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SUBSTITUTION AND ELIMINATION

SN1, SN2, E1 & E2 REACTIONS


Dr Md Ashraful Alam

When a nucleophile (electron donor, e.g., OH-) reacts with an alkyl halide, the
halogen leaves as a halide

Nu:

..
Br
.. :

..
: Br
.. :

There are two competing reactions of alkyl halides with nucleophiles.


1) substitution
Nu:

H
-

The Nu:- replaces the halogen on the -carbon.

2) elimination
H
Nu:

X-

Nu

C
X

X-

Nu

The Nu:- removes an H+ from a -carbon &


the halogen leaves forming an alkene.

2nd Order Nucleophilic Substitution Reactions, i.e., S N2 reactions


There are two kinds of substitution reactions, called S N1 and SN2.
As well as two kinds of elimination reactions, called E1 and E2.
Lets study SN2 reactions first. SN2 stands for Substitution,
Nucleophilic, bimolecular. Another word for bimolecular is 2 nd
order.
Bimolecular (or 2nd order) means that the rate of an SN2 reaction is
directly proportional to the molar concentration of two reacting
molecules, the alkyl halide substrate and the nucleophile:
Rate = k [RX] [Nu:-] (This is a rate equation and k is a constant).
The mechanism of an SN2 reaction is the one shown on slide #2:

Nu:

C
X

X-

Nu

Note that the nucleophile must hit the back side of the -carbon.
The nucleophile to C bond forms as the C to X bond breaks.
No C+ intermediate forms. An example is shown on the next slide.
3

2nd Order Nucleophilic Substitution Reactions, i.e., S N2 reactions


..
..

:O

H
H +

..
..

Br :

..
..O

H
C

..
Br :
..

..
..O

H
C

HH

..
+ : Br :
..

transition state

The rate of an SN2 reaction depends upon 4 factors:


1.
The nature of the substrate (the alkyl halide)
2.
The power of the nucleophile
3.
The ability of the leaving group to leave
4.
The nature of the solvent

1. Consider the nature of the substrate:


Unhindered alkyl halides, those in which the back side of the -carbon is
not blocked, will react fastest in SN2 reactions, that is:
Me

>>

>>

>>

While a methyl halides reacts quickly in SN2 reactions, a 3 does not react.
The back side of an -carbon in a 3 alkyl halide is completely blocked.
4

Effect of nature of substrate on rate of SN2 reactions:


H3C

H3C

H3C

Br

methyl bromide

H3C

CH2

CH

Br

H3C

Br

Br

H3C

H3C

ethyl bromide

isopropyl bromide

t-butyl bromide

SPACE FILLING MODELS SHOW ACTUAL SHAPES AND RELATIVE SIZES

Back side of -C
of a methyl halide
is unhindered.

Me>>

Back side of -C of a
1 alkyl halide is
slightly hindered.

>>

Back side of -C of a
2 alkyl halide is
mostly hindered.

>>

decreasing rate of SN2 reactions

Back side of -C of a
3 alkyl halide is
completely blocked.

Effect of the nucleophile on rate of SN2 reactions:


The -carbon in vinyl and aryl halides, as in 3 carbocations, is completely
hindered and these alkyl halides do not undergo SN2 reactions.

H2C

CH

Br

Br

vinyl bromide

bromobenzene

Nu:H2C

CH

Br

Nu:Br

The overlapping p-orbitals that form the -bonds in vinyl and aryl halides
completely block the access of a nucleophile to the back side of the
-carbon.
6

Effect of nature substrate on rate of SN2 reactions:


2. Consider the power of the nucleophile:

Reactivity

Nu:-

Relative Reactivity

very weak

HSO4-, H2PO4-, RCOOH

< 0.01

weak

ROH

HOH, NO3-

100

F-

500

Cl-, RCOO-

20 103

NH3, CH3SCH3

300 103

N3-, Br-

600 103

OH-, CH3O-

2 106

CN-, HS-, RS-, (CH3)3P:, NH2- ,RMgX, I-, H-

> 100 106

fair

good
very good

increasing

The better the nucleophile, the faster the rate of SN2 reactions.
The table below show the relative power or various nucleophiles.
The best nucleophiles are the best electron donors.

Effect of nature of the leaving group on rate of SN2 reactions:


3. Consider the nature of the leaving group:
The leaving group usually has a negative charge
Groups which best stabilize a negative charge are the best leaving groups,
i.e., the weakest bases are stable as anions and are the best leaving groups.
Weak bases are readily identified. They have high pKb values.

pKb = 23

pKb = 22

pKb = 21

pKb = 11

pKb = -1.7

pKb = -2

pKb = -21

I-

Br -

Cl-

F-

HO-

RO-

H2N-

30,000

10,000

200

Increasing leaving ability


Iodine (-I) is a good leaving group because iodide (I-) is non basic.
The hydroxyl group (-OH) is a poor leaving group because hydroxide (OH-)
is a strong base.
8

Effect of the solvent on rate of SN2 reactions:


4. Consider the nature of the solvent:
There are 3 classes of organic solvents:

Protic solvents, which contain OH or NH2 groups. Protic solvents


slow down SN2 reactions.

Polar aprotic solvents like acetone, which contain strong dipoles but no
OH or NH2 groups. Polar aprotic solvents speed up SN2 reactions.

Non polar solvents, e.g., hydrocarbons. SN2 reactions are relatively slow
in non polar solvents.
Protic solvents (e.g., H2O, MeOH, EtOH, CH3COOH, etc.) cluster around the
Nu:- (solvate it) and
its energy (stabilize it) and reduce its reactivity via
+ lower

H-bonding.
OR

H
RO H
+

X:

+
H

H OR
+

OR

A solvated anion (Nu:-) has reduced nucleophilicity,


reduced reactivity and increased stability

A solvated nucleophile has


difficulty hitting the -carbon.

CH3

N:

acetonitrile

: O:

Effect of the solvent on rate of SN2 reactions:

H3C

CH3

acetone

Polar Aprotic Solvents solvate the cation counterion of the nucleophile but
not the nucleophile.
Examples include acetonitrile (CH3CN), acetone (CH3COCH3),
dimethylformamide (DMF) [(CH3)2NC=OH], dimethyl sulfoxide, DMSO
[(CH3)2SO], hexamethylphosphoramide, HMPA {[(CH3)2N]3PO} and
dimethylacetamide (DMA).

:O :
H

..

: O:

CH3

H3C
CH3

S
..

.. ..
[(CH3)2N]3P O
..

CH3

Polar aprotic solvents solvate metal cations


leaving the anion counterion (Nu: -) bare and
thus more reactive
:O:

.. _
+
:
CH3C O
.. Na

CH3CN :

H3C

HMPA

DMSO

DMF

:O:

H3C

CH3

N
CH3

DMA

C CH3

N
..
+

C N:

..

:O:

Na

: N C CH3
+

.. _
:
CH3C O
..

..
N C CH3
+

10

Effect of the solvent on rate of SN2 reactions:

Non polar solvents (benzene, carbon tetrachloride, hexane, etc.) do not solvate
or stabilize nucleophiles.
SN2 reactions are relatively slow in non polar solvents similar to that
in protic solvents.
Cl

benzene

Cl
Cl

CH3CH2CH2CH2CH2CH3

C
Cl

n-hexane

carbon
tetrachloride

11

1st Order Nucleophilic Substitution Reactions, i.e., S N1 reactions


CH3
H3C

3
C

CH3

rapid

Br

H3C

Na+ I-

Na+ Br-

CH3

CH3

3 alkyl halides are essentially inert to substitution by the SN2 mechanism


because of steric hindrance at the back side of the -carbon.
Despite this, 3 alkyl halides do undergo nucleophilic substitution reactions
quite rapidly , but by a different mechanism, i.e., the SN1 mechanism.
SN1 = Substitution, Nucleophilic, 1st order (unimolecular).
SN1 reactions obey 1st order kinetics, i.e., Rate = k[RX].
The rate depends upon the concentration of only 1 reactant, the
alkyl halide-not the nucleophile
The order of reactivity of substrates for SN1 reactions is the reverse of SN2
3
R3C-Br

>

2
R2HC-Br

>

1
RH2C-Br

>

vinyl
CH2=CH-Br

increasing rate of SN1 reactions

>

phenyl
-Br

>

Me

H3C-Br
12

Mechanism of SN1 reactions


The mechanism of an SN1 reaction occurs in 2 steps:
CH3
..
3
H3C C
Br
.. :
CH3

1.
- Br -

CH3
H3C

C+
CH3

rapid
2.

..
Na+ :I :..

CH3
H3C

..
..I :

Na+ Br-

CH3

3 C+

Reaction Steps
1.
the slower, rate-limiting dissociation of the alkyl halide forming a C+
intermediate
2.
a rapid nucleophilic attack on the C+

Note that the nucleophile is not involved in the slower, rate-limiting step.

13

The Rate of SN1 reactions


The rate of an SN1 reaction depends upon 3 factors:
1. The nature of the substrate (the alkyl halide)
2. The ability of the leaving group to leave
3. The nature of the solvent
The rate is independent of the power of the nucleophile.

1. Consider the nature of the substrate:


Highly substituted alkyl halides (substrates) form a more stable C+.
increasing rate of SN1 reactions

more
stable

CH3

CH3
H3C

C+

H3C

tertiary
3

CH3

C+

CH3
>

secondary
2

less
stable
H

C+

H
>

primary
1

C+
H

>

methyl

14

Stability of Carbocations
Alkyl groups are weak electron donors.
They stabilize carbocations by donating electron density by induction
(through bonds)
CH3

H3C

Inductive effects:
Alkyl groups donate (shift) electron
density through sigma bonds to
electron deficient atoms.
This stabilizes the carbocation.

C+
CH3

They stabilize carbocations by hyperconjugation (by partial overlap of the


alkyl C-to-H bonds with the empty p-orbital of the carbocation).
vacant p orbital
of a carbocation

overlap (hyperconjugation)

sp 2
hybridized
carbocation

..
C

Csp3-Hs
sigma bond
orbital

H
H

HYPERCONJUGATION

15

Stability of Carbocations
Allyl and benzyl halides also react quickly by SN1 reactions because
their carbocations are unusually stable due to their resonance forms
which delocalize charge over an extended system

H2C

CH

CH2

HC CH2

H2C

H2C

CH

1 allyl carbocation

H2C+

CHR

HC CHR

2 allyl carbocation

1 benzylic

+
C

C
H
+

C
H

2 benzylic

H
H

C
H

+
C
R

16

Relative Stability of All Types of Carbocations


Increasing C+ stability and rate of SN1 reaction
+
C H2

+
C HR
+
C R2

3 C +

3 benzylic
CH3

C+
CH3

3 allylic

2 C +

1 C +

CH3

CH3

>
+
CH2 CH CR2

1 benzylic

2 benzylic

+
CH2 CH CHR

2 allylic

>

CH3

C+
H

>

CH3

C+
H

>

+
CH2 CH
vinyl C

+
>

>

+
phe nyl

H C+
H

+
m ethyl C

+
CH2 CH CH2

1 allylic

Note that 1 allylic and 1 benzylic C+s are about as stable as 2alkyl C+s.
Note that 2 allylic and 2 benzylic C+s are about as stable as 3 alkyl C+s.
Note that 3 allylic and 3 benzlic C+s are more stable than 3 alkyl C+s
Note that phenyl and vinyl C+s are unstable. Phenyl and vinyl halides do not
usually react by SN1 or SN2 reactions
17

Effect of nature of the leaving group on rate of SN1 reactions:

2. Consider the nature of the leaving group:


The nature of the leaving group has the same effect on both SN1 and SN2
reactions.
The better the leaving group, the faster a C+ can form and hence the faster will
be the SN1 reaction.
The leaving group usually has a negative charge
Groups which best stabilize a negative charge are the best leaving groups,
i.e., the weakest bases are stable as anions and are the best leaving groups.
Weak bases are readily identified. They have high pKb values.

pKb = 23

pKb = 22

pKb = 21

pKb = 11

pKb = -1.7

pKb = -2

pKb = -21

I-

Br -

Cl-

F-

HO-

RO-

H2N-

30,000

10,000

200

Increasing leaving ability

Iodine (-I) is a good leaving group because iodide (I-) is non basic.
The hydroxyl group (-OH) is a poor leaving group because hydroxide (OH-) is
a strong base.
18

Effect of the solvent on rate of SN1 reactions:

3. Consider the nature of the solvent:


For SN1 reactions, the solvent affects the rate only if it influences the
stability of the charged transition state, i.e., the C+. The Nu:- is not
involved in the rate determining step so solvent effects on the Nu:- do not
affect the rate of SN1 reactions.
Polar solvents, both protic and aprotic, will solvate and stabilize the
charged transition state (C+ intermediate), lowering the activation energy
and accelerating SN1 reactions.
Nonpolar solvents do not lower the activation energy and thus make SN1
reactions relatively slower
The relative rates of an SN1 reaction due to solvent effects are given
(CH3)3C-Cl + ROH (CH3)3C-OR + HCl
H2O
100,000

20% EtOH (aq)


14,000

40% EtOH (aq)

EtOH

100

reaction rate increases with polarity of solvent


19

Effect of the solvent on rate of SN1 reactions:


Solvent polarity is usually expressed by the dielectric constant, , which
is a measure of the ability of a solvent to act as an electric insulator.
Polar solvents are good electric insulators because their dipoles surround
and associate with charged species.
Dielectric constants of some common solvents are given in the following
table
name

dielectric constant

name

aprotic solvents

dielectric constant
protic solvents

hexane

1.9

acetic acid

6.2

benzene

2.3

acetone

20.7

diethyl ether

4.3

ethanol

24.3

chloroform

4.8

methanol

33.6

HMPA

30

formic acid

58.0

DMF

38

water

80.4

DMSO

48
20

Effect of the nucleophile on rate of SN1 reactions:

Consider the nature of the Nucleophile:


Recall again that the nature of the nucleophile has no effect on the rate of
SN1 reactions because the slowest (rate-determining) step of an SN1
reaction is the dissociation of the leaving group and formation of the
carbocation.
All carbocations are very good electrophiles (electron acceptors) and even
weak nucleophiles, like H2O and methanol, will react quickly with them.
The two SN1 reactions will proceed at essentially the same rate since the
only difference is the nucleophile.
CH3
3
H3C C Br

CH3

Na+ I-

H3C

CH3

Na+ Br-

K+ Br-

CH3

CH3
CH3
3
H3C C Br

CH3

K+ F-

H3C

CH3
21

Elimination Reactions, E1 and E2:


We have seen that alkyl halides may react with basic nucleophiles such as NaOH
via substitution reactions.
..
..

:O

H
H +

..
..

Br :

..
..O

H
C

..
Br :
..

..
..O

HH

H
C
H

..
+ : Br :
..

transition state

Also recall our study of the preparation of alkenes. When a 2 or 3 alkyl halide
is treated with a strong base such as NaOH, dehydrohalogenation occurs
producing an alkene an elimination (E2) reaction.
KOH in ethanol
Br

bromocyclohexane

KBr

H2O

-HBr

KOH

cyclohexene (80 % yield)

Substitution and elimination reactions are often in competition. We shall


consider the determining factors after studying the mechanisms of elimination.
22

E2 Reaction Mechanism
There are 2 kinds of elimination reactions, E1 and E2.
E2 = Elimination, Bimolecular (2nd order). Rate = k [RX] [Nu:-]
E2 reactions occur when a 2 or 3 alkyl halide is treated with a strong
base such as OH-, OR-, NH2-, H-, etc.
H
OH-

Br

Br- +

HO H

The Nu:- removes an H+ from a -carbon &


the halogen leaves forming an alkene.

All strong bases, like OH-, are good nucleophiles. In 2 and 3 alkyl halides
the -carbon in the alkyl halide is hindered. In such cases, a strong base
will abstract (remove) a hydrogen ion (H+) from a -carbon, before it hits
the -carbon. Thus strong bases cause elimination (E2) in 2 and 3 alkyl
halides and cause substitution (SN2) in unhindered methyl and 1 alkyl
halides.
23

E2 Reaction Mechanism
In E2 reactions, the Base to H bond formation, the C to H bond breaking,
the C to C bond formation, and the C to Br bond breaking all occur
simultaneously. No carbocation intermediate forms.
B:H

R
C

C
R

+
R

H
R

R
C

C
R

B H +

X-

Reactions in which several steps occur simultaneously are called concerted


reactions.
Zaitsevs Rule:
Recall that in elimination of HX from alkenes, the more highly substituted
(more stable) alkene product predominates.
Br

CH3CH2O-Na+

CH3CH

CH3CH2CHCH3
EtOH

CHCH3

2-butene
major product
( > 80%)

CH3CH2CH

CH2

1-butene
minor product
( < 20%)

24

E2 Reactions are antiperiplanar


E2 reactions, do not always follow Zaitsevs rule.
E2 eliminations occur with anti-periplanar geometry, i.e., periplanar
means that all 4 reacting atoms - H, C, C, & X - all lie in the same
plane. Anti means that H and X (the eliminated atoms) are on opposite
sides of the molecules.
Look at the mechanism again and note the opposite side & same plane
orientation of the mechanism:

B:H

R
C

C
R

+
R

H
R

C
R

B H +

X-

25

Antiperiplanar E2 Reactions in Cyclic Alkyl Halides


When E2 reactions occur in open chain alkyl halides, the Zaitsev
product is usually the major product. Single bonds can rotate to the
proper alignment to allow the antiperiplanar elimination.
In cyclic structures, however, single bonds cannot rotate. We need to
be mindful of the stereochemistry in cyclic alkyl halides undergoing E2
reactions.
See the following example.
Trans 1-chloro-2-methylcyclopentane undergoes E2 elimination with
NaOH. Draw and name the major product.
H3C

H
H

H
Cl

Na+ OHE2

H3C

H
H

Non Zaitsev product


is major product.

3-methylcyclopentene

NaCl

HOH

H3C
H

Little or no Zaitsev (more stable)


product is formed.

1-methylcyclopentene
26

E1 Reactions
Just as SN2 reactions are analogous to E 2 reactions, so SN1 reactions have
an analog, E1 reaction.
E1 = Elimination, unimolecular (1st order); Rate = k [RX]
CH3
CH3

C Br
CH3

CH3

slow
- Br-

CH3
H

rapid

C+
C
H

CH3
C

H
B:-

CH3

B H

Br

E1 eliminations, like SN1 substitutions, begin with unimolecular


dissociation, but the dissociation is followed by loss of a proton from the
-carbon (attached to the C +) rather than by substitution.
E1 & SN1 normally occur in competition, whenever an alkyl halide is treated
in a protic solvent with a nonbasic, poor nucleophile.
Note: The best E1 substrates are also the best S N1 substrates, and
mixtures of products are usually obtained.
27

E1 Reactions
As with E2 reactions, E1 reactions also produce the more highly substituted
alkene (Zaitsevs rule). However, unlike E2 reactions where no C + is
produced, C+ rearrangements can occur in E1 reactions.
e.g., t-butyl chloride + H2O (in EtOH) at 65 C t-butanol + 2-methylpropene
CH3
CH3

C Cl
CH3

H2O, EtOH
65C

CH3
CH3

C OH
CH3
64%

S N1
product

CH3
C

+
CH3

C
H
36%

E1
product

In most unimolecular reactions, S N1 is favored over E1, especially at low


temperature. Such reactions with mixed products are not often used in
synthetic chemistry.
If the E1 product is desired, it is better to use a strong base and force the E2
reaction.
Note that increasing the strength of the nucleophile favors S N1 over E1. Can
you postulate an explanation?
28

Predicting Reaction Mechanisms


1. Non basic, good nucleophiles, like Br- and I- will cause substitution not
elimination. In 3 substrates, only SN1 is possible. In Me and 1
substrates, SN2 is faster. For 2 substrates, the mechanism of
substitution depends upon the solvent.
2. Strong bases, like OH- and OR-, are also good nucleophiles.
Substitution and elimination compete. In 3 and 2 alkyl halides, E2 is
faster. In 1 and Me alkyl halides, SN2 occurs.
3. Weakly basic, weak nucleophiles, like H2O, EtOH, CH3COOH, etc.,
cannot react unless a C+ forms. This only occurs with 2 or 3
substrates. Once the C+ forms, both SN1 and E1 occur in competition.
The substitution product is usually predominant.
4. High temperatures increase the yield of elimination product over
substitution product. (G = H TS) Elimination produces more
products than substitution, hence creates greater entropy (disorder).
5. Polar solvents, both protic and aprotic, like H2O and CH3CN,
respectively, favor unimolecular reactions (SN1 and E1) by stabilizing
the C+ intermediate. Polar aprotic solvents enhance bimolecular
reactions (SN2 and E2) by activating the nucleophile.
29

Predicting Reaction Mechanisms

alkyl
halide
(substrate)

good Nu
strong base

e.g., bromide

e.g., ethoxide

strong bulky base


e.g., t-butoxide

Br

C2H5O

(CH3)3CO

Me

SN2

SN2

SN2

no reaction

SN2

SN2

E2 (SN2)

no reaction

SN2

E2

E2

SN1, E1

SN1

E2

E2

SN1, E1

good Nu

good Nu
nonbasic

very poor Nu
nonbasic

e.g., acetic acid

CH3COOH

Strong bulky bases like t-butoxide are hindered. They have difficulty hitting
the -carbon in a 1 alkyl halide. As a result, they favor E2 over SN2
products.

30

Predicting Reaction Mechanisms


The nucleophiles in the table on slide 30 are extremes. Some nucleophiles
have basicity and nucleophilicity in between these extremes. The reaction
mechanisms that they will predominate can be interpolated with good
success.
Predict the predominant reaction mechanisms the following table.
-

alkyl
halide
(substrate)

v. gd. Nu
..
moderate
. .base
e.g., cyanide

CN-

4.7
pkb =

v. gd. Nu
..
moderate
.. base

fair Nu
..
weak base
..

e.g., alkyl sulfide

e.g., carboxylate

6.0 /
pkb =

RCOO
9
pkb =

RS-, also HS-

alcohol
(substrate)

HI
HBr
HCl

Me

SN2

7.0
SN2

SN2

Me

SN2

SN2

SN2

SN2

SN2

SN2

SN2

E2

SN1

E2

E2

E2

SN1

HCl, HBr and HI are assumed to be in aqueous solution, a protic solvent.


31

Alkylation of Alkynides
Recall the preparation of long alkynes.
1. A terminal alkyne (pKa = 25) is deprotonated with a very strong base
R-C C-H

NaNH2

R-C C:- Na+ + NH3

2. An alkynide anion is a good Nu:- which can substitute (replace) halogen


atoms in methyl or 1 alkyl halides producing longer terminal alkynes

R-C C: - Na+ + CH3CH2-X

R-C C-CH2CH3

NaX

The reaction is straightforward with Me and 1 alkyl halides and proceeds via
an SN2 mechanism
Alkynide anions are also strong bases (pKb = -11) as well as good Nu: -s, so
E2 competes with SN2 for 2 and 3 alkyl halides

CH3(CH2)3CC:- Na+ + CH3-CH(Br)-CH3 CH3(CH2)3CCCH(CH3)2 (7% SN2)


+ CH3(CH2)3CCH + CH3CH=CH2 (93% E2)
32

Preparation of Alkyl Halides from Alcohols


Alkyl halides can be prepared from alcohols by reaction with HX, i.e., the
substitution of a halide on a protonated alcohol.
3
..
(Lucas Test)
(CH
)
C
OH
33
SN1
..

+
(CH3)3C OH
.. 2

Cl

- H2O

..
:
(CH3)3C Cl
..

(CH3)3C +

H2O

.. : Cl :
..

Rapid. 3 C+ is stabilized by protic sovent (H2O)

OH- is a poor leaving group, i.e., is not displaced directly by nucleophiles.


Reaction in acid media protonates the OH group producing a better leaving
group (H2O). 2 and 3 alcohols react by SN1 but Me and 1 alcohols react
by SN2.
1
SN 2

CH3CH2

..
OH
..

Cl

CH3CH2

OH2+

.. : Cl :
..

CH3CH2Cl

H2O

Very slow. Protic solvent inhibits the nucleophile.

Draw the mechanism of the reaction of isopropyl alcohol with HBr.


What products form if concentrated H2SO4 is used in place of aq. HCl?
33

Preparation of Alkyl Halides from Alcohols


Alternative to using hydrohalic acids (HCl, HBr, HI), alcohols can be
converted to alkyl halides by reaction with PBr3 which transforms OH- into a
better leaving group allowing substitution (SN2) to occur without
rearrangement.
Br
1
SN2

CH3(CH2)4CH2

:P
..
OH
..

Br

Br
ether

CH3(CH2)4CH2

+ PBr 2
O
..
H

CH3(CH2)4CH2Br
Br

34

Preparation of Alkenes from Alkyl Halides


On Slide 22 we noted that 2 and 3 alkyl halides can be dehydrohalogenated
with a strong base such as OH- producing an alkene.
KOH in ethanol
Br

KBr

H2O

-HBr

bromocyclohexane

KOH

cyclohexene (80 % yield)

Clearly, this is an E2 reaction.


Predict the mechanism that occurs with a Me or 1 alkyl halide.
Predict the products and mechanism that occur with isopentyl chloride and
KOH

35

Summary of SN /Elimination Reactions


Alkyl Halide Substrate Reactivity:

methyl

CH3

CH3

C Br
H

CH3

C Br
H

unhindered substrates favor S N2


do not form a stable C +
do not react by S N1 or E1

CH3

C Br
H

CH3

C Br
CH3

hindered substrates. S N2 increasingly unfavorable, E2 is OK


form increasingly stable C +
favors SN1 and E1. E2 is OK

E2 reactions possible with strong bases


E2 reactions possible with strong bulky bases (t-butoxide)

36