CH203

Lecture 29
November 12, 2014

Alkene reac;ons

A-B

H3C

CH3

CH3

CH3

CH3

CH3

syn addition product

anti addition product

Thermodynamics of an addi;on reac;on

The reac;on enthalpy Ho for the addi;on of Br2 to 2,3-dimethyl-2-butene is calculated

by subtrac;ng the sum of all BDEs of bonds formed from the sum of all BDEs of bonds
broken:

Ho = BDEs (broken) BDEs (formed)

The reac;on is exothermic because stronger bonds are made in the product compared
to those broken in the star;ng materials.

6

Thermodynamics of an addi;on reac;on

Thermodynamics of an addi;on reac;on

+
C

H
C

C
8

Thermodynamics of an addi;on reac;on

Reac%ve intermediate a species which exists in a high energy
well on a reac;on coordinate diagram. It has a short but
measurable life;me.

Transi%on state a species which exists at the top of a hill on a
reac;on coordinate diagram. It has no prac;cal measurable
life;me.

Rate-determining step (some;mes called the rate-limi%ng step)
the slowest step in a series of steps. It is the step with the highest
hill to go over.

Electrophilic addi;ons
The key reac;on theme in common alkene addi;on to pi bonds is
called electrophilic addi;on. The key step in these mechanisms
involves the pi electrons of the alkene reac;ng as a nucleophile
with an electrophile in a bond-making step.

A nucleophile donates an electron pair to an electrophile to form
a new bond. Any molecule or ion with a free pair of electrons or at
least one pi bond can act as a nucleophile. Because nucleophiles
donate electrons, they are Lewis bases.

An electrophile accepts an electron pair from a nucleophile to
form a new bond. Because electrophiles accept electrons, they are
Lewis acids. Most electrophiles are posi;vely charged, have an
atom that carries a par;al posi;ve charge, or have an atom that
does not have an octet of electrons.
10

Electrophilic addi;ons
What makes a molecule a good electrophile?

1. A full or par;al posi;ve charge.
H
O

H
O

H+

+
H

11

Electrophilic addi;ons
What makes a molecule a good electrophile?

1. A full or par;al posi;ve charge.

CH3
C
H3C

!+ !H Br

+
CH3

12

Electrophilic addi;ons
What makes a molecule a good electrophile?

2. An atom with an incomplete octet.

CH3
C

H3C

CH3
B

CH3

H3C

CH3

13

Electrophilic addi;ons
What makes a molecule a good electrophile?

3. A weak bond which can be broken to leave a stable ion.
H
Br

Br

HH
C

14

Addi;on of HX
The hydrogen halides (HCl, HBr, and HI) add to alkenes to give
haloalkanes. These addi;ons may be carried out either with pure
reagents (neat) or in the presence of a polar solvent, such as ace;c
acid.

15

Addi;on of HX
The addi;on of HX to an alkene is regioselec;ve. One regioisomer
is formed in preference to all others which might be formed. In the
case of HX, the regiochemistry is predicted by Markovnikovs Rule:

In the addi;on of HX to an alkene, H adds to the

carbon of the double bond having the greater
number of hydrogens.

16

Addi;on of HX

Thats what Im talking

about.

17

Addi;on of HX

Addi;on of HBr to an alkene happens in two steps. First the alkene

acts as a nucleophile and forms a bond with the electrophilic
hydrogen of HBr. Then the bromide anion, which is now the
nucleophile, bonds to the carboca;on, which is now the electrophile.

18

Addi;on of HX

Carboca;ons, also called carbonium ions, have an incomplete octet

and a full posi;ve charge. They are Lewis acids and excellent
electrophiles. As they are at, any stereochemical center which
becomes a carboca;on in a reac;on is racemized.
19

Addi;on of HX

20

Addi;on of HX

21

Addi;on of HX

22

Addi;on of HX
A restatement of Markovnikovs Rule:

When an asymmetrical alkene undergoes electrophilic addi;on, the product that
predominates is the one that results from the more stable of the two possible
carboca;on intermediates.

So...
H
CH3

Br
CH3

HBr (no radicals)

Br

or

CH3
?
H

23

Addi;on of HX
H
CH3

CH3

HBr (no radicals)

or

2o carbocation,
higher energy

CH3
H

benzylic carbocation,
lower energy

When an asymmetrical alkene undergoes

electrophilic addi;on, the product that
predominates is the one that results from
the more stable of the two possible
carboca;on intermediates.
H

Br
CH3

CH3

Br
not formed

H
major product
24

Addi;on of HX carboca;on stability

Alkyl groups stabilize a carboca;on by induc;on and by hyperconjuga;on.

25

Addi;on of HX carboca;on stability by induc;on

H2C

+
C

CH2

CH2

+
C

CH2

CH2

+
C

CH2

C
H

Increasing donation of electron density through the C-C sigma bonds

by induction.
Increasing delocalization of the positive charge.
Increasing stability.

26

Addi;on of HX carboca;on stability by hyperconjuga;on

Hyperconjuga;on in a carboca;on system is the overlap of an

adjacent C-H or C-C sigma bond with a the empty p orbital to
give an extended molecular orbital that delocalizes the posi;ve
charge and increases the stability of the system.
27

Addi;on of HOH acid-catalyzed hydra;on

CH2

H3C

Cl

H3C

OH

2M HCl
+

28

Addi;on of HOH acid-catalyzed hydra;on

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