Chapter 5: Elimination

Learning Objectives
By the end of this section, you should be able to apply concepts related to basic organic techniques
such as:

• Outline the preparations of alkenes from various methods

• Illustrate E1 and E2 mechanisms
• Apply Zaitsev’s Rule to predict major products in elimination reactions
• Explain the effect of stereochemistry on E1 and E2 mechanisms
• Compare and contrast E1 and E2 reactions in terms of kinetics, stereochemistry and
reactivities
• Sketch energy profile diagrams for elimination mechanisms
• Evaluate the factors involved in the competition between elimination and nucleophilic
substitution reactions

Preparation of alkenes

Reaction Type Starting Description

material
Electrophilic Addition Alkynes - Addition with H-X/ X-X/ H-H

C≡C  C=C

1,2-elimination Dihalides - Dehalogenation using Zn (R-X  C=C)

- 1,2- refers to TWO ADJACENT (Usually Br)
POSITIONS.

Alkyl halides - Dehydrohalogenation using a base (R-X  C=C)

Alcohol - Dehydration using an acid catalyst

- H+ can be conc H2SO4 or H3PO4 (180oC)
1,2-elimination reactions

Components involved
Components Description Example
A base - Usually a strong base is used - E.g. OH- (hydroxide), CH3CH2O –
(ethoxide), (CH3)3CO – (t – butoxide)
At least 1 β-H - A β-H is a hydrogen that is attached to
the β-carbon.
- The β-carbon is attached to the α-carbon
which is attached to the leaving group
(eg. X)
A good leaving - A weak base is a good leaving group - E.g. Br – and H2O
group
Alcoholic - Required to dissolve both RX and :B- - E.g. OH– /EtOH, EtO– /EtOH
solvents

 1,2 elimination on unsymmetrical alkenes often yields a mixture of isomers

 Zaitsev’s Rule: In the 1,2-elimination of an unsymmetrical alkene, the preferred product usually is the more
substituted alkene  any atom conncected to C=C that is not H
 Ease of formation:

 E.g.

 2 possible mechanisms:
Concerted (E2) Stepwise (E1)

1. The breaking of the C-Br bond, abstraction of the 1. The breaking of C-Br bond occurs first to from a carbocation
β-hydrogen by the base to form the C=C double bond intermediate
occurs at the same time 2. Subsequently, abstraction of the β-hydrogen by the base to
form the C=C double bond
 E2 and E1 Reactions of in 1,2-elimination
E2 E1
Mechanism E = Elimination, 2 = 2 molecules are involved in the rate-determining step S = Substitution, N = Nucleophilic, 1 = 1 molecule is involved in the rate-determining step
- Concerted  Occurs in 1 step without intermediates - Stepwise  The C-X bond breaks first, followed by abstraction of the β-hydrogen
- 3 products: alkene, LG and neutral protonated base - 3 products: alkene, LG and charged protonated base (if a weak base is used it becomes
- Steps: neutral which is more common)
Additional steps: If LG is poor, protonation of LG of substrate occurs before the 1st slow - Steps:
step 1. Formation of an intermediate carbocation when the C-X bond is broken, and the
leaving group leaves (rds)
2. The base (nucleophile) abstracts the β-hydrogen, where the e - pair from C-H bond
1. The strong base abstracts the β-hydrogen to form the π C=C bond and break the C-X bond
forms the π C=C double bond in the alkene product  if there are more than 1 β-
to kick out the leaving group simultaneously
hydrogen, the one which results in the more substituted product is selected.

3. There may be additional steps to stabilise the reaction:

- If LG is poor, protonation of LG of substrate occurs before the 1 st slow step
- If there is a carbocation rearrangement, add a step for every rearrangement
(check after 1st step)

Kinetics - Bimolecular mechanism: rate of reaction depends on both base (nucleophile) and alkyl halide
(substrate) in the rds.
- Rate law equation for all: Rate = K [Alkyl Halide]1 [Base]1  2nd order overall
- An increase in the concentration of the substrate (RX) or the base will increase the rate of E2
reactions proportionately.
- Unimolecular mechanism: rate of reaction depends only on the alkyl halide (substrate) in
the rds.
- Rate law equation for all: Rate = k [Alkyl Halide]1  1st order overall

Zaitsev’s rule - The more substituted alkene produced is the major product
- Hence the nucleophile will attack H that results in the more substituted alkene
- This results in a mixture of products obtained with the most substituted one as the major product (Zaitsev’s rule)
- Substituents are the atoms (not H!), that are bound to the 2 C involved in the double bond

Energy profile - The energy diagram: - The energy diagram:

diagram - 1 peak  1 TS - 2 peak  2 TS
- NO valley  NO intermediates - 1 valley  1 intermediates
- Transition state: Highest energy, highly unstable, fleeting existence, 4 partial bonds - Transition state: Highest energy, highly unstable, fleeting existence, 4 partial bonds
- Intermediates MUST have a higher energy than reactants
- Observation: Formation of the carbocation has the highest Ea., so it is the rds.
Substrate (alkyl - E2 mechanisms do not really show significant substrate preference as they do not produce - E1 mechanisms favours the formation of the most stable carbocation
halide) unstable intermediates or transition states. - The formation of the carbocation intermediate is the rds.
- Therefore, all 3o/2o/1o substrates proceed with similar rates. - Therefore, the more stable the carbocation intermediate, the faster the rds, the faster the
overall reaction.

- Carbocations are destabilised when the + charge is intensified  occurs when

carbocations are attached to a e- withdrawing group (e.g. -X, -CN, -NO2, -CHO, -COR)
- Carbocations are stabilised when the + charge is dispersed  occurs when carbocations
are attached to a e- donating group (e.g. -R, -OH, -NH )

- Alkyl groups serves as e- donating groups and thus ↑ in alkyl substituents, ↑ stability 
increases the rate of reaction
- Hence, the order of stability is 10(very rare) <20<30

- Usually 1o - Only 30 or 20
- Although in theory, 2o and 3o are possible
Rearrangement - Rearrangement does not occur as it is a concerted reaction - Rearrangement is a key characteristic of E1 reactions  occurs after 1st step, before base (nucleophilic) attack
reactions - During nucleophilic substitution it is sometimes observed that in the end product, the alkene double bond is found
between 2 C different from the C that had the Beta H
- Rearrangements take place in such a way that a less stable carbocation is converted to a more stable one, which increases
the rate of reaction. However, the rearrangement does not change the up and down position of cyclohexane.
- If possible, the carbocation will change from 10 to 20 to 30 if there it β carbon and a H / CH3
- 2 types of rearrangements:
 - Hence this results in a mix of products that are major and minor (one with rearrangement and one without)

Nucleophile - The E2 reaction occurs when an alkyl halide is treated with ONLY a strong base - The E2 reaction occurs when an alkyl halide is treated with ONLY a weak base
- E.g. hydroxide (OH-) or alkoxide (RO-) ion. Others like Cl- or I- do not work as they are not bases - E.g. H2O and R-OH (alcohols)

Leaving group - As the leaving group as its own will be negatively charged, good leaving groups are those with a negative charge well stabilised by charge dispersal &/or resonance
- Hence, the weaker the LG as a base, the better it is as a leaving group (inversely related)
- Relative stability (Better) of nucleophiles:

- However stronger bases like OH-, NH2-, OR-, F- do NOT undergo Sn2 unless protonated (as mentioned earlier)

-
Solvents - Solvents doesn’t really matter, as long as the solvent is able to dissolve the components - Polar Protic is favourable
- Usually these are alcohols - Polar protic solvents stabilise both carbocations & LG (if anionic) by separating &
solvating the intimate ion pair via ion-dipole interactions

Stereo- - An elimination reaction can occur in two stereochemically different ways: Syn and Anti - There is no geometrical requirement on the E1 reaction because the halide and hydrogen
chemistry For elimination are lost in separate steps, and a ring conformation change can occur.
cyclohexenes - Co-planar: orbitals on the same plane; Peri-planar: orbitals approximately planar - The empty p orbital of the LG will always remain axial during ring flips, once it has left
- Criteria: - This means that the H-C and C-X orbitals do not need to be coplanar originally
1. Alignment of βH-C and C-X (bonds, look at the lines) orbitals  Must be co-planar (aka axial or - Obtaining the more stable Zaitsev’s product is the main concern from the E1 reaction
equatorial in cyclohexane rings), alkyl halides with non-coplanar orbitals cannot occur

2. Steric hinderance in TS  Less steric hinderance is preferred, strained alkyl halides are not
favored. (Anti Vs Syn)

Syn elimination

- β-H and X- leave the alkyl halide molecule from the same side of the C=C bond
- Less common for E2 reactions because :
1. Alignment of orbitals: Both syn and anti elimination allow the alkene product to from with its
p- orbitals in the coplanar arrangement required for the π bond formation (double bond).
2. Steric hinderance: A syn-periplanar elimination will result in an eclipsed conformation in the
TS, which creates a repulsive interaction and thus, raising the energy of the TS.
Anti elimination

- β-H and X leave the alkyl halide molecule from opposite side of the C=C bond
- More common for E2 reactions because:
1. Alignment of orbitals: Both syn and anti elimination allow the alkene product to from with its
p- orbitals in the coplanar arrangement required for the π bond formation (double bond).
2. Steric hinderance: An anti-periplanar elimination will result in a staggered conformation in the
TS, hence minimising any steric hinderance between the base and LG, thus minimising energy
of the TS.
Elimination of alcohol substrates

 Dehydration of alcohols can undergo E1/E2 mechanisms depending on the substrate type.
 An acid is required

Step 1 Step 2

- Protonation of -OH group is necessary - E1: for 2o and 3o alcohols

to convert it into a weaker base (H2O)
and a better leaving group - E2: for 1o alcohols

Elimination of alcohol substrates

 Summary of characteristics

Strong base
Competition between E2 and SN2
 SN2 substitution and E2 elimination occur together, often leading to a mixture of products.
 If a weakly basic nucleophile (RS -, I-, CN-, NH3, Br-) is used in a polar aprotic solvent, SN2 substitution
predominates. If a strong base such as CH 3CH2O-, OH- or NH2- is used, E2 predominates.
 If bulky 3 substrates are used, E2 predominates as it is too hindered for the nucleophile to approach the -
carbon closely in an SN2 mechanism.

Competition between E1 and SN1

 E1 and SN1 reactions normally occur together whenever an alkyl halide is treated in a protic solvent with a
non-basic nucleophile. Thus, the best E1 substrates are also the best SN1 substrates, and mixtures of
substitution and elimination products are usually obtained. E1 products are often produced as the minor
product as nucleophilic attack are typically much faster than the abstraction of the -hydrogen by the weak
base.
 In the example above, ethanol serves as a base in the elimination and as a nucleophile in the substitution.
Determining Factors for substitution and Elimination reactions

Very weakly basic Moderately Strongly Strong Nuc/ Bulky and

Nucleophile basic basic Very weakly strongly basic
basic ((CH3)3CO-,
[(CH3)2CH]2N-)

Substrate
Primary (10) - Straight chain Sn2 Sn2 with Sn2 E2:
10: Sn2 minor E2 Sn2 is not
- Branched 10: favourable as
Slow Sn1 for the nucleophile
rearrangement is too hindered
and due to to approach the
steric α-C closely
Secondary (20) - Straight chain Sn2 E2 with Sn2 E2:
20: Sn2 minor Sn2 Sn2 is not
- Branched 20: favourable as
Sn1 for the nucleophile
rearrangement is too hindered
and due to to approach the
steric α-C closely
Tertiary (30) Sn1 with minor Sn1 with E2 Sn1 with minor E2:
E1: minor E1: E1: Sn2 is not
As Nucleophilic As They are so non- favourable as
attack are much Nucleophilic basic to the the nucleophile
faster than the attack are point where Sn1 is too hindered
abstraction of β-H much faster predominates. to approach the
by weak base than the α-C closely
abstraction of
β-H by weak
base

Weak Nuc/ Weak Base H2O , ROH , PR3 (anything neutral), HSO4 (acids)
Strong Nuc/ Strong Base H2N- , NR2- , H- , HC≡C- , HO-, RO-
Moderate Nuc/ RCOO-, Cl-, Br-, CH3CO2-
Moderate Base
Bulky and strongly basic (CH3)3CO-, [(CH3)2CH]2N-
Strong Nuc/ Weak base -SH , -CN, N3-, RS-, I-
Weak Nuc/ Strong base F-

CNOFClBrI

 When considering 3, 2, and 1 substituent, take not substituents which have branches on the b carbon

 Weak Nuc: H2O and alcohols

 Strong Nuc: OH-,RO-, Amides, amines: NR2-, NH2-

 Sn1 tertiary, secondary, primary, and weak to moderate Nuc (only for tertiary)
 E1 tertiary with weak to moderate Nuc

 Sn2, primary, secondary, moderate to strong Nuc  exception for weak nuc in pri and secondary
 E2 Secondary, tertiary, strong Nuc
Factors that impact Nucleophilicity and Basicity

 Basicity: Ability to attract H+ atoms

 Nucleophilicity: Need to donate e- to form covalent bonds with Carbon atoms

 Steric hindrance
 Basicity: With more e- donating alkyl groups, basicity increases as the negative charge of the base
increases and increases the base ability to attract H+ atoms
 Nucleophilicity: With more alkyl groups, Nucleophilicity reduces as the hinderance prevents a
strong formation of covalent bonds

 Group trends
 Basicity: Going down the group, basicity decreases as electronegativity decreases
 Nucleophilicity: Going down the group, Nucleophilicity increases as electronegativity decreases
Exclusive: Only one
product (or one type of
β carbon)