Aldehyde, Ketone and Carboxylic Acid

Part-01

Organic Compounds having group are called carbonyl compounds and group is known as
carbonyl group. It's general formula is CnH2nO (n = 1, 2, 3......) Carbonyl compounds are grouped into two
categories

(a) Aldehydes: Aldehyde group is (also known as formyl group). It is a monovalent group

Carbon atom of group is of 1° nature i.e.

(b) Ketones: The carbonyl group is a Ketonic group when its both the valencies are satisfied by alkyl group.
It is a bivalent group.

Carbon atom of group is of 2° nature i.e.

Ketones are further classified as:

(i) Simple or symmetrical ketones: Having two similar alkyl groups.

(ii) Mixed or unsymmetrical ketones: Having two different alkyl groups.

Ex. (Ketones): Symmetrical Unsymmetrical

(Acetone or Dimethyl ketone) (Ethyl methyl ketone)

Propanone Butanone

Structure: In compounds C-atom is sp2 hybridised which forms three  bonds and one  bond. The
unhybridised atomic orbital of C-atom and the parallel 2p orbital of oxygen forms the π bond in group.

The C—C—O / H—C—O bond angle is 120º

Due to electronegativity difference in C and O atoms, the group is polar.

Hence aldehydes and Ketones possess considerable dipole moment.

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Aldehyde, Ketone and Carboxylic Acid Part-01

General Methods of Preparation

1. From alcohol
(a) By Oxidation of Alcohols:
PCC
CH2Cl2
R—CH2—OH R—C—H
PDC
O
CH2Cl2 Aldehyde

R O
[O]
R—CH—OH R—C—R
Secondary alcohol Ketones

R
[O]
R—C—OH No oxidation

R
3°alcohol

(b) Dehydrogenation of alcohols:

CH3CH2OH ⎯⎯⎯⎯→Cu CH3CHO (Acetaldehyde)
300°C

2. From Hydrocarbons
(a) By Reductive Ozonolysis Of Alkenes
O O
(i) O3
H3C—C CH—CH3 H3C—C—CH3 CH3—C—H
(ii) Zn/H2O
CH3

(b) By Hydration of Alkynes (Kucherov Reaction)

OH O
dil.H2SO4/
H3C—C CH H3C—C CH2 H3C—C—CH3
HgSO4
enol keto

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 Aldehyde, Ketone and Carboxylic Acid
Part-02

General Methods of Preparation

3. From Aromatic Hydrocarbons
(a) Gatterman Koch Reaction
H O
C

AlCl3 or
+ CO + HCl
Cu2Cl2

(b) Etard reaction

Benzaldehyde is formed by oxidation of methyl benzene in presence of CrO 2Cl2
CH3 CH(OCrOHCl2)2 CHO

CS2 H/H2O
+ CrO2CI2

Toluene Chromyl (Chromium complex)

chloride

(c) Oxidation using CrO3 (Chromic oxide)

CH3 CH(OCOCH3)2 CHO

273-283 K H/H2O
+ CrO3 + (CH3CO)2O


(Acetic anhydride) (Benzylidene diacetate)

(d) By side chain chlorination followed by hydrolysis.

Side chain chlorination of toluene gives benzal chloride which on hydrolysis gives benzaldehyde.
CH3 CHCl2 CHO

Cl2/hv H2O

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 Aldehyde, Ketone and Carboxylic Acid
Part-03

General Methods of Preparation

4. From Cyanides
(a) Stephen’s Reduction
Nitriles are reduced to corresponding imine with SnCl2 in the presence of HCl, which on hydrolysis gives
corresponding aldehyde.
H3O+
R—CN + SnCl2 + HCl R—CH=NH R—CH=O
DIBAL–H → Diisobutyl almunium hydride [AlH(i-Bu)2]: is also used to obtained aldehyde from cyanide/ester
1. AlH(i-Bu)2
R—CN R—CH=O
2. H2O
1. AlH(i-Bu)2
CH3—CH=CH—CH2—CH2—CN CH3—CH=CH—CH2—CH2—CHO
2. H2O
O O
1. AlH(i-Bu)2
CH3(CH2)9—C—OC2H5 CH3(CH2)9—C—H + C2H5OH
2. H2O
(b) Reaction with Grignard reagent
Treating a nitrile with Grignard reagent followed by hydrolysis yields a ketone.
ether NMgBr H3O+
CH3—CH2—CN + C6H5MgBr CH3CH2—C
C6H5

H3O+ O
CH3—CH2—C=NH C2H5—C + NH3
C6H5
C6H5
(1-Phenylpropanone)

5. From Acid Chloride

2RMgX + CdCl2 → R2Cd + 2MgXCl
2R’—C—Cl + R2Cd → 2R’—C—R + CdCl2

O O
ketone

Physical Properties
State: Only formaldehyde is gas, all other carbonyl compounds upto C11 are liquids and C12 onwards solid.
Solubility: C1 to C3 (formaldehyde, acetaldehyde and propionaldehyde) and acetone are highly soluble in water
due to polarity of bond and can form H–bond with water molecule. C5 onwards are insoluble in water.

1
Solubility 
Molecular weight

H-bonding

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Aldehyde, Ketone and Carboxylic Acid Part-03

Boiling point: Boiling point  Molecular weight

Boiling point order is - Alcohol > Ketone > Aldehydes > Alkane (of comparable molecular mass)

This is because in alcohols intermolecular H-bonding is present but in carbonyl compounds H-bonding doesn't
exist, instead dipole-dipole and vander waal force of attraction is present. Alkanes are non-polar.

Density: Density of carbonyl compounds is lower than water.

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 Aldehyde, Ketone and Carboxylic Acid
Part-04

Chemical Properties
Carbonyl compounds undergo following reactions:
1. Nucleophilic addition reactions (NAR)
NAR is characteristic reaction of aldehydes and ketones

Mechanism
E
O O O
Nu E
C C C
rds fast
R R’ R Nu R’ R Nu R’
Aldehyde/Ketone

Generally rate towards NAR  Electrophilicity of carbonyl group (for aldehyde)

1
 (for ketone)
Steric hindrance

Generally, Rate towards NAR:

Aldehyde > Ketone

O O
C C
R R R H

Aliphatic > Aromatic > Aliphatic > Aromatic

aldehyde aldehyde ketone ketone
O O O O

C C C C
R H H R R R

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Aldehyde, Ketone and Carboxylic Acid Part-04

Stereochemistry of Reaction
NU
NU
E C
C R’
R’ OE
R’ Nu O R
R
Enantiomers
C O
R R
Nu R OE
O E
Aldehyde/Ketone R’ C
R’ C
NU
NU

Note:
If RR’ then racemic mixture will be formed.
(50 % ‘d’ and 50% ‘I’)
If R = R’ then racemic mixture is not obtained.

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 Aldehyde, Ketone and Carboxylic Acid
Part-05

(i) Reaction with HCN/OH

HCN – weak acid
HCN + OH CN + H2O
Pure HCN – Rate of reaction is slow so reaction is base catalyzed.
Mechanism
O O OH
CN H–O–H
C C C
R R’ R CN R’ R CN R’

Aldehyde/Ketone (Cyanohydrin)

Illustration 1.
Which of the following will react with HCN to form racemic mixture ?
O O O O
(1) C (2) C (3) C (4) C
H H H3C H Ph Ph H3C CH3
Solution:
CN

CH3—C—H + H—CN CH3—C—H

O OH
Product has chiral carbon
In remaining no chiral carbon in product.

(ii) Reaction With NaHSO3 (sodium hydrogensulpite / sodium bisulphite)

O ONa OH
NaHSO3 H Bisulphite addition
C C C compound
transfer
R R’ R R’ R R’
SO3H SO3Na
Aldehyde/ketone (White crystalline product)
(Water soluble)

Note:
Reaction is sterically sensitive and given by all aldehydes, aliphatic methyl ketones
O O

—C—CH3 R—C—CH3
(methyl ketone) (aliphatic methyl ketone)

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Aldehyde, Ketone and Carboxylic Acid Part-05

Note:
The bisulphite addition compound can be converted back to the original carbonyl compound by treating it with
dilute acid or base.
Hence this reaction is useful for separation and purification of aldehydes (and some ketones)

(iii) Reaction With Grignard Reagent ( RMgX)

O OH
(ii) H/H2O
CH3—MgBr + H—C—H H—C—H 1° alcohol

CH3

O OH
(ii) H/H2O
CH3—MgBr + H3C—C—H H3C—C—H 2° alcohol

CH3

O OH
(ii) H/H2O
CH3—MgBr + H3C—C—CH3 H3C—C—CH3 3° alcohol

CH3

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 Aldehyde, Ketone and Carboxylic Acid
Part-06

(iv) Reaction with ROH (Alcohol) (addition then elimination)

O OH OR’
R’OH R R’OH R
C C C + H2O
dry HCl dry HCl
R H H OR’ H OR’
Hemi-acetal Acetal

O OH OR’
R’OH R R’OH R
C C C + H2O
dry HCl dry HCl
R R R OR’ R OR’
Hemi-ketal Ketal

Note:
1. To move equilibrium in forward direction excess ROH used and H2O is removed.
2. Aq. HCl not used as it will shift equilibrium in backward direction.
3. HCl used to make ‘C’ of carbonyl group more electrophilic.
H
O O OH
H
C C C
R H R H R H
more electrophilic
4. Acetals and ketals are hydrolysed with aq. mineral acid to yield corresponding aldehydes and ketones.

Mechanism
H
O O OH OH2
R R
H R’OH
C C C C
R H R H H H–O–R’ H OR’

R OR’ R H–OR’ R
C –H C R’OH C
H OR’ H OR’ H OR’

R H–O–R’ R OR’
–H2O
Directly C=O + C
H H OR’
H–O–R’

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 Aldehyde, Ketone and Carboxylic Acid
Part-07

(v) Reaction with H2O

R R OH
H
C=O + H2O C
H R’ OH
Aldehdye/Ketone Unstable hydrate
(generally)

Mechanism
H
O O OH
H H2O
C C C
R R’ R R’ R R’
OH

(vi) Reaction with NH3 and Its Derivatives (addition then elimination)
R pH 4-5 R
C O + H2N—H C N—H + H2O
R’ R’
Aldehyde/Ketone

R pH 4-5 R
C O + H2N—Z C N—Z + H2O
R’ R’
Aldehyde/Ketone NH2–Z – Ammonia derivatives
Ex : NH2OH (hydroxyl amine)
NH2NH2 (hydrazine)

Note:
1. Mild acidic medium used – To make ‘C’ of carbonyl group more electrophilic.
2. It is an addition elimination reaction.
R H R
C O + N—NH2 C N—NH2
R’ H R’
(Hydrazine) (Hydrazone)

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Aldehyde, Ketone and Carboxylic Acid Part-07

R H R
C O + N—NH—Ph C N—NH—Ph
R’ H R’
(Phenyl hydrazine) (Phenyl hydrazone)

R H R
C O + N—OH C N—OH
R’ H R’
(Hydroxyl amine) (Oxime)

O O
R H R
C O + N—NH—C—NH2 C NH—C—NH2
R’ H R’
(Semi-carbazide) (Semi-carbazone)

O2N
R H R
C O + N—NH NO2 C N—NH NO2
R’ H R’

(2,4 Dinitrophenyl hydrazine) (2,4 Dinitrophenyl hydrazone)

(2,4-DNP or Brady’s reagent)

2,4-DNP Test: Aldehyes and ketone react with 2,4-DNP to give red, orange, yellow ppt.

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 Aldehyde, Ketone and Carboxylic Acid
Part-08

2. Reduction of aldehyde/ketone:
The nature of product depends upon the reducing agent used.
(i) Reducing agents are
⚫ Red P/HI at 150°C
⚫ Zn-Hg/HCl [Clemmensen reduction]
⚫ (i) N2H4 (ii) [Wolff Kishner reduction]

(ii) Reducing agents are

⚫ Metal + H2
⚫ LiAlH4
⚫ NaBH4
⚫ Na + C2H5OH

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 Aldehyde, Ketone and Carboxylic Acid
Part-09

3. Oxidation of aldehyde/ketone:
Aldehydes are easily oxidised to carboxylic acids on treatment with strong oxidising agents like KMnO4, K2Cr2O7.
Ketones are oxidised under vigorous conditions, i.e., strong oxidising agents and at elevated temperatures.
[O]
R—CHO R—COOH
[O]
R—CH2—C—CH2—R’ R—COOH + R’—CH2COOH + R—CH2COOH + R’—COOH
(By clevage of C1—C2 bond) (By clevage of C2—C3 bond)
O

Oxidation of only aldehyde

Reducing character: Aldehydes are easily oxidised so they are strong reducing agents.
(i) Tollens' reagent: It oxidises aldehydes. Tollens' reagent is ammoniacal silver nitrate solution
(AgNO3+NH4OH) ⎯⎯→ [Ag(NH3)2]OH
RCHO+[Ag(NH3)2]OH ⎯⎯→ + Ag + H2O
Silver mirror

(ii) Fehling's solution: It is a mixture of aqueous CuSO4, NaOH and sodium potassium tartarate.
Fehling solution A– aq. solution of CuSO4
Fehling solution B– Roschelle salt (Sodium potassium tartarate + NaOH)
Fehling solution A + Fehling solution B (Dark blue colour of cupric tartarate)
RCHO + Cu+2 + OH- ⎯⎯→ + Cu2O
(Cuprous oxide–Red ppt.)
Cu2+ ⎯⎯→ Cu+
(Cupric - Blue) (Cuprous - Red ppt.)

(iii) Benedict's solution: It is a mixture of CuSO4 + sodium citrate + NaOH. It provides Cu+2. It is reduced
by aldehyde to give red ppt of cuprous oxide.
RCHO + Cu2+ + OH- ⎯⎯→ + Cu2O
(Cuprous oxide–Red ppt.)

(iv) Schiff's reagent: Dilute solution of p-roseaniline hydrochloride or magenta dye, is a pink coloured dye
and is known as schiff's dye.
Its pink colour is discharged by passing SO2 gas and the colourless solution obtained is called schiff's
reagent aldehyde reacts with this reagent to restore the pink colour.

Note:
1. All above four methods are used to distinguished aldehydes and ketones.
2. Aromatic aldehyde does not give F.S. and B.S. test.

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 Aldehyde, Ketone and Carboxylic Acid
Part-10

4. Oxidation of methyl ketone (haloform reaction):

When methyl ketones react with halogen in the presence of base oxidation of methyl ketones take place.
O O
R—C—CH3 + 3X2 + 4NaOH R—C—ONa + CHX3 (Haloform)

Salt of carboxylic acid

CHCl3 – Chloroform (liquid)
CHBr3 – Bromoform (liquid)
CHI3 – Iodoform (yellow solid)

Ketones → Methyl ketones undergo haloform reaction

O
R—C—CH3

Aldehydes → Only acetaldehyde can undergo haloform reaction

O
H3C—C—H

Alcohols → Alcohols of the following type also undergo haloform reaction

OH

—CH—CH3

NaOH + X2 is also a mild oxidizing agent

OH O
NaOX
H3C—CH—CH3 H3C—C—CH3
(Gives iodoform test)

NaOX
H3C—CH2—OH H3C—CHO
(Gives iodoform test)

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Aldehyde, Ketone and Carboxylic Acid Part-10

Illustration 1.
Which of the following compounds will give positive iodoform test?
O O
(i) H3C—CH2—C—H (ii) H3C—C—NH2

(iii) H3C—CH2—C—H (iv) H3C—CH2—CH—CH3

I OH
(v) Ph—CH2—OH (vi) Ph—CH—OH

CH3
Solution:
Ans. (iii), (iv), (vi)

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 Aldehyde, Ketone and Carboxylic Acid
Part-11

5. Aldol Condensation:
Carbonyl compounds which contain -H atoms undergo condensation with dil. NaOH to give aldol. Aldol
contains both alcoholic and carbonyl group, which on heating in alkaline medium gets converted into , -
unsaturated carbonyl compound.

Mechanism of aldol condensation: It takes place in the following two stages:

(i) Formation of Carbanion
(ii) Combination of carbanion with other carbonyl molecule.

(i) Formation of Carbanion: -H atom of group are quite acidic which can be removed as
proton, by a base

Carbanion thus formed is stable because of resonance –

(ii) Combination of carbanion with other carbonyl molecule:

Identical carbonyl compounds ⎯⎯→ Simple or self aldol condensation.

Different carbonyl compounds ⎯⎯→ Mixed or crossed aldol condensation.

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Aldehyde, Ketone and Carboxylic Acid Part-11

Simple or Self condensation:

Mixed or Crossed aldol Condensation:

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 Aldehyde, Ketone and Carboxylic Acid
Part-12

6. Cannizzaro Reaction:
Those aldehydes which do not contain  - H atom give this reaction, with conc. NaOH or KOH: Products are Salt
of carboxylic acid and alcohol
In this reaction one molecule of aldehyde is oxidised to acid, while other is reduced to alcohol, such type of
reactions are called redox reaction.
Conc.
HCHO + HCHO ⎯⎯⎯→ HCOONa + CH3OH
NaOH,

Mechanism involved in Cannizzaro’s reaction:

(a) Rapid reversible addition of OH to one molecule of HCHO.

(b) Transfer of hydride ion H to second molecule of HCHO

When molecules are same ⎯⎯

→ Simple cannizzaro reaction
Two different molecules ⎯⎯
→ Mixed cannizzaro reaction

Note:
1. In mixed or crossed cannizzaro reaction more reactive aldehyde is oxidised and less reactive aldelyde is
reduced.
HCHO + C6H5CHO ⎯⎯⎯
NaOH

⎯→ HCOONa + C6H5CH2OH
Oxidized Reduced
(Sodium formate) (Benzyl alcohol)
2. Ketone does not give Cannizzaro due to poor leaving tendency.
CHO CH2OH
O O
Ex. conc.NaOH + H—C—ONa
+ H—C—H

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Aldehyde, Ketone and Carboxylic Acid Part-12

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.
CHO CHO

HNO3/H2SO4
273–283 K
NO2
Benzaldehyde m-Nitrobezaldehyde

Carboxylic acid
Organic compounds having –COOH group are called Carboxylic acids. This functional group is composed of

Carbonyl and hydroxyl (–OH) group.

+ —OH ⎯⎯→
Carbonyl group Hydroxyl group Carboxylic group
The properties of the carboxylic group are not simply the combined properties of these two groups, but it has
its own distinctive properties. The acidic nature of carboxylic acids is due to the presence of replacable H-atom
in the Carboxylic group.

Classification:
Monocarboxylic acid (RCOOH): Having one carboxylic group, also called monobasic acid.
General molecular formula - CnH2nO2 ( n = 1, 2, 3, ........). Higher mono carboxylic acids are called fatty acids.
Dicarboxylic acid: Having two carboxylic groups, also called dibasic acid.

Ex. Oxalic acid

Tricarboxylic acid: Having three carboxylic groups also called tribasic acid.

Ex. Citric acid

Structure: The carbon atom of –COOH group is sp2 hybridised, this C- atom is in centre and thus bond angle
around C-atom is 120º.

General Methods of Preparation

1. By Oxidation of alcohols and carbonyl compounds:
Oxidation is carried out by acidified K2Cr2O7 or KMnO4.
[O]
RCH2OH ⎯⎯⎯⎯⎯⎯
K Cr O / H SO
→ RCHO ⎯⎯⎯
[O]
→ RCOOH
2 2 7 2 4

Acids are third oxidation products of alkane.

R—H ⎯⎯⎯
[O]
→ R—OH ⎯⎯⎯
[O]
→ R—CHO ⎯⎯⎯
[O]
→ R—COOH

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Aldehyde, Ketone and Carboxylic Acid Part-12

2. From Alkyl Benzenes

Oxidation using

(a) KMnO 4 / H

(b) KMnO4 / OH / 

(c) K 2Cr2 O7 / H

C(H,,O) COOH COO

or

CH3 COOH

(No oxidation)

(No hydrogen, no bond, no oxygen)

3. By hydrolysis of alkane nitriles or cyanides:

Complete hydrolysis takes place in acidic medium (dil. HCl). Or in alkaline medium

4. From Grignard's reagent:

Carbon dioxide
Solid CO2 (dry ice) is used

5. By hydrolysis of acid derivatives:

Z = —Cl, —OCOR, —OR, —NH2

Reactivity order of acid derivatives: RCOCl > (RCO)2 O > RCOOR > RCONH 2
HOH
RCOCl dil. acid → RCOOH + HCl
⎯⎯⎯⎯
HOH
(RCO)2O ⎯⎯⎯⎯
dil. acid → 2RCOOH
HOH
RCOOR' ⎯⎯⎯⎯
dil. acid → RCOOH + R'OH
HOH
R—CONH2 ⎯⎯⎯⎯
dil. acid → RCOOH + NH3

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Aldehyde, Ketone and Carboxylic Acid Part-12

Physical Properties
Carboxylic acids from C1— C4 are completely soluble in water.
1
Solubility 
molecular weight
Solubility is due to intermolecular H - bonding with water molecules.
Boiling point: B. P.  Molecular weight,

B. P. Carboxylic acids > alcohol

This is because in acids two oxygen atoms take part in H - bonding (while in alcohol only one O - atom takes
part).

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 Aldehyde, Ketone and Carboxylic Acid
Part-13

Reactions of Carboxylic Acids (Chemical properties)

1. Formation of Anhydrides
H/
O O O O
R—C—OH + HO—C—R R—C—O—C—R
P2O5

Note:
O
P2O5
R—C—NH2 R—CN + H2O


2. Esterification Reaction
Carboxylic acids react with alcohols or phenols in the presence of an acid (conc.H2SO4 or dry HCl) to form esters.
This method is called Fischer esterification.
O
H
RCOOH + R’OH R—C—OR’ + H2O
O O
H
H3C—C—OH + CH3OH H3C—C—OCH3 + H2O
O O
18
C—OH C—OCH3
18 H
+ CH3OH + H2O

Mechanism
••
OH OH
O H OH R’—OH
••
Proton
R—C •• R—C •• R—C—O—R’ R—C—O—R’
O—H O—H transfer
••
OH H OH2
Carboxylic acid
Tetrahedral intermediate

-H2O

O -H O—R’
R—C R—C ••
••
O—R’ O—H
••

Ester Protonated ester

1
Rate of esterification 
Steric hindrance

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Aldehyde, Ketone and Carboxylic Acid Part-13

Reactivity of alcohols
CH3

H3C—C—OH < H3C—CH—OH < H3C—CH2—OH

CH3 CH3
3°Alcohol 2°Alcohol 1°Alcohol

Reactivity of acids
CH3

H3C—C—COOH < H3C—CH—COOH < H3C—CH2—COOH

CH3 CH3

3. Reaction with PCl3, PCl5, SOCl2

PCl3
3R—COOH 3R—COCl + H3PO3
PCl5
R—COOH R—COCl + POCl3 + HCl

R—COOH SOCl2 R—COCl + SO2 + HCl

4. Reaction with Ammonia


R—COOH + NH3 R—COONH4 R—CONH2 + H2O
(Ammonium carboxylate) (Amide)


H3C—COOH + NH3 H3C—COONH4 H3C—CONH2 + H2O
(Acetic acid) (Ammonium acetate) (Acetamide)

COOH CONH2
NH3
+ H2O


COOH COONH4 CONH2

NH3 
+ 2H2O
COOH COONH4 CONH2

(Phthalic acid) (Ammonium phthalate) (Phthalamide)

Strong
–NH3 heating

O O CO
—C—NH—C— NH
(Imide) CO
(Phthalimide)

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Aldehyde, Ketone and Carboxylic Acid Part-13

5. Reduction
Carboxylic acids are reduced to primary alcohols by lithium aluminum hydride 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.
(i) LiAlH4/ether or B2H6
R—COOH R—CH2OH
(ii) H3O+

6. Decarboxylation
Removal of CO2 from carboxylic acid is known as decarboxylation.
Reagent used: NaOH + CaO (Soda lime)
NaOH/CaO
CH3COOH CH4 + Na2CO3


-keto carboxylic acids

-keto acid can be easily decarboxylated by heating only (no need of sodalime)
O O

CH3—C—CH2—COOH  CH3—C—CH2—H + CO2

(-Keto acid) (Acetone)
O O
COOH

+ CO2

O O
HOOC COOH

+ 2CO2

7. Hell Vohlard Zelinsky (HVZ) Reaction

Carboxylic acids having  hydrogen atom are halogenated at the  position on treatment with chlorine or
bromine in the presence of small amount of red phosphorous to give -halocarboxylic acids.
 (i) X2/Red P 
R—CH2—COOH R—CH—COOH
(ii) H2O
X
Cl
 
H3C—CH2—COOH P/Cl2 H3C—CH—COOH P/Cl2 H3C—C—COOH

Cl Cl
8. Ring Substitution
Aromatic carboxylic acids undergo electrophilic substitution reactions in which the carboxyl group acts as a
deactivating and meta-directing group. They however, 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).

[3]
Aldehyde, Ketone and Carboxylic Acid Part-13

COOH COOH

Conc. HNO3 +
(i)
Conc. H2SO4 NO2
m-Nitrobenzoic acid
COOH COOH

Br2/FeBr3
(ii)
Br
m-Bromobenzoic acid

[4]
 Aldehyde, Ketone and Carboxylic Acid
Part-14

••
Chemical Reaction of acid derivatives R—C—Z

O
•• •• •• •• ••
–Z may be → –OR, –X, –OCOR, –NH2

R—C—OR R—C—X R—C—O—C—R R—C—NH2

O O O O O
ester Acid halide Anhydride Amide
Characteristic reaction of acid derivative is nucleophilic substitution reaction (NSR)
••
Ex. R—C—Z + E—Nu R—C—Nu + E—Z

O O
Acid derivative Product

Mechanism
••
O O
•• O
••
CH3—C + Nu CH3—C—Nu CH3—C—Nu + Z

Z Z
In this reaction Z is leaving group and weak bases are good leaving groups.
Reactivity order: CH3COCl > CH3COOCOCH3 > CH3COOC2H5 > CH3CONH2

1. Reaction with water (Hydrolysis)

•• ••
Ex. R—C—Z + H—OH R—C—OH + Z—H

O O
Hydrolysis of acid derivative gives carboxylic acid.

(i) CH3—CH2—C—Cl + H—OH CH3—CH2—C—OH

O O
Acid halide

(ii) H
Ph—CH2—C—O—CH3 + H—OH Ph—CH2—C—OH + CH3—OH

O O
(ester)
(iii) H CH3—NH2
CH3—C—NH—CH3 + H—OH CH3—C—OH +

O O H CH3—NH3
(Amide)

[1]
Aldehyde, Ketone and Carboxylic Acid Part-14

2. Reaction with Alcohol

•• •• ••
R—C—Z + R—OH R—C—OR + Z—H

O O
(ester)
C—Cl –HCl C—O—CH2—CH3
(i) + CH3—CH2—OH
O O

(ii) CH3—C—O—CH2—CH3 + CH3—OH CH3—C—O—CH3 + CH3—CH2—OH

O O
Transesterification → formation of ester from another ester

3. Reaction with Ammonia

•• •• ••
R—C—Z + NH2—H CH3—C—NH2 + Z—H

O O
(amide)

(i) Base ••
CH3—C—Cl + NH2—H CH3—C—NH2

O O

(ii) CH3—C—O—CH3 + R—NH—H CH3—C—NH—R + CH3—OH

O O
Amine Amide

(iii) CH3—C—O—C—CH3 + NH2—NH—H CH3—C—NH—NH2 + CH3—C—OH

O O O O

4. Reaction with Grignard reaction

•• NSR ••
R—C—Z + RMgX R—C—R + ZMgX

O O
ketone

(i) CH3—C—Cl + EtMgCl CH3—C—Et + MgCl2

O O
ketone
If RMgX is used in excess than alcohol is obtained
CH3 CH3

C—Cl C—CH3 CH3MgCl C—CH3 H–OH C—CH3

+ CH3MgCl
O O OMgCl OH

NSR
(ii) CH3—C—O—CH3 + PhMgBr CH3—C—Ph

O O
ketone

[2]