INTRODUCTION

OF
CARBONYL COMPOUNDS
 Introduction of carbonyl compounds

Organic compounds containing carbon-oxygen double bond

(>C=O) called carbonyl group, which is one of the most
important functional groups in organic chemistry.

Carbonyl compounds's general formula is Cn H2nO (n = 1, 2, 3......)

 Classification of carbonyl compounds

Carbonyl compounds are classified as aldehyde and ketone.

O
(a) Aldehydes : Aldehyde group is ∥ (also known as formyl
−C−H
group) where its valency is satisfied by alkyl or aryl group.

(b) Ketones : The carbonyl group (>C=O) is a Ketonic group where its
both the valencies are satisfied by alkyl or aryl group. It is a bivalent
group.
 Ketones are further classified as

(i) Simple or Symmetrical ketones :

R
Having two similar alkyl or aryl groups. C=O
R

(ii) Mixed or unsymmetrical ketones :

R
Having two different alkyl or aryl groups. C=O
R’

EXAMPLE CH3 CH3CH2

C=O C=O
CH3 CH3

2–Propanone 2–Butanone
 EXAMPLE

CHO
CH3CHO

Ethanal
(Acetaldehyde) Benzaldehyde

Br O O
| || ||
H3C—CH—CH2—C—H CH3—C—CH3
  
2-propanone
3- bromobutanal (Acetone)
(𝛽-Bromobutyraldehyde)
 EXAMPLE

O O
|| ||
C C CH3
CH3 CH2

1-phenylethanone 1-phenylpropane-1-one
(Acetophenone) (Propiophenone)

O
||
C

Diphenylmethanone
(Benzophenone)
Question Draw the structures of the following compounds.
(i) 3-Methylbutanal (ii) p-Nitropropiophenone
(iii) p-Methylbenzaldehyde (iv) 4-Methylpent-3-en-2-one
(v) 4-Chloropentan-2-one (vi) 3-Bromo-4-phenylpentanoic acid
(vii) p,p’-Dihydroxybenzophenone (viii) Hex-2-en-4-ynoic acid

SOLUTION
Question Write the IUPAC names of the following ketones and aldehydes.
Wherever possible, give also common names.
(i) CH3CO(CH2)4CH3 (ii) CH3CH2CHBrCH2CH(CH3)CHO
(iii) CH3(CH2)5CHO (iv) Ph-CH=CH-CHO

CHO
(v) (vi) PhCOPh

SOLUTION
Special Point

O O O O

:
— C — OH, — C — X, — C — NH2, — C — OR,

In all the functional group given above, lone pair of electrons on Z

atom and double bond are in conjugation
O
so resonance occurs.

:
−C−Z

These functional group have carbonyl group still they are not
carbonyl compounds because carbonyl group takes part in resonance
with the lone pair of electrons.
 Structure of carbonyl compounds

The carbonyl carbon atom is sp2-hybridised and forms three sigma

(s) bonds. In addition, the oxygen atom also has two non bonding
electron pairs.

sp2 C -bond O
••
 Structure of carbonyl compounds

The fourth valence electron of carbon remains in its 𝜋-orbital and

forms a 𝜋-bond with oxygen by overlap with 𝜋-orbital of an oxygen.

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.

-bond

sp2 C O
••
 Structure of carbonyl compounds

The bond angles are approximately 120° as expected of a trigonal

coplanar structure.

120°

120° C O
••
120°
Fig.Orbital diagram for the formation of carbonyl group
The carbon-oxygen double bond is polarised due to higher
electronegativity of oxygen relative to carbon.

Carbonyl compounds have substantial dipole moments and are polar

than ethers.

Hence, the carbonyl carbon is an electrophilic (Lewis acid), and

carbonyl oxygen, a nucleophilic (Lewis base) centre.

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.
O O–
|| |
C C+

(A) (B)
 What is the structure of 2,4-hexanedione?
Question
O O
(A) (B)
O O
O

(C) (D)
O O
O

Ans. (C)
 What is the name of the following compound?
Question O
CHO

(A) (R)-2-formylcyclohexanone
(B) (R)-2-aldehydecyclohexanone
(C) (S)-2-formylcyclohexanone
(D) (S)-2-aldehydecyclohexanone

Ans. (A)
 PREPARATION
OF
CARBONYL COMPOUNDS
 Preparation of carbonyl compounds

From Hydrocarbon

(A) Ozonolysis of Alkene:

By reductive ozonolysis of alkene carbonyl compounds (Aldehyde or

ketone) are prepared.
(i) O3
C=C C = O + O = C + ZnO
(ii) Zn / H2O

C=C
O O

Zn trap oxygen:- Zn + [O] → ZnO

Question (i) O3

(ii) Zn/H2O

Ans. 2 O
Question (i) O3

(ii) Zn/H2O

Ans. O
O
Question X on reaction with O3/Zn, H2O gives CO2 + EtCHO + CH3CHO. What is X ?

Ans. (X : EtCH = C = CHCH3)

(B) Hydration of alkyne

Kucherov reaction : Hydration of alkyne in presence of H2SO4 and

HgSO4 give carbonyl compounds.

OH O
H2SO4 (40%)
CH  CH + H2O CH2=CH CH3 – C – H
HgSO4 (1%)
60 to 70°C
only acetylene given aldehyde. All other alkyne given ketone

Addition of water (H2O) takes place according to markovnikov’s rule.

H2SO4
CH3 – C ≡ CH +H2O CH3 – C = CH2 CH3 – C -CH3
HgSO4
OH O

The reaction is most useful for terminal alkyne because internal

alkyne gives mixture.

O O
H2SO4
R – C ≡ C – R’+ H2O R – C– CH2 – R’+ R –CH2–C–R
HgSO4
mixture
 𝐇𝐠𝐒𝐎𝟒
Question
𝐇𝟑 𝐎+

Ans. 2-butanone
Question H3CO CC CH3 Hg2+/H3O+

Ans. H3CO C–CH2 CH3

O
 An acylic hydrocarbon P, having molecular formula C6H10, gave acetone
as the only organic product through the following sequence of
reactions, in which Q is an intermediate organic compound.

(JEE-ADV.
2011)
O
(i) Dil H2SO4 / HgSO4 (i) conc.H2SO4(cat. amount
P Q C
(ii) NaBH4 / Ethanol (ii) O3
C6H10 H3 C CH3
(iii) dil. acid (iii) Zn / H2O
 The structure of compound P is - (JEE-ADV.
Question
2011)
(A) CH3CH2CH2CH2—C≡ C—H (B) CH3CH2C ≡C—CH2CH3
H3 C H3 C
(C) H—C—C≡C—CH3 (D) H3C—C—C≡C—H
H3 C H3 C

Ans. (D)
 The structure of compound Q is - (JEE-ADV.
Question
2011)
OH OH
H3 C H3 C
(A) H—C—C—CH2CH3 (B) H3C—C—C—CH3
H3 C H3 C
H H

OH OH
H3 C
(C) H—C—CH2CHCH3 (D) CH3CH2CH2CHCH2CH3
H3 C

SOLUTION

Ans. (B)
(C) Oxo process or carbonylation or Hydro formylation reaction

(only for aldehyde) (Industrial method)

At high temperature and pressure, alkene reacts with water gas

(CO + H2) in the presence of cobalt complex which acts as
catalyst, leads to formation of aldehyde as product.

[Co(CO)4]2
R—CH=CH2 + CO + H2 R—CH—CH2
170°C , 250 atm
H C=O
H
 Co2(CO)8
CH3—CH=CH2 + CO + H2 CH3—CH2—CH2—CHO
170°C , 250
(75 %)

+ CH—CH—CH3 25 %
CHO

Note

The net reaction appears to be an addition of formaldehyde

through antimarkownikoff rule
 CH3 (i) Co2 (CO)8
Question C = CH2 + CO + H2
CH3 (ii) H2/Ni

SOLUTION

CH3
Ans. CH – CH2 – CH2–OH
CH3
(D) Wacker process

When alkene is reacted with acidified aqueous solution of PdCl2 and

cupric chloride, aldehyde or ketone can be obtained.

CuCl2
CH2=CH2 + PdCl2 + H2O air or O2
CH3—CHO + Pd + 2HCl
O
CuCl2
CH3—CH = CH2 + PdCl2 + H2O air or O2
CH3—C—CH3 + Pd + 2HCl
(E) Hydroboration Oxidation of alkynes

Terminal alkynes give aldehyde and Nonterminal alkynes gives

ketones

(I) BH3 / THF tautomerise

CH3–CCH CH3—CH=CH CH3—CH2—C—H
(II) H2O / OH⊝
OH O

(I) BH3 / THF tautomerise Me—C—Et

CH3–CC–CH3 CH3—C=CH—CH3
(II) H2O / OH⊝
O
OH
Preparation of carbonyl compounds

From alcohols

By Oxidation

(i) Mild oxidizing agent oxidise 1° alcohol to aldehyde and 2° alcohol

into ketone.

Mild oxidizing agent ⇒ PCC, PDC, Collin’s reagent etc.

 O
PCC
CH3 – CH2 – OH CH3 – C –H
1° Alcohol aldehyde

OH O
PCC
CH3 – CH – CH2 – CH3 CH3 – C –CH2 – CH3
2° Alcohol ketone

PCC
3° Alcohol No reaction
(ii) Strong oxidizing agent oxidise 1° - Alcohol to carboxylic acid and
2°- Alcohol to ketone.

⊕ ⊕
Strong oxidizing gent ⇒ K2Cr2O7/H , KMnO4/ H
 O O
KMnO4 [O]
CH3 – CH2 – OH CH3 – C – H CH3 – C – OH
1°-Alcohol Carboxylic acid

OH O
KMnO4
CH3 – CH – CH3 CH3 – C – CH3
2°-Alcohol ketone

CH3
KMnO4
CH3 – C – OH No reaction
CH3
3°-Alcohol
Question The most suitable reagent for the conversion of
R — CH2—OH → R—CHO is :-

(1) CrO3 (2) PCC (Pyridinium chlorochromate)

(3) KMNO4 (4) K2Cr2O7

SOLUTION

Ans. (2)
(iii) Oppenauer Oxidation

Oxidation of alcohol with aluminum tertiary butoxide in acetone is

oppenauer oxidation.

O
Al(OCMe3)3
R – CH – R R – C – CH3
Acetone
OH ketone
2°-Alcohol

Note

It cannot oxidizes C = C, C ≡ C
R2CH – OH + Al (OCMe3)3 Me3 COH + Al (OCHR2)3

(R2CH – O)2 – Al – O
CR2
O O H
3 C – R + (Me2 CH – O)3Al C
R M M
e e
 OH
Question
Al(OCMe3)3
Acetone

SOLUTION

Ans.
 OH
Question Al(OCMe3)3
CH3 – CH – CH2 – CH = CH2
Acetone

SOLUTION

O
Ans. CH3 – C – CH2 – CH = CH2
(iv) Catalytic dehydrogenation

Vapour of primary or secondary alcohols are mixed with air and

passed over reduced copper at 300°C then primary alcohol undergo
give aldehyde and secondary alcohol give ketone tertiary alcohol
dehydration to given alkene.

Cu
R – CH2 – OH R – CHO + H2
300°C
1°-Alcohol aldehyde

O
Cu
R – CH – R R – C – R + H2
300°C
OH ketone
2°-Alcohol
 CH3
Cu
CH3
CH3 – C – OH CH2 = C + H2O
300°C
CH3
CH3
3°-Alcohol alkene

CH3 CH3
Cu
CH3 – C – OH CH2 – C + H2O
300°C
CH2 CH3 CH – CH3

3°-Alcohol alkene
(v) From vicinal diols

Carbonyl compounds are obtained on oxidation of vicinal diols by

periodic acid or Lead tetraacetate

HIO4
R—CH—CH—R 2R—CHO + H2O
or (CH3COO)4 Pb
OH OH

R
HIO4 R
R—CH—C—R 2R—CHO + O = C
or (CH3COO)4 Pb R
OH OH
(vi) MnO2 (Manganese dioxide)

It is mild oxidizing agent.

It oxidise allylic and benzylic alcohol

O
MnO2
CH2 = CH—CH—CH2 CH2 = CH—C—CH2
OH OH OH

O
MnO2
CH2 = CH—CH2—OH CH2 = CH—C—H
Preparation of carbonyl compounds

By alkaline hydrolysis of Geminal dihalide

Terminal geminal dihalide give aldehyde and other geminal dihalide

give ketones

Cl –2KCl OH
R—CH + 2KOH R—CH R—CHO+H2O
Cl OH
Terminal aldehyde
geminal
dihalide
 Cl OH
–2KCl
R—C—R + 2KOH R—C—R R—C—R+ H2O
Cl OH O
geminal ketone
dihalide
Question Which of the following on heating with aqueous KOH, produces
acetaldehyde ?
(1) CH2ClCH2Cl (2) CH3CHCCl2 (AIEEE-2009)

(3) CH3COCl (4) CH3CH2Cl

SOLUTION

Ans. (2)
Preparation of carbonyl compounds

Preparation of aldehyde from reduction

(i) Rosenmund reduction :

When acid chloride (Acyl chloride) is hydrogenated over

catalyst, palladium on barium sulphate then aldehyde is
form. This reaction is called Rosenmund reduction.
 O O
H2
CH3 – C – Cl CH3 – C H + HCl
Pd – BaSO4

O O
CH3 – C Cl CH3 – C H + HCl
H H

O O
C – Cl C–H
H2
Pd – BaSO4 + HCl
This method cannot be used in the preparation of formaldehyde
because formyl chloride is unstable at rooms temperature. It
decompose into CO + HCl

By this method only aldehydes are prepared.

(ii) Stephen reduction:

When nitriles are reacted with stannous chloride in the presence

of hydrochloric acid followed by hydrolysis given aldehyde. This
reaction is called Stephen reduction.

(i) SnCl2 + HCl

R – CN R – CHO
(ii) H3O⊕
 Mechanism
·SnCl2
H—Cl  NH
⊕ SnCl2
R – C ≡ N: R – C ≡ NH R – C ≡ NH
R · ·SnCl
2

HCl
2–
Cl Cl ⊕ NH
R H2N SnCl2
HCl
Cl—Sn—Cl R H
NH2 R
⊕ Cl Cl

H2O
SnCl4
⊕
NH3 H
⊝
Cl
H
R O R O
NH4Cl
 HCl ⊕ ⊖ SnCl2 ⊕
R–CN R – C ≡ N Cl [R – CH =NH2 ]2 SnCl62–
HCl
Aldimine chlorostannate

H2O

2R – CHO + (NH4)2SnCl6

Stephen reaction can be expressed as

⊕
SnCl2 H3O
CH3 – C ≡ N HCl
CH3 – CH = NH CH3 – CHO
Acetonitrile Acetaldimine
(Methyl
cyanide)
(iii) Diisobutylaluminumhydride (DIBAL-H)

H— Al

Since it is sterically crowded hence it is highly selective hydride

transfer reagent
O
R—C—OR’

R—C N
DIBAL-H
O R—CHO
H2 O
R—C—Cl

O R
R—C—N
R
Preparation of aromatic aldehyde

(i) Etard reaction

Chromyl chloride oxidises methyl group to a chromium complex,

which on hydrolysis gives corresponding benzaldehyde.

CH3 CH(OCrOHCl2)2
CS2
+ CrO2Cl2

Toluene Chromium complex

H3O+
CHO

Benzaldehyde
Toluene or substituted toluene is converted to benzylidene
diacetate on treating with chromic oxide in acetic anhydride. The
benzylidene diacetate can be hydrolyzed to corresponding
benzaldehyde with aqueous acid.

CH3 CH(OCOCH3)2
273–283K
+ CrO3 + (CH3CO)2O

H3O+ 

CHO

Benzaldehyde
(ii) Side chain chlorination followed by hydrolysis

Side chain chlorination of toluene gives benzal chloride, which on

hydrolysis gives benzaldehyde.

CH3 CHCl2 CHO

Cl2/h H2O
373K
Toluene Benzal chloride Benzaldehyde
NUCLEOPHILIC ADDITION
OF
CARBONYL COMPOUNDS
 Nucleophilic Addition

Addition of H2O General Introduction

Addition of NH2-Z Addition of HCN

Addition of ROH Addition of sodium Hydrogen sulphite

Addition of chloroform Addition of Grignard reagent

Addition of PCl5
 Nucleophilic Addition

General Introduction

Addition reaction where a p-bond is removed by the creation of

two new covalent bonds by the addition of a nucleophile is called
nucleophilic addition reaction (AdN).

Nucleophilic addition reactions are most common on carbonyl

compounds.
The general form is

O OH
H+
C + Nu– C
Nu
Nucleophilic Addition

The mechanism involves two steps. In the first and the slow step,
the Nu– approaches at 45° angle to the plane of C = 0 and adds, to
carbon. A tetrahedral alkoxide ion intermediate is produced.

Step-1
O O–
Slow
C Nu– C
Nu
Tetrahedral
intermediate
Nucleophilic Addition

In the second step, the intermediate gets protonated.

Step-2
O– OH

C + H3O+ C
Nu Nu
 Classification of Nucleophile

Nucleophiles can be negatively charged (Nu–) or neutral (Nu).

Negative Neutral
Nucleophile Nucleophile

H–O– (Hydroxide)

: : : :
(water) H–O–H

R3–C– (Carbanion) (Alcohol) R–O–H

RO– (Alkoxide ion) (Ammonia) NH3

(Cyanide)
∘
N  C– (1 -Amine)

:
R – NH2

H–C  C– (Acetylide) (Thioalcohol) R – SH

:
In Case of stronger nucleophiles

Strong nucleophiles (anionic) add directly to the C = O to form the

intermediate alkoxide. The alkoxide is then protonated on work up
with dilute acid.
O O– OH
H+
C C C
work-up
Nu Nu
Nu–

Examples of such nucleophilic systems are RMgX, RLi, LiAlH4, NaBH4.

In Case of weaker nucleophiles

Weaker nucleophiles (neutral) require that C = O be activated prior

to the attack. This is achieved by protonating the carbonyl oxygen,
which makes the system more electrophilic.

+
O OH OH OH
: :
+
H Nu–H –H+
C C C C
+ Nu
Nu–H

Examples of such nucleophilic systems are H20 , R-OH, R-NH2, etc.

Note

In general, aldehydes are more reactive than ketones in AdN

reaction.

Transition state for addition is less crowded and lower in energy for
an aldehyde than for a ketone.

Aldehydes have one large substituent bonded to the C = 0 group, a

ketone has two.

Aldehyde C = O group is more polarisable than that of ketone.

Note

Ketones have more alkyl groups, which stabilise the C = 0 carbon

inductively.

Electron withdrawing groups raise the reactivity of C = 0 group while

Electron donating groups groups lower it.
(iii) Gatterman–Koch reaction

When benzene or its derivative is treated with carbon monoxide and

hydrogen chloride in the presence of anhydrous aluminum chloride or
cuprous chloride, it gives benzaldehyde or substituted benzaldehyde.

CHO
CO, HCl
Anhyd. AlCl3/CuCl

Benzene Benzaldehyde

Note

This reaction is not applicable to phenol and phenol ether substrates.

(iv) Gatterman aldehyde synthesis

When benzene is treated with liquid HCN and HCl gas in presence of
anhydrous AlCl3 it yields aromatic aldehyde.

H H
AlCl3 
HCl + HCN N
Cl AlCl3

H H H H

+ N –AlCl3 +H2O
NH –NH3 O
Cl AlCl3
Benzene
(v) Reimer–Tiemann reaction

Phenol on refluxing with chloroform and NaOH (aqueous) followed by

acid hydrolysis yields o-hydroxy benzaldehyde (As major product).
When CCl4 is used salicylic acid is formed

OH OH OH
CHO
(1) CHCl3/NaOH/
+
(2) H

(Major) CHO
(Minor)
E formation →
Cl Cl Cl
⊝
RDS slow
H—C Cl + NaOH C Cl C
–Cl
Cl Cl ⨁ Cl
E
1. RDS of Reimer-tiemann reaction is formation of carbene so this
reaction is independent of aromaticity.

2. If NaOH is used as base then attack of dichloro carbene is favoured

at ortho-position because chelation take place is in between Na+ and
attacking carbene.

3. If this chelation is non-effective then para attack is favoured.

4. If KOH or larger metal containing base is used then steric factor

dominates over chelation and para attack favoured.
 ⊝
CHCl3 + OH⊝ → H2O + CCl3
⊝
CCl3 + → :CCl2 + Cl⊝

OH O⊝ Cl ⊝
O O
⊝ Cl
H Cl
OH–, H2 O : CCl2
Cl
H

OH⊝

H
OH H O⊝ O

O Cl
Example OH OH

+ CHCl3 + NaOH

CHO
OH OH
me
+ CHCl3 + NaOH

CHO
OH O

+ CHCl3 + NaOH

CHCl2
In the Reimer–Tiemann reaction, the o–isomer predominates, but if one
of the o–position is occupied, the aldehyde group tends to go the p–
position;
e.g. guaiacol forms vanillin.

OH OH
O O
CH3 NaOH CH3
CHCl3

guaiacol O

vanillin.
Preparation of carbonyl compounds

Preparation of Ketones

(i) From Dialkyl Cadmium

Acid chloride reacts with dialkyl cadmium to force ketone.

 O O
2R’ – C – Cl + CdR2 2R’ – C – R + CdR2

X
CdCl2 + 2RMgx CdR2 + 2Mg
Cl
Dialkyl cadmium

O
O
R’– C – Cl R
Cd 2R’– C – R + CdCl2
R
R’– C – Cl
O
 Mechanism
⊖
O
O O
+ –
2R’– C – Cl + Cd R2 R’ C Cl Cd2 2R’– C – R + CdCl2
+

R 2

By this method only ketones are prepared.

Acid chloride reacts with organocopper compounds to form ketone.

O O
C – Cl C – CH3
+ (CH3)2 CuLi + CH3Cu + LiCl
 O
Question
2CH3 – C – Cl + (Ph – CH2)2 Cd

SOLUTION

O
Ans. 2CH3 – C – CH2 – Ph + CdCl2
(ii) From nitrile :

Alkane nitrile reacts with Grignard reagent followed by acidic

hydrolysis to form ketone.

– ⊕
H2O/H
R’– C ≡ N + R MgX R’– C = NMgx R’– C = O
R R

H – C ≡ N + RMgx R—H
(major)

H H
H3O⊕
C = NMgX C=O
R R
(minor)
(iii) Friedal crafts acylation reaction

Benzene when reacted with acid chloride in presences of

anhydrous AlCl3 gives ketone.

O
O C – CH3
Anhyd. AlCl3
+ CH3 – C – Cl + HCl
Acetophenone

O O
+ C Anhyd. AlCl3 C
Cl Cl
Excess Benzophenone
 O
Question
C – Cl
+ Anhyd. AlCl3

SOLUTION

O
C + HCl
Ans.
Benzophenone
(iv) By Dry distillation of calcium salts

Dry distillation of calcium or barium salts of carboxylic acid give

carbonyl compound.

Calcium or Barium salt of formic acid given aldehyde and all other
salt of carboxylic acid given ketone.

O
H–C–O O
Ca Δ
H – C – H + CaCO3
H–C–O
O
 O
CH3 – C – O O
Ca Δ
CH3 – C – CH3 + CaCO3
CH3 – C – O
O

When a mixture of two salts is heated, three products are formed

in which cross product is major product.

O O
CH3 – C – O O–C–H O O O
Δ
Ca + Ca CH3 – C – H + H – C – H + CH3 – C – CH3
CH3 – C – O O–C–H Major
+ 2CaCO3
O O
 O O
Question
CH3 – CH2 – C – O O – C – CH3 Dry distillation
Ba Ba
CH3 – CH2 – C – O + O – C – CH3
O O

SOLUTION

O O O
Ans. C2H5 – C – C2H5 + CH3 – C – CH3 + C2H5 – C – CH3 + 2CaCO3
Major
 O O
Question
Ph – C – O O–C–H Dry distillation
Ba Ba
Ph – C – O + O – C –H
O O

SOLUTION

O O O
Ans. Ph – C – Ph + H – C –H + Ph – C – H + 2CaCO3
Major
 O
Question C–O dry distillation
Ca
C–O
O

SOLUTION

Ans.
By passing the vapours of carboxylic acids over manganous oxide
(MnO) at 300°C. Carbonyl compounds are formed.

This method is analogous to the above method.

O O O
MnO
H – C – OH + HO – C – H Δ
H – C – H + CO2 + H2O

O O O O
MnO
CH3 – C – OH + HO – C – H CH3 – C – H + H – C – H
Δ
(Major)
O
+ CH3 – C – CH3 + CO2 + H2O
 O O O
MnO
CH3 – C – OH + HO – C – CH3 Δ
CH3 – C – CH3 + CO2 + H2O

(v) By heating 𝛽 – Keto carboxylic acid

O O O

CH3 – C – CH2 – C – OH CH3 – C – CH3 + CO2
(vi) From Alkyl lithium and Carboxylic acid

O OLi OH
H3O
R—C—OH + 2R Li R—C—OLi R—C—OH
R R
–H2O

O
R—C—R

EXAMPLE
OLi O
COOH C—OLi C—CH3
H3O+
+ 2CH3Li CH3
(vii) Hydroboration Oxidation of alkynes using disiamylborane

(C5H11)2BH :- disiamylborane

An important application of disiamylborane is its addition reaction to

terminal alkynes.

Terminal alkynes give aldehyde and Nonterminal alkynes gives

ketones.
 (C5H11)2BH / THF tautomerise
CH3–CCH (II) H2O / OH⊝
CH3—CH=CH CH3—CH2—C—H
OH O
Aldehyde

(C5H11)2BH / THF tautomerise Me—C—Et

CH3–CC–CH3 CH3—C=CH—CH3
(II) H2O / OH⊝
O
OH
Ketone

Hydroboration of internal alkynes is not a particularly useful

procedure because a mixture of products will often be obtained ,
unless the triple- bond is symmetrically substituted.
Physical
properties

Boiling point

Solubility

State

Odour
Boiling point

Boiling point of compounds having same functional group increases

with increase in molecular weight.

EXAMPLE

CH3COCH3 CH3CH2COCH3 CH3CH2COCH2CH3

> >
Boiling point of compounds having same molecular formula but with
different functional group depends upon interaction between them.

Alcohol > Carbonyl compounds > ether > Alkane

Compound B.p. M.wt.

n-Butane 273 58
Methoxyethane 281 60
Propanal 322 58
Acetone 329 58
Propan-1-ol 370 60
Alcohol > Carbonyl compounds > ether > Alkane

This is because in alcohols intermolecular H-bonding is present but

in carbonyl compounds H-bonding doesn't exist, instead dipole-
dipole Vander Waal force of attraction
−
is present.
𝛅
O
R 𝛅+ 𝛅
−
𝛅+ 𝛅+ −
𝛅 𝛅+ R
C=O H H O=C
R R‘

In ether, bond are not highly polar than the carbonyl, hence its
boiling pint is lower than the alcohol and carbonyl compounds.

Alkanes are non-polar so it has lowest boiling point than ether,

alcohol and carbonyl compound.
Question Arrange the following compounds in the increasing order of their boiling
points:

CH3CH2CH2CHO, CH3CH2CH2CH2OH, H5C2 –O-C2H5 , CH3CH2CH2CH3

(i) (ii) (iii) (iv)

SOLUTION

Ans. (ii) > (i) > (iii) > (iv)

Physical
properties

Boiling point

Solubility

State

Odour
Solubility

C1 to C3 (formaldehyde, acetaldehyde and propionaldehyde) and

acetone are freely soluble in water because they can form H—
bond with water molecule.

C4 onwards are insoluble in water but soluble in organic solvent

like benzene, ether, methanol, chloroform etc.
Physical
properties

Boiling point

Solubility

State

Odour
 State

Only formaldehyde is gas while all other aldehyde up to C11 are

liquids.

Ketones up to eleven carbon atoms are volatile liquids.

All other carbonyl compound, C12 and onwards are solid.

Physical
properties

Boiling point

Solubility

State

Odour
Odour

Lower aldehydes give unpleasant sharp pungent odour.

As the number of carbon atoms increases the odour becomes less

pungent and more fragrant, hence they are used in blending of
perfumes and flavoring agent.

Acetone is inflammable liquid.

Uses of Aldehydes and Ketones

Act as solvents.

Act as starting materials and reagents for the synthesis of other

products.

Formalin (40% solution of formaldehyde)- Used for preserving

biological specimens, bakelite, urea, formaldehyde glues and other
polymers products.

Acetaldehyde used in the manufacture of acetic acid, ethyl acetate,

vinyl acetate, polymers and drugs.
Uses of Aldehydes and Ketones

Benzaldehyde used in perfumery and in dye industries.

Butyraldehyde, vanillin, camphor, etc., are well known for their

odours and flavours.

Acetone and ethyl methyl ketone are common industrial solvents.

Question Which of the following compounds will show highest dipole moment ?

O O
(I) O (II) (III) O (IV)
O

(1) (II) (2) (III) (3) (I) (4) (IV)

[JEE-Main-
2017]

Ans. (3)
NUCLEOPHILIC ADDITION
OF
CARBONYL COMPOUNDS
 Nucleophilic Addition

Addition of H2O General Introduction

Addition of NH2-Z Addition of HCN

Addition of ROH Addition of sodium Hydrogen sulphite

Addition of chloroform Addition of Grignard reagent

Addition of PCl5
 Nucleophilic Addition

General Introduction

Addition reaction where a p-bond is removed by the creation of

two new covalent bonds by the addition of a nucleophile is called
nucleophilic addition reaction (AdN).

Nucleophilic addition reactions are most common on carbonyl

compounds.
The general form is

O OH
H+
C + Nu– C
Nu
Nucleophilic Addition

The mechanism involves two steps. In the first and the slow step,
the Nu– approaches at 45° angle to the plane of C = 0 and adds, to
carbon. A tetrahedral alkoxide ion intermediate is produced.

Step-1
O O–
Slow
C Nu– C
Nu
Tetrahedral
intermediate
Nucleophilic Addition

In the second step, the intermediate gets protonated.

Step-2
O– OH

C + H3O+ C
Nu Nu
 Classification of Nucleophile

Nucleophiles can be negatively charged (Nu–) or neutral (Nu).

Negative Neutral
Nucleophile Nucleophile

H–O– (Hydroxide)

: : : :
(water) H–O–H

R3–C– (Carbanion) (Alcohol) R–O–H

RO– (Alkoxide ion) (Ammonia) NH3

(Cyanide)
∘
N  C– (1 -Amine)

:
R – NH2

H–C  C– (Acetylide) (Thioalcohol) R – SH

:
In Case of stronger nucleophiles

Strong nucleophiles (anionic) add directly to the C = O to form the

intermediate alkoxide. The alkoxide is then protonated on work up
with dilute acid.
O O– OH
H+
C C C
work-up
Nu Nu
Nu–

Examples of such nucleophilic systems are RMgX, RLi, LiAlH4, NaBH4.

In Case of weaker nucleophiles

Weaker nucleophiles (neutral) require that C = O be activated prior

to the attack. This is achieved by protonating the carbonyl oxygen,
which makes the system more electrophilic.

+
O OH OH OH
: :
+
H Nu–H –H+
C C C C
+ Nu
Nu–H

Examples of such nucleophilic systems are H20 , R-OH, R-NH2, etc.

Note

In general, aldehydes are more reactive than ketones in AdN

reaction.

Transition state for addition is less crowded and lower in energy for
an aldehyde than for a ketone.

Aldehydes have one large substituent bonded to the C = 0 group, a

ketone has two.

Aldehyde C = O group is more polarisable than that of ketone.

Note

Ketones have more alkyl groups, which stabilise the C = 0 carbon

inductively.

Electron withdrawing groups raise the reactivity of C = 0 group while

Electron donating groups groups lower it.
 The order of reactivity of aldehyde/ketone towards Nucleophile.

HCHO >CH3CHO > CH3—C—CH3 > Ph—C—CH3 > Ph—C—Ph

|| || ||
O O O

More is the 𝛿+ change on carbonyl carbon, more will be reactivity

towards nucleophile.

Aromatic aldehydes are less reactive than aliphatic aldehydes

toward AdN reactions. Electron donating resonance effect of
aromatic ring makes C = 0 less electrophilic.
O O– O–
C +
C C
H H H

+
Question Pick the choice(s) that correctly describe(s) the decreasing order of
reactivity towards AdN.
O O O O O O

(A) CH3―C ― C ― C ― CH3 > CH3―C ― C ― CH3 > > CH3―C ― CH3

(B) Br ― CH2―CHO > CH3 ― CHO > CH3COCH3> Br ― CH2 ― CO ― CH3

+
(C) (CH3)2C = OH > (CH3)2C = O > (CH3)2C = NH

(D) H3COCH3 > Cl― CH2COCH3 > O2N ― CH2COCH3

Ans. (A,C)
 Nucleophilic Addition

Addition of H2O General Introduction

Addition of NH2-Z Addition of HCN

Addition of ROH Addition of sodium Hydrogen sulphite

Addition of chloroform Addition of Grignard reagent

Addition of PCl5
Nucleophilic Addition of H2O (Hydration)

Most carbonyl compounds undergo reversible hydration in aqueous

solution:

In general, we can quote as follows :-

Keq OH
R2C = O + H2O R2C
OH
Carbonyl
Gem diol
compound

Gem diol
Keq = [Carbonyl compound]
Note that,

Keq ∝ stability of gem diol

∝ electrophilicity of C=O

Aldehydes and ketones react with water to give 1, 1-diol (gem diol).
Hydration reaction is reversible.

CH3 CH3 OH
C O + H2O C
CH3 CH3 OH
0.1%
Base catalysed nucleophilic addition of H2O

Base catalysed addition of H2O is piloted by HO–, a more powerful

nucleophile than H2O.

O O– OH
H–O–H
OH–
C CH3 — C — CH3 CH3 — C — CH3
CH3 CH3
OH OH

Though this reaction is rapid, but the equation still lies on the side
of acetone and water.
 Acid catalysed nucleophilic addition of H2O

Protonation of C = O makes it more electrophilic in acid catalyzed

hydration

+
O OH OH OH

:
H3O+ H2O: –H+
C C CH3 — C — CH3 CH3 — C — CH3
CH3 CH3 CH3 CH3
OH2 OH
+

But here also equation still lies on the side of acetone and water.
Keq. (at 20°C) for some aldehyde and ketone is given below.

Compound Keq. (at 20°C)

(i) HCHO 2 × 103

(ii) CH3CH=O 1.4

(iii) CH3COCH3 2 × 10–3

So for most aldehyde and all

ketones equilibrium is shifted to
backward direction. So gemdiol
form cannot be isolated.
Factors that will help isolation of gemdiol

Steric factor

Steric factor can retard as well as can promote hydration.

OH
O + H2O
OH
(90%)

120° − 60° 109.5° − 60°

Angle strain = = 30° Angle strain = = 24.25°
2 2

cyclopropanone form readily isolable hydrate. Here during hydrate

formation there is a relief of angle strain in product side.
 Hydrogen bonding

In all the below cases gemdiols are stable due to intramolecular

hydrogen bonding.

H
Cl O
(i) Cl3C–CH=O + H2O Cl—C–CH (chloral hydrate)
Cl O
chloral H
Stable
(5 membered chelation
due to H bonding)
 H
F O
(ii) F3C–CH=O + H2O F—C–CH (chloral hydrate)
F O
chloral H
Stable
(5 membered chelation
due to H bonding)

H
O O O
(iii) Ph–C–C–C–Ph + H2O Ph–C–C——C–Ph (Hydrate stable)
O O O O
(Diphenyl H
propantrione) Stable
(5 membered chelation
due to H bonding)
 O O H
O (Ninhydrin Hydrate)
(iv) O + H2O
O
O O
H
(Ninhydrin)
Stable
(5 membered chelation
due to H bonding)
 Arrange Order of keq towards H2O :
Question
CH=O CH=O CH=O

NO2 OMe

(i) (ii) (iii)

Ans. (i) > (ii) > (iii)

 Arrange Order of keq towards H2O :
Question
ClCH2CH=O Cl2CHCH=O Cl3C–CH=O
(i) (ii) (iii)

Ans. (i) (ii) (iii)

> >
 Rank the following compounds in order of decreasing amount of
Question hydrate present at equilibrium.
O O
CHO Br CHO
Br

(I) (II) (III) (IV)

(A) III > I > II > IV (B) III > II > I > IV

(C) I > III > II > IV (D) I > II > III > IV

Ans. (A)
 The hydration reaction of carbonyl compounds proceeds as follows.
Question OH
C = O + H2O C
OH
Out of the following, the extent of hydration reaction towards the
product side is highest in the case of
H H
O2N Cl
O O
(A) (B)

Cl Cl
(C) O (D) O
Cl H3C
Ans. (C)
 Nucleophilic Addition

Addition of H2O General Introduction

Addition of NH2-Z Addition of HCN

Addition of ROH Addition of sodium Hydrogen sulphite

Addition of chloroform Addition of Grignard reagent

Addition of PCl5
Addition of HCN (Cyanohydrin formation)

Aldehydes and ketones react with hydrogen cyanide (HCN) to yield

cyanohydrins. This reaction occurs very slowly with pure HCN.

Addition of HCN is reversible and base catalysed. Equilibrium

favours adduct.

⊝
O O CN HO CN
C C C
H CN– H HCN H

Mandelonitrile
Mechanism

Step-1
– –
HCN + OH H2O + CN

Step-2

⊝ O– H+ OH
C = O + CN C C
CN CN
(Tetrahedral (Cyanohydrin)
intermediate)
 (i) KCN H3O+ 
Question CH3CH=O
(ii) H+
X1 Y1 Z1. what is the X1, Y1, Z1 ?

O
Ans.
O—C
X1  CH3CH–CN Y1  CH3CH–CO2H Z1  HC3–CH CH–CH3
| | C—O
OH OH O
 HCN
± glyceraldehyde + KOH
How many products are possible ?
Question

Ans. (Total 4 product (2 pair of racemic mixtures)

 O
Question
HCN LiAlH4 NaNO2 + HCl
+ Base
X Y Z.What are X, Y, & Z ?

O
OH OH
Ans. X= Y= Z=
CN CH2–NH2
 (JEE-Main-
Question O OH 2021)
“X” LiAlH4
CN “Y”
H HCN, H2O H3O
(Major product)
H
Consider the given reaction, Identify 'X' and 'Y' :
OH OH
(1) X - NaOH Y– NH
H (2) X – HNO3 Y–
H NH2
OH OH
(3) X – NaOH Y– (4) X – HNO3 Y– NH2
H NH2 H

Ans. (3)
 The final product 'A' in the following reaction sequence
Question
HCN 95% H2SO4
CH3CH2―C―CH3 ? A
Heat
(JEE-Main-
O
2022)
CH3
(1) CH3―CH=C―COOH (2) CH3―CH=C―CN
CH3
OH
(3) CH3―CH―C―COOH (4) CH3―CH=C―CONH2
CH3 CH3

Ans. (1)
 The number of stereoisomers formed in a reaction of (±) Ph(C=O)
Question
C(OH)(CN)Ph with HCN is_____.
(JEE-Main-
2022)

Ans. (3)
 Nucleophilic Addition

Addition of H2O General Introduction

Addition of NH2-Z Addition of HCN

Addition of ROH Addition of sodium Hydrogen sulphite

Addition of chloroform Addition of Grignard reagent

Addition of PCl5
Addition of NH2-Z (Addition of ammonia and its derivative)

Nucleophiles such as NH3 and its derivative NH2-Z add to the

carbonyl system.

The reaction is reversible and catalysed by acid (at pH = 5 to 6

reaction is optimum).

The equation favours the product formation due to rapid

dehydration of the intermediate to form >C=N-Z
In general, we can quote as follows :-

(a) When the amine is primary

O Z
Z–NH2 N
C + H2O
C
pH = 5 to 6

An imine

Mechanism

+ + NH2–Z OH –H2O
C=O + H C=OH C + C=N–Z + H+
NH2–Z
(b) When the amine is secondary

pH = 5 to 6
O + N + H2O
N
H
An enamine
A
secondary
amine
Mechanism + +
H H
R

⊝
⊝
⊝OH

⊝
⊝O⊝ ⊝OH
R R

⊝
O⊝ + R―NH

⊝
+N +N N

⊝
R R R R
H H
B– Neutral
tetrahedral
intermediate
A carbinolamine

H +
R + R O—H

⊝
HB + N N
R R N―R
⊝
Enamine H
B– R
+ H2O
Note

Such nucleophilic addition reactions of ammonia derivatives across

carbonyl compounds proceed at maximum rate at an intermediate
pH range 4–5 but slow down as pH increases and decreases.

In low acidic medium, the catalytic advantage does not exist.

In high acidic medium the nucleophilicity of the ammonia derivative

is destroyed
 Z Reagent Derivative Product

–H NH3 (Ammonia) >C=NH Imine

–R RNH2 (1° amine) >C=NR Schiff's base

NH2OH >C=N–OH Oxime

–OH (Hydroxylamine)

NH2–NH2 >C=N–NH2 Hydrazone

–NH2
(Hydrazine)
NH2–NH–Ph >C=N–NHPh Phenyl
–NH—
(Phenyl hydrazine) hydrazone
–NH NO2 2,4-D.N.P. C=N–NH NO2
2,4-Dinitrophenyl 2,4-Dinitrophenyl
hydrazine hydrazone
NO2 NO2
NH2–NH–C–NH2
–NH–C–NH2
O C=N–NH–C–NH2 (Semicarbazone)
O (Semicarbazide) O
Mechanism

Step-1
– –
HCN + OH H2O + CN

Step-2

⊝ O– H+ OH
C = O + CN C C
CN CN
(Tetrahedral (Cyanohydrin)
intermediate)
 (i) KCN H3O+ 
Question CH3CH=O
(ii) H+
X1 Y1 Z1. what is the X1, Y1, Z1 ?

O
Ans.
O—C
X1  CH3CH–CN Y1  CH3CH–CO2H Z1  HC3–CH CH–CH3
| | C—O
OH OH O
 HCN
± glyceraldehyde + KOH
How many products are possible ?
Question

Ans. (Total 4 product (2 pair of racemic mixtures)

 O
Question
HCN LiAlH4 NaNO2 + HCl
+ Base
X Y Z.What are X, Y, & Z ?

O
OH OH
Ans. X= Y= Z=
CN CH2–NH2
 (JEE-Main-
Question O OH 2021)
“X” LiAlH4
CN “Y”
H HCN, H2O H3O
(Major product)
H
Consider the given reaction, Identify 'X' and 'Y' :
OH OH
(1) X - NaOH Y– NH
H (2) X – HNO3 Y–
H NH2
OH OH
(3) X – NaOH Y– (4) X – HNO3 Y– NH2
H NH2 H

Ans. (3)
 The final product 'A' in the following reaction sequence
Question
HCN 95% H2SO4
CH3CH2―C―CH3 ? A
Heat
(JEE-Main-
O
2022)
CH3
(1) CH3―CH=C―COOH (2) CH3―CH=C―CN
CH3
OH
(3) CH3―CH―C―COOH (4) CH3―CH=C―CONH2
CH3 CH3

Ans. (1)
 The number of stereoisomers formed in a reaction of (±) Ph(C=O)
Question
C(OH)(CN)Ph with HCN is_____.
(JEE-Main-
2022)

Ans. (3)
 Nucleophilic Addition

Addition of H2O General Introduction

Addition of NH2-Z Addition of HCN

Addition of ROH Addition of sodium Hydrogen sulphite

Addition of chloroform Addition of Grignard reagent

Addition of PCl5
Addition of NH2-Z (Addition of ammonia and its derivative)

Nucleophiles such as NH3 and its derivative NH2-Z add to the

carbonyl system.

The reaction is reversible and catalysed by acid (at pH = 5 to 6

reaction is optimum).

The equation favours the product formation due to rapid

dehydration of the intermediate to form >C=N-Z
In general, we can quote as follows :-

(a) When the amine is primary

O Z
Z–NH2 N
C + H2O
C
pH = 5 to 6

An imine

Mechanism

+ + NH2–Z OH –H2O
C=O + H C=OH C + C=N–Z + H+
NH2–Z
(b) When the amine is secondary

pH = 5 to 6
O + N + H2O
N
H
An enamine
A
secondary
amine
Mechanism + +
H H
R

∶
∶
∶ OH

∶
∶ O∶ ∶ OH
R R

∶
O∶ + R―NH

∶
+N +N N

∶
R R R R
H H
B– Neutral
tetrahedral
intermediate
A carbinolamine

H +
R + R O—H

∶
HB + N N
R R N―R
∶
Enamine H
B– R
+ H2O
Note

Such nucleophilic addition reactions of ammonia derivatives across

carbonyl compounds proceed at maximum rate at an intermediate
pH range 4–5 but slow down as pH increases and decreases.

In low acidic medium, the catalytic advantage does not exist.

In high acidic medium the nucleophilicity of the ammonia derivative

is destroyed
 Z Reagent Derivative Product

–H NH3 (Ammonia) >C=NH Imine

–R RNH2 (1° amine) >C=NR Schiff's base

NH2OH >C=N–OH Oxime

–OH (Hydroxylamine)

NH2–NH2 >C=N–NH2 Hydrazone

–NH2
(Hydrazine)
NH2–NH–Ph >C=N–NHPh Phenyl
–NH—
(Phenyl hydrazine) hydrazone
–NH NO2 2,4-D.N.P. C=N–NH NO2
2,4-Dinitrophenyl 2,4-Dinitrophenyl
hydrazine hydrazone
NO2 NO2
NH2–NH–C–NH2
–NH–C–NH2
O C=N–NH–C–NH2 (Semicarbazone)
O (Semicarbazide) O
Case -1 (when Z= –H)
H
O N
NH3 + H2O
C C
pH = 5 to 6
R R’ R R’
Carbonyl An imine
compound

Case -2 (when Z= –OH)

O OH
N
C NH2—OH + H2O
C
pH = 5 to 6
R R’ R R’
Carbonyl
compound An Oxime
Case -3 (when Z= –R)

R
O N
RNH2 + H2O
C C
pH = 5 to 6
R H R H
An Schiff’S Base
aldehyde

Schiff base formed when 1° aliphatic/aromatic amine reacts with

aldehyde.
Case -4 (when Z= –NH2)

NH2
O N
C + H2O
NH2—NH2 C
R R’ pH = 5 to 6 R R’
Carbonyl
compound An hydrazone

Case -5 (when Z= –NH—Ph)

O NHPh
N
C + H2O
NH2—NH—Ph C
R R’ R R’
pH = 5 to 6
Carbonyl
compound An phenylhydrazone
Case -6 (when Z= –NH NO2 )

NO2

O
C 2,4–D.N.P R
C=N–NH NO2 + H2O
R
R R’ pH = 5 to 6
NO2
Carbonyl
compound 2,4-Dinitrophenyl
hydrazone

2,4 DNP derivative are yellow, orange or red solids it is used to

identify all aldehydes and ketones.

2.4.D.N.P. also used to distinguish a carbonyl compound from

noncarbonyl compound.
 Case -7 (when Z= –NH–C–NH2 )
O

O
C Semicarbazide R
R C=N–NH–C–NH2 + H2O
R R’ pH = 5 to 6 O
Carbonyl
compound Semicarbazone

Semicarbazone are white crystals.

 H2/Ni
Question CH3CH=O + NH3 X1 Y1. What are X1 and Y1 ?

Ans. X1  CH3CH=NH ; Y1  CH3CH2–NH2

 CH=CH2
Question
Br2 Alcoholic KOH HgSO4 + H2SO4(1%)
X1 X2 X3
(CCl4) Followed by NaNH2

NH2–NH2
What are X1, X2, X3 and X4 ?

X4

CH–CH2 CCH
Ans. X1  X2 
Br Br

CH3
C–CH3 X4  C=N–NH2
X3 
O
Question The smallest aldehyde and its next higher homologue reacts with
NH2OH. What are the total number of organic product.

Ans. (3)
 What will be the product when formaldehyde reacts with ammonia ?
Question
Find out number of N–N linkage in the product.

Ans.
N
Structure of Urotropin : , N N , N–N linkage in the product = 0
N
 Aliphatic Ketone (M.wt. = 86) when reacts with NH2–NH2, find out
Question
number of possible hydrozones in product side.

Ans. 6 Products (Hydrazone)

 Compound X(molecular formula : C3H6O) gives –ve 2.4.D.N.P. test.
Question
Also X does not react with sodium methyl. What is X ?

Ans. X : CH3O–CH=CH2
 Which compound reacts with aldehyde to from hydrazone (C=N–NH
Question
linkage) and yellow ppt with AgNO3 ?

+ – + –
(A) NH2–NH3Cl (B) NH–NH3Cl

+ – + –
(C) NH3I (D) O2N NH–NH3Br
NO2

Ans. (D)
Question Which one of the following compounds will give orange precipitate when
treated with 2,4-dinitrophenyl hydrazine ?
[JEE-Main-
O 2021]
OH
OCH2CH3
(1) (2)

O
O O

C–OH CH3
(3) (4)

OH

Ans. (4)
 Nucleophilic Addition

Addition of H2O General Introduction

Addition of NH2-Z Addition of HCN

Addition of ROH Addition of sodium Hydrogen sulphite

Addition of chloroform Addition of Grignard reagent

Addition of PCl5
Addition of sodium Hydrogen sulphite (NaHSO3)

Sodium hydrogen sulphite addes to aldehyde and ketone to form the

addition products.

R R OH
O + NaHSO3 C
H H SO3Na
Mechanism

In highly basic medium HSO−

3 + OH ⇌ SO3 + H2 O, SO3 is the attacking
− 2− 2−

nucleophile.

O–
R R O– H2O R OH
C = O+ S=O C C
H H SO3– H SO3Na
O–
(Water soluble
crystalline
compound)
Note

The position of the equilibrium lies largely to the right hand side to
most aldehyde and to the left for most ketone

This reaction is applicable for all aldehyde, ketones having

ketomethyl groups and cyclic ketones O
O
;
.

The product if heated with dilute acid, carbonyl compound can be

regenerated.
Note

This reaction is used as means of separating carbonyl compounds

from non-carbonyl compounds.
Question Given below are two statements :
Statement I : The nucleophilic addition of sodium hydrogen sulphite to an
aldehyde or a ketone involves proton transfer to form a stable ion.
Statement II : The nucleophilic addition of hydrogen cyanide to an
aldehyde or a ketone yields amine as final product.
In the light of the above statements, choose the most appropriate answer
from the options given below :
(1) Both Statement I and Statement II are true. [JEE-Main-
2021]
(2) Statement I is true but Statement II is false.
(3) Statement I is false but Statement II is true.
(4) Both Statement I and Statement II are false.

Ans. (2)
 Nucleophilic Addition

Addition of H2O General Introduction

Addition of NH2-Z Addition of HCN

Addition of ROH Addition of sodium Hydrogen sulphite

Addition of chloroform Addition of Grignard reagent

Addition of PCl5
Addition of ROH (hemiacetal,acetal,hemiketal,ketal formation)

Aldehydes react with one equivalent of monohydric alcohol in

presence of dry HCl to yield alkoxy alcohol inter mediate, known as
hemiacetal, which further react with one more molecule of alcohol
to give a gem dialkoxy compound known as acetal.
For Aldehyde :

••
••
H—Cl
••
R'OH OR' H+ OR' –H2O +
C R—C—H RCH RCH RCH–OR'
+
R H OH OH2
+O R'OH
H Hemiacetal
𝒂-hydroxy ether
OR'
H+ + RCH
OR'
Acetal
gemdiether
For ketone :
O

••
••
HCl/R'OH H+/R'OH
C OH OR'
R2C R2C
R R OR' OR'
(hemiketal) (ketal)

For ketone the reaction lies to reactant side, but they can offen be
made reactive with 1,2 diol (Ethylenediol) as shown below.
CH2OH
dry HCl
R CH2OH R O—CH2
C=O C + H2O
R R O—CH2
Ethylene glycol
ketal

The above reaction is used to protect carbonyl group.

Note

So acetal and ketal categories are of the following types.

OH OH
C C
H OR OR
Hemi acetal Hemi ketal

OR OR
C C
H OR’ OR’

acetal ketal
To shift the equilibrium in forward direction (acetal/ketal
formation), the H2O has to be removed or by using excess acid
catalyst (passing HCl continuously).

Hemi acetal / hemi ketal, both are highly unstable in acidic

conditions as well as basic condition .
OH
C H+
C=O + ROH
H OR H
Hemi acetal

OH –
C OH
C=O + ROH
–H2O
H OR H
Hemi acetal
acetal / ketal, both are highly unstable in acidic conditions and can
be hydrolysed into carbonyl compound.

OR
C H+ / H2O
C=O + ROH + R’OH
H OR’ H
acetal

acetal / ketal, both are highly stable in basic conditions

OR Base
C No reaction (acidic Hydrogen not available)

H OR’
acetal
 O O
Question

CO2Et CH2OH

To carry out the following conversion in three steps, what should be the
reagents used.

Ans. CH2OH dry HCl ; LiAlH ; H O+

4 3
CH2OH
Question O O

Cl CH–CH3
OH
To carry out the following conversion in four steps, what should be the
reagents used.

Ans. CH3OH (2 eq.) /H+ ; Mg(R2O) ; CH3CHO ; H3O+

 CH2OH
Question CH2OH Mg MeCH2CH=O
4 –bromobutanal X Y Z
dry HCl Et2O H2O+

What are X, Y, Z ?

Ans. O O
X  CH2–CH2–CH2–CH Y  CH2–CH2–CH2–CH
O O
Br MgBr

Z CH2–CH2–CH2–CH=O
HO–CH–Et
 Acetone
Cis cyclopentane 1,2 diol X. What is X ?
Question Dry HCl

Ans. O
(X)
C
O
 We know nucleophilic addition reaction are reversible. In which of the
Question following and reaction, equilibrium will lie largely towards left?
O
+ R – O–Na+
(A) H3C CH3

O
acid
+ H3C – OH
(B) H3C CH3

O
+ HC  C–Na+
(C) H3C CH3

O
+ R – MgX
(D) H3C CH3
Ans. (B)
 In the following reaction
Question [JEE-Main(January)-
HCl
Aldehyde + Alcohol Acetal 2019]
Aldehyde Alcohol
HCHO tBuOH

CH3CHO MeOH
The best combinations is :
(1) HCHO and MeOH (2) HCHO and tBuOH
(3) CH3CHO and MeOH (4) CH3CHO and tBuOH

Ans. (1)
 Nucleophilic Addition

Addition of H2O General Introduction

Addition of NH2-Z Addition of HCN

Addition of ROH Addition of sodium Hydrogen sulphite

Addition of chloroform Addition of Grignard reagent

Addition of PCl5
Addition of Grignard reagent

A nucleophilic addition reaction is a chemical addition reaction in

which a nucleophile forms sigma bond with an electron deficient
species.

H2O R
C―
―O + R ― MgX C
OH

Mechanism

R
  𝛿+ 𝛿− RDS   H2O R
R MgX + C―
―O C ― O MgX C
OH
 Formation of alcohol using Grignard reagent

Formation of primary alcohol using Grignard reagent

H2O
RMgX + HCHO R ― CH2 ― OH
1 alcohol

Mechanism

R
  H 𝜹+ 𝜹− H   H2O
R MgX + C―
―O C ― O MgX R ― CH2 ― OH
H H
1 alcohol
 Formation of alcohol using Grignard reagent

Formation of secondary alcohol using Grignard reagent

H2O
RMgX + R’CHO R’ ― CH ― OH
R
2 alcohol

Mechanism

R
  R’ 𝛿 + 𝛿 − R’   H2O
R MgX + C――O C ― O MgX R’ ― CH ― OH
H H
R
2 alcohol
 Formation of alcohol using Grignard reagent

Formation of tertiary alcohol using Grignard reagent

O OH
H2O
RMgX + R’ ― C― R’ R’ ― CH ― R’
R
3 alcohol

Mechanism

R OH
  R’ 𝛿 + 𝛿 − R’   H2O
R MgX + C――O C ― O MgX R’ ― CH ― R’
R’ R’
R
3 alcohol
 Find major product of given below reaction
Question
O
1. Mg, ether
H—C—CH2CH2CH2CH2—Cl A
2. H3O+

HO

Ans.
 Find major product of given below reaction
Question
1. NBS
Ph—CH3 A
2. Mg , Et2O
3. O , H3O+

OH
Ans. Ph—CH2—C—CH3
CH3
 Find major product of given below reaction
Question
O
1. MgCl
H
2. H+,H2O

HO H
Ans.
 Find product of given below reaction
Question
1.Et MgBr
Ph —C ≡ C—H A
2.Ph2CO

OH
Ans. Ph—C≡C—C—Ph
Ph
 Find product of given below reaction
Question
1.Mg , THF
Br A
2.
O

Ans . OH
 Find product of given below reaction
Question
O
1. MgBr
2. H+, H2O

HO
Ans.
 Find product of given below reaction
Question
Cl
1.Mg , Et2O
A
2.

Br CHO
N

Cl
Ans.
N
OH
 Find product of given below reaction
Question
H2O
CH3 ― CH ― MgBr + HCHO
CH3

OH
Ans. CH3—CH—CH2
CH3
 CH2CH3
Question Grignard Reagent + Carbonyl compound
H2O
CH3 ― C ― CH ― CH3
[X] [Y] OH CH3
X and Y can be
CH3
(A) CH3 ―MgBr + CH3 ― CH2 ― C ― CH ― CH3
O
(B) CH3 ―CH ― MgBr & CH3 ― CH2 ― C ― CH3
CH3 O

(C) CH3 ―CH ― CH2 ― MgBr + CH3 ― C ― CH2 ― CH3

CH3 O

(D) CH3 ― CH2 ― MgBr + CH3 ― CH ― CHO

CH3
Solution

Ans. (A,B)
Question For the following conversion, choose the appropriate set of reagents to
be used in the given order.

CHO CHO

H OH CH3 OH

(A) HOCH2CH2OH/H+, PCC/CH2Cl2, CH3MgCl/H3O+

(B) CH3O–/CH3OH, CH2I
(C) HOCH2CH2OH/H+, CH3MgI/H3O+, PCC/CH2Cl2
(D) CH3MgI/H3O+, PCC/CH2Cl2

Ans. (A)
 The aldehydes which will not form Grignard product with one equivalent
Question
Grignard reagents are :
[JEE-Main(January)-
2019]
CHO CHO
(A) (B)
HO2C

CHO CHO
(C) (D)
H3CO HOH2C
(1) (B), (C), (D) (2) (B), (D)
(3) (B), (C) (4) (C), (D)

Ans. (2)
Conjugate addition versus direct addition

Direct addition

Nucleophiles, depending on their nature, now can give direct or

conjugate addition.

Strong and aggressive nucleophiles such as

Grignard reagent, organolithium compound, lithium aluminium
hydride, sodium borohydride give direct addition.

O HO CH3
1. CH3MgBr
Direct addition
2. H3O+
 O OH
1. LiAlH4
CH3—CH==CH—C—CH3 CH3—CH==CH—CH—CH3
2. H3O+
Direct addition
Conjugate addition

weak and relatively stable nucleophiles acts intelligently.

They attack the carbon-carbon double bond to give conjugate

addition.

The net result is destruction of a ‘bad bond’ (unstable bond) and

survival of a 'good bond' (stable carbonyl group), a thermodynamic
outcome.

Cyanide ions, amines, thiols, halides and nucleopniles generated

from malonic ester, acetoacetic ester and Grignard reagent
carrying bulky alkyl group, lithium dialkyl cuprate give conjugate
addition.
Conjugate addition

O O
1. (CH3)2CuLi Conjugate addition
2. H3O+
CH3
 The major product in the following reaction is
Question [IIT-JEE(ADV.)-
O
1. CH3MgBr, dry ether, 0°C 2014]
Cl 2. aq. acid
CH3

O OH
(A) H3C (B)
CH3 H2C CH3
CH3

(C) (D) CH3

O CH2 CH3
O

Ans. (D)
 O (i) C2H5MgBr,, dry ether
Question (ii) H2O, HCl P [JEE-Main-
(Major product) 2021]
Consider the above reaction, the major product 'P' is:
OH OH
(1) (2)

OH OH
(3) (4)
Cl
Cl

Ans. (3)
 Nucleophilic Addition

Addition of H2O General Introduction

Addition of NH2-Z Addition of HCN

Addition of ROH Addition of sodium Hydrogen sulphite

Addition of chloroform Addition of Grignard reagent

Addition of PCl5
Addition of chloroform in presence of base

Acetone react with chloroform and form chloritone compound which

is hypnotic in nature

H3C H3C OH
KOH
O + CHCl3
H3C H3C CCl3

Chloritone
Mechanism

–
CHCl3 + KOH CCl3

H3C H3C O– H3C OH

– +H2O
O + CCl3
–OH–
H3C H3C CCl3 H3C CCl3

Chloritone

Reaction proceeds through the formation of tetrahedral

intermediate.
 Nucleophilic Addition

Addition of H2O General Introduction

Addition of NH2-Z Addition of HCN

Addition of ROH Addition of sodium Hydrogen sulphite

Addition of chloroform Addition of Grignard reagent

Addition of PCl5
 Addition of PCl5 (phosphorous pentachloride)

Aldehydes or ketones react with PCl5 to give gem-dihalides.

Cl
(i) CH𝟑CHO + PCl5 CH3CH + POCl3
Cl
Aldehyde
Ethylidene chloride

Cl
(ii) (CH𝟑)2C = O + PCl5 (CH3)2C + POCl3
Ketone Cl
2,2-Dichloropropane
OXIDATION
OF
CARBONYL
The following reagents are used to oxidise RCHO to carboxylic
acids. They cannot oxidise ketone because it is very difficult to
oxidise ketone at room temperature :

(1) Tollen’s reagent

(2) Fehling’s soln

(3) Benedtict soln

(4) Schiff’s reagent

(5) HgCl2
1. With Tollen's reagent

RCHO (aldehydes) can be easily oxidised to RCOOH (except HCHO

that can be oxidized to CO2) by weak oxidising agents like
ammonical AgNO3 (Tollen’s reagent) hence they are better reducing
agents.AC

Tollens reagent [ammoniacal AgNO3; Ag NH3 2]

+

AgNO3 + 2NH3 → Ag NH3 2

+1
+ NO−
3

Colorless solution called

tollen’s reagent

It oxidises RCH = O → RCO2H

but R2C=O cannot be oxidised
Aldehydes reduce Tollen’s reagent to Ag and appears in the form of
silver mirror is called silver-mirror test. It is given by all aldehydes
and reducing sugars.


RCHO + 2[Ag(NH3)2+] + 3OH– RCOO– + 2Ag + 4NH3 + 2H2O
Silver mirror
This test is also given by reducing sugars. Carbohydrates reacts
with Tollen’s reagent forms a silver mirror on the inner walls of the
test tube. This confirms the presence of reducing sugars. Silver
ions are reduced to metallic silver.

(i) [Ag(NH3)2]OH
RCHO RCOOH + Ag (Silver mirror)
(ii) H+
(i) H–C–OH (only monocarboxylic acid which has reducing power due
|| to presence of –CH=O linkage)
O

OH– H2 O
(ii) RCH–OCH3 RCH–OCH3 RCH=O + CH3OH
| |
OH O– + H2O Give +ve test with
(hemiacetal) Tollen’s reagent
(Basic medium)

O OH
(iii)

N=0
NHOH
(iv) Tollens
(phenyl Hydroxyl amine) Reagent +Ag mirror
(v) RCH–C–CH3
| ||
OH O
a-hydroxy ketone give +ve tollen’s test.

(vi) Terminal alkyne RCCH ; HCCH reacts with tollen’s reagent.

HCCH + 2AgNO3 + 2NH4OH AgCCAg + 2H2O + 2NH4NO3

(white ppt.)

RCCH + AgNO3 + NH4OH RCCAg + H2O + NH4NO3

(white ppt.)
Terminal alkyne does not give +ve silver mirror test with Tollen’s
reagent but gives white colour ppt with Tollen’s reagent.
Nonterminal alkyne does not react with Tollen’s reagent. So
Tollen’s reagent is useful to distinguish

(i) Aldehyde v/s ketone.

(ii) Terminal alkyne vs nonterminal alkyne.
(iii) HCO2H vs any monocarboxylic acid other than HCO2H.
Question Silver Mirror test is given by which one of the following compounds?
(1) Formaldehyde (2) Benzophenone (3) Acetaldehyde (4) Acetone

(AIEEE-2011)
SOLUTION

Ans. (1,3)
 Positive Tollen's test is observed for :
Question (JEE.ADV-2016)
H O
CHO
(A) H H (B)
H
OH O
Ph
(C) Ph (D) Ph Ph
O

SOLUTION

Ans. (ABC)
 The correct sequence of reagents for the following conversion will be :-
Question
O HO CH3
(JEE.MAIN-2017)

HO CH3
CHO
CH3
(1) [Ag(NH3)2]+ OH–,H+/CH3OH,CH3MgBr
(2) CH3MgBr, H+/CH3OH, [Ag(NH3)2]+OH–
(3) CH3MgBr, [Ag(NH3)2]+OH–, H+/CH3OH

(4) [Ag(NH3)2]+ OH–,H+/ CH3MgBr, CH3OH

Ans. (1)
 An unsaturated hydrocarbon X absorbs two hydrogen molecules on
Question catalytic hydrogenattion, and also gives following reaction :
O3 Ag NH3 2 +
X A
ZnΤH2 O
(JEE.MAIN-
B (3 − oxo − hexanedicarboxylic acidሻ
2020)
X will be :-
O
(1) (2) (3) (4)

SOLUTION

Ans. (1)
 OH
Question
CHO O
OH
OH (JEE.MAIN-
(I) (II) (III) (IV) 2021)

Which among the above compound/s does/do not form Silver mirror when
treated with Tollen's reagent?
(1) (I), (III) and (IV) only (2) Only (IV)
(3) Only (II) (4) (III) and (IV) only

SOLUTION

Ans. (3)
Question In Tollen's test for aldehyde, the overall number of electron(s)
transferred to the Tollen's reagent formula [Ag(NH3)2]+ per aldehyde
group to form silver mirror is_______. (Round off to the Nearest integer)

SOLUTION (JEE.MAIN-
2021)

Ans. (2)
2. With Fehling’s solution

It is a mixture of Fehling A and Fehling B solution.

Fehling A  Aqueous solution of CuSO4

Fehling B  Sodium potassium tartarate (Rochelle salt)

CO2Na
H OH
H OH

CO2K
(Rochelle salt)
2. With Fehling solution

During the reaction, Cu2+ (tartarate) complex is formed which is

deep blue coloured solution called Fehling solution.

It acts as an oxidising reagent; oxidises aldehyde RCH=O ⎯→

RCO2H. But ketone can not be oxidised.

Cu2+ (tartarate)
RCHO Fehling solution RCO2– + Cu2O¯ (red precipitrate)
Aldehydes (except benzaldehyde) reduce Fehling’s solution (Cu2+
reduced to Cu+) which is an alkaline solution of cupric (Cu2+) ion
complexed with tartrate ion.


RCHO + 2Cu2+ + 3OH– RCOO– + Cu2O + 2H2O
red ppt.

Aldehydes also reduce Benedict’s solution (Cu2+ complexed with

citrate ion) to Cu+
All reducing carbohydrates give positive fehling's test with fehling
solution. Carbohydrates which has aldehyde functional group (not
aromatic aldehyde) and alpha hydroxy carbonyl also gives positive
fehling's test (e.g. fructose ). While Ketones give negative fehling’s
test.
Note
OH
CHO
Aromatic aldehyde, PhCHO; gives –ve Fehling test but
+ve tollens test.

So oxidising power : Tollens reagent > Fehling solution.

2. HCO2H ; RCH—C—R (a-hydroxy ketone) ;
| ||
OH O

OH
O
HO OH ; RCH–OCH3 (Hemiacetal)
|
OH
HO OH
Also give, +ve fehling test.

3. Glucose and Fructose give both +ve fehling and Tollens test.

4. Fehling gives –ve test with terminal and nonterminal alkyne.

5. Tollen’s and fehling cannot oxidise any alcohol to carbonyl product

or carboxylic acid.
6. To distinguish terminal and non terminal alkynes, for Eg. 1-butyne
and 2-butyne the following reagent can be used.
(i) AgNO3 + NH4OH (ii) Cu2Cl2 + NH4OH
(iii) RMgX (iv) NaH
(v) NaNH2

Reagents 1-butyne 2-butyne Observation

(i) AgNO3 + NH4OH ✓  White ppt.
(ii) Cu2Cl2 + NH4OH ✓  Red ppt.
(iii) RMgX ✓  Gas evolution RH 
(iv) NaH ✓  Gas evolution H2 
(v) NaNH2 ✓  Gas evolution NH3
7. HCCH + Cu2Cl2 + 2NH4OH Cu2C2 + 2H2O + 2NH4Cl
Cuprous acetylide
(red colour ppt)

2RCCH + Cu2Cl2 + NH4OH (RCC)2Cu2 + 2H2O + 2NH4Cl

 Other Exception

(i) Glyoxal give –ve tollen’s and fehling test.

(ii) Tartaric acid give +ve Tollen’s test HO2C–CH–CH–CO2H

OH OH
OH O

(iii) + 2Ag+ + 2e + 2H+ + 2Ag

Tollens (mirror)
OH reagent O
Question 1- propanol & 2- propanol can be best distinguished by:

(A) Oxidation with alkaline KmNO4 followed by reaction with fehling

solution
(B) Oxidation with acidic dichromate followed by reaction with
fehling solution.

(C) Oxidation by heating with copper followed by reaction with

fehling solution.

(D) Oxidation with concentrated H2SO4 followed by reaction with

fehling solution.

SOLUTION Ans. (C)

 The desired product X can be prepared by reacting the major product of
Question the reactions in LIST-I with one or more appropriate reagents in LIST-II.
(given, order of migratory aptitude: aryl > alkyl > hydrogen)

(JEE-ADV.-
LIST-I LIST-II
2018)

Ph O
HO
P. Ph Me + H2SO4 1. l2, NaOH
OH Ph OH
Me
Ph
Ph Me
H2N X
Q. Ph H + HNO2 2. [Ag(NH3)2]OH
OH
Me
Question LIST-I LIST-II
Ph
HO
R. Ph + H2SO4 3. Fehling solution
Me
OH
Me
Ph
S. Br H
Ph + AgNO3 4. HCHO, NaOH
OH
Me 5. NaOBr

The correct option is

(A) P → 1; Q → 2,3; R → 1,4; S → 2,4 (B) P → 1,5; Q → 3,4; R → 4,5; S → 3
(C) P → 1,5; Q → 3,4; R → 5; S → 2,4 (D) P → 1,5; Q → 2,3; R → 1,5; S → 2,3

SOLUTION Ans. (D)

3. With Benedict's solution

Sodium citrate + NaOH + NaHCO3 + CuSO4

H2O
RCHO + Cu2+ RCOOH + Cu

 
RCOO– Cu2O (red ppt.)
 Carbohydrates which has aldehyde functional group (not aromatic
aldehyde) or having alpha hydroxy ketone gives positive benedict
test it is in mild basic medium.

CuSO4 Cu++ + 𝑆𝑂42−

2Cu++ + Reducing Sugar Cu+

Cu+ Cu2O ppt

Glucose (Blue-Red Solution),

Galactose (Orange-Red Solution)
Maltose (Dark-Brown with Brick-Red Solution),
Fructose (Dark-Brown with Brick-Red Solution)
Xylose (Brick-Red solution)
Note

All carbohydrates having hemi-acetal group (reducing sugar) give

tollen’s, fehling’s and benedict’s test.

a-hydroxy keton’s give tollen’s, fehling’s and benedict’s test.

Sucrose and poly sachharides are non reducing sugars, do not give
benedict’s test, fehling’s test and tollen’s test.
4. With Schiff's reagent

Schiff's Reagent is aq. solution of following base decolourised by

passing SO2.

Aldehyde restore pink colour of Schiff's reagent.

NH2 NH2

SO2
C Colourless solution (Schiff's Reagent)

 RCHO

NH C
2
l RCOOH + Pink colour
p-Rosaniline Hydrochloride
Magenta colour (Fuschin base)
5. HgCl2 solution (mercuric chloride)

It is an also used to oxidised RCHO but not ketone.

RCHO + HgCl2 + H2O RCOOH + 2HCl + Hg2Cl2



RCHO + Hg2Cl2 + H2O RCOOH + 2HCl + 2Hg grey ppt.

Oxidation of ketone

Ketone do not undergo oxidation easily and on vigorous oxidation

yield acids with lesser number of carbon atoms.

Oxidation of ketones take place according to Popoff’s rule

Popoff’s rule states that unsymmetrical ketones, the C=O bond

remains with the smaller chain.

O
[O]
CH3—C—CH2—CH3 CH3—C—OH + CH3—C—OH
O O
 KMnO4/H+
Question CH3–CH2–CH2–C–CH3
O

SOLUTION

Ans. CH3–COOH + CH3–CH2–COOH

Question O
KMnO4/H+

SOLUTION

O
Ans. OH

OH
O
Miscellaneous Oxidation
Oxidation by using SeO2

SeO2 in acetic acid or acetic anhydride at 100-140°C, oxidises active

methyl and active methylene group to aldehyde Or ketone,
respectively, e.g.,

O OO
SeO2
–CH2–C– –C–C–

O O
SeO2
–C–CH3 –C–CHO
Mechanism

The oxidation is carried out in aqueous acetic acid medium and

hence the reagent is selenious acid (H2SeO3). The reaction
proceeds by the attack of selenious acid on the enol form of the
substrate to yield selenate ester which eliminates H2O and selenium
to give the product.

O OH
O—H –H2O
Taut
+ Se
H O OH

O O
–H2O
+ Se
O O—Se—O—H
H
Selenate ester
EXAMPLE

O O
(i) SeO2/MeCOOH

Active methylene (CH2) group

O
Ph Ph
SeO2/MeCOOH
(ii)
O (Active (–CH2) group O
 EXAMPLE

(iii) Me CHO SeO2/MeCOOH

OHC CHO

Active methyl group

O O
(iv)
SeO2/MeCOOH
Me Me Me CHO

(Active (Me) group)

 EXAMPLE

COOEt COOEt
SeO2/MeCOOH
(v) O
COOEt COOEt
DEM (Active(–CH2) group Diethylmesooxalate
 EXAMPLE

CHO O
Me Me Me
+
SeO2/MeCOOH
(vi) Me O Me
O (Ethylglyoxal) O
Butanone
(Major) Diacetyl
(Active (–CH2) group)
(Minor)
(Active (–Me) group)

+
O
CHO
Me
O
Baeyer-villiger oxidation

Baeyer-villiger oxidation is the oxidative cleavage of a carbon-

carbon bond adjacent to a carbonyl which converts ketones to
esters and cyclic ketones to lactones.

It can be carried out with peracids such as MCPBA, or with

hydrogen peroxide and a lewis acid.

O O
O 18
18
R–C–O–O–H
R C R R C O R
Or
mCPBA
Or
H2SO5 / CF3CO3H
Migratory aptitude

—H > 3° > 2° > – Ph > 1° > –CH3

O O
mCPBA C
CH3
CH3 O
 O
Question
Ph COOOH
CH2Cl2

SOLUTION

O
Ans. (67%)
O
 O
Question H2O2
BF3 Ether

SOLUTION

Ans. O (62%)
O
 O
Question
O

CF3C—O—O—H

SOLUTION

O
Ans.
 O
Question H2SO5
CH3—C—H

SOLUTION

Ans. O

CH3—C—OH
OXIDATION
OF
CARBONYL
The following reagents are used to oxidise RCHO to carboxylic
acids. They cannot oxidise ketone because it is very difficult to
oxidise ketone at room temperature :

(1) Tollen’s reagent

(2) Fehling’s soln

(3) Benedtict soln

(4) Schiff’s reagent

(5) HgCl2
1. With Tollen's reagent

RCHO (aldehydes) can be easily oxidised to RCOOH (except HCHO

that can be oxidized to CO2) by weak oxidising agents like
ammonical AgNO3 (Tollen’s reagent) hence they are better reducing
agents.AC

Tollens reagent [ammoniacal AgNO3; Ag NH3 2]

+

AgNO3 + 2NH3 → Ag NH3 2

+1
+ NO−
3

Colorless solution called

tollen’s reagent

It oxidises RCH = O → RCO2H

but R2C=O cannot be oxidised
Aldehydes reduce Tollen’s reagent to Ag and appears in the form of
silver mirror is called silver-mirror test. It is given by all aldehydes
and reducing sugars.


RCHO + 2[Ag(NH3)2+] + 3OH– RCOO– + 2Ag + 4NH3 + 2H2O
Silver mirror
This test is also given by reducing sugars. Carbohydrates reacts
with Tollen’s reagent forms a silver mirror on the inner walls of the
test tube. This confirms the presence of reducing sugars. Silver
ions are reduced to metallic silver.

(i) [Ag(NH3)2]OH
RCHO RCOOH + Ag (Silver mirror)
(ii) H+
(i) H–C–OH (only monocarboxylic acid which has reducing power due
|| to presence of –CH=O linkage)
O

OH– H2 O
(ii) RCH–OCH3 RCH–OCH3 RCH=O + CH3OH
| |
OH O– + H2O Give +ve test with
(hemiacetal) Tollen’s reagent
(Basic medium)

O OH
(iii)

N=0
NHOH
(iv) Tollens
(phenyl Hydroxyl amine) Reagent +Ag mirror
(v) RCH–C–CH3
| ||
OH O
a-hydroxy ketone give +ve tollen’s test.

(vi) Terminal alkyne RCCH ; HCCH reacts with tollen’s reagent.

HCCH + 2AgNO3 + 2NH4OH AgCCAg + 2H2O + 2NH4NO3

(white ppt.)

RCCH + AgNO3 + NH4OH RCCAg + H2O + NH4NO3

(white ppt.)
Terminal alkyne does not give +ve silver mirror test with Tollen’s
reagent but gives white colour ppt with Tollen’s reagent.
Nonterminal alkyne does not react with Tollen’s reagent. So
Tollen’s reagent is useful to distinguish

(i) Aldehyde v/s ketone.

(ii) Terminal alkyne vs nonterminal alkyne.
(iii) HCO2H vs any monocarboxylic acid other than HCO2H.
Question Silver Mirror test is given by which one of the following compounds?
(1) Formaldehyde (2) Benzophenone (3) Acetaldehyde (4) Acetone

(AIEEE-2011)
SOLUTION

Ans. (1,3)
 Positive Tollen's test is observed for :
Question (JEE.ADV-2016)
H O
CHO
(A) H H (B)
H
OH O
Ph
(C) Ph (D) Ph Ph
O

SOLUTION

Ans. (ABC)
 The correct sequence of reagents for the following conversion will be :-
Question
O HO CH3
(JEE.MAIN-2017)

HO CH3
CHO
CH3
(1) [Ag(NH3)2]+ OH–,H+/CH3OH,CH3MgBr
(2) CH3MgBr, H+/CH3OH, [Ag(NH3)2]+OH–
(3) CH3MgBr, [Ag(NH3)2]+OH–, H+/CH3OH

(4) [Ag(NH3)2]+ OH–,H+/ CH3MgBr, CH3OH

Ans. (1)
 An unsaturated hydrocarbon X absorbs two hydrogen molecules on
Question catalytic hydrogenattion, and also gives following reaction :
O3 Ag NH3 2 +
X A
ZnΤH2 O
(JEE.MAIN-
B (3 − oxo − hexanedicarboxylic acidሻ
2020)
X will be :-
O
(1) (2) (3) (4)

SOLUTION

Ans. (1)
 OH
Question
CHO O
OH
OH (JEE.MAIN-
(I) (II) (III) (IV) 2021)

Which among the above compound/s does/do not form Silver mirror when
treated with Tollen's reagent?
(1) (I), (III) and (IV) only (2) Only (IV)
(3) Only (II) (4) (III) and (IV) only

SOLUTION

Ans. (3)
Question In Tollen's test for aldehyde, the overall number of electron(s)
transferred to the Tollen's reagent formula [Ag(NH3)2]+ per aldehyde
group to form silver mirror is_______. (Round off to the Nearest integer)

SOLUTION (JEE.MAIN-
2021)

Ans. (2)
2. With Fehling’s solution

It is a mixture of Fehling A and Fehling B solution.

Fehling A  Aqueous solution of CuSO4

Fehling B  Sodium potassium tartarate (Rochelle salt)

CO2Na
H OH
H OH

CO2K
(Rochelle salt)
2. With Fehling solution

During the reaction, Cu2+ (tartarate) complex is formed which is

deep blue coloured solution called Fehling solution.

It acts as an oxidising reagent; oxidises aldehyde RCH=O ⎯→

RCO2H. But ketone can not be oxidised.

Cu2+ (tartarate)
RCHO Fehling solution RCO2– + Cu2O¯ (red precipitrate)
Aldehydes (except benzaldehyde) reduce Fehling’s solution (Cu2+
reduced to Cu+) which is an alkaline solution of cupric (Cu2+) ion
complexed with tartrate ion.


RCHO + 2Cu2+ + 3OH– RCOO– + Cu2O + 2H2O
red ppt.

Aldehydes also reduce Benedict’s solution (Cu2+ complexed with

citrate ion) to Cu+
All reducing carbohydrates give positive fehling's test with fehling
solution. Carbohydrates which has aldehyde functional group (not
aromatic aldehyde) and alpha hydroxy carbonyl also gives positive
fehling's test (e.g. fructose ). While Ketones give negative fehling’s
test.
Note
OH
CHO
Aromatic aldehyde, PhCHO; gives –ve Fehling test but
+ve tollens test.

So oxidising power : Tollens reagent > Fehling solution.

2. HCO2H ; RCH—C—R (a-hydroxy ketone) ;
| ||
OH O

OH
O
HO OH ; RCH–OCH3 (Hemiacetal)
|
OH
HO OH
Also give, +ve fehling test.

3. Glucose and Fructose give both +ve fehling and Tollens test.

4. Fehling gives –ve test with terminal and nonterminal alkyne.

5. Tollen’s and fehling cannot oxidise any alcohol to carbonyl product

or carboxylic acid.
6. To distinguish terminal and non terminal alkynes, for Eg. 1-butyne
and 2-butyne the following reagent can be used.
(i) AgNO3 + NH4OH (ii) Cu2Cl2 + NH4OH
(iii) RMgX (iv) NaH
(v) NaNH2

Reagents 1-butyne 2-butyne Observation

(i) AgNO3 + NH4OH ✓  White ppt.
(ii) Cu2Cl2 + NH4OH ✓  Red ppt.
(iii) RMgX ✓  Gas evolution RH 
(iv) NaH ✓  Gas evolution H2 
(v) NaNH2 ✓  Gas evolution NH3
7. HCCH + Cu2Cl2 + 2NH4OH Cu2C2 + 2H2O + 2NH4Cl
Cuprous acetylide
(red colour ppt)

2RCCH + Cu2Cl2 + NH4OH (RCC)2Cu2 + 2H2O + 2NH4Cl

 Other Exception

(i) Glyoxal give –ve tollen’s and fehling test.

(ii) Tartaric acid give +ve Tollen’s test HO2C–CH–CH–CO2H

OH OH
OH O

(iii) + 2Ag+ + 2e + 2H+ + 2Ag

Tollens (mirror)
OH reagent O
Question 1- propanol & 2- propanol can be best distinguished by:

(A) Oxidation with alkaline KmNO4 followed by reaction with fehling

solution
(B) Oxidation with acidic dichromate followed by reaction with
fehling solution.

(C) Oxidation by heating with copper followed by reaction with

fehling solution.

(D) Oxidation with concentrated H2SO4 followed by reaction with

fehling solution.

SOLUTION Ans. (C)

 The desired product X can be prepared by reacting the major product of
Question the reactions in LIST-I with one or more appropriate reagents in LIST-II.
(given, order of migratory aptitude: aryl > alkyl > hydrogen)

(JEE-ADV.-
LIST-I LIST-II
2018)

Ph O
HO
P. Ph Me + H2SO4 1. l2, NaOH
OH Ph OH
Me
Ph
Ph Me
H2N X
Q. Ph H + HNO2 2. [Ag(NH3)2]OH
OH
Me
Question LIST-I LIST-II
Ph
HO
R. Ph + H2SO4 3. Fehling solution
Me
OH
Me
Ph
S. Br H
Ph + AgNO3 4. HCHO, NaOH
OH
Me 5. NaOBr

The correct option is

(A) P → 1; Q → 2,3; R → 1,4; S → 2,4 (B) P → 1,5; Q → 3,4; R → 4,5; S → 3
(C) P → 1,5; Q → 3,4; R → 5; S → 2,4 (D) P → 1,5; Q → 2,3; R → 1,5; S → 2,3

SOLUTION Ans. (D)

3. With Benedict's solution

Sodium citrate + NaOH + NaHCO3 + CuSO4

H2O
RCHO + Cu2+ RCOOH + Cu

 
RCOO– Cu2O (red ppt.)
 Carbohydrates which has aldehyde functional group (not aromatic
aldehyde) or having alpha hydroxy ketone gives positive benedict
test it is in mild basic medium.

CuSO4 Cu++ + 𝑆𝑂42−

2Cu++ + Reducing Sugar Cu+

Cu+ Cu2O ppt

Glucose (Blue-Red Solution),

Galactose (Orange-Red Solution)
Maltose (Dark-Brown with Brick-Red Solution),
Fructose (Dark-Brown with Brick-Red Solution)
Xylose (Brick-Red solution)
Note

All carbohydrates having hemi-acetal group (reducing sugar) give

tollen’s, fehling’s and benedict’s test.

a-hydroxy keton’s give tollen’s, fehling’s and benedict’s test.

Sucrose and poly sachharides are non reducing sugars, do not give
benedict’s test, fehling’s test and tollen’s test.
4. With Schiff's reagent

Schiff's Reagent is aq. solution of following base decolourised by

passing SO2.

Aldehyde restore pink colour of Schiff's reagent.

NH2 NH2

SO2
C Colourless solution (Schiff's Reagent)

 RCHO

NH C
2
l RCOOH + Pink colour
p-Rosaniline Hydrochloride
Magenta colour (Fuschin base)
5. HgCl2 solution (mercuric chloride)

It is an also used to oxidised RCHO but not ketone.

RCHO + HgCl2 + H2O RCOOH + 2HCl + Hg2Cl2



RCHO + Hg2Cl2 + H2O RCOOH + 2HCl + 2Hg grey ppt.

Oxidation of ketone

Ketone do not undergo oxidation easily and on vigorous oxidation

yield acids with lesser number of carbon atoms.

Oxidation of ketones take place according to Popoff’s rule

Popoff’s rule states that unsymmetrical ketones, the C=O bond

remains with the smaller chain.

O
[O]
CH3—C—CH2—CH3 CH3—C—OH + CH3—C—OH
O O
 KMnO4/H+
Question CH3–CH2–CH2–C–CH3
O

SOLUTION

Ans. CH3–COOH + CH3–CH2–COOH

Question O
KMnO4/H+

SOLUTION

O
Ans. OH

OH
O
Miscellaneous Oxidation
Oxidation by using SeO2

SeO2 in acetic acid or acetic anhydride at 100-140°C, oxidises active

methyl and active methylene group to aldehyde Or ketone,
respectively, e.g.,

O OO
SeO2
–CH2–C– –C–C–

O O
SeO2
–C–CH3 –C–CHO
Mechanism

The oxidation is carried out in aqueous acetic acid medium and

hence the reagent is selenious acid (H2SeO3). The reaction
proceeds by the attack of selenious acid on the enol form of the
substrate to yield selenate ester which eliminates H2O and selenium
to give the product.

O OH
O—H –H2O
Taut
+ Se
H O OH

O O
–H2O
+ Se
O O—Se—O—H
H
Selenate ester
EXAMPLE

O O
(i) SeO2/MeCOOH

Active methylene (CH2) group

O
Ph Ph
SeO2/MeCOOH
(ii)
O (Active (–CH2) group O
 EXAMPLE

(iii) Me CHO SeO2/MeCOOH

OHC CHO

Active methyl group

O O
(iv)
SeO2/MeCOOH
Me Me Me CHO

(Active (Me) group)

 EXAMPLE

COOEt COOEt
SeO2/MeCOOH
(v) O
COOEt COOEt
DEM (Active(–CH2) group Diethylmesooxalate
 EXAMPLE

CHO O
Me Me Me
+
SeO2/MeCOOH
(vi) Me O Me
O (Ethylglyoxal) O
Butanone
(Major) Diacetyl
(Active (–CH2) group)
(Minor)
(Active (–Me) group)

+
O
CHO
Me
O
Baeyer-villiger oxidation

Baeyer-villiger oxidation is the oxidative cleavage of a carbon-

carbon bond adjacent to a carbonyl which converts ketones to
esters and cyclic ketones to lactones.

It can be carried out with peracids such as MCPBA, or with

hydrogen peroxide and a lewis acid.

O O
O 18
18
R–C–O–O–H
R C R R C O R
Or
mCPBA
Or
H2SO5 / CF3CO3H
Migratory aptitude

—H > 3° > 2° > – Ph > 1° > –CH3

O O
mCPBA C
CH3
CH3 O
 O
Question
Ph COOOH
CH2Cl2

SOLUTION

O
Ans. (67%)
O
 O
Question H2O2
BF3 Ether

SOLUTION

Ans. O (62%)
O
 O
Question
O

CF3C—O—O—H

SOLUTION

O
Ans.
 O
Question H2SO5
CH3—C—H

SOLUTION

Ans. O

CH3—C—OH
Haloform Reaction
Haloform Reaction

Acetaldehyde and methyl ketone reacts rapidly with halogen in the

presence of alkali to give haloform and acid salt.

O
|| NaOH
CH3—C—H X2 CHX3 + HCOONa

Iodoform Reaction

O
||
NaOH
CH3—C—H CHI3+ HCOONa
I2
Yellow ppt.
 Mechanism

O H O O X
|| | RDS || – || |
X—X
R—C—CH + –OH R—C—CH2 R—C—CH + X–
|
H
O– –
OH
|
R—C = CH2
O
|| –
R—C—CH
|
X X—X

X
R—C—C
|| | X
O H
Mechanism

O O
X – || – ||
R—C—C + OH R—C—CX2
X—X
R—C—CX3
|| | X
O H
–
OH

O –
O O
|| – || – |
R—C—O + CHX3 R—C—O—H + CX3 R—C—CX3
|
OH
Note

Balanced haloform reaction will be as follows

CH3 COCH3 + 3X2 + 4NaOH ⎯⎯→ CH3 CO2 Na + CHX3 + 3NaX + 3H2 O

Since in haloform reaction, breaking of halogen bond does not

involve in RDS step.

Rate of Haloform : F2 ≃ Cl2 ≃ Br2 ≃ I2

Important Compounds for Haloform Reaction

Alcohol

Among Primary alcohol only ethanol shows

haloform reaction. O
I2 NaOH
CH3CH2OH H3C−C − H CHI3 + HCOONa
I2
Yellow ppt
I2
CH3CH2—OH No Reaction
H2O
Important Compounds for Haloform Reaction

Alcohol

On electrolysis an alcoholic solution (ethanol) of sodium chloride

gives sweet smelling liquid of CHCl3.

Liquid brine (aq. NaCl) on electrolysis given NaOH + Cl2

O
Cl2 NaOH
CH3CH2OH H3C−C − H CHCl3 + HCOONa
Cl2
Sweet
smelling
liquid
Secondary alcohol can show haloform reaction.

OH
| NaOH
CHI3 + CH3COONa
H3C—CH—CH3 I2
yellow ppt
2-propanol with bleaching powder gives sweet smelling liquid of CHCl3

CaOCl2 + H2O ⎯⎯→ Cl2 + Ca(OH)2

bleaching powder

Me O Me
OH + Cl2 ⎯⎯→ O + 2HCl
Me Me
3Cl2+Ca(OH)2

(CH3COO)2 Ca + CHCl3
Sweet
smelling
liquid
Tertiary alcohol can’t be oxidized to methyl ketone hence it will
not give haloform test.

OH
|
H3C—C—CH3 NaOH No Reaction
| I2
CH3
 Note

Active methylene compound also give haloform test.

Me—C—14CH2 — C — Me
NaOH
I2
2Me—C—ONa + 14CHI
3
|| || ||
O O O
Haloform Reaction in acidic medium

Acetaldehyde and methyl ketone reacts with halogen in the presence

of acidic medium to give monohalogenated product.

O O

CH3 H+, H2O CH2I

+ I2 + HI
 Mechanism

Step -I
••
H2O
H H +
| O | O–H H OH
CH2—C + H+ CH2—C C== C + H3O+
Ph Ph H Ph

Step -II
•• X +
OH | O–H
X—X + CH2 = C CH2—C + X–
Ph Ph
Step -III

X + X
| O–H O
CH2—C + X– CH2—C + HX
Ph Ph
 Successive halogenation is slow because halogen decreases
nucleophilicity of enol hence only monohalogenated product will
formed.

In acidic medium rate of haloform slower than haloform in basic

medium.

EXAMPLE

O O
Br2 OH Br2
HOAc
Br
 Identify the compounds which can show iodoform test and complete the
Question reaction ?
I I
(1) I (2) I (3) I (4)
I I I

O
OH OH
(5) OH (6) OH (7) (8)
O
O
(9) (10)
O

SOLUTION

Ans. (1, 2, 5, 7, 8, 9)
 Identify the compounds which can show iodoform test and complete the
Question reaction ?
O O O
|| || ||
(1) CH3—C—O—Me (2) CH3—C C—CH3
O
O
(4) I
(3) HO O
I

(5) Hexanal (6) H3CO–CO–CH2–CO–OCH3

(7) H–CO–CH2–CO–H (8) CH3–CO–CO2H (9) CH3CO2H
(10) CI3CHO

SOLUTION

Ans. (3, 4, 6, 7, 8, 10)

Question Which of the reagent is used to convert 2–Butanone into propanoic acid -
(A) NaOH, I2/H+ (B) Tollen's reagent
(C) Fehling solution (D) NaOH, NaI/H+

SOLUTION

Ans. (A)
 𝒊 𝐌𝐞𝐌𝐠𝐁𝐫 𝟐𝒆𝒒
Ethylmethanoate 𝐖+𝐗
Question (𝐢𝐢) 𝑯𝟑 𝑶+ 𝐨𝐫𝐠𝐚𝐧𝐢𝐜 𝐩𝐫𝐨𝐝𝐮𝐜𝐭
𝐂𝐚𝐎𝐂𝒍𝟐
W CHCl3 + Y
𝐂𝐚𝐎𝐂𝒍𝟐
X CHCl3 + Z
𝐃𝐫𝐲
Y+Z Organic product(s) + CaCO3
𝐃𝐢𝐬𝐭𝐢𝐥𝐥𝐚𝐭𝐢𝐨𝐧

Which of the following organic product can be formed on dry distillation

reaction
(I) CH3 – CHO (II) CH3– CO – CH3
(III) CH3 – CH = CH – CH3 (IV) HCHO
(A) I and II only (B) II and III only
(C) I, II and IV only (D) II and IV only

SOLUTION

Ans. (C)
Question Reaction in which product can show positive haloform test :-
H3O
(A) CH3MgBr + PhCN

H3O
(B) CH3—CH2MgBr + Ph—COOEt
(1 : 1)
NH4Cl
(C) CH3MgBr + H—C—OMe
(1 : 1) ||
O
NH4Cl
(D) CH3MgBr + H—C—H
||
O

SOLUTION
Question In which reaction haloform is obtained as one product :-
(A) Electrolysis of ethanolic aqueous solution of NaCl
(B) Isopropanol with bleaching powder
(C) Chlorination of methane in sun light
(D) Chloral is treated with NaOH

SOLUTION

Ans. (A, B, C, D)
Question An organic compound P(C5H10O) reacts 1015 times faster than ethylene
with dilute H2SO4, It gives 2 products Q,R. both gives +ve iodoform
test. P can be :

(A) O (B) O

(D) O
(C) O

SOLUTION

Ans. (B, C)
 O O
Question
NaOH CH3COOH
(I) + Cl2 P (II) + Cl2 Q

1 : 1 1 : 1
(mole) (mole) (mole) (mole)
Organic product P & Q are respectively -
O O O O
Cl Cl Cl Cl
(A) (B)
, ,

O O O O
Cl Cl Cl Cl
(C) Cl (D) Cl Cl
, ,
SOLUTION

Ans. (C)
Question After completion of the reactions (I and II), the organic compound(s) in
the reaction mixtures is(are)
O
Reaction I : Br2 (1.0 mol) (JEE ADV-
H3C CH3 aqueous/NaOH 2013)
(1.0 mol)
O
Reaction II : Br2 (1.0 mol)
H3C CH3 CH3 COOH
(1.0 mol)
 O O O O O
Question
H3C CH2Br H3C CBr3 Br3C CBr3 BrH2C CH2Br H3C ONa
P Q R S T

CHBr3
U
(A) Reaction I : P and Reaction II : P
(B) Reaction I : U, acetone and Reaction II : Q acetone
(C) Reaction I : T, U, acetone and Reaction II : P
(D) Reaction I : R, acetone and Reaction II : S acetone

SOLUTION

Ans. (C)
 ALDOL
REACTION
Aldol reaction

Aldol condensation is seen in case of carbonyl compounds containing

𝛼 −hydrogens.

The addition reaction of enol or enolate to the carbonyl group of

aldehyde or ketones is known as aldol addition.

The 𝛽-hydroxyaldehyde and 𝛽-hydroxyketones so obtained under go

dehydration in the second step to produce a conjugated enone.

Dilute bases such as NaOH, KOH, Ba(OH)2 or are used as reagents,

aldol condensation are also catalysed by acids.
Aldol reaction

Reaction between two same aldehyde/ketone is called self aldol

reaction.

O H O
1. dil. NaOH
H3C—C—H CH3—C==CH—C—H
2. 
(,  – unsaturated aldehyde )
Mechanism

Step - 1 H
⊖
O
⊖
dil. OH CH2==C—H
H—C—CH2
(enolate ion)
O

Step - 2 O
⊖
O
⊖
O O
r.d.s
CH2==C—H + CH3—C—H CH3—C—CH2—C—H

H2O

H O OH O

CH3—C==CH—C—H + H2O  CH3—C—CH2—C—H
(,  – unsaturated aldehyde ) aldol
Here all steps are reversible so for better yield of product heat is
required so that condensation takes place. Now reaction will become
irreversible at last step and good yield of product obtained.

⊖
For above aldol reaction, rate = [CH3CHO]2 [OH]1
 Note

1. To avoid polymerization, we use dil. NaOH.

⊖
H O ⊖
H O O
OH
CH2—CH==CH—C—H CH2==C—CH==C—H + CH3—C—H

H𝟐O 

O
(Polymerisation) CH3—HC==CH2— CH==CH—C—H
 Note

2. In basic medium of aldol reaction, dehydration step follows E1cb

mechanism.

OH O H O

CH3—C—CH2—C—H CH3—C==CH—C—H + H2O 
E1cb
(,  – unsaturated aldehyde )
Question CH3—CH2—C—H
||
Dil NaOH / ∆

SOLUTION

Ans.
CH3—CH2—CH=C—C—H
| ||
H3C O
Question O Dil NaOH

||
SOLUTION

Ans. O
|| OH
|
 Dil NaOH
Question C6H5—CH2—CHO

SOLUTION

Ans.
Ph
|
Ph—CH2—CH—CH—C—H
| ||
OH O
 C6H5—C—CH3 Dil NaOH / ∆
Question ||
O

SOLUTION

CH3
|
Ans. Ph—C—CH—C—Ph
||
O
 ALDOL
REACTION
Aldol reaction

Aldol condensation is seen in case of carbonyl compounds containing

𝛼 −hydrogens.

The addition reaction of enol or enolate to the carbonyl group of

aldehyde or ketones is known as aldol addition.

The 𝛽-hydroxyaldehyde and 𝛽-hydroxyketones so obtained under go

dehydration in the second step to produce a conjugated enone.

Dilute bases such as NaOH, KOH, Ba(OH)2 or are used as reagents,

aldol condensation are also catalysed by acids.
Aldol reaction

Reaction between two same aldehyde/ketone is called self aldol

reaction.

O H O
1. dil. NaOH
H3C—C—H CH3—C==CH—C—H
2. 
(,  – unsaturated aldehyde )
Mechanism

Step - 1 H
⊖
O
⊖
dil. OH CH2==C—H
H—C—CH2
(enolate ion)
O

Step - 2 O
⊖
O
⊖
O O
r.d.s
CH2==C—H + CH3—C—H CH3—C—CH2—C—H

H2O

H O OH O

CH3—C==CH—C—H + H2O  CH3—C—CH2—C—H
(,  – unsaturated aldehyde ) aldol
Here all steps are reversible so for better yield of product heat is
required so that condensation takes place. Now reaction will become
irreversible at last step and good yield of product obtained.

⊖
For above aldol reaction, rate = [CH3CHO]2 [OH]1
 Note

1. To avoid polymerization, we use dil. NaOH.

⊖
H O ⊖
H O O
OH
CH2—CH==CH—C—H CH2==C—CH==C—H + CH3—C—H

H𝟐O 

O
(Polymerisation) CH3—HC==CH2— CH==CH—C—H
 Note

2. In basic medium of aldol reaction, dehydration step follows E1cb

mechanism.

OH O H O

CH3—C—CH2—C—H CH3—C==CH—C—H + H2O 
E1cb
(,  – unsaturated aldehyde )
Question CH3—CH2—C—H
||
Dil NaOH / ∆

SOLUTION

Ans.
CH3—CH2—CH=C—C—H
| ||
H3C O
Question O Dil NaOH

||
SOLUTION

Ans. O
|| OH
|
 Dil NaOH
Question C6H5—CH2—CHO

SOLUTION

Ans.
Ph
|
Ph—CH2—CH—CH—C—H
| ||
OH O
 C6H5—C—CH3 Dil NaOH / ∆
Question ||
O

SOLUTION

CH3
|
Ans. Ph—C—CH—C—Ph
||
O
Aldol reaction in acidic Medium

O H O
1. H+ / H2O
H3C—C—H CH3—C==CH—C—H
2. 
(,  – unsaturated aldehyde )

Step - 1

Formation of enol


O H O—H OH
H+ OH2
H3C—C—H CH2— C—H CH2==CH
(enol)
 Step - 2
 H 
OH O—H OH O OH O
H2C==CH + CH3—C—H H3C— CH—CH2—CH H3C— CH—CH2—CH
–H

H


O H O OH2 O

H3C— CH==CH—C—H H3C— CH—CH—C—H H3C— CH—CH2—C—H
(,–unsaturated aldehyde)
Note

No heat is required in acid catalyzed.

In acid catalyzed of aldol reaction, dehydration step follow

E1 mechanism.

OH O H O
E1
H3C— CH—CH2—C—H CH3—C==CH—C—H + H2O 
(,  – unsaturated aldehyde )
 O
Question Conc. H2SO4


SOLUTION

Ans.

Mesitylene
or
1,3,5-trimethylbenzene
 Product ‘D’ is :
Question
O
|| ⊝
H2/Pt CrO3
OH 
CH3—C—H A B excess C H2SO4
D

(A) CH3–CH2–CH = CH2

(B) CH3–CH2–CH2–CHO

(C) CH3–CH2–CH2–COOH

(D) CH2 = CH – CH = CH2

SOLUTION

Ans. (C)
 For the given reaction :
Question
H+ P (major)
(i) O3 OH / 
Q R (Major)
∆ (ii) H2O/Zn
OH

The (R) is :

CHO CHO
(B)
(A)

⊝
COO
(C) (D)
OH

SOLUTION

Ans. (A)
 ⊖
Question CH3CHO + 3HCHO dil.OH

SOLUTION

Ans. HO OH
H
C

HO O
Intramolecular aldol reaction

Reaction between two aldehyde/ketone in the same molecule is called

intra molecular aldol reaction

O O O
⊖
H H
OH H

H H
 Mechanism

O O O⊖
⊖
O
OH
H H  6 4 2
H 5 3 1 H
H H
H H

H2O

O OH O

H  H
–H2O
Note If in intramolecular aldol reaction, there is competition
between different ring size formation

7 v/s 5 **

7 v/s 6 ** ** 6 v/s 5
Ring size

4 v/s 5 ** ** 5 v/s 8
 O
Question
Dil NaOH

SOLUTION

Ans.

OH
 O
Question
Dil NaOH / ∆

SOLUTION

O
Ans.
 O
Question –
OH CH3MgBr Zn–Hg
heat A CuBr B conc. HCl C ; the product ‘C’ is
O
O

(A) (B)

(C) (D)

SOLUTION

Ans. (C)
 Product ‘Y’ formed in the given reaction is :
Question
–
O3/Zn OH/
X Y

O O

(A) (B)

O
O

(D)
(C)

OH
SOLUTION

Ans. (B)
 Consider following intramolecular aldol condensation reaction :
Question O
–
X OH ; X can be :


(A) (B)
O O O
O
O O
(C) (D)
O O

SOLUTION

Ans. (D)
 The major product obtained in the following reaction is :
Question CO2Et
NaOEt/
O
O
O O
(A) (B)
COEt
CO2Et

O O
(C) (D)
CO2Et

CO2Et
SOLUTION

Ans. (D)
 In the following reactions, products A and B are :
Question
O O JEE.MAINS.2019
dil NaOH
H3C H3C H3C H [A]

H3O+
[A] [B]

O O
OH H2C
H3C H H
[A] A= ; B=
H3C H3C
CH3 CH3
 O O
Question OH H3C
C
H3C H H
[B] A= ; B=
H3C H3C
CH3 CH3

O O
CH CH3
[C] A= CH3 ; B = CH3
HO

O O
CH3 CH3
[D] A= CH3 ; B = CH3
HO
SOLUTION

Ans. (D)
 The major product of the following reaction is -
Question
O
I. KOH, H2O
(JEE-ADV.
II. H+ , Heat
2015)
CH3
O
C CH3
O O
(A) (B)

O
O CH3
CH3
(C) (D)

SOLUTION
Ans. (A)
Cross aldol

Reaction below two different aldehyde/ketone is called

cross aldol reaction,

For better cross aldol product, one compound must be enolizable and
other compound not, and also that other compound must be more
electrophilic than the compound (who enolizable).

O HO O
NaOH
Me—C—H + HCHO cross aldol
H—C—CH2—C—H
H


CH2==CH—CHO
(Acrolein)
 ⊝
(i) OH
Question (ii)CHCHO
(iii) 
O

SOLUTION

Ans. CH – C6H5

||
||
O
 The major product formed in the following reaction is:
Question CH2
O
O

H3C H+ dil.NaOH

The (R) is :
O OH
OH O
(A) (B) H3C
H3C

OH O

(C) H3C (D)

OH
SOLUTION

Ans. (A)
 The major product of the following reaction sequence is :
Question O
(JEE-ADV.
(i) HCHO (excess) / NaOH, heat 2016)
(ii) HCHO / H+ (catalytic amount)

O O O O OH

(A) (B)

O O O OH
HO
(C) (D)

OH
SOLUTION

Ans. (A)
 Retro Aldol

The aldol condensation is reversible.

Both under acidic and basic condition, diacetone alcohol undergoes

retro-aldol reaction to give an equilibrium mixture containing good
amount of acetone.

Let us depict the base catalyzed retro-aldol condensation of diacetone

alcohol.

OH O ⊖ O O
Conc.OH / H2O
+
H3C CH3 CH3 CH3 CH3 CH3
CH3
 Mechanism

OH O O– O O
HO–
H3C CH3 H3C CH3 H3C CH3
CH3 CH3

+
O O O
H2O
CH3 CH3 + CH3 CH3 –
H2C CH3
 O
Question
⊖
Conc. OH/H2O

OH

Ans. OH

O
 O

CH3
CH3 under acidic condition can give
OH
O
CH3

(A) (B)

OH CH3
O
CH3
CH3
(C) (D)
O
CH3 CH3
SOLUTION

Ans. (B)
Nitro Aldol

The nitroaldol reaction is a base catalyzed C–C bond –forming

reaction between nitroalkanes and aldehydes or ketones .
OH
NO2 O R’’
Base (cat.) O2N
+
R R’ H R’’ R R’

If acidic protons are available ( i.e. when R = H), the products tend
to eliminate water to give nitroalkenes.

therefore only small amount of base should be used if the isolation

od the 𝛽 − hydroxy nitro- compounds is desired.
 EXAMPLE

OH–
CH3NO2 + PhCHO PhCH(OH)CH2NO2

OH–
CH3CH2NO2 + HCHO CH3CH(NO2)CH2OH

OH–
PhCH2NO2 + Me3CCHO PhCH(NO2)CH(OH )CMe3
 O
Question KOH
CH3—NO2 + 

SOLUTION

NO2
Ans.
 CHO
Question + CH3NO2
NaOH


SOLUTION

NO2
Ans.
 (i) NaCN
Question R I (ii) DIBAL–H
(iii) CH3NO2 / NaOMe
(iv) Base(py)

SOLUTION

R NO2
Ans.
Cyano Aldol

The 𝛼 – H atoms of nitriles are also acidic ; but less than those of
carbonyl compounds .

There fore nitriles having 𝛼 – H atom with comparable acidities

undergo condensation of the aldol type.
Ph
–
OEt / EtOH PhCH = C—C≡N
PhCHO + (Ph) CH2CN
EXAMPLE

OH–
CH3CN + PhCHO PhCH(OH)CH2CN

OH–
CH3CH2CN + HCHO CH3CH(CN)CH2OH

OH–
PhCH2CN + Me3CCHO PhCH(CN)CH(OH )CMe3
 O
Question NaOH
Ph—CH2—CN + H—C—H 

SOLUTION

CN
Ans. Ph—CH==CH2
 O
Question NaOH
Me—CN + H—C—H 

SOLUTION

Ans. NC—CH==CH2
 EXAMPLE

O O
dil. KOD, D2O
CH3—C—H CH3—CH==CH—C—H
(acetaldehyde) 

O D3C O
dil. KOD, D2O
CH3—C—CH3 C==CD—C—CD3

(acetone) D3C
O D3C O
⊖
OD
CD3—C—CD3 C==CD—C—CD3

D3C
Reason :–
In ketone, Nu– addition reaction slow before attack so all –H replace
with deuterium, then after aldol reaction takes place.
 Find the product (P) of given below reaction
Question
O
Ba(OH)2
(P)


SOLUTION

O
Ans.
 Find the product (P) of given below reaction
Question
O
Ba(OD)2
D2O,  (P)

SOLUTION

D
D
D O
Ans.
D
D D
CANNIZARO
REACTION
Cannizaro Reaction

Generally those carbonyl compound who don’t have –H shows

cannizaro reaction.

O O
Conc. NaOH
2 H—C—H CH3—OH + H—C—OH
(alcohol) (acid)
 Mechanism

Step 2
𝐇 H H Hydride ion
⊝ Step 1 | | ⊖
𝐎𝐇 C==O H—O—C—O⊝ C== O
transfer HCOOH + CH3O
(fast) | | Slow (R.D.S.)
𝐇 H H

Step 3
Proton
exchange

⊖
CH3—OH + HCOO
alcohol Acid
 Mechanism When the concentration of base is high.

𝐇 H H H
| ⊝ | ⊝
|
⊝ Step 1 ⊝
𝐎𝐇 C==O H O—C—O Step 2 𝐎—C—O C== O
(fast) | ⊝ | |
𝐇 H 𝑂𝐻 H H

Step 3
H⊝ transfer
Slow R.D.S.

⊖ ⊖
HCOO + CH3O
Salt of Salt of
acids alcohols
Note

Cannizaro reaction is a redox reaction .

It is also a disproportionation reaction.

Migration of hydride ion is rate determining step in the cannizaro

reaction

Rate expression :
r = k [mono anion] [carbonyl compound]

r = k [–OH] [C.C]2
Note

Hence the Cannizzaro reaction when the concentration of base is

low follows third-order kinetics, second-order w.r.t. carbonyl
⊝
compound, and first-order w.r.t. O H ions.

when the concentration of base is high then the rate expression will
be as r = k [Carbonyl compound]2 [–OH]2.

From the above rate expression we can conclude that in presence of

high concentration of base reaction is bimolecular and 4th order in
kinetics.
EXAMPLE

O
C—H CH2—OH COONa
⊖
Conc. OH
+
 O
Question ⊖
Conc. OH
Me3C—C—H

SOLUTION

⊖
Me3C—CH2—OH + Me3C—COO
CANNIZARO
REACTION
Cannizaro Reaction

Generally those carbonyl compound who don’t have –H shows

cannizaro reaction.

O O
Conc. NaOH
2 H—C—H CH3—OH + H—C—OH
(alcohol) (acid)
 Mechanism

Step 2
𝐇 H H Hydride ion
⊝ Step 1 | | ⊖
𝐎𝐇 C==O H—O—C—O⊝ C== O
transfer HCOOH + CH3O
(fast) | | Slow (R.D.S.)
𝐇 H H

Step 3
Proton
exchange

⊖
CH3—OH + HCOO
alcohol Acid
 Mechanism When the concentration of base is high.

𝐇 H H H
| ⊝ | ⊝
|
⊝ Step 1 ⊝
𝐎𝐇 C==O H O—C—O Step 2 𝐎—C—O C== O
(fast) | ⊝ | |
𝐇 H 𝑂𝐻 H H

Step 3
H⊝ transfer
Slow R.D.S.

⊖ ⊖
HCOO + CH3O
Salt of Salt of
acids alcohols
Note

Cannizaro reaction is a redox reaction .

It is also a disproportionation reaction.

Migration of hydride ion is rate determining step in the cannizaro

reaction

Rate expression :
r = k [mono anion] [carbonyl compound]

r = k [–OH] [C.C]2
Note

Hence the Cannizzaro reaction when the concentration of base is

low follows third-order kinetics, second-order w.r.t. carbonyl
⊝
compound, and first-order w.r.t. O H ions.

when the concentration of base is high then the rate expression will
be as r = k [Carbonyl compound]2 [–OH]2.

From the above rate expression we can conclude that in presence of

high concentration of base reaction is bimolecular and 4th order in
kinetics.
EXAMPLE

O
C—H CH2—OH COONa
⊖
Conc. OH
+
 O
Question ⊖
Conc. OH
Me3C—C—H

SOLUTION

⊖
Me3C—CH2—OH + Me3C—COO
 O
Question ⊖
Conc. OH
Me2CH—C—H

SOLUTION

Aldol NO
Cannizzaro YES
Question In Cannizzaro reaction given below : (AIEEE-2009)
⊝
OH
2PhCHO PhCH2OH + PhCO⊝
2

the slowest step is :-

(1) The abstraction of proton from the carboxylic group
(2) The deprotonation of PhCH2OH
(3) The attack of at the carboxyl group
(4) The transfer of hydride to the carbonyl group

SOLUTION

Ans. (4)
 ⊖
Question CH3CHO + HCHO OH
excess

SOLUTION

Ans. HO OH

⊖
+ HCOO
HO
OH
 The number of aldol reaction (S) that occurs in the given transformation
Question is.
HO OH
CH3CHO + 4HCHO Conc. aq. NaOH
excess

HO
OH
(A) 1 (B) 2 (C) 3 (D) 4

SOLUTION (JEE-ADV.-2012)

Ans. (C)
Cannizzaro reaction in deuterium containing aldehyde

(C—H) bond is weaker than (C—D) bond, so H⊝ transfer takes place

rather than D⊝ transfer in slow, rate-determing step.

⊖ O
OH ||
D—C—H + D—C—H D—C—O⊝ + DCH2OH
O O
 Mechanism
𝐇
𝐇 H C ==O D
⊝
(fast) | 𝐃 |
𝐎𝐇 C==O HO—C—O⊝ HO—C== O + H—C—O⊝
Slow
Step 1 | R.D.S.
| |
𝐃 D H
D Step 2
H⊝
Step 3 exchanges

D
|
O⊝—C==O + H2C—OH
|
D

So from above, it can be concluded that kinetic isotopic effect is

observed in cannizaro reaction.
 O
Question || –
OH
D—C—D

SOLUTION

D—COO– + CD3—OH
 O
Question || –
OD
D—C—D

SOLUTION

D—COO– + CD3—OD
X3C—CHO (X = F, Cl, Br, I) does not undergo Cannizzaro reaction

X O X O⊝
|| ⊝ | R.D.S.
••
⊝
𝐎H
X—C—C X—C—C—OH Slow
X3C + H—C—OH
| | ||
X step
H X H O

Intramolecular
H⊝ transfer

CHX3 + HCOO⊝

Due to –I effect of three X-atoms, C—C bond is weaker than C—H

bond. Thus H⊝ ion (hydride ion) transfer does not take place. Hence,
it does not undergo Cannizzaro reaction.
EXAMPLE

O ⊖
O
Conc. OH ⊖ ⊕
Cannizzaro NO
Cl3C—C—H CHCl3 + H—C—ONa

Haloform YES
Question Trichloroacetaldehyde was subjected to assumed Cannizzaro's reaction by
using NaOH. The mixture of the products contains sodium
trichloroacetate and another compound. The other compound is :
(1) 2,2,2–Trichloropropanol (2) Chloroform
(3) 2,2,2–Trichloroethanol (4) Trichloromethanol

SOLUTION (AIEEE-2011)

Ans. (3)
Cross Cannizzaro reaction

O O ⊖
Conc. OH ⊖
Ph—C—H + H—C—H HCOO + PhCH2OH
Less More
reactive reactive

More reactive will oxidize and less reactive will reduce.

Cross Cannizzaro Redox YES

Disproportionation NO

But Cannizzaro Redox YES

Disproportionation YES
Mechanism

Ph
𝐇 H C ==O
⊝ (fast) | H
𝐎𝐇 C==O HO—C—O⊝ Slow HO—C== O + PhCH2—O⊝
Step 1 | R.D.S.
|
𝐇 H Step 2 H

Step 3 H⊝
exchanges

HCOO⊝ + PhCH2OH
Note

Aliphatic aldehyde are more reactive than aromatic aldehydes.

–
Aldehydes containing e- withdrawing groups (-I or –R or both –I
–
and –R) are more reactive than those containing e- donating groups
(+I or +R or both +I and +R) or with hyperconjugation (H.C)
EXAMPLE

O O ⊖
Conc. OH ⊖
(1) Me3C—C—H + H—C—H Me3C—CH2—OH + HCOONa⊕

O O
⊖
Conc. OH
(2) Me2CH—C—H + H—C—H

Aldol reaction show but not show Cannizzaro reaction.

Intramolecular Cannizzaro Reactions

When dialdehyde or a ketoaldehyde, lacking 𝛼 – H atom, is reacted

with a strong base, it undergoes internal crossed cannizaro
reaction .

O O OH O
⊖
Conc. OH
H—C—C—H CH2—C—OH
Mechanism

O O OH O
⊖
Conc. OH
H—C—C—H CH2—C—OH

H+ (work up)

⊖
O O H O
H—C—C—H H—C—C—OH
O—H O⊖
 EXAMPLE

O
O O ⊖
H O O—C
(i) OH (iii)  * *
Ph—C—C—H (ii) H+ Ph—C—C—OH Ph—CH CH—Ph
OH C—O
O
Total of product = 3

On heating dimer will be formed in the above reaction.

 Br
Question Ph—C—CH
⊖
OH
Br
O

SOLUTION

⊖
Ph—CH—COO
OH
 ⊖
CHO (i) OH
Question ⊕
(ii) H /∆
CHO

SOLUTION

O
Question CHO OHC
(IIT-2003)
𝐢 𝐍𝐚𝐎𝐇 𝐞𝐱𝐜𝐞𝐬𝐬 𝟏𝟎𝟎°𝐂

ሺ𝐢𝐢) 𝐇 + Τ𝐇𝟐 𝐎
CHO OHC
any one of the products formed is :
COOH HOOC CH2OH CH2OH

(A) (B)

COOH HOOC CH2OH CH2OH

O
O
CH2OH COOH

(C) (D)

O
COOH CH2OH O
SOLUTION

Ans. (C)
 PERKIN
AND
REFORMATSKY
 Perkin reaction

Condensation reaction between aromatic aldehyde and aliphatic acid

anhydride having at least two alpha hydrogen in the presence of a
base is known as Perkin reaction.
In this reaction, the anion of an acid anhydride adds to an aromatic
aldehyde to produce an 𝛽 aryl 𝑎, 𝛽, unsaturated acid. In order to
prevent side reactions, the base that is used to make the anion of
the anhydride is usually the sodium salt of the acid corresponding to
the anhydride.
O O
⊖
CH3COONa
Ph—CHO + CH3—C—O—C—CH3 CH3COOH + Ph—CH==CH—COOH
acetic anhydride (cinnamic acid)
 Mechanism

H O O O O O
| || || || O⊝ O
CH3 – C – O⊝Na
⊕
⊝ || || | ||
CH2 – C – O – C C H2 – C – O – C CH2 = C – O – C
CH3
CH3 O CH3
||
Ph – C – H

CH3
|
O C O⊝ O⊝ O O
OCOCH3 | || ||
Ph – CH Ph – CH O Ph – C – CH2 – C – O – C
CH2 – C – O⊝ | CH3
CH2 C H
|| ||
O O
H3C—C—O—C—CH3
O O
 OCOCH3
Ph – CH
CH2 – C – O⊝
||
O
H3C—C—O—C—CH3
O O
O
OCOCH3 O ||
|| –CH3 – C – OH
Ph – CH O O + CH3 – C – O⊝
|| ||
CH – C – O – C – CH3 O O
| || ||
H Ph – CH = CH – C – O – C – CH3
HOH

O O
|| ||
Ph – CH = CH – C – OH + CH3 – C – OH
 Short trick

O H O
CH3COONa
Ph—CH== O + H2 C—C—O—C—CH3
H OH

O
Ph—CH==CH—C—OH + CH3—COOH
(cinnamic acid)
 Note

Perkin reaction doesn’t usually take place with aliphatic aldehyde

EXAMPLE

Me O O Me Me O
C2H5COONa
Ph—CHO + H2C—C—O—C—CH2 Ph—CH==C—C—OH

O
H
O CH3COONa
H H OH COOH
CH==O O
Ph
 (i) (CH3CH2CO)2 O/CH3–CH2–COONa, 
Question H3C CHO A
(ii) H/H2O, 

SOLUTION

Ans. H3C CH = C—COOH

|
CH3
 OH
Question (i) (CH3CO)2 O/CH3COONa, 
B  C
(ii) H3O
CHO

SOLUTION

OH

Ans. CH=CH2—COOH
(B)
O O

(C)
Question (i) (CH3CO)2 O/CH3COONa, 
D
(ii) H/H2O, 
O CHO

SOLUTION

Ans.
O CH = CH—COOH
 In the perkin reaction which one of the following intermediates gives
Question compound (I) O O
|| ||
C6H5 – CH = CH – C – O – C – CH3
(I)
O
O⊝ O O ||
| || || O – C – CH3
(A) C6H5 – CH – CH2 – C – O – C – CH3 (B) C6H5 – CH
CH2 – COO⊝
O O
|| ⊝ ||
O – C – 𝐂 H2 O – C – CH3
(C) C6H5 – CH O (D) C6H5 – CH O
|| ||
CH2 – C – OH CH2 – C – O – C – CH3
||
O
SOLUTION

Ans. (A)
Question COOH
CHO
+ X
𝐂𝐇𝟑 𝐂𝐎𝐎𝐍𝐚
(IIT-2005)
MeO MeO

What is X?
(A) CH3COOH (B) BrCH2, COOH (C) (CH3CO)2O (D) CHO–COOH

SOLUTION

Ans. (C)
 PERKIN
AND
REFORMATSKY
 Perkin reaction

Condensation reaction between aromatic aldehyde and aliphatic acid

anhydride having at least two alpha hydrogen in the presence of a
base is known as Perkin reaction.
In this reaction, the anion of an acid anhydride adds to an aromatic
aldehyde to produce an 𝛽 aryl 𝑎, 𝛽, unsaturated acid. In order to
prevent side reactions, the base that is used to make the anion of
the anhydride is usually the sodium salt of the acid corresponding to
the anhydride.
O O
⊖
CH3COONa
Ph—CHO + CH3—C—O—C—CH3 CH3COOH + Ph—CH==CH—COOH
acetic anhydride (cinnamic acid)
 Mechanism

H O O O O O
| || || || O⊝ O
CH3 – C – O⊝Na
⊕
⊝ || || | ||
CH2 – C – O – C C H2 – C – O – C CH2 = C – O – C
CH3
CH3 O CH3
||
Ph – C – H

CH3
|
O C O⊝ O⊝ O O
OCOCH3 | || ||
Ph – CH Ph – CH O Ph – C – CH2 – C – O – C
CH2 – C – O⊝ | CH3
CH2 C H
|| ||
O O
H3C—C—O—C—CH3
O O
 OCOCH3
Ph – CH
CH2 – C – O⊝
||
O
H3C—C—O—C—CH3
O O
O
OCOCH3 O ||
|| –CH3 – C – OH
Ph – CH O O + CH3 – C – O⊝
|| ||
CH – C – O – C – CH3 O O
| || ||
H Ph – CH = CH – C – O – C – CH3
HOH

O O
|| ||
Ph – CH = CH – C – OH + CH3 – C – OH
 Short trick

O H O
CH3COONa
Ph—CH== O + H2 C—C—O—C—CH3
H OH

O
Ph—CH==CH—C—OH + CH3—COOH
(cinnamic acid)
 Note

Perkin reaction doesn’t usually take place with aliphatic aldehyde

EXAMPLE

Me O O Me Me O
C2H5COONa
Ph—CHO + H2C—C—O—C—CH2 Ph—CH==C—C—OH

O
H
O CH3COONa
H H OH COOH
CH==O O
Ph
 (i) (CH3CH2CO)2 O/CH3–CH2–COONa, 
Question H3C CHO A
(ii) H/H2O, 

SOLUTION

Ans. H3C CH = C—COOH

|
CH3
 OH
Question (i) (CH3CO)2 O/CH3COONa, 
B  C
(ii) H3O
CHO

SOLUTION

OH

Ans. CH=CH2—COOH
(B)
O O

(C)
Question (i) (CH3CO)2 O/CH3COONa, 
D
(ii) H/H2O, 
O CHO

SOLUTION

Ans.
O CH = CH—COOH
 In the perkin reaction which one of the following intermediates gives
Question compound (I) O O
|| ||
C6H5 – CH = CH – C – O – C – CH3
(I)
O
O⊝ O O ||
| || || O – C – CH3
(A) C6H5 – CH – CH2 – C – O – C – CH3 (B) C6H5 – CH
CH2 – COO⊝
O O
|| ⊝ ||
O – C – 𝐂 H2 O – C – CH3
(C) C6H5 – CH O (D) C6H5 – CH O
|| ||
CH2 – C – OH CH2 – C – O – C – CH3
||
O
SOLUTION

Ans. (A)
Question COOH
CHO
+ X
𝐂𝐇𝟑 𝐂𝐎𝐎𝐍𝐚
(IIT-2005)
MeO MeO

What is X?
(A) CH3COOH (B) BrCH2, COOH (C) (CH3CO)2O (D) CHO–COOH

SOLUTION

Ans. (C)
Reformatsky reaction

–haloester when treated with Zn it gives organometallic halo ester

which provides the attacking Nucleophile for the another reactant,
which is a carbonyl compound.

When nucleophile attacks on carbonyl compound it gives an

intermediate which upon acidic hydrolysis followed by heating
result in formation of 𝛼, 𝛽-unsaturated acid.

Br O
COOH
(i) Zn
R—CHO + CH2—C—OEt (ii) H3O+
R
(ii)  𝛼, 𝛽-unsaturated acid
Mechanism

Step-1

O O—ZnBr
Br Zn
OEt OEt
(Zinc enolate)
 Br— Zn
O Br— Zn
O O O

R H OEt R OEt

H2O

OH O OH O
H3O+
R OH R OEt


COOH
R
Question C6H5COCH3 + BrCH3COOEt
1. Zn
2. H3O 
A

SOLUTION

C6H5–C=CH–COOH
Ans. |
CH3
(E/Z)
 O
Question || (i) Zn
(ii) PhCHO
OEt (iii) H3O 
B
Br

SOLUTION

Ph – CH = C – COOH
Ans. |
CH3
(E/Z)
 Br
Question Ph | OEt + CH3CHO
(i) Zn/Ether
C
(iii) H3O 
||
O

SOLUTION

CH–CH3
Ph || OH
Ans.
||
O
 O
Question
1. Zn (i) 
+ BrCH2COOEt 2. H3 O
D (ii) Se/
E

a-tetralone

SOLUTION
HO CH2COOH

(D)
Ans.
CH2–COOH

(E)

-Naphthylacetic acid
Question Br
| (i) Zn/EtO (i) 
EtO – C – CH – CH2CH2CH2–CH2– CHO (ii) H3O
F (ii) Se/
G
||
O

SOLUTION

COOH COOH
Ans. OH
(F) (G)
 COOPh
Question Br
(i) Zn/Et2O
(ii) CH2O
H
(iii) H3O, 

SOLUTION

COOH
Ans. CH2OH
 Benzil Benzilic Acid
Rearrangement And
Tishchenko Reaction
Benzil benzilic acid rearrangement

The benzylic acid rearrangement is formally the 1,2- rearrangement

of 1,2- diketone to form 𝛼-hydroxy – carboxylic acids using a base.

O O
Ph 1. HO– Ph
Ph 2. H+ OH
O HO
Ph
benzil benzilic acid
Mechanism

O O O O⊝ O⊝ O
|| || ⊝ Fast || | | ||
R.D.S.
Ph—C—C O H Ph—C—C—OH Ph—C—C—OH
| Slow |
|
Ph Ph Ph

Fast

OH O
| ||
Ph—C—C—O⊝
|
Ph

Rate = k[Benzil][HO⊝]
Note

When two aryl groups are different, the one with less eത -donating
substituent on the benzene ring will migrate.

O O O⊝ OH
|| || ⊝ | |
OH
C—C OMe O== C—C OMe
|
Ph
 Et
Question
O ⊝
𝐎H

O
Me

SOLUTION

Et

Ans. OH
COO⊝
Me
 Me
Question O
NaOMe

O
OMe

SOLUTION

Me

Ans. OH
C—OMe
||
OMe O
Question
O ⊝
𝐎H

SOLUTION

OH
Ans. COO⊝
Tischenko Reaction

The tischenko reaction is a disproportionation reaction that allows

the preparation of esters from two equivalents of an aldehyde.

Al(OC2H5)3
2CH3CHO CH3COOCH2CH3
−H2O
Ethyl ethanoate
Mechanism

The mechanism is uncertain, but there is a possibility involving an H⊝

ion shift as in the M.P.V. reduction.

The aluminium alkoxide acts as a lewis acid to coordinate with one

molecule of the aldehyde, and to facilitate the addition of second
equivalent of the aldehyde, generating a hemiacetal intermediate.
 Mechanism

⊕
RCH== O + Al(OEt)3 RC H—O—Al(OEt)3

R—CH== O

R
⊕ | ⊖
Al(OEt)3 + RCH2—O—C—R HC —O—C—O—A l(OEt)3
|| | |
O R H
 Al(OEt)3
Question 2MeCHO
Acetaldehyde

SOLUTION

O
||
Ans. Me—C— O—CH2—Me
Ethyl acetane
 Al(OEt)3
Question 2MeCH2CHO
Propanal

SOLUTION

O
||
Ans. MeCH2C— O—CH2CH2Me
Propyl propanoate
 Al(OEt)3
Question 2HCHO
Formaldehyde

SOLUTION

O
||
Ans. H—C— O—Me
Methyl formate
 Claisen
And
Dieckmann
Condensation
Claisen condensation

The Claisen condensation between esters containing 𝛼- hydrogens ,

promoted by a base such as sodium ethoxide, affords
𝛽- ketoesters.

The driving force is the formation of the stabilized anion of the

𝛽- ketoester.

O O O
(i) RONa
2Me – C – OR Me – C –CH2 – C – OR
(ii) Acidification
(-keto ester)
Note

The use of stronger bases, e.g. sodium amide or sodium hydride

instead of sodium ethoxide, often increases the yield.
 Mechanism

H O O
||
O⊝
| || ⊝
RO Na ⊝ Me–C–OR
|
CH2 – C – OR 𝐂 𝐇𝟐 – COOR Me – C – CH2 – COOR
–ROH (rds) |
OR
⊝
–R–O
⊝
O⊝ O O O
| || | ⊝ ||
Na Me – C = CH – COOR RO Na
Me–C–CH=C–OR Me – C – CH– COOR
|
Acidification H

O O
|| ||
Me – C – CH2 – C – OR
Question (i) EtOK
MeCOOEt A
(ii) Acidification

SOLUTION

O O
|| ||
Ans. Me—C—CH2—C—OEt
 (i) MeOK
Question EtCOOMe
(ii) Acidification
B

SOLUTION

O O
|| * ||
Ans. Et—C—CH—C—OMe
|
CH3
(R/S)
Question MeCOOMe + EtCOOMe
(i) MeOK
C
(ii) Acidification

SOLUTION

Ans. (4 products)
 (i) C2H5ONa
Question C6H5COOC2H5 + CH3COOC2H5 D + D'
Ethyl benzoate (ii) Acidification

SOLUTION

Ans. C6H5COCH2COOC2H5, CH3COCH2COOC2H5

Ethtl benzolyacetate
Question COOC2H5
(i) C2H5ONa
| + C6H5CH2COOC2H5 E [Cross Product]
(ii) Acidification
COOC2H5

SOLUTION

C6H5—CHCOOC2H5
Ans. |
COCOOC2H5
Diethyl--oxalyphenyl
acetate
Dieckmann condensation

The Dieckmann condensation is the intramolecular chemical reaction

of diesters with base to give –keto esters.

O O
O
1. base
OR 2. H+
OR
O ROH

OR
Mechanism

O O O⊖ OR O
⊖
OR OR OR
H ⊖ OR
O O

OR OR

⊖
O O O
O O O
⊖
OR H+ OR RO OR
H
Question PhOOC
COOPh (i) PhONa
(ii) Acidification
F

SOLUTION

O
||
Ans. *
—C—OPh
||
O
(R/S)
Question CH2CH2COOEt (i)C2H5 ONa H3O
C2H5—N G H (Piperidone derivative)

(ii)Acidification
CH2CH2COOEt

SOLUTION

COOEt

(G) C2H5—N O
Ans.

(H) C2H5—N O
 KNOEVENGEL
CONDENSATION AND
MICHAEL REACTION
Knoevenagel condensation

The aldol condensation of 1, 3 dicarbonyl compounds (active

methylene compounds) with an aldehyde or ketone in presence of
weak base is called Knoevenagel reaction.

(i) R2NH
O O
(ii) H3O+
+ O
(iii) 
EtO OEt CO2H
H
Mechanism

O O⊝
O O

EtO OEt
EtO OEt
H H (enolate)
••
R2NH

tEO O
tEO O
H
O
O⊝
O
⊝
O OEt
OEt
 tEO O
tEO O
H
O
O⊝
O
⊝
O OEt
OEt
Workup

OEt O⊝ OEt O
CO2Et ••
R2NH
O O
CO2Et
H
H HO OEt HO OEt
COOH
H3O
∆
COOH COOH
H
 EXAMPLE

(i)
N
NO2 NO2
Et—CHO + H2C H
Et—CH = CH
NO2 (ii) H3O+ NO2
(iii) 
 EXAMPLE

(i) MeNH2
COOMe (ii) H3O+
MeOOC—CHO + H2C HOOC—CH = CH—COOH
COOMe (iii) 

– H2O

O
(final product)
Question CH3CHO + H2C(COOR)2
(i) Piperidine
(ii) H3O, 
A

SOLUTION

Ans. CH3 – CH = CH – COOH

Cinnamic acid
Question C6H5CHO + H2C(COOR)2 (i) Piperidine
(ii) H3 O, 
B

SOLUTION

Ans. C6H5 – CH=CH – COOH

Cinnamic acid
Question HOOC – CHO + H2C(COOR)
(i) Piperidine
(ii) H3O, 
C
Glyoxalic aacid

SOLUTION

Ans. HOOC – CH = CH – COOH

Maleic acid
 O
Question O ||
|| C–Me Et2NH
Ph – C – H + CH2 D

C– OEt
||
O

SOLUTION

O
||
Ans. C–Me
Ph – CH = C
C– OEt
||
O
 O
Question || nC2H11NH2
Ph – C – H + CH3–NO2 
E

SOLUTION

Ans. (Ph – CH = CH – NO2)

Question Me CN
O
||
CH3C—NH2
C=O + CH2 F
CH3COOH, 
Me COOR

SOLUTION

Me CN
Ans. C=C
Me COOR
Question O
CN || NaOEt
CH2 + Ph – C – H 
G
NO2

SOLUTION

NC
Ans. C = CH – Ph
O2N
Michael reaction

Michael Addition : 𝛼-𝛽 unsaturated carbonyl compound undergo

michael reaction with compounds having active methylene. When the
nucleophile is an enolate the addition reaction has a special name
MICHAEL REACTON.
Michael reaction

Michael donor Michael acceptor

O O
O O X = –H/R/
–OR/NP2 OEt , H/CH3 ,
X X
O O
O
O
,

O CN NO2
,
Michael Addition

Conjugate addition (1, 4-addition) is also called Michael addition.

More stable enolate (Michael Donor)

Less reactive 𝛼, 𝛽 unsaturated carbonyl group (Michael acceptor).

COOEt CO2Et
H2C = CH—CN + CH2 EtONa/EtOH NC—CH2—CH2—CH
COOEt CO2Et
 Mechanism

O
O O O O ||
|| ||
⊝
O H(base) || || R – CH = CH – C – R
β α
R – C – CH– C – R R – C – CH – C – R
| –H2O ⊝
,  unsaturated
H carbonyl compound

O O
|| O || O⊝
R–C || R–C |
HO–H
CH – CH – CH2 – C – R CH – CH – CH = C – R
R–C | –OH⊝ R–C |
|| R || R
O O
EXAMPLE

O
O O
O
+ AcOH/H2O

O
O
Question O O O
|| || || OH⊝
CH3 – C – CH2 – C – CH3 + CH2 = CH – C—H –H2O ?

SOLUTION

O
||
CH2 – CH2 – CH
|
Ans. CH3 – C – CH – C
||
– CH3
||
O O
Question O
|| COOEt CH3CH2O⊝
CH3CH = CH – C – CH3 + CH2 ?
COOEt

SOLUTION

O
||
CH3–CH–CH2–C–CH3
Ans.
O
||
CH(–C–OCH2CH3)2