CHEMISTRY 202

Chapter 8
Reactions of Alkenes, part 1

H H
p
s
p
H H
• Suggested problems:
• 46, 47, 48, 51, 55, 56, 58, 60, 61, 63, 65
• REVIEW
• Last semester, we learned about the properties of
alkenes
• 1) Structure H H
p
s
p
H H

• An alkene is sp2 hybridized

2
• The double bond is shorter and stronger than a single bond

H H
Bond length (pm) Bond strength (kcal/mol) p
Single bond
(ethane)
154 83
s
Double bond 133 146 p
(ethylene)
H H
• It is also a two-component bond
Bond strength (kcal/mol)
Sigma (s) 83
Pi (p) 63
146
• The p component is weaker, electron rich, and lies on the
surface of the molecule
• It is this p component that is responsible for the reactivity
of alkenes
3
 Nomenclature
• Trivial (based on the name of alkane)
CH 3

H 3C CH 3 Ethane H 3C C CH 3 Isobutane

CH 3
H 2C CH2 Ethylene Isobutylene
C
H 3C CH2

4
 Nomenclature
• IUPAC
• Based on the longest continuous chain bearing the
functional groups.
• Location of double bond is given by the number

1-butene

2-methyl-2-pentene

5
 Nomenclature
• Alkenes can exist as geometric isomers
H 3C CH 3

= Similar groups on the same side

H H
CIS
H 3C H

Similar groups on the opposite side =

H CH 3

TRANS 6
 Nomenclature
• E/Z System
• Name based on highest priority groups
H 3C CH 3
Would be named cis because
similar groups (CH3) are on the same side
H Cl

But in E/Z system, highest priority groups

(circled) are based on atomic number

7
 Stability of mono-olefins
R R R R R H

> >
R R R H R H
R H R R

>
H R H H

R H H H

>
H H H H
8
 Stability of poly-olefins

> >
C C
C C C C C
C C
C C C C

Conjugated
Alternating Double bond
Isolated on same carbon
Separated by at least 1 CH2 group

9
• In the current chapter, we will look not at the
formation of alkenes but the reactions that olefins
undergo

• These are primarily reactions with:

• A) Electrophiles
• B) Oxidizing Agents
• C) Polymerization Reactions
• See page 415 and 416 for a summary of reactions

• Let us begin with reactions of alkenes with

electrophiles…

10
• An electrophile is a species with an incomplete
octet and usually a positive charge
• Examples of electrophiles are:
• a) H+, proton
. +:
• b) Br , Bromonium ion (not :Br: , bromide ion)
:

:
:

:
O
• c) NO2 d)
S OH

• e) can be neutral as long as group has an

incomplete octet in its outer shell
Cl Cl Cl
:

B Cl :
Al Cl Fe Cl
: : :
:

Cl Cl Cl
11
• Everything with a positive charge is not an
electrophile
• for example, sodium ion (Na+)

Na+ electronic configuration

Outer shell
complete

Is OH+ an electrophile?
12
 IS OH+ AN ELECTROPHILE?

OXYGEN

No new electron added, so it has the

OH+ same electronic configuration as O
Therefore, it is an electrophile

OH- Is OH- an electrophile?

13
 IS OH- AN ELECTROPHILE?

Complete octet
Not an electrophile!
OH-

In fact, OH- is a nucleophile!

14
• We will look at the following:
I. Addition Electrophiles
• A) Addition of Symmetrical Reagents
• 1. Hydrogenation
• a) Mechanism
• b) Geometry of products
• 2. Halogenation
• a) Bromine test for unsaturation
• b) Mechanism
• c) Geometry of addition (syn vs. anti)

15
I. Addition Electrophiles (continued)
• B) Addition of Unsymmetrical Reagents
• 1. Addition of hydrogen halides (HCl, HBr, HI)
• Markovnikov’s rule
• a) General mechanism - carbocations
• b) Unusual case of HBr
• 2. Addition of H2O
• a) Catalytic – H2SO4 or H3PO4
• b) Oxymercuration- Demercuration
• c) Hydroboration-oxidation
• 3. Halohydrin Formation
• 4. Carbene Reactions
• a) Generation of carbenes
• b) Singlet and triplet carbenes
• c) Reaction of carbenes
16
II. Oxidation Reactions
1. Epoxides
a) Formation
b) Nucleophilic ring opening
2. Glycol formation by MnO4-
3. Oxidative Cleavage
a) MnO4-
b) O3
c) Use in Determination of Structure

III. Polymerization Reactions

1) Free radical polymerization
2) Cationic Polymerization
3) Anionic Polymerization
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 Electrophilic Addition to Alkenes
• Let’s begin with the addition of symmetrical reagents
• H2 or X2 (Br2 or Cl2)
• A) Hydrogenation

H H
Pt
H 3C C CH2 + H2 H 3C C CH2

H H

18
 General Mechanism
catalyst
Step 1. Hydrogen is absorbed on catalyst H
H

Step 2. Alkene is absorbed H

H H C
next to hydrogen
H H C H

Step 3. Hydrogen is transferred H CH2

to alkene H C H2
Notice that hydrogen is added to the same side
of the alkene – to give the corresponding alkane CH3
C H3
Step 4. Alkene dissociates from
catalyst surface
19
• Some things to remember…
• There are no rearrangements
H2/Pt

• It is a stereospecific reaction

H2/Pt
H
One particular stereoisomer of
starting material gives one particular
H
stereoisomer of the product

No trans isomer is formed

20
• Let’s try some examples
D
H
D2/Pd

H
D

• Try this problem:

Ph H

?
D2

Ni
Ph H

21
 Ph
Ph H
D2 H D

Ni H D
Ph H
Ph
(meso)

Ph
Ph H
D2 H D

Ni D H
H Ph
Ph
(enantiomers)

Since this reaction is catalytic, the reverse reaction (dehydrogenation) can take place.

Industrial processes include the hardening of oils and the synthesis of trans fats in margarine
22
 Alkene stability: Heat of hydrogenation
• A measure of alkene stability
• Heat of hydrogenation
H 3C
H2 H 2C CH 3
C CH2
+ heat
Pt H 3C
H

• The amount of energy released is a measure of the

stability of the alkene.
• The lower the heat of hydrogenation, the more
stable the alkene

23
Alkene stability: Heat of hydrogenation

30.1 kcal/mol

28.3 kcal/mol

27.4 kcal/mol

24
• Addition of Halogens ( Cl2 or Br2)

• Note this reaction is ionic, not free radical.

• Light is not required!
• Mechanism

acyclic bromonium ion

trans addition

• No free carbocation – no rearrangements

25
 trans product

Could also produce enantiomer

26
• Iodine is not useful because it adds reversibly
Free rotation elimination

I2

• This reaction can sometimes be used to invert

configuration of an alkene

27
Bromine Test for Unsaturation
• When a brownish-red solution is added to a solution
of a material containing a double bond
• The color disappears instantly
• This is a test for a multiple bond (double or triple)
• Bromine test for unsaturation

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https://bradchem.wordpress.com/2016/11/06/describe-how-bromine-water-can-be-used-to-test-for-a-double-bond/