Since 1996 9414248318, 9468590309, 0141-2719117

1
Unit % 12 Aldehydes, Ketones and Carboxylic Acids Marks %
06

Aldehydes and Ketones

Aldehydes and ketones are those hydrocarbons derivatives which contains >𝐂 = 𝐎
group. In aldehydes, the carbonyl group is bonded to a carbon and hydrogen while in
the ketones; it is bonded to two carbon atoms. Thus in aldehyde, functional group is
−𝐂𝐇𝐎, which is known as aldehyde group. This group always present at the end of
carbon chain. The functional group which presents in ketone is known as ketonic
group. The structure of this group is presented as follows:
−𝐂 − 𝐂 − 𝐂 − It is clear from this functional group that, ketonic group is always present
𝐎 in the middle of the chain.
Nomenclature of Cabonyl Compounds 
The general formula for both aldehydes and ketones is 𝐂𝐧 𝐇𝟐𝐧 𝐎. Nomenclature of
aldehyde in common name systems is Alkyl aldehyde. Where aldehyde functional
group does not included with alkyl. If aldehyde functional group is included in
common name nomenclature system, then nomenclature will be done by the help of
following table:
Number of Carbon Prefix Suffix
𝟏𝐂 Form aldehyde
𝟐𝐂 Acet aldehyde
𝟑𝐂 Propion aldehyde
𝟒𝐂 (𝐧, iso) Butyr aldehyde
𝟓𝐂 (𝐧, iso, active, secondary or tertiary) Valer aldehyde
In derived name system nomenclature of aldehyde is alkyl acetaldehyde. Where, a
carbon and the −𝐂𝐇𝐎 functional group binded with the carbon, is known as
acetaldehyde. In 𝐈. 𝐔. 𝐏. 𝐀. 𝐂., they are named as follows:
 Largest carbon chain containing −𝐂𝐇𝐎 group is selected.
 Numbering is done in this way that the −𝐂𝐇𝐎 functional group gets the least
number.
 Now at last the name is written as:
Substitute(If there is) + alk + ane + al
Nomenclature of symmetrical ketone in common name systems is dialkyl ketone and
is alkyl alkyl ketone for the unsymmetrical ketone. If both the groups attached to
ketonic group are same, then it is known as simple ketones ans if both the groups are
different, then it is mixed ketones. In 𝐈. 𝐔. 𝐏. 𝐀. 𝐂., they are named as follows:
 Largest carbon chain containing ketonic group is selected.
 Numbering is done in this way that the ketonic functional group gets the least
number.
 Now at last the name is written as:
Substitute(If there is) + alk + ane + one
Gen. Structural formula Common Name 𝐈. 𝐔. 𝐏. 𝐀. 𝐂.
formula
𝐂𝟑 𝐇𝟒 𝐎 𝐂𝐇𝟐 = 𝐂𝐇 − 𝐂𝐇𝐎 Acryl aldehyde, Propenal
Vinyl aldehyde,
 Acroline
𝐂𝟒 𝐇𝟔 𝐎 𝐂𝐇𝟑 − 𝐂𝐇 = 𝐂𝐇 − 𝐂𝐇𝐎 Crotonalhehyde But−𝟐 −ene−𝟏 −al
𝐂𝟗 𝐇𝟖 𝐎
𝐂𝐇𝟐 𝐎
𝐂𝟔 𝐇𝟓 − 𝐂𝐇 = 𝐂𝐇 − 𝐂𝐇𝐎
𝐇 − 𝐂𝐇𝐎
Cinnemaldehyde
Formaldehyde
𝟑 −Phenylpropenal
Methanal 2
𝐂𝟐 𝐇𝟒 𝐎 𝐂𝐇𝟑 − 𝐂𝐇𝐎 Methylaldehyde, Ethanal
Acetaldehyde
𝐂𝟑 𝐇𝟔 𝐎 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇𝐎 Ethylaldehyde, Propanal
Propionaldehyde
𝐂𝐇𝟑 − 𝐂𝐎 − 𝐂𝐇𝟑 Dimethyl ketone, Propanone
Acetone
𝐂𝟒 𝐇𝟖 𝐎 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇𝐎 Propylaldehyde, Butanal
Butyraldehyde
𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝐎 Isopropylaldehyde, 𝟐 −Methylpropanal

𝐂𝐇𝟑
Isobutyraldehyde
𝐂𝐇𝟑 − 𝐂𝐎 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 Ethylmethyl ketone Butanone
𝐂𝟓 𝐇𝟏𝟎 𝐎 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇𝐎 Butylaldehyde, Pentanal
Valeraldehyde
𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 𝟐° −Butylaldehyde, 𝟐 −Methylbutanal

𝐂𝐇𝐎 𝟐° −Valeraldehyde
𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝐎 Isobutylaldehyde, 𝟑 −Methylbutanal

𝐂𝐇𝟑
Isovaleraldehyde
𝐂𝐇𝐎 𝟑° −Butylaldehyde, 𝟐, 𝟐 − Dimethylpropa
𝟑 −Valeraldehyde,
°
nal
𝐂𝐇𝟑 − 𝐂 − 𝐂𝐇𝟑
Pivalaldehyde
𝐂𝐇𝟑
𝐂𝐇𝟑 − 𝐂𝐎 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 Methylpropyl ketone 𝟐 −Pentanone

𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐎 − 𝐂𝐇𝟑 Isopropylmethyl 𝟐 − Methylbutan −𝟐 −

𝐂𝐇𝟑 ketone one

𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐎 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 Diethyl ketone 𝟑 −Pentanone

𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂 − 𝐂𝐇 − 𝐂𝐇𝟑 Di isopropyl ketone 𝟐, 𝟒 − dimethylpentan

𝐂𝐇𝟑 𝐎 𝐂𝐇𝟑 −𝟑 −one
𝐂𝐇𝟑 − 𝐂 = 𝐂𝐇 − 𝐂 − 𝐂𝐇𝟑 Mestyl oxide 𝟒 −methylpent−𝟑 −
𝐂𝐇𝟑 𝐎 en−𝟑 −one
𝐈. 𝐔. 𝐏. 𝐀. 𝐂. name of some other carbonyl compouns are:
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝐎 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇 = 𝐂𝐇 − 𝐂𝐇𝐎

𝐁𝐫 𝐂𝐇𝟑
𝟒 −Bromo−𝟑 −methylheptanal Pent−𝟐 −enal
In common name system for aldehydes and ketons, the location of the substituent in
the carbon chain is indicated by Greek letters ∝, 𝛃, 𝛄, 𝛅 etc. The ∝ carbon being the one
directly linked to the functional group, 𝛃 carbon the next, and so on. For example,
𝛃 ∝ ∝ 𝛃′
𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝐎 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇 − 𝐂𝐇𝐎 𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝓵

𝐂𝐇𝟑 𝐂𝐇𝟑 𝐂𝓵 𝐎
𝛃 −Methylbutyraldehyde ∝ − Methylbutyraldehyde ∝, 𝛃′ −Dichlorodiethylketone
𝛃 ∝ ∝ ∝′
𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝐎 𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝐎 𝐂𝓵 − 𝐂𝐇 − 𝐂 − 𝐂𝐇𝟐 − 𝐂𝓵

𝐁𝐫 𝐎𝐂𝐇𝟑 𝐁𝐫 𝐎
𝛃 −Methylbutyraldehyde ∝ − Methoxypropionaldehyde
∝ −Bromo −∝, ∝ ′ −dichloroacetone
Since 1996 9414248318, 9468590309, 0141-2719117

The rules same applies to cyclic ketones in 𝐈. 𝐔. 𝐏. 𝐀. 𝐂., where the carbonyl carbon is
3
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. For
example,
𝐇𝟑 𝐂 𝐂𝐇𝐎 𝐎 𝐎
−𝐂𝐇𝐎 𝐂𝐇𝟑
𝐂𝐇𝟑
Cyclohexanecarbaldehyde 𝟐 −Methylcyclohexanone
𝟑 −Methylcyclohexanecarbaldehyde 𝟑 −Methylcyclopentanone
The name of the simplest aromatic aldehyde carrying the aldehyde group on a
benzene ring is benzenecarbaldehyde in 𝐈. 𝐔. 𝐏. 𝐀. 𝐂. . However, the common name
benzaldehyde is also accepted by 𝐈. 𝐔. 𝐏. . 𝐂.. For examples,
𝐂𝐇𝐎
𝐂𝐇𝐎 𝐂𝐇𝐎

𝐂𝐇𝐎
𝐍𝐎𝟐 𝐁𝐫
𝟒 −Nitrobenzenecarbaldehyde 𝟑 −Bromobenzenecarbaldehyde Phthaldehyde
𝟒 −Nitrobenzaldehyde 𝟑 −Bromobenzaldehyde Benzene−𝟏, 𝟐 −dicarbaldehyde
Alkyl phenyl ketones are usually named by adding the acyl group as prefix to phenone.
Alkyl phenyl ketones are those simple aeromatic ketone in which ketonic group is
directly attached with benzene ring. In same condition, benzene ring is written as the
phenyl substitute in 𝐈. 𝐔. 𝐏. 𝐀. 𝐂.. For example,
𝐎 𝐎 𝐎

𝐂 𝐂 𝐂𝐇𝟑 𝐂
𝐂𝐇𝟑 𝐂𝐇𝟐

Acetophenone Propionophenone Benzophenone

𝟏 −Phenylethan−𝟏 −one 𝟏 −Phenylpropan−𝟏 −one 𝟏, 𝟐 −diphenylmethanone
General Methods of Synthesis for Cabonyl Compounds 
A. For both the Aldehydes and Ketones 
1) By ozonolysis of Alkenes 
On reaction with ozone, alkene gives ozonide. Hydrolysis of ozonide in the
presence of zinc powder gives aldehyde and ketone. 𝐇𝟐 𝐎𝟐 is also prepared
in this method, which reacts immediately with zinc powder to give zinc
oxide and water. If zinc is not present in this reaction then nascent oxygen
further oxidises aldehyde(if it forms as a product) into carboxylic acid.
𝐎
𝐙𝐧/𝐇𝟐 𝐎
𝐂𝐇𝟐 = 𝐂𝐇𝟐 + 𝐎𝟑 𝐂𝐇𝟐 𝐂𝐇𝟐 𝟐𝐂𝐇𝟐 𝐎
Ethene Ozone −𝐇𝟐 𝐎𝟐 Formaldehyde
𝐎 𝐎
Ethene ozonide
𝐙𝐧 + 𝐇𝟐 𝐎𝟐 𝐙𝐧𝐎 + 𝐇𝟐 𝐎
𝐎
𝐙𝐧/𝐇𝟐 𝐎
𝐑 − 𝐂𝐇 = 𝐂𝐇 − 𝐑 + 𝐎𝟑 𝐑 − 𝐂𝐇 𝐂𝐇 − 𝐑 𝟐𝐑 − 𝐂𝐇𝐎
Symetrical Ozone −𝐇𝟐 𝐎𝟐 Alkyl aldehyde
Disubstituted alkene 𝐎 𝐎
 Ozonide
𝐙𝐧 + 𝐇𝟐 𝐎𝟐 𝐙𝐧𝐎 + 𝐇𝟐 𝐎
Since 1996 9414248318, 9468590309, 0141-2719117

𝐎
4
𝐑 𝐑 𝐑 𝐑 𝐙𝐧/𝐇𝟐 𝐎 𝐑
𝐂=𝐂 + 𝐎𝟑 𝐂 𝐂 𝐂=𝐎
𝐑 𝐑 𝐑 𝐑 −𝐇𝟐 𝐎𝟐 𝐑
𝐎 𝐎
Tetrasubstituted alkene Ozonide Ketone
𝐙𝐧 + 𝐇𝟐 𝐎𝟐 𝐙𝐧𝐎 + 𝐇𝟐 𝐎
2) By Hydrolysis of Alkynes 
Addition of water to ethyne in the presence of dilute 𝐇𝟐 𝐒𝐎𝟒 and 𝐇𝐠𝐒𝐎𝟒 gives
acetaldehyde. All other alkynes give ketones in this reaction. Methanal is not
prepared by this method.
dil 𝐇𝟐 𝐒𝐎𝟒 Rearrangement
𝐂𝐇 ≡ 𝐂𝐇 + 𝐇𝟐 𝐎 𝐂𝐇𝟐 = 𝐂𝐇 − 𝐎𝐇 𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇 = 𝐎
𝐇𝐠𝐒𝐎𝟒 , 𝟑𝟑𝟑𝐊
Ethyne Unstable enol form Acetaldehyde
dil 𝐇𝟐 𝐒𝐎𝟒 Rearrangement
𝐑 − 𝐂 ≡ 𝐂𝐇 + 𝐇𝟐 𝐎 𝐑 − 𝐂 = 𝐂𝐇 − 𝐇 𝐑 − 𝐂 − 𝐂𝐇𝟐 − 𝐇
𝐇𝐠𝐒𝐎𝟒 , 𝟑𝟑𝟑𝐊
𝐎𝐇 𝐎
Other alkyne Unstable enol form Ketone
dil 𝐇𝟐 𝐒𝐎𝟒 Rearrangement
𝐂𝐇𝟑 − 𝐂 ≡ 𝐂𝐇 + 𝐇𝟐 𝐎 𝐂𝐇𝟑 − 𝐂 = 𝐂𝐇 − 𝐇 𝐂𝐇𝟑 − 𝐂 − 𝐂𝐇𝟐 − 𝐇
𝐇𝐠𝐒𝐎𝟒 , 𝟑𝟑𝟑𝐊
𝐎𝐇 𝐎
Propyne Unstable enol form Acetone
3) By Dehydrogenation of alcohols 
When the vapours of a primary or a secondary alcohol are passed over heated
copper at 𝟓𝟕𝟑 𝐊, dehydrogenation takes place and an aldehyde or a ketone is
formed while tertiary alcohols undergo dehydration.
𝐂𝐮, 𝟓𝟕𝟑𝐊
R—𝐂𝐇𝟐 —OH R—C𝐇𝐎
−H2
R R
𝐂𝐮, 𝟓𝟕𝟑𝐊
R—CH—OH R—C=O
−H2
B. Method of Preparations only for Aldehydes 
1) By Rosenmund reaction 
Acid chloride when reduced with hydrogen in boiling xylene in presence of
palladium catalyst over barium sulphate gives aldehydes in good yield. This
reaction is called Rosenmund reduction.
𝐏𝐝 − 𝐁𝐚𝐒𝐎𝟒
𝐑 − 𝐂 − 𝐂𝓵 + 𝐇𝟐 𝐑 − 𝐂𝐇𝐎 + 𝐇𝐂𝓵

𝐎
𝐏𝐝 − 𝐁𝐚𝐒𝐎𝟒
𝐂𝟔 𝐇𝟓 − 𝐂 − 𝐂𝓵 + 𝐇𝟐 𝐂𝟔 𝐇𝟓 − 𝐂𝐇𝐎 + 𝐇𝐂𝓵

𝐎
Benzoyl chloride Benzaldehyde
Generally, aldehydes on further reduction give alcohol but here barium sulphate
acts as poison for 𝐏𝐝 catalyst and prevent the reduction of aldehyde to alcohol.
Formaldehyde cannot be prepared by this method because 𝐇𝐎𝐂𝓵 is unstable at
room temperature.
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 60, Shiv Colony, Kisaan Marg, Near Arjun Nagar Bipaas, Tonk
Phatak
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Since 1996 9414248318, 9468590309, 0141-2719117

2) By Stephen Reaction 
Nitriles are reduced to corresponding aldimine with stannous chloride in the
presence of hydrochloric acid, which on hydrolysis give corresponding aldehyde. 5
This reaction is known as Stephen reaction.
𝐒𝐧𝐂𝓵𝟐 𝐚𝐧𝐝 𝐇𝐂𝓵 𝐇𝐎𝐇
𝐑 − 𝐂 ≡ 𝐍 + 𝟐𝐇 𝐑 − 𝐂𝐇 = 𝐍 𝐑 − 𝐂𝐇𝐎 + 𝐍𝐇𝟑
Alkyl cyanide + Alkyl aldimine Alkyl aldehyde
In above reaction we can use diisobutylaluminium hydride, (𝐃𝐈𝐁𝐀𝐋 − 𝐇) as
redusing reagent in place of stannous chloride and hydrochloric acid.
Alternatively, nitriles are selectively reduced to imines followed by hydrolysis to
aldehydes.
(𝐢) 𝐀𝓵𝐇(𝐢 − 𝐁𝐮)𝟐
𝐑−𝐂≡𝐍 𝐑 − 𝐂𝐇𝐎
(𝐢𝐢) 𝐇𝟐 𝐎
Alkyl cyanide + Alkyl aldehyde
(𝐢) 𝐃𝐈𝐁𝐀𝐋 − 𝐇
𝐂𝐇𝟑 − 𝐂𝐇 = 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐍 𝐂𝐇𝟑 − 𝐂𝐇 = 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇𝐎
(𝐢𝐢) 𝐇𝟐 𝐎
Alkyl cyanide + Alkyl aldehyde
Similarly, esters are also reduced to aldehydes with 𝐃𝐈𝐁𝐀𝐋 − 𝐇.
(𝐢) 𝐃𝐈𝐁𝐀𝐋 − 𝐇
𝐂𝐇𝟑 (𝐂𝐇𝟐 )𝟗 − 𝐂 − 𝐎𝐂𝟐 𝐇𝟓 𝐂𝐇𝟑 (𝐂𝐇𝟐 )𝟗 − 𝐂 − 𝐇
(𝐢𝐢) 𝐇𝟐 𝐎
𝐎 𝐎
3) 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. This reaction is known as
Gatterman-Koch reaction.
𝐂𝐇𝐎
𝐂𝐎, 𝐇𝐂𝓵
𝐀𝐧𝐡𝐲𝐝𝐫𝐨𝐮𝐬 𝐀𝓵𝐂𝓵𝟑
Benzene Benzaldehyde
𝐂𝐇𝟑 𝐂𝐇𝟑
𝐂𝐇𝐎
𝐂𝐎, 𝐇𝐂𝓵
𝐀𝐧𝐡𝐲𝐝𝐫𝐨𝐮𝐬 𝐀𝓵𝐂𝓵𝟑
Toluene 𝟐 −Methylbenzaldehyde
4) By Oxidation of Aeromatic Hydrocarbon 
(i) Chromyl chloride oxidises methyl group to a chromium complex, which on
hydrolysis gives corresponding benzaldehyde. This reaction is called Etard
reaction.
𝐂𝐇𝟑 𝐂𝐒𝟐 𝐂𝐇(𝐎𝐂𝐫𝐎𝐇𝐂𝓵𝟐 )𝟐 𝐇𝟐 𝐎 𝐂𝐇𝐎
+ 𝐂𝐫𝐎𝟐 𝐂𝓵𝟐
𝐇+
Toluene Chromyl chloride Chromium complex Benzaldehyde
(ii) 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.
𝐂𝐇𝟑 𝐂𝐫𝐎𝟑 𝐂𝐇(𝐎𝐂𝐎𝐂𝐇𝟑 )𝟐 𝐇𝟐 𝐎 𝐂𝐇𝐎
+ (𝐂𝐇𝟑 𝐂𝐎)𝟐 𝐎
 𝟐𝟕𝟑 − 𝟐𝟖𝟑𝐊 𝐇+
Toluene Acetic anhydride Benzylidene diacetate Benzaldehyde
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5) By Hydrolysis of Banzal chloride 
Side chain chlorination of toluene gives benzal chloride, which on hydrolysis
gives benzaldehyde. This is a commercial method of manufacture of 6
benzaldehyde.
𝐂𝐇𝟑 𝐡𝛎 𝐂𝐇𝐂𝓵𝟐 𝐇𝟐 𝐎 𝐂𝐇𝐎
+ 𝐂𝓵𝟐
𝟑𝟕𝟑 𝐊
Toluene Chlorine Benzal chloride Benzaldehyde
C. Method of Synthesis For Ketones Only 
1) By addition of Grignard reagent on Cyanide 
An addition product is obtained on reaction with alkyl cyanide which on
hydrolysis gives ketone.
𝐑′ 𝐑′
𝟐𝐇𝟐 𝐎
𝐑 − 𝐂 ≡ 𝐍 + 𝐑′ − 𝐌𝐠𝐗 𝐑 − 𝐂 = 𝐍 𝐌𝐠𝐗 𝐑 − 𝐂 = 𝐎 + 𝐍𝐇𝟑
−𝐌𝐠(𝐗)𝐎𝐇
𝐂𝟔 𝐇𝟓 𝐂𝟔 𝐇𝟓
𝟐𝐇𝟐 𝐎
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂 ≡ 𝐍 + 𝐂𝟔 𝐇𝟓 𝐌𝐠𝐁𝐫 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂 = 𝐍 𝐌𝐠𝐁𝐫 𝐂𝐇𝟑 𝐂𝐇𝟐 𝐂 = 𝐎
−𝐌𝐠(𝐗)𝐎𝐇
−𝐍𝐇𝟑
Ethyl cyanide Phenyl magnesium bromide Propionophenone
2) By Cadmium Chloride 
Treatment of acyl chlorides with dialkylcadmium, prepared by the reaction of
cadmium chloride with Grignard reagent, gives ketones.
𝟐 𝐑 − 𝐌𝐠 − 𝐗 + 𝐂𝐝𝐂𝓵𝟐 𝐑 𝟐 𝐂𝐝 + 𝟐 𝐌𝐠(𝐗)𝐂𝓵
𝟐 𝐑′ − 𝐂 − 𝐂𝓵 + 𝐑 𝟐 𝐂𝐝 𝟐 𝐑′ − 𝐂 − 𝐑 + 𝐂𝐝𝐂𝓵𝟐

𝐎 𝐎
3) By 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.
𝐎

𝐀𝐧𝐡𝐲𝐝𝐫𝐨𝐮𝐬 𝐀𝓵𝐂𝓵𝟑 𝐂−𝐑

+ 𝐑 − 𝐂 − 𝐂𝓵

𝐎
Benzene Acid chloride Acyl benzene
When benzene or substituted benzene is treated with acetyl chloride in the
presence of anhydrous aluminium chloride, this reaction is known as Friedel-
Crafts acetylation reaction.
𝐎

𝐀𝐧𝐡𝐲𝐝𝐫𝐨𝐮𝐬 𝐀𝓵𝐂𝓵𝟑 𝐂 − 𝐂𝐇𝟑

+ 𝐂𝐇𝟑 − 𝐂 − 𝐂𝓵

𝐎
Benzene Acetyl chloride Acetophenone
4) By Benzoylation 
When benzene or substituted benzene is treated with benzoyl chloride, it forms
benzophenone. This reaction is known as benzoylation.
𝐎
𝐎
 𝐀𝐧𝐡𝐲𝐝𝐫𝐨𝐮𝐬 𝐀𝓵𝐂𝓵𝟑 𝐂 − 𝐂𝟔 𝐇𝟓
+ 𝐂𝟔 𝐇𝟓 − 𝐂 − 𝐂𝓵

Benzene Benzoyl chloride Benzophenone

Physical Properties of Carbonyl Compounds 
1) Physical state, Colour and Odour 
Methanal is a gas at room temperature. Ethanal is a volatile liquid. Other
aldehydes and ketones are liquid or solid at room temperature. The lower
7
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.
2) Solubility in Water 
The lower members of aldehydes and ketones such as methanal, ethanal and
propanone are miscible with water, because they form hydrogen bond with
water.
𝐎 𝛅−
𝛅+ 𝛅− 𝛅+ 𝛅+ 𝛅− 𝛅+
𝐂 = 𝐎……… 𝐇 𝐇………𝐎 = 𝐂

The solubility of aldehydes and ketones decreases rapidly on increasing the

length of alkyl chain. Carbonyl compounds having five carbons and above is less
soluble or insoluble in water. All aldehydes and ketones are fairly soluble in
organic solvents like benzene, ether, methanol, chloroform, etc.
3) Boiling Point 
Aldehydes and ketones have polar carbonyl group >𝐂 = 𝐎. Thus, strong dipole-
dipole intermolecular attraction exists between its molecules.
𝛅+ 𝛅− 𝛅+ 𝛅− 𝛅+ 𝛅− 𝛅+ 𝛅−
……… 𝐂 = 𝐎……… 𝐂 = 𝐎……… 𝐂 = 𝐎………𝐂 = 𝐎………

The boiling points of aldehydes and ketones are higher than hydrocarbons and
ethers of comparable molecular masses due to intermolecular interaction. But
this intermolecular interaction is lower compare to strong hydrogen bond of
alcohols. So, that’s why their boiling points are lower than those of alcohols of
similar molecular masses. In isomeric aldehydes and ketones, the boiling point of
ketones is higher than aldehyde. Generally, as molecular masses of aldehydes and
ketones increases, boiling point also increases.
Structure and Nature of Carbonyl Group 
The carbonyl carbon atom is 𝐬𝐩𝟐 hybridised and forms three sigma (𝛔) bonds. The
fourth valence electron of carbon remains in its 𝐩 − orbital and forms a 𝛑 −bond with
oxygen by overlap with 𝐩 −orbital of oxygen. In addition, the oxygen atom also has
two non bonding electron pairs. Thus, the carbonyl carbon and the three atoms
attached to it lie in the same plane and the 𝛑 −electron cloud is above and below this
plane. The bond angles are approximately 𝟏𝟐𝟎° as expected of a trigonal planar
structure.

The electronegativity of oxygen is much higher than that of the carbon, so there
𝛑 −electron density is shifted towards the oxygen. Therefore, carbon-oxygen double
bond is polarised and there is partial positive charge on carbon atom and partial
negative charge on oxygen atom.
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Therefore, the carbonyl carbon is an electrophilic i.e, Lewis acid, and carbonyl oxygen,
a nucleophilic i.e., Lewis base centre. Carbonyl compounds have high dipole moments
than ethers. The high polarity of the carbonyl group is explained on the basis of
resonance involving a neutral and a dipolar structures as shown.
𝛅+ 𝛅−
>𝐂 = 𝐎 >𝐂 − 𝐎
Chemical Properties of Carbonyl Compound 
The chemical reactions of carbonyl compounds can be classified in following groups:
 Nucleophilic Addition Reactions
 Nucleophilic Addition Elimination Reactions
 Oxidation, Reduction and Halogenation
 Reactions due to 𝛂 −hydrogen
 Others reactions
Nucleophilic Addition Reactions
We known that carbonyl group has polar nature in carbonyl compounds. Here, the
electronegativity of oxygen is more than carbon, so oxygen atom is partially negative
and carbon is partially positive. Therefore, after the bond cleavage 𝛑 −electrons are
shifted towards the oxygen. So, due to complete octate of oxygen, it gets stability.
While the carbon does not complete its octate, therefore it is unstable. So, that’s why
nucleophile attacks first at carbon. Hence, reaction starts with the attack of
nucleophile so the reactions of carbonyl compounds are nucleophilic addition
reaction.
A nucleophile 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. The hybridisation of carbon changes from 𝐬𝐩𝟐 to 𝐬𝐩𝟑 in this process,
and a tetrahedral alkoxide intermediate is produced. This intermediate captures a
proton or cation from the reaction medium to give the electrically neutral product.
This all process is shown in the following fig.:

Therefore, nucleophilic addition reaction is completed in following two steps:

In first step, the intermediate anion is formed with the attack of nucleophile on
carbonyl group.
>𝐂 = 𝐎 + 𝐍̅̈ u >𝐂— 𝐎̅
Carbonyl group nucleophile Nu
In second step, the product is formed with the attack of remaining positive part of
reagent on intermediate anion.
>𝐂— 𝐎̅ + 𝐄+ >𝐂— 𝐎𝐄
Nu Nu
Intermediate anion Electrophile Product
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Aldehydes, Ketones and Carboxylic Acids
The nucleophilic addition reactions depands on the following two fectors:
9
(i) Inductive Effect  The attack on carbonyl group is easy when positive charge on
carbonyl carbon is more. So, +𝐈 effect group like −𝐑 etc., decreases positive
density on carbon. Therefore, this type of groups decreases the reactivity of
carbonyl compound. Contrariwise, −𝐈 effect group like −𝐗, −𝐍𝐎𝟐 , −𝐂𝐍 etc.,
increases positive density on carbon. Therefore, this type of groups increases
the reactivity of carbonyl compound.
The number of alkyl groups on ketones is more as compared to aldehydes.
Hence, aldehydes are more reactive towards nucleophilic addition reaction as
compare to ketones. Therefore, decreasing order of reactivity for different
aldehydes and ketones are:
Formaldehyde > Alkyl aldehyde > Ketone
(ii) Steric Effect  It is clear from the above detail that after the attack of
nucleophile on carbonyl group, bond angle of 𝐂 − 𝐎 decreases, that is value of
bond angle decreases from 𝟏𝟐𝟎° to 𝟏𝟎𝟗°𝟐𝟖′. So, the presence of bulk sized alkyl
group attached with carbonyl group increases steric hinderence. So, reactivity of
related carbonyl group decreases.
Size of alkyl group is very large compared to hydrogen, that’s the reason,
reactivity of alkyl aldehyde is more than formaldehyde and reactivity of alkyl
aldehyde is more than ketone. On increasing molecular mass, the size of alkyl
group increases. Due to this reactivity of higher aldehyde is less than lower
aldehyde. Similarly, due to biger size of alkyl group, reactivity of higher ketone
is also less than lower ketone. The size of alkyl group of branched aldehydes is
bulky compared to unbranched aldehydes. Therefore, due to high steric
hinderence the reactivity of branched aldehyde is lower than unbranched
aldehydes. Similarly, the reactivity of branched ketone is lower than
unbranched ketones.
The phenyl group is present in aromatic carbonyl compounds in place of alkyl
group. Because of which it creates hinderence to the attack of nucleophile.
Secondly, the carbon atom of the aromatic carbonyl group is less electrophilic
than carbon atom of the aliphatic carbonyl group. The polarity of the carbonyl
group is reduced in aromatic carbonyl compound due to resonance and hence it
is less reactive than aliphatic carbonyl compounds.
Some of the nucleophile addition reactions of carbonyl compounds are:
1) Addition of hydrogen cyanide 
Aldehydes and ketones react with hydrogen cyanide to yield cyanohydrins. This
reaction occurs very slowly with pure 𝐇𝐂𝐍. Therefore, it is catalysed by a base and
the generated cyanide ion being a stronger nucleophile readily adds to carbonyl
compounds to yield corresponding cyanohydrin.
>𝐂 = 𝐎 + 𝐇𝐂𝐍 >𝐂— 𝐎𝐇
𝐂𝐍
Cyanohydrin
Mechanism :
𝐇𝐂𝐍 + 𝐎𝐇 − 𝐂𝐍 − + 𝐇𝟐 𝐎
Base Nucleophile
>𝐂 = 𝐎 + 𝐂𝐍 − >𝐂— 𝐎̅
 𝐂𝐍
>𝐂— 𝐎̅ + 𝐇 +
>𝐂— 𝐎𝐇
𝐂𝐍 𝐂𝐍
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Cyanohydrins are useful synthetic intermediates. These can be easily hydrolysed
to give 𝜶 −hydroxy acids.
𝐇 𝐇 𝐇𝐎𝐇 𝐇

𝐇
𝐂 = 𝐎 + 𝐇𝐂𝐍

𝐇 𝐂𝐍
C— 𝐎𝐇 C— 𝐎𝐇

𝐇 𝐂𝐎𝐎𝐇
1
Formaldehyde Formaldehyde cyanohydrin Glycolic acid
𝐂𝐇𝟑
𝐂 = 𝐎 + 𝐇𝐂𝐍
𝐂𝐇𝟑
C— 𝐎𝐇
𝐇𝐎𝐇 𝐂𝐇𝟑
C— 𝐎𝐇 0
𝐇 𝐇 CN 𝐇 𝐂𝐎𝐎𝐇
Acetaldehyde Acetaldehyde cyanohydrin Lactic acid
2) Addition of sodium bisulphite 
Sodium hydrogensulphite adds to aldehydes and ketones to form the addition
products.
𝐂𝐇𝟑 𝐂𝐇𝟑
𝐂 = 𝐎 + 𝐍𝐚𝐇𝐒𝐎𝟑 𝐂— 𝐎𝐇

𝐇 𝐇 𝐎𝐒𝐎𝟐 𝐍𝐚
Acetaldehyde Acetaldehyde sodium hydrogensulphite adductant
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 carbonyl
compounds.
3) By addition of Grignard reagent 
The first step of the reaction is the nucleophilic addition of Grignard reagent to
the carbonyl group to form an adduct. Hydrolysis of the adduct yields an alcohol
by dil 𝐇𝟐 𝐒𝐎𝟒 or dil 𝐇𝐂𝓵. All three types of alcohols are produced by the reaction of
Grignard reagents with aldehydes and ketones.
Formaldehyde gives primary alcohol.
𝐑′ 𝐑′
𝐇 𝐇 𝐇𝟐 𝐎 𝐇
𝐂 = 𝐎 + 𝐑′ − 𝐌𝐠𝐗 𝐂 − 𝐎𝐌𝐠𝐗 𝐂 − 𝐎𝐇
𝐇 𝐇 −𝐌𝐠(𝐗)𝐎𝐇 𝐇
Methanal Alkyl magnesium halide Primary alcohol
Alkyl aldehyde gives secondary alcohol.
𝐑′ 𝐑′
𝐑 𝐑 𝐇𝟐 𝐎 𝐑
′
𝐂 = 𝐎 + 𝐑 − 𝐌𝐠𝐗 𝐂 − 𝐎𝐌𝐠𝐗 𝐂 − 𝐎𝐇
𝐇 𝐇 −𝐌𝐠(𝐗)𝐎𝐇 𝐇
Alkanal Alkyl magnesium halide Secondary alcohol
Ketone gives tertiary alcohol.
𝐑′ 𝐑′
𝐑 𝐑 𝐇𝟐 𝐎 𝐑
′
𝐂 = 𝐎 + 𝐑 − 𝐌𝐠𝐗 𝐂 − 𝐎𝐌𝐠𝐗 𝐂 − 𝐎𝐇
𝐑 𝐑 −𝐌𝐠(𝐗)𝐎𝐇 𝐑
4) Addition of alcohols and glycols 
Aldehydes react with one mole 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 alkane known as acetal as shown in the reaction.
𝐎𝐂𝐇𝟑 𝐎𝐂𝐇𝟑
𝐂𝐇𝟑 𝐇𝐂𝓵 𝐠𝐚𝐬 𝐂𝐇𝟑 𝐂𝐇𝟑 OH, 𝐇𝐂𝓵 𝐠𝐚𝐬 𝐂𝐇𝟑
 𝐂 = 𝐎 + 𝐂𝐇𝟑 − 𝐎𝐇 𝐂 − 𝐎𝐇 𝐂 − 𝐎𝐂𝐇𝟑
𝐇 𝐇 −𝐇𝟐 𝐎 𝐇
Ethanal Methanol Hemiacetal Acetal
𝟏 −Methoxy ethanol 𝟏, 𝟏 −Dimethoxy ethane or Methylal
Ketones react with ethylene glycol under similar conditions to form cyclic ketal,
which is known as ethylene glycol ketals.
𝐂𝐇𝟑 𝐇𝐎 − 𝐂𝐇𝟐 𝐇𝐂𝓵 𝐠𝐚𝐬 𝐂𝐇𝟑 𝐎 − 𝐂𝐇𝟐

𝐂𝐇𝟑
𝐂=𝐎 +
𝐇𝐎 − 𝐂𝐇𝟐 − 𝐇𝟐 𝐎 𝐂𝐇𝟑
𝐂
𝐎 − 𝐂𝐇𝟐 1
Acetone Ethylene glycol Cyclic ketal
Dry hydrogen chloride protonates the oxygen of the carbonyl compounds and
therefore, increases the electrophilicity of the carbonyl carbon facilitating the 1
nucleophilic attack of ethylene glycol. Acetals and ketals are hydrolysed with
aqueous mineral acids to yield corresponding aldehydes and ketones
respectively.
Nucleophilic Addition Elimination Reactions
Carbonyl compounds in the presence of acid react with ammonia or ammonia
derivatives and forms addition products from which one molecule of water is removed
and final product is obtained. Overall reaction is as follows:
𝐇— 𝐍 − 𝐇

𝐂 = 𝐎 + 𝐍𝐇𝟐 − 𝐇 𝐂 − 𝐎𝐇 𝐂=𝐍−𝐇
−𝐇𝟐 𝐎
Ammonia Unstable step Product
𝐙— 𝐍 − 𝐇

𝐂 = 𝐎 + 𝐍𝐇𝟐 − 𝐙 𝐂 − 𝐎𝐇 𝐂=𝐍−𝐙
−𝐇𝟐 𝐎
Ammonia derivative Unstable step Product
1) Addition of Ammonia and Amines 
Carbonyl compounds react with ammonia and form imine.
>𝐂 = 𝐎 + 𝐇𝟐 𝐍 − 𝐇 >𝐂 = 𝐍 − 𝐇 + 𝐇𝟐 𝐎
Ammonia Imine
Carbonyl compounds react with alkyl ammine and form Substituted imine. This is
also known as Schiff’s base.
>𝐂 = 𝐎 + 𝐇𝟐 𝐍 − 𝐑 >𝐂 = 𝐍 − 𝐑 + 𝐇𝟐𝐎
Alkyl amine Substituted imine (Schiff’s base)
2) Addition of Ammonia derivatives 
Carbonyl compounds react with ammonia derivatives and forms following
products:
— 𝐙 Group Ammonia derivative Product
𝟏. — 𝐎𝐇 𝐍𝐇𝟐 — 𝐎𝐇 >𝐂 = 𝐍 — 𝐎𝐇
Hydroxyl amine Oxime
𝟐. — 𝐍𝐇𝟐 𝐍𝐇𝟐 — 𝐍𝐇𝟐 >𝐂 = 𝐍— 𝐍𝐇𝟐
Hydrazine Hydrazone
𝟑. — 𝐍𝐇— 𝐂𝟔 𝐇𝟓 𝐍𝐇𝟐 — 𝐍𝐇— 𝐂𝟔 𝐇𝟓 >𝐂 = 𝐍 — 𝐍𝐇— 𝐂𝟔 𝐇𝟓
Phenyl hydrazine Phenyl hydrazone
𝟒. 𝐍𝐎𝟐 𝐍𝐎𝟐 𝐍𝐎𝟐
— 𝐍𝐇— — 𝐍𝐎𝟐 𝐍𝐇𝟐 — 𝐍𝐇— — 𝐍𝐎𝟐 >𝐂 = 𝐍— 𝐍𝐇— — 𝐍𝐎𝟐

𝟐, 𝟒 −Dinitrophenyl 𝟐, 𝟒 −Dinitrophenyl
hydrazine (𝟐, 𝟒 − 𝐃𝐍𝐏) hydrazone
 𝟓. — 𝐍𝐇— 𝐂— 𝐍𝐇𝟐 𝐍𝐇𝟐 — 𝐍𝐇— 𝐂— 𝐍𝐇𝟐 >𝐂 = 𝐍— 𝐍𝐇— 𝐂— 𝐍𝐇𝟐

𝐎 𝐎 𝐎
Semicarbazide Semicarbazone
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𝐂𝐇𝟑 −𝐇𝟐 𝐎 𝐂𝐇𝟑

𝐂𝐇𝟑
C=O + 𝐇𝟐 𝐍—OH
𝐂𝐇𝟑
C=N—OH

Acetone Hydroxyl amine Acetone oxime or dimethyl ketoxime

1
𝐂𝐇𝟑 −𝐇𝟐 𝐎 𝐂𝐇𝟑

𝐇
C=O + 𝐇𝟐 𝐍—𝐍𝐇𝟐
𝐇
C=N—𝐍𝐇𝟐 2
Acetaldehyde Hydrazine Acetaldehyde hydrazone
𝐂𝟔 𝐇𝟓 −𝐇𝟐 𝐎 𝐂𝟔 𝐇𝟓
C=O + 𝐇𝟐 𝐍—𝐍𝐇— 𝐂𝟔 𝐇𝟓 C= 𝐍— 𝐍𝐇— 𝐂𝟔 𝐇𝟓
𝐇 𝐇
Benzaldehyde Phenyl hydrazine Benzaldehyde Phenyl hydrazone
𝐂𝐇𝟑 𝐍𝐎𝟐 −𝐇𝟐 𝐎 𝐂𝐇𝟑 𝐍𝐎𝟐
C=O + 𝐇𝟐 𝐍—𝐍𝐇— — 𝐍𝐎𝟐 C= 𝐍— 𝐍𝐇— — 𝐍𝐎𝟐
𝐂𝐇𝟑 𝐂𝐇𝟑
Acetone 𝟐, 𝟒 −Dinitrophenyl hydrazine Acetone 𝟐, 𝟒 −Dinitrophenyl hydrazone
(Yellow precipitate)
𝐂𝐇𝟑 −𝐇𝟐 𝐎 𝐂𝐇𝟑
C=O + 𝐇𝟐 𝐍—𝐍𝐇— 𝐂𝐎— 𝐍𝐇𝟐 C=N—𝐍𝐇— 𝐂𝐎— 𝐍𝐇𝟐
𝐇 𝐇
Acetaldehyde Semicarbazide Acetaldehyde Semicarbazone
The product formed by reaction of aldehyde and ketones with ammonia
derivatives are crystalline solids. These are used to identify aldehydes and ketones.
Semicarbazide has two — 𝐍𝐇𝟐 groups but one of these which is directly attached to
>𝐂 = 𝐎 is involved in resonance asshown below:
𝐇𝟐 𝐍 = 𝐂— 𝐍𝐇— 𝐍𝐇𝟐 𝐍𝐇𝟐 — 𝐂— 𝐍𝐇— 𝐍𝐇𝟐 𝐍𝐇𝟐 — 𝐂— 𝐍𝐇— 𝐍𝐇𝟐

𝐎 𝐎 𝐎

As a result of resonance, electron density on — 𝐍𝐇𝟐 group decreases and hence it

does not act as a nucleophile. In contrast, the lone pair of electrons on the
— 𝐍𝐇𝟐 group (i.e, attached to— 𝐍𝐇— ) is not involved in resonance and therefore,
available for nucleophilic attack on the >𝐂 = 𝐎 group of the carconyl compounds.
Oxidation and Reduction
Oxidation Reactions 
1) By Strong Oxidising agent 
Aldehydes are easily oxidised to carboxylic acids on treatment with strong
oxidising agents like nitric acid, potassium permanganate, potassium
dichromate, etc.
𝐂𝐇𝟑 — 𝐂— 𝐇 𝐀𝐜𝐢𝐝𝐢𝐜 𝐊𝐌𝐧𝐎𝟒 𝐂𝐇𝟑 — 𝐂— 𝐎𝐇
+ [𝐎]
𝐎 𝐎
𝐀𝐜𝐢𝐝𝐢𝐜 𝐊𝐌𝐧𝐎𝟒
𝐂𝟔 𝐇𝟓 — 𝐂𝐇𝐎 + [𝐎] 𝐂𝟔 𝐇𝟓 — 𝐂𝐎𝐎𝐇
Benzaldehyde Benzoic acid
 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.
𝐀𝐜𝐢𝐝𝐢𝐜 𝐊𝐌𝐧𝐎𝟒
𝐂𝐇𝟑 − 𝐂 − 𝐂𝐇𝟑 𝐂𝐇𝟑 − 𝐂𝐎𝐎𝐇 + 𝐂𝐎𝟐 + 𝐇𝟐 𝐎
[𝐎]

Since 1996
𝐎
9414248318, 9468590309, 0141-2719117 1
𝟏 𝟐 𝟑 𝟒 𝟓 𝟔
𝐂𝐇𝟑 — 𝐂𝐇𝟐 — 𝐂— 𝐂𝐇𝟐 — 𝐂𝐇𝟐 — 𝐂𝐇𝟑
𝐀𝐜𝐢𝐝𝐢𝐜 𝐊𝐌𝐧𝐎𝟒
𝐂𝐇𝟑 𝐂𝐎𝐎𝐇 + 𝐂𝐇𝟑 𝐂𝐇𝟐 𝐂𝐇𝟐 𝐂𝐎𝐎𝐇
3
[𝐎] (By cleavage of 𝐂𝟐 − 𝐂𝟑 )
𝐎 + 𝟐 𝐂𝐇𝟑 𝐂𝐇𝟐 𝐂𝐎𝐎𝐇
(By cleavage of 𝐂𝟑 − 𝐂𝟒 )
𝟏 𝟐 𝟑 𝟒 𝟓 𝟔 𝟕 𝐀𝐜𝐢𝐝𝐢𝐜 𝐊𝐌𝐧𝐎𝟒
𝐂𝐇𝟑 — 𝐂𝐇𝟐 — 𝐂— 𝐂𝐇𝟐 — 𝐂𝐇𝟐 — 𝐂𝐇𝟐 — 𝐂𝐇𝟑 𝐂𝐇𝟑 𝐂𝐎𝐎𝐇 + 𝐂𝐇𝟑 𝐂𝐇𝟐 𝐂𝐇𝟐 𝐂𝐇𝟐 𝐂𝐎𝐎𝐇
[𝐎] (By cleavage of 𝐂𝟐 − 𝐂𝟑 )
𝐎 + 𝐂𝐇𝟑 𝐂𝐇𝟐 𝐂𝐎𝐎𝐇 + 𝐂𝐇𝟑 𝐂𝐇𝟐 𝐂𝐇𝟐 𝐂𝐎𝐎𝐇
(By cleavage of 𝐂𝟑 − 𝐂𝟒 )
2) By Weak Oxidising agent 
Aldehydes are easily oxidised with weak oxidising agents to carboxylic acids of
same number of carbon atom. Thus, aldehyde is used as strong reducing agent.
Weak oxidising agents only oxidise aldehydes but they do not oxidise ketones.
So, following weak oxidising agents are used for the chemical distinguishing
between aldehydes and ketones.
a) By Tollen’s Reagent 
Ammonical silver nitrate solution is called Tollen’s Reagent. On warming any
aromatic or aliphatic aldehyde with Tollen’s Reagent, it is reduced into silver
metal. This silver metal is deposited at the inner surface of walls of test
tube, which is known as silver mirror. Because, ketone does not do this,
therefore this test can be used for the chemical distinguish between the
aldehyde and ketones. This test is also known as silver mirror test. The
following reaction takes place in this test:
𝐀𝐠𝐍𝐎𝟑 + 𝐍𝐇𝟒 𝐎𝐇 𝐀𝐠𝐎𝐇 + 𝐍𝐇𝟒 𝐍𝐎𝟑
𝐀𝐠𝐎𝐇 + 𝟐𝐍𝐇𝟒 𝐎𝐇 [𝐀𝐠(𝐍𝐇𝟑 )𝟐 ]𝐎𝐇 + 𝟐𝐇𝟐 𝐎
Tollen's reagent
𝐑𝐂𝐇𝐎 + [𝐀𝐠(𝐍𝐇𝟑 )𝟐 ]+ + 𝟑 𝐎𝐇 − 𝐑𝐂𝐎𝐎− + 𝐀𝐠 ↓ + 𝟐 𝐍𝐇𝟑 + 𝟐 𝐇𝟐 𝐎
Tollen’s Reagent Silver mirror
b) By Fehling’s Reagent 
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. It gives blue colour
solution of 𝐂𝐮(𝐎𝐇)𝟐. On heating an aldehyde with Fehling’s reagent, a reddish
brown solution is obtained because 𝐂𝐮(𝐎𝐇)𝟐 is converted to red colour 𝐂𝐮𝟐 𝐎.
Aldehydes are oxidised to corresponding carboxylate anion. Ketones and
aromatic aldehydes do not respond to this test.
𝐑𝐂𝐇𝐎 + 𝟐 𝐂𝐮𝟐+ + 𝟓 𝐎𝐇 − 𝐑𝐂𝐎𝐎− + 𝐂𝐮𝟐 𝐎 + 𝟑 𝐇𝟐 𝐎
Fehling solution Red colour solution
Reduction Reactions 
1) By Strong Redusing agent 
 The carbonyl group of aldehyde and ketone is reduced to — 𝐂𝐇𝟐 — group on
reduction with the following strong redusing agents:
a) Clemmensen reduction 
The carbonyl group of aldehydes and ketones is reduced to alkane on
treatment with zincamalgam and concentrated hydrochloric acid.
𝐂𝐇𝟑 𝐙𝐧 − 𝐇𝐠 𝐂𝐇𝟑
𝐂=𝐎 + 𝟒𝐇 𝐂𝐇𝟐
𝐇 Conc. 𝐇𝐂𝓵 𝐇

Since 1996
Ethanal Ethane
9414248318, 9468590309, 0141-2719117
1
b) Wolff-Kishner reduction 
The carbonyl group of aldehydes and ketones is reduced to alkane on
4
treatment with hydrazine followed by heating with sodium or potassium
hydroxide in high boiling solvent such as ethylene glycol at 𝟒𝟕𝟑𝐊.
𝐂𝐇𝟑 −𝐇𝟐 𝐎 𝐂𝐇𝟑 𝐇𝐎𝐂𝐇𝟐 − 𝐂𝐇𝟐 𝐎𝐇 𝐂𝐇𝟑
𝐂 = 𝐎 + 𝐇𝟐 𝐍 − 𝐍𝐇𝟐 𝐂 = 𝐍 − 𝐍𝐇𝟐 𝐂𝐇𝟐 + 𝐍𝟐
𝐂𝐇𝟑 𝐂𝐇𝟑 𝐊𝐎𝐇, 𝟒𝟕𝟑𝐊 𝐂𝐇𝟑
Propanone Hydrazine Hydrazone Propane
2) By Weak Redusing agent 
Aldehydes and ketones are reduced to the corresponding alcohols by sodium
borohydride (𝐍𝐚𝐁𝐇𝟒 ) or lithium aluminium hydride (𝐋𝐢𝐀𝓵𝐇𝟒 ). Formaldehyde yield
methanol, Alkyl aldehydes yield primary alcohols whereas ketones give
secondary alcohols. From this method tertiary alcohols can not be obtained.
𝐋𝐢𝐀𝓵𝐇𝟒
𝐇 − 𝐂𝐇𝐎 + 𝟐𝐇 𝐂𝐇𝟑 − 𝐎𝐇
Formaldehyde Methanol
𝐋𝐢𝐀𝓵𝐇𝟒
𝐑 − 𝐂𝐇𝐎 + 𝟐𝐇 𝐑 − 𝐂𝐇𝟐 − 𝐎𝐇
𝐋𝐢𝐀𝓵𝐇𝟒
𝐑 − 𝐂 − 𝐑 + 𝟐𝐇 𝐑 − 𝐂𝐇 − 𝐑

𝐎 𝐎𝐇
Ketones Secondary alcohols
Aldehydes and ketones are reduced to the corresponding alcohols by addition of
hydrogen in the presence of catalysts. The usual catalyst is a finely divided metal
such as platinum, palladium or nickel.
𝐏𝐭
𝐑 − 𝐂𝐇𝐎 + 𝐇𝟐 𝐑 − 𝐂𝐇𝟐 − 𝐎𝐇
𝐏𝐭
𝐑 − 𝐂 − 𝐑 + 𝐇𝟐 𝐑 − 𝐂𝐇 − 𝐑

𝐎 𝐎𝐇
Halogenation Reaction 
Oxidation of methyl ketones by sodium hypohalite or haloform reaction 
Ketones having at least one methyl group linked to the carbonyl carbon atom 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.
𝐑— 𝐂— 𝐂𝐇𝟑 + 𝐍𝐚𝐎𝐗 𝐂𝐇𝐗 𝟑 + 𝐑 − 𝐂 − 𝐎𝐍𝐚

𝐎 𝐎
Sodium hypohalite Haloform
𝐂𝐇𝟑 𝐂𝐇𝟑 𝐂𝐇𝟑 𝐂𝐇𝟑
𝐂=𝐂 𝐂𝐇𝟑 + 𝐍𝐚𝐎𝐂𝓵 𝐂=𝐂 𝐎𝐍𝐚 + 𝐂𝐇𝐂𝓵𝟑
𝐇 𝐂 𝐇 𝐂
𝐎 𝐎
Sodium hypochlorite Chloroform
Iodoform reaction with sodium hypoiodite is also used for detection of 𝐂𝐇𝟑 𝐂𝐎 − group
or 𝐂𝐇𝟑 𝐂𝐇(𝐎𝐇) − group.
𝟐𝐍𝐚𝐎𝐇 + 𝐈𝟐 𝐍𝐚𝐎𝐈 + 𝐍𝐚𝐈 + 𝐇𝟐 𝐎
𝐂𝐇𝟑 — 𝐂— 𝐂𝐇𝟑 + 𝟑𝐍𝐚𝐎𝐈 𝐂𝐈𝟑 — 𝐂— 𝐂𝐇𝟑 + 𝟑𝐍𝐚𝐎𝐇

𝐎 𝐎
Acetone Tri iodoacetone
𝐍𝐚𝐎 𝐇 + 𝐂𝐈𝟑 — 𝐂— 𝐂𝐇𝟑 𝐂𝐇𝐈𝟑 + 𝐇𝐂𝐎𝐎𝐍𝐚

𝐎
Reactions due to α −hydrogen
1
Those carbonyl compounds which have ∝ −hydrogen are acidic in nature. The acidity
of ∝ − hydrogen atoms of carbonyl compounds is due to the strong electron
withdrawing effect (−𝐈 effect) of the carbonyl group and resonance stabilisation of the
5
conjugate base.
𝐇 − 𝐎− + −𝐂 ∝ − 𝐂 − −𝐂 − 𝐂 − −𝐂 = 𝐂 − + 𝐇 − 𝐎𝐇

𝐇 𝐎 𝐎 𝐎

The aldehydes and ketones undergo a number of reactions due to ∝ −hydrogen. Some
of are:
1) Aldol condensation 
Aldehydes and ketones having at least one ∝ −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 ∝
, 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.
𝐇
di𝓁 𝐍𝐚𝐎𝐇 −𝐇𝟐 𝐎
𝐂𝐇𝟑 − 𝐂 − 𝐇 + 𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝐎 𝐂𝐇𝟑 − 𝐂 − 𝐂𝐇𝟐 − 𝐂𝐇𝐎 𝐂𝐇𝟑 − 𝐂𝐇 = 𝐂𝐇 − 𝐂𝐇𝐎
∆
𝐎 𝐎𝐇 Butan−𝟐 −elal
Ethanal Ethanal 𝟑 −Hydroxybutanal (Crotonaldehyde)
(Aldol) (Aldol condensation product)
𝐂𝐇𝟑 𝐂𝐇𝟑
di𝓁 𝐍𝐚𝐎𝐇 −𝐇𝟐 𝐎
𝐂𝐇𝟑 − 𝐂 + 𝐇 − 𝐂𝐇𝟐 − 𝐂 − 𝐂𝐇𝟑 𝐂𝐇𝟑 − 𝐂 − 𝐂𝐇𝟐 − 𝐂 − 𝐂𝐇𝟑
∆
𝐎 𝐎 𝐎𝐇 𝐎 𝐂𝐇𝟑

Propanone 𝟒 −Hydroxy−𝟒 −Methylpentan−𝟐 −one 𝐂𝐇𝟑 − 𝐂 = 𝐂𝐇 − 𝐂 − 𝐂𝐇𝟑

(Ketol) 𝐎
𝟒 −Methylpent−𝟑 −en−𝟐 −one (Mestyl oxide)
(Aldol condensation product)
2) Cross aldol condensation 
When aldol condensation is carried out between two different aldehydes or
different ketones or one aldehyde and one ketone, it is called cross aldol
condensation. If both of them contain ∝ −hydrogen atoms, it gives a mixture of
four products. This is illustrated below by aldol reaction of a mixture of ethanal
and propanal.
 𝐂𝐇𝟑 𝐂𝐇𝐎 (𝐢) di𝓁 𝐍𝐚𝐎𝐇 𝐂𝐇 − 𝐂𝐇𝟑 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 𝐂𝐇 − 𝐂𝐇𝟑 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑
+ + + +
𝐂𝐇𝟑 𝐂𝐇𝟐 𝐂𝐇𝐎 (𝐢𝐢) ∆ 𝐂𝐇 − 𝐂𝐇𝐎 𝐂 − 𝐂𝐇𝐎 𝐂 − 𝐂𝐇𝐎 𝐂𝐇 − 𝐂𝐇𝐎

Butan−𝟐 −elal 𝐂𝐇𝟑 𝐂𝐇𝟑 Pent−𝟐 −enal

𝟐 −Methylpent−𝟐 −enal 𝟐 −Methylbut−𝟐 −enal
(From 𝟐 molecules (From 𝟐 molecules (From 𝟏 molecule of ethanal
of ethanal) of propanal) and 𝟏 molecule of propanal)
Simple aldol condensation product Cross aldol condensation product
Since 1996 9414248318, 9468590309, 0141-2719117

If any one aldehyde or ketone not having ∝ −hydrogen, is present in cross aldol
condensation then only one product is formed. For example,
(𝐢) di𝓁 𝐍𝐚𝐎𝐇
−𝐂𝐇𝐎 + −𝐂 − 𝐂𝐇𝟑

𝐎
(𝐢𝐢) ∆
−𝐂𝐇 = 𝐂𝐇 − 𝐂 −

𝐎
1
Benzalaldehye Acetophenone 𝟏, 𝟑 −Diphenylprop−𝟐 −en−𝟏 −one
(Benzalacetophenone)
Others reaction
6
1) Cannizzaro reaction 
Aldehydes which do not have an ∝ −hydrogen atom, undergo disproportionation
reaction on heating with concentrated alkali. In this reaction, one molecule of the
aldehyde is reduced to alcohol while another is oxidised to carboxylic acid salt.
That is, a −𝐂𝐇𝐎 group is converted into −𝐂𝐇𝟐𝐎𝐇 then other −𝐂𝐇𝐎 group is
converted into −𝐂𝐎𝐎− . Formaldehyde (𝐇𝐂𝐇𝐎) , benzaldehyde (𝐂𝟔 𝐇𝟓 𝐂𝐇𝐎) ,
chloral(𝐂𝐂𝓵𝟑𝐂𝐇𝐎), pivaldehyde [(𝐂𝐇𝟑 )𝟑 𝐂 − 𝐂𝐇𝐎] do not have an ∝ −hydrogen atom,
so they exhibit Cannizzaro reaction.
𝐍𝐚𝐎𝐇
𝟐𝐇𝐂𝐇𝐎 𝐂𝐇𝟑 𝐎𝐇 + 𝐇𝐂𝐎𝐎𝐍𝐚
Methanal Methanal Sodium methanoate
𝐊𝐎𝐇
𝟐𝐂𝟔 𝐇𝟓 𝐂𝐇𝐎 𝐂𝟔 𝐇𝟓 −𝐂𝐇𝟐 𝐎𝐇 + 𝐂𝟔 𝐇𝟓 𝐂𝐎𝐎𝐊
Benzaldehyde benzyl alcohol Potassium benzoate
2) Electrophilic substitution reaction 
⊝ ⊝ ⊝
𝐇 𝐎 𝐇 𝐎 𝐇 𝐎 𝐇 𝐎 𝐇 𝐎
𝐂 𝐂 𝐂 𝐂 𝐂

⊕ ⊖

It is clear from the resonance structures that aromatic aldehydes and ketones
undergo electrophilic substitution at the ring in which the carbonyl group acts as
a deactivating and meta-directing group. For example,
𝐍𝐎𝟐
𝐇𝟐 𝐒𝐎𝟒
−𝐂𝐇𝐎 + 𝐇𝐍𝐎𝟑 −𝐂𝐇𝐎 + 𝐇𝟐 𝐎
𝟐𝟕𝟑 − 𝟐𝟖𝟑𝐊
Benzalaldehye 𝐦 −Nitrobenzaldehyde
Uses of Carbonyl Compounds 
1) Formaldehyde is well known as formalin (𝟒𝟎% aqueous solution of
formaldehyde) solution used to preserve biological specimens and to prepare
bakelite, urea-formaldehyde glues and other polymeric products.
2) Acetaldehyde is used primarily as a starting material in the manufacture of
acetic acid, ethyl acetate, vinyl acetate, polymers and drugs.
3) Acetone and ethyl methyl ketone are common industrial solvents.
4) Benzaldehyde is used in perfumery and in dye industries.
5) Many aldehydes and ketones, e.g., butyraldehyde, vanillin, acetophenone,
camphor, etc. are well known for their odours and flavours.
𝐂𝐇𝐎

𝐎𝐂𝐇𝟑
𝐎𝐇
Vanillin
9414248318, 9468590309

Carboxylic Acids
Carbon compounds containing a carboxyl functional group, −𝐂𝐎𝐎𝐇 are called
1
carboxylic acids. The carboxyl group, consists of a carbonyl group(>𝐂 = 𝐎) attached to
a hydroxyl group(−𝐎𝐇), hence its name carboxyl. Large numbers of carboxylic acids are
7
found in nature. Some higher members of aliphatic carboxylic acids (𝐂𝟏𝟐 − (𝐂𝟏𝟖 ) known
as fatty acids, occur in natural fats as esters of glycerol.
Nomenclature of Carboxylic Acids 
Carboxylic acids may be aliphatic (𝐑𝐂𝐎𝐎𝐇) or aromatic (𝐀𝐫𝐂𝐎𝐎𝐇) depending on the
group, alkyl or aryl, attached to carboxyl carbon. The general formula of aliphatic
carboxylic acids are 𝐂𝐧 𝐇𝟐𝐧+𝟏 𝐂𝐎𝐎𝐇 or 𝐂𝐧 𝐇𝟐𝐧 𝐎𝟐.
The common names end with the suffix −ic acid and have been derived from Latin or
Greek names of their natural sources. For example, formic acid (𝐇𝐂𝐎𝐎𝐇) was first
obtained from red ants (Latin: formica means ant), acetic acid (𝐂𝐇𝟑 𝐂𝐎𝐎𝐇) from vinegar
(Latin: acetum, means vinegar), propionic acid (𝐂𝐇𝟑 𝐂𝐇𝟐 𝐂𝐎𝐎𝐇) is the first fat (Latin:
proton, means first and pion, means fat), butyric acid (𝐂𝐇𝟑 𝐂𝐇𝟐 𝐂𝐇𝟐 𝐂𝐎𝐎𝐇) from rancid
butter (Latin: butyrum, means butter), valeric acid (𝐂𝐇𝟑 𝐂𝐇𝟐 𝐂𝐇𝟐 𝐂𝐇𝟐 𝐂𝐎𝐎𝐇) is obtained by
root of valerian plant (Latin: valeriana, means flowering plant). The carbon of carboxyl
functional group is always included in common name nomenclature system, and then
nomenclature will be done by the help of following table:
Number of Carbon Prefix Suffix
𝟏𝐂 Form ic acid
𝟐𝐂 Acet ic acid
𝟑𝐂 Propion ic acid
𝟒𝐂 (𝐧, iso) Butyr ic acid
𝟓𝐂 (𝐧, iso, secondary or tertiary) Valer ic acid
In derived name system nomenclature of carboxylic acid is alkyl acetic acid. Where, a
carbon and the −𝐂𝐎𝐎𝐇 functional group binded with the carbon, is known as acetic
acid. In 𝐈. 𝐔. 𝐏. 𝐀. 𝐂., they are named as follows:
 Largest carbon chain containing −𝐂𝐎𝐎𝐇 group is selected.
 Numbering is done in this way that the −𝐂𝐎𝐎𝐇 functional group gets the least
number.
 Now at last the name is written as:
Substitute(If there is) + alk + ane + oic acid
Gen. Structural formula Common Name 𝐈. 𝐔. 𝐏. 𝐀. 𝐂.
formula
𝐂𝟑 𝐇𝟒 𝐎𝟐 𝐂𝐇𝟐 = 𝐂𝐇 − 𝐂𝐎𝐎𝐇 Acrylic acid Propenoic acid
𝐂𝟒 𝐇𝟔 𝐎𝟐 𝐂𝐇𝟑 − 𝐂𝐇 = 𝐂𝐇 − 𝐂𝐎𝐎𝐇 Crotonic acid But−𝟐 −enoic acid
𝐂𝟗 𝐇𝟖 𝐎𝟐 𝐂𝟔 𝐇𝟓 − 𝐂𝐇 = 𝐂𝐇 − 𝐂𝐎𝐎𝐇 Cinnemic acid 𝟑 −Phenylpropenoic acid
𝐂𝐇𝟐 𝐎𝟐 𝐇 − 𝐂𝐎𝐎𝐇 Formic acid Methanoic acid
 𝐂𝟐 𝐇𝟒 𝐎𝟐 𝐂𝐇𝟑 − 𝐂𝐎𝐎𝐇 Acetic acid Ethanoic acid
𝐂𝟑 𝐇𝟔 𝐎𝟐 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐎𝐎𝐇 Propionic acid Propanoic acid
𝐂𝟒 𝐇𝟖 𝐎𝟐 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐎𝐎𝐇 Butyric acid Butanoic acid
𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐎𝐎𝐇 Isobutyric acid 𝟐 −Methylpropanoic acid

𝐂𝐇𝟑
𝐂𝟓 𝐇𝟏𝟎 𝐎𝟐 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐎𝐎𝐇 Valeric acid Pentanoic acid
𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑

𝐂𝐎𝐎𝐇
𝟐° −Valeric acid
1
𝟐 −Methylbutanoic acid

𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐎𝐎𝐇 Isovaleric acid 𝟑 −Methylbutanoic acid

𝐂𝐇𝟑
𝐂𝐎𝐎𝐇
8
𝟑° −Valeric acid, 𝟐, 𝟐 − Dimethylpropanoic
𝐂𝐇𝟑 − 𝐂 − 𝐂𝐇𝟑 Pivalic acid acid

𝐂𝐇𝟑
𝐂𝟔 𝐇𝟓 − 𝐂𝐇𝟐 − 𝐂𝐎𝐎𝐇 Phenyl acetic acid 𝟐 −Phenylethanoic acid
𝐇𝐎𝐎𝐂 − 𝐂𝐎𝐎𝐇 Oxalic acid Ethanedioic acid
𝐇𝐎𝐎𝐂 − 𝐂𝐇𝟐 − 𝐂𝐎𝐎𝐇 Malonic acid Propanedioic acid
𝐇𝐎𝐎𝐂 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐎𝐎𝐇 Succinic acid Butane−𝟏, 𝟒 −dioic acid
𝐇𝐎𝐎𝐂 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐎𝐎𝐇 Gluteric acid Pentane−𝟏, 𝟓 −dioic acid
𝐇𝐎𝐎𝐂 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐎𝐎𝐇 Adipic acid Hexane−𝟏, 𝟔 −dioic acid
In common name system for carboxylic acid, the location of the substituent in the
carbon chain is indicated by Greek letters ∝, 𝛃, 𝛄, 𝛅 etc. The ∝ carbon being the one
directly linked to the functional group, 𝛃 carbon the next, and so on. For example,
γ β ∝ β ∝
𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐎𝐎𝐇 𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇 − 𝐂𝐎𝐎𝐇

𝐂𝐇𝟑 𝐂𝐇𝟑 𝐁𝐫 𝐂𝐇𝟑

β, γ −Dimethyl valeric acid β −Bromo−∝ − methylbutyric acid
𝟑, 𝟒 −Dimethylpentanoic acid 3 −Bromo−𝟐 − methylbutanoic acid
When the carboylic acid group is attached to a ring, the suffix carboxylic acid is added
after the full name of the cycloalkane in 𝐈. 𝐔. 𝐏. 𝐀. 𝐂.. The numbering of the ring carbon
atoms start from the carbon atom attached to the carboxylic acid group. For example,
𝐇𝟑 𝐂 𝐂𝐎𝐎𝐇 𝐇𝐎𝐎𝐂 𝐂𝐎𝐎𝐇

𝟑 −Methylcyclohexanecarboxylic acid Cyclohexane−𝟏, 𝟐 −dicarboxylic acid

In noncylic carboxylic acid, if all carbon of carboxylic functional groups are not
included in main carbon chain then we can also used carboxylic acid as a suffix in
𝐈. 𝐔. 𝐏. 𝐀. 𝐂.. For example,
𝐇𝐎𝐎𝐂 − 𝐂𝐇𝟐 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐎𝐎𝐇 𝐇𝐎𝐎𝐂 − 𝐂𝐇 − 𝐂𝐎𝐎𝐇

𝐂𝐎𝐎𝐇 𝐂𝐎𝐎𝐇
Propane−𝟏, 𝟐, 𝟑 −tricarboxylic acid Methane−𝟏, 𝟐, 𝟑 −tricarboxylic acid
The name of the simplest aromatic carboxlic acid carrying the carboxylic group on a
benzene ring is benzenecarboxylic acid in 𝐈. 𝐔. 𝐏. 𝐀. 𝐂.. However, the common name
benzoic acid is also accepted by 𝐈. 𝐔. 𝐏. 𝐀. 𝐂.. For examples,
𝐂𝐎𝐎𝐇
𝐂𝐎𝐎𝐇

𝐂𝐎𝐎𝐇
𝐂𝐇𝟑
𝟒 −Methylbenzenecarboxylic acid Benzene−𝟏, 𝟐 −dicarboxylic acid
𝟒 −Methylbenzoic acid Phthalic acid
General Methods of Synthesis for Cabonyl Compounds 
1) 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.
𝐃𝐫𝐲 𝐞𝐭𝐡𝐞𝐫 𝐇𝟐 𝐎
𝐑— 𝐌𝐠𝐗 + 𝐎 = 𝐂 = 𝐎 𝐎 = 𝐂— 𝐎𝐌𝐠𝐗 𝐎 = 𝐂— 𝐎𝐇
−𝐌𝐠(𝐗)𝐎𝐇
𝐑 𝐑
 9441248318, 01412719117 Aldehyde, Ketones and Carboxylic Acids
Since 1996 9414248318, 9468590309, 0141-2719117

2) Oxidation under strong oxidising agent of Primary Alcohol 

Primary alcohols are readily oxidised to carboxylic acids with common oxidising
1
agents such as potassium permanganate in neutral, acidic or alkaline medium or
by potassium dichromate and chromium trioxide in acidic media (Jones Reagent).
𝐇 𝐇 𝐎𝐇
9
𝐀𝐜𝐢𝐝𝐢𝐜 𝐊 𝟐 𝐂𝐫𝟐 𝐎𝟕 [𝐎]
𝐑 − 𝐂 − 𝐎 + [𝐎] 𝐑−𝐂=𝐎 𝐑−𝐂=𝐎
−𝐇𝟐 𝐎
𝐇 𝐇
𝐀𝐜𝐢𝐝𝐢𝐜 𝐊𝐌𝐧𝐎𝟒 [𝐎]
𝐂𝐇𝟑 — 𝐎𝐇 + [𝐎] 𝐇 − 𝐂𝐇𝐎 𝐇 − 𝐂𝐎𝐎𝐇
−𝐇𝟐 𝐎
−𝐇𝟐 𝐎 [𝐎]
𝐂𝐇𝟑 (𝐂𝐇𝟑 )𝟖 𝐂𝐇𝟐 𝐎𝐇 + [𝐎] 𝐂𝐇𝟑 (𝐂𝐇𝟑 )𝟖 𝐂𝐇𝐎 𝐂𝐇𝟑 (𝐂𝐇𝟑 )𝟖 𝐂𝐎𝐎𝐇
𝐂𝐫𝐎𝟑 − 𝐇𝟐 𝐒𝐎𝟒
Dacan−𝟏 −ol Jones Reagent Dacanal Dacanoic acid
3) By Hydrolysis of Acid Derivatives 
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.
𝐑𝐂𝐎𝐂𝓵 + 𝐇𝟐 𝐎 𝐑𝐂𝐎𝐎𝐇 + 𝐇𝐂𝓵
𝐂𝐇𝟑 — 𝐂— 𝐂𝓵 𝐎𝐇− / 𝐇𝟐 𝐎 𝐂𝐇𝟑 — 𝐂— 𝐎− 𝐇𝟑 𝐎+ 𝐂𝐇𝟑 — 𝐂— 𝐎𝐇

𝐎 −𝐂𝓵− 𝐎 𝐎
Acetyl chloride Acetate ion Acetic acid
Anhydrides on the other hand are hydrolysed to corresponding acids.
𝐑— 𝐂— 𝐎— 𝐂— 𝐑 + 𝐇𝟐 𝐎 𝟐𝐑𝐂𝐎𝐎𝐇

𝐎 𝐎
𝐂𝟔 𝐇𝟓 𝐂𝐎𝐎𝐂𝐎𝐂𝐇𝟑 + 𝐇𝟐 𝐎 𝐂𝟔 𝐇𝟓 𝐂𝐎𝐎𝐇 + 𝐂𝐇𝟑 𝐂𝐎𝐎𝐇
Benzoic ethanoic anhydride Benzoic acid Ethanoic acid
Acidic hydrolysis of esters gives directly carboxylic acids while basic hydrolysis
gives carboxylates, which on acidification give corresponding carboxylic acids.
𝐇𝟑 𝐎+
𝐂𝟔 𝐇𝟓 𝐂𝐎𝐎𝐂𝐇𝟑 𝐂𝟔 𝐇𝟓 𝐂𝐎𝐎𝐇 + 𝐂𝐇𝟑 𝐎𝐇
Methyl benzoate Benzoic acid Methanol
𝐍𝐚𝐎𝐇 𝐝𝐢𝐥 𝐇𝐂𝓵
𝐂𝐇𝟑 𝐂𝐇𝟐 𝐂𝐎𝐎𝐂𝟐 𝐇𝟓 𝐂𝐇𝟑 𝐂𝐇𝟐 𝐂𝐎𝐎𝐍𝐚 𝐂𝐇𝟑 𝐂𝐇𝟐 𝐂𝐎𝐎𝐇 + 𝐍𝐚𝐂𝓵
Ethyl propanoate −𝐂𝟐𝐇𝟓 𝐎𝐇 Sodium propanoate Propanoic acid
Acid amides are hydrolysed to corresponding acid with acidified water.
𝐇𝟑 𝐎+
𝐂𝐇𝟑 𝐂𝐎𝐍𝐇𝟐 𝐂𝐇𝟑 𝐂𝐎𝐎𝐇 + 𝐍𝐇𝟑
Ethanamide Ethanoic acid
𝐇𝟑 𝐎+
𝐂𝟔 𝐇𝟓 𝐂𝐎𝐍𝐇𝟐 𝐂𝟔 𝐇𝟓 𝐂𝐎𝐎𝐇 + 𝐍𝐇𝟑
Benzamide Benzoic acid
4) By Hydrolysis of Nitriles 
 Complete hydrolysis of alkyl cyanides gives acid amide then it converts into
carboxylic acid.
𝐇+ 𝐨𝐫 𝐎𝐇− 𝐑𝐞𝐚𝐫𝐫𝐚𝐧𝐠𝐞𝐝 𝐇𝟑 𝐎+
𝐑— 𝐂 ≡ 𝐍 𝐑— 𝐂 = 𝐍𝐇 𝐑— 𝐂— 𝐍𝐇𝟐 𝐑— 𝐂— 𝐎𝐇
𝐇𝟐 𝐎 −𝐍𝐇𝟑
𝐎𝐇 𝐎 𝐎
Alkane nitrile Unstable enol form Alkanamide Alkanoic acid
𝐇+ 𝐨𝐫 𝐎𝐇− 𝐑𝐞𝐚𝐫𝐫𝐚𝐧𝐠𝐞𝐝 𝐇𝟑 𝐎+
𝐂𝐇𝟑 — 𝐂 ≡ 𝐍 𝐂𝐇𝟑 — 𝐂 = 𝐍𝐇 𝐂𝐇𝟑 — 𝐂— 𝐍𝐇𝟐 𝐂𝐇𝟑 — 𝐂— 𝐎𝐇
𝐇𝟐 𝐎 −𝐍𝐇𝟑
𝐎𝐇 𝐎 𝐎
Ethanenitrile Unstable enol form Ethanamide Ethanoic acid
Since 1996 9414248318, 9468590309, 0141-2719117

5) By Oxidation of Alkylbenzenes 
2
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
0
side chain. Primary and secondary alkyl groups are oxidised in this manner while
tertiary group is not affected. Because, the first carbon of side chain of benzene
ring should be have, at least one oxidising hydrogen.
𝐂𝐇𝟑 𝐂𝐎𝐎𝐊 𝐂𝐎𝐎𝐇

𝐊𝐎𝐇 𝐇𝟑 𝐎+
𝐊𝐌𝐧𝐎𝟒
Toluene Potassium benzoate Benzoic acid
𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 𝐂𝐎𝐎𝐊 𝐂𝐎𝐎𝐇

𝐊𝐎𝐇 𝐇𝟑 𝐎+
𝐊𝐌𝐧𝐎𝟒
𝐧 −Propylbenzene Potassium benzoate Benzoic acid
𝐂𝐇𝟑
𝐂𝐇 𝐂𝐎𝐎𝐊 𝐂𝐎𝐎𝐇
𝐂𝐇𝟑
𝐊𝐎𝐇 𝐇𝟑 𝐎+
𝐊𝐌𝐧𝐎𝟒
Cumene Potassium benzoate Benzoic acid
Suitably substituted alkenes are also oxidised to carboxylic acids with these
oxidising reagents.
𝐂𝐇 = 𝐂𝐇𝟐 𝐂𝐎𝐎𝐊 𝐂𝐎𝐎𝐇

𝐊𝐎𝐇 𝐇𝟑 𝐎+
𝐊𝐌𝐧𝐎𝟒
Styrene Potassium benzoate Benzoic acid
Physical Properties of Carboxylic Acids 
1) Physical state, Colour and Odour 
Aliphatic carboxylic acids upto nine carbon atoms are colourless liquids at room
temperature with unpleasant odours like rotten butter. The higher acids are wax
like solids and are practically odourless due to their low volatility.
2) Solubility in Water 
Simple aliphatic carboxylic acids having upto four carbon atoms are miscible in
water due to the formation of hydrogen bonds with water. The solubility
decreases with increasing number of carbon atoms. Higher carboxylic acids are
practically insoluble in water due to the increased hydrophobic interaction of
hydrocarbon part. Benzoic acid, the simplest aromatic carboxylic acid is nearly
insoluble in cold water. Carboxylic acids are also soluble in less polar organic
solvents like benzene, ether, alcohol, chloroform, etc.
3) Boiling Point 
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. The carbonyl group of carboxylic acid is binded with 𝐎 − 𝐇 bond. Due to
its strong −𝐈 effect, the 𝐎 − 𝐇 bond of carboxylic acids is more polar than alcohols.
Therefore, in carboxylic acids, the hydrogen bonds are not broken completely
even in the vapour phase. In fact, most carboxylic acids exist as dimer in the
vapour phase or in the aprotic solvents. Due to presence of dimer, the molecular
mass of ethanoic acid is found to be 𝟏𝟐𝟎 whereas it is actually 𝟔𝟎.
Since 1996 9414248318, 9468590309, 0141-2719117

−𝐂
𝐎…… 𝐇 − 𝐎
𝐂−
2
𝐎 − 𝐇…… 𝐎
Dimer In vapour state or in aprotic solvent
Structure and Nature of Carboxylic acid Functional Group 
1
The carboxyl carbon atom of carboxylic acid is 𝐬𝐩𝟐 hybridised and forms two sigma (𝛔)
bonds by the co-axial overlap with 𝐩 −orbital of its two 𝐎 atoms. The fourth valence
electron of carbon remains in its 𝐩 −orbital and forms a 𝛑 −bond with oxygen by
overlap with 𝐩 −orbital of oxygen. Thus, all bonds to the carboxyl carbon lie in one
plane in carboxylic acids and are separated by about 𝟏𝟐𝟎°.
The carboxylic carbon is less electrophilic than carbonyl carbon because of the
possible resonance structure shown below:
—𝐂 − 𝐎 − 𝐇 —𝐂 = 𝐎 − 𝐇

𝐎 𝐎

It is also clear from the resonance structure that double bond character decreases in
carboxylic acid. Thus, they do not show characteristic reactions of carbonyl
compounds like nucleophilic addition reaction.
Chemical Properties of Carboxylic Acids 
The chemical reactions of carboxlic acids can be classified in following groups:
 Reactions Involving Cleavage of 𝐎 − 𝐇 Bond
 Reactions Involving Cleavage of 𝐂 − 𝐎𝐇 Bond
 Reactions Involving −𝐂𝐎𝐎𝐇 Group
 Substitution Reactions in the Hydrocarbon Part
 Ring Substitution Reactions for Aromatic Carboxylic Acids
Reactions Involving Cleavage of O − H Bond
Acidity 
The acidic nature of carboxylic acid can be explained by their resonance structure:
—𝐂 − 𝐎 − 𝐇 —𝐂 = 𝐎 − 𝐇

𝐎 𝐎

Due to this, the charge distribution in carboxylic acid, as depicted in its resonance
structures, causes the oxygen of −𝐎𝐇 group to be positive. Therefore, oxygen strongly
attracts electrons of 𝐎 − 𝐇 bond and releases hydrogen in the form of 𝐇+ ion. Thus
carboxylic acid is acidic in nature.
The other reason of carboxylic acid, acidic nature is that the carboxylate ion obtained
by ionisation of carboxylic acid also shows resonance and its resonance structures are
more stable than carboxylic acids. Therefore carboxylic acid forms stable carboxylate
ion after ionisation and releases hydrogen in the form of 𝐇+ . The stability of
carboxylate ion is understood by its resonance structures:
—𝐂 − 𝐎 —𝐂 = 𝐎

𝐎 𝐎

Carboxylic acid and carboxlate ion both are stabilised by resonance but the resonance
energy of carboxylate ion is more because both the structures are equivalent.
Whereas two resonating structures of carboxylic acids are not equivalent and charges
are separate as positive and negative charges. Thus, carboxylate ion is more stable
than carboxylic acid.
The carboxylic acids like alcohols evolve hydrogen with electropositive metals and
form salts with alkalies similar to phenols. However, unlike phenols they react with
weaker bases such as carbonates and hydrogencarbonates to evolve carbon dioxide.
2
This reaction is used to detect the presence of carboxyl group in an organic compound.
𝟐 𝐑 − 𝐂𝐎𝐎𝐇 + 𝟐 𝐍𝐚
𝐑 − 𝐂𝐎𝐎𝐇 + 𝐍𝐚𝐎𝐇
𝐑 − 𝐂𝐎𝐎𝐇 + 𝐍𝐚𝐇𝐂𝐎𝟑
𝟐 𝐑 − 𝐂𝐎𝐎𝐍𝐚 + 𝐇𝟐
𝐑 − 𝐂𝐎𝐎𝐍𝐚 + 𝐇𝟐 𝐎
𝐑 − 𝐂𝐎𝐎𝐍𝐚 + 𝐇𝟐 𝐎 + 𝐂𝐎𝟐
2
Sodium hydrogen carbonate Sodium carboxylate
𝟐 𝐂𝐇𝟑 − 𝐂𝐎𝐎𝐇 + 𝐍𝐚𝟐 𝐂𝐎𝟑 𝟐 𝐂𝐇𝟑 − 𝐂𝐎𝐎𝐍𝐚 + 𝐇𝟐 𝐎 + 𝐂𝐎𝟐
Acetic acid Sodium carbonate Sodium acetate
Carboxylic acids dissociate in water to give resonance stabilized carboxylate anions
and hydronium ion.
𝐑 − 𝐂𝐎𝐎𝐇 + 𝐇𝟐 𝐎 𝐑 − 𝐂𝐎𝐎− + 𝐇𝟑 𝐎+
For the above reaction:
+ −
[𝐇𝟑 𝐎 ] [𝐑𝐂𝐎𝐎 ]
𝐊 𝐞𝐪 = [𝐑𝐂𝐎𝐎𝐇] [𝐇𝟐 𝐎]
+ −
[𝐇𝟑 𝐎 ] [𝐑𝐂𝐎𝐎 ]
or 𝐊 𝐞𝐪 × [𝐇𝟐 𝐎] = [𝐑𝐂𝐎𝐎𝐇]
+ −
[𝐇𝟑 𝐎 ] [𝐑𝐂𝐎𝐎 ]
or 𝐊𝐚 = [𝐑𝐂𝐎𝐎𝐇]
Where 𝐊 𝐞𝐪 , is equilibrium constant and 𝐊 𝐚 is the acid dissociation constant. For
convenience, the strength of an acid is generally indicated by its 𝐩𝐊 𝐚 value rather than
its 𝐊 𝐚 value. The relation between 𝐩𝐊 𝐚 and 𝐊 𝐚 is:
𝐩𝐊 𝐚 = −𝐥𝐨𝐠 𝐊 𝐚
The 𝐩𝐊 𝐚 value of 𝐇𝐂𝓵 is −𝟕. 𝟎, where as 𝐩𝐊 𝐚 of carboxylic acids, alcohol and phenols are
𝟒 − 𝟓, 𝟏𝟓 − 𝟏𝟔 and 𝟏𝟎 respectively. Smaller the 𝐩𝐊 𝐚 , the stronger the acid. Therefore,
carboxylic acids are weaker than mineral acids, but they are stronger acids than
alcohols and many simple phenols.
The reason that carboxylic acids are stronger acids than simple phenols is explained by
the following resonance structure of carboxylate and phenoxide ion:
—𝐂 − 𝐎 —𝐂 = 𝐎

𝐎 𝐎
carboxylate ion
𝐎 𝐎 𝐎 𝐎 𝐎

⊖ ⊖

Phenoxide ion ⊖

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 charge is at the less
electronegative carbon atom. Therefore, resonance in phenoxide ion is not as
important as it is in carboxylate ion. Further, the negative charge is delocalised over
two electronegative oxygen atoms in carboxylate ion whereas 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 acid easily releases hydrogen in the form of 𝐇+ with comparation of phenol.
That’s why carboxylic acids are more acidic than phenols.
Let us examine how a compound in which hydroxyl group attached to an carbonyl
group is more acidic than the one in which hydroxyl group is attached to an alkyl
group. The ionisation of an alcohol and a carboxylic acid takes place as follows:
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𝐑 − 𝐎𝐇
Stable
𝐑 − 𝐎− + 𝐇 +
Unstable
2
𝐑 − 𝐂𝐎𝐎− + 𝐇 +
𝐑 − 𝐂𝐎𝐎𝐇
Less stable More stable
The carboxylate ion obtained by ionisation of carboxylic acid is more stable than
3
carboxylic acid due to resonance. Therefore carboxylic acid easily form stable
carboxlate ions by losing protons whereas the alkoxide ion obtained by ionisation of
alcohol does not show resonance, even it is unstable because of the negative charge is
localised on oxygen. Therefore, alcohol does not lose proton easily, so alcohols are
less acidic than carboxylic acids.
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. The −𝐈 effect of different groups will be in following order:
𝐂𝟔 𝐇𝟓 (𝐏𝐡) < 𝐈 < 𝐁𝐫 < 𝐂𝓵 < 𝐅 < 𝐂𝐍 < 𝐍𝐎𝟐 < 𝐂𝐅𝟑
So, the following acids are arranged in order of increasing acidity:
𝐁𝐫𝐂𝐇𝟐 𝐂𝐎𝐎𝐇 < 𝐂𝓵𝐂𝐇𝟐 𝐂𝐎𝐎𝐇 < 𝐅𝐂𝐇𝟐 𝐂𝐎𝐎𝐇 < 𝐍𝐂 − 𝐂𝐇𝟐 𝐂𝐎𝐎𝐇 < 𝐍𝐎𝟐 𝐂𝐇𝟐 𝐂𝐎𝐎𝐇
Conversely, electron donating groups decrease the acidity by destabilising the
conjugate base. The +𝐈 effect of different groups will be in following order:
𝐂𝐇𝟑 < 𝐂𝟐 𝐇𝟓 < 𝐂𝟑 𝐇𝟕 < 𝐂𝟒 𝐇𝟗
𝐂𝐇𝟑

𝐂𝐇𝟑 𝐂𝐇𝟐 𝐂𝐇𝟐 𝐂𝐇𝟐 < 𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 < 𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 − < 𝐂𝐇𝟑 − 𝐂 −

𝐂𝐇𝟑 𝐂𝐇𝟑
Thus, the following acids are arranged in order of increasing acidity:
𝐂𝐇𝟑 𝐂𝐇𝟐 𝐂𝐎𝐎𝐇 < 𝐂𝐇𝟑 𝐂𝐎𝐎𝐇 < 𝐇𝐂𝐎𝐎𝐇
𝐂𝐇𝟑

𝐂𝐇𝟑 − 𝐂 − 𝐂𝐎𝐎𝐇 < 𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐎𝐎𝐇 < 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐎𝐎𝐇

𝐂𝐇𝟑 𝐂𝐇𝟑
If number of −𝐈 group increases, then the bonded electrons of 𝐎 − 𝐇 bond shifted
towards oxygen atom also increases. Therefore, the degree of the positive charge on 𝐇
atom increases. So, releasing of 𝐇+ ion increases and acidic strength also increases. For
example,
𝐂𝓵𝐂𝐇𝟐 𝐂𝐎𝐎𝐇 < 𝐂𝐇𝐂𝓵𝟐 𝐂𝐎𝐎𝐇 < 𝐂𝐂𝓵𝟑 𝐂𝐎𝐎𝐇
The distance of −𝐈 group towards −𝐂𝐎𝐎𝐇 group increases, and then −𝐈 effect decreases.
The bonded electrons of 𝐎 − 𝐇; bond going away from oxygen atom. Therefore, the
degree of the positive charge on 𝐇 atom decreases. So, releasing of 𝐇+ ion decreases
and acidic strength also decreases. For example,
 𝐂𝐇𝟑 𝐂𝐇𝟐 𝐂𝐇(𝐂𝓵)𝐂𝐎𝐎𝐇 > 𝐂𝐇𝟑 𝐂𝐇(𝐂𝓵)𝐂𝐇𝟐 𝐂𝐎𝐎𝐇 > 𝐂𝓵𝐂𝐇𝟐 𝐂𝐇𝟐 𝐂𝐇𝟐 𝐂𝐎𝐎𝐇
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 𝐬𝐩𝟐 hybridised carbon to which carboxyl carbon is attached. For
example,
𝐂𝟔 𝐇𝟓 𝐂𝐎𝐎𝐇 > 𝐂𝟔 𝐇𝟓 𝐂𝐇𝟐 𝐂𝐎𝐎𝐇
Benzoic acid Phenyl benzoic acid
𝐂𝐇𝟐 = 𝐂𝐇— 𝐂𝐎𝐎𝐇 > 𝐂𝐇𝟑 — 𝐂𝐇 = 𝐂𝐇𝟐 — 𝐂𝐎𝐎𝐇
Acrylic acid Crotonic acid
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The presence of electron withdrawing group on the phenyl of aromatic

2
carboxylic acid increases their acidity while electron donating groups decrease
their acidity. For example, 4
𝐇𝐎𝐎𝐂— — 𝐂𝐇𝟑 < 𝐇𝐎𝐎𝐂— < 𝐇𝐎𝐎𝐂— — 𝐍𝐎𝟐

𝟒 −Methoxybenzoic acid Benzoic acid 𝟒 −Nitrobenzoic acid

On the basis of above theory, the following acids are arranged in order of increasing
acidity:
𝐂𝐅𝟑 𝐂𝐎𝐎𝐇 > 𝐂𝐂𝓵𝟑 𝐂𝐎𝐎𝐇 > 𝐂𝐇𝐂𝓵𝟐 𝐂𝐎𝐎𝐇 > 𝐍𝐎𝟐 𝐂𝐇𝟐 𝐂𝐎𝐎𝐇 > 𝐍𝐂 − 𝐂𝐇𝟐 𝐂𝐎𝐎𝐇 > 𝐅𝐂𝐇𝟐 𝐂𝐎𝐎𝐇 >
𝐂𝓵𝐂𝐇𝟐 𝐂𝐎𝐎𝐇 > 𝐁𝐫𝐂𝐇𝟐 𝐂𝐎𝐎𝐇 > 𝐇𝐂𝐎𝐎𝐇 > 𝐂𝓵𝐂𝐇𝟐 𝐂𝐇𝟐 𝐂𝐎𝐎𝐇 > 𝐂𝟔 𝐇𝟓 𝐂𝐎𝐎𝐇 > 𝐂𝟔 𝐇𝟓 𝐂𝐇𝟐 𝐂𝐎𝐎𝐇
> 𝐂𝐇𝟑 𝐂𝐎𝐎𝐇 > 𝐂𝐇𝟑 𝐂𝐇𝟐 𝐂𝐎𝐎躜
Reactions Involving Cleavage of C − O Bond
1) Formation of anhydride 
Carboxylic acids on heating with mineral acids such as 𝐇𝟐 𝐒𝐎𝟒 or with 𝐏𝟐 𝐎𝟓 give
corresponding anhydride.
𝐑𝐂𝐎𝐎𝐇 𝐏𝟐 𝐎𝟓 𝐑— 𝐂— 𝐎— 𝐂— 𝐑 + 𝐇𝟐 𝐎
+
𝐑𝐂𝐎𝐎𝐇 𝐎 𝐎
2) Esterification 
Carboxylic acids are esterified with alcohols or phenols in the presence of a
mineral acid such as concentrated 𝐇𝟐 𝐒𝐎𝟒 or 𝐇𝐂𝓵 gas as a catalyst.
𝐇𝟐 𝐒𝐎𝟒
𝐂𝟔 𝐇𝟓 𝐎𝐇 + 𝐂𝐇𝟑 𝐂𝐎𝐎𝐇 𝐂𝐇𝟑 𝐂𝐎𝐎𝐂𝟔 𝐇𝟓 + 𝐇𝟐 𝐎
𝐇+
𝐂𝟐 𝐇𝟓 𝐎𝐇 + 𝐂𝐇𝟑 𝐂𝐎𝐎𝐇 𝐂𝐇𝟑 𝐂𝐎𝐎𝐂𝟐 𝐇𝟓 + 𝐇𝟐 𝐎
Mechanism %&
𝐇𝟐 𝐒𝐎𝟒 𝐇 + + −𝐎𝐒𝐎𝟑 𝐇
𝐂𝐇𝟑 — 𝐂— 𝐎𝐇 𝐇+ 𝐂𝐇𝟑 — 𝐂— 𝐎𝐇 𝐂𝐇𝟑 — 𝐂 + — 𝐎𝐇

: 𝐎: 𝐇𝐎+ 𝐇𝐎
𝐂𝟐 𝐇𝟓 — 𝐎+ — 𝐇 𝐂𝟐 𝐇𝟓 — 𝐎

𝐂𝐇𝟑 — 𝐂 + — 𝐎𝐇 𝐂𝟐 𝐇𝟓 𝐎̈𝐇 𝐂𝐇𝟑 — 𝐂— 𝐎𝐇 −𝐇+ 𝐂𝐇𝟑 — 𝐂— 𝐎𝐇

𝐇𝐎 𝐇𝐎 𝐇𝐎
𝐎𝐂𝟐 𝐇𝟓 𝐎𝐂𝟐 𝐇𝟓 𝐎𝐂𝟐 𝐇𝟓

𝐂𝐇𝟑 — 𝐂— 𝐎𝐇 𝐇+ 𝐂𝐇𝟑 — 𝐂— 𝐎+ — 𝐇 −𝐇𝟐 𝐎 𝐂𝐇𝟑 — 𝐂 +

𝐇𝐎 𝐇𝐎 𝐇 𝐇𝐎
𝐂𝐇𝟑 — 𝐂 + — 𝐎𝐂𝟐 𝐇𝟓 𝐂𝐇𝟑 — 𝐂— 𝐎𝐂𝟐 𝐇𝟓 −𝐇+ 𝐂𝐇𝟑 — 𝐂— 𝐎𝐂𝟐 𝐇𝟓
 𝐇𝐎 𝐇𝐎+ 𝐎
+ −
𝐇 + 𝐎𝐒𝐎𝟑 𝐇𝐒𝐎𝟒 𝐇𝟐 𝐒𝐎𝟒
3) Formation of acid chloride 
The hydroxyl group of carboxylic acids, behaves like that of alcohols and is easily
replaced by chlorine atom on treating with 𝐏𝐂𝓵𝟓, 𝐏𝐂𝓵𝟑 or 𝐒𝐎𝐂𝓵𝟐.
𝐂𝐇𝟑 𝐂𝐎𝐎𝐇 + 𝐏𝐂𝓵𝟑 𝐂𝐇𝟑 𝐂𝐎𝐂𝓵 + 𝐇𝟑 𝐏𝐎𝟑
𝐂𝐇𝟑 𝐂𝐎𝐎𝐇 + 𝐏𝐂𝓵𝟓 𝐂𝐇𝟑 𝐂𝐎𝐂𝓵 + 𝐏𝐎𝐂𝓵𝟑 + 𝐇𝐂𝓵
𝐂𝐇𝟑 𝐂𝐎𝐎𝐇 + 𝐒𝐎𝐂𝓵𝟐 𝐂𝐇𝟑 𝐂𝐎𝐂𝓵 + 𝐒𝐎𝟐 + 𝐇𝐂𝓵
Thionyl chloride is preferred because the other two products (𝐇𝐂𝓵 and 𝐒𝐎𝟐 ) are
gaseous and escape the reaction mixture making the purification of the products
easier.
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4) Formation of acid amide 

Carboxylic acids react with ammonia to give ammonium salt which on further
heating at high temperature gives amides.
∆
𝐂𝐇𝟑 𝐂𝐎𝐎𝐇 + 𝐍𝐇𝟑 𝐂𝐇𝟑 𝐂𝐎𝐎𝐍𝐇𝟒 𝐂𝐇𝟑 𝐂𝐎𝐍𝐇𝟐 + 𝐇𝟐 𝐎
Ethanoic acid Ammonium ethanoate Ethanamide
∆
𝐂𝟔 𝐇𝟓 𝐂𝐎𝐎𝐇 + 𝐍𝐇𝟑 𝐂𝟔 𝐇𝟓 𝐂𝐎𝐎𝐍𝐇𝟒 𝐂𝟔 𝐇𝟓 𝐂𝐎𝐍𝐇𝟐 + 𝐇𝟐 𝐎
Benzoic acid
𝐂𝐎𝐎𝐇
Ammonium banzoate
𝐂𝐎𝐎𝐍𝐇𝟒 ∆
Banzamide
𝐂𝐎𝐎𝐍𝐇𝟐
2
+ 𝐍𝐇𝟑
𝐂𝐎𝐎𝐇
Phthalic acid
𝐂𝐎𝐎𝐍𝐇𝟒
Ammonium phthalic acid
𝐎
−𝟐𝐇𝟐 𝐎 𝐂𝐎𝐎𝐍𝐇𝟐
Phthalamide 5
𝐂
𝐍𝐇 ∆
𝐂
−𝐍𝐇𝟑
𝐎
Phthalimide
Reactions Involving −COOH Group
1) Reduction 
Carboxylic acids are reduced to primary alcohols by lithium aluminium hydride or
better with diborane.
(𝐢) 𝐋𝐢𝐀𝓵𝐇𝟒
𝐑 − 𝐂𝐎𝐎𝐇 + 𝟔𝐇 𝐑 − 𝐂𝐇𝟐 𝐎𝐇
(𝐢𝐢) 𝐇𝟑 𝐎+
(𝐢) 𝐁𝟐 𝐇𝟔
𝐂𝐇𝟑 − 𝐂𝐎𝐎𝐇 + 𝟔𝐇 𝐂𝐇𝟑 − 𝐂𝐇𝟐 𝐎𝐇
(𝐢𝐢) 𝐇𝟑 𝐎+
Diborane does not easily reduce functional groups such as ester, nitro, halo, etc,.
Sodium borohydride does not reduce the carbonyl group.
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). The reaction is
known as decarboxylation. We can obtain one less carbon alkane from the
carboxylic acid in this reaction.
𝐂𝐚𝐎
𝐑𝐂𝐎𝐎𝐍𝐚 + 𝐍𝐚𝐎𝐇 𝐑―𝐇 + 𝐍𝐚𝟐 𝐂𝐎𝟑
𝐂𝐚𝐎
𝐂𝐇𝟑 𝐂𝐎𝐎𝐍𝐚 + 𝐍𝐚𝐎𝐇 𝐂𝐇𝟑 ―𝐇 + 𝐍𝐚𝟐 𝐂𝐎𝟑
Sodium acetate Methane
3) Kolbe electrolysis 
Alkali metal salts of carboxylic acids also undergo decarboxylation on electrolysis
of their aqueous solutions and form hydrocarbons having twice the number of
carbon atoms present in the alkyl group of the acid. The reaction is known as
Kolbe electrolysis.
𝐂𝐇𝟑 𝐂𝐎𝐎𝐊 𝐄𝐥𝐞𝐜𝐫𝐨𝐥𝐲𝐬𝐢𝐬
𝐂𝐇𝟑 𝐂𝐎𝐎𝐊 + 𝟐 𝐇𝟐 𝐎 𝐂𝐇𝟑 ―𝐂𝐇𝟑 + 𝟐𝐂𝐎𝟐 + 𝟐𝐊𝐎𝐇 + 𝐇𝟐
Sodium acetate Ethane
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Substitution Reactions in the Hydrocarbon Part
Halogenation 
Carboxylic acids having an 𝛂 − hydrogen are halogenated at the 𝛂 − position on
6
treatment with chlorine or bromine in the presence of small amount of red
phosphorus to give 𝛂 −halocarboxylic acids. The reaction is known as Hell-Volhard-
Zelinsky reaction (𝐇. 𝐕. 𝐙. ) . The reaction takes place at high temperature. At low
temperature, reaction is very slow. Red phosphorous changes the carboxylic acid to
acid halide which is more reactive than acids. So, acid halide can be easily
halogenated. Acid halide is hydrolysed to acid after the halogenation.
(𝐢) 𝐑𝐞𝐝 𝐏
𝐂𝐇𝟑 𝐂𝐎𝐎𝐇 + 𝐂𝓵𝟐 𝐂𝓵𝐂𝐇𝟐 𝐂𝐎𝐎𝐇 + 𝐇𝐂𝓵
(𝐢𝐢) 𝐇𝟐 𝐎
If halogens are taken in excess all 𝛂 −hydrogen atoms are replaced by halogen atoms.
𝐗
𝐑𝐞𝐝 𝐏/𝐗 𝟐 𝐑𝐞𝐝 𝐏/𝐗 𝟐
𝐑 − 𝐂𝐇𝟐 − 𝐂𝐎𝐎𝐇 𝐑 − 𝐂𝐇 − 𝐂𝐎𝐎𝐇 𝐑 − 𝐂 − 𝐂𝐎𝐎𝐇
𝐗 = 𝐂𝓵, 𝐁𝐫 𝐗 = 𝐂𝓵, 𝐁𝐫
𝐗 𝐗
Methanoic acid has no 𝛂 −hydrogen atom so it does not undergo 𝐇. 𝐕. 𝐙. reaction.
Ring Substitution Reactions for Aromatic Carboxylic Acids
Aromatic carboxylic acids undergo electrophilic substitution reactions in which the
carboxyl group acts as a deactivating and meta-directing group. For example,
1) Halogenation 
𝐂𝐎𝐎𝐇 𝐂𝐎𝐎𝐇
𝐅𝐞𝐁𝐫𝟑
+ 𝐁𝐫𝟐
−𝐇𝐁𝐫 𝐁𝐫
Benzoic acid 𝐦 −Bromo benzoic acid
2) Nitration 
𝐂𝐎𝐎𝐇 𝐂𝐎𝐎𝐇
𝐇𝟐 𝐒𝐎𝟒
+ 𝐇𝐍𝐎𝟑
−𝐇𝟐 𝐎 𝐍𝐎𝟐
Benzoic acid 𝐦 −Nitro benzoic acid
3) Friedel-Crafts reaction 
Benzoic acid does not undergo Friedel-Crafts reaction, because the carboxyl group
is deactivating and the catalyst aluminium chloride (Lewis acid) gets bonded to
the carboxyl group.
Uses of Carboxylic Acid 
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.
3) Hexanedioic acid (Adipic acid) is used in the manufacture of nylon−𝟔, 𝟔.
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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 Aldehydes, Ketones and Carboxylic Acids 