Chapter Eight

Alkenes and Alkynes I.

Addition Reactions

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Sect 8.1: Addition

Reactions
Y
C

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Addition of H-X
H

H
C

H
X

X
H
H

X
H
H
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Addition of Water
H

H
C

O
H

H+ catalyst

H
C

H
OH

OH

H+ catalyst

O
H

H
H
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Sect. 8.2: Introduction

to Mechanisms
mechanism
two step
rate determining step (i.e. slow
step)
energy diagram
transition states
intermediates
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MECHANISM
STEP-BY-STEP ACCOUNT OF WHAT HAPPENS

:Xstep 1

C C

C C
+
E

step 2

X
C C
E

Intermediate

intermediates are
formed during a
reaction but are
not products

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ENERGY PROFILE
two step reaction
intermediate

TS1

E
N
E
R
G
Y

TS2
-

C C
+ E
step 1

C C
+

step 2

product C C
E
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ACTIVATED COMPLEXES

correspond to transition states for each

step
-

X
C C

X
C C

C C
+
E

intermediate

+
C

+E

C C

ACTIVATED show bonds in the process of breaking or forming

COMPLEXES (bonds are half formed or half broken)
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Sect 8.3: Electrophilic

Addition to a Double Bond

CH2

CH2

CH2 CH2

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Hyperconjugation

Empty
p-orbital

H
C
H

C
H

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CARBOCATION STABILITY
HYPERCONJUGATION

..

C C

electrons in an adjacent

C-H bond help to stabilize

the positive charge of the
carbocation by proximity
(overlap)

R
H
R
R

C R
R +
R

Most
stable

C
+

tertiary

>

CH
+

R CH R
+
secondary

>

CH2
+

R CH2
+

primary

Least
stable

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Can you recognize the

following carbocations? 1o,
o
o
2
,
3
+
+

+
+

o
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Sect 8.4: Addition of

Hydrogen Halides:
Markovnikovs rule
CH
3

Br
C

H3C

CH3

major
product

H-Br

C
H3C

CH2
CH3
H
C
H3C

minor
product

H
Br
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Markovnikovs Rule
In the ionic addition of an acid to the
carbon-carbon double bond of an alkene,
the hydrogen of the acid attaches itself to
the carbon atom which already holds the
greater number of hydrogens.
Them that has, gets!
The richer get richer!
(V. W. Markovnikov -- 1838 1904)
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Markovnikov
Markovnikov

Not
Markovnikov
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WWU -- Chemistry

MARKOVNIKOV RULE
When adding HX to a double bond the
hydrogen of HX goes to the carbon
which already has the most hydrogens

CH2
+ HCl

CH3
Cl

..... conversely, the anion X adds to the most

highly substituted carbon ( the carbon with
most alkyl groups attached).
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REGIOSELECTIVE
REACTION
CH3
CH3

C CH2

HCl

CH3
CH3

CH3

C CH3 + CH3 CH CH2

Cl
major

Cl
minor

one of the possible products is formed

in larger amounts than the other one
Compare

REGIOSPECIFIC

only one of the possible products is

formed (100%).
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Mechanism (Markovnikov)
1)

CH CH2

slow

+
+ H

Electrophile

2)

CH-CH2 H +

_
Br

CH-CH2 H

Secondary C+
fast

Nucleophile

CH CH2 H
Br

Major product
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Mechanism (antiMarkovnikov)
1)

+
CH CH2 + H

slow

CH CH2+

Primary
carbocation
2)

CH
H

+
CH
2

_
+ Br

fast

CH CH2 Br
H

Minor!
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COMPETING PATHWAYS
rate-determining step
higher energy
intermediate

slower
faster

lower energy
intermediate

rate-determininng
(slow) step
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Markovnikov Addition to
an Alkene
CH3

CH3
C

CH2

CH3

CH3 C

CH3
CH2 H

X
major product

CH3 C

CH2 X

H
minor product

X = Cl, Br, I

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Mechanism
CH3

1)

C
CH3

CH2

H
CH

H
C

CH3

CH3

Electrophile

CH3

2)

CH2

slow

CH3

fast

C+

CH3

X
CH3

Nucleophile

CH2

H
C

CH2

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SOME ADDITIONAL EXAMPLES

only major product is shown

CH3
+ HCl

CH2
+ HCl

CH CH2
+ HCl

CH3
Cl

CH3
Cl

CH CH3
Cl

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Sect 8.5 Addition of

Sulfuric Acid to an Alkene
R

CH CH2

H2SO4

(cold, concentrated)

CH CH2 H
O

OH
an alkyl hydrogen sulfate

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ALKYL HYDROGEN SULFATES

C C

O S O H
OSO3 H

SLOW
O

C C
+
H

C C
H

H O S O H

alkyl hydrogen sulfate

O
cold
FOLLOWS
MARKOVNIKOFF
RULE

OH
C C

water
room temp

H
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Addition of Water to an
Alkene
R

CH CH2

H2O

H2SO4

CH CH2 H
OH
an alcohol

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Mechanism of Hydration
1)

2)

3)

CH CH2

CH CH2 H

CH CH2 H

+ OH2

H2SO4

slow

CH CH2 H

H2O

HSO4

CH CH2 H

+ OH2
O

_
+

HSO4

CH CH2 H
OH

OH

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Sect 8.6 Addition of

Bromine to an Alkene
Br
R

CH CH

Br2

CCl4
or CH2Cl2

CH CH

Br

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ADDITION OF BROMINE
Br
C C

CCl4

Br
C C

C C
+
Br

SLOW

Br

Br Br

+
Br

Br

alkene polarizes bromine

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THE REACTION IS STEREOSPECIFIC

ANTI ADDITION

Br

H open carbocation
Br

syn

Br

anti
would give both
cis and trans

Br
syn

anti

H
H

Br

Br
cis compound
NOT OBSERVED

H
Br

Br

H
trans compound
ACTUAL PRODUCT
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WHAT WOULD EXPLAIN FORMATION

OF ONLY THE trans PRODUCT ?
..... A BRIDGED OR CYCLIC INTERMEDIATE

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CYCLIC BROMONIUM ION

note size of
bromine

+
+
Br

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BRIDGED BROMONIUM ION

Br

Br
Br

Br

bridging
blocks approach
from this side
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FORMATION OF ENANTIOMERS
symmetric
intermediate

Br

Addition could also start

from the top with bromide
attacking the bottom.

Br

H
Br
H

Br
ENANTIOMERS

Br
H

Br
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ADDITION OF BROMINE TO 2-BUTENE

CH3

CH CH CH3
+
Br2

CH3
H

CH3 *CH * CH CH3

Br

Br

2n possible stereoisomers
CH3
H

cis-2-butene

CH3
H

H
CH3

trans-2-butene

WILL THESE STEREOISOMERS GIVE THE SAME PRODUCTS?

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NO ! THEY GIVE DIFFERENT PRODUCTS

CH3

CH3

CH3

cis
H

trans

CH3

Br2 / CCl4
Br
CH3

Br

Br

H + H
CH3 CH3

enantiomers

Br2 / CCl4
Br
H

Br
CH3

H
CH3

Br
H
CH3

meso

These results can only be explained by stereospecific anti addition.

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cis

Br

H
H
H3C

Br
H
H

CH3

H3C

Br
Br

CH3
Br+

ADD TO
LEFT

Br
H
H3C

ADD TO
RIGHT

H
CH3

Br

H
H3C

Br

Br

ROTATE

ROTATE

Br Br

Br Br
ENANTIOMERS

H
H3C

H
CH3

CH3
H

H3C

H
H

CH3
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trans

CH3
H

H3C

Br
Br

Br

Br

CH3

H
H3C

Br+

ADD TO
LEFT

Br
H
H3C

ADD TO
RIGHT

CH3
H
Br

Br

ROTATE

H
H3C

CH3
H
ROTATE

Br Br

Br Br
MESO

Br

H
H3C

H
CH3

CH3

H3C
H

IDENTICAL (also meso)

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Bromination of an
Unsymmetrical Alkene
+

Br

1)
R

CH CH2

+ Br

CH

. _
: Br:
.

CH2

C
H

CH

CH2

Br

Br

Br

2)

Br

slow

C
Br

anti-addition
(stereospecific)
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Stereochemistry of
Bromination of Alkenes
Simple alkenes: Addition of bromine
or chlorine goes exclusively anti, with
the formation of a bridged ion
If a resonance-stabilized open-chain
carbocation is possible, there may be
a mixture of mechanisms, with some
molecules reacting via a bridged ion
and some molecules reacting via an
open-chain carbocation
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Stereochemistry of
Bromination of Alkenes
--Part Two
In cases where a resonance-stabilized
carbocation is possible, if the solvent
is made more polar (acetic acid or
nitromethane), the proportion of
molecules reacting via an open-chain
carbocation increases.
For simple alkenes, changing solvents
has little or no effect on
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stereochemistry.

Sect 8.7 Halohydrin

Formation
OH
R-CH=CH-R

Br2
H2O

CH

CH

+ HBr

Br
a bromohydrin

Br2 +
H2O

HOBr

+
HBr

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Mechanism
Br
R

CH2 +

CH

Br

slow

Br

CH

CH2

CH

CH2

O
H

Br

CH2

Br
CH

CH2 +

CH

Br

Br
R

Br
R

CH

CH2

O
H
H

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Sect. 8.8: Carbocation

Rearrangements
CH3

CH3
CH3

C
CH3

CH

CH2

HCl

CH3

CH

Cl

CH3

major
rearranged!!

H
CH2

CH3
+

CH3 C

H
CH

CH2

CH3 Cl
minor
not rearranged!!

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Sect 8.10 Free Radical

Addition of HBr to Alkenes
(anti-Markovnikov!)
R

CH CH2

HBr

ROOR

CH CH2 Br
H

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ADDITION OF HBr
conc.
HBr
CH2

Markovnikov
Addition
CH3
Br

conc.
HBr
CH2

Oxygen

CH2Br
H

Anti-Markovnikov
Addition
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1)

light or

..
O.
..

heat

2)

..
.
O
..

Br

..

O
..

..
.O
..

..
: Br .
..

hydrogen abstraction

3)

4)

..

: Br .
..

Br

CH2 CH R

CH2 CH R
.

slow

Br

Br

CH2 CH R
.

Br

CH2 CH R

..
.
: Br
... .

hydrogen abstraction
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STABILITY OF CARBON RADICAL INTERMEDIATES

Radicals are electron-deficient just like carbocations
and have the same stability order.
R

R
lowest
energy

R C R <
tertiary

R C H
secondary

highest
energy

< R CH2 < CH3

primary

methyl

and they are stabilized by resonance and / or hyperconjugation.

()
()

( )
CH2

()

()

()
CH2

etc.

()
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Sect. 8.11 and 8.12: Hydrogenation

of Alkenes and alkynes
R

CH CH R

Pt, Pd,
H2

or Ni

CH CH R
H

syn-addition
R
R

(stereospecific)
R

H2
lindlar
catalyst H

H
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Hydrogenation of Alkenes
R

CH CH R

H2

Pt, Pd,

CH CH R

or Ni

syn-addition
(stereospecific)

Also PtO2 -- sometimes Ru, Rh,

or Re
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HYDROGEN ADSORBS ON THE SURFACE OF THE CATALYST

n H2 +

Pt(H .)2n

Pt

Pt

Pt

H.

Hydrogen Adsorbed on
Catalyst Surface

.H
Pt

H.

H.

finely-divided
particles
dispersed in
solution

.H
Pt

Pt

.H
Pt

Pt

Pt

Pt

Pt

Pt
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MECHANISM OF HYDROGENATION

.H

.H

.H

.H

.H

.H
.H

CATALYST

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MECHANISM OF HYDROGENATION

.
.
.H H H .
H
.
.
.H H H
.H H.

HYDROGEN
ADSORBS

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MECHANISM OF HYDROGENATION
R

. .
.
.
.H H H .
H
.
.
.H H H
.H H.

ALKENE
APPROACHES

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MECHANISM OF HYDROGENATION

. ..
.
.H H H .
H
.
.
.H H H
.H H.

ALKENE PICKS UP
TWO HYDROGENS

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MECHANISM OF HYDROGENATION
R

..
H

.
.

.H

.H

.H

.H

.H

ALKANE IS
FORMED

.H
.H
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BOTH HYDROGENS ADD TO THE SAME

SIDE OF THE DOUBLE BOND
CH3
not
H
observed
anti
addition

CH3
CH3

H
CH3
CH3

CH3

H syn
addition
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EXAMPLES
Pt

CH3 + H2

CH3 CH CH CH3 + H2

CH3

Pt

CH3 CH2 CH2 CH3

CH3

CH2
+ H2

Pt

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Sect. 8.12: Addition to

Alkynes
R

C-H

H-X

H
C

H-X

anti
addition

C-H

Br2

Br

R
C
Br

C
H

anti addition

Br2

Br

Br

Br

Br

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Hydration of an Alkyne

C-H

H2O

H2SO4
HgSO4

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Hg2+
R

slow

2+ Hg

Mechanism of

Alkyne Hydration
Hg+

R
C
O

- H+

C
H

Hg+

R
C
H

H
H

acid
hydrolysis

Hg2+

H
C

R
C

H
ENOL

KETO

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Keto-Enol Tautomerism
Tautomers: Two compounds with
different structures but which exist in
equilibrium.
Most often, the two structures differ by
the position of a proton.
NOTE CAREFULLY: This is equilibrium,
not resonance!
H
R
R
H
C

H O
. :

H
ENOL

:O
..

H
KETO
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Sect. 8.13: Addition of

HCN and acetic acid to an
alkyne
O

R
R

CH3

OH

C
H

O
O

C
CH3

H-C

N
C

C
H

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Sect. 8.14: Addition

Polymers
H

H
C

catalyst

H
ethylene

polyethylene

a macromolecule with very high molecular weight

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Polymerization of propene
H

CH3
C

catalyst

three different forms

syndiotactic, isotactic and atactic

H
CH3

CH3

CH3

CH3
isotactic

CH3

CH3

CH3

CH3
syndiotactic
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Polymer Problems
Be sure to look at the mechanism of
free radical polymerization of
styrene (p. 733-735).
In-Text Problems 8-27, 8-28, and 829
End of chapter problems: 59, 60,
and 62

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Highlights of Chapter 8
HX addition to alkenes/ Markovnikovs
Rule
Addition of water to alkenes, H+ catalyst
Addition of halogens to alkenes/
stereochem.
Addition of X2 / H2O to alkenes
Carbocation rearrangements
Free-radical addition of HBr (Anti-Mark.)
Hydrogenation
Additions to alkynes
Addition polymers
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