Skip to main content

Organic Chemistry 1: An open textbook

8. NUCLEOPHILIC SUBSTITUTIONS AND ELIMINATIONS

Search
Search for:

8.5. Elimination reactions

Alkyl halides undergo elimination via two common mechanisms, known as E2 and E1,
which show some similarities to SN2 and SN1, respectively.  In E2, elimination shows a
second order rate law, and occurs in a single concerted step (proton abstraction at
Cα occurring at the same time as Cβ-X bond cleavage).  In E1, elimination goes via a first
order rate law, in two steps (Cβ-X bond cleavage occurring first to form a carbocation
intermediate, which is then ‘quenched’ by proton abstraction at the alpha-carbon). 

These
mechanisms are important in laboratory organic chemistry.  As explained below, which
mechanism actually occurs in a laboratory reaction will depend on the  identity of the R
groups (ie., whether the alkyl halide is primary, secondary, tertiary, etc.) as well as on
the characteristics of the base.

E1 and E2 reactions in the laboratory

E2 elimination reactions in the laboratory are carried out with relatively strong bases,
such as alkoxides (deprotonated alcohols, –OR).  2-Bromopropane will react with
ethoxide, for example, to give propene.
Propene is not the only product of this reaction, however – the ethoxide will also to
some extent act as a nucleophile in an SN2 reaction.

Chemists carrying out laboratory nucleophilic substitution or elimination reactions

always have to be aware of the competition between the two mechanisms, because
bases can also be nucleophiles, and vice-versa.  However, a chemist can tip the scales
in one direction or another by carefully choosing reagents.  Primary carbon electrophiles
like 1-bromopropane, for example, are much more likely to undergo substitution (by the
SN2 mechanism) than elimination (by the E2 mechanism) – this is because the
electrophilic carbon is unhindered and a good target for a nucleophile.

SN1 and E1 mechanisms are unlikely with such compounds because of the relative
instability of primary carbocations.

The nature of the electron-rich species is also critical.  Acetate, for example, is a weak
base but a reasonably good nucleophile, and will react with 2-bromopropane mainly as
a nucleophile.
In order to direct the reaction towards elimination rather than substitution, heat is often
used. This is because elimination leads to an increase in the number of molecules (from
two to three in the above example), and thus an increase in entropy.  High temperatures
favor reactions of this sort, where there is a large increase in entropy.  Substitution does
not usually involve a large entropy change, so if S N2 is desired, the reaction should be
done at the lowest temperature that allows substitution to occur at a reasonable rate.

Also, a strong hindered base such as tert-butoxide can be used.  The bulkiness of tert-

butoxide makes it difficult for the oxygen to reach the carbon (in other words, to act as a
nucleophile).  It is more likely to pluck off a proton, which is much more accessible than
the electrophilic carbon).

E1 reactions occur by the same kinds of carbocation-favoring conditions that have

already been described for SN1 reactions (section 8.3.):  a secondary or tertiary
substrate, a protic solvent, and a relatively weak base/nucleophile.  In fact, E1 and SN1
reactions generally occur simultaneously, giving a mixture of substitution and
elimination products after formation of a common carbocation intermediate.  When tert-
butyl chloride is stirred in a mixture of ethanol and water, for example, a mixture of  SN1
products (2-methylpropan-2-ol and tert-butyl ethyl ether) and E1 product (2-
methylpropene) results.  Heat is used if elimination is desired, but mixtures are still
likely.
 EXERCISE

A straightforward functional group conversion that is often carried out in the undergraduate
organic lab is the phosphoric acid-catalyzed dehydration of cyclohexanol to form cyclohexene. 
No solvent is necessary in this reaction – pure liquid cyclohexanol is simply stirred together with
a few drops of concentrated phosphoric acid. In order to drive the equilibrium of this reversible
reaction towards the desired product, cyclohexene is distilled out of the reaction mixture as it
forms (the boiling point of cyclohexene is 83  C, significantly lower than that of anything else in
o

the reaction solution). Any cyclohexyl phosphate that might form from the competing S 1 N

reaction remains in the flask, and is eventually converted to cyclohexene over time. Draw a
mechanism for the cyclohexene synthesis reaction described above.  Also, draw a mechanism
showing how the undesired cyclohexyl phosphate could form.
Show Solution

Next, let’s put aside the issue of competition between nucleophilic substitution and
elimination, and focus on the regioselectivity of elimination reactions.  In many cases an
elimination reaction can result in more than one constitutional isomer or stereoisomer. 
The elimination products of 2-chloropentane provide a good example:
This reaction is both regiospecific and stereospecific. In general, more substituted
alkenes are more stable, and as a result, the product mixture will contain less 1-butene
than 2-butene (this is the regiochemical aspect of the outcome, and is often referred to
as Zaitsev’s rule). In addition, trans–alkenes are generally more stable than cis-
alkenes, so we can predict that more of the trans product will form compared to
the cis product.

However, certain other eliminations (which we will not be studying) favor

the least substituted alkene as the predominant product, due to steric factors.   Such a
product is known as the Hoffmann product, and it is usually the opposite of the product
predicted by Zaitsev’s Rule.

E2 Eliminations
E2, bimolecular elimination, was proposed in the 1920s by British chemist Christopher
Kelk Ingold. Unlike E1 reactions, E2 reactions remove two substituents with the addition
of a strong base, resulting in an alkene.

Introduction

E2 reactions are typically seen with secondary and tertiary alkyl halides, but a hindered
base is necessary with a primary halide. The mechanism by which it occurs is a single
step concerted reaction with one transition state. The rate at which this mechanism
occurs is second order kinetics, and depends on both the base and alkyl halide. A good
leaving group is required because it is involved in the rate determining step. The leaving
groups must be coplanar in order to form a pi bond; carbons go from sp 3 to
sp2 hybridization states.
General Reaction

In this reaction Ba represents the base and X representents a leaving group, typically a
halogen. There is one transition state that shows the concerted reaction for the base
attracting the hydrogen and the halogen taking the electrons from the bond. The product
be both eclipse and staggered depending on the transition states. Eclipsed products
have a synperiplanar transition states, while staggered products have antiperiplanar
transition states. Staggered conformation is usually the major product because of its
lower energy confirmation.

An E2 reaction has certain requirements to procede:

 A strong base is necessary especially necessary for primary alkyl halides.

Secondary and tertiary primary halides will procede with E2 in the precesence of a
base (OH-, RO-, R2N-)
 Both leaving groups (the H and the X) should be on the same plane, this allows
the double bond to form in the reaction. In the reaction above you can see both
leaving groups are in the plane of the carbons.
 Follows Zaitsev’s rule, the most substituted alkene is usually the major product.
 Hoffman Rule, if a sterically hindered base will result in the least substituted
product.

Reaction coordinate diagram

 KEY FEATURES OF THE E2 ELIMINATION

The main features of the E2 elimination are:

 It usually uses a strong base (often –OH or –OR) with an alkyl halide
 Primary, secondary or tertiary alkyl halides are all effective reactants, with tertiary
reacting most easily.  With primary alkyl halides, a substituted base such as KO tBu
and heat are often used to minimize competition from S N2.
 The H and the leaving group should normally be antiperiplanar (180 o) to one
another.
 Zaitsev’s Rule applies, unless a very hindered base such as KO tBu is used, so
the more substituted alkene is usually major.

FURTHER READING

 Wikipedia-Elimination reaction
  http://www.chemhelper.com/e2.html

References

1. Vollhardt, K. Peter C., and Neil E. Schore. Organic Chemistry Structure and

Function. New York: W. H. Freeman, 2007.
2. Organic chemistry, by Marye Anne Fox, James K. Whitesell

E1 Reactions
Unimolecular elimination (E1) is a reaction in which the removal of an HX substituent
results in the formation of a double bond. It is similar to a unimolecular nucleophilic
substitution reaction (SN1) in particular because the rate determining step involves
heterolysis (losing the leaving group) to form a carbocation intermediate. Because the
rate determining (slow) step involves only one reactant, the reaction is unimolecular with
a first order rate law.  Since these two reactions behave similarly, they compete against
each other. Many times, both will occur simultaneously to form different products from a
single reaction. However, one can be favored over the other by using hot or cold
conditions.

General reaction

An E1 reaction involves the deprotonation of a hydrogen nearby (usually one carbon

away, or the beta position) the carbocation resulting in the formation of an alkene
product. In order to accomplish this, a base is required. For a simplified model, we’ll
take B to be a base, and LG to be a halogen leaving group.
As can be seen above, the preliminary step is the leaving group (LG) leaving on its own.
Because it takes the electrons in the bond along with it, the carbon that was attached to
it loses its electron, making it a carbocation. Once it becomes a carbocation, a base
(B−B−) deprotonates the intermediate carbocation at the beta position, which then
donates its electrons to the neighboring C-C bond, forming a double bond. Unlike E2
reactions, which require the proton to be anti to the leaving group, E1 reactions only
require a neighboring hydrogen. This is due to the fact that the leaving group has
already left the molecule. The final product is an alkene along with the HB byproduct.

Reactivity

Due to the fact that E1 reactions create a carbocation intermediate, rules present
in SN1SN1 reactions still apply.

As expected, tertiary carbocations are favored over secondary, primary and methyls.  In
general, primary and methyl carbocations do not proceed through the E1 pathway for
this reason, unless there is a means of carbocation rearrangement to move the positive
charge to a nearby carbon. Secondary and tertiary carbons form more stable
carbocations, thus this formation occurs quite rapidly.

Secondary carbocations can be subject to the E2 reaction pathway, but this generally
occurs in the presence of a good / strong base. Adding a weak base to the reaction
disfavors E2, essentially pushing towards the E1 pathway. In many instances, solvolysis
occurs rather than using a base to deprotonate. This means heat is added to the
solution, and the solvent itself deprotonates a hydrogen. The medium can affect the
pathway of the reaction as well. Polar protic solvents may be used to hinder
nucleophiles, thus disfavoring E2 / SN2 from occurring.

Acid catalyzed dehydration of secondary / tertiary alcohols

We’ll take a look at a mechanism involving solvolysis during an E1 reaction of

cyclohexanol in sulfuric Acid.
  Step 1: The OH group on the cyclohexanol is hydrated by H 2SO4, represented as
H+. This allows the OH to become an H2O, which is a better leaving group.
 Step 2: Once the OH has been protonated, the H 2O molecule leaves via a
heterolysis step, taking its electrons with it. This creates a carbocation
intermediate on the attached carbon.
 Step 3: Another H2O molecule comes in to deprotonate the beta carbon, which
then donates its electrons to the neighboring C-C bond. The carbons are
rehybridized from sp3 to sp2, and thus a pi bond is formed between them.

Mechanism for Alkyl Halides

This mechanism is a common application of E1 reactions in the synthesis of an alkene.

Once again, we see the basic 2 steps of the E1 mechanism.

1. The leaving group leaves along with its electrons to form a carbocation
intermediate.
2. A base deprotonates a beta carbon to form a pi bond.

How are regiochemistry & stereochemistry involved?

In some cases we see a mixture of products rather than one discrete one. This can
happen whenthe carbocation has two or more nearby carbons that are capable of being
deprotonated.  In many cases one major product will be formed, the most stable
alkene.  In terms of regiochemistry, Zaitsev’s rule states that when more than one
product can be formed, the more substituted alkene is the major product.

Unlike E2 reactions, E1 is not stereospecific. Thus, a hydrogen is not required to be

anti-periplanar to the leaving group.

In this example, we can see two possible pathways for the reaction. One in which the
methyl on the right is deprotonated, and another in which the CH2 on the left is
deprotonated. Either pathway leads to a plausible product, but it turns out that pent-2-
ene is the major product. As stated by Zaitsev’s rule, deprotonation will mainly happen
at the most substituted carbon to form the more substituted (and more stable) alkene. In
practice, the pent-2-ene product will be formed as a mixture of cis and trans alkenes,
with the trans being the major isomer since it is more stable; only the trans is shown in
the figure above.

KEY FEATURES OF THE E1 ELIMINATION

The main features of the E1 elimination are:

 It usually uses a weak base (often ROH) with an alkyl halide, or it uses an
alcohol in the presence of H2SO4 or H3PO4.
 Only secondary or tertiary alkyl halides are effective reactants, with tertiary
reacting most easily.  Heat is often used to minimize competition from S N1.
 The reaction is not stereoselective, so cis/trans mixtures are usual.
 Zaitsev’s Rule applies, so the more substituted alkene is usually major.

Outside links
Khan Academy video on E1

PROBLEMS

1)     Which of these steps is the rate determining step (A or B)?

What is the major product formed (C or D)?

2) In order to produce the most stable alkene product, from which carbon should the base
deprotonate (A, B, or C)?
If the carbocation were to rearrange, on which carbon would the positive charge go onto without
sacrificing stability (A, B, or C)?

3) Predict the major product of the following reaction.

4) (True or False) – There is no way of controlling the product ratio of E1 / Sn1 reactions.
5) Explain why the presence of a weak base / nucleophile favors E1 reactions over E2.

ANSWERS
Show Answer

FURTHER READING

 Comparing the E1 and E2 Reactions

 Elimination Reactions Are Favored By Heat

 Comparing the E1 and E2 Reactions

 Bulky Bases In Elimination Reactions

Videos

Outside Sources

1. Vollhardt, K. Peter C., and Neil E. Schore. Organic Chemistry Structure and
Function. New York: W. H. Freeman, 2007.
2. McMurry, J., Simanek, E. Fundamentals of Organic Chemistry, 6th edition.
Cengage Learning, 2007.

LICENSES AND ATTRIBUTIONS

Previous Next