Magical Chemistry @ FTA ,+2 HSS/VHSS – Aldehydes, Ketones and Acids

ALDEHYDES, KETONES AND ACIDS

XII ORGANIC CHEMISTRY CHAPTER 3
Organic compounds containing Carbon-Oxygen double bond called carbonyl group. It is one of
the most important functional group in Organic Chemistry.
ALDEHYDES AND KETONES
In aldehydes, the carbonyl group is bonded to a carbon and hydrogen.
In ketones, the carbonyl group is bonded to two carbon atoms.
The carbonyl compounds in which the carbonyl group is bonded to oxygen are known as
carboxylic acids and their derivatives.
The carbonyl compounds in which the carbon is attached to nitrogen are called amides.
The carbonyl compounds in which the carbon is attached to halogens are called acyl halides.
The general formulas of these classes of compounds are given below.

NOMENCLATURE OF ALDEHYDES AND KETONES

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.
HCHO Formaldehyde Methanal
CH 3 CHO Acetaldehyde Ethanal
(CH 3 ) 2 CHCHO Isobutyraldehyde 2-Methylpropanal
CH 3 COCH 2 CH 2 CH 3 Methyl n-propyl ketone Pentan-2-one
(CH 3 ) 2 CHCOCH(CH 3 ) 2 Diisopropyl ketone 2,4-Dimethylpentan-3-one

Write the structures of the following compounds.

(i) α-Methoxypropionaldehyde (ii) 3-Hydroxybutanal (iii) Di-sec. butyl ketone
(iv) 2-Hydroxycyclopentane carbaldehyde (v) 4-Oxopentanal (vi) 4-Fluoroacetophenone

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Preparation of Aldehydes and Ketones

1. By oxidation of alcohols: Primary alcohols on oxidation with mild oxidising agents like CrO 3 to give
aldehydes while secondary alcohols give ketones.
R-CH2OH [O] R-CHO
R2CHOH [O] R2CO
2. By dehydrogenation of alcohols: Alcohols when heated with Cu or Silver catalyst at 573K, we get
carbonyl compounds. Primary alcohols give aldehydes, while secondary alcohols give ketones.
R-CH2OH Cu/573 K R-CHO
R2CHOH Cu/573 K R2CO
3. By ozonolysis of alkenes: Alkenes add ozone followed by hydrolysis with zinc dust and water, we get
aldehydes or ketones.

Preparation of Aldehydes
4.Rosenmund reduction. Acid chloride is converted to benzaldehyde using palladium on barium
sulphate . Here acid chloride(acyl chloride) is hydrogenated over catalyst, palladium on barium
sulphate.

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5. Stephen reaction.:-
reaction.:-Nitriles
Nitriles or cyanides are converted to aldehyde using stannous chloride . At first
Nitriles( cyanide) are reduced to corresponding imine with stannous chloride in the presence of
hydrochloric acid, which on hydrolysis give corresponding aldehyde.

Nitriles are selectively reduced by Di-isobutyl aluminium hydride, (DIBAL-H) to imines followed by
hydrolysis to aldehydes.

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

6.Etard reaction. Toluene is converted in to Benzaldehyde using chromyl chloride (CrO 2Cl2 ) in
carbondisulphide . Chromyl chloride oxidises methyl group of toluene to a chromium complex, which
on hydrolysis gives corresponding benzaldehyde. Aromatic aldehydes (benzaldehyde and its derivatives)
are prepared from aromatic hydrocarbons by this methods:

7.with chromic oxide in acetic anhydride. Toluene is also converted in to Benzaldehyde with chromic
oxide in acetic anhydride.Here benzylidene diacetateis first formed at first which then hydrolysed to
corresponding benzaldehyde

8. by side chain chlorination followed by hydrolysis

Side chain chlorination of toluene gives benzal chloride.Benzal chloride on hydrolysis gives
benzaldehyde. This is a commercial method of manufacture of benzaldehyde.

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9. By Gatterman – Koch reaction: Benzene is converted to benzaldehyde using CO and HCl in

anhydrous AlCl3 or CuCl.
CuCl. 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:
chlorides:-Treatment of acyl chlorides with dialkyl cadmium gives ketones.
Di alkyl Cadmium is prepared by the reaction of cadmium chloride with Grignard reagent,

2. From nitriles :-Treating

:-Treating a nitrile with Grignard reagent followed by hydrolysis yields a ketone.

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

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.
The boiling points are lower than those of alcohols of similar molecular masses due to absence of
intermolecular hydrogen bonding.
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.

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Chemical Reactions
Since aldehydes and ketones both possess the carbonyl functional group, they undergo similar chemical
reactions.
1. Nucleophilic addition reactions
(i) Mechanism of nucleophilic addition reactions
A nucleophile attacks the electrophilic carbon atom of the polar carbonyl group from a direction
approximately perpendicular to the plane of sp hybridised orbitals of carbonyl carbon .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

(ii) Reactivity
Aldehydes are generally more reactive than ketones in nucleophilic addition reactions due to
steric 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 carbon more effectively than in former.
Benzaldehyde to be more reactive or less reactive in nucleophilic addition reactions than
propanal? Explain
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 as shown below and hence it is less reactive than propanal
Some important examples of nucleophilic addition andnucleophilic addition-elimination reactions:
Addition of hydrogen cyanide (HCN): Aldehydesand ketones react with hydrogen cyanide (HCN)
to yield cyanohydrins.

Addition of sodium hydrogensulphite: Sodium hydrogensulphite adds to aldehydes and ketones to form
the addition products.

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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 (LiAlH 4 ) as well as by
catalytic hydrogenation
R-CHO [H] R-CH2OH
R2CO [H] R2CHOH

(ii) Reduction to hydrocarbons:

a.Clemmensen reduction Aldehydes and ketones can be reduced to the corresponding hydrocarbons by
treating with zinc amalgam and conc. HCl . Here the
the carbonyl group of aldehydes and ketones is
reduced to CH 2 group

b. Wolff-Kishner reduction Aldehydes and ketones can be reduced to the corresponding hydrocarbons
by treating with hydrazine followed by heating with sodium or potassium hydroxide in high boiling
solvent such as ethylene glycol .

3.Oxidation
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.

R-CHO [O] R-COOH

CH3-CHO [O] CH3-COOH

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.

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Tests to distinguish Aldehydes and 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.

4. Aldol condensation Reaction: Aldehydes and ketones having at least one α-hydrogen atom when
treated with dilute alkali, we get β-hydroxy aldehydes (aldol) or β-hydroxy ketones (ketol) respectively.
This is known as Aldol reaction. The product formed contains both aldehydic (ketonic) and alcoholic
group. So the name aldol or ketol is used. The aldol or ketol on heated undergo dehydration to give α, β-
unsaturated aldehyde or ketone. This reaction is called Aldol condensation.

2CH3-CHO dil. NaOH CH3-CH(OH)-CH2-CHO CH3-CH=CH-CHO

Ethanal 3-Hydroxybutanal (aldol) But-2-enal (Crotanaldehyde)

5. Cross aldol condensation: When aldol condensation is carried out between two different aldehydes or
ketones, it is called cross aldol condensation. If both of them contain α-hydrogen atoms, we get a mixture
of four products.
CH3-CHO + CH2-CH2-CHO NaOH/∆ CH3-CH=CH-CHO + CH3-CH2-CH=C(CH3)-CHO
Ethanal Propanal But-2-enal 2-methylpent-2-enal
+ CH3-CH=C(CH3)-CHO + CH3-CH2-CH=CH-CHO
2-methylbut-2-enal Pent-2-enal
Ketones can also be used as one component in the cross aldol reactions.

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6. Cannizzaro Reaction: Aldehydes having no α-hydrogen atom (e.g. HCHO, C6H5-CHO, CCl3-CHO etc),
when treated with Conc. alkali (NaOH or KOH) undergo self oxidation and reduction
(disproportionation) to form one molecule of the alcohol and one molecule of carboxylic acid salt. This
reaction is called Cannizzaro reaction.

2 HCHO Conc. KOH CH3-OH + H-COOK

Formaldehyde methanol potassium formate

7.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

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

CARBOXYLIC ACIDS
Carbon compounds containing a carboxyl functional group, –COOH are called carboxylic acids.
The carboxyl group, consists of a carbonyl group attached to a hydroxyl group, hence its name carboxyl.
Carboxylic acids may be aliphatic (RCOOH) or aromatic (ArCOOH) depending on the group, alkyl or
aryl, attached to carboxylic carbon.
Nomenclature and Structure of Carboxyl Group
In the IUPAC system, aliphatic carboxylic acids are named by replacing the ending –e in the name
of the corresponding alkane with – oic acid. In numbering the carbon chain, the carboxylic carbon is
numbered one.

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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
structure shown below:

Methods of Preparation of Carboxylic Acids

1. From primary alcohols and aldehydes
Primary alcohols are readily oxidised to carboxylic acids with common oxidising agents such as
potassium permanganate (KMnO4 ) in neutral, acidic or alkaline media or by potassium dichromate
(K 2 Cr 2 O 7 ) and chromium trioxide (CrO3 ) in acidic media (Jones reagent).
R-CH2OH alkaline KMnO4/H3O + R-COOH
CH3-CH2-OH CrO3/H2SO4 CH3-COOH
Aldehydes on oxidation with mild oxidising agents like CrO3 or Tollen’s reagent to give carboxylic acids.
R-CHO [O] R-COOH
CH3-CHO [O] CH3-COOH

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2. From alkylbenzenes: Aromatic carboxylic acids can be prepared by vigorous oxidation of alkyl
benzenes with chromic acid or acidic or alkaline potassium permanganate. The entire side chain is
oxidised to the carboxyl group irrespective of length of the side chain. Primary and secondary alkyl
groups are oxidised in this manner while tertiary group is not affected.

3. From nitriles and amides

Nitriles are hydrolysed to amides and then to acids in the presence of H + or OH - as catalyst. Mild
reaction conditions are used to stop thereaction at the amide stage

4. From Grignard reagents

Grignard reagents react with carbon dioxide (dry ice) to form salts of carboxylic acids which in turn give
corresponding carboxylic acids after acidification with mineral acid.

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5. From acyl halides and anhydrides

Acid chlorides when hydrolysed with water give carboxylic acids or more readily hydrolysed with
aqueous base to give carboxylate ions which on acidification provide corresponding carboxylic acids.
Anhydrides on the other hand are hydrolysed to corresponding acid(s) with water.

6. From esters
Acidic hydrolysis of esters gives directly carboxylic acids while basic hydrolysis gives carboxylates, which
on acidification give corresponding carboxylic acids.

Physical Properties
Carboxylic acids are higher boiling liquids than aldehydes,
ketones and even alcohols of comparable molecular masses. This is
due to more extensive association of carboxylic acid
molecules through intermolecular hydrogen bonding.

Chemical Reactions
A ) Reactions Involving Cleavage of O–H Bond
Acidity Reactions with metals and alkalies

carboxylic acids are more acidic than phenols.

In carboxylate ion. ,the negative charge is de localised over
two electronegative oxygen atoms whereas

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it is less effectively delocalised over one oxygen atom and less electronegative carbon atoms in
phenoxide 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:

Substituents may affect the stability of the conjugate base and thus, also affect the acidity of the
carboxylic acids.
Electron withdrawing groups increase the acidity of carboxylic acids by stabilising the conjugate
base through delocalisation of the negative charge by inductive and/or resonance effects. Conversely,
electron donating groups decrease the acidity by destabilising the conjugate base.

Direct attachment of groups such as phenyl group to the carboxylic acid, increases the acidity of
corresponding carboxylic acid, This is because of greater electronegativity of sp hybridised carbon
to which carboxyl carbon is attached.
The presence of electron withdrawing group on the phenyl of aromatic carboxylic acid increases
their acidity while electron donating groups decrease their acidity.

B ) Reactions Involving Cleavage of C–OH Bond

1.Formation of anhydride:
anhydride: Carboxylic acids on heating with mineral acids like H2SO4 or with P2O5
undergo dehydration to give acid anhydrides.
R-COOH + HOOC-R P2O5/∆ (R-CO)2O + H2O
CH3-COOH + HOOC-CH3 H+ /∆ (CH3-CO)2O + H2O
Acetic acid acetic anhydride
2.Esterification
Carboxylic acids are esterified with alcohols or phenols in the presence of a mineral acid such as
concentrated H 2 SO 4 or HCl gas as a catalyst.

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3. Reactions with PCl 5 , PCl 3 and SOCl 2

R-COOH + PCl3 R-COCl + H3PO3

R-COOH + PCl5 R-COCl + POCl3+ HCl
R-COOH + SOCl2 R-COCl + SO2 + HCl
4. Reaction with ammonia
Carboxylic acids react with ammonia to give ammonium salt which on further heating at high
temperature give amides. For example:

C) Reactions Involving –COOH Group

1. Reduction: Carboxylic acids when reduced with lithium aluminium hydride or with diborane, primary
alcohols are formed. Diborane does not reduce functional groups like ester, nitro, halo, etc. Sodium
borohydride does not reduce the carboxyl group.
R-COOH i) LiAlH4/ether or B2H6 ii) H3O + R-CH2OH

CH3-COOH i) LiAlH4/ether or B2H6 ii) H3O+ CH3-CH2OH

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2. Decarboxylation:
i) When sodium salts of carboxylic acid are heated with sodalime (a mixture of NaOH and CaO), they
undergo decarboxylation (elimination of CO2) to form alkanes.

R-COONa + NaOH CaO/∆ R-H + Na2CO3

CH3-COONa + NaOH CaO/∆ CH4 + Na2CO3

ii) Kolbe’s electrolysis: When an aqueous solution of sodium or potassium salt of carboxylic acid is
electrolysed, we get alkanes having twice the number of carbon atoms that present in the alkyl group of
the acid. This reaction is known as Kolbe electrolysis.

2 R-COOK + 2H2O electrolysis R-R + 2KOH + H2 + 2CO2

2 CH3-COOH + 2 H2O electrolysis CH3-CH3 + 2KOH + H2 + 2CO2

D) Substitution Reactions in the Hydrocarbon Part

1.Halogenation [HVZ Reaction] Carboxylic acids having an α-hydrogen atom, when treated with halogen
(chlorine or bromine) in the presence of red phosphorus, we get α-halocarboxylic acids. This reaction is
known as Hell-Volhard-Zelinsky(HVZ) reaction. This reaction is synthetically important since the halogen
atom can be replaced by other groups.

2. Electrophilic substitution reactions:( Ring substitution); The –COOH group is a deactivating group and
meta-directing. So on electrophilic substitution reactions, we get meta derivatives.

Uses of Carboxylic Acids

Methanoic acid is used in rubber, textile, dyeing, leather and electroplating industries.
Ethanoic acid is used as solvent and as vinegar in food industry.
Hexanedioic acid is used in the manufacture of nylon-6, 6.
Esters of benzoic acid are used in perfumery.
Sodium benzoate is used as a food preservative.
Higher fatty acids are used for the manufacture of soaps and detergents.

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