UNIT 5: ELIMINATION REACTIONS

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Outlines
UNIT 5: ELIMINATION REACTIONS
5.1. Definition
5.2. E2 Mechanism
5.3. E1 Mechanism
5.4. Elimination versus Substitution
5.5. Alkenes - The Products of Elimination
5.6. Application of Elimination Reactions

5.6.1. Dehydration of Alcohols

5.6.2. Dehydrohalogenation of Alkyl Halides
5.6.3. Vicinal Dihalides
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 5.1. Definition

 There are two mechanisms of elimination - E2 and E1, just as there are two
mechanisms of substitution, SN2 and SN1.
 The E2 mechanism is bimolecular elimination.
 The E1 mechanism is unimolecular elimination.
 The E2 and E1 mechanisms differ in the timing of bond cleavage and bond
formation, analogous to the SN2 and SN1 mechanisms.
 E2 and SN2 reactions have some features in common, as do E1 and S N1
reactions.
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 5.2. E2 Mechanism of Elimination Reactions

v = k [substrate] [base]

 As in the SN2 reaction, the rate is dependent on the concentration of both reaction
partners 4
 5.2. E2 Mechanism of Elimination Reactions

 The most common mechanism for dehydrohalogenation is the E2

mechanism.
 It exhibits second-order kinetics, and both the alkyl halide and the base
appear in the rate equation, i.e.,

rate = k[(CH3)3CBr][¯OH]

 The reaction is concerted - all bonds are broken and formed in a single step.
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 5.2. E2 Mechanism of Elimination Reactions

 There are close parallels between E2 and SN2 mechanisms in how the identity
of the base, the leaving group, and the solvent affect the rate.

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5.2. E2 Mechanism of Elimination Reactions
Energy Diagram for an E2 Reaction

In the transition state, the C-H and C-

Br bonds are partially broken, the O-H
and π bonds are partially formed, and
both the base and the departing leaving
group bear a partial negative charge.

Fig.1: Energy Diagram for an E2 Reaction Mechanism 7

 5.2. E2 Mechanism of Elimination Reactions
Transition States in E2 Mechanisms
 The increase in E2 reaction rate with increasing alkyl substitution can be rationalized in
terms of transition state stability.
 In the transition state, the double bond is partially formed.
 This increases the stability of the double bond with alkyl substituents stabilizing the
transition state (i.e., lowers Ea), which increases the rate of the reaction.

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 5.2. E2 Mechanism of Elimination Reactions
The Zaitsev (Saytzeff) Rule
 Recall that when alkyl halides have two or more different  carbons, more than one alkene
product is formed.
 When this happens, one of the products usually predominates.
 The major product is the more stable product - the one with the more substituted double
bond.
 This phenomenon is called the Zaitsev rule.

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 5.2. E2 Mechanism of Elimination Reactions
The Zaitsev (Saytzeff) Rule
H

H CH2 H
CH3 C2H5ONa
H
H3 C Br H3 C CH3
31%

H CH3 H CH3
CH3 C2H5ONa
H
H3C Br H3C CH3
69%
 If multiple products are possible then, the most stable is the most substituted one.
 More substituted: product and transition state lower in energy. 10
 5.2. E2 Mechanism of Elimination Reactions
Bases in E2 Mechanisms
 E2 reactions are generally run with strong, negatively charged bases like ¯OH and ¯OR.
 The base appears in the rate equation, so the rate of the E2 reaction increases as the
strength of the base increases.
 Two strong, sterically hindered nitrogen bases called DBN and DBU are also sometimes
used.

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 5.2. E2 Mechanism of Elimination Reactions
Two Examples of the E2 Reaction used in Organic Synthesis

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 5.2. E2 Mechanism of Elimination Reactions
Effects of Leaving Group and Solvent on E2 Reactions
 Because the bond to the leaving group is partially broken in the transition
state, the better the leaving group the faster the E2 reaction.
 Polar aprotic solvents increase the rate of E2 reactions.

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 5.2. E2 Mechanism of Elimination Reactions
Effect of Alkyl Halide Structure on E2 Reactions
 The SN2 and E2 mechanisms differ in how the alkyl halide structure affects the reaction
rate.
 As the number of R groups on the carbon with the leaving group increases, the rate of the
E2 reaction increases.

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 5.2. E2 Mechanism of Elimination Reactions
Reactivities of Alkyl Halides

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 5.2. E2 Mechanism of Elimination Reactions
Product Stability and Rate of E2 Reactions
 Increasing the number of R groups on the carbon with the leaving group forms more highly
substituted, more stable alkenes in E2 reactions.
 In the reactions below, since the disubstituted alkene is more stable, the 3° alkyl halide
reacts faster than the 1° alkyl halide.

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 5.2. E2 Mechanism of Elimination Reactions
Stereochemistry of E2 Reactions
 The transition state of an E2 reaction consists of four atoms from an alkyl halide - one
hydrogen atom, two carbon atoms, and the leaving group (X) - all aligned in a plane.
 There are two ways for the C-H and C-X bonds to be coplanar.

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 5.2. E2 Mechanism of Elimination Reactions
Stereochemistry of E2 Elimination Reactions

B: B:
H X
H
C C C C C C

X
syn anti
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 5.2. E2 Mechanism of Elimination Reactions
Stereoselectivity of E2 Reactions
 A reaction is stereoselective when it forms predominantly or exclusively one
stereoisomer when two or more are possible.
 The E2 reaction is stereoselective because the more stable stereoisomer is formed
preferentially.

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 5.2. E2 Mechanism of Elimination Reactions
Regioselectivity of E2 Reactions

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 5.2. E2 Mechanism of Elimination Reactions
E2 Mechanism Summary

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 5.3. E1 Mechanism of Elimination Reactions

v= k [substrate]
 The mechanism is similar to that of the S N1 reaction: the first step is
formation of the carbocation via heterolytic cleavage. 22
 5.3. E1 Mechanism of Elimination Reactions
 The dehydrohalogenation of (CH3)3CCI with H2O to form (CH3)2C=CH2 can be
used to illustrate the second general mechanism of elimination, the E1
mechanism.
 An E1 reaction exhibits first-order kinetics:

rate = k[(CH3)3CCI]

 The E1 reaction proceeds via a two-step mechanism: the bond to the

leaving group breaks first before the  bond is formed.
 The slow step is unimolecular, involving only the alkyl halide.
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 5.3. E1 Mechanism of Elimination Reactions

 In an E2 reaction, the leaving group comes off as the  proton is removed, and the
reaction occurs in one step.
 However, in an E1, the leaving group comes off before the  proton is removed,
and the reaction occurs in two steps. 24
5.3. E1 Mechanism of Elimination Reactions
Energy Diagram for an E1 Reaction

 Since the E1 mechanism

has two steps, there are
two energy barriers.
 Step one is the rate-
limiting steps.

Fig.2: Energy Diagram for an E1 Reaction Mechanism 25

 5.3. E1 Mechanism of Elimination Reactions
Effect of Alkyl Halide Structure on E1 Reactions
 The rate of an E1 reaction increases as the number of R groups on the carbon with the
leaving group increases.

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 5.3. E1 Mechanism of Elimination Reactions
Effect of Base on the E1 Reaction
 The strength of the base usually determines whether a reaction follows the E1 or E2
mechanism.
 Strong bases like ¯OH and ¯OR favor E2 reactions.

 Weaker bases like H2O and ROH favor E1 reactions.

 Electro-releasing groups that stabilizing the carbocation
 Good leaving groups
 Solvent of high ionizing strength
 The base play no role in the RDS of the E1 mechanism.
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 5.3. E1 Mechanism of Elimination Reactions
Regioselectivity of E1 Reactions
 E1 reactions are regioselective, favoring formation of the more substituted, more stable
alkene.

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 5.3. E1 Mechanism of Elimination Reactions
Comparison of E1 and E2 Mechanisms
 The strength of the base is the most important factor in determining the mechanism
for elimination.

A comparison of E1 and E2 Mechanisms 29

 5.3. E1 Mechanism of Elimination Reactions
E1 Mechanism Summary

 Because E1 reactions often occur with a competing SN1 reaction, E1 reactions of alkyl
halides are much less useful than E2 reactions. 30
 5.4. Elimination Versus Substitution Reactions
Competition Between Substitution and Elimination

Alkyl halides can undergo SN2, SN1, E2 and E1.

1) decide whether the reaction conditions favor SN2/E2 or SN1/E1

 SN2/E2 reactions are favored by a high concentration of nucleophile/strong base

 SN1/E1 reactions are favored by a poor nucleophile/weak base

2) decide how much of the product will be the substitution product and how much of
the product will be the elimination product.
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 5.4. Elimination Versus Substitution Reactions
Consider SN1/E1 Conditions

Summary of the Products Expected in Substitution and Elimination Reactions

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 5.4. Elimination Versus Substitution Reactions

Consider the SN2/E2 Conditions

Relative Reactivities of Alkyl Halides

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 5.4. Elimination Versus Substitution Reactions
A Bulky Base Encourages Elimination Over Substitution

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 5.4. Elimination Versus Substitution Reactions

 Elimination and substitution reactions are competing processes: in this case, the tertiary
carbocation gives
 primarily elimination in the presence of a strong base (EtO–)
 mainly substitution if there is only a good nucleophile present 35
E2 vs SN2
5.4. Elimination Versus Substitution Reactions

 There is a strong similarity between the E2 and S N2 reactions: strong nucleophiles favor
substitution, while strong bases favor elimination 36
 5.4. Elimination Versus Substitution Reactions
Steric Bulkiness Favors Elimination

 We already saw that SN2 substitution on a tertiary carbon is not possible, therefore E2
elimination will prevail.
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 5.4. Elimination Versus Substitution Reactions
Other Examples

 Note that at a primary carbon atom, only SN2 and no SN1 substitution is possible
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5.4. Elimination Versus Substitution Reactions

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 5.4. Elimination Versus Substitution Reactions
Predicting Reaction Mechanisms (SN1, SN2, E1, or E2)

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 5.4. Elimination Versus Substitution Reactions
Predicting Reaction Mechanisms (SN1, SN2, E1, or E2)

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 5.4. Elimination Versus Substitution Reactions
Predicting Reaction Mechanisms (SN1, SN2, E1, or E2)

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 5.4. Elimination Versus Substitution Reactions
Predicting Reaction Mechanisms (SN1, SN2, E1, or E2)

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 5.4. Elimination Versus Substitution Reactions
Predicting Reaction Mechanisms (SN1, SN2, E1 or E2)

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 5.4. Elimination Versus Substitution Reactions
Predicting Reaction Mechanisms (SN1, SN2, E1 or E2)

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 5.4. Elimination Versus Substitution Reactions
Predicting Reaction Mechanisms (SN1, SN2, E1 or E2)

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 5.4. Elimination Versus Substitution Reactions
When is the Reaction SN1, SN2, E1, or E2?
 Good nucleophiles that are weak bases favor substitution over elimination.
 These include I¯, Br¯, HS¯, ¯CN, and CH3COO¯.

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 5.4. Elimination Versus Substitution Reactions
SN1 and E1 Reactions
 SN1 and E1 reactions have exactly the same first step—formation of a carbocation.
 They differ in what happens to the carbocation.

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 5.4. Elimination Versus Substitution Reactions
Bulky Bases Favor Elimination
 Bulky non-nucleophilic bases favor elimination over substitution.
 KOC(CH3)3, DBU, and DBN are too sterically hindered to attack tetravalent carbon.
 They are, however, able to remove a small proton, favoring elimination over substitution.

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 5.5. Alkenes – The Products of Elimination
 Alkenes are classified according to the number of carbon atoms bonded to the carbons of
the double bond.

Classifying alkenes by the number of R groups bonded to the double bond

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 5.5. Alkenes – The Products of Elimination
 The stability of an alkene increases as the number of R groups bonded to the double bond
carbons increases.

 The higher the percent s-character, the more readily an atom accepts electron density.
Thus, sp2 carbons are more able to accept electron density and sp3 carbons are more
able to donate electron density.
 Consequently, increasing the number of electron donating groups on a carbon atom
able to accept electron density makes the alkene more stable.
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 5.5. Alkenes – The Products of Elimination

> > >

Tetrasubstituted Trisubstituted Geminal Disubstituted Trans Disubstituted

> >

Cis Disubstituted Monosubstituted Unsubstituted

 Higher Alkyl Substitution = Higher Alkene Stability

 Note stability trends of Disubstituted Alkenes
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 5.5. Alkenes – The Products of Elimination
 trans-2-Butene (a disubstituted alkene) is more stable than cis-2-butene (another
disubstituted alkene), but both are more stable than 1-butene (a monosubstituted alkene).

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5.5. Alkenes – The Products of Elimination

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 5.6. Application of Elimination Reactions
6.6.1. Dehydration of Alcohols

β-Elimination Reactions

 dehydration of alcohols: X = H; Y = OH

X C C Y C C + X Y
b a

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 5.6. Application of Elimination Reactions
6.6.1. Dehydration of Alcohols
 Dehydration takes place under acidic rather than basic condition.

H H
-H+ -H2O
R C CH2R' R C CH2R' RCHCH2R' RCH=CHR'
OH OH2

E1 Mechanism

Carbocation intermediate:
 More substituted alkene will be formed
 Reactivity order of alcohols: 3° > 2° > 1° 56
 5.6. Application of Elimination Reactions
6.6.1. Dehydration of Alcohols
CH3 CH3

H3 C OH H 3C OH2
+
H
CH2 CH2
H H

-H2O

Base
CH2 CH3
-H+
+ H 2O H
H 3C CH3 C CH3
H2
E1 Elimination Reaction Mechanism 57
 5.6. Application of Elimination Reactions
5.6.2. Dehydrohalogenation of Alkyl Halides

Dehydrohalogenation of alkyl halides: X = H; Y = Br, etc.

X C Ca Y C C + X Y
b

rate = k[(CH3)3CBr][¯OH]

 The most common mechanism for dehydrohalogenation is the E2 mechanism.

 It exhibits second-order kinetics, and both the alkyl halide and the base appear in the rate
equation.
 The reaction is concerted—all bonds are broken and formed in a single step. 58
 5.6.2. Dehydrohalogenation of Alkyl Halides
H H
2 eq. NaNH2
R R R R

Br Br

 Compounds with halogens on adjacent carbons:

 VICINAL Dihalides (above compound: vicinal dibromide)

 Entails consecutive E2 Elimination Reactions

 NaNH2 strong enough to effect both Eliminations in 1 Pot

 Need 3 equivalents NaNH2 for terminal alkynes 59

 5.6.2. Dehydrohalogenation of Alkyl Halides
Examples

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 5.6. Application of Elimination Reactions
6.6.3. Vicinal Dihalides
 Two elimination reactions are needed to remove two moles of HX from a dihalide
substrate.
 Two different starting materials can be used—a vicinal dihalide or a geminal dihalide.

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 6.6.3. Vicinal Dihalides
Consecutive E2 Elimination Reactions Alkynes

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 End of Unit 5
References
G. L. Patrick, Instant Notes, Organic Chemistry, 2nd Ed., 2004, Sec., L
L. G. WA D E, Organic Chemistry, 8th, Ed. 2013, Ch., 6

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