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Jeevan
Jeevan
Elimination
Reaction of Alkyl Halides
Organic compounds
with an electronegative
atom or an electron-
withdrawing group
bonded to a sp3 carbon
undergo substitution or
-
elimination reactions
tion
u
stit
b
Su
Eli
m
ina
ti o
n
Halide ions are good
leaving groups.
Substitution reaction on
these compounds are alkyl fluoridealkyl chloride alkyl bromidealkyl iodide
easy and are used to get
a wide variety of
compounds
Alkyl Halides in Nature
bromomethane methanol
If concentration of (1)
is doubled, the rate of
the reaction is If concentration of (1)
doubled. and (2) is doubled, the
rate of the reaction
If concentration of (2) quadruples.
is doubled, the rate of
the reaction is
doubled.
Substitution Reaction with
Halides
(1)
(2)
bromomethane methanol
Rate law:
rate = k [bromoethane][OH-]
Transition state
activation
energy: ∆ G2
Energy
activation
energy: ∆ G1
(R)-2-bromobutane (S)-2-butanol
Factor Affecting SN2
pKa HX
Reactions
relative rates of reaction
The
HO leaving
-
+ RCH I group
2 RCH2OH + I
-
30 000
-10
- -
HO + RCH2Br RCH2OH + Br 10 000
-9
- -
HO + RCH2Cl RCH2OH + Cl 200
-7
- -
HO + RCH2F RCH2OH + F 1
The nucleophile
3.2
pKa Nuclephilicity
SN2 Reactions With Alkyl
Halides
an alcohol
a thiol
an ether
a thioether
an amine
an alkyne
a nitrile
Substitution Reactions With
Halides
1-bromo-1,1-dimethylethane 1,1-dimethylethanol
Rate law:
If concentration of (1)
is doubled, the rate of rate = k [1-bromo-1,1-
the reaction is dimethylethane]
doubled.
this reaction is an example of a
If concentration of (2) SN1 reaction.
is doubled, the rate of S stands for substitution
the reaction is not N stands for nucleophilic
doubled. 1 stands for unimolecular
Mechanism of SN1
Reactions
Alkyl halide Relative rate
≈0*
The rate of reaction depends on
the concentrations of the alkyl
halide only.
≈0*
When the methyl groups of 1-
bromo-1,1-dimethylethane are
replaced with hydrogens the
reaction rate slow down. 12
slow
C-Br bond
breaks
fast
Proton
dissociation
Mechanism of SN1
Reactions
Rate determining
step Carbocation
intermediate
∆G R++ X-
+
R-OH2
R-OH
Mechanism of SN1
Reactions
Inverted
configuration Same
relative the alkyl configuration as
halide the alkyl halide
Factor Affecting SN1
reaction
Two factors affect the rate of a SN1 reaction:
• The ease with which the leaving group dissociate from
the carbon
• The stability of the carbocation
As in the case of SN2,
The more the
the weaker base is the
substituted the
leaving group, the less
carbocation is, the
tightly it is bonded to
more stable it is and
the carbon and the
therefore the easier it is
easier it is to break the
to form.
bond
SN1 SN2
A two-step mechanism A one-step mechanism
A unimolecular rate-determining A bimolecular rate-determining
step step
Products have both retained and Product has inverted configuration
inverted configuration relative to relative to the reactant
the reactant
Reactivity order: Reactivity order:
3o > 2o > 1o > methyl methyl > 1o > 2o > 3o
Elimination Reactions
1-bromo-1,1-dimethylethane 2-methylpropene
Rate law:
rate = k [1-bromo-1,1-dimethylethane][OH-]
Br- is
eliminated The mechanism shows
that an E2 reaction is a
one-step reaction
Elimination Reactions
1-bromo-1,1-dimethylethane 2-methylpropene
Rate law:
If concentration of (1)
is doubled, the rate of
rate = k [1-bromo-1,1-
the reaction is
dimethylethane]
doubled.
2-bromobutane 20%
1-butene
The most stable alkene
is the major product of
the reaction for both E1
and E2 reaction
90% 10%
25% 75%
100%
Competition Between
Substitution and Elimination
• SN1/E1 conditions: