E2

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 Alkyl Halides and Elimination Reactions
General Features of Elimination:
• Removal of the elements HX is called
dehydrohalogenation.
• Dehydrohalogenation is an example of  elimination.
• The curved arrow formalism shown below illustrates
how four bonds are broken or formed in the process.

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 Alkyl Halides and Elimination Reactions
General Features of Elimination:
• The most common bases used in elimination reactions
are negatively charged oxygen compounds, such as
HO¯ and its alkyl derivatives, RO¯, called alkoxides.

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Kebasaan ialah ukuran kemampuan
pereaksi untuk menerima sebuah proton
dalam reaksi asam-basa.
-OH bertindak sebagai basa :
HCl + -OH H2O + Cl-
CH3CHBr - CH3 + HO- CH3CH CH2

Nukleofilisitas ialah kemampuan suatu

pereaksi untuk menyebabkan terjadinya
reaksi subsitusi.
CH3CH2Br + -OH CH3CH2OH + Br-
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 Alkyl Halides and Elimination Reactions
Classification of Alkenes:
• Alkenes are classified according to the number of
carbon atoms bonded to the carbons of the double bond.

Figure 8.1 Classifying alkenes by the number

of R groups bonded to the double bond

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 Alkyl Halides and Elimination Reactions
Alkene: The Products of Elimination
• Because of restricted rotation, two stereoisomers of
2-butene are possible. cis-2-Butene and trans-2-butene
are diastereomers, because they are stereoisomers
that are not mirror images of each other.

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 Alkyl Halides and Elimination Reactions
Alkene: The Products of Elimination
• Whenever the two groups on each end of a carbon-
carbon double bond are different from each other,
two diastereomers are possible.
• Conversely, when one carbon of a double bond has
two identical groups attached, cis-trans isomers are
not possible.

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 Alkyl Halides and Elimination Reactions
Alkene: The Products of Elimination
• In general, trans alkenes are more stable than cis
alkenes because the groups bonded to the double bond
carbons are further apart, reducing steric interactions.

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 Alkyl Halides and Elimination Reactions
Alkene: 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 an sp2 carbon atom makes the alkene more
stable. 12
 Alkyl Halides and Elimination Reactions
Alkene: 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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 Stability of Alkenes
Heats of Hydrogenation

Structural H°
Name Formula [kJ (kcal)/m ol]
Ethylene CH2 =CH2 -137 (-32.8)
Propene CH3 CH=CH2 -126 (-30.1)
1-Butene -127 (-30.3)

cis-2-Butene -120 (-28.6)

trans-2-Butene -115 (-27.6)

2-Methyl-2-butene -113 (-26.9)

2,3-Dimethyl-2-butene -111 (-26.6)

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 Alkyl Halides and Elimination Reactions
Mechanisms of Elimination: E2
• 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.
• The base appears in the rate equation, so the rate of the E2
reaction increases as the strength of the base increases.
• E2 reactions are generally run with strong, negatively
charged bases like ¯OH and ¯OR. Two strong sterically
hindered nitrogen bases called DBN and DBU are also
sometimes used.

1,5-diazabicyclo[4,3,0]non-5-ene 1,8-diazabicyclo[5,4,0]undec-7-ene

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 Alkyl Halides and Elimination Reactions
Mechanisms of Elimination: E2
• 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.
Thus, increasing the stability of the double bond with alkyl
substituents stabilizes the transition state (i.e., lowers Ea,
which increases the rate of the reaction.

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 Alkyl Halides and Elimination Reactions
Mechanisms of Elimination: E2
• 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 10 alkyl halide.

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 Role of the Solvent
In an SN1, a carbocation and halide ion are formed

– Solvation provides the energy for X- being formed

– In SN1 the solvent “pulls apart” the alkyl halide
– SN1 cannot take place in a nonpolar solvent or in the gas
phase
– Increasing the polarity of the solvent will INCREASE
the rate of Rx if none of the REACTANTS are charged.
– If reactants are charged it will DECREASE the rate.
 Role of the Solvent
• So….
• In an SN1 reaction, the reactant is RX. The
intermediate is charged and is STABILIZED by a
POLAR solvent

A POLAR solvent increases the rate

of reaction for an SN1 reaction.

(However, this is true only if the reactant is uncharged.)

*
 Role of the Solvent In SN2
• In an SN2 reaction, one of the reactants is the
nucleophile (usually charged).
• The POLAR solvent will usually stabilize the
nucleophile.

A POLAR solvent decreases the rate

of reaction for an SN2 reaction.

(However, this is true only if the nucleophile is charged.)

 Polar Aprotic Solvents
• Polar Aprotic Solvents include:
– DMF N,N-dimethylformamide
– DMSO dimethylsulfoxide
– HMPA hexamethylphosphoramide
– THF Tetrahydrofuran
– And even… acetone
 Polar Aprotic Solvents
Polar Aprotic Solvents
– do not H bond
– solvate cations well
– do NOT solvate anions (nucleophiles) well
– good solvents for SN2 reactions
 Polar Aprotic Solvents
• DMSO
• DMF
• Acetone
• HMPA
 Nucleophile Review
Effectiveness Nucleophile
Br - , I -
HO- , CH 3 O- , RO -
strong
CN - , N 3 -
CH3 S - , RS -
CH3 CO2 - , RCO 2
-

moderate CH3 SH, RSH, R 2 S

NH3 , RNH 2 , R 2 NH, R 3 N
H2 O
weak CH3 OH, ROH
CH3 CO2 H, RCO 2 H
 Alkyl Halides and 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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Stereochemistry of the E2 Reaction:

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 Alkyl Halides and Elimination Reactions
Stereochemistry of the E2 Reaction:
Figure 8.7 Two possible geometries for the E2 reaction

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 Alkyl Halides and Elimination Reactions
Base:
E1 Base strength not important
E2 Needs a strong base
Substrate:
E1 3o > 2o (1o C+ is unstable)
E2 3o > 2o > 1o
Solvent:
E1 Enhanced by polar protic solvent
E2 Solvent may vary, aprotic preferred
Leaving Group:
E1 Good LG important to form C+
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E2 Good LG enhances reaction
 Alkyl Halides and Nucleophilic Substitution
Results of E1 vs E2 mechanisms:
Kinetics:
E1 rate = k[RX]
E2 rate = k[RX][B:]
Alkene Orientation:
E1 Zaitzev
E2 Zaitzev
Stereochemistry:
E1 No requirement for C+
E2 Anti, coplanar arrangement is best
Rearrangements:
E1 rearrangements common
E2 rearrangements not possible
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 Alkyl Halides and Elimination Reactions
Predicting the Mechanism for SN1, SN2, E1 or E2.

• Good nucleophiles that are weak bases favor

substitution over elimination. Certain anions generally
give products of substitution because they are good
nucleophiles but weak bases. These include I¯, Br¯,
HS¯, ¯CN, and CH3COO¯.

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 Alkyl Halides and Elimination Reactions
Predicting the Mechanism for SN1, SN2, E1 or E2.

• Bulky nonnucleophilic bases favor elimination over

substitution. KOC(CH3)3, DBU, and DBN are too
sterically hindered to attack tetravalent carbon, but
are able to remove a small proton, favoring
elimination over substitution.

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 Alkyl Halides and Nucleophilic Substitution
Halide Conditions Mechanism

1o strong nucleophile SN2

strong bulky base E2

2o strong base & nucleophile SN2 & E2

strong bulky base E2
weak base and nucleophile SN1 & E1

3o weak base and nucleophile SN1 & E1

strong base E2

Higher temp. favors elimination over substitution.

 Role of the Solvent
In an SN1, a carbocation and halide ion are formed

– Solvation provides the energy for X- being formed

– In SN1 the solvent “pulls apart” the alkyl halide
– SN1 cannot take place in a nonpolar solvent or in the gas
phase
– Increasing the polarity of the solvent will INCREASE
the rate of Rx if none of the REACTANTS are charged.
– If reactants are charged it will DECREASE the rate.
 Role of the Solvent
• So….
• In an SN1 reaction, the reactant is RX. The
intermediate is charged and is STABILIZED by a
POLAR solvent

A POLAR solvent increases the rate

of reaction for an SN1 reaction.

(However, this is true only if the reactant is uncharged.)

*
 Role of the Solvent In SN2
• In an SN2 reaction, one of the reactants is the
nucleophile (usually charged).
• The POLAR solvent will usually stabilize the
nucleophile.

A POLAR solvent decreases the rate

of reaction for an SN2 reaction.

(However, this is true only if the nucleophile is charged.)

 Polar Aprotic Solvents
• Polar Aprotic Solvents include:
– DMF N,N-dimethylformamide
– DMSO dimethylsulfoxide
– HMPA hexamethylphosphoramide
– THF Tetrahydrofuran
– And even… acetone
 Polar Aprotic Solvents
Polar Aprotic Solvents
– do not H bond
– solvate cations well
– do NOT solvate anions (nucleophiles) well
– good solvents for SN2 reactions
 Polar Aprotic Solvents
• DMSO
• DMF
• Acetone
• HMPA
 Nucleophile Review
Effectiveness Nucleophile
Br - , I -
HO- , CH 3 O- , RO -
strong
CN - , N 3 -
CH3 S - , RS -
CH3 CO2 - , RCO 2
-

moderate CH3 SH, RSH, R 2 S

NH3 , RNH 2 , R 2 NH, R 3 N
H2 O
weak CH3 OH, ROH
CH3 CO2 H, RCO 2 H
1-kloro- 1,2-difenilpropana + OR -
1-kloro- 1,2-difenilpropana + OR-

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B C
 B C
D