Reagent :- Na/dry Ether

Reactant :- Alkyl halide/Aryl halide

Wurtz reaction

Dry
R—X + 2Na + X—R R—R + 2NaX
ether

Fittig Reaction

Na
Cl
Dry ether

Aryl halide
 Wurtz–Fittig Reaction

Na
Cl + R—Cl R + + R—R
Dry ether
Alkyl
Aryl halide halide

Reagent :- Zn/dry Ether

Reactant :- Alkyl halide

From Frankland Reagent

Zn
2CH3 Br CH3 CH3 + ZnBr2
dry ether
 Reagent :- Cu/dry Ether
Reactant :- Aryl halide

Ullmann Reaction

Cu
dry ether
 Reagent :- Red P + HI

Red P + HI
R—I R—H + I2


Reduction of alcohol, aldehyde, ketone, carboxylic acid in presence of

Red P and HI

Alcohol

Red P + HI Red P + HI
R—OH R—I R—H + I2
 

No. of moles of (Red P + HI) required = 2

Reagent :- Red P + HI

Reactant Product Reagent No. of moles required

R—I R—H 1
R—OH R—H 2
O
R—CH3—H 4
R—C—H
Red P + HI
O
R—CH2—R 4
R—C—R
O
R—CH3 6
R—C—OH
 EXAMPLE

Calculate the number of moles of (Red P + HI) required for reduction of :

CH2—COOH
I
X(Red P + HI)

I—H2C CH2—COCH3
OH

Solution

Ans : 14
 Reagent :- AlCl3 + HCl
Reactant :- Alkane

Isomerisation

Unbranched chain alkanes on heating with AlCl3 + HCl are converted

into more branched chain alkanes.

CH3
AlCl3 + HCl
CH3—CH2—CH2—CH3 CH3—CH—CH3

n-Butane Isobutane
 EXAMPLE
[JEE Main–2023]
In the following reaction ‘X’ is
Anhy. AlCl3
CH3(CH2)4CH3 HCl, D
X
major product

(A) CH3(CH2)4CH2Cl (B) Cl—CH2—(CH2)4—CH2—Cl

(C) CH3CH—(CH2)2CH3 (D)

CH3
Solution

Ans : (C)
 Reagent :- Cr2O3/Al2O3/Mo2O3, High T,P
Reactant :- Alkane

Aromatization

Cr2O3/Al2O3
CH3(CH2)4 CH3 + 4H2
500° C
n-Hexane Benzene

CH3

Cr2O3/Al2O3
CH3(CH2)5 CH3 + 4H2
500° C
n-Heptane
Toluene
 EXAMPLE
[JEE Main–2021]
Identify A in the given chemical reaction.
CH3
CH2
Mo2O3
CH2 CH3 ‘A’
773K, 10-20 atm
CH major product
CH2 CH3
CH3 CH3
(A) (B) (C) (D)

Solution

Ans : (D)
 Reagent :- X2 + h / 

Halogenation of alkanes

h
CH4 + Cl2 ⎯⎯→ CH3Cl + HCl
(Excess)

h𝑣
CH4 + Cl2 CCl4
(Excess)

h𝑣
H3C—CH=CH2 + X2 H2C—CH=CH2 + H3C—CH—CH2
CCl4

X X X
 EXAMPLE

Presence of which reagent will affect the reversibility of the following

reaction, and change it to a irreversible reaction :
[JEE Main–2021]
hv
CH4 + I2 CH3—I + HI
Reversible
(A) HOCl (B) dilute HNO2
(C) Liquid NH3 (D) Concentrated HIO3

Solution

Ans : (D)
 Reagent :- NBS + h  X2/ High Temp.

Allylic Substitution

NBS
CH2=CH—CH3 CH2=CH—CH2Br
h

For allylic & benzylic halogenation , use NBS, h𝑣 in presence of non

polar solvent like CCl4
 EXAMPLE

NBS alc.KOH
A B
CCl4/hv ∆

Identify 'B' product :-

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

OH
OH

Solution

Ans : (B)
 Reagent :- PPh3=CR2
Reactant :- Aldehyde/ketone

Wittig reaction

R’ R’ R
C=O PPh3=CR2 C=C + Ph3P=O
R’’ R’’ R
 Reagent :- H—X
Reactant :- Alkene/Alkyne

R—CH=CH2 + H—Br R—CH—CH2 (Hydrohalogenation)

Br H

R—O—H+H—X R — X + H2O
Br
H3C–C C–H + HBr H3C–C–CH3
(excess)
Br
Me — O — Et + HI MeI + EtOH

Me Me
Me ——O—Me + HI Me —— I + MeOH
Me Me
 EXAMPLE

The major product of the following reaction is : [JEE Mains–2019]

O
HI (excess)
∆

NC O
OH I OH I
(1) (2) (3) (4)

NC I NC OH NC OH NC I

Solution

Ans : (1)
 EXAMPLE
[JEE Main–2023]
In the following given reaction 'A' is
CH3
|
C CH2

||
+ HBr 'L'
major product
CH3
CH3 Br CH3
Br CH3 CH3
Br
(A) (B) (C) CH3 (D) Br

Solution

Ans : (D)
EXAMPLE

Ph
H—Br

Solution

Ans :
Ph Ph
+
Br Br
Diastereomers
Reagent :- X2/CCl4 and X2/H2O , Interhalogen
Reactant :- Alkene

CCl4
+ Br—Br

H2O
H3C—CH=CH2 + Br2 H3C—CH—CH2

OH Br
Reagent :- X2/CCl4 and X2/H2O
Reactant :- Alkene/Alkyne

Br Br
CH2Cl2
H3C–CCH + Br2 H3C–C–CH
(excess)
Br Br

Cl
Cl Cl
3Cl2 / hv Benzene hexachloride
∆ (BHC) or Gammaxane
Cl Cl or lindane
C6H6
Cl
(C6H6Cl6)
EXAMPLE

CH3
Br2
CCl4

Solution

Ans : Diastereomers

Br + Br

Br Br
Reagent :- NOCl (Tilden’s Reagent)
Reactant :- Alkene

Cl

H3C—CH=CH2 + O=N—Cl H3C—CH—CH2

NO
 EXAMPLE

Major product ‘P’ formed in the following reaction is :- [JEE Mains–2023]

OH Br2
P
NaHCO3 Major
O
Product
Br
(1) Br OH (2) Br O

O O
Br
OH
(3) Br OH (4)

O O
Solution

Ans : (2)
EXAMPLE

Br

Br2/CCl4
Br

OH

HOBr
Br

Cl

NOCl
NO
 Reagent :- H+/H2O
dil.H2SO4 or dil.H3PO4
Reactant :- Alkene

Hydration of alkenes

H+
H2C == CH2 + H2O CH3 — CH2 — OH

OH
dil.H2SO4 |
CH3—CH—CH== CH2 CH3—C—CH2—CH3
| |
CH3 CH3

dil.H2SO4/
OH
(or)H3O+
EXAMPLE

H / H 2O

Solution

H H-OH OH
 Reagent :- (i) Hg(OAc)2, H2O
(ii) NaBH4, OH⊝
Reactant :- Alkene

oxymercuration demercuration (OMDM)

a a
(i) Hg(OAc)2,H2O
CH—CH=CH2 CH—CH—CH3
b
(ii) NaBH4, OH⊝
b |
OH

If a = b = H  1° alcohol
a = R and b = H  2° alcohol
a = R and b = R  3° alcohol
 Reagent :- (i) B2H6/THF
(ii) H2O2/HO–
Reactant :- Alkene

Hydroboration Oxidation (HBO)

(i) B2H6/THF (i) B2H6/THF

RCH2CH2—OR R—CH=CH2 RCH2CH2—OH
(ii) H2O2 /RO― (ii) H2O2 /HO―
(i) B2H6/THF
(ii) CH3COOH

RCH2CH3
 EXAMPLE [JEE MAIN ONLINE 2022]
Choose the correct option for the following reactions.
CH3
(BH3)2 Hg(OAc)2 , H2O
B H3C—C—CH=CH2 A
H2O2/OH⊝ NaBH4
CH3
(1) ‘A’ and ‘B’ are both Markovnikov addition products.
(2) ‘A’ is Markovnikov product and ‘B’ is anti-Markovnikov product.
(3) ‘A’ and ‘B’ are both anti-Markovnikov products.
(4) ‘B’ is Markovnikov and ‘A’ is anti-Markovnikov product.

Solution

Ans : (2)
 EXAMPLE
The major product [B] in the following sequence of reactions is :-
(i) B2H6 dil.H2SO4
CH3—C = CH—CH2CH3 [A] [B]
|
⊝
∆
(ii) H2O2, OH
CH(CH3)2 [JEE Mains 2020]
CH3—C—CH2CH2CH3 CH2=C—CH2CH2CH3
(1) || (2)
C |
CH(CH3)2
H3C CH3
(3) CH3—CH—CH=CH—CH3 (4) CH3—C=CH—CH2CH3
| |
CH(CH3)2 CH(CH3)2

Solution

Ans : (1)
Reagent :- Moist and dry Ag2O
Reactant :- Alkyl halide

Moist Ag2O
R—OH

R—X
dry Ag2O
R—O—R
 EXAMPLE
[JEE MAIN ONLINE 2019]
OCH3
Conc. HBr(excess)
heat

CH=CH2

OH Br Br OH
(2) (3) (4)
(1)

CH2CH2Br CH2CH2Br Br–CHCH3 Br–CHCH3

Solution

Ans : (4)
Lucas test

It is a test mainly used to distinguish between primary, secondary

and tertiary alcohols.

anhyd. ZnCl2
R — OH + HCl RCl (turbidity)
+ HCl
 Reagent :- Conc. HCl + anhyd. ZnCl2 (Lucas reagent)

Lucas Test

Lucas reagent
Test Testing with a mixture of conc. HCl and anhyd.
ZnCl2

Does not from turbidity at room temperature

Primary alcohol
(turbidity is obtained only upon heating)

Secondary alcohol Turbidity formed in 5 to 10 minutes

Tertiary alcohol Turbidity is formed immediately

(2) Victor - Meyer test

This is colour test for alcohol (primary, secondary & tertiary) .

Primary alcohol ⎯⎯→ Red colour

Secondary alcohol ⎯⎯→ Blue colour

Tertiary alcohol ⎯⎯→ No colour

This test is used to differentiate 1°, 2° and 3° alcohols,

 Reagent :- HBr + Peroxide
Reactant :- Alkene

Anti Markovnikov Rule or Peroxide Effect or Kharasch Rule

HBr CH3—CH—CH3
|
Br
Ionic mechanism

CH3—CH == CH2

HBr
CH3—CH2—CH2—Br
R—O—O—R
Free radicals mechanism
 Reagent :- Red hot Fe Tube
Reactant :- Alkyne

Cyclic polymerisation

Red hot Red hot

3CH≡CH 3CH3—C≡CH
iron tube iron tube
Benzene
Mesitylene

Red hot
3CH3—C  C—CH3
iron tube
 Reagent :- KMnO4/H  K2Cr2O7/H
Reactant :- Benzene and it’s derivative

Side Chain Oxidation

CH3 COOH

K2Cr2O7/H
 Me COOH
Me K2Cr2O7/H COOH
o-Xylene

Me COOH

K2Cr2O7/H
m-Xylene
COOH
Me
Me COOH

p-Xylene K2Cr2O7/H

Me COOH
Reagent :- Cl2, AlCl3 / Cl2, UV
Reactant :- Benzene
Cl

Cl2
AlCl3

Cl
Cl Cl
Cl2(excess) Hexachloro benzene(C6Cl6)
AlCl3 Cl Cl
Cl
Cl
Cl Cl Benzene hexachloride (C6H6Cl6)
3Cl2 or Gammaxene
or Lindane
UV/500K Cl Cl (used as an insecticides)
Cl
 Reagent :- SO2Cl2 + h

Reed Reaction

h𝑣
R — H + SO2Cl2 R — Cl + HCl  + SO2 
 Reagent :- Br2,CCl4 ∆
Reactant :- RCOOAg

Hunsdiecker Reaction

AgOH
RCOOH RBr + CO2
Br2,CCl4 ∆

This method is used to decreases in number of carbon chain.

This reaction goes via Ionic Radical Mechanism.

Reagent :- PCl3 or Red P + X2

SN2
3R OH + PCl3 3R Cl + H3PO3
inversion

O O
PCl3
R—C—OH R—C—Cl

O O
PCl3
R—S—OH R—S—Cl

O O

OH
PCl3 No reaction
 EXAMPLE

Find the product A,B,C formed in the following reaction is :

HI
HO A
Red P + I2
B
Red P + HI
C

Solution

Ans : I
I

(A) (B) (C)

Reagent :- PCl5

SN2
R—OH + PCl5 R—Cl + POCl3 + HCl ↑
inversion

O PCl5
R' R RCl + R’Cl + POCl3
ether

O O

R—C—OH + PCl5 R—C—Cl + HCl + POCl3

Carboxylic acid

O
R C OR' + PCl5 RCOCl + R'Cl + POCl3
 Reagent :- PCl5

O O O O

R—C—O—C—R’ + PCl5 R—C—Cl + R’—C—Cl + POCl3

(Anhydride)

O Cl Cl

R—C—H + PCl5 R—C—H + POCl3

O Cl
Cl Cl Cl
Cl
C POCl3
C + P +
R' R
R' R Cl Cl
O

R—C—NH2 + PCl5 R—C ≡ Nሷ

 Reagent :- SOCl2

Darzen’s reaction

SNi
ROH + SOCl2 R—Cl + SO2↑ + HCl ↑

OH

SOCl2
No reaction

R C—OH SOCl2 R C—Cl

O O
 EXAMPLE

The major product formed in the following reaction is :

Me SOCl2
A

H OH
SOCl2
Et B
py

Solution

Ans : Me Me

A= H Cl B = Cl H

Et Et
SN i SN 2
 EXAMPLE
Identify A in the given reaction. [JEE (Main)-2021]
OH
SOCl2
A (Major Product)
HO CH2OH
OH OH Cl Cl

(1) (2) (3) (4)

OH CH2Cl Cl CH2Cl Cl CH2Cl OH CH2OH

Solution

Ans : (2)
 Reagent :- NaI, Dry acetone

Finkelstein Reaction

Dry
R—X + NaI R—I + NaX
acetone
X = Cl, Br

Note

(1) NaCl or NaBr is precipitated in dry acetone, which is driving force.

(2) NaCl & NaBr are insoluble in dry acetone while NaI is soluble.

(3) SN2 mechanism is involved and hence inversion takes place.

EXAMPLE

The major product formed in the following reaction is :

Me

NaI
H Cl
acetone

Solution

Ans : Me

I H

D
 Reagent :- Metal Fluoride (CoF2), DMSO

Swarts Reaction

The synthesis of alkyl fluorides is best accomplished by heating an

alkyl chloride/ bromide in presence of metallic fluoride such as
AgF, Hg2F2, HgF2, CoF2 or SbF3.

DMSO
CH3—X + AgF CH3—F + AgX
X = Br, Cl, I

F is a good nucleophile in polar aprotic solvent hence this reaction

⊝

occurs via SN2 mechanism.

 EXAMPLE

The major product formed in the following reaction is :

Me
AgF
H Cl DMSO

Solution

Ans : Me

F H

D
 Reagent :- Metal + Acid

Reducing agent
R—X R—H

Reducing agents may be

 Zn + HCl
 Sn + HCl Metal + acid

 Fe + HCl
 Zn + CH3COOH
 Reagent :- KCN, AgCN, KNO2, AgNO2
Reactant :- Alkyl halide

KCN
R—X R—CN

Ag—CN:

R—NC

KNO2
R—X R—O—N=O
••
Ag—O—N=O

R—NO2
 Reagent :- Aq. NaOH/KOH

SN2 Reaction

aq. NaOH
R—X R—OH
aq. KOH
 Reaction with primary unhindered alkyl halide and methyl halide
with nucleophile follows SN2 reaction except bulky nucleophile

Reaction with Reaction with

Oxygen Nucleophile Sulphur Nucleophile

O
|| ⊝
⊝O—C—CH (Oac) KSH
R—X 3
R—OAc R—X R—SH
AcOH

⊝OCH
⊝SPh
R—X 3
R—OCH3 R—X R—SPh
CH3OH

••
OH2
••

R—X R—OH
Reaction with Nitrogen Nucleophile

KNH2
R—X R—NH2 + HX
••
NH3
R—X R—NH2 + HX

••
NH2R
R—X R—NH—R + HX

•• ••
R—X + NHR2 R3N + HX

•• 
R—X + NR3 NR4X⊝

⊝
SN2  ⊝
R—X + N3 R—N=N + N
 EXAMPLE
In SN2 reactions, the correct order of reactivity for the following
compounds : [JEE (Main)-2014]
CH3Cl, CH3CH2Cl, (CH3)2CHCl and (CH3)3CCl is :
(1) CH3CH2Cl > CH3Cl > (CH3)2CHCl > (CH3)3CCl
(2) (CH3)2CHCl > CH3CH2Cl > CH3Cl > (CH3)3CCl
(3) CH3Cl > (CH3)2CHCl > CH3CH2Cl > (CH3)3CCl
(4) CH3Cl > CH3CH2Cl > (CH3)2CHCl > (CH3)3CCl

Solution

Ans : (4)
 EXAMPLE
Which of the following compounds will show retention in configuration
⊕
on nucleophic substitution by OH ion ? [JEE (Main)-2020]
CH3—CH—CH2Br CH3—CH—Br
(1) | (2) |
C2H5 C6H5
Br
CH3—CH—Br |
(3) | (4) CH3—C—H
CH3 |
C6H13
Solution

Ans : (1)
 EXAMPLE
The major product of the following reaction, if it occurs by SN2
mechanism is : OH [JEE (Main)-2021]

K2CO3
+ Br acetone
O
O
(1) (2)
OH

O
(3) O (4)

Solution

Ans : (4)
 EXAMPLE
[JEE (Main)-2022]
The major product of the following reaction is:
I ⊝⊕

F PhSNa
DMF

NO2

SPh I SPh SPh

F SPh F SPh
(1) (2) (3) (4)

NO2 NO2 NO2 NO2

Solution

Ans : (1)
 EXAMPLE
[JEE Mains–2023]
Match List I with List II
Bromopropane is reacted with reagents in List I to give product in List II

LIST I - Reagent LIST II - Product

A. KOH (alc) I. Nitrile
B. KCN II. Ester
C. AgNO2 III. Alkene
D. H3CCOOAg IV. Nitroalkane
(1) A-IV, B-III, C-II, D-I (2) A-III, B-I, C-IV, D-II
(3) A-I, B-II, C-III, D-IV (4) A-I, B-III, C-IV, D-II

Solution

Ans : (2)
 Reagent :- Polar Protic Solvent
Reactant :- Alkyl Halide

SN1 Reaction

Reaction of alkyl halide with polar protic solvent follows SN1 reaction.

OH Cl
HCl
EXAMPLE
[JEE Main–2023]
OH

H+
Major product
∆

In the above reaction. Left hand side and right hand side rings are
named as ‘A’ and ‘B’ respectively. They undergo ring expansion. The
correct statement for this process is:
(A) Finally both rings will become six membered each.
(B) Finally both rings will become five membered each.
(C) Only ‘A’ will become 6 membered.
(D) Ring expansion can go upto seven membered rings
Solution

Ans : (A)
 EXAMPLE
Compound from the following that will not produce precipitate on
reaction with AgNO3 is : [JEE Mains–2023]

Br
(1) (2) Br

(3) Br (4) CH=CH–CH2–Br

Solution

Ans : (1)
 Reagent :- Alc.KOH/NaOH or bulky base
Reactant :- Alkyl Halide

This reagent follows E2 mechanism

CH2
H(a) CH2—H(b) CH3 CH3—CH2—C
CH3—CH=C
CH3 + CH3
CH3—CH —C—Br
+ alc. KOH (a) (b)
CH3 Saytzeff alkene Hoffmann’s alkene
(more substituted alkene) (less substituted alkene)
More stable Less stable
(Major) (Minor)
 EXAMPLE
In the given reactions sequence, the major product ‘C’ is :
[JEE Main–2022]
HNO3 Br2 alcoholic
C8H10 ⎯⎯→ A ⎯⎯→ B ⎯⎯⎯→ C
H2SO4  KOH

NO2
(A) C=CH2 (B) O2N CH=CH2

NO2
(C) O2N C=CH2 (D) CH=CH2
NO2

Solution

Ans : (B)
 Reagent :- Alc.KOH/NaOH or bulky base
Reactant :- Alkyl Halide

H CH3
| | ⊝
H3C CH3 CH3—H2C
OC(CH3)3 H
CH3—C—C— CH2 C=C + C=C
(CH3)3COH CH3
| | | H H H
H Br H 28% 72%
Saytzeff product Hoffmann product
 EXAMPLE
Identify the correct statement for the below given transformation.
C2H5ONa
CH3–CH2–CH2–CH–CH3 A + B [JEE Main–2022]
C2H5OH
| (Major) (Minor)
N(CH )
3 3

(A) A - CH3CH2CH = CH–CH3, B – CH3CH2CH2CH = CH2, Saytzeff products

(B) A - CH3CH2CH = CH–CH3, B – CH3CH2CH2CH = CH2, Hafmann products
(C) A - CH3CH2CH2CH = CH2, B – CH3CH2CH = CHCH3, Hofmann products
(D) A - CH3CH2CH2CH = CH2, B – CH3CH2CH = CHCH3, Saytzeff products

Solution

Ans : (C)
 Reagent :- Polar Protic Solvent + 
Reactant :- Alkyl Halide or Alcohol

CH3 CH3 CH3

Solvolysis(H2O)
H3CH2C—C—Cl H3C—CH == C—CH3 + H3C—CH2—C=CH2

CH3 Saytzeff alkene Hoffmann alkene
(More substituted alkene) (Less substituted alkene)
(More stable) (Less stable)
(Major) (Minor)

OH CH3 CH2
H2SO4

+ + H2O

93% 7%
 EXAMPLE
Find out the major product from the following reaction.

H2 SO4 Concentrated ∆ [JEE Main–2023]

OH

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

Solution

Ans : (A)
 EXAMPLE

Decreasing order of dehydration of the following alcohols is

[JEE Main–2023]
OH OH OH OH

a b c d
(A) a > d > b > c (B) b > d > c > a
(C) b > a > d > c (D) d > b > c > a

Solution

Ans : (B)
 EXAMPLE
The major product (A) formed in the reaction given below is :
[JEE (Main)-2021]
CH3–CH2–CH–CH2–Br
CH3OH
+ CH3O ⊝ A
(Major product)
(1) CH3–CH2–CH–CH2Br (2) CH3–CH2–C=CH2

OCH3
(3) CH3–CH2–CH–CH2–OH (4) CH3–CH2–CH–CH2–OCH3

Solution
Ans : (2)
 Reagent :- NaOH + CaO + 

Soda–lime Decarboxylation

NaOH/CaO
RCOOH R—H + CO2


H O
O O
||
| || 
CH3—C—OH
O=C C—OH
CH2
Heating Effect

O
OH 
OH O + H2O
||
O O
Succinic acid (Succinic anhydride)

O
O
OH 
OH O + H2O
||
O O
glutaric acid (Glutaric anhydride)
 O
CH2—C—OH
H2C
 O + CO2 + H2O
H2C
CH2—C—OH
O
Adipic acid

O
O
C—OH
(CH2)5 
+ CO2 + H2O
C—OH
O
Pimelic acid
KOLBE'S ELECTROLYSIS

O
 
Electrolysis
R—C—O Na R—R + CO2 + H2 + NaOH

Anode Cathode

Sodium or potassium salt of carboxylic acid on electrolysis in

aqueous solution gives alkane along liberation of CO2 and H2.

After electrolysis the solution becomes alkaline

 EXAMPLE
 
H COO Na
C Electrolysis
C H2 O
 
H COO Na
(Sodium maleate)

Solution

Ans : CH

CH
 Reagent :- SnCl2 + HCl, H3O⊕

Stephen’s Reaction

O
(i) SnCl2/HCl (ii) H3O+
R—CN R—CH=NH R—C—H
 Reagent :- CrO2Cl2, CS2

Etard’s Reaction

CH3 CH(Ocr(OH)Cl2)
CS2
+ CrO2Cl2 2

Toluene Chromium complex

H3O+

CHO

Benzaldehyde
 Reagent :- CO, HCl, Anhyd. AlCl3/CuCl

Gatterman–Koch reaction

CHO
CO, HCl
Anhyd. AlCl3/CuCl

Benzene Benzaldehyde
 Reagent :- (i) CHCl3, NaOH, , (ii) H

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)
 Reagent :- (i) CHCl3, NaOH

Carbylamine Reaction (Iso cyanide test)


R—NH2 + CHCl3 + 3KOH RNC + 3KCl + 3H2O


Ph—NH2 + CHCl3 + 3KOH PhNC + 3KCl + 3H2O

This test is given by 1° Aliphatic or aromatic amine.

 Reagent :- NaOH + X2 or NaOI

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 CHX3 + HCOONa
X2

Example

I O Me—C—CH2—C—Me
OH , || ||
I , , O O
Give +ve haloform test
 Reagent :- NaOH + X2 or NaOI

Hoffmann Bromamide degradation

O
R — C — NH2 + Br2 + 4NaOH R — NH2 + Na2CO3 + 2NaBr + 2H2O

Only primary amide give Hoffmann & primary amine formed.

 Reactant Reagent Product Name
O NaN3 R—NH2 Curtius
R—C—Cl H2O

O
NaOH R—NH2
Lossen
R—C—NH—OTs H2O

O N3H R—NH2
Schmidt
R—C—OH H2O
 Reagent :- PhSO2Cl (Hinsberg reagent)

O O
RNH2
Ph—S—Cl Ph—S—N—R + HCl

O O H
(N-alkylbenzenesulphonamide)
(soluble in alkali)

O O
R2NH
Ph—S—Cl Ph—S—N—R + HCl

O O R
(N,N-dialkylbenzenesulphonamide)
(insoluble in alkali)
O
R3N
Ph—S—Cl No reaction

O
 Reagent :- CS2 + HgCl2

Hoffmann Mustard Oil Test

S S
HgCl2
R—NH2 + C == S R—NH—C—SH R—N == C == S + HgS + 2HCl

S S
HgCl2
R2NH + C == S R2N—C—SH No Black ppt

R3N + C == S No reaction
 Reagent :- [Ag(NH3)2]+ (Tollen's reagent)

Tollen’s Test

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.

AgNO3 + 2NH3 [Ag(NH3)2]+1 + NO−

3


RCHO + 2[Ag(NH3)2+] + 3OH– RCOO– + 2Ag + 4NH3 + 2H2O
Silver mirror
 Fehling Test

Cu2+ (tartarate)
RCHO RCO2– + Cu2O (red precipitrate)
Fehling solution

Benedict Test

Sodium citrate + NaOH + NaHCO3 + CuSO4

H2 O
RCHO + Cu2+ RCOOH + Cu

 
RCOO – Cu2O (red ppt.)
 Reactant Tollen Fehling Benedict
R—CHO
(Aliphatic)
Ar—CHO
(Aromatic)
O

H/R—C—CH—R

OH
(-Hydroxy carbonyl
compounds)

R—C—R
Reagent :- 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

COOEt COOEt
SeO2/MeCOOH
O
COOEt COOEt
DEM (Active(–CH2) group Diethylmesooxalate
 Reagent :- H2O
Reactant :- Aldehyde/ketone

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

Gem diol
Keq = [Carbonyl compound]

O
O
Ph—C—C—C—Ph
Cl3C—CH=O F3C—CH=O O
O O
chloral fluoral
(Diphenyl O
propantrione) (Ninhydrin)
Reagent :- HCN or KCN
Reactant :- Aldehyde/ketone

–
 O H+ OH
C = O + CN C C
CN CN
(Tetrahedral (Cyanohydrin)
intermediate)
 EXAMPLE

The final product 'A' in the following reaction sequence

HCN 95% H2SO4
[JEE MAIN 2022]
CH3CH2―C―CH3 ? A
Heat

O
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

Solution
Ans : (1)
Reagent :- NaHSO3
Reactant :- Aldehyde/ketone

R R OH
O + NaHSO3 C
H H SO3Na
(Water soluble
crystalline compound)

It involves proton transfer to form a stable ion.

This reaction is applicable for all aldehydes, ketones having

ketomethyl groups.
 Reagent :- Alcohol (ROH)
Reactant :- Aldehyde/ketone

In Acidic Medium

••

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

In the following reaction [JEE MAIN (Jan.) 2019]

HCl
Aldehyde + Alcohol Acetal
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

Solution

Ans : (1)
 EXAMPLE [JEE MAIN 2021]

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.
(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.

Solution
Ans : (2)
 Reagent :- dilute NaOH or weak base
Reactant :- Aldehyde/Ketone

Aldol Reaction

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

Intramolecular Aldol Reaction

O O O

H
⊖
OH
H H

H H
 EXAMPLE

In the following reactions, products A and B are : JEE MAINS 2019

O O

dil NaOH
H3C H3C H3C H [A]

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

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

O
O CH3
CH3
(C) (D)

Solution Ans : (A)

 Reagent :- dilute NaOH or weak base
Reactant :- Aldehyde/Ketone

Cross Aldol

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

CH2== CH—CHO
(Acrolein)
 Reagent :- dilute NaOH or weak base
Reactant :- Aldehyde/Ketone

Nitro Aldol

OH
NO2 O R’’
Base (cat.) O2N
+
R R’ H R’’ R R’
 Reagent :- dilute NaOH or weak base
Reactant :- Aldehyde/Ketone

Cyano Aldol

Ph
–
PhCHO + (Ph) CH2CN
OEt / EtOH PhCH = C—C≡N
 Reagent :- -haloester + Zn
Reactant :- Aldehyde/Ketone

Reformatsky Reaction

Br O
(i) Zn COOH
R—CHO + CH2—C—OEt R
(ii) H3 O+
(ii)  𝛼, 𝛽-unsaturated acid
 Reagent :- Active methylene compounds + base
Reactant :- Aldehyde/Ketone

Knoevenagel Condensation

(i) R2NH
O O
(ii) H3O+
+ O
(iii) 
EtO OEt CO2H
H
 Reagent :- Acid Anhydride + base
Reactant :- Aromatic Aldehyde

Perkin Reaction

O O
⊖
CH3COONa
Ph—CHO + CH3—C—O—C—CH3 CH3COOH + Ph—CH==CH—COOH
acetic anhydride (cinnamic acid)
 Reagent :- Electron deficient Alkene or Alkene bonded with EWG
Reactant :- Active methylene compounds + base

Michael Reaction

COOEt
CH2 EtONa/EtOH CO2Et
+ H2C = CH—CN NC—CH2—CH2—CH
COOEt Michael acceptor CO2Et
Michael donor
Hydrolysis reaction
RNH2 + HCOOH
R–NC
O
R—CN
R—C—OH
O O
R—C—NH2 R—C—OH
O O
R—C—OR’ H+/H2O R—C—OH + R’OH
O O
R—C—Cl R—C—OH
O O O
R—C—O—C—R R—C—OH
 Reagent :- Acid or Base
Reactant :- Carboxylic Acid + alcohol

Esterification reaction

Treatment of a carboxylic acid with an alcohol in presence of an

acid catalyst gives an ester. This reaction is called Fischer
esterification.

H2SO4
R—COOH + R’—OH RCOOR’ + H2O

O O
18 H+ 18
R—C—OH + R'—OH R—C—OR' + H2O
 Reagent :- Na-Mg
Reactant :- Aldehyde/ketone

O HO OH
Na/Mg
benzene

CH3 CH3 CH3

|
H2SO4
H3C—C C—CH3 
CH3—C C—CH3
| ||
OH OH CH3 O
Pinacol Pinacolone
Migration ability order

OCH3 CH3

> > > H – > 3° R – > 2° R – > 1° R –

 EXAMPLE
Ph CH3
H/
Ph CH3
OH OH
Solution

Ph CH3 Ph CH3 Ph CH3

H Step-2
Ph CH3 Ph CH3 Ph CH3
Step-1 –H2O 
OH OH O O O
H H
H H Step-3
1,2-methyl shift

CH3 Ph CH3
CH3
Ph Step-4
Ph
O: 
Ph O CH3
H
 EXAMPLE

Consider the following reactions : [JEE MAIN ONLINE 2019]

Ag2O
ppt
A ZnCl2
Hg2/H NaBH4 Turbidity with
B C
Conc. HCl 5 minutes
'A' is :
(1) CHCH (2) CH3–CCH
(3) CH2=CH2 (4) CH3–CC–CH3

Solution

Ans : (2)
 EXAMPLE

In the Victor-Meyer's test, the colour given by 1°, 2° and 3° alcohols

are respectively :- [JEE MAIN 2014]
(1) Red, blue, colourless (2) Colourless, red, blue
(3) Red, blue, violet (4) Red, colourless, blue

Solution

Ans : (1)
 Reagent :- RO– (Alkoxide Ion)
Reactant :- Alkyl Halide

Williamson’s Ether Synthesis

SN2 mechanism
RONa + RX R—O—R
Example

OH O
OH–
Cl
 EXAMPLE

Allyl phenyl ether can be prepared by heating : [JEE MAIN 2014]

(1) CH2=CH—CH2—Br + C6H5ONa
(2) C6H5—CH=CH—Br + CH3—ONa
(3) C6H5Br + CH2=CH—CH2—ONa
(4) CH2=CH—Br + C6H5—CH2—ONa

Solution

Ans : (1)
 HYDROLYSIS OF ETHER

H/H2O
R—O—R' R—OH + R'—OH
Or dil. H2SO4 or H3O

Case (I) Case (II)

R R’ R R’
3° 3° 3° 3°
3° 2° 2° 3°
3° 1° 1° 3°
2° 2° 2° 2°
2° 1° 1° 2°

In all above cases cleavage of open chain ether follow SN1 pathway.
 Reagent :- Peroxy acid, dry Ag2O
Reactant :- Alkene

Epoxides

O O

C=C + R—C—OOH C—C + R—C—OH

Peroxy acid
O
Epoxide

O OH
CH2== CH2 + 1 O2
Ag H2 O
CH2— CH2 CH2—CH2
2 
OH
(anti addition)
 Reagent :- Organometallic Compound

RMgX,  Grignard Reagent

R2CuLi,  Gilman Reagent Corey house Reagent

R2Zn  Frankland Reagent

R2Cd dialkyl cadium

(a) Acid-Base reaction

Compounds having active hydrogen give acid base reaction with

Grignard reagent

X
R―MgX + H―A RH + Mg
A
 R―SO3H
(a) Acid-Base reaction
R―COOH

ROH

RSH

NH3

R―NH2
RMgX
R2NH

H2O

Ph―OH

R―CCH
(b) Nucleophilic Substitution Reaction

Grignard reagent with primary and secondary alkyl halide follows

SN2 mechanism.

SN2 Br
CH3―MgBr + CH3―CH2―Cl CH3―CH2―CH3 + Mg
Cl
 Nucleophilic Addition Reaction

R
H2 O
R―MgX + C=O C—OH nucleophilic addition reaction
 EXAMPLE
[JEE Mains–2021]
For the following :
1. Br2/Fe/∆
2. Mg/dry ether
3. CH3OH Products
OCH3 H OCH3
(1) + HMgBr + Mg
(2) Br

CH3 OH Br H
+ Mg + Mg
(3) Br (4) OCH3

Solution

Ans : (2)
 H2O
RMgX + HCHO R―CH2―OH
1 alcohol

H2O
RMgX + R’CHO R’―CH―OH

R 2 alcohol

O OH
H2O
RMgX + R’―C―R’ R’―CH―R’

R 3 alcohol
H2O
R―MgX + CO2 R―COOH

H2O
R―MgX + R’―CN R―C―R’

O
 Reagent :- R2CuLi (Gilman reagent)

Corey-House Synthesis

R (1° or 2°)
Li CuX ⨁ R'X
R—X RLi [R—Cu] Li
R—R'
Ether

(may be 1°, 2°, 3°) Lithiumdialkylcuprate

Bu2CuLi
Et2O
O O
Reagent :- R2Cd
Reactant :- Acyl halide

THF
CH3 ― C ― Cl + R2Cd CH3 ― C ― R

O O
EXAMPLE

Find major product of given below reaction

O
1. Mg, ether
H—C—CH2CH2CH2CH2—Cl A
2. H3O+
Solution

Ans : HO
Nucleophilic Addition Elimination Reaction

O O

RMgX + R’―C―LG R’―C―R + LG–

Where LG = —X (Cl, Br) , —OR, —O— C —R,

 R
RMgX/H3O+
CH3—CH2―MgBr + CH3―C―Cl CH3―C―CH2CH3 CH3―C―CH2CH3

O O OH

R
RMgX/H3O+
CH3―MgI + CH3―C―O―C―CH3 CH3―C―CH3 CH3―C―CH3

O O O OH

R
RMgX/H3O+
Ph―MgBr + CH3―CH2―C―O―CH3 Ph―C―CH2CH3 Ph―C―CH2CH3
O O OH
 EXAMPLE
(i) NaI, H3PO4 [JEE Mains–2023]
(ii) Mg, Dry ether
H3C—CH2—CH—CH3 [X]
| (iii) D2O
OH Product

Product [X] formed in the above reaction

H
is : |
(1) H3C—CH2—CH—CH3 (2) H3C—CH2—C—CH3
| |
D OH
(3) H3C—CH2—CH=CH2 (4) H3C—CH=CH—CH3

Solution

Ans : (1)
 EXAMPLE
The major product (Y) in the following reactions is : [JEE Mains–2020]
CH3
CH3–CH–C≡CH
HgSO4,H2SO4 (i) C2H5MgBr, H2O
X Y
H2 O (ii) Conc. H2SO4/Δ
CH2 CH3

(1) H3C – C – CH – CH3 (2) CH3 – CH – C = CH – CH3

C2H5 CH3
CH3 CH3
(3) CH3 – C = C – CH3 (4) CH3 – CH – C = CH2
CH2CH3 CH2CH3

Solution
Ans : (3)
Hydroxylation

| |
Oxidation of carbon-carbon double bond to —C — C— is known as
| |
hydroxylation. OH OH

Alkene

[O]
C=C OH —C=C— OH
Hydroxylation

Alkyne

[O] O O
—CC— || ||
Hydroxylation —C—C—
 Hydroxylation Reagent
Syn addition Anti addition

1. cold dilute alkaline 1% cold KMnO4 4. Peroxyacetic acid with H2O

(Baeyer’s reagent ) O
(a) CH3—C—O—O—H
2. [OsO4/NaHSO3] O
(b) C—O—O—H
3. OsO4/H2O2] Peroxy benzoic acid
O
(c) H—C—O—O—H
Peroxyformic acid
O
(d) C—O—O—H

Cl Metachloro perbenzoic
acid (MCPBA)
5. dry Ag2O/H2O
 1. Oxidation by Baeyer's reagent (A test for unsaturation)

Baeyer Reagent Baeyer Reagent Baeyer Reagent

Reactant Alkene Alkyne

Product Vicinal diol Diketone

Stereochemistry : syn addition.

> C== C< + H2O + [O] OH–

> C — C< Glycol
KMnO4
(cis–addition)
OH OH

Note

Reagent 2 & 3 work as same

 Anti hydroxylation

OH
H+, H2O
C=C + R—C—OOH —C—C— —C — C—
O O OH
Trans glycol

Stereochemistry : anti addition in diol formation.

HOOC COOH COOH
Reagent I, II & III H OH
H H Syn-mechanism H OH
Maleic acid COOH
Meso-tartaric
acid

COOH
HOOC H
Reagent I, II & III H OH
Syn-mechanism HO H
H COOH
Fumaric acid COOH
 Reagent :- (i) Hot alkaline KMnO4 , (ii) Hot acidic KMnO4
(iii) Hot acidic K2Cr2O7
Reactant :- Alkene & Alkyne

Oxidative Cleavage

KMnO4/H+ KMnO4/H+ KMnO4/H+ KMnO4/H+ KMnO4/H+ KMnO4/H+

.= CH2 .= CH R .= CR1R2
Reactant . CH group . CR group
group group group

O.= CR1R2
Product CO2 RCOOH CO2 RCOOH
group

Carbon Carboxylic Carbon Carboxylic

Ketone
dioxide acid dioxide acid
EXAMPLE O
Hot KMnO4 + CO2

CH2
Cold/dil/alkaline KMnO4 OH OH

H O
C Hot alkaline KMnO4
H + CO2

OH CH
2
(i) RCO3H

Solution OH
(ii) H2O/H+

O
(i) RCO3H
 Ozonolysis

Reductive Oxidative
ozonolysis ozonolysis

1. O3/Zn, H2O 1. O3/H2O

2. O3/H2/Pd 2. O3/Ag2O

3. O3/Me2S 3. O3/H2O2

4. O3/Ph3P
 4. O3/Per-acid


It gives aldehyde and ketone It give acids and ketones
 O O
H2O/Zn
R—C—H + R—C—R

R R R O R Reductive Ozonolysis

C C C C
H R R
H O–O
O O
O O
O Ozonide
H2 O
R—C—H + R—C—R + H2O2

H2O2 O

R—C—OH
Oxidative Ozonolysis
 Reductive Ozonolysis Products (O3/Zn, H2O)

O3/Zn, H2O O3/Zn, H2O O3/Zn, H2O O3/Zn, H2O O3/Zn, H2O O3/Zn, H2O

= CH R = CR1R2
Reactant = CH2 group
group group  CH group  CR group

O = CHR O = CR1R2
Product HCHO diketone
group group

Keto
Formaldehyde Aldehyde Ketone diketone
aldehyde
 Oxidative Ozonolysis Products

O3/H2O2 O3/H2O2 O3/H2O2 O3/H2O2 O3/H2O2 O3/H2O2

Reactant
= CH2 = CHR = CR1R2  CH  CR
group group group group group

O=CR1R2
Product CO2 RCOOH CO2 RCOOH
group

Carbon Carboxylic Carbon Carboxylic

Ketone
dioxide acid dioxide acid
 EXAMPLE
i O3
2-hexene Products [JEE Main–2023]
ii H2 O

The two product formed in above reaction are-

(A) Butanoic acid and acetic acid
(B) Butanal and acetic acid
(C) Butanal and acetaldehyde
(D) Butanoic acid and acetaldehyde

Solution

Ans : (A)
 EXAMPLE

A hydrocarbon ‘X’ with formula C6H8 uses two moles of H2 on catalytic

hydrogenation of its one mole. On ozonolysis, ‘X’ yields two moles of
methane dicarbaldehyde. The hydrocarbon ‘X’ is : [JEE Main–2023]
(A) hexa-1, 3, 5-triene (B) 1-methylcyclopenta-1, 4-diene
(C) cyclohexa-1, 3-diene (D) cyclohexa-1, 4-diene

Solution

Ans : (D)
EXAMPLE
(i) O3
(A)
(ii) Zn / H2O

H3C—C=CH2

CH3 (i) O3
(B)
(ii) H2O

Solution

O O
(A) CH3—C—CH3 + H—C—H

O O O
[O] [O]
(B) CH3—C—CH3 + H—C—H H—C—OH CO2 + H2O
EXAMPLE CH3
CH3
(i) O3
(ii) Zn / H2O

o-xylene

Solution CH3
CH3 O H3C O
+ 2
O O
CH3
CH3 O H3C O
2 +
O H3C O
OXIDATION REACITON OF ALCOHOLS

O
[O]
R—CH2—OH R—C—H

R O
[O]
R—CH—OH R—C—R

[O]
3° alcohol (No Reaction)
 KMnO4/H+
Or KMnO4/OH–
R—COOH

K2Cr2O7/H+
R—COOH
H2CrO4
R—COOH
Chronic acid
CrO3/dil H2SO4
or acetone
R—COOH
= H2CrO4

R—CH2—OH Collins reagent

R—CHO
(1° Alcohol) CrO3. 2C5H5N

PCC
R—CHO
PDC
R—CHO
Swern
DMSO + (COCl2)2 R—CHO
pyridine

Red hot Cu
R—CHO
 KMnO4/H+
Or KMnO4/OH–

K2Cr2O7/H+

H2CrO4
Chronic acid

CrO3/dil H2SO4
or acetone
= H2CrO4
R—CH—OH Collins reagent R—C—OH
CrO3. 2C5H5N
R O
PCC
(2° Alcohol)
PDC

Swern
DMSO + (COCl2)2
pyridine

Red hot Cu
3° alcohol (No Reaction)

Red hot
But 3° alcohol Alkene
Cu
Reagent :- MnO2
Reactant :- allylic or benzylic 1° and 2° alcohol

OH H
MnO2

H O

OH O

MnO2
 Reagent :- Al(OCMe3)3 in acetone
Reactant :- Alcohol

Oppenaur’s Oxidation

(i) Commonly used bases are aluminium tert-butoxide.

Al(OCMe3)3
R2CHOH + (CH3)2CO R2CO + CH3CH(OH)CH3
2°Alcohol Acetone Ketone 2°Alcohol
 Reagent :- Al(OCHMe2)3 in isopropanol
Reactant :- Ketone

MPV Reduction

Al(OCHMe2)3
R—C—R’ + CH3—CH—CH3 R—CH—R’ + CH3—C—CH3
|| | | ||
O OH OH O
 Reagent :- (i) HIO4.2H2O (ii) NaIO4 (iii) Pb(OAc)4
Reactant :- Cis 1, 2–diol

R R
R R R—C—C—R R R
HIO4 2H2O
R—C—C—R O O R—C + C—R
(2)
OH OH I O O
O O

Cyclic periodate
ester
(i) Two adjacent (— O H) groups

R—CH2—CH—R’ 1 mol of R—CH + R’CH

HIO4
OH OH O O

(ii) Two adjacent (— CHO) groups

1 mol of
CH — CH 2H—C—OH
HIO4
O O O
(iii) Two adjacent —C— and —C— groups
O OH

R— C— CH—R’ 1 mol of R— C—OH + R’—CH

HIO4
O OH O O
 Reagent :- Per Acid
Reactant :- Carbonyl group

Baeyer-villiger oxidation
O O
O 18
R–C–O–O–H 18

R—C—R R C O R
Or
mCPBA
Or
H2SO5 / CF3CO3H

Migratory apptitude —H > 3° > 2° > – Ph > 1° > –CH3

O O
mCPBA C
CH3
CH3 O
 Reagent :- (1) (i) LiAlH4/Ether (2) (i) NaBH4/EtOH
(ii) H2O/H2SO4 (ii) H2O

Lithium Aluminium Hydride (LiAlH4) LAH

LAH Can reduce those functional group which has multiple bond in
b/w two different electronegative atom.

O O–
|| |
LAH H2O
C C RCH2—OH
R H R | H
H

D2O

RCH2—OD
Example
O
X SBH
R—C—OH
LAH
R—CH2—OH

O O
LAH
X SBH
R—C—O —C—R 2R—CH2OH

SBH LAH
X R—CN R—CH2—NH2
O
SBH || LAH
X R—C—NH2 R—CH2—NH2

O
|| LAH
SBH
R—CH2—OH R—C—X R—CH2—OH
 O
SBH || LAH
RCH2—OH R C H RCH2—OH

|
|
OH O OH
| || |
SBH LAH
R—CH—R R C R R—CH—R

|
|
O
SBH || LAH
RCH2—OH R C Cl RCH2—OH

|
|
 It can reduce 1° and 2° alkyl halide into Alkane but not 3°

SBH LAH CH3—CH3

X CH3—CH2—Cl
SN2

SBH LAH
CH3—CH2—CH3 CH3—CH—Cl CH3—CH2—CH3
SN1 SN2

—
CH3

CH3 CH3
—

—
SBH LiAlH4 CH3
CH3—C—H CH3—C—Cl CH2=C
SN1 E2 + H2
—

—
CH3
CH3 CH3
 EXAMPLE

The major product of the following reaction is [JEE MAIN (April) 2019]
LiAlH4
CH3CH=CHCO2CH3
(1) CH3CH2CH2CHO (2) CH3CH2CH2CO2CH3
(3) CH3CH=CHCH2OH (4) CH3CH2CH2CH2OH

Solution

Ans : (3)
 EXAMPLE

The major product of the following reaction is : [JEE MAIN (Jan.) 2019]
O
NaBH4
EtOH
OH OH

(1) (2)
OEt
O OH

(3) (4)

Solution
Ans : (4)
 EXAMPLE
[JEE Mains–2019]
The major product of the following reaction is:
O
CH3N NaBH4

OH OH
(1) CHN (2) CH3N

OH OH
(3) CH3N (4) CH3N

Solution

Ans : (3)
 EXAMPLE
The major product 'X' formed in the following reaction is :
O O [JEE Mains–2019]
CH2–C–OCH3 NaBH4
⎯⎯⎯
MeOH
→X
O
OH OH
CH2CH2OH CH2–C–H
(1) (2)

OH OH O
CH2CH2OH CH2–C–OCH3
(3) (4)

Solution

Ans : (4)
 Reagent :- AlH(i-Bu)2) / at 78°C

Diisobutyl Aluminium Hydride [DIBAL-H/Inert solvent]

O O
DIBAL-H
R—C—OR R—C—H
–78°C
O
DIBAL-H H2O/H+
R—C ≡ N R—CH = NH R—C—H
–78°C

O O
DIBAL-H
R—C—Cl R—C—H
–78°C

O
DIBAL-H
R—C—H R—CH2—OH
Room temp.
 EXAMPLE
O
O [JEE MAIN 2021]

(i) DIBAl–H, Toluene, –78C

“P”
(ii) H3O (Major Product)

The product "P" in the above reaction is :

OH OH

(1) COOH (2) CHO

O
O–C–H

(3) (4) CHO

Solution
Ans : (2)
 EXAMPLE
[JEE Mains–2019]
The major product of the following reaction is:
CN
(i) DIBAL-H
O
(ii) H O +
3

O
CHO CHO
CHO CH=NH
(1) O (2) O (3) OH (4)
OH
O OH
CHO
Solution

Ans : (3)
Reagent :- B2H6/THF

Reactant Remark Product

O
Reduced slowly —CH2OH
—C—H
O OH
Reduced slowly
—C— —CH—
O
Reduced slowly R—CH2OH + ROH
R—C—OR
O
Reduced —CH2OH
—C—OH
O
Reduced R—CH2—NH2
R—C—NH2
 Reagent :- Na/C2H5OH
Reactant :- Alkyl cyanide

Mendius Reduction (Complete Reduction)

Na/C2H5OH
R―C≡N + 4[H] R―CH2―NH2

 ⊝ Na/C2H5OH
R―N≡C R―NH―CH3
 Reagent :- Na/liq. NH3
Reactant :- Alkyne, Benzene and it’s derivatives

Birch reduction

Alkyne

Na/liq. NH3
R H
R—C  C —R C=C (anti addition)
H R
Benzene and it’s derivatives

Na/ liq NH3



G
G H
Na/NH3
 G = –NO2, –COOH, –CHO, –CN)

G = E.W.G H H
G G
H
Na/NH3 H G = –R, –OR, –NH2)
 H
G = E.D.G H
 Reagent :- [Na/C2H5OH]
Reactant :- Ester

Bouvealt-Blanc Reduction

O
|| [Na/C2H5OH]
R—C—OR R—CH2OH + ROH

This reagent also reduced as given below :-

Reagent Na/C2H5OH Na/C2H5OH Na/C2H5OH Na/C2H5OH Na/C2H5OH

Reactant Aldehyde Ketone Cyanide Ester acid halide

Product 1° alcohol 2° alcohol 1° amine 1° alchol 1° alchol

 Reagent :- Zn-Hg/Conc. HCl
Reactant :- Aldehyde and Ketone

Clemmensen Reduction

It is used to prepare alkanes from carbonyl compounds (Aldehyde and

ketones in absence of acid sensitive groups).

O
Zn–Hg/Conc. HCl
CH3—C—CH3 CH3—CH2—CH3


In this reaction —C— is converted into —CH2—

 Reagent :- N2H4/OH–  ethylene glycol
Reactant :- Aldehyde and Ketone

Wolff-Kishner Reduction

O
NH2NH2/OH
CH3—C—CH3 CH3—CH2—CH3 + N2


Note

Wolff-kishner reduction is avoid to use for compounds which have

base sensitive groups. [Like : Halogens, Acid halide, Esters, Anhydride]
 Reactant :- BDC H3PO2 /
OH + H3PO3
H2 O
I
(stable at room Temp.) C2H5OH
+ CH3CHO
(water insoluble)
Cl
F N NBF4
Kl  H2 O Cu2Cl2 /
 HBF4
HCl
Fluoroboric
acid N NCl Br
Balz-Schiemann Benzene
reaction Diazonium Cu2Br2 / Sandmeyer
fluoroborate reaction
HBr
NaNO2 Cu, ∆ Cu/HCl Cu/HBr CN

NO2 CuCN /
Cl Br
HCN

Gatterman reaction
Coupling with phenol

Phenol gives coupling reaction in basic medium

⊕ pH 10-11 ⊖
N=N + OH N =N OH + Cl + H2O

p-Hydroxyazobenzene
(orange dye)
Coupling with Aniline

⊕ 
pH 5-6
N=N + NH2 N =N NH2 + Cl + H2O
mild
Acidic medium p-Aminoazobenzene
(yellow dye)
  
N2Cl NMe2

+ —N=N— —NMe2

 
N2Cl
NMe2
HO3S— —N = N— —NMe2
+
Methyl orange (Indicator)
SO3H


NMe2

N2Cl

—
COOH
—

—N=N— —NMe2
+
COOH
Methyl red (Indicator)
Coupling with 𝛽-Naphthol

H

OH

N2Cl + Basic medium

N=N
-naphthol
HO
Orange color dye
Coupling with -Naphthol

 OH
OH 
N2Cl
Para red dye
+
N

N
 Reagent :- conc. HNO3 + conc. H2SO4 (Nitrating mixture)
conc. HNO3 + conc. HNO2
⊕ ⊖
Δ NO + NO
N2O5 ⎯→ 2 3
⊕ ⊖
Δ
BF4NO2 ⎯→ NO2 + BF4
Reactant :- Benzene, phenol, aniline etc.

Nitration

NO2

conc. HNO3
+ H2O
conc. H2SO4

Electrophile : Nitroniumion (NO2)

 Toluene

CH3 CH3
O2N NO2
conc. HNO3+
TNT (Trinitrotoluene)
conc. H2SO4
(excess) Explosive yellow solid

NO2
Aniline

NH2 NH2 NH2 NH2

NO2
HNO3 + H2SO4
+ +
288K
NO2
NO2
2% 47% 51%
Phenol

OH OH OH
NO2
dil.HNO3
+

o–nitrophenol
NO2
p–nitrophenol
1) Intramolecular H bond 1) Intermolecular H bond
2) Steam volatile 2) Less volatile

OH OH
O2N NO2
Conc.HNO3

NO2
 Reagent :- conc. H2SO4
conc. H2SO4 + SO3 (oleum)
Reactant :- Benzene, phenol, aniline etc.

Sulfonation
SO3H

+ conc. H2SO4 + H2O

Benzene sulphonic acid

O
Electrophile : H—O—S or SO3
O
Sulfonium ion
 SULPHONATION OF ANILINE

NH2 NH3HSO4 NH2 NH3

H2SO4 453-473K

SO3H SO3
Anilinium Sulphanilic acid/ Zwitter ion
hydrogensulphate p-Aminobenzene
sulphonic acid
 Reagent :- Cl2/AlCl3 Br2/FeBr3
HOX X2/H2O

Halogenation

Cl

AlCl3
+ Cl2 + H—Cl

Electrophile : Chloronium ion (Halonium ion)

Phenol

OH OH OH
Br
Br2 in CS2 at 0C +

Br (Minor)
(Major)

OH OH
Br Br
H2O
+ 3Br2 0–5C

Br
Aniline

Br2
CS2 or CCl4 NH2
NH2
Br Br
2,4,6–Tribromoaniline
(white ppt.)
Aniline Br2 Br
H2 O
 EXAMPLE
1. Br2/Fe/Δ
2. Mg/dry ether [JEE MAIN 2021]
For the following : Product
3. CH3OH

OCH3 H
(1) (2) OCH3
+ HMgBr + Mg
Br

CH3 Br
(3) OH H
+ Mg (4) + Mg
Br OCH3

Solution

Ans : (2)
 Reagent :- Alkyl Halide (R−X) + Lewis Acid

Friedel Craft’s Alkylation

CH3

Anhyd. AlCl3
+ CH3Cl + HCl


Toluene
Electrophile : CH3
 Reagent :- Acid chloride
Acid anhydride + Lewis acid + H2O

Friedel Crafts Acylation

R O
C
O
AlCl3
+ R—C—Cl + Al(OH)3 + HCl
H2 O
Acid chloride
O
O O C O
1. AlCl3
R
+ C C 2. H2O + C
R O R R OH
Acid anhydride

Electrophile : R—C=O R—C≡O (Acylium ion)

  O OH
NO2 N(CH3)3 C

Don’t show Friedel craft reaction

EWG group attached to benzene ring do not undergo Friedel -Crafts

reactions except haloarene.
Aryl and vinylic halides cannot be used as the halide component because
they do not form carbocations readily.
Cl

No reaction
AlCl3

No reaction

Cl
 EXAMPLE

Among the following reaction(s) which gives (give) tert-butyl benzene

as the major product is(are)
Br
Cl

(A) NaOC2H5 (B) AlCl3

OH
(C) (D)
H2SO4 BF3. OEt2

[JEE Advanced 2016]

Solution

Ans : (B, C, D)
EXAMPLE

CH3CH2CH2—Cl/AlCl3

CH3CH(Cl)CH3/AlCl3

CH3CH2CH2—OH/H

CH3CH(OH)CH3/H

CH3—CH == CH2/H

Solution

Ans :
CH3
CH
CH3
Gattermann-Koch reaction

CO,HCl
Benzene or its derivative Benzaldehyde or substituted
Anhy.AlCl3/CuCl
benzaldehyde

CHO

CO, HCl
Anhy.AlCl3/CuCl

Benzene Benzaldehyde
 Reagent :- Strong base
Reactant :- EWG (NO2) substituted Aryl Halide

SNAr mechanism

Cl
NaOH
Room
No reaction
temperature.
Cl
OH
NaOH 623 K
300 atm/H+

Cl OH

15% NaOH
160° C/H+

NO2 NO2
 Cl OH
NO2 NO2
NaOH/100°C, H+

NO2 NO2

OH
Cl
O 2N NO2
O2N NO2
H2O/warm

NO2 NO2
 EXAMPLE
[JEE Mains–2020]
In the following reaction A is :
(i) Br2, hv H O
(ii) KOH (alc.)
A (iii) O3
(iv) (CH3)2S
(v) NaOH (aq) + ∆

(1) (2) (3) (4)

Solution

Ans : (3)
Kolbe’s Schmidt Reaction

OH
⊝
O OH OH
COOH COOH
(i) OH⊝ (iii) HCl
+
(ii) CO2

COOH (Major)
(Minor)
 Reagent :- 
Reactant :- Allyl phenyl ethers

Claisen–rearrangement

Allyl phenyl ethers rearrange to o–allyl phenol when heated at 200C.

 
CH2 OH 
O 
 CH2
200C 

2–allylphenol

This rearrangement is known as Claisen–rearrangement

 Reagent :- X2/Red P
Reactant :- Carboxylic acid

HVZ Reaction

O O
(i) X2/Red P
R—CH2—C—OH R—CH—C—OH
(ii) H2O
X
 EXAMPLE

The major aromatic product C in the following reaction sequence will be :

[JEE Mains–2020]
O HBr
(excess), (i) KOH(Alc.) O3
(A) B C
 Zn/H3O+

OH OH Br Br
(1) (2) (3) (4)
CO2H CHO CHO CO2H

Solution

Ans : (2)
 Gabriel phthalimide synthesis

O
C
(i) alc.KOH
NH R—NH2 (1° Aliphatic Amine)
(ii) R–X
C
(iii) OH/H2O
O

(1) Gabriel phthalimide reaction follow SN2 mechanism

(2) Only 1° Aliphatic Amine are prepared by this Reaction

 Reagent :- HNO2
Reactant :- Amines

HNO2  ⊖
R—NH2 R—N2X
a diazonium salt

R1 HNO2 R1
N—H N—N== O
R2 R2
A n–nitrosamine
(a yellow oily liquid)

R1 R1
 ⊖
R2—N + HNO2 R2—N—H NO2

R3 R3
 Reagent :- H2/Ni, Pt, Pd
Reactant :- Alkenes and Alkynes

Alkenes and alkynes on catalytic hydrogenation gives alkanes

Ni, Pt or Pd
C==C + H2 CH—CH

Alkene Alkane

Ni, Pt or Pd
—C C— + 2H2 —CH2—CH2—

Alkyne Alkane
 Lindlar’s catalyst (H2/Pd,CaCO3,quinoline)

Stereochemistry : Syn addition.

R1 R2
C=C
Pd/CaCO3
R1—CC—R2 + H2 S-quinoline
H H
cis-Alkene
Rosenmund Reaction (H2/Pd,BaSO4,quinoline)

O
|| H2,Pd,BaSO4,S
CH3—C—Cl CH3—CHO
Example

H3C CH3
H2,Pd,BaSO4,S
CH3–CC–CH3 C C
H H

cis-2- butene