L14 - (JLD 3.0) - Reaction Mechanisms - 02 Sept

3.
Free Radical Substitution

& Addition
Reaction Mechanisms 14
Anupam Gupta
Anupam Gupta
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& Addition
Reaction Mechanisms 14
Anupam Gupta
Reaction Mechanism
Nucleophilic substitution reaction:

Elimination reactions: Addition reactions:
● SN2 ● E1 ● Nucleophilic Addition to
● SN1 ● E2 carbonyls
● SNi ● E1cB ● Electrophilic Addition to
● SN2Ar ● Ei pi-bonds
● SN2Th
● Benzyne Mechanism
Electrophilic Substitution reactions

● EAS
● Characteristic Reaction of Alkanes
● Chain reactions
Free Radical Substitution Mechanism
● Mechanism involve three steps:
○ Chain Initiation
○ Chain Propagation
○ Chain Termination
Chain initiation step Chain propagation step
(Xo + R - H ⟶ Ro + HX)
Chain propagation Chain termination step
(Ro + X - X ⟶ R - X + XO) (XO + XO ⟶ X2)

This is a free radical substitution reaction. Which of the following steps is
the initiation step
A.
B.
C.
D.
Which of the following steps of this reaction is the first propagation step
A.
B.
C.
D.
Which of the following steps of this reaction is the termination step?
A.
B.
C.
D. All of these
Free Radical Substitution - Reactivity
Relative relativity of alkanes

The alkane which will form more stable radical will be more reactive towards halogenation
● R - H : 3o > 2o> 1o > CH4
Relative reactivity of halogen

● Order of reactivity is F2 > Cl2 > Br2 > I2
Free Radical Substitution - Thermodynamics
Value of ΔH for each step (Kcal/mole)

Steps of Halogenation
F Cl Br I
+38 +58 +46 +36
-32 +1 +16 +33
-70 -26 -24 -20

Reactions of Alkanes - Free Radical Substitution
Chain initiation step Chain propagation step
(X2 ⟶ Xo + Xo) (Xo + R - H ⟶ Ro + HX)

Chain propagation Chain termination step
(Ro + X - X ⟶ R - X + XO) (XO + XO ⟶ X2)

R
Chlorination of CH4 involves following steps
Which of the following is rate determining?
A. Step (i)
B. Step (ii)
C. Step (iii)
D. Step (i) the & (iii) both
Which of the following reaction has zero activation energy
A. B.
C. D.
Initiators : Which can initiate the chain reaction, Initiators are R2O2, Perester etc.
Inhibitors : A substance that slow down or stop the reaction are known as inhibitors
For example O2 is a good inhibitor
all reactive alkyl free radicals are consumed so reaction become stop for a period
of time.
Free Radical Substitution - Reactivity vs Selectivity
Reactivity & Selectivity
Reactivity : Cl2 > Br

Selectivity : Br2 > Cl2
A faster reaction is less selective and a slower reaction is more selective.
Relative yield = Relative Reactivity X probability factor.

CH3 - CH2 - CH3 + Br2 ⟶ CH3 - CH2 - CH2Br + CH3CH(Br)CH3
% yield of I = 3.48 %
% yield of II = 96.72 %
Other Halogenating agents :
Chlorination : SO2 Cl2 / R2O2

Bromination : SO2Br2 / R2O2
Halogenation with SO2Cl2

Which of the following orders is correct for the reactivity of the indicated
H atoms among these compounds in monochlorinations?
A. I > II > III
B. III > II > I
C. II > III > I
D. II > I > III
Free Radical Addition reaction of Alkene & Alkyne
Reagents HBr/R2O2, hv [Kharasch Effect or Peroxide Effect]

R2O2/hv
General Reaction R -CH = CH2 + HBr R - CH2 - CH2 - Br
Mechanism : hv
1. R - O - O - R 2RO
….Chain
Initiation steps
2. RO˙ + HBr ROH+ Br˙
Mechanism
3. R - CH = CH2 R -ĊH - CH2 -Br(2oṘ) + R - CH - ĊH2 (1oṘ)

+ Br˙ I ….Chain
(major) Br propagating
(minor) steps
4. R - ĊH - CH2 - Br + HBr R - CH2 - CH2 - Br + Br˙
Br˙ repeats step (3)

Mechanism
How will you obtain 1-bromopropane from propene?
A. Markovnikov addition
B. Anti-Markovnikov addition
C. Electrophilic addition
D. Using thionyl chloride
Free Radical Allylic and Benzylic substitution reaction
Free Radical Allylic and Benzylic substitution reaction
Reagents Cl2/hv or Δ, Br2/hv or Δ, NBS or NCS
NBS = N -Bromosuccinimide NCS = N -Chlorosuccinimide

Product is:
A. B.
C. D.
3-Methyl-pent-2-ene on reaction with HBr in presence of peroxide forms an
addition product. The number of possible stereoisomers for the product is :
A. Six
B. Zero
C. Two
D. Four
The major product of the following reaction is:
A. B.
C. D
.
The product of the reaction given below is :
A. B.
C. D
.
Product is:
A. B.
C. D.
Anti Markownikoff addition of HBr is not observed in
A. Propene
B. 1-Butene
C. But-2-ene
D. Isobutene
The carbon atoms at which bromination will take place are
A. 1, 2 and 3
B. 4 and 5
C. 1, 3, 4 and 5
D. 1, 3 and 4
In the presence of peroxide, HCl and HI do not give anti-Markovnikov's
addition of alkenes because:
A. One of the steps is endothermic in HCl and HI [2014]
B. Both HCl and HI are strong acids
C. HCl is oxidizing and the HI is reducing
D. All the steps are exothermic is HCl and HI
The addition of HI in the presence of peroxide catalyst does not follow
anti-Markovnikov's rule because
A. HI is a strong reducing agent. [2013]
B. H-I bond is too strong to be broken homolytically.
C. I atom combines with H atom to give back HI.
D. Iodine atom is not reactive enough to add across a double bond.
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3.

Free Radical Substitution

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Free Radical Substitution

Nucleophilic substitution reaction:

● SN2 ● E1 ● Nucleophilic Addition to

● SNi ● E1cB ● Electrophilic Addition to

Electrophilic Substitution reactions

Chain initiation step Chain propagation step

Chain propagation Chain termination step

(Ro + X - X ⟶ R - X + XO) (XO + XO ⟶ X2)

Relative relativity of alkanes

Relative reactivity of halogen

Value of ΔH for each step (Kcal/mole)

-32 +1 +16 +33

-70 -26 -24 -20

Chain initiation step Chain propagation step

(X2 ⟶ Xo + Xo) (Xo + R - H ⟶ Ro + HX)

Chain propagation Chain termination step

(Ro + X - X ⟶ R - X + XO) (XO + XO ⟶ X2)

Which of the following is rate determining?

Reactivity : Cl2 > Br

Relative yield = Relative Reactivity X probability factor.

CH3 - CH2 - CH3 + Br2 ⟶ CH3 - CH2 - CH2Br + CH3CH(Br)CH3

Other Halogenating agents :

Chlorination : SO2 Cl2 / R2O2

Halogenation with SO2Cl2

Reagents HBr/R2O2, hv [Kharasch Effect or Peroxide Effect]

3. R - CH = CH2 R -ĊH - CH2 -Br(2oṘ) + R - CH - ĊH2 (1oṘ)

4. R - ĊH - CH2 - Br + HBr R - CH2 - CH2 - Br + Br˙

Br˙ repeats step (3)

Reagents Cl2/hv or Δ, Br2/hv or Δ, NBS or NCS

NBS = N -Bromosuccinimide NCS = N -Chlorosuccinimide

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