Take Home Practice Problems: Competition between SN2, SN1, E2 and E1

1. Give the show the mechanism (arrow pushing) that produces the indicated product.

a)

b)
 c)

2. Only a substitution product is obtained when the following compound is

treated with sodium methoxide, a strong base. Explain why no
elimination product is found in the mixture.
3. Draw the product that will be formed in an E2 reaction of the following bromoalkanes.
a) (1S, 2S)-1-bromodiphenylpropane

b) (1S, 2R)-1-bromodiphenylpropane

c) (R)-3-bromo-2,2-dimethylhexane

d) (3R,4R)-3-bromo-2,2,4-trimethylhexane
4. Rank the following compounds in order of most reaction to least reactive in an E2 reaction.

5. Which reaction in each pair of substitution reactions will take place more rapidly? Justify
your response and provide the products of each reaction.

a) CH3Br + OH- 

CH3Br + H2O 

A methyl bromide will not form a carbocation, so this must be a bimolecular substitution.
Therefore, a strong nucleophile (OH-) will lead to a faster reaction.

b) CH3CH2Br + NH3  (in Et2O)

CH3CH2Br + NH3  (in EtOH)

An primary bromide will not form a carbocation, so this must be a bimolecular

substitution. Therefore, an aprotic solvent will destabilize the nucleophile, making it
stronger and making the SN2 reaction faster.
c) CH3CCl(CH3)2 + CH3COO-  (in DMSO)

CH3CCl(CH3)2 + NaCl  (in H2O)

This is a tertiary chloride. This cannot undergo a bimolecular substitution due to steric
strain. Therefore, only the unimolecular substitution can occur. In a unimolecular
reaction the use of a protic solvent is preferred because it can stabilize the carbocation
formed. Increasing the stability of the carbocation will decrease the activation energy of
the rate determining step. This will increase the rate of the reaction.

d) (CH3)3Br in a solvent of H2O

(CH3)3Br in a solvent of CH3CH2OH

This is a tertiary chloride. This cannot undergo a bimolecular substitution due to steric
strain. Therefore, only the unimolecular substitution can occur. In a unimolecular
reaction the use of a protic solvent is preferred because it can stabilize the carbocation
formed. Since water is can form stronger hydrogen bonding attractions with the
carbocation than ethanol, water will stabilize the carbocation to a greater degree than
ethanol.

e) (CH3)3CCH2CH2Cl + CH3S- 

(CH3)3CCH2CH2Cl + (CH3)2CHS- 

A primary chloride will not form a carbocation, so this must be a bimolecular substitution.
SN2 reactions are faster when there is less steric strain. In this case, the steric strain is
coming from the nucleophile. (CH3)2CHS- is much larger than CH3S-.
6. When 2-bromo-2,3-dimethylbutane reacts with a base under E2 conditions, two alkenes (2,3-
dimethyl-1-butene and 2,3-dimethyl-2-butene are formed.

a) Which of the following bases (A, B, C or D) would form the highest percentage of the
1-alkene?

b) Which would give the lowest percentage of the 2-alkene?

7. Give the major product(s) that you would expect to be formed by the following reactions.
Determine if the major product is formed by the SN1, SN2, E1 or E2 mechanism. When
relevant clearly indicate any stereochemistry and mark relevant designations on your structure
(i.e. R, S, E, Z, etc)

a)

SN2 This is a primary alkyl halide and will not spontaneously form a carbocation, so
unimolecular reactions are practically impossible. The reagent is a strong base and a
strong nucleophile. However, with little steric strain around the primary carbon (and the
base is not abnormally large), the nucleophilic substitution will be the major product.
(There may be small amounts of E2 product, since the base is of medium size and protic
solvent is used, but this will be far from the major product.)

b)

E2 This is a primary alkyl halide and will not spontaneously form a carbocation, so
unimolecular reactions are practically impossible. The reagent is a strong base and a
strong nucleophile. However, this would be a very big nucleophile. It creates a large
amount of steric strain in a SN2 reaction. The energy of the SN2 transition state will be
too high, which makes the Ea too large to be feasible. However, the E2 reaction is not
hindered by steric strain since it is attacking a beta hydrogen on the outside of the
molecule. Therefore, the E2 reaction will product the major product.

c)

SN2 This is a secondary alkyl halide. Secondary alkyl halides very rarely ionize to form
a carbocation (this isn’t the same case for heated protonated alcohols, so be careful). The
reagent is a strong nucleophile, but not a strong base. SH - is not a strong enough base to
 remove a beta hydrogen, so the E2 reaction is very unlikely. However, SH - is a very
strong nucleophile, so even though it may encounter some steric strain, this reaction will
under a bimolecular nucleophilic substitution. Remember that SN2 reactions invert the
stereochemistry of the substrate!

d)

SN2 This is a secondary alkyl halide. Secondary alkyl halides very rarely ionize to form
a carbocation. The reagent is a strong nucleophile, but not a strong base. Cl - is not a
strong enough base to remove a beta hydrogen, so the E2 reaction is very unlikely.
However, Cl- is a strong nucleophile, so even though it may encounter some steric strain,
this reaction will under a bimolecular nucleophilic substitution. (This aprotic solvent is
nice for this SN2 reaction, because it speeds it up even further.) Remember that SN2
reactions invert the stereochemistry of the substrate!

e)

SN1 This is a tertiary alkyl halide which can ionize to form a carbocation. Since the
reagent is weak, there is plenty of time for the carbocation to form in this case. (The
protic solvent will even help to stabilize the carbocation formed.) Under unimolecular
conditions, it is hard to control whether the reaction will be SN1 or E1. Usually, if the
reaction is not heated, the unimolecular substitution will provide the major product, but I
would suspect there would an appreciable amount of the minor E1 product as well.
Remember that the carbocation intermediate can be attacked by the nucleophile from
either side. In this case, we will create a pair of diastereomers.
f)

SN2 This is a primary alkyl halide and will not spontaneously form a carbocation, so
unimolecular reactions are practically impossible. The reagent is a strong nucleophile, but
not a strong base. The I- will not be able to remove a beta hydrogen. The major product
is produced by an SN2 mechanism because the nucleophile can easily attack without any
steric strain.

g)

E2 This is a tertiary alkyl halide which will not undergo SN2 reactions no matter the
strength of the nucleophile. Tertiary alkyl halides can ionize and form a carbocation for a
unimolecular mechanism, however, the strong base OH- will not “wait” for the
carbocation to form before it takes a beta hydrogen to perform and E2 reaction.

h)

SN1 This is a tertiary alkyl alcohol which can ionize to form a carbocation after being
protonated by a strong acid. Since the reagent is weak (it’s an acid), there is plenty of
time for the carbocation to form in this case. Under unimolecular conditions, it is hard to
control whether the reaction will be SN1 or E1. Usually, if the reaction is not heated, the
unimolecular substitution will provide the major product, but I would suspect there would
an appreciable amount of the minor E1 product as well.
i) CH3CH2CH2CH2Br + CH3CH2ONa (in an acetone solvent)

SN2 This is a primary alkyl halide and will not spontaneously form a carbocation, so
unimolecular reactions are practically impossible. The reagent is a strong base and a
strong nucleophile. However, with little steric strain around the primary carbon (and the
base is not abnormally large), the nucleophilic substitution will be the major product.
(There may be small amounts of E2 product, since the base is of medium size, but using
an aprotic will enhance the SN2 reaction without increasing the amount of minor E2
product formed.)

j) CH3CH2CH2CH2Br + (CH3)3CONa (in a (CH3)3COH solvent)

E2 This is a primary alkyl halide and will not spontaneously form a carbocation, so
unimolecular reactions are practically impossible. The reagent is a strong base and a
strong nucleophile. However, this would be a very big nucleophile. It creates a large
amount of steric strain in an SN2 reaction. The energy of the SN2 transition state will be
too high, which makes the Ea too large to be feasible. However, the E2 reaction is not
hindered by steric strain since it is attacking a beta hydrogen on the outside of the
molecule. Therefor the E2 reaction will produce the major product.

k)

E1 This is a secondary alcohol. When protonated by a strong acid and heated, it can form
a carbocation. Since there is no strong nucleophile or base present, this carbocatin will
form, then it will rearrange in this case! Under unimolecular conditions we can favour the
eliminatin reaction by using heat.
l) (CH3)3CBr + CH3ONa (in a DMSO solvent)

E2 This is a tertiary alkyl halide which will not undergo SN2 reactions no matter the
strength of the nucleophile or with help from the solvent. Tertiary alkyl halides can ionize
and form a carbocation for a unimolecular mechanism, however, the strong base OH - will
not “wait” for the carbocation to form before it takes a beta hydrogen to perform and E2
reaction.

m)

SN2 This is a secondary alkyl halide. Secondary alkyl halides very rarely ionize to form
a carbocation. The reagent is a strong nucleophile, but not a strong base. I - is not a strong
enough base to remove a beta hydrogen, so the E2 reaction is very unlikely. However, I -
is a strong nucleophile, so even though it may encounter some steric strain, this reaction
will under a bimolecular nucleophilic substitution. (This solvent is nice for this SN2
reaction, because it speeds it up even further.) Remember that SN2 reaction invert the
stereochemistry of the substrate.

n)

SN1 This is a tertiary alkyl halide which can ionize to form a carbocation. Since the
reagent is weak, there is plenty of time for the carbocation to form in this case. (The
protic solvent will even help to stabilize the carbocation formed.) Under unimolecular
conditions, it is hard to control whether the reaction will be SN1 or E1. Usually, if the
reaction is not heated, the unimolecular substitution will provide the major product, but I
would suspect there would an appreciable amount of the minor E1 product as well.
Remember, that the carbocation intermediate can be attacked by the nucleophile from
either side.
o) 3-chloropentane + CH3ONa (in a solvent of methanol)

E2 This is a secondary alkyl halide which is very unlikely to ionize to form a

carbocation. The reagent is a strong base and a strong nucleophile. The strong
nucleophile will encounter steric strain from the secondary alkyl halide, slowing the
mechanism down. However, the strong base doesn’t not encounter this steric strain
because it can easily attack the beta hydrogen on the exterior of the molecule. Therefore,
the E2 product will be major. (The methanol solvent will also slow the SN2 reaction.)

p) (S)-3-bromo-3-methylhexane in ethanol

SN1 This is a tertiary alkyl halide which can ionize to form a carbocation. Since the
reagent is weak, there is plenty of time for the carbocation to form in this case. (The
protic solvent will even help to stabilize the carbocation formed.) Under unimolecular
conditions, it is hard to control whether the reaction will be SN1 or E1. Usually, if the
reaction is not heated, the unimolecular substitution will provide the major product, but I
would suspect there would an appreciable amount of the minor E1 product as well.
Remember that the carbocation intermediate can be attacked by the nucleophile from
either side. In this case, we will create a pair of enantiomers.

q)

SN1 This is a tertiary alkyl halide which can ionize to form a carbocation. There is no
strong base present that could perform an E2 mechanism, but there is a strong
nucleophile. However, the strong nucleophile cannot attack the tertiary carbon because
the steric strain is too high. The carbocation must first form and then the nucleophile can
react. Under unimolecular conditions, it is hard to control whether the reaction will be
SN1 or E1. Usually, if the reaction is not heated, the unimolecular substitution will
provide the major product, but I would suspect there would an appreciable amount of the
minor E1 product as well.
r) (R)-2-bromobutane + KOH in DMF

E2 This is a secondary alkyl halide which is very unlikely to ionize to form a

carbocation. The reagent is a strong base and a strong nucleophile. The strong
nucleophile will encounter steric strain from the secondary alkyl halide, slowing the
mechanism down. However, the strong base doesn’t not encounter this steric strain
because it can easily attack the beta hydrogen on the exterior of the molecule. Therefore,
the E2 product will be major. (I suspect there will be an appreciable amount of the minor
SN2 product because the nucleophile is small, and an aprotic solvent is used.)

s) (2R,3R)-2-bromo-3-methylpentane + KOH in CH 3OH at 75 ˚C.

E2 This is a secondary alkyl halide which is very unlikely to ionize to form a

carbocation. The reagent is a strong base and a strong nucleophile. The strong
nucleophile will encounter steric strain from the secondary alkyl halide, slowing the
mechanism down. However, the strong base doesn’t not encounter this steric strain
because it can easily attack the beta hydrogen on the exterior of the molecule. Therefore,
the E2 product will be major. (The protic solvent will also slow the SN2 reaction.)
8. You need to create a cyclic alkene from 4-tert-butyl-1-chlorocyclohexaene using potassium
hydroxide in a heated alcoholic solvent. You have the choice to use trans-4-tert-butyl-1-
chlorocyclohexane or cis-4-tert-butyl-1-chlorocyclohexane. Which should you choose and
why? Provide the product of your reaction.
9. Give the mechanism (arrow pushing) for the formation of each of the following products.
10. Textbook Research Challenge (Section 7.12): Provide a mechanism for each of the
following reactions.

(CH3)3COH + HCl  (CH3)3CCl + H2O

CH3CH2CH2OH + HCl  CH3CH2CH2Cl + H2O

Textbook Research Challenge (Section 7.9): 1 ° carbocations are too unstable to form, however, the following
substitution product can be observed (in small amounts) for the reaction below. Use your textbook to determine
the mechanism for this reaction. Define the term “concerted” with respect to this mechanism.