Methods of preparation

Alkene Physical properties

Chemical properties
 Elimination reactions

When an atoms or groups are eliminated from a compound during

a reaction, the reaction is known as Elimination reaction.

Types of elimination

(i) 1–1 Elimination/– Elimination/  Elimination : When both

atoms or groups are eliminated from same site then elimination
is known as  Elimination .

C—C—Y C—C
|
X
(ii) 1–2 Elimination/– Elimination/  Elimination : When both atoms
or groups are eliminated from vicinal site then elimination is
known as  Elimination .

C—C C==C
| |
X W

(iii) 1–3 Elimination/– Elimination/  Elimination : When both

atoms or groups are eliminated from 1,3 position then
elimination is known as  Elimination .

C C
C C C——C
| |
X Y
Elimination
reactions

E1 Reaction

E2 Reaction

E1Cb Reaction (Unimolecular conjugate base reaction)

 E1 Reaction (Unimolecular reaction)

Proton and leaving group depart in two different step.

(a) First step: Slow step involves ionisation to form carbocation

(b) Second step: Abstraction of proton

E1 Reaction of alkyl halide :

Mechanism: Step 1 : Formation of the carbocation (RDS)

| | solvolysis | | ⊝

—C—C + X
—C—C—
| | | |
H X H
Mechanism:

⊖
Step 2 : Base 𝐁 abstracts a proton (H+) from –carbon (fast)

| |
—C—C C=C +B–H
| |
⊝ H Alkene

:
B
Characteristics of E1 reaction

It is unimolecular, two step process.

It is first order reaction.

Kinetics: Rate  [substrate] Alkyl halide

Rate = k [substrate]

Reaction intermediate is carbocation, so rearrangement is possible

In the second step, a base abstracts a proton from the carbon atom
adjacent to the carbocation, and forms alkene.
Characteristics of E1 reaction

The reaction is endothermic, as the reaction involves breaking of

s-bond and formation of p-bond.

No Kinetic Isotopic effect is present.( No C-H bond is involved in

transitation state)

Saytzeff alkene dominates over hofmann alkene

Energetics: The free energy diagram for the E1 reaction is :

TS(1)
TS(2)

| |

Free energy
—C—C
⊝ | | ⊝
B H

:
| | X
—C—C—
⊝
| |
H X

:
B ⊝
C=C + BH + X
Progress of reaction
Reactivity towards E1 reaction  stability of carbocation

Reactivity order of R—X : [if X is same] :–

CH3CH2—Cl [1] < (CH3)2CH—Cl [2] < (CH3)3C—Cl (3)

Reactivity order of R—X : [if R is same] :–

R—F < R—Cl < R—Br < R—I

Example

: :
CH3OH

CH3 H CH3
| CH3OH | |
CH3—CH2—C—CH3 CH3—CH—C—CH3
| D 
Br

CH3
| H CH3 
CH3—CH2—C==CH2 + C=C + CH3OH2
CH3 CH3
Major
 Example

Me Me
|  |  
H rearrangement
Me—C—CH2—OH Me—C—CH2 Me—C—CH2—Me
| D | |
Me Me Me


–H

CH2==C—CH2—Me + Me—C=CH—Me
| |
Me Me
(Major)
Example

OCH3

CH2—Br CH2
CH3OH 
H
D
E2 Reaction (Bimolecular reaction)

E2 Reaction of alkyl halide :

Mechanism:

:
B
d–
H B---H
| | |

---
⊝
—C—C— ---
—C—C— C=C + X + BH
| | |

---
X X d–
Transition state
Characteristics of E2 reaction

This is a single step, bimolecular reaction

It is a second order reaction

Kinetics → Rate  [Substrate] [Reagent] Alkyl halide Base

Rate = k [Substrate] [Reagent]

Rearrangement is not possible

Anti-Elimination is observed
Characteristics of E2 reaction

Kinetic Isotopic effect is present, as the reaction involves the

breaking of C-H bond in transition state.

The reaction is endothermic, as the reaction involves breaking of

2-s bond and formation of 1- p bond.

Both saytzeff and hofmann alkenes may be obtained.

Usually, saytzeff alkene dominates and is found in major

concentration.
Reactivity towards E2 reaction  stability of product alkene

Reactivity order of R—X : [if X is same] :–

CH3CH2—Cl [1] < (CH3)2CH—Cl [2] < (CH3)3C—Cl (3)

CH2==CH2 CH3—CH==CH2 CH3—CH==CH2

CH3
Reactivity order of R—X : [if R is same] :–

R—F < R—Cl < R—Br < R—I

Positional orientation of elimination → In most E1 and E2
eliminations where there are two or more possible elimination
products, the product with the most highly substituted double bond
will predominate. This rule is called the saytzeff or zaitsev rule.

⊝
(a) CH3
B CH3—CH = C
H(a) CH2—H(b) CH3
saytzeff product
CH3—CH—C—Br (more substituted alkene)
CH3
(b) CH2
CH3—CH2—C
CH3
Hofmann’s product
(less substituted alkene)
Formation of the Hoffmann product

Bulky bases can also accomplish dehydrohalogenations that do not

follow the saytzeff rule.

Due to steric hindrance, a bulky base abstracts a less hindered

proton, often the one that leads to formation of the least highly
substituted product, called the Hoffmann product.
 Example

H CH3
| | ⊝
OCH2CH3 H3C CH3 CH3—H2C H
CH3—C—C—CH2 C=C + C=C
| | | CH3CH2OH CH3
H H3C H
H Br H 71% 29%
Saytzeff product Hoffmann product

H CH3
| | ⊝
OC(CH3)3 H3C CH3 CH3—H2C H
CH3—C—C—CH2 C=C + C=C
| | | (CH3)3COH CH3
H H H
H Br H 28% 72%
less Saytzeff product Hoffmann product
hindered
Example

CH3
| EtO¯ CH3
CH2—C—Br H2C = C
| | EtOH CH3
H CH3

CH3 CH3 CH3

  | EtO¯
| |
CH2—CH—C—CH3 EtOH
CH3—CH = C—CH3 + CH2 = CH—C—CH3
| | | (Major) (Minor)
H Br H (more stable alkene) (less stable alkene)
E1Cb Reaction (Unimolecular conjugate base reaction)

In the E1 Cb, H leaves first and then the X. This is a two step
process, the intermediate is a carbanion.

Mechanism:

⊕
Step - I Removal of a proton (𝐇) by a base, generating a carbanion

H
| | base
⊝ |

:
—C—C—X —C—C—X
| | | |

Step - II Carbanion looses a leaving group to form alkene

 Condition for the E1CB

Substrate must be containing acidic hydrogens and poor leaving groups.

Example

⊝
B
O H O O
|| | Base
|| ⊝ ||
Ph—S—CH—CH2 Ph—S—CH—CH2 Ph—S—CH = CH2
|| | || | ||
O OPh O OPh O
 Example
⊝
B
H F F
| | ⊝
|
X2C—C—F X2C—C—F X2C = CF2
| |
F F

Example

B:
H
| R ⊝ R R
O—C O—C O=C
| R | R R
CN CN
 Preparation of alkenes From Alkylhalide(By dehydrohalogenation)

Dehydrohalogenation is the elimination of a hydrogen and a

halogen from an alkyl halide to form an alkene.

Example For Bases

01  Hot alcoholic solution of KOH (EtO¯ / EtOH)

02  NaNH2

03  t-BuO¯ / t-BuOH
It is single step and synchronous process.

Removal of proton, the formation of multiple bond between C and

C and the release of the leaving group X take place simultaneously.

The ease of dehydrohalogenation show the order :

Reactivity order of R—X : [if X is same] :–

CH3CH2—Cl [1] < (CH3)2CH—Cl [2] < (CH3)3C—Cl (3)

CH2==CH2 CH3—CH==CH2 CH3—CH==CH2

CH3
Reactivity order of R—X : [if R is same] :–

R—F < R—Cl < R—Br < R—I

 Example
⊝
OCH3
CH3OH

CH3—CH2—CH—CH3
Br CH3
CH3–C–O
⊝

CH3
(CH3)3COH

Sterically hindered base as it abstracts H+ from less hindered

– Carbon
 Example

CH3 ⊝
OCH3
CH3—C—CH—CH2—CH==CH2 CH3OH
H Br
 Example

⊝
OCH3
CH3—CH—CH—CH3 CH3OH
H F
Example

H3C H
CH3
Br CH3–C–O
⊝

CH3
(CH3)3COH
H
 Example

Which of the following is most reactive towards alc.KOH

(i) CH3—CH2—Br (ii) CH3—CH2 —CH2—Br

(i) CH2==CH—Br (ii) CH3—C—CH2—CH2—Br

O
Example

H H
Alc.KOH Alc.KOH
CH3—C—CH A B
Cl Cl
Example

H Cl
NaNH2 NaNH2 NaNH2
CH3—C—CH A B C
H Cl
Example

H Cl H
Alc.KOH (excess)
CH3—C—C—CH
H Cl H
Example

H
Alc.KOH (excess)
H H

H
Cl Cl
Example

H H
H Cl Alc.KOH (excess)

H H
Cl H
Preparation of alkenes From Alcohols (By Dehydration)

Alcohols on heating with conc. H2SO4 give alkenes with the

elimination of water molecule. This is known as acid catalysed
dehydration of alcohols.

Reagents used: (1) Conc. H2SO4/D (2) Conc. H3PO4/D

(3) Al2O3/D

Conc. H2SO4
H3C—CH2—OH H2C CH2 + H2O
D
Mechanism:

H Slow
H3C—CMe2—OH H3C—CMe2—OH2 H3C—CMe2

H2C CMe2
Example

CH3 CH2
Conc. H2SO4
H3C—C—OH H3C—C + H2O
D
CH3 CH3
NOTE

All the steps of this reaction are reversible in nature as well as the
overall reaction is reversible in nature

Intermediate carbocation is formed in dehydration so

rearrangement may be possible in carbocation

It is an example of E1 mechanism

Reactivity towards dehydration  Carbocation stability

Example

Correct order of dehydration with Conc. H2SO4

(A) CH3CH2—OH [1] (B) (CH3)2CH—OH [2] (C) (CH3)3C—OH (3)

OH OH OH

(A) (B) (C)

Example

CH2—OH
Conc. H3PO4
D
Example

CH3
CH3
OH Conc. H3PO4
D
Example

CH3
Conc. H2SO4
H3C—C—CH2—CH2—CH2—OH
D
CH3
Example

CH3
Conc. H2SO4
CH2—CH2—CH2— C—CH2—OH
D
CH3
Example
Example

H Al2O3
D

No H
No Carbocation
No Rearrangement
NOTE

Conc. H2SO4
H2C CH2
170, D
Intramolecular Dehydration

CH3—CH2—OH

Conc. H2SO4
CH3—CH2—O— CH2—CH3
110, D
Intermolecular Dehydration
NOTE

Al2O3
H2C CH2
350°
Intramolecular Dehydration

CH3—CH2—OH

Al2O3
CH3—CH2—O— CH2—CH3
250°
Intermolecular Dehydration
There are two types of dihalides

Geminal dihalides : In which the two halogen atoms are attached to

the same carbon atom.

Vicinal dihalides : In which the two halogen atoms are attached to

the adjacent carbon atoms.
 Preparation of alkenes From Vicinal dihalide(By dehalogenation)

Vicinal dihalides on treatment with zinc metal eliminate a

molecule of ZnX2 to form an alkene. This reaction is known as
dehalogenation. This is carried out by E2 mechanism.

Reagent used: NaI/acetone

Zn dust/D

Example
X
NaI/acetone
—C—C— Or —C==C— + NaX + IX
Zn dust/D or
X
—C==C— + ZnX2
Example

CH2—CH2—CH2 Zn dust
D
Br Br

Cl Cl
Zn dust
CH—CH D
Cl Cl

Cl Cl
Zn dust
CH3—C—CH
D
Cl Cl
From gem dihalide : Higher alkene obtained

Cl
Zn dust
𝟐𝐂𝐇𝟑 𝐂𝐇 𝐂𝐇𝟑 — 𝐂𝐇 = 𝐂𝐇— 𝐂𝐇𝟑 + 𝟐𝐙𝐧𝐂𝐥𝟐
D
Cl

Cl
Zn dust
𝟐𝐂𝐇𝟑 — 𝐂𝐇𝟐— 𝐂𝐇
D
Cl
 Preparation of alkenes by Pyrolysis of Ester

Example

400–500C
CH3—C—O—CH2—CH—R CH3COOH + CH2 = CHR
O H

Example
  D
CH3—C—O—CH—CH2—CH3
O  CH3

CH3—COOH + CH—CH2—CH3 + CH ==CH—CH3

CH2 CH3
(Major) (Minor)
NOTE

In the reaction to form an alkene a -hydrogen from alkyl ester is

attracted by oxygen atom of keto group & Hoffmann's alkene will be
the major product.

Follow Hoffmann's Rule : Less substituted or less stable alkene is

major product.
Example

D
O—C—CH3
O
Example

O
CH2—O—C—CH3
O D
CH2—O—C—CH3
 Preparation of alkenes By Pyrolysis of Tetra Alkyl Ammonium ion

CH3

CH3—N—CH—CH2—CH3 CH—CH2—CH3
⊖
CH3 ⊖ CH3 CH2 CH2
   OH 1 more stable
CH3—N—CH—CH2—CH3 Major product
CH3
CH3 CH3  ⊖
 CH3—N—CH—CH—CH3 CH = CH—CH3
CH3CH3 CH3
2 less stable minor product
NOTE

In this reaction –hydrogen of tetra-alkyl ammonium ion is attracted

by a base and alkene is formed.

In this reaction intermediate is carbanion. So yield of product

depends on stability of carbanion.

In this reaction Hoffmann's Rule is followed.

Example
CH3 H CH3
⊖
 OH
CH3—N—CH2—CH2 CH3—N + CH2 ==CH2 + H2O
CH3 CH3

Example

CH3

⊖ CH2== CH—CH3 (minor)
  OH
CH3—N—CH2—CH2—CH3
CH2—CH3 CH2== CH2 (major)
 
Example

H
⊝
OH
 D
N CH2—H
H3C CH3
Example

⊝
OH
Ph—CH—CH—CH2
D
H NMe3H

 Preparation of alkenes By Pyrolysis of Trialkyl amine oxide

Similar to pyrolysis of tetra alkyl ammonium hydroxide and follow

Hoffmann rule.

Example

CH3 CH3

CH3—N—O
⊝ D
CH2==CH2 + N—OH
CH2—CH2—H CH3
CH3 CH3

CH3—N—O
⊝ D
CH2==CH—CH3 + N—OH
CH2—CH—H CH3
CH3
Preparation of alkenes By Kolbe's Method

Electrolysis of potassium or sodium salt of saturated dicarboxylic

acid gives alkene.

electrolysis
CH2COONa CH2 + 2CO2 + NaOH + H2

CH2COONa CH2 At Cathode

At Anode

electrolysis
CH3—CH—COONa CH3—CH + 2CO2 + NaOH + H2
CH2COONa CH2
At Cathode
At Anode
 Example

O
O
C—O⊝ Na D
Na O⊝
From Alkynes (By catalytic Hydrogenation)

R1 R2
Pd/CaCO3
R1—CC—R2 + H2 C= C
Lindlar’s
catalyst
H H
cis-Alkene

R1 R2
R—CC—R + H2
Pd/BaSO4 C= C
Rosenmund H H
catalyst
cis-Alkene

Lindlar’s catalyst and rosenmund catalyst converts alkynes only to

alkenes and there is no further reduction to alkanes.
Example

Pd/CaCO3
CH3−C ≡ C−CH2−CH3
Lindlar’s
catalyst

Pd/BaSO4

Rosenmund
catalyst
Solution
 BIRCH REDUCTION

Reduction of alkyne to alkene in presence of Na–liq NH3 and C2H5OH

R1 H
Na
R1—CC—R2 C= C
Liq. NH3
H R2
Alkyne trans-Alkene

Example
CH3 H
Na C= C
CH3−C ≡ C−CH3 Liq. NH3
H CH3
Mechanism:

R1 R1 H
Na C= C H−NH2 C= C
R1−C≡C−R2
R2 R2

Na

R1 H R1 H
C==C H2N −H C=C
H R2 R2
Example
Na
CH3−CH2−C≡C−CH2−CH3 Liq. NH3

Solution
NOTE

This process of reduction is not eligible when terminal alkynes are

taken (R–CCH) because terminal alkynes form sodium salt with
Na metal.

Na 𝟏
R—CC—H R—CC Na + H
Liq. NH3 𝟐 2
Example
Na
CH3−CH2−C≡C−CH2−CH2−CH3 A
Liq. NH3

Pd/CaCO3
B
Lindlar’s
catalyst

Pd/BaSO4
C
Rosenmund
catalyst

Ni, Pt or Pd
D
D
Example
Solution
CH3 CH2
H
A
C=C
H CH2− CH2 −CH3

CH3 CH2
CH2− CH2 −CH3

B , C C=C
H H

D CH3−CH2−CH2−CH2−CH2−CH2−CH3
 Wittig reaction

The Wittig reaction is a chemical reaction of an aldehyde or ketone with

a phosphorus ylides, also called Wittig reagents.

R’’’ R’’
C=O C−O R’’’ R’
R’’ R’’’ C=C + Ph3P =O
⊖  R’’ R
R’−C−PPh3 R’−C −PPh3

R R

(R, R', R" and R''' may be hydrogen or any alkyl group)

The Triphenyl group of phosphorane has a strong tendency to pull

oxygen atom of the aldehyde or ketone via a cyclic transition state
forming an alkene.
Mechanism:

R’ R’ R’
⊖ 
PPh3  Ph Li
R—C—I R—C—PPh3 R—C == PPh3
H H O
R’’–C–R’’’

O R’
P + R—C== C—R’’’

Ph Ph Ph R’’
Example O
⊖ 
PPh3 Ph Li H—C—CH3
CH3—I A B C

Solution


CH3—I + PPh3 CH3—PPh3
A
⊖ 
 Ph Li
CH2—PPh3 CH2==PPh3
H B
H
CH2== PPh3 O == C CH2==CH—CH3
C
CH3
Example CH2—Cl O
⊖ 
PPh3 Ph Li H—C—H
A B C

Solution

CH2—PPh3
CH2—Cl
PPh3 H A

⊖ 
Ph Li

CH2== PPh3 O CH==CH2

H—C—H
B C
Example Prepare (CH2==CH—CH==CH2) using wittig reaction.

Solution


PPh3 
⊖
Ph Li
CH3—I CH2—PPh3 CH2==PPh3
O
H
CH2=CH–C–H

CH2==CH—CH==CH2
OR
Example
Solution

Cl PPh3 PPh3 ⊖  PPh3

Ph Li
H O
H–C–H

OR
(CH2==CH—CH==CH2)
Example CH==CH
Prepare using Wittig's reaction.

Solution

CH—pph3
CH2—I CH== pph3
⊖ 
PPh3 H Ph Li

O
–C–H

CH==CH
Example O
(i) D
—C—CH2—CH2—CH2—CH==PPh3 A
(ii) H2/Pd–C

Solution
C
O
PPh3

H2/Pd–C

H
H A
 Physical Properties of Alkenes

Physical properties Homologus series Isomers

C1 – C3: gases
Physical state C4 – C20: liquids
> C20 : solids

Dipole moment (m) cis > trans

Polarity cis > trans (for Cab=Cab

type of alkenes)
Physical properties Homologus series Isomers

Melting point increases with M.W. trans > cis

(due to more packing
capacity

Boiling point Increases with M.W. cis > trans

# branching decreases
C B.P.

C −C =C < C − C = C −C
Polarity increases
boiling point increases
Physical properties Homologus series Isomers

Practically insoluble cis > trans

in water but fairly
Solubility Polarity increases
soluble in nonpolar
solubility in polar
solvents like
solvents
benzene petroleum
ether, etc. increases.

Stability trans > cis

cis isomers has more
Vander
Waals repulsion
 Addition Reaction

Addition of H2
Ni, Pt or Pd
R— CH = CH2 + H2 R— CH2 — CH3 + Heat of Hydrogenation

NOTE

Reaction is exothermic, It is called heat of hydrogenation.

1 1
Stability of alkene ∝ heat of hydrogenation reactivity of alkene with H
∝
2

The process is used to obtain vegetable (saturated fats) ghee from

hydrogenation of oil.
 Electrophilic Addition Reactions (EAR)

Because of the presence of >C=C< bond in molecules, alkenes generally

take part in the addition reactions.

E
d+ d– (RDS) ⊕ |
C == C + E — Nu 𝐂 —C + Nu– C—C
| |
E Nu
Addition product

From mechanism point of view, the addition in alkenes is generally electrophilic

in nature which means that attacking reagent which carries the initial attack is
an electrophile (E+).
 Electrophilic Addition Reactions (EAR)

General Mechanism:

RDS Nu
CH3—CH=CH2 + E CH3—CH—CH2 CH3—CH—CH2
slow
E Nu E
Or

CH3—CH—CH2
E
NOTE

1. 1st step is the rate determining step (rds) of this reaction.

2. Carbocation intermediate is formed so rearrangement may be possible.

3. Rate of EAR  Nucleophilicity of alkene.

+𝐌 +𝐇 +𝐈

–𝐌 –𝐇 –𝐈
Compare reactivity order for EAR of following compounds ?

(A) H3C—C=CH2 (B) H3C—CH=CH2 (C) CH2=CH2

CH3

Solution

EDG
EDG
H3C
C=CH2 H3C—CH=CH2 CH2=CH2
H3C
EDG

(A) > (B) > (C)

Compare reactivity order for EAR of following compounds?

(A) H3C (B) H3C (C) H3C

C=CH2 C=CH2 C=CH2
H3C—O H3C O2N

Solution

EDG EDG EDG

H3C H3C H3C
C=CH2 C=CH2 C=CH2
H3C—O H3C O2N
EDG EDG EWG

(A) > (B) > (C)

Compare reactivity order for EAR of following compounds?

HC=CH2 HC=CH2 HC=CH2 HC=CH2

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

NO2 Cl CH3 OH

Solution

HC=CH2 HC=CH2 HC=CH2 HC=CH2

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

EWG EWG EDG EDG
NO2 Cl CH3 OH

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

 Carbocation Rearrangement

Observed in those reactions in which carbocation is formed as a

intermediate.

Less stable carbocation rearranges itself to more stable carbocation via

transition state.

H
⊕ d+↑ d+↓ ⊕
(1) CH3—CH2—CH2 CH3—C—CH2 CH3—CH—CH3

H
Bond Bond
breaking formation

(Transition state : 1, 2 shift)

 H

(2) H3C CH CH2 H3C C CH2

CH3 CH3
 H

(2) H3C CH CH2 H3C C CH2

CH3 CH3
 CH3 CH3 H

(3) H3C C CH2 CH2 H3C C CH CH2

CH3 CH3
 CH3 CH3 H CH3

(3) H3C C CH2 CH2 H3C C CH CH2 H3C C CH CH3

CH3 CH3 CH3

 CH3 CH3 H CH3

(3) H3C C CH2 CH2 H3C C CH CH2 H3C C CH CH3

CH3 CH3 CH3

(4)

CH2—CH2 CH—CH3 CH2—CH3

(5)

(6) H3C—CH=CH

Note Cunsaturated never rearranges.

Ring Expansion

If there is C next to a 4 or 5 membered ring then ring expansion takes place.

4 membered ring converts into a 5 membered ring and 5 membered ring

converts into a 6 membered ring

(7)
(8)

(9)
Ring Contraction


RC

RC
 Reaction with Conc. H—X (Halogen Acid)

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

Br H

Mechanism:

Br
R—CH=CH2 + H R—CH—CH2 R—CH—CH3
H Br
Note

1. Carbocation intermediate is formed so make more stable carbocation.

2. Rate of reaction- HI > HBr > HCl > HF

 H—Br
H3C—CH2—CH=CH2 ?
Solution

H3C—CH2—CH=CH2 + H H3C—CH2—CH—CH3

Br

H3C—CH2—CH—CH3
Br
 Markovnikov's Rule

In case of electrophilic addition to carbon-carbon multiple bond electrophile

will get added to that carbon of multiple bond which after addition
generates more stable carbocation

R—CH=CH2 + H—Br R—CH—CH2

Br H
NOTE

1. Markovnikov’s rule is not applicable if alkene is symmetrical.

H3C—CH=CH—CH3

2. Markovnikov’s rule is not applicable in the cases where double bonded

carbon is directly attached to strong electron withdrawing group like (–
⨁
NO2, –CHO, –CCl3, – NH3 )

O2N—CH=CH2 + H—Br

H3N—CH=CH2 + H—Br
 Example

H—Br
H3C—CH—CH=CH2 ?
CH3

Solution

H3C—CH—CH=CH2 + H H3C—CH—CH—CH3 H3C—C—CH2—CH3

CH3 CH3 CH3

Br

Br
H3C—C—CH2—CH3
CH3
Example

CH3
H—Br
H3C—C—CH=CH2 ?
CH3

Solution

CH3 CH3
H3C—C—CH=CH2 + H H3C—C—CH—CH3
CH3 CH3

Br CH3 CH3
Br
H3C—C—CH—CH3 H3C—C—CH—CH3

CH3 CH3
Example

H—Br
CH=CH—CH3 ?

Solution

H
CH=CH—CH3 CH—CH2—CH3

Br

CH—CH2—CH3
Br
Example

CH=CH2
H—Cl
?

Solution

CH=CH2 CH—CH3 CH—CH3

H

CH3 CH3
Cl
Example

CH=CH2
H—Cl
?
Example

H—Br
?
Example

H—Br
?
Example

H—Br
CH3—O—CH==CH2 ?
Example


F3N—CH==CH2 H—Br
?
Anti Markovnikov Rule or Peroxide Effect or Kharasch Rule

In the presence of oxygen of peroxides the addition of HBr on

unsaturated unsymmetrical compound takes place contrary to
markovnikov rule. This is called peroxide effect and is due to the
difference in the mechanism of the addition.

In the normal markovnikov addition the mechanism is ionic.

In the presence of peroxide the addition of HBr takes place via free
radicals.
 HBr
CH3—CH—CH3 markovnikov addition
|
Br
Isopropyl bromide

CH3—CH==CH2

HBr
CH3—CH2—CH2—Br Anti markovnikov
R—O—O—R addition
n-propyl bromide
 Mechanism:

Chain initiation:
(a) R—O—O—R ⎯⎯→ 2RO•
(b) HBr + RO• ⎯⎯→ ROH + Br•

Chain propagation:
HBr
CH3—CH—CH2Br ⎯⎯→ CH3CH2CH2Br + Br
2° free radical more stable (major)

CH3—CH==CH2 + Br
Br Br
| |
HBr
CH3—CH—CH2 ⎯⎯→ CH3CHCH3 + Br
1° free radical less stable
Mechanism:

Chain termination:

R• + •R ⎯⎯→ R—R

R• + •Br ⎯⎯→ R—Br

•Br + •Br ⎯⎯→ Br—Br

Reaction with X2 / CCl4
Br
CCl4
H3C—CH=CH2 + Br2 H3C—CH—CH2 (Halogenation)
Br

Mechanism:

RDS
H3C—CH=CH2 + Br—Br H3C—CH—CH2
Br
Cyclic Bromonium ion
Br
Br
H3C—CH—CH2 H3C—CH—CH2
Br Br
NOTE

In this reaction alkene acts as a nucleophile while halogen acts as

an electrophile.
When positive charge is
shared between three or four atoms

In this reaction non-classical carbocation gets form so no rearrangement

is possible.

Reaction intermediate : Cyclic halonium ion.

Reactivity of halogens: F2 >> Cl2 > Br2 > I2

NOTE

Reaction with F2 is explosive.

Reaction with I2 is reversible

H3C—CH=CH2 + I2 H3C—CH—CH2
I I

Test of Unsaturation
Br2
Unknown organic compound Reddish brown colour disappears
CCl4
Unsaturation may be present
Example

C C Br2
C==C
H H CCl4

NOTE

Reactant Addition Product

Cis Anti Threo
Trans Anti Erythro
Cis Syn Erythro
Anti Syn Threo
Example

C H Br2
C==C
H C CCl4

NOTE

Reactant Addition Product

Cis Anti Threo
Trans Anti Erythro
Cis Syn Erythro
Anti Syn Threo
Example

C C—C Br2
C==C
H H CCl4

NOTE

Reactant Addition Product

Cis Anti Threo
Trans Anti Erythro
Cis Syn Erythro
Anti Syn Threo
Example

C H Br2
C==C
H C—C CCl4

NOTE

Reactant Addition Product

Cis Anti Threo
Trans Anti Erythro
Cis Syn Erythro
Anti Syn Threo
Example

CCl4
+ Cl2 ?
Example

CCl4
+ Br2 ?
Reaction with X2 / H2O or HOX (Hypohalous Acid)

H2O
H3C—CH=CH2 + Br2 H3C—CH—CH2
OH Br

Mechanism:

RDS
H3C—CH=CH2 + Br—Br H3C—CH—CH2 (Cyclic bromonium ion)
Br
OH
H2O
H3C—CH—CH2 H3C—CH—CH2 (Major)
Br Br
NOTE

No carbocation intermediate is formed so no rearrangement is

possible.

Reaction intermediate – cyclic halonium ion.

Example

Cl2/H2O or
Ph—CH=CH2
HOCl

Solution

OH
H2O
Ph—CH—CH2 Ph—CH—CH2
Cl Cl
Example

C C Br2
C==C
H H H2O

NOTE

Reactant Addition Product

Cis Anti Threo
Trans Anti Erythro
Cis Syn Erythro
Anti Syn Threo
Example

C H Br2
C==C
H C H2O

NOTE

Reactant Addition Product

Cis Anti Threo
Trans Anti Erythro
Cis Syn Erythro
Anti Syn Threo
Example

C C—C Br2
C==C
H H H2O

NOTE

Reactant Addition Product

Cis Anti Threo
Trans Anti Erythro
Cis Syn Erythro
Anti Syn Threo
Example

C H Br2
C==C
H C—C H2O

NOTE

Reactant Addition Product

Cis Anti Threo
Trans Anti Erythro
Cis Syn Erythro
Anti Syn Threo
Reaction with NOCl (Tilden’s Reagent)

Cl
H3C—CH=CH2 + O=N—Cl H3C—CH—CH2
NO

Mechanism:

Cl
NO—Cl Cl
H3C—CH=CH2 H3C—CH—CH2 H3C—CH—CH2
RDS
N NO
O
Example Br

Br2/CCl4
Br

OH

HOBr
Br

Cl

NOCl
NO
Reaction with Dilute H2SO4 Or H+/H2O Or H3O+

R—CH=CH2 + H2O H R—CH—CH2 (Acidic hydration)

OH H

Mechanism:

H H
O OH
H H2O
R—CH=CH2 R—CH—CH3 R—CH—CH3 R—CH—CH3
NOTE

1. Reaction is reversible.
2. Carbocation formation step is rds.
3. Rearrangement of C+ will take place, if possible
4. Forward reaction is acidic hydration of alkene and backward
reaction is acidic dehydration of alcohol (Elimination reaction).
Example
H / H2O
CH3—CH—CH=CH2
CH3

Solution

H
CH3—CH—CH=CH2 H3C—CH—CH—CH3
CH3 CH3

OH
H–OH
H3C—C—CH2—CH3 H3C—C—CH2—CH3

CH3 CH3
Example

H / H2O

Solution

H H-OH OH
Example

H / H2O
Example

H / H2O
Reaction with Conc. H2SO4

R—CH=CH2 + H2SO4 R—CH—CH3

OSO3H
Alkyl hydrogen sulphate

Cold concentrated sulphuric acid adds to alkenes in accordance with

Markovnikov rule to form alkyl hydrogen sulphate by the
electrophilic addition reaction.
 Hydroboration Oxidation (HBO)

(i) BH3 / THF

R—CH=CH2 R—CH—CH2
(ii) H2O2 / OH H OH
(Alcohol)

Mechanism:

BH3 / THF H2O2/OH

R—CH=CH2 R—CH—CH2 R—CH—CH2
H — BH2 H BH2 H OH
Anti markovnikov
addition
NOTE

Diborane readily reacts with alkenes giving trialkyl boranes.

This reaction follows Anti-markovnikov rule and alcohol is formed

as a product.

No carbocation intermediate is formed so no rearrangement takes

place.
Example (i) BD3 / THF
CH3—CH2—CH=CH2
(ii) H2O2 / OH

Solution

(i) BD3 / THF

CH3—CH2—CH=CH2 CH3—CH2—CH—CH2
D — BD2 D BD2

H2O2/OH

CH3—CH2—CH—CH2
D OH
Example
(i) BH3 / THF
CH3
(ii) H2O2 / OH

Solution

CH3 CH3

CH3 H H2O2/OH
H
BH3 / THF

H H
BH2 OH
Example
(i) BD3 / THF

(ii) H2O2 / OH
CH3 CH2−CH3

Solution

BD3 / THF Me Et H2O2/OH Me Et

Me Et
BD2 D OH D
Example OH

For above conversion Reagent ' X ‘ is

(1) Dil. H2SO4 (2) (i) Hg(OAc)2, H2O

(ii) NaBH4 / OH

(3) (i) BH3 / THF (4) All

(ii) H2O2 / OH

ANS. (3)
 Oxymercuration Demercuration (OMDM)

The OMDM reaction is an electrophilic addition organic reaction that

transforms an alkene into an alcohol.

REAGENT :
(i) (CH3COO)2 Hg / H2O or Hg(OAc)2 / H2O

(ii) NaBH4 / OH

Example (i) Hg(OAc)2, H2O

R—CH=CH2 R—CH—CH2
(ii) NaBH4 / OH OH H

(Alcohol)
Mechanism:

O
O O
H3C—C—O
Hg H3C—C—O—Hg + H3C—C—O
H3C—C—O
Electrophile
O

O
R—CH=CH2 + Hg—O—C—CH3 R—CH—CH2
HgOAc
 H H O O
O OH
H—OH O—C—CH3 + CH3—C—OH
R—CH—CH2 R—CH—CH2 R—CH—CH2
HgOAc HgOAc HgOAc

(Demercuration) NaBH4/ OH

OH
R—CH—CH2
H
NOTE

In this reaction addition of water takes place and alcohol is formed as a

product.

No carbocation intermediate is formed so no rearrangement takes

place.

Markovnikov addition of water.

Example
(i) Hg(OAc)2, D2O
H3C—CH=CH2
(ii) NaBH4 / OH

solution

D—OD
H3C—CH=CH2 + Hg—O—C—CH3 CH3—CH—CH2
O OD HgOAc

NaBH4/ OH

CH3—CH—CH2
OD H
Example
(i) Hg(OAc)2/ H2O
H3C—C=CH2
(ii) NaBD4 / OH
CH3

solution
OH
H—OH
H3C—C=CH2 + Hg—O—C—CH3 H3C—C — CH2

CH3 O CH3 HgOAc

(ii) NaBD4 / OH

OH
CH3—C — CH2

CH3 D
Hydroformylation or Oxo reaction

Alkenes react with Carbon monoxide and hydrogen at 100 – 150°C

temperature and high pressure (200 atm) in the presence of Cobalt
catalyst to produce an aldehyde

It does not follows markovnikov rule.

The net reaction is the addition of a H–atom to one of the Olefinic

bond and a formyl (–CHO) group to the other.
Example

R—CH2—CH2—CHO
Co/150C
R—CH==CH2+ CO + H2
high pressure
R—CH—CH3

CHO
 Alkenylation (Addition of alkene)

In presence of H2SO4 or H3PO4 at 80°C dimerisation of isobutylene

take place gives two isomer of octene.

CH3 CH3 CH3 CH3 CH3

H2SO4, 80C
2CH3—C==CH2 CH2==C—CH2—C—CH3 + CH3—C==CH—C—CH3

CH3 CH3
 Mechanism:

CH3 CH3

CH3—C==CH2 + H CH3—C—CH3


CH3 CH3 CH3 CH3


CH3—C==CH2 + C—CH3 CH3—C—CH2—C—CH3


CH3 CH3
–H

CH3 CH3 CH3

CH2 ==C— CH2—C—CH3 CH3—C==CH—C—CH3

CH3 CH3
 Oxidation Reaction

Alkenes are easily oxidised by oxidising agents. Oxidising agents attack

on double bond and product formed during oxidation depends on
oxidising agents.

Combustion reaction

𝟑𝒏
CnH2n + O2 ⎯⎯→ nCO2 + nH2O
𝟐

𝟑𝒏
One mole of alkene requires moles of O2 for complete combustion.
𝟐
Example
Ozonolysis

A test for unsaturation in a molecule

R R
O3/H2O/Zn
C O+O C
H R
R R Reductive Ozonolysis
C C
H R
O O R R
O3/H2O C O+O C
HO R
Oxidative Ozonolysis
 When ozone is passed through an alkene in an inert solvent, it adds across
the double bond to form an ozonide. Ozonides are explosive compound
they are not isolated.
O O
H2O/Zn
R—C—H + R—C—R

Zn + H2O2 ZnO + H2O

R R R O R
C C Reductive Ozonolysis
C C
H R R
H O–O
O O
O Ozonide O O
H2O
R—C—H + R—C—R + H2O2

H2O2 O
R—C—OH
Oxidative Ozonolysis
In oxidative ozonolysis oxidation of aldehyde takes place while oxidation
of ketones does not take place.

If formic acid is formed in oxidative ozonolysis then it further oxidises

into CO2.

[O]
H—C—OH CO2 + H2O
O
 Ozonolysis of alkenes helps in locating the position of double bond in an
alkene. It can be achieved by joining together the carbon atoms of the two
carbonyl compounds formed as the products of ozonolysis with double
bond.

Example

H H

CH3 − C = O + O = C − CH3 ⎯⎯→ CH3− CH = CH − CH3

H H

H−C=O + O = C − CH2−CH3 ⎯⎯→ CH2=CH − CH2 − CH3

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
(i) O3
(A)
(ii) Zn / H2O

H3C—C=CH—CH3
CH3 (i) O3
(B)
(ii) H2O

Solution

O O
(A) H3C—C—CH3 + CH3—C—H

O O O
(B) H3C—C—CH3 + CH3—C—H CH3—C—OH
Example
CH3
(i) O3
H3C—C=C—CH3
(ii) Zn / H2O
CH3

Solution

O
2 H3C—C—CH3
Example
(i) O3
(ii) Zn/H2O

Solution

O
O
O
O
Example
(i) O3
H2C=C=CH2
(ii) Zn / H2O

Solution

O
H2C=C=CH2 2 H—C—H + CO2
Example
(i) O3
(ii) Zn / H2O

Solution

O
3
O
Glyoxal
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
Example
(i) O3
(A)
(ii) Zn / H2O

H3C—CC—CH3
(i) O3
(B)
(ii) H2O

Solution

O O
(A) H3C—C—C—CH3

O
(B) 2 H3C—C—OH
Example
(i) O3
(A)
(ii) Zn / H2O

H3C—CC—H
(i) O3
(B)
(ii) H2O

Solution

O O
(A) H3C—C—C—H
O
(B) H3C—C—OH + CO2
Example

(i) O3
(A)
(ii) Zn / H2O

Solution

(A)
OHC C CHO
O CHO
Example (i) O3
CH3—CC—(CH2)6—CH==CH—CH3
(ii) Zn / H2O (A)

(i) O3
(B)
(ii) Zn / H2O (Excess)

(i) O3
(C)
(ii) H2O
(limited)

(i) O3
(D)
(ii) H2O (Excess)
Example
Solution

(A) CH3—CC—(CH2)6—CHO + CH3—CHO

O O
(B) CH3—C—C—(CH2)6—C—H + CH3CHO

O O
(C) CH3—CC—(CH2)6—C—OH + CH3—C—OH

O O O O
(D) CH3—C—OH + HO—C—(CH2)6—C—OH + CH3—C—OH
 Hydroxylation

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

(A) Oxidation by Baeyer's reagent (A test for unsaturation): Alkenes on

passing through dilute alkaline 1% cold KMnO4 (i.e., Baeyer's reagent)
decolourise the pink colour of KMnO4 and gives brown ppt MnO2 and
glycol.

> C==C< + H2O + [O] OH–

> C—C< Glycol
KMnO4
(cis–addition)
OH OH
(B) By OsO4:

R — CH R — CH—O O R — CH—OH
H2O
|| +OsO4 | Os | +H2OSO4
R — CH R — CH—O O R — CH—OH
cis - addition

(C) By peracid:

O OH
–HCOOH –H2O
> C==C < + H—C—O—O—H > C—C < >C—C<

O HO
Trans glycol
Epoxidation

Alkenes reacts with oxygen in the presence of Ag catalyst at

250°–400° C to form epoxide.

O OH
1 Ag H2O
CH2==CH2 + O CH2—CH2 CH2—CH2
2 2 D
OH

(anti addition)
Epoxidation

Prileschiaev reaction: When an alkene is treated with perbezoic

acid an epoxide is formed. Such an epoxidation is known as
Prileschiave reactions.

RCH==CH2 + C6H5COOOH R—CH

O + C6H5COOH
CH2
Epoxide
 Syn addition
Meso compound
cis alkene
Anti addition
Racemic mixture

Syn addition
Racemic mixture
trans alkene
Meso compound
Anti addition

Syn addition 𝐨𝐧 𝐚𝐥𝐤𝐞𝐧𝐞 → 𝐇𝟐 𝐎𝟐 , 𝐁𝐚𝐞𝐲𝐞𝐫′𝐬 𝐫𝐞𝐚𝐠𝐞𝐧𝐭, 𝐎𝐬 𝐎𝟒 Τ𝐇𝟐 𝐎

𝐀𝐧𝐭𝐢 𝐚𝐝𝐝𝐢𝐭𝐢𝐨𝐧 𝐨𝐧 𝐚𝐥𝐤𝐞𝐧𝐞 → 𝐗 𝟐 , 𝐇𝐎𝐗, 𝐑𝐂𝐎𝐎 𝐇Τ𝐇𝟐 𝐎, 𝐀𝐠 𝟐 𝐎Τ𝐇𝟐 𝐎

 Hydrocarbon
Oxidation By Strong Oxidising Agent (Oxidative Cleavage)

The alkenes themselves are readily oxidised to acid or ketone by

means of acid permagnate or acid dichromate. If HCOOH is formed, it
further oxidized to CO2 and H2O.

𝟓𝐎
𝐂𝐇𝟑 𝐂𝐇 = 𝐂𝐇𝟐 ⎯⎯→𝐂𝐇𝟑 𝐂𝐎𝐎𝐇 + 𝐂𝐎𝟐 + 𝐇𝟐 𝐎

𝟒𝐎
𝐂𝐇𝟑 𝐂𝐇 = 𝐂𝐇𝐂𝐇𝟑 → 𝟐𝐂𝐇𝟑 𝐂𝐎𝐎𝐇

CH3 4[O] CH3

C==CH2 C==O + CO2 + H2O
CH3 CH3
Oxidation with retention of Carbon-Carbon bond-(Waker process)

Example

𝐏𝐝𝐂𝐥𝟐
𝐂𝐇𝟐 𝐂𝐇𝟐 + 𝐇𝟐 𝐎𝟐 ⎯⎯→ 𝐂𝐇𝟑 𝐂𝐇𝐎
𝐂𝐮𝐂𝐥𝟐
 Allylic and Benzylic Hydrogens

The sp2 carbons of an alkene are called vinylic carbons. An sp3 carbon that
is adjacent to vinylic carbon is called an allylic carbon. A hydrogen bonded
to a vinylic carbon is called a vinylic hydrogen, and a hydrogen bonded to
an allylic carbon is called an allylic hydrogen.

Vinylic carbons

RCH2—CH=CH—CH2R

Allylic carbons
Example

Total number of allylic hydrogens in following compound is ?

Solution

CH3
H

H 7
H
H
Allylic substitution

When alkenes are treated with Cl2 or Br2 at high temp. , one of their allylic
hydrogen is replaced by halogen atom

Cl2 (Low conc.)

CH2 = CH−CH3 CH2 = CH−CH2−Cl + HCl
2500 C
(Free Radical Substituation)

Cl
Cl2 (High conc.)
CH2−CH−CH3
0
25 C
Cl
(Electrophilic Addition )

High temp. favours allylic substitution while low temp. favours

electrophilic addition
High Conc. of halogen favours addition while low conc. of halogen favours
substitution

Reagents used for halogenation at allylic and benzylic position.

1. NBS (N-Bromosuccinimide)
O

N—Br N-Bromosuccinimide

O
2. NCS (N-Chlorosuccinimide)
O

N—Cl N-chlorosuccinimide

O
 Reaction with N-bromosuccinimide (NBS)

∆
CH2 = CH−CH3 + NBS
CCl4

Mechanism:

O O
∆
Initiation : N—Br N + Br

O O
Propagation :

STEP -1

CH2 = CH−CH3 + Br CH2 = CH−CH2 + HBr

STEP -2

CH2 = CH−CH2 + Br2 CH2 = CH−CH2 − Br + Br

NOTE

Role of NBS : Its role is to provide slow and constant supply of Bromine
which favours substitution

O O

N—Br + HBr N—H + Br2

O O
Succinimide

Succcinimide formed is insoluble in CCl4

Example
NBS
hn

Solution
Example
CH2—CH3

NBS

Solution
Example Which of the following is more reactive towards NBS?

CH3 CH2CH3

(A) (B)

Solution

Reactivity towards NBS  stability of free radical

CH2 CHCH3

Ans. (B)
 Isomerisation

Alkene on heating to 500° to 700 °C or on heating in presence of

catalyst [AlCl3 or Al2(SO4)3] undergo isomerisation.

Example

Catalyst
CH3CH2—CH==CH2 CH3—CH==CH—CH3 + CH3—C==CH2
D

—
1–Butene 2–Butene
CH3
Isobutylene
Uses

In plastic formation.

In oxy ethylene welding

As food preservatives and ripening fruits

As general anaesthetic (C2H4 with 10% O2)

Uses

In preparation of mustard gas

CH2 CH2 CH2Cl CH2Cl

+ S2Cl2 +

==

—
==

—
+ S
CH2 CH2 CH2—S—CH2
2,2' or (, ') dichloro
diethyl-sulphide (mustard gas)
Polymerisation

Any process in which relatively small molecules, called monomers

combine chemically to produce a very large chain like or network like
molecule, called a polymer.

The monomer molecules may be all alike, or they may represent two,
three, or more different compounds

Molecular weight of polymer is simple multiple of monomer.

Polymerization can be carried out by free radical or ionic mechanism.

Polymerisation

Polythene is obtained by the polymerisation of ethene molecules at high

temperature, high pressure in the presence of a catalyst.

High temp. / Pressure

n(CH2=CH2) ( CH2—CH2 )n
Catalyst
Polythene

High temp. / Pressure

n(CH3—CH=CH2) ( CH—CH2 ) n
Catalyst
CH3
Polypropene
Use of Polymers

Polymers are used for the manufacture of plastic bags, squeeze bottles,
refrigerator dishes, toys, pipes, radio and T .V. cabinets etc.

Polypropene is used for the manufacture of milk crates, plastic buckets

and other moulded articles.
 KCP/TCP
Dienes

Dienes are the unsaturated hydrocarbons with carbon-carbon

double bonds in their molecules.

These are represented by the general formula CnH2n–2 which

means that they are isomeric with alkynes (functional isomers).
However, their properties are quite different from those of
alkynes.

Depending upon the relative positions of the two double bond,

dienes are classified in three types:
Dienes

Isolated dienes or non conjugated dienes :

In an isolated diene, the two double bonds are separated by
more than one single bond. For example

CH3

—
CH2 == CH—CH2—CH== CH2 CH2 == CH—CH—CH== CH2
Penta–1,4–diene 3–Methylpenta–1, 4–diene
 Cunjugated dienes:
In a conjugated diene, the two double bonds are present in the
conjugated or alternate position and are separated by a single
bond.
CH3

—
CH2 == CH—CH== CH2 CH2 == C—CH== CH—CH3
Buta-1,3-diene 2-Methylpenta-1,3-diene

Commulate dienes:
In this case, the two double bonds in the molecules are present at
adjacent positions. For example

CH2 == C== CH2 CH2 == C== CH—CH3

Propa-1,2–diene Buta–1, 2–diene
 Example

CH CH2 H-Br (1 mole)

CH2 CH
 solution

CH CH2 H-Br (1 mole)

CH2 CH
CH * CH2
CH2 CH
H
Br
1, 2- addition

CH2=CH—CH—CH3 (KCP)

H
 Br ⊝
CH2—CH=CH—CH3 CH2—CH=CH—CH2

Br
1, 4- addition
(TCP)
 KCP TCP
KCP is formed as major product at TCP is formed as major product at
low temp (–80°C to 5°C) higher temp (15°C to 80°C)

KCP is formed by more collision TCP is most stable product (It may
probability (i.e 1, 2 – addition) 1, 4 – addition product or 1, 2 –
addition product )
It depend on path i.e Ea It do not depend on path
(Activation energy or energy
barrier)
\ It is formed by lower energy
barrier.
Example

HCl (1 mole)
 solution

HCl (1 mole)

H—Cl
CH2 Cl

H
1, 2- addition
 (KCP)
CH2
CH2
H
CH2 Cl
 Cl ⊝

H
1, 4- addition
(TCP)
Example

H–Cl
CH—CH=CH2
(1 mole)
solution
Cl H
H–Cl
CH—CH=CH2 CH—CH—CH2
(1 mole)
1, 2- addition
(KCP & TCP)

+ CH=CH—CH2

Cl H

1, 4- addition