanal

2-Ethylbutanal

CH3CH=CHCH2CH2CHO
Hex-4-enal
 In Aromatic aldehydes, –CHO group is directly attached to the
benzene ring. The name of the simplest aromatic aldehyde carrying
aldehyde group on benzene is benzene carbaldehyde.
However the common name benzaldehyde is also accepted by
IUPAC. The other aromatic aldehydes are therefore, named as
substituted benzaldehydes. In case of substituted aromatic aldehydes,
the positions of the substituents in benzene ring with respect to –CHO
group are indicated either by suffixes ortho, meta or para or by
numbers 1, 2, 3… etc. with the carbon bearing the –CHO group as
number 1.
For example -

3-Hydroxy 4-Methoxybenzaldehyde Benzaldehyde

2-Methylbenzaldehyde 4-Nitrobenzaldehyde
 The aldehydic group may also be present in the side chain.
For example –

3-Phenylprop-2-enal 2- Phenylethanal

b) Ketone
Common system

In the common system, ketones are named by using the name of alkyl
groups present in the molecule. For example –

Dimethyl ketone Ethyl methyl ketone

CH3CH2COCH2CH3
Diethyl ketone Methyl n-propylketone
 IUPAC system

In IUPAC system, the ketones are known as alkanones. The

individual members are named by following the general rules as:

 The longest chain carrying the carbonyl group is considered as the

parent chain and the name is derived by replacing the terminal –e of
the name of corresponding alkane by the suffix –one.
 In case of substituted ketones, the parent chain is numbered in such a
way that the keto group gets the lowest number.
 The position of the carbonyl group and the substituents is indicated by
numbers. For example,

Propanone Pentan-2-one

CH3 -CH2 –CO-CH2 -CH3

Pentan-3-one
4-Methylpent-3-en-2-one

2-Methylcyclohexane 2, 4 Dimethylpentan-3-one
 Important note – If the compound contains both aldehyde and
ketonic groups, then aldehyde group is considered as principal functional
group ketonic group is regarded as substituent. It is named as prefix oxo–
along with a number to indicate its position.

(3-Oxopentanal)

Preparation of both aldehyde and ketones

I. FROM OXIDATION OF ALCOHOLS
Oxidation of primary and secondary alcohols leads to the formation
of aldehydes and ketones. The oxidation is possible with the help of
common oxidizing agents are KMnO4, K2Cr2O7, and CrO3. Aldehyde
and Ketone preparation is possible by oxidation of primary and
secondary alcohol by agents such as PCC (pyridinium
chlorochromate), Collins reagents (Chromium trioxide-pyridine
complex), and Cu at 573 K.

II. BY DEHYDROGENATION OF ALCOHOLS

This preparation method applies in case of conversion of volatile
alcohols to aldehydes. It is generally used in industrial application.
Vapours of alcohol are passed through heavy metal catalysts such as
Cu or Ag in this technique. Primary alcohol produces aldehyde
whereas secondary alcohol produces ketones, respectively.

III. FROM HYDROCARBONS

This method is further divided into two separate methods. They are

 By ozonolysis of alkenes
 By hydration of alkynes
 Ozonolysis of Alkenes
Formation of aldehyde and ketone is possible by ozonolysis of
alkenes. Ozonolysis is a reaction method in which addition of ozone
molecules or O3 to an alkene compound leads to the formation of
ozonide. Reduction of the ozonide compound with the help of zinc
dust and water produces the smaller molecules, which in this case
will be the respective aldehydes and ketones. The reaction produces
aldehydes, ketones and in some cases both the compounds on the
basis of the substitution arrangement of the alkene compounds.

Hydration of Alkynes
Alkynes follow Markovnikov’s rule in the presence of a proper
catalyst to produce ketones. All alkynes react with water in the
presence of HgSO4 and H2SO4 to form ketones. However, the
reaction of ethyne with water in the presence of the catalyst (HgSO4
and H2SO4) leads to the formation of acetaldehyde. This is an only
exception where alkyne on hydration produces acetaldehyde. Rest all
the alkyne on hydration produces ketones.

IV. WACKERS PROCESS

Alkenes can be converted to aldehydes and ketones by treating with
an acidified aqueous solution of palladium chloride (PdCl2)
containing a catalytic amount of cupric chloride (CuCl2) in the
presence of air or oxygen. This method is known as Wacker’s
process.
 Preparation of Aldehyde
I. From acyl chloride (acid chloride)
Acyl chloride/acid chloride undergoes hydrogenation in the presence
of a catalyst such as barium sulfate (BaSO4) or Palladium (Pd) to
form aldehydes. Aldehyde formation with this process is possible
after the partial poisoning of the reaction by the addition of
compounds such as sulfur or quinolone. This is an important step for
the formation of aldehydes. This is also known as Rosenmund’s
Reaction.
In this reaction, Sulphur or quinolone behaves as poison for catalysts
and causes partial poisoning to stop further reduction of aldehydes
into alcohols. However, it is not possible to prepare formaldehyde
from this reaction because the acyl chloride form, formyl chloride, is
not stable at room temperature. It is not possible to prepare Ketones
by this reaction.

II. From nitriles and esters

Preparation of Aldehydes is possible with the help of nitriles.
Reduction of nitriles with the compound Stannous Chloride (SnCl2) in
the presence of HCl leads to the formation of the nitrile compound’s
corresponding imine form. The imine compound undergoes
hydrolysis to yield the corresponding aldehydes. The reaction is
known as Stephen’s Reduction.
Ketones cannot be prepared by this method.
 Moreover, nitriles can undergo reduction by the compound DIBAL-H
or di-isobutyl aluminum hydride for the formation of imines. The
imines further undergo hydrolysis thereby forming aldehyde
compounds.

Similarly, esters are also reduced to aldehyde with DIBAL-H

III. From hydrocarbons

Formation of Aromatic Aldehyde, benzaldehydes and the derivatives
of benzaldehyde, is possible with the help of aromatic hydrocarbons
primarily by two methods.

a) Oxidation of methylbenzene
Toluene and the derivatives of toluene undergo oxidation with the help
of a strong oxidizing agent to form benzoic acids. However, it is
possible to stop the reaction at the aldehyde stage with the help of
proper reagents. The reagents can convert the methyl group to an
intermediate that cannot undergo further oxidation easily. Oxidation of
methylbenzene or toluene falls under two categories on the basis of
reagents used in the reaction

 Use of chromyl chloride

Oxidizing agent chromyl chloride can oxidize and convert methyl
group to a chromium complex. The chromium complex undergoes
hydrolysis to produce benzaldehyde. We refer to this reaction as
Etard Reaction. In this reaction, methylbenzene/toluene
undergoes oxidation process with the reagent of chromyl chloride
 (CrO2Cl2) present in solution form in CCl4 or in CS2 thereby
forming chromium complex.

 Use of chromic oxide

It is possible to oxidize toluene or substituted toluene to aldehydes
on treatment with reagents such as Chromium oxide, chromium
trioxide, with acetic anhydride. This reaction leads to the formation
of benzylidene diacetate. The intermediate or in this case
benzylidene diacetate can undergo further hydrolysis to
corresponding benzaldehyde with aqueous acid.

b) By side chain chlorination followed by hydrolysis

Preparation of aldehydes is possible by side chain halogenation,
more specifically side chain chlorination, followed by
hydrolysis. Side chain chlorination of toluene yields benzal
chloride which undergoes hydrolysis leads to the formation of
benzaldehyde. The preparation technique is also the commercial
way of benzaldehyde manufacture.

c) By Gatterman-koch reaction

When benzene and its derivatives undergo treatment with carbon

monoxide and HCl in the presence of a Lewis acid such as
cuprous chloride/ anhydrous aluminum chloride leads to the
formation of benzaldehyde or substitution of benzaldehyde
 compounds. This reaction method refers to as Gatterman-Koch
Reaction

Preparation of ketones
 From acyl chlorides
Ketone formation is possible by the treatment of acyl chloride with di-
alkyl cadmium [(R)2 Cd]. Cadmium chloride reacts with the Grignard
reagent to form ketones.

 From nitriles
Nitrile undergoes treatment with nitrile with Grignard reagent and
further undergoes hydrolysis to form ketones.

 From benzene or substituted benzene

Aromatic ketone formation is possible from benzene or substituted
benzenes. The most suitable preparation technique for an aromatic
aldehyde is Friedel-Crafts acylation reaction. In this reaction benzene
 or substituted benzenes undergoes treatment with an acid chloride or
acid anhydride to form ketones. The reaction occurs in the presence
of a catalyst such as Lewis acid such as anhydrous AlCl3 (anhydrous
aluminium chloride)

Physical properties of aldehydes and ketones

1) Boiling Point
At room temperature, methanol behaves as a gas whereas ethanol is in
liquid form that is volatile in nature. The boiling point of methanol and
ethanol is -19o C and +21o C. Thus, the boiling point of ethanol is
nearly at room temperature. Moreover, all other aldehydes and ketones
are either liquid or solid at room temperature.

The boiling point of these compounds increases with increase in

molecular weight. Additionally, the strength of intermolecular forces is
also responsible for the boiling point of aldehydes and ketones.
However, the boiling points of these organic compounds are higher in
comparison to hydrocarbons or ethers having nearly similar molecular
masses.

The reason for such behavior is the weak molecular association of these
compounds occurring due to dipole-dipole interactions. Similarly, the
boiling of aldehydes and ketones are lower than alcohol of nearly same
molecular masses. The reason is lack of intermolecular hydrogen
bonding.

The size of the boiling point is governed by the strengths of the

intermolecular forces.
Vander Waals Dispersion Force
The boiling point of aldehydes and ketones depends on the numbers of
the carbon atom. It increases with increase in the number of atoms of
carbon. The longer the molecules become and with the increase in the
number of electrons, the attraction between the compounds increases.

Vander Waals Dipole-Dipole Attraction

Aldehydes and ketones are polar in nature due to the presence of the
carbon-oxygen double bond. This creates an attraction between the
permanent dipoles and with the nearby present molecules. Hence, the
reason why this compound has a higher boiling point in comparison to
the hydrocarbons of similar size.

Refer to the table below to note the arrangement of boiling points in the
increasing order of the compounds having molecular masses from 58 to
60.

Name of the compound Molecular mass Boiling point (k)

n- Butane 58 273

Methoxyethane 60 281

Propanal 58 322

Acetone 58 329

Propan-1-ol 60 370

2) Solubility
Generally, these aldehydes and ketones are soluble in nature with
respect to water. However, the solubility gradually decreases with the
increase in the alkyl chain length. Therefore, lower members such as
methanal, ethanal, and propanone demonstrate miscible nature with
all proportions of water.
 This happens due to the ability of the lower members of the aldehydes
and ketones to develop hydrogen bong with water. However, these
compounds are unable to form hydrogen bonds with themselves. The
reason for such behavior is dispersion forces and dipole-dipole
interaction.
Usually, all aldehydes and ketones are relatively soluble in organic
solvents such as ether, methanol, benzene, chloroform, etc. The lower
members of these classes of compounds demonstrate the
characteristic sharp pungent odours but the odour converts to more
fragrant smell with an increase in the size of molecules.
Hence, aldehydes and ketones are used in different industrial
applications. In fact, there are certain naturally occurring aldehydes
and ketones that help in the blending of perfumes and also act as
flavouring agents.

Chemical reactions
1) Nucleophilic addition reactions
We will be able to convert multiple bonds into different functional
groups with the help of addition reactions. The reaction will help to
convert the unsaturated compounds to saturated and more functional
species. Contrary to this, aldehydes and ketones undergo nucleophilic
addition reaction.

 Mechanism of Nucleophilic Addition Reaction

We know that carbonyl carbon demonstrates sp2 hybridization and
together the structure is coplanar. A nucleophile acts on the polar
carbonyl’s electrophilic carbon atom perpendicular to the orbital
demonstration sp2 hybridization of the carbonyl carbon structure.
However, on the attack of the nucleophile, the hybridization of the
 carbon atom changes from sp2 hybridization of sp3 hybridization
thereby forming tetrahedral alkoxide intermediate complex. This
intermediate complex will take a proton from reaction medium to
produce an electrically neutral compound. Hence, the reaction results in
the addition of nucleophile and hydrogen in the carbon-oxygen double
bond.

 Reactivity of Aldehydes and Ketones

Aldehydes are more reactive and readily undergo nucleophilic
addition reactions in comparison to ketones. Aldehydes demonstrate
more favourable equilibrium constants for addition reactions than
ketones because of electronic and steric effect. In the case of ketones,
two large substituents are present in the structure of ketones which
causes steric hindrance when the nucleophile approaches the carbonyl
carbon.
However, aldehydes contain one substituent and thus the steric
hindrance to the approaching nucleophile is less. Moreover,
electronically aldehydes demonstrate better reactivity than ketone.
 This is because ketones contain two alkyl groups which decrease the
electrophilicity of carbonyl carbon atom more than aldehydes.

 Some important examples of nucleophilic addition

and nucleophilic addition-elimination reactions:

a) Addition of hydrogen cyanide (HCN):

Aldehydes and ketones undergo reaction with HCN to produce
cyanohydrins. The reaction progresses very slowly by using pure
hydrogen cyanide. Hence, base as a catalyst helps to speed up the
reaction. This is because catalysis helps in the generation of
cyanide ion (CN) which acts as a stronger nucleophile and adds to
carbonyl compounds to produce the corresponding cyanohydrin.
Cyanohydrins are important synthetic intermediates.

b) Addition of sodium hydrogensulphite: Sodium

hydrogensulphite adds to aldehydes and ketones to
form the addition products.
Addition of Sodium Hydrogen Sulphite to aldehydes and ketones
will result in the formation of the addition of products. The
equilibrium position of the reaction for aldehydes will be on the
right-hand side but the equilibrium position of the reaction for
will be on the left-hand side because of the steric effect.
The hydrogen sulphite compound form from the sodium
hydrogen sulphite addition is water soluble. Therefore, it can be
 converted back to parent carbonyl compound by treatment of the
compound with dilute mineral acid or alkali. The reaction is also
useful for the purification and separation processes of aldehydes.

c) Addition of Grignard reagents

Grignard Reagents or R-MgX demonstrates polar nature. In this
compound, the carbon atom is electronegative in nature and the
Mg atom is electropositive in nature. The polar nature of the
Grignard Reagents helps the compound reacts with aldehydes and
ketone to produce additional products. The addition products
undergo decomposition reaction to give alcohol with water or
dilute sulphuric acid.

Necessary Points to Note in this Reaction

 If Grignard Reagent reacts with formaldehyde (HCHO), the
reaction will form primary alcohol as the product.
 If the reagent reacts with aldehydes other than HCHO, the
reaction will produce secondary alcohols.
 Ketone reaction with the reagent will produce tertiary alcohols.

d) Addition of alcohols
Aldehydes undergo reaction with the monohydric alcohol to
produce hemiacetals or alkoxyalcohol intermediate. The
hemiacetal will further undergo reaction with an alcohol to
produce gem-dialkoxy compound or acetal. The reaction is
carried out in the presence of dry hydrogen chloride. On
application of similar conditions, ketone undergoes reaction with
ethylene glycol to produce cyclic compounds or ethylene glycol
ketals.
 The dry hydrogen chloride present in the reaction protonates the
oxygen atom present in the carbonyl structure thereby increasing
the electrophilicity of the carbonyl carbon. Thus, it helps in the
nucleophilic attack of ethylene glycol. Further hydrolysis of
acetals and ketals with mineral acids (aqueous) will help in
retrieval of respective aldehydes and ketones.

e) Addition of ammonia and its derivatives

Many nucleophiles like ammonia and derivatives of ammonia
(H2N-Z) can also be added to the carbonyl group of aldehydes
and ketones. The reaction of ammonia and its derivatives is
reversible and the reaction happens in the presence of acid to
form addition products. The reaction equilibrium will help the
product formation because of fast dehydration of the intermediate
complex. Thus, the reaction finally forms the compound >C=N-Z.
In the structure >C=N-Z, Z can be alkyl, OH, aryl, NH2,
NHCONH2, C6H5NH, etc.
2) Reduction
 Reduction to alcohols: Aldehydes and ketones are reduced to
primary and secondary alcohols respectively by sodium
borohydride (NaBH4) or lithium aluminium hydride (LiAlH4) as
well as by catalytic hydrogenation.

 Reduction to hydrocarbons: The carbonyl group of aldehydes and

ketones is reduced to CH2 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 CH3CO group or
CH3CH(OH) group which produces CH3CO group on
oxidation.
4) Reactions due to alpha- hydrogen

 Acidity of alpha-hydrogen 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.

Ketones can also be used as one component in the

cross aldol reactions.
 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.

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.
 Conclusion

In this investigatory project, we have examined the properties

of aldehydes and ketones. Specifically, we have taken a look
at the reactivity of the carbonyl carbon in nucleophilic
addition reactions and examined how aldehydes and ketones
can be oxidized and reduced. We also came to know about
uses of aldehydes and ketones and as well as about their
physical properties.
Bibliography