Organic Chemistry Addition Reactions

Organic Chemistry
ABCT2423
Reaction of Alkenes:
Addition Reactions
Dr. Chau Ming SO

Office: Y843
Email: bccmso@polyu.edu.hk
1
Handout for “ALKENES”
Hydrogenation of Alkenes
Electrophilic Addition of Hydrogen halides to Alkenes
Regioselectivity of Hydrogen Halide Addition:
Markovnikov's Rule
Addition of sulfuric acid (H2SO4) to alkenes
Acid-Catalyzed Hydration of Alkenes (Alkenes to Alcohols)
Hydroboration-Oxidation of Alkenes (Alkenes to Alcohols)
Addition of Halogens to Alkenes
Addition Reaction: Hydrohalogenation
2
Hydrogenation of Ethylene
H H H H
   
C C + H—H H C C H
H H H H
Exothermic H° = –136 kJ/mol

Catalyzed by finely divided Pt, Pd, Rh, Ni
3
• Mechanism of
alkene
hydrogenation
• The reaction takes

place with syn
stereochemistry on
the surface of
insoluble catalyst
particles
4
Heats of Hydrogenation of Isomers
126
119
115
CH3CH2CH2CH3
5
Can be used to measure relative stability of isomeric alkenes
Syn Addition
syn addition
H
CO2CH3 CO2CH3
H2, Pt
CO2CH3 CO2CH3
H
(100%) 6
Markovnikov's Rule
7
Electrophilic Addition of
Hydrogen Halides to Alkenes
 –
C C + H—X H C C X
CH3CH2 CH2CH3
HBr
C C
CHCl3, -30 °C
H H
CH3CH2CH2CHCH2CH3
(76%)
Br
8
rate-determining
Mechanism formation of a
carbocation
carbocation intermediate.
+C C H
.. –
:X
.. :
..
H X:
..
..
C C :X
.. C C H
9
Markovnikov's Rule
10
Regioselectivity of Hydrogen Halide
Addition:Markovnikov's Rule
Markovnikov's Rule
• When an unsymmetrically substituted alkene

reacts with a hydrogen halide, the hydrogen
adds to the carbon that has the greater
number of hydrogen substituents, and the
halogen adds to the carbon that has the
fewer hydrogen substituents.
11
Markovnikov's Rule
Example 1
HBr CH3CH2CHCH3
CH3CH2CH CH2
acetic acid (80%)
Br
CH3 CH3
H
HBr
C C CH3 C CH3
acetic acid
CH3 H Br (90%)
HCl CH3
CH3 (100%)
0°C Cl 12
Mechanistic Basis for Markovnikov's Rule:
Example 1
+
CH3CH2CH2—CH2
primary carbocation is less stable then
secondary carbocation
secondary +
CH3CH2CH—CH3 + Br –
carbocation
HBr
CH3CH2CH CH2 HBr CH3CH2CHCH3

13
Br
H
secondary Example 2
carbocation is less
+ CH3
stable then tertiary
carbocation H
H H
tertiary
Cl–
+ CH3 carbocation
HCl
H
HCl CH3
CH3
0°C Cl
14
Important Consideration: Rearrangements
Cl ─ H H2C CHCH(CH3)2 3-methyl-1-butene

HCl, 0 °C
tertiary
H H cation
hydride
secondary + shift
+
cation CH3CHC(CH3)2 CH3CHC(CH3)2
CH3CHCH(CH3)2 CH3CH2C(CH3)2
Cl Minor Product Major Product Cl 15

Markovnikov's Rule
16
concentrated
H-OSO2OH
CH3CH CH2 CH3CHCH3
OSO2OH
Isopropyl
hydrogen sulfate
Follows Markovnikov's rule:

yields an alkyl hydrogen sulfate
17
(Mechanism)
..
CH3CH CH2 + H O
.. SO2OH
slow
+ ..–
CH3CH CH3 + :O SO2OH
..
fast
CH3CHCH3
:OSO
.. 2OH 18
Markovnikov's Rule
19
Acid-Catalyzed Hydration of Alkenes
H3C H CH3
50% H2SO4
C C CH3 C CH2CH3
50% H2O
H3C CH3 OH (90%)
Follows Markovnikov's Rule
• reaction is acid catalyzed;

• typical hydration medium is
• 50% H2SO4 and 50% H2O 20
(Mechanism)
Step (1) Protonation of double bond
H3C H
+
C CH2 + H O:
H3C H
slow
H3C H
+
C CH3 + :O:
H3C H 21
(Mechanism)
Step (2) Capture of carbocation by water
H3C H
+
C CH3 + :O:
H3C H
fast
CH3 H
+
CH3 C O:
CH3 H 22
(Mechanism)
Step (3) Deprotonation of oxonium ion
CH3 H H
: +
CH3 C +O :O:
CH3 H H
fast
CH3 H
.. +
CH3 C O: + H O:
CH3 H H 23
Markovnikov's Rule
24
Synthesis Question
How can we prepare 1-decanol from 1-decene?
OH
Need a method for hydration of
alkenes with a regioselectivity opposite to
Markovnikov's rule.
25
Synthesis Question
• A two-step reaction sequence called

hydroboration-
oxidation converts alkenes to alcohols with a
regiochemistry opposite to Markovnikov's rule.
1. hydroboration
2. oxidation
OH
26
Hydroboration Step
C C + H—BH2 H C C BH2
Hydroboration can be viewed as the addition

of borane (BH3) to the double bond.
Hydroboration reagents:
H
Diborane (B2H6) + O
H2B BH2 - BH3
H Borane-tetrahydrofuran
complex (H3B-THF)
27
Oxidation Step
H2O2, HO–
H C C BH2 H C C OH
• Organoborane formed in the hydroboration

step is oxidized with hydrogen peroxide.
28
Features of
Hydroboration-Oxidation
• Hydration of alkenes
• Regioselectivity opposite to Markovnikov's rule
• No rearrangement
• Stereospecific syn addition
Example
H3C CH3 H OH
1. H3B-THF
C C CH3 C C CH3
2. H2O2, HO–
H3C H CH3 H (98%)
29
Syn Addition
• H and OH become attached to same face of

double bond
CH3 1. B2H6 CH3

2. H2O2, NaOH
HO
H H
only product is trans-2-methylcyclopentanol

(86%) yield
30
Syn Addition
• Syn addition of H and B to double bond
• B adds to the less substituted carbon
31
Markovnikov's Rule
32
C C + X2 X C C X
• Electrophilic addition to double bond forms a

vicinal dihalide
Br2
CH3CH CHCH(CH3)2 CH3CHCHCH(CH3)2
CHCl3
0 °C Br Br (100%)
33
Addition of Halogens to Alkenes (Scope)
Practically useful to Cl2 and Br2
F2 addition proceeds with explosive violence

I2 addition is endothermic: Slow reaction
34
Stereochemistry of Halogen Addition
H
H Br2 trans-1,2-
Br Dibromocyclopentane
80% yield; only product
H Br H
H
H Cl
Cl2
H H
Cl
trans-1,2-Dichlorocyclooctane
35
73% yield; only product
(Mechanism)
H2C CH2 + Br2 BrCH2CH2Br
+ .. –
C C + : Br :
..
: Br :
..
No obvious explanation for anti addition
provided by this intermediate.
36
(Mechanism)
H2C CH2 + Br2 BrCH2CH2Br
.. –
C C + : Br :
..
: Br :
+
Formation of Cyclic bromonium ion 37
(Stereochemistry)
.. –
: Br :
..
..
Br +
..
..
: Br :
..
• Attack of Br– from side opposite
C—Br bond of bromonium ion gives
..
anti addition :
Br
38
..
Markovnikov's Rule
39
• Alkenes react with X2 to form vicinal dihalides
C C + X2 X C C X
• Alkenes react with X2 in water to give vicinal

halohydrins
C C + X2 + H2O X C C OH
+ H—X
40
H2O
H2C CH2 + Br2 BrCH2CH2OH
(70%)
H
Cl2
H OH
H2O
H Cl H
anti addition: only product
41
Mechanism
O :
..
..
Br +
..
+
O
..
Bromonium ion is
intermediate
Water is nucleophile that ..
:
attacks bromonium ion 42Br
..
Regioselectivity
H3C CH3
Br2
C CH2 CH3 C CH2Br
H2O
H3C OH
(77%)
• Markovnikov's rule applied to halohydrin

formation:
• the halogen adds to the carbon having the
greater number of hydrogens.
43
Alkenes
1. Understanding the mechanism and

regeioselectivity of the hydrogenation reaction.
2. Understanding the mechanism of the electrophilic
addition of hydrogen halides reaction.
3. Able to apply the Markovikov’s rule to predict the
regioselectivity of the addition products.
4. Understanding the mechanism and the
regioselectivity of different kinds of addition
reactions.
5. Able to apply the addition reactions to convert
alkenes to desired products.
44

Organic Chemistry Addition Reactions

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Organic Chemistry Addition Reactions

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Organic Chemistry

Dr. Chau Ming SO

Exothermic H° = –136 kJ/mol

• The reaction takes

• When an unsymmetrically substituted alkene

CH3CH2CH CH2 HBr CH3CH2CHCH3

Cl ─ H H2C CHCH(CH3)2 3-methyl-1-butene

Cl Minor Product Major Product Cl 15

Follows Markovnikov's rule:

Follows Markovnikov's Rule

• reaction is acid catalyzed;

How can we prepare 1-decanol from 1-decene?

• A two-step reaction sequence called

Hydroboration can be viewed as the addition

• Organoborane formed in the hydroboration

• H and OH become attached to same face of

CH3 1. B2H6 CH3

only product is trans-2-methylcyclopentanol

• B adds to the less substituted carbon

• Electrophilic addition to double bond forms a

Practically useful to Cl2 and Br2

F2 addition proceeds with explosive violence

• Alkenes react with X2 to form vicinal dihalides

• Alkenes react with X2 in water to give vicinal

• Markovnikov's rule applied to halohydrin

1. Understanding the mechanism and

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