ALDEHYDES,

KETONES AND
CARBOXYLIC ACIDS -1
GENERAL INTRODUCTION,
NOMENCLATURE AND
PREPARATION OF ALDEHYDES AND KETONES
In aldehydes, the carbonyl group is bonded to a carbon and hydrogen
In ketones, it is bonded to two carbon atoms.

In carboxylic acids and their derivatives (e.g. esters, anhydrides), carbonyl group is
bonded to oxygen

In compounds where carbon is attached to nitrogen – amides

In compounds where carbon is attached to halogens- acyl halides

NOMENCLATURE:
HHHH
ALIPHATIC COMPOUNDS

AROMATIC COMPOUNDS
ALDEHYDES
HCHO Formaldehyde Methanal
CH3CHO Acetaldehyde Ethanal
(CH3)2CHCHO Isobutyraldehyde 2-Methylpropanal
γ-Methylcyclohexane 3-Methylcyclohexane
carbaldehyde carbaldehyde

CH3CH(OCH3 )CHO α-Methoxy propionaldehyde 2-Methoxypropanal

CH3CH2CH2CH2CHO Valeraldehyde Pentanal

CH2=CHCHO Acrolein Prop-2-enal

Phthaldehyde Benzene-1,2-dicarbaldehyde

m-Bromobenzaldehyde 3-Bromobenzaldehyde
KETONES

Acetone Propanone

Acetophenone 1-Phenylethanone

Propiophenone 1- Phenylpropanone

C𝐻3 COC𝐻2 C𝐻2 C𝐻3 Methyl n-propyl ketone Pentan-2-one

(CH3)2 CHCOCH(CH3)2 Diisopropyl ketone 2,4-Dimethylpentan-3-one

α-Methylcyclohexanone 2-Methylcyclohexanone

(CH3)2 C=CHCOC𝐻3 Mesityl oxide 4-Methylpent-3-en-2-one

IUPAC Nomenclature
1. Write the structures of the following compounds:
(i) α-Methoxy propionaldehyde
(ii) 3-Hydroxybutanal
(iii) 2-Hydroxycyclopentane carbaldehyde
(iv) 4-OxopentanaI
(v) Di-sec.butylketone
(vi) 4-Fluoroacetophenone
Answers:
12.2 Name the following compounds according to IUPAC system of nomenclature:
(i) C𝑯𝟑 CH(C𝑯𝟑 )CH2CH2CHO 4-Methyl pentanal

(ii) C𝑯𝟑 CH2COCH(𝑪𝟐 𝑯𝟓 )CH2CH2Cl 6-Chloro-4-ethylhexan-3-one

(iii) C𝑯𝟑 CH=CHCHO But-2-en-l-al

(iv) C𝑯𝟑 COCH2COC𝑯𝟑 Pentane-2,4-dione

(v) C𝑯𝟑 CH(C𝑯𝟑 )CHCH2C(C𝑯𝟑 )𝟐 COC𝑯𝟑 3,3,5-Trimethyl-hexan-2-one

(vi) (CH3)𝟑 CCH2COOH 3,3-Dimethyl butanoic acid

(vii) OHC𝑪𝟔 𝑯𝟒 CHO-p Benzene-1,4-dicarbaldehyde

2.3. Draw the structures of the following compounds.

(i ) 3-Methylbutanal (vii) 3-Bromo-4-phenylpentanoic acid

(ii) p-Methylbenzaldehyde

(iii) 4-Chloropentan-2-one

(iv) p, p’-Dihydroxybenzophenone

(v) p-Nitropropiophenone (viii) Hex-2-en-4-ynoic acid

(vi) 4-Methylpent-3-en-2-one.
12.4. Write the IUPAC names of the following ketones and aldehydes. Wherever possible, give also common names

(i ) CH3CO(CH2)4CH3 Methyl n-pentyl ketone Heptan-2-one

(ii) CH3CH2CH BrCH2CH(CH3)CHO 𝛄 𝐁𝐫𝐨𝐦𝐨 −∝ −𝒎𝒆𝒕𝒉𝒚𝒍 4- 𝐁𝐫𝐨𝐦𝐨 − 𝟐 −

𝒄𝒂𝒑𝒓𝒐𝒂𝒍𝒅𝒆𝒉𝒚𝒅𝒆 𝒎𝒆𝒕𝒉𝒚𝒍 𝒉𝒆𝒙𝒂𝒏𝒂𝒍

(iii) CH3(CH2)5CHO Enanthaldehyde Heptanal

(iv) Ph—CH=CH—CHO β –Phenyl acrolein 3-Phenylprop-2-enal

Cyclopentane carbaldehyde Cyclopentane carbaldehyde

(vi) PhCOPh Benzophenone Diphenylmethanone

.
➢In aldehydes, the carbonyl group ( )C=O) is bonded to carbon and hydrogen,
while in the ketones, it is bonded to two carbon atoms
Nature of Carbonyl Group
➢The carbon and oxygen of the carbonyl group are sp2 hybridized and the carbonyl double bond contains
one σ bond and one π-bond
➢ 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 an 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 coplanar structure
..
SS
➢Oxygen atom in carbonyl group is far more electronegative than carbon atom

➢As a result, the oxygen atom tends to attract the electron cloud of the π-bond towards itself, i. e., the π-
electron cloud of >C = O is unsymmetrical.
➢Hence carbonyl carbon acquires positive charge and carbonyl oxygen carries negative charge.
➢Hence, the carbonyl carbon is an electrophilic (Lewis acid), and carbonyl oxygen, a nucleophilic (Lewis base)
centre.
➢Thus, the carbonyl group is polar in nature.
➢Carbonyl compounds have substantial dipole moments and are polar than ethers. The high polarity of the
carbonyl group is explained on the basis of resonance involving a neutral (A) and a dipolar (B) structures as
shown..
Preparation of Aldehydes and Ketones
1. By oxidation of alcohols:
(a) Primary alcohols are oxidised to corresponding aldehydes (same number of carbon
atoms)using Chromic anhydride or PCC

Secondary alcohols are easily oxidised to ketones with the same number of carbon
atoms using chromic anhydride
 2. By dehydrogenation of alcohols
1° and 2° alcohols give corresponding alcohols when their vapours are passed over
heated copper at 573 K(300ºC)
(i)Primary alcohols undergo dehydrogenation to give aldehydes

(ii) Secondary alcohols also undergo dehydrogenation to give ketones

3. From Hydrocarbons:
(i) By ozonolysis of alkenes:
➢ Ozonolysis of alkenes followed by reaction with zinc dust and water gives
aldehydes or ketones or a mixture of both depending upon the alkene.
➢ Used to determine the position of the C=C bond
4. By hydration of alkynes:
Addition of water to ethyne in presence of dil : 𝐻2 𝑆𝑂4 and 𝐻𝑔𝑆𝑂4 gives acetaldehyde.
All other alkynes give corresponding ketones.(follows Markovnikov’s Rule)
PREPARATION OF ALDEHYDES
1. ROSENMUND REDUCTION: ( From acyl chlorides)
Acid chlorides are easily reduced to the corresponding aldehydes by passing 𝐻2 gas
through boiling xylene solution of acid chloride in presence of Pd catalyst supported
over 𝐵𝑎𝑆𝑂4 and partially poisoned by the addition of sulphur or quinoline

This reaction is called Rosenmund Reduction.

Methanal (Formaldehyde) cannot be prepared by this method since formyl chloride,
HCOCl, is unstable at room temperature.
2. From nitriles and esters:
➢ When an ethereal solution of a nitrile is reduced with stannous chloride in presence
of HCl gas at room temperature , imine hydrochloride is precipitated. This upon
hydrolysis with boiling water gives aldehydes.

This reaction is called Stephen Reaction.

➢ Nitriles are selectively reduced by Diisobutylaluminium Hydride (DIBAL-H)
{[𝐶𝐻3 )2 𝐶𝐻𝐶𝐻2 ]2 𝐴𝑙𝐻, } to imines which upon hydrolysis give aldehydes.
➢Esters are also reduced to aldehydes with DIBAL-H
➢ Carried out at low temperature 195K

➢From Hydrocarbons:
➢(i)Strong oxidising agents oxidise toluene and its derivatives to benzoic acids. However
,it is possible to stop at the aldehyde stage with suitable reagents.
(a) ETARD REACTION -With chromyl chloride (𝐶𝑟𝑂2 𝐶𝑙2):
Toluene can be oxidised to benzaldehyde with a solution of chromyl chloride in C𝑆2 or
𝐶𝐶𝑙4 . The brown chromium complex thus precipitated is separated and decomposed with
dilute acids (hydrolysis) to give benzaldehyde. This reaction is called Etard Reaction
(b)Aromatic aldehydes can be prepared by the oxidation of toluene and its derivatives
with chromium trioxide in acetic anhydride.
The gem-diacetate (Benzylidene diacetate)first formed is isolated and then hydrolysed
with alkali or an acid such as dil .𝐻2 𝑆𝑂4 or HCl to give the corresponding aromatic
aldehyde

(ii)By side chain chlorination followed by hydrolysis:

Side chain chlorination of toluene gives benzal chloride which upon hydrolysis gives
benzaldehyde.(commercial method of manufacture of benzaldehyde)
(iii)Gattermann- Koch Reaction:
When a mixture of CO and HCl gas is passed through a solution of benzene or
toluene in nitrobenzene at 323K in presence of a catalyst consisting of anhydrous
𝐴𝑙𝐶𝑙3 and a small amount of CuCl, benzaldehyde or p-tolualdehyde is formed.
PREPARATION OF KETONES
1. From acyl chlorides:
Prepared by the action of dialkyl cadmium ( prepared by the reaction of cadmium
chloride 𝐶𝑑𝐶𝑙2 with Grignard reagent) on an acid chloride.

2.From nitriles:
Both aliphatic and aromatic ketones can be prepared by the action of a suitable
Grignard reagent on an alkyl or aryl nitrile followed by acid hydrolysis of the
intermediate product.
3. From benzene or substituted benzene:
When benzene or substituted benzene is treated with acid chloride in presence of
anhydrous 𝐴𝑙𝐶𝑙3 , 𝑖𝑡 𝑔𝑖𝑣𝑒𝑠 𝑡ℎ𝑒 𝑐𝑜𝑟𝑟𝑒𝑠𝑝𝑜𝑛𝑑𝑖𝑛𝑔 𝑘𝑒𝑡𝑜𝑛𝑒.
This reaction is known as Friedal-Crafts Acylation Reaction
Questions:
Answers:

i) C5H5N𝐻 + Cr 𝑂3 𝐶𝑙 − (PCC)
(ii) Anhydrous Cr𝑂3
(iii) Cr𝑂3 in the presence of acetic anhydride/ or 1) Cr𝑂2 𝐶𝑙2 2) H-OH (hydrolysis)
(iv) (Di isobutyl)aluminium hydride (DIBAL-H)
(v) PCC
(vi) 𝑂3 /𝐻2 𝑂-Zn dust
12.2
Answers:12.2

(ii)

(iii)
(iv)

4-
ALDEHYDES, KETONES AND
CARBOXYLIC ACIDS-2

PHYSICAL AND CHEMICAL PROPERTIES

OF ALDEHYDES AND KETONES
PHYSICAL PROPERTIES OF ALDEHYDES AND KETONES
➢ Methanal is a gas at room temperature and ethanal is a volatile liquid. Other
aldehydes and ketones are liquid or solid at room temperature.
➢Boiling point of aldehydes and ketones are somewhat higher than those of non –polar
compounds (hydrocarbons) and weakly polar compounds (ethers) of comparable
molecular masses.
➢ Reason: The aldehydes and ketones contain polar carbonyl groups and hence
undergo weak intermolecular association due to dipole-dipole interactions between
the opposite ends of the dipoles.

➢ Boiling points of aldehydes and ketones are lower than those of alcohols of similar
molecular masses.
➢ Reason: Due to the absence of intermolecular hydrogen bonding
➢2. Solubility:
➢Lower aldehydes and ketones containing upto 4 C-atoms are soluble in water due
to H- bonding between polar carbonyl group and the water molecules.

➢ Solubility rapidly falls off as the size of the alkyl group increases with increasing
molecular mass. As a result , the higher members are insoluble in water (from C-5
onwards)
➢Solubility of aromatic aldehydes and ketones is much lower than their
corresponding aliphatic analogues because of larger hydrocarbon part in their
molecules
➢ All aldehydes and ketones are fairly soluble in organic solvents (like benzene,
ether, 𝐶𝐻𝐶𝑙3, alcohols ..etc)
QUESTIONS:
1.

ans: C𝑯𝟑 C𝑯𝟐 C𝑯𝟐 C𝑯𝟑 < 𝑪𝟐 𝑯𝟓 -O- 𝑪𝟐 𝑯𝟓 < C𝑯𝟑 C𝑯𝟐 C𝑯𝟐 CHO < C𝑯𝟑 C𝑯𝟐 C𝑯𝟐 C𝑯𝟐 𝐎𝐇

2.

ans: CH3CH2CH3 < CH3OCH3 < CH3CHO <CH3CH2OH

NUCLEOPHILIC ADDITION REACTIONS
Mechanism of nucleophilic addition reaction
•The carbonyl group is polar in nature.
• Due to greater electronegativity of oxygen, the
carbon atom of the carbonyl group carries a
partial +ve charge and behaves as an Electrophile.
•Therefore, a nucleophile can easily
attack the electrophilic C-atom of the carbonyl
group from a direction approximately
perpendicular to the plane of the 𝑠𝑝2 hybridised orbitals of the carbonyl carbon.
•During this process, complete transfer of π- electrons of the carbon- oxygen double bond
takes place from carbon to oxygen atom, the hybridization of carbon changes from 𝑠𝑝2 to
𝑠𝑝3 and a tetrahedral alkoxide intermediate is formed.
•This intermediate then picks up a proton either from the solvent or from the reagent to give
electrically neutral product.
•REACTIVITY
•Aldehydes are generally more reactive than ketones in nucleophilic addition reactions due
to: (i) Steric hindrance (ii) Electronic factors ( +I effect )
➢Steric hindrance:
• In aldehydes (except methanal), there is only one alkyl group but in ketones there are 2
alkyl groups.
•The presence of 2 relatively large substituents in ketones hinders the approach of
nucleophile to the carbonyl carbon atom (crowding more)
• As the crowding increases , the reactivity decreases accordingly.
➢Electronic factors:
•The ease with which a nucleophile attacks the carbonyl group depends upon the
electron deficiency ie., magnitude of the positive charge on the carbonyl carbon atom.
• Since an alkyl group has electron donating inductive effect (+I effect), therefore ,
greater the number of alkyl groups attached to the carbonyl group, greater is the
electron density on the carbonyl carbon and lower is the reactivity towards
nucleophilic addition reactions.
Examples of nucleophilic addition reaction
(a) Addition of HCN:
Aldehydes and ketones react with HCN to give cyanohydrins.
With pure HCN , reaction occurs very slowly.
Therefore, it is catalysed by a base.
The 𝐶𝑁 − 𝑖𝑜𝑛 thus generated being a strong nucleophile readily adds to the carbonyl
compounds to give the corresponding cyanohydrins
(b)Addition of sodium hydrogen sulphite:
•𝑁𝑎𝐻𝑆𝑂3 𝑎𝑑𝑑𝑠 to aldehydes and ketones to form addition products.
•The position of the equilibrium lies largely to the right for most of the aldehydes and to
the left for most ketones due to steric reasons.
•When heated with dilute mineral acids or aqueous alkali, these adducts decompose
to regenerate the original aldehyde or the ketone.
(c) Addition of Grignard reagent:
d) Addition of alcohols:- Acetal and Ketal Formation
Aldehydes react with one equivalent of a monohydric alcohol in the presence of dry
hydrogen chloride gas to give first alkoxyalcohol intermediates called Hemiacetals.
These then react with one more molecule of alcohol to give gem- dialkoxy
compounds known as acetals

Ketones do not react with monohydric alcohols but do so with dihydric alcohols
(Ethylene Glycol) to give cyclic ketals (Ethylene glycol ketal)
•ROLE OF DRY HCl GAS
•Dry hydrogen chloride protonates the oxygen atom of the carbonyl compound
thereby increasing the electrophilicity of the carbonyl carbon and hence
facilitating the nucleophilic attack by the alcohol molecule
•Dry HCl gas also absorbs the water produced in these reactions and thereby
shifting the equilibrium in the forward direction.

➢The reaction is reversible. Therefore acetals and ketals are hydrolysed by

dilute acids to regenerate the original aldehydes and ketones.
(e) Addition of ammonia and its derivatives
•Aldehydes and ketones react with a number of ammonia derivatives such as
Hydroxylamine (𝑁𝐻2 𝑂𝐻), 𝐻𝑦𝑑𝑟𝑎𝑧𝑖𝑛𝑒( 𝑁𝐻2 − 𝑁𝐻2 ), Phenyl hydrazine
(𝐶6 𝐻5 𝑁𝐻𝑁𝐻2 ), 2,4-Dinitrophenyl hydrazine (Brady’s Reagent) and
semi carbazide ( 𝑁𝐻2 𝐶𝑂𝑁𝐻𝑁𝐻2 ) in weakly acidic medium to form compounds
containing C = N group.

•The reaction is reversible and is catalysed by acids.

•The equilibrium favours the product formation due to the rapid
dehydration of the tetrahedral addition product to form
Some N-substituted derivatives of Aldehydes and Ketones
2. Reduction.
(i) Reduction to alcohols:
Aldehydes and ketones are reduced to primary and secondary alcohols by NaB𝐻4 𝑜𝑟𝐿𝑖𝐴𝑙𝐻4
or by catalytic hydrogenation.
(ii)Reduction to hydrocarbons:
CLEMMENSEN REDUCTION
The carbonyl group of aldehydes and ketones is reduced to 𝐶𝐻2 group on treatment with
zinc amalgam and conc: HCl

WOLFF-KISHNER REDUCTION:
The aldehyde or the ketone is heated with hydrazine and KOH or potassium tert-
butoxide in a high boiling solvent such as ethylene glycol, the carbonyl group is reduced
to 𝐶𝐻2 group
3. Oxidation.
➢Aldehydes are easily oxidised to carboxylic acids containing same number of carbon
atoms on treatment with common oxidising agents like 𝐻𝑁𝑂3, 𝐾𝑀𝑛𝑂4 , 𝐾2 𝐶𝑟2 𝑂7 etc.
•Even mild oxidising agents like Tollen’s reagent and Fehling's reagent also can
oxidise aldehydes.

➢Ketones are generally oxidised under vigorous conditions

ie; strong oxidising agents and at elevated temperature.
•Oxidation involves carbon-carbon bond cleavage to give a mixture of
carboxylic acids with lesser number of carbon atoms than the parent ketone.
Reduction of Tollen’s reagent (mild oxidising agent):
➢Used to distinguish between aldehydes and ketones.
➢Tollen’s reagent is an ammoniacal solution of silver nitrate .
➢When an aldehyde is heated with Tollen’s reagent, the latter is reduced to metallic
silver which deposit on the walls of the test tube as silver mirror.
➢The silver thus formed shines like a mirror. Hence, the test is known as silver mirror
test

➢Both aliphatic and aromatic aldehydes reduce Tollen’s reagent.

➢Ketones cannot be oxidised by mild oxidising agents like Tollen’s reagent
Reduction of Fehling’s Solution (mild oxidising agent).
➢Fehling’s solution is made up of Fehling solution A and Fehling solution B
➢Fehling solution A is aqueous 𝐶𝑢𝑆𝑂4
➢Fehling solution B is alkaline sodium potassium tartrate (Rochelle salt)
➢These two solutions are mixed in equal proportion before the test.
➢On heating an aldehyde with the Fehling’s solution, a reddish brown ppt is
obtained.
➢Aldehydes are oxidised to corresponding carboxylate anion.

➢This test is given by aliphatic aldehydes only.

➢Aromatic aldehydes do not respond to this test.
HALOFORM REACTION:
➢Aldehydes and ketones containing 𝐶𝐻3 CO- on treatment with an excess of halogen
in presence of alkali to produce a haloform.
➢Aldehydes and ketones having 𝐶𝐻3 CO- are oxidised by sodium hypohalite to
sodium salts of corresponding carboxylic acids having one carbon atom less than
that of the 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:
When the haloform reaction is carried out with sod. Hypoiodite, NaOI or NaOH/
𝐼2 ,yellow ppt of iodoform is obtained. Due to the formation of yellow ppt. of
iodoform in this reaction, it is known as iodoform test and is used for characterising
compounds containing 𝐶𝐻3 CO- group or any group such as 𝐶𝐻3 CH(OH)- which
can be easily oxidised to group 𝐶𝐻3 CO- by halogens
REACTION DUE TO α- HYDROGEN.
➢α- hydrogen in aldehydes and ketones are acidic in nature.
➢The acidity is due to the strong electron with drawing effect of the carbonyl group and
resonance stabilisation of the conjugate base.
➢ALDOL CONDENSATION
➢Shown by aldehydes and ketones having α- hydrogen
➢Carried out in presence of dilute alkali as catalyst
➢Form β-hydroxy aldehyde (aldol) or β-hydroxy ketone (ketol)
➢These β-hydroxy aldehydes or β-hydroxy ketones are collectively called as ALDOLS and
the reaction is called aldol condensation
➢{Two molecules of an aldehyde or ketone condense in the presence of dilute alkali(dil.
NaOH,𝑁𝑎2 𝐶𝑂3 ..)to form an unsaturated aldehyde or ketone – (β-hydroxy aldehyde or β-
hydroxy ketone) }
Self aldol condensation
Aldol formation

Ketol formation
CROSS ALDOL CONDENSATION:
When aldol condensation is carried out between 2 different aldehydes and /or ketones, it is
called cross aldol condensation
Examples of cross aldol condensation:
CANNIZZARO REACTION
Aldehydes which do not have an alpha hydrogen atom undergo self oxidation and
reduction (disproportionate) 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
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

Acetophenone meta Nitro acetophenone

USES OF ALDEHYDES AND KETONES
➢40% solution of formalin is used to preserve biological specimens and to
prepare Bakelite ( a phenol–formaldehyde resin), urea- formaldehyde glues
and other polymeric products.
➢Acetaldehyde is primarily used as a starting material in the manufacture of
acetic acid , ethyl acetate, vinyl acetate, polymers , drugs etc
➢Benzaldehyde is used in perfumery and dye industries
➢Acetone and ethyl methyl ketone used as industrial solvents.
➢Butyraldehyde, vanillin, acetophenone, camphor etc. are known for their
odours and flavours
ALDEHYDES,
KETONES AND
CARBOXYLIC ACIDS
STRUCTURE, PREPARATION
AND PROPERTIES OF
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.

➢Carboxylic acids may be aliphatic (RCOOH) or aromatic (ArCOOH) depending on the

group, alkyl or aryl, attached to carboxylic carbon.
➢Some higher members of aliphatic carboxylic acids (𝐶12 – 𝐶18 ) known as fatty acids, (
in natural fats as esters of glycerol).
➢Carboxylic acids serve as starting material for several other important organic
compounds such as anhydrides, esters, acid chlorides, amides, etc. Since carboxylic
acids are amongst the earliest organic compounds
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 PREPARATIN 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 (𝐾2 𝐶𝑟2 𝑂7 ) and chromium trioxide (𝐶𝑟𝑂3 ) in
acidic media (Jones reagent).

Carboxylic acids are also prepared from aldehydes by the use of mild oxidizing
agents
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 boiling
mineral acids or alkalis (𝐻 + or 𝑂𝐻 − ) as catalyst.
➢Mild reaction conditions are used to stop the reaction 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.
➢

➢Grignard reagents and nitriles can be prepared from alkyl halides .

➢The above methods are useful for converting alkyl halides into corresponding
carboxylic acids having one carbon atom more than that present in alkyl halides.
➢Conversion of ethanol to propanoic acid
Conversion of ethanol to propanoic acid
(1)

(2) Conversion using Grignard reagent

5. From acyl halides and anhydrides:
Acid chlorides when hydrolysed with water give carboxylic acids
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
➢Basic hydrolysis gives carboxylates, which on acidification give corresponding
carboxylic acids.
PHYSICAL PROPERTIES
PHYSICAL PROPERTIES:
➢Aliphatic carboxylic acids up to nine carbon atoms are colourless liquids at room
temperature with unpleasant odours.
➢ The higher acids are wax like solids and are practically odourless due to their low
volatility.
➢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
➢Most carboxylic acids exist as cylic dimer in the vapour phase or in the aprotic
solvents(organic solvents).
➢Simple aliphatic carboxylic acids having up to 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
(due to large hydrocarbon part).
➢Carboxylic acids are also soluble in less polar organic solvents like benzene, ether,
alcohol, chloroform, etc.
Chemical properties of carboxylic acids
1) Acidity (i.e. reactions involving breaking of O-H bond)
Carboxylic acids are the most acidic among all the organic compounds
But they are weaker than mineral acids (nitric HNO3, sulphuric H2SO4 and Hydrochloric acid HCl)
In Aqueous solution they ionize and exist in dynamic equation between carboxylate ion + hydronium
ion

According to law of mass action, the equation constant K can be expressed as

𝑅𝐶𝑂𝑂− [𝐻3 𝑂+ ]
K=
𝑅𝐶𝑂𝑂𝐻 [𝐻2 𝑂]

Since 𝐻2 𝑂 is taken in excess its conc. [𝐻2 𝑂] is constant

Therefore,
𝑅𝐶𝑂𝑂− [𝐻3 𝑂+ ]
K x [𝐻2 𝑂] = = 𝐾𝑎
𝑅𝐶𝑂𝑂𝐻

𝐾𝑎 = dissociation constant of the acid

➢ Ka is directly proportional to [𝐻3 𝑂+ ]or [H+] ions.

➢ Therefore, it is a measure of the strength of an acid. Greater the value of ka, greater is
the tendency of the acid to ionize and hence stronger is the acid
➢ Strength of the acid is generally indicated by its pka value rather than it ka value
pka = -log ka
➢ Smaller the numerical value of pka, stronger is the carboxylic acid i.e. it is a better
proton donor

Strong acids have pka < 1 (HCl = -2, 𝑯𝟐 𝑺𝑶𝟒 = -9, CF3COOH = 0.23)
Acids with pka values between 1 and 5 are moderately strong acids (CH3COOH =
4.76, benzoic acid = 4.19)
Weak acids have pka values between 5 and 15
Extremely weak acids have pka values > 15
Carboxylic acids are weaker acids than mineral acids but are stronger acids than
alcohols (pka 16 for ethanol) and simple phenol (pka =,10)
Cause of acidic nature of carboxylic acids and structures of carboxylate anions
Carboxylic acids may be regarded as a resonance hybrid of I and II

Due to the presence of +ve charge, oxygen atoms attracts the electrons of the O-H
bond towards itself. As a result, the O-H bond weakness and ultimately breaks to split
off a proton. This is responsible for the acidic nature of the carboxyl group

After removal of a proton, the resulting carboxylate ion is also stabilised by resonance
Comparison of acidic character of alcohols and carboxylic acids

Both R-OH and R-COOH contain an OH group but carboxylic acids are much stronger
acids
It is due to the reason that both carboxylic acids and carboxylate anion are stabilized by
resonance and neither the alcohol (ROH) nor the alkoxide ion (RO-) are stabilised by
resonance
Comparison of acidic character of phenols and carboxylic acids
12.20 Although phenoxide ion has more number of resonating structures than
carboxylate ion, carboxylic acid is a stronger acid than phenol. Why?
Both are acidic but carboxylic acids are stronger acids than phenols

In case of phenoxide ion, (II – IV) carry a –ve charge on the less electronegative carbon
atom. Therefore, their contribution towards the resonance stabilization of phenoxide ion
is very small. Whereas in carboxylate ion, the –ve charge is on the highly electro –ve
oxygen atoms
Therefore carboxylates is much more resonance stabilized than phenoxide ion and the
release of proton form carboxylic acids is much more easier than phenols
Effect of substituents on the acid strength of aliphatic acids
EWG→ increases the stability of carboxylate ion by dispersing the –ve charge and hence
greater the acidity of the acid
EDG→ lower the stability of the carboxylate ion by intensifying the –ve charge and hence
lower the acidity of the sub carboxylic acid

The foll: substituents increases the acidity of carboxylic acid follows the order:
Phenyl < I < Br <Cl <F < CN < N𝑶𝟐 < 𝑪𝑭𝟑
Effect of electron withdrawing substituents
➢ Effect of halogen atoms

The halogen atom (i.e. Cl) has Electron withdrawing effect i.e. –I effect. Therefore, it
withdraws electron from the O-H bond and electron density in O-H bond decreases i.e. it
facilitates the release of H+ ions by making O-H bond weaker
➢Effect of nature of halogens
Electron withdrawing effect(-I effect) of halogen decreases in the order : F>Cl>Br>I
Therefore, the acidic strength of 𝛼 – halo acids decreases in the order:
𝑭𝑪𝑯𝟐 𝑪𝑶𝑶𝑯 > 𝑪𝒍𝑪𝑯𝟐 𝑪𝑶𝑶𝑯 > 𝑩𝒓𝑪𝑯𝟐 𝑪𝑶𝑶𝑯 > 𝑰𝑪𝑯𝟐 𝑪𝑶𝑶𝑯
Fluoracetic acid > Chloroacetic acid > Bromoacetic acid > Iodoacetic acid
➢Effect of number of halogen atoms
➢Greater the number of electron withdrawing substituents, greater is the dispersal
of –ve charge and stronger the acid.
➢Therefore, trichloroacetic acid C𝐶𝑙3 COOH is a stronger acid than dichloro acetic acid
𝐶𝐻𝐶𝑙2 COOH which in turn is stronger than monochloroacetic acid 𝐶𝐻2 𝐶𝑙COOH
➢Effect of position of halogen atom
Inductive effect decreases rapidly with distance.
Therefore, 𝛼-chlorobutyric acid is stronger than 𝛽-chlorobutyric acid and which in turn
is stronger than 𝛾-chlorobutyric acid
Effect of hybridization of C atom carrying the COOH group
Direct attachment of vinyl and phenyl group increases the acidity of the carboxylic
acid.
This is due to greater electronegativity of sp2 hybridized carbon atom directly attached
to COOH group
Resonance in Acrylic acid →
With respect to electron withdrawing group and electron donating groups, the following
acids are arranged in the order of their decreasing acidity
Effect of substituents on the acid strength of aromatic acids
➢Electron donating groups like R (alkyl), -OH group, -NH2 etc. tend to decrease
➢while electron withdrawing groups increases the acid strength of substituted benzoic acids
Effect of the substituents is more pronounced at p- than at m-positions
Ortho substituted benzoic acids are usually stronger acids than benzoic acid regardless of the
nature of substituents – ortho effect
Acidity Reactions with metals and alkalies:
➢ The carboxylic acids evolve hydrogen with electropositive metals
➢ Form salts with alkalies.
➢

➢They react with weaker bases such as carbonates and hydrogen carbonates
to evolve carbon dioxide. (Not Phenols)
This reaction is used to detect the presence of carboxyl group in an organic
compound.
2 Reactions Involving Cleavage of C–OH Bond
1. Formation of anhydride
Carboxylic acids on heating with mineral acids such as 𝐻2 𝑆𝑂4 or with 𝑃2 𝑂5 give
corresponding anhydride

2. Esterification :
• Carboxylic acids undergo esterification reaction with alcohols or phenols
• In the presence of a mineral acid such as concentrated 𝐻2 𝑆𝑂4 or HCl gas as a catalyst
Mechanism:
Esterification of carboxylic acid with alcohols is a nucleophilic acylation reaction
Step1: Protonation of the carboxyl group
Step 2: Nucleophilic attack by the alcohol molecule
Step 3: Loss of a molecule of water and a proton
12.18
(iii) During the preparation of esters from a carboxylic acid and an alcohol in the
presence of an acid catalyst, the water or the ester should be removed as soon as it is
formed. Why?
The formation ester from a carboxylic acid and an alcohol in presence of an acid as
catalyst is a reversible reaction

To shift the equilibrium in the forward direction, the water or the ester formed should
be removed as fast as it is formed
3. Reactions with 𝑷𝑪𝒍𝟓 , 𝑷𝑪𝒍𝟑 and 𝑺𝑶𝑪𝒍𝟐
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 .
Thionyl chloride (𝑆𝑂𝐶𝑙2 ) is preferred because:
(i) the other two products are gaseous and escape the reaction mixture
(ii) makes the purification of the products easier
4. Reaction with ammonia
Carboxylic acids react with ammonia to give ammonium salt which on further heating
at high temperature give amides
(1)

(2)

(3)
3 Reactions Involving –COOH Group
1. Reduction
➢Carboxylic acids are reduced to primary alcohols by 𝐿𝑖𝐴𝑙𝐻4 or better with diborane.
➢Diborane does not easily reduce functional groups such as ester, nitro, halo, etc.
➢ Sodium borohydride does not reduce the carboxyl 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.

➢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
Substitution Reactions in the Hydrocarbon Part
Halogenation

HELL-VOLHARD-ZELINSKY REACTION (HVZ REACTION)

➢ Carboxylic acids having an α-hydrogen are halogenated at the α-position on treatment

with chlorine or bromine in the presence of small amount of red phosphorus to give α-
halo carboxylic acids.
➢ The reaction is known as Hell-Volhard-Zelinsky reaction.
2. Ring substitution
Aromatic carboxylic acids undergo electrophilic substitution reactions in which the
carboxyl group acts as a deactivating and meta-directing group.
They do 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 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.