ORGANOHALOGENS

Pintaka Kusumaningtyas

General useful of organohalogens are as

solvent, insecticide, and basic material for

making synthetic organic compound.
The most of organohalogens compounds is
synthetic.
Anesthethics (halothane and methoxy
flurene) are the examples of safe
organohalogen
Many organohalogen compounds are toxic,
and must be handled carefully, for examples :
CCl4 and CHCl3 can cause liver damage if
over inhaled.
Insecticides in agriculture can pollute our
environment

Types of Organohalogen
compounds

Alkyl halide (R-X) :

(Iodomethane)
(Chloroethane)

Aryl halide (Ar-X) :

(Bromobenzene)

(Poly-chlorinated biphenyl)
Halide Vinylic :
(Chloroethene)
(2-bromo-2-butene)

Alkyl Halides
Pintaka
Kusumaningtyas

What is an Alkyl Halide ?

Alkyl halide is an alkane derivative-compound

containing at least one carbon-halogen bond (CX). The symbol is R-X.

X (F, Cl, Br, I) replaces H
Can contain many C-X bonds
Properties and some uses:
Fire-resistant solvents
Refrigerants
Pharmaceuticals and precursors

Physical Properties
Halogens

(X) are more electronegative than Carbon

(C), so carbon has partial positive charge.
Carbon can be attacked by a nucleophile, and
Halogen can leave with the electron pair.
Alkyl halides are weak polar molecules. C-X bond is
polar, so it exhibits dipole-dipole interactions.
Halogenated hydrocarbon doesnt form hydrogen
bonding and insoluble in water.

The Polar Carbon-Halogen Bond

The electronegative halogen atom in alkyl halides creates a
polar CX bond, making the carbon atom electron
deficient.
Electrostatic potential maps of four simple alkyl halides
illustrate this point.

Figure. Electrostatic potential maps of four halomethanes (CH 3X)

7

Nomenclature

Naming Alkyl Halides

10

Naming if Two Halides or Alkyl are Equally

Distant from Ends of Chain
11

Begin at the end nearer the substituent whose name

comes first in the alphabet
If there are more than one different halogens, so the
priorities of naming is based on reactivity of halogen,
the sequence is F Cl Br I. However, the name
writing is still based on the alphabet. For example : 3chloro-2-fluorobutane
Write name for this following chemical structure :

Exercises :

give the names for

following chemical structures

CH3

CH CH2CH3
Cl

(CH3)3CBr

Common Name
13

Common names are often used for simple alkyl

halides. To assign a common name:
Name all the carbon atoms of the molecule as a
single alkyl group.
Name the halogen bonded to the alkyl group.
Combine the names of the alkyl group and halide,
separating the words with a space.

Many Alkyl Halides That Are Widely

Used Have Common Names

Trivial Names
15

CH2X2 is called methylene halide.

CHX3 is a haloform.
CX4 is carbon tetrahalide.
Examples:

CH2Cl2 is methylene chloride

CHCl3 is chloroform
CCl4 is carbon tetrachloride.

Classes of Alkyl Halides

16

Methyl halides: only one C, CH3X

Primary: C to which X is bonded has only one C-C

bond.
Secondary: C to which X is bonded has two C-C bonds.
Tertiary: C to which X is bonded has three C-C bonds.

Figure. Examples of 1, 2, and 3 alkyl halides

Figure. Four types of organic halides (RX) having X near a bond

17

18

Exersice : classify these alkyl

halides and write 2 types of
name for them :
CH3

CH CH3

CH3CH2F

Cl

(CH3)3CBr

CH3I

Exersice : write the structural

formula for these compounds
a). 1,1-dibromobutane
b). 3-chloro-1-butene
c). 2-fluoro-1-ethanol

Dihalides
20

Geminal dihalide: 2 halogen atoms are

bonded to the same carbon
Vicinal dihalide: 2 halogen atoms are
bonded to adjacent carbons.

H H
Br

H Br
geminal dihalide

H C

Br

Br H
vicinal dihalide

Uses of Alkyl Halides

21

Solvents - degreasers and dry cleaning fluid

Reagents for synthesis of other compounds
Anesthetic: Halothane is CF3CHClBr

Freons, chlorofluorocarbons (CFC)

CHCl3 used originally (toxic and carcinogenic)

Freon 12 (CF2Cl2) now replaced with Freon 22
(CF2CHCl), not as harmful to ozone layer.

Pesticides - DDT banned in U.S.

REACTIONS OF ALKYL
HALIDES

Substituti
ons
and
Eliminatio
ns

23

Alkyl Halides React with

Nucleophiles and Bases
Alkyl

halides are polarized at the carbon-halide

bond, making the carbon electrophilic
Nucleophiles will replace the halide in C-X bonds
of many alkyl halides (reaction as Lewis base)
Nucleophiles that are also Brnsted bases can
produce elimination

Nucleophiles Vs Bases
Nucleophiles and bases are structurally
similar: both have a lone pair or a bond.
They differ in what they attack.

25

Nucleophilicity Vs
Basicity
Although nucleophilicity and basicity
are
interrelated,
they
are
fundamentally different.
Basicity is a measure of how
readily an atom donates its
electron pair to a proton.
Nucleophilicity is a measure of
how readily an atom donates its
electron pair to other atoms.

26

Nucleophilicity parallels basicity in three instances:

1. For two nucleophiles with the same nucleophilic atom, the
stronger base is the stronger nucleophile.
The relative nucleophilicity of OH and CH3COO, two oxygen
nucleophiles, is determined by comparing the pKa values of
their conjugate acids (H2O = 15.7, and CH3COOH = 4.8). OH
is a stronger base and stronger nucleophile than CH 3COO.
2. A negatively charged nucleophile is always a stronger
nucleophile than its conjugate acid.
OH is a stronger base and stronger nucleophile than H2O.
3. Right-to-left-across a row of the periodic
nucleophilicity increases as basicity increases:

table,

27

 Nucleophilicity does not parallel basicity when steric hindrance

becomes important.
Steric hindrance is a decrease in reactivity resulting from the
presence of bulky groups at the site of a reaction.
Steric hindrance decreases nucleophilicity but not basicity.
Sterically hindered bases that are poor nucleophiles are called
nonnucleophilic bases.

28

Nucleophilic Substitution (SN)

Reaction
Substitution Nucleophilic Unimolecular
(SN1)
Substituion Nucleophilic Bimolecular
(SN2)

General Features of Nucleophilic

Substitution
Three components are
necessary in any substitution reaction.

30

The Leaving Group

In a nucleophilic substitution reaction of RX, the CX bond is
heterolytically cleaved, and the leaving group departs with the
electron pair in that bond, forming X:. The more stable the
leaving group X:, the better able it is to accept an electron pair.

For example, H2O is a better leaving group than OH because H2O

is a weaker base.
31

Leaving Group Ability

Electron-withdrawing
Stable

once it has left (not a strong base)

Polarizable to stabilize the transition state.

Chapter 6

32

 There are periodic trends in leaving group ability:

33

34

35

 Negatively charged nucleophiles like OH and HS are used as

salts with Li+, Na+, or K+ counterions to balance the charge. Since
the identity of the counterion is usually inconsequential, it is often
omitted from the chemical equation.

When a neutral nucleophile is used, the substitution product bears

a positive charge.

36

Mechanisms of Nucleophilic
Substitution
In a nucleophilic substitution:

But what is the order of bond making and bond breaking? In theory,
there are three possibilities.

[1] Bond making and bond breaking occur

at the same time.

In this scenario, the mechanism is comprised of one step. In such a

bimolecular reaction, the rate depends upon the concentration of
both reactants, that is, the rate equation is second order.
37

[2] Bond breaking occurs before bond making.

In this scenario, the mechanism has two steps and a

carbocation is formed as an intermediate. Because
the first step is rate-determining, the rate depends
on the concentration of RX only; that is, the rate
equation is first order.
38

[3] Bond
breaking.

making

occurs

before

bond

This mechanism has an inherent problem. The

intermediate generated in the first step has 10
electrons around carbon, violating the octet rule.
Because two other mechanistic possibilities do not
violate a fundamental rule, this last possibility can
be disregarded.
39

Consider reaction [1] below:

Kinetic data show that the rate of reaction [1]

depends on the concentration of both reactants,
which suggests a bimolecular reaction with a onestep mechanism. This is an example of an SN2
(substitution nucleophilic bimolecular) mechanism. 40

Consider reaction [2] below:

Kinetic data show that the rate of reaction [2]

depends on the concentration of only the alkyl
halide. This suggests a two-step mechanism in
which the rate-determining step involves the alkyl
halide only. This is an example of an SN1
(substitution nucleophilic unimolecular) mechanism.
41

 Furthermore, when the substitution product bears a positive

charge and also contains a proton bonded to O or N, the initially
formed substitution product readily loses a proton in a Br nstedLowry acid-base reaction, forming a neutral product.

To draw any nucleophilic substitution product:

Find the sp3 hybridized carbon with the leaving group.
Identify the nucleophile, the species with a lone pair or
bond.
Substitute the nucleophile for the leaving group and assign
charges (if necessary) to any atom that is involved in bond
breaking or bond formation.
42

Kinetics of Nucleophilic
Substitution
Rate is change in concentration with time
Depends on concentration(s), temperature,

inherent nature of reaction (activation energy)

A rate law describes relationship between the
concentration of reactants and rate of conversion
to products determined by experiment.
A rate constant (k) is the proportionality factor
between concentration and rate
Example: for S P
an experiment might find
Rate = k [S]

(first order)

Reaction Kinetics
The

study of rates of reactions is called kinetics

Rates decrease as concentrations decrease but
the rate constant does not
The rate law depends on the mechanism
The order of a reaction is sum of the exponents
of the concentrations in the rate law the
example below is second order

Experiments show that for the

reaction :
OH- + CH3Br CH3OH + BrRate = k[OH-][CH3Br]

The Reaction of (SN2)

SN2 = Substitution,
Nucleophilic, Bimolecular

The mechanism of an SN2 reaction would be

drawn as follows. Note the curved arrow
notation that is used to show the flow of
electrons.

46

Stereochemistry
All SN2 reactions proceed with backside attack of
the nucleophile, resulting in inversion of
configuration (Walden Inversion) at a stereogenic
center.
Figure. Stereochemistry of the S 2 reaction
N

47

Stereochemistry of SN2
Walden Inversion (Configuration Inversion)

Chapter 6

48

Figure. Two examples of inversion

of configuration in the SN2 reaction

49

SN2 Transition State

The

transition state of an SN2 reaction has a

planar arrangement of the carbon atom and
the remaining three groups.

Exersice :
Write

the equation of reaction (that show

stereochemistry using dimensional
formula) for SN2 reaction from (S)-2bromobutane with CN- and give a sign the
configuration of product using (R) and (S)
system.

An energy diagram for the SN2 reaction:

52

The Kinetics of SN2 Reaction

One

type of SN2 reaction has the following

characteristics:
Reaction occurs with inversion at reacting center
Follows second order reaction kinetics
rate = k [Nu:-][RX]

The

rate of reaction is affected by the reactivity of

substrates (alkyl halides) and nucleophiles.

Effects of Structure to
Reactivity

The rate of reaction is affected by reactivity of

substrate, and reactivity is affected by the
structure of substrate.
For examples :
Bromomethane reacts 30 times faster than
bromoethane (If bromoethane reaction needs
an hour to finish a half of reaction, so
bromomethane only needs 1/30 times of those
(or 2 minutes) to finish a half of reaction)

54

Effect of Ea to Kinetics and Product

of
Reactions
The higher the E , the slower the reaction rate.
a

Thus, any factor that increases Ea decreases the

reaction rate.

55

Order of Reactivity in SN2

The

more alkyl groups connected to the

reacting carbon, the slower the reaction

Steric Hindrance in SN2 Reaction

Methyl and 1 alkyl halides undergo SN2 reactions

with ease.
2 Alkyl halides react more slowly.
3 Alkyl halides do not undergo SN2 reactions. This
order of reactivity can be explained by steric
effects. Steric hindrance caused by bulky R groups
makes nucleophilic attack from the backside more57

Steric Effect in SN2 Reaction

58

 Increasing the number of R groups on the carbon

with the leaving group increases crowding in the
transition state, thereby decreasing the reaction
rate.
The SN2 reaction is fastest with unhindered
halides.

59

Relative Reactivity of
Nucleophiles
Depends on reaction and conditions
More basic, nucleophiles react faster

(for

similar structures).
Better nucleophiles are lower in a column of
the periodic table
Anions are usually more reactive than neutrals

Exercise :
How does the SN2 reaction rates effects between CH3I an
If the concentration of second reactant becomes twice fa
whereas all of other variables keep still constant?

63

Alkyl Halides and Nucleophilic

Substitution

64

The Reaction of SN1

SN1 = Substitution,
Nucleophilic, Unimolecular

The mechanism of an SN1 reaction would be drawn as follows:

Note the curved arrow formalism that is used to show the flow of
electrons.

Key features of the SN1 mechanism are that it has two steps, and
carbocations are formed as reactive intermediates.
66

SN1 Mechanism (1)

Step 1 : Formation of carbocation (slow)
(CH3)3C Br

(CH3)3C

+ Br

Chapter 6

67

SN1 Mechanism (2)

Step 2 : Nucleophilic attacks carbocation
+

(CH3)3C

+ H O H

(CH3)3C O H
H

Step 3 : Loss of H+ (if needed) from

protonated alcohol
(CH3)3C O H + H O H

(CH3)3C O H

+ H3O

H
68

Since

SN1 reactions involve ionization, so

these reactions are helped by polar
solvent, such as H2O, that can stabilize
the ion by solvation.

Stereochemistry of SN1 Reaction

The

planar
intermediate
should lead to
loss of chirality
A free
carbocation is
achiral
Product should
be racemic

Stereochemistry of SN1
Racemization: inversion and retention

=>
72

SN1 in Reality
Carbocation

is biased to react on side opposite

leaving group
Suggests reaction occurs with carbocation
loosely associated with leaving group during
nucleophilic addition
Alternative that SN2 is also occuring is unlikely

Effects of Ion Pair Formation

If

leaving group
remains associated,
then product has
more inversion than
retention
Product is only
partially racemic
with more inversion
than retention
Associated
carbocation and
leaving group is an
ion pair

The Rate of SN1 Reactions

The

specific rate of SN1 reaction does not

depend on nucleophile reaction, but only
depend on alkyl halide concentration.
Its due to the reaction between R + and Nuoccurs very quickly => this combination
only occurs if the carbocations is formed.
The overall rate of reaction is determined
by the rate of RX ionization, and then form
carbocation (R+)
This ionization step is called ratedetermining step or rate-limiting step.

Rate-Limiting Step
The

overall rate of a reaction is

controlled by the rate of the slowest
step

SN1

reaction is the first order in rate :

Rate SN1 = k [RX]

Nucleophiles in SN1
Since

nucleophilic addition occurs after

formation of carbocation, reaction rate is
not affected normally by nature or
concentration of nucleophile

SN1 Energy Diagram

Step through highest
energy point is ratelimiting

rate = k[RX]

Figure.
An energy diagram
for the SN1 reaction:

79

Effect of Leaving Group on SN1

Critically

dependent on leaving group

Reactivity: the larger halides ions are better leaving

groups

In

acid, OH of an alcohol is protonated and leaving

group is H2O, which is still less reactive than halide
p-Toluensulfonate (TosO -) is excellent leaving group

Characteristics of the SN1

Reaction
Tertiary

alkyl halide is most reactive by

this mechanism
The effect of the type of alkyl halide on
SN1 reaction rates can be explained by
considering carbocation stability.

Factors Increasing
Carbocation Stability
1.Inductive
effect
2.Hyperconjugat
ion
82

Inductive Effect For

Increasing Carbocation
Stability
Inductive effect
is the pull of electron

density to a positive charge carbon

through bonds, so it bears partial
positive charge for adjacent atoms and
polarizes the next bonds, then stabilize
the carbocation.
Alkyl groups are electron donating groups
that stabilize a positive charge. So, the
greater the number of alkyl groups
attached to a carbon with a positive
charge, the more stable will be the

83

The Number of R groups

Effect to Carbocation
Stability
Carbocations are classified as primary (1),
secondary (2), or tertiary (3), based on
the number of R groups bonded to the
charged carbon atom.
As the number of R groups increases,
carbocation stability increases.

84

Figure.
Electrostatic potential
maps for differerent
carbocations

85

The Hammond Postulate

86

 The Hammond postulate relates reaction rate to stability. It

provides a quantitative estimate of the energy of a transition
state.
The Hammond postulate states that the transition state of a
reaction resembles the structure of the species (reactant or
product) to which it is closer in energy.
87

Hyperconjugation Effect For

Increasing Carbocation Stability
Hyperconjugation is the spreading out of charge by the overlap
of an empty p orbital with an adjacent bond. This overlap
(hyperconjugation) delocalizes the positive charge on the
carbocation, spreading it over a larger volume, and this
stabilizes the carbocation.
Example: CH3+ cannot be stabilized by hyperconjugation, but
(CH3)2CH+ can.

88

Carbocation
Rearrangements
Carbocations

can rearrange to form a more stable

carbocation :
Hydride shift: H- on adjacent carbon bonds with
C+.
Methyl shift: CH3- moves from adjacent carbon if
no Hs are available.

90

Hydride Shift
H

Br H
CH3

CH3

C C CH3

C C CH3
H CH3

H CH3

H
CH3

CH3

C C CH3

C C CH3
H CH3

H CH3
H
CH3

C C CH3
H CH3

Nuc

H Nuc
CH3

C C CH3
H CH3
91

Methyl Shift
CH3

Br CH3
CH3

CH3

C C CH3

H CH3

H CH3

CH3

CH3
CH3

CH3

C C CH3

CH3

C C CH3
H CH3

C C CH3
H CH3

H CH3
CH3

C C CH3

Nuc

CH3

CH3 Nuc
C C CH3
H CH3
92

The Substitution Reaction

of Allylic and Benzylic
Halides

Allylic and Benzylic Halides

Allylic

and benzylic intermediates are

stabilized by delocalization of charge.
Primary allylic and benzylic are also more
reactive in the SN2 mechanism

Delocalized Carbocations
Delocalization

of cationic charge enhances

stability
Primary allyl is more stable than primary
alkyl
Primary benzyl is more stable than allyl

The Substitution Reaction

of Vinyl Halides & Aryl
Halide

Vinyl Halides and Aryl Halides.

Vinyl and aryl halides do not undergo S N1 or SN2 reactions,
because heterolysis of the CX bond would form a highly
unstable vinyl or aryl cation.
Figure. Vinyl halides and nucleophilic substitution mechanisms

98

The Nucleophile
Substitution and Organic
Synthetis

Nucleophilic Substitution and Organic

Synthesis.

To carry out the synthesis of a particular compound, we must

think backwards, and ask ourselves the question: What starting
material and reagents are needed to make it?
If we are using nucleophilic substitution, we must determine what
alkyl halide and what nucleophile can be used to form a specific
product.

101

To determine the two components needed for

synthesis, remember that the carbon atoms come
from the organic starting material, in this case, a
1 alkyl halide. The functional group comes from
the nucleophile, HO in this case. With these two
components, we can fill in the boxes to
complete the synthesis.

102

The Factors That

Determine The SN1 or
SN2 Mechanism
The
The

structure of alkyl halide

nature of nucleophile and

base
The nature of solvent
Concentration of nucleophile and
base

The Effect of Alkyl Halides Structures

105

The Nature of The Nucleophile

Strong nucleophiles (which usually bear a negative
charge) present in high concentrations favor S N2
reactions.
Weak nucleophiles, such as H2O and ROH favor SN1
reactions by decreasing the rate of any competing
SN2 reaction.
Let us compare the substitution products formed
when the 2 alkyl halide A is treated with either the
strong nucleophile HO or the weak nucleophile H2O.
Because a 2 alkyl halide can react by either
mechanism, the strength of the nucleophile
determines which mechanism takes place.
106

 The strong nucleophile favors an SN2 mechanism.

The weak nucleophile favors an SN1 mechanism.

107

 A better leaving group increases the rate of both S N1 and SN2

reactions.

108

The Nature of The Solvent

Polar protic solvents like H2O and ROH
favor SN1 reactions because the ionic
intermediates (both cations and anions)
are stabilized by solvation.
Polar aprotic solvents favor SN2 reactions
because nucleophiles are not well
solvated, and therefore, are more
nucleophilic.
109

Polar Protic Solvent Effects

Polar

protic solvents (O-H or N-H) reduce the

strength of the nucleophile. Hydrogen bonds
must be broken before nucleophile can attack
the carbon.

110

 In polar protic solvents, nucleophilicity increases down a column of the

periodic table as the size of the anion increases. This is the opposite of
basicity.

Figure . Example of polar protic solvents

111

Polar Aprotic Solvent Effects

Polar

aprotic solvents (no O-H or N-H) do not

form hydrogen bonds with nucleophile

Examples:

CH3 C N
acetonitrile

O
H

CH3
CH3

dimethylformamide
(DMF)

H3C
CH3
acetone
Chapter 6

112

 Polar aprotic solvents also exhibit dipoledipole

interactions, but they have no OH or NH bonds. Thus,
they are incapable of hydrogen bonding.

Figure. Examples of polar aprotic solvents

113

 In polar aprotic solvents, nucleophilicity

parallels basicity, and the stronger base is
the stronger nucleophile.
Because basicity decreases as size
increases down a column, nucleophilicity
decreases as well.

114

Effects of Solvent on Energies

Polar

solvent stabilizes transition state and

intermediate more than reactant and product

Solvent Is Critical in SN1

Stabilizing

carbocation also stabilizes

associated transition state and controls rate

Solvation of a
carbocation by water

Polar Solvents Promote Ionization

Polar,

protic and unreactive Lewis base

solvents facilitate formation of R+
Solvent polarity is measured as dielectric
polarization (P)
Nonpolar solvents have low P
Polar SOLVENT have high P values

Temperature Effects

118

In an endothermic reaction, the transition

state resembles the products more than
the reactants, so anything that stabilizes
the product stabilizes the transition state
also. Thus, lowering the energy of the
transition state decreases Ea, which
increases the reaction rate.
If there are two possible products in an
endothermic reaction, but one is more
stable than the other, the transition state
that leads to the formation of the more
stable product is lower in energy, so this
reaction should occur faster.

119

Figure. An endothermic reactionHow the energy of

the transition state and products are related

120

In the case of an exothermic reaction, the

transition state resembles the reactants
more than the products. Thus, lowering
the energy of the products has little or no
effect on the energy of the transition
state.
Since Ea is unaffected, the reaction rate is
unaffected.
The conclusion is that in an exothermic
reaction, the more stable product may or
may not form faster, since Ea is similar for
both products.

121

Figure. An exothermic reactionHow the energy of the transition

state and products are related

122

 The Hammond postulate estimates the relative energy of

transition states, and thus it can be used to predict the relative
rates of two reactions.
According to the Hammond postulate, the stability of the
carbocation determines the rate of its formation.
Figure. Energy diagram for carbocation formation in two different SN1 reactions

123

124

SN2
Primary,

secondary
or methyl
Strong nucleophile
Polar
Rate

aprotic solvent

= k[halide][Nuc]
Inversion at chiral
carbon
No rearrangements

or

SN1?

Tertiary
Weak

nucleophile (may
also be solvent)
Polar protic solvent,
silver salts
Rate = k[halide]
Racemization of
optically active
compound
Rearranged

Chapter 6

products

125

Elimination Reaction

Alkyl Halides: Elimination

Elimination

is an alternative pathway to substitution

Opposite of addition
Generates an alkene
Can compete with substitution and decrease yield,
especially for SN1 processes

In

the elimination of HX from an alkyl halide,

the more highly substituted alkene product
predominates

Zaitsevs Rule for Elimination

Reactions (1875)

Mechanisms of Elimination
Reactions
Ingold nomenclature: E elimination
E1: X- leaves first to generate a carbocation

a base abstracts a proton from the

carbocation

E2:

Concerted (one step) transfer of a proton

to a base and departure of leaving group

The E1 Reaction
Competes

with SN1 and E2 at 3 centers

V = k [RX]

Stereochemistry of E1 Reactions
E1

is not stereospecific and there is no

requirement for alignment
Product has Zaitsev orientation because
step that controls product is loss of proton
after formation of carbocation

The E2 Reaction Mechanism

A

proton is transferred to base as leaving

group begins to depart
Transition state combines leaving of X and
transfer of H
Product alkene forms stereospecifically

E2 Reaction Kinetics
One

step rate law has base and alkyl

halide
Transition state bears no resemblance to
reactant or product
Rate = k[R-X][B]
Reaction goes faster with stronger base,
better leaving group

Geometry of Elimination E2
Antiperiplanar

allows orbital overlap and

minimizes steric interactions

E2 Stereochemistry
of the developing orbital in the
transition state requires periplanar
geometry, anti arrangement

Overlap

Allows orbital overlap

E2 Stereochemistry

Chapter 6

136

Predicting Product
E2 is stereospecific
Meso-1,2-dibromo-1,2-diphenylethane

with base gives cis 1,2-diphenyl

RR or SS 1,2-dibromo-1,2-diphenylethane
gives trans 1,2-diphenyl

Elimination From
Cyclohexanes
Abstracted

proton and leaving group should

align trans-diaxial to be anti periplanar (app)
in approaching transition state.
Equatorial groups are not in proper alignment

Kinetic Isotope Effect

Substitute deuterium for hydrogen at position
Effect on rate is kinetic isotope effect (kH/kD =

deuterium isotope effect)

Rate is reduced in E2 reaction

Heavier isotope bond is slower to break

Shows C-H bond is broken in or before rate-limiting step

A Closer Look
H
H O
H

CH3

CH3

C
H

CH3

H3O

CH3

Chapter 6

140

=>

E1
Tertiary

> Secondary
Weak base
Good ionizing
solvent
Rate

= k[halide]
Saytzeff product
No required
geometry
Rearranged

or

E2?

Tertiary

> Secondary
Strong base required
Solvent polarity not
important
Rate = k[halide]
[base]
Saytzeff product
Coplanar leaving
groups (usually anti)
No rearrangements

products
141

Comparing E1 and E2
Strong

base is needed for E2 but not for E1

E2 is stereospecifc, E1 is not
E1 gives Zaitsev orientation

Substitution or Elimination?
Strength

of the nucleophile determines

order: Strong nuc. will go SN2 or E2.
Primary halide usually SN2.
Tertiary halide mixture of SN1, E1 or E2
High temperature favors elimination.
Bulky bases favor elimination.
Good nucleophiles, but weak bases,
favor substitution.
Chapter 6

143

Summary of Reactivity:
SN1, SN2, E1, E2
Alkyl

halides undergo different reactions in

competition, depending on the reacting
molecule and the conditions
Based on patterns, we can predict likely
outcomes.

Secondary Halides?
Mixtures of products are common.

=>
145