2

Slides done by KARTIKA SINGH

 Complete Crash Course

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 NEET
Crash Course

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Coupon Code :- AA2020
Type :- vdnt.in/NEETCC
26 July
Exam Date
For

NEET 2020
650
NEET 2020
How
Will Help
You !
Lets
HALOALKANES
Nature of C-X bond
The C-X bond is
polar in nature
Structure
Dipole moment of CH3Cl is greater than the
dipole moment of CH3F.
So according to the formula of Dipole moment..

Dipole moment = Partial charge on atom * Bond length..

CH3Cl has more dipole moment than CH3F...

 Methods of
preparation of alkyl
halides
Preparation of Alkyl Halides
Halogenation of alkane
Preparation of alkyl halide

A) FROM ALKANES :

1) Free radical halogenation:

hν
R – H + X2 R–X + H–X
Alkane or Alkyl
Δ halide

Summary of the reaction :

It is an oxidation reaction

It follows free radical chain mechanism

Mechanism of Monochlorination
of Methane :
Mechanism of Monochlorination of Methane :

Initiation step : hυ
Cl Cl 2 Cl·

Propagation step :
Cl· + H CH3 ·
CH3 + HCl

H3C· + Cl Cl H 3C Cl + Cl·

Termination step :
Cl· + ·Cl Cl2
H3C· + ·CH3 H 3C CH3

Cl· + ·CH3 H 3C Cl
 Note : However when CH4 is treated with excess of Cl2 all four hydrogen atoms
would be successively replaced by Cl to finally form CCl4

Alternate propagation steps

Cl· + H CH2 Cl HCl + ·CH2 Cl
·
CH2Cl + Cl Cl CH2Cl2 + Cl·

So on and so Forth….. CHCl3 and CCl4 is formed

So under which circumstances
Do we get monochlorinated
Or polychlorinated major
product?
Reactant conc. Product

CH4 Cl2

High Less CH3–Cl

Less High CCl4

The reactivity of halogens :
hν
R – H + X2 R–X + H–X
or
Δ
F2 > Cl2 > Br2 > I2

Violent Slow
& Explosive & reversible
hυ or Δ
CH4 + I2 CH3 – I + HI
Some more examples :
H ∇ H In all these reactions
hυ or monohalogen
H C H + Cl2 H C Cl + HCl
product is formed
H H
Methane Methyl Chloride
∇
hυ or
CH3 CH3 + Cl2 CH3 CH2Cl + HCl
Ethane Ethyl Chloride

Br
∇
hυ or
+ Br2 + HBr

Cyclohexane Cyclohexyl
Bromide
2) Reaction with SO2Cl2 (Sulphuryl Chloride)
2) Reaction with SO2Cl2 (Sulphuryl Chloride)

R H + SO2Cl2 R Cl + HCl + SO2

O O
Cl S Cl OR Cl S Cl
O O
3) Hydrohalogenation of Alkene (Addition of H – X).

[3a] Addition to symmetrical Alkene

HX
CH2 CH2 CH CH2 Or CH CH2
X H H X
Ethene Ethyl Halide

[3b] Addition to unsymmetrical Alkene.

HX
R – CH2 CH2 R – CH CH2 R – CH CH2
And
X H H X
Alkene Major Minor
Example-1:

CH3
+–
HCl
CH3 C CH CH2 CH3
Example-1:

CH3 CH3
+–
HCl Cl–
CH3 C CH CH2 CH3 H 3C C CH2 CH2 CH3
+

CH3
CH3 C CH CH2 CH3
Cl H
(Markownikov Product)
 Anti – Markownikov Addition -

Peroxide
H 3C CH CH2 + H Br CH3 CH2 CH2
H2O2 or RO – OR
Br
Propene n – Propyl Bromide

Note:

Since this reaction is carried out in presence of

peroxide which favours homolytic fission, it follows
free radical mechanism.
α – Halogenation / Allylic / Benzylic Halogenation

a) Free radical Halogenation of alkene

α X2
CH2 CH CH3 CH2 CH CH2 X
hυ or (Allyl Halide)
Alkene
Δ
b) N – Bromo succinimide (NBS)

N – Br (N – Bromo Succinimide)

∝
NBS CH2
R CH2 CH CH2 R CH CH

Allylic Carbon Br
Some Special Reactions
Finkelstein Reaction
a) Finkelstein Rxn: Reaction follows SN2
Mechanism
NaF
R– F Acetone
R – Cl + NaI R – I + NaCl
R – Br NaBr
(10/ 20)
–
In acetone - Nu : order F– > Cl– > Br– > I–
Swarts Reaction
b) Swartz Reaction :
Reaction follows SN2
R - Cl DMSO Mechanism
Ag - Cl
R - Br + AgF or
R – F + Ag - Br
R-I DMF
Ag - I
(10/ 20)
Alternative Reagents - SbF3, HgF2, CoF3

DMF and DMSO

are polar aprotic
solvents
Preparation of Alkyl Halides
From alcohols
ALCOHOLS :
HX
R – X + H 2O ...SN1/SN2
PX3
R – X + H3PO3 ...SN2

R OH PX
5 R – X + POX3 + HX ….SN
2
SOCl2
R – X + HX + SO2 …SN
or SOBr2
(X = Cl/Br) i
SOCl2/
SOBr2
R – Cl + HCl + SO2 …SN
Pyridine
R – Br + HBr + SO2 2
Reaction with H – X : R – OH + HX R – X + H 2O
: : ⊕ ⊕

:
R O H +H R OH2 + X : :
attack

:
if stable C ⊕ if stable C ⊕
can’t be can be
formed SN2 SN1 formed

R – X + H 2O R ⊕ + H 2O

:
Reactivity Order : X
For different degrees of alcohols R–X
30 > 20 > 10 alcohols. [stability of C⊕]
For different Haloacids
HI > HBr > HCl > HF
Of Alkyl Halides
Nucleophilic Substitution
Reactions
 Nucleophilic Substitution
Bimolecular Reaction (SN2)
 MECHANISM

In this reaction inversion of configuration takes place

Thus the order of reactivity followed is:
Primary halide > Secondary halide > Tertiary
halide

Reason:
Steric
Hindrance
 Nucleophilic Substitution
Unimolecular Reaction (SN1)
 Overall
RACEMISATION
takes place
Example
 Reason: 3°
carbocation is
more stable
How to decide whether SN1 or SN2 ?
Let’s do a question
Predict the order of reactivity of the following compounds
in SN1 and SN2 reactions:
C6H5CH2Br, C6H5CH(C6H5)Br, C6H5CH(CH3)Br,
C6H5C(CH3)(C6H5)Br
Predict the order of reactivity of the following compounds
in SN1 and SN2 reactions:
C6H5CH2Br, C6H5CH(C6H5)Br, C6H5CH(CH3)Br,
C6H5C(CH3)(C6H5)Br
Due to the
Answer stability of
carbocation
C6H5C(CH3)(C6H5)Br > C6H5CH(C6H5)Br > C6H5CH(CH3)Br
> C6H5CH2Br (SN1)

C6H5C(CH3)(C6H5)Br < C6H5CH(C6H5)Br < C6H5CH(CH3)Br

< C6H5CH2Br (SN2)
Due to steric
hindrance
Elimination Reaction
Reaction with Metals
WURTZ REACTION
Wurtz Reaction
Reaction with Grignard Reagent
2) Action of Grignard's Reagent

S N2 R – R′ + Mg X
:
R MgX + R′ X 2
(1°) Alkanes
Grignard's
Reagent
3) Frankland Reaction :

Dry
R X + Zn + X R R – R + ZnX2
ether
Alkanes

Frankland Reaction follows

free radical mechanism
similar to wurtz reaction
 Reaction with KCN & AgCN

Reactions of Alkyl Halides

Action of KCN , AgCN
C) Reaction with KCN/Ag CN

:
N C C
K–C :
N ≡ +–
K :C N + C X

:
ionic ⊕
Ambident :C N C
Nucleophile
:

Ag–C N
covalent +
+ C X Ag–C N C

C – C bond is stronger
than C – N bond
Thus, the reactions in general are :
CN

:
:
Ambident

R–X + KCN R–CN + KX

Cyanide

R–X + AgCN R–NC + KX

isocyanide
 Reaction with KNO2 & AgNO2

Action of KNO2 , AgNO2

D) Reaction with KNO2/AgNO2

:
:
: :
:
O–N=O
:
⊕ – Ambident
:
:

:
: :

:
: :
K–O–N=O ≡ K O–N=O
: : :
Nucleophile
ionic Ambident [Nitrite ion]
Nucleophile –

: :
:
–O is better nucleophilic

: :

:
:
R – X + KNO2 R– O – N = O + KX
:

:
site than –N=
alkyl nitrite
:
: :
:

Ag–O–N=O :
:

R – X + AgNO2 O + AgX

: :
:
+
R–N
– : :
O :
Nitro Alkane
Reactions of Alkyl Halides
Reduction reactions
Reduction Rxns : R X R H

1) Hydrogenolysis :

Ni/Pd/Pt
R X + H2 R H + HX
Temp. and
Pressure

2) Using Red P and HI :

R I R H
R OH red P R H

R CHO HI R CH3
R COOH R CH3
Reactions of Alkyl Halides
Williamson’s Synthesis
E) Williamson’s Synthesis of Ethers :
– + S N2
R
0
X + R′ O Na R O R′ + NaX
(1 ) Sodium Alkoxide

– +
2 R′ O H + 2 · Na 2 R′ O Na + H·H·2H

(i) Na
R′ OH R′ O R
(ii) R – X
(10)
Let’s do some
examples
 Example 1
CH3
CH3 C O–Na+ + CH3 Br
CH3 Methyl bromide
Sod. Tert. butoxide

Example 2
CH3
CH3 O–Na++ CH3 C Br
H CH2
Tert. Butyl bromide
 Example 1
CH3 CH3
CH3 C O–Na+ + CH3 Br CH3 C O CH3 + NaBr
CH3 Methyl bromide CH3
Sod. Tert. butoxide Tert. Butyl methyl
ether

Example 2
CH3 CH3
CH3 O–Na++ CH3 C Br CH3 C + CH3 OH
H CH2 CH2 + NaBr
Tert. Butyl bromide isobutene
HALOARENES
Aryl halides are compounds where halogen is
directly attached to an aromatic ring

They have the general formula ArX,

Preparation of Haloarenes
From hydrocarbons by Electrophilic
Substitution
 ARYL HALIDES
Preparation Reactions :

1) EAS [ Electrophilic aromatic substitution :

H X
Fe OR FeX3
+ X + HX
2 or
AlX3
Halo benzene
Example :
NO2 NO2
Br2 / Fe
–NO2 : meta directing
Nitrobenzene Electrophile: Br+ (bomonium ion)
Br
m–Nitro bromobenzene
Preparation of Aryl Halides
Sandmeyer reaction
 Sandmeyer Reaction :
⊕
NH2 N ≡ N Cl X
HSO4–
NaNO2+ HCl, 00 – 50C SNAr
+ N2
if H2SO4 Cu2X2
Aniline Benzene Cuprous Halide
diazonium (X = Cl/Br)
chloride
Cu + HX
Gatterman RXN
Preparation of Aryl Halides
Using Diazonium salt
 Balz-SchieMann reaction
⊕

:
NH2 N ≡ N Cl F
NaNO2,
HCl, 00–50 C HBF4 OR
+ BF3 + N2↑
AsF6

Aniline Fluorobenzene
 Preparation of iodobenzene

Preparation of lodobenzene :
NH2 ⊕ ..
N ≡ N Cl I
NaNO2,
HCl, 00–50 C KI
+ N2↑

Aniline Iodobenzene
 Preparation of benzene from diazonium salt :
⊕ ..
NH2 N ≡ N Cl

NaNO2, HCl, 00–50 C H3PO2

Aniline Benzene
Let’s solve some
problems
Q. Convert benzene into m-bromoiodobenzene
Q. Convert benzene into m-bromoiodobenzene
I

Br
Conc. HNO3 +
Conc. H2SO4
KI
+
N2. Cl–
NO2

Br
NaNO2,
Br2 / Fe HCl, O0 – 50c

NO2 NH2
Sn / HCl

Br Br
Q. 2. Find the products :

Br2 / hυ
CH3

Toluene Br2 + Fe
Q. 2. Find the products :
Free radical Halogenation
CH2 – Br At allylic or benzylic position

Br2 / hυ Side chain

CH3
Halogenation

CH3

Toluene Br2 + Fe Nuclear Aromatic electrophilic

Halogenation substitution
Br
Chemical Reactions of
Haloarenes
Nucleophilic Substitution
Reaction
Aryl halide do not readily undergo nucleophilic substitution reaction

:
: X:

:
X+
:
– Partial double bond character ,
: Shorter the bond stronger it is
 :
Also, :X : Phynilium ion
+
1
Like SN
Not stable

However, they can be made to under nucleophilic substitution

under drastic condition or by introducing strong EWG at
ortho and para position with respect to the halogen atom.
 Dow’s Process

The presence of a nitro group at ortho or para to chlorine

increases its reactivity. Further, as the number of such
NO2 groups increases the reactivity is increased.
However, no effect on reactivity of haloarenes is
observed by the presence of electron
withdrawing group at meta-position.
-NO2 group at para position

Carbanion is
stabilised
-NO2 group at ortho position
Carbanion is
stabilised
-NO2 group at meta position

the presence of nitro group at meta- position does not

stabilise the negative charge and no effect on reactivity is
observed by the presence of –NO2 group at meta-position
Some important
points
Points to be remembered :

Halogen atom which is ortho or para with respect to EWG is replaced.

More the number EWG’s faster is the nucleophilic substitution.

The leaving group ability at aromatic nucleus

Ar – F > Ar – Cl > Ar – Br > Ar – I
EAS [ Electrophilic Aromatic
Substitution ]
Reaction
Resonance structures of Chlorobenzene

Since the electron density is high at ortho and para

positions therefore the attack of Nucleophile takes
place at these positions.
Halogenation
Nitration
Sulphonation
Friedel Crafts Reaction

Alkylation
Acylation
Reaction with Metals
 1) Fitting Reaction
dry
Ar X + 2Na+ X Ar Ar Ar + 2NaX
ether Biaryl
Aryl Halide
 2) Wurtz–Fittig Reaction :
dry
Ar X + 2Na + X R Ar R + 2NaX
ether
Aryl Halide Alkyl Halide
3) Ullmann Reaction :

Red hot
Ar I + 2Cu + II Ar
Ar Ar Ar + 2CuI
Sealed Biaryl
Aryl Iodide Cu tube
Let’s do some
conversions
Q. 1) Propene to 1-nitropropane :

CH3 CH CH2 CH3 CH2 CH2 NO2

 Solution :
HBr/R2O2
CH3 CH CH2 CH3 CH2 CH2 Br
Antimarkownikov
AgNO2

CH3 CH2 CH2 NO2

Q. 2) Toluene to Benzyl Alcohol :
CH3 CH2OH
Q. 2) Toluene to Benzyl Alcohol :
CH3 CH2OH

Solution :
CH3 CH2Br CH2OH

Br2 /hυ Aq. KOH

Or
S N2
NBS
Q. 3) Ethanol to Ethyl Fluoride :

CH3 CH2 OH CH3 CH2 F

 PBr3 AgF
Solution : CH3–CH2 OH CH3 – CH2 Br CH3 – CH2 F
Swartz rxn
Q. 4) Benzene to 4-Bromo nitrobenzene
Br

NO2
Q. 4) Benzene to 4-Bromo nitrobenzene
Br

NO2

Solution :
Br Br
Br2 conc.HNO3
Fe conc.H2SO4

NO2
Q. 5) Ethanol to Propane nitrile
Q. 5) Ethanol to Propane nitrile

CH3 – CH2 – OH CH3 – CH2 – CN

KCN
PBr3
CH3 – CH2 – Br
Q. 6) But-1-ene to n-butyl iodide :
Q. 6) But-1-ene to n-butyl iodide :

CH3 CH2 CH CH2 CH3 CH2 CH2 CH2 I

NaI
HBr acetone
CH3 CH2 CH2 CH2 Br
R 2 O2
Finklestein rxn
Q. 7) Chlorobenzene to p-Nitrophenol :
Q. 7) Chlorobenzene to p-Nitrophenol :
Cl OH

Cl NO2

conc. HNO3 Aq. NaOH

conc. H2SO4 Activated SNAr
NO2
Q. 8) t-Butylbromide to iso-butylbromide :
Q. 8) t-Butylbromide to iso-butylbromide :
CH3 CH3
CH3 C CH3 CH3 CH CH2 Br
Br
CH3 HBr/R2O2
alc KOH Antimarkownikov
CH3 C CH2
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