CH 06

Chapter 6
Ionic Reactions
Nucleophilic
Substitution and
Elimination Reactions of
Alkyl
Halides
Created by
Professor William Tam & Dr. Phillis
Chang
Copyright 2014 by John Wiley & Sons, Inc. All rights reserved.
About The Authors

These PowerPoint Lecture Slides were created and prepared by
Professor William Tam and his wife, Dr. Phillis Chang.
Professor William Tam received his B.Sc. at the University of Hong
Kong in 1990 and his Ph.D. at the University of Toronto (Canada) in
1995. He was an NSERC postdoctoral fellow at the Imperial College
(UK) and at Harvard University (USA). He joined the Department of
Chemistry at the University of Guelph (Ontario, Canada) in 1998 and
is currently a Full Professor and Associate Chair in the department.
Professor Tam has received several awards in research and teaching,
and according to Essential Science Indicators, he is currently ranked
as the Top 1% most cited Chemists worldwide. He has published four
books and over 80 scientific papers in top international journals such
as J. Am. Chem. Soc., Angew. Chem., Org. Lett., and J. Org. Chem.
Dr. Phillis Chang received her B.Sc. at New York University (USA) in
1994, her M.Sc. and Ph.D. in 1997 and 2001 at the University of
Guelph (Canada). She lives in Guelph with her husband, William, and
their son, Matthew.
2014 by John Wiley & Sons, Inc. All rights reserved.
Table of Contents
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
(hyperlinked)
Alkyl Halides
Nucleophilic Substitution Reactions
Nucleophiles
Leaving Groups
Kinetics of a Nucleophilic Substitution Reaction: An SN2
Reaction
A Mechanism for the SN2 Reaction
Transition State Theory: Free-Energy Diagrams
The Stereochemistry of SN2 Reactions
The Reaction of tert-Butyl Chloride with Water: An SN1
Reaction
Carbocations
Factors Affecting the Rates of SN1 and SN2 Reactions
Organic Synthesis: Functional Group Transformations Using
SN2 Reactions
Elimination Reactions of Alkyl Halides
The E2 Reaction
The E1 Reaction
Table of Contents
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
Alkyl Halides
Nucleophilic Substitution Reactions
Nucleophiles
Leaving Groups
Kinetics of a Nucleophilic Substitution Reaction: An SN2
Reaction
Transition State Theory: Free-Energy Diagrams
The Reaction of tert-Butyl Chloride with Water: An SN1
Reaction
Carbocations
Factors Affecting the Rates of SN1 and SN2 Reactions
Organic Synthesis: Functional Group Transformations Using
SN2 Reactions
Elimination Reactions of Alkyl Halides
The E2 Reaction
The E1 Reaction
In this chapter we will consider:
What groups can be replaced (i.e.,

substituted) or eliminated
The various mechanisms by which

such processes occur
The conditions that can promote

such reactions
1. Alkyl Halides
An alkyl halide has a halogen

atom bonded to an sp3-hybridized
(tetrahedral) carbon atom
The carbonchlorine and carbon

bromine bonds are polarized
because the halogen is more
electronegative than carbon
Iodine does not have a permanent

dipole, but the bond is easily
polarizable
Iodine is a good leaving group due

to its polarizability, i.e. its ability
to stabilize a negative charge due
to its large atomic size
C X
X = Cl, Br, I
Halogens are more

electronegative than carbon
Different Types of Organic

Halides
Alkyl
halides (haloalkanes)
sp3
Attached to
1 carbon atom
Cl
Attached to
Attached to
2 carbon atoms 3 carbon atoms
C
Br
a 1o chloride a 2o bromide
C
I
a 3o iodide
Vinyl halides (Alkenyl halides)

sp2
Aryl halides
sp2
X
benzene or aromatic ring
Acetylenic halides (Alkynyl

halides)
sp
X
sp
C
Alkyl halides
sp2
Prone to undergo
Nucleophilic
Substitutions (SN) and
Elimination Reactions
(E) (the focus of this
Chapter)
sp2
sp
Different reactivity than alkyl

halides, and do not undergo SN or
E reactions
2. Nucleophilic Substitution
Reactions
Nu + C
(nucleophile)
The Nu
donates
an e pair
to the
substrate
(substrate)
The bond
between
C and LG
breaks,
giving both
e from the
bond to LG
Nu
(product)
The Nu uses
+ X
(leaving
group)
The LG
its e pair to
gains the
form a new
pair of e
covalent bond originally
with the
bonded
substrate C
in the
substrate
Timing of The Bond Breaking &

Bond Making Process
Two types of mechanisms

1st type: SN2 (concerted
mechanism)
R
HO
Br
C
R
transition state (T.S.)
2nd type: SN1 (stepwise

Step (1):
mechanism)
R
R
(k1)
R C Br
R C +Br
slow
R
R
r.d.s.
k1 << k2 and
Step (2)
R
R
H
(k2)
R C +H2O
R C O
H
fast
R
R
fast
k3
3. Nucleophiles
A reagent that seeks a positive

center
Nucleophile nucleus loving
phile derived from the Greek

word
philia meaning loving
Has an unshared pair of e

e.g.:
HO , CH3O , H2N
H2O, NH3
(negative charge)
(neutral)
This is the positive

center that the
Nu seeks
Examples:
HO
(Nu
O
H
(Nu
H H
+
C
CH3 Cl
) (substrate)
H H
+
C
H
CH3 Cl
)
(substrate)
H H
+ Cl
C
CH3 OH
(product) (L.G.)
H H
C
H + Cl
CH3 O
(L.G.)
H
H H
(product)
C
+ H3O
CH3 OH
4. Leaving Groups
To be a good leaving group, the

substituent must be able to leave as a
relatively stable, weakly basic
molecule or ion
e.g.: I, Br, Cl
,
TsO
,
MsO
, H2O, NH3
O
OTs =
O S
O
CH3 (Tosylate)
O
OMs = O S CH3 (Mesylate)
O
. Kinetics of a Nucleophilic
Substitution Reaction:
An SN2 Reaction
The rate of the substitution

reaction is linearly dependent on
the concentration of HO and
CH3Br
Overall, a second-order reaction
5A.How Do We Measure the

Rate of This Reaction?
e.g.:
HO
(Nu )
H
+
H
C Cl
HO C
H
(substrate)
H
(product)
+ Cl
(leaving
group)
The rate of reaction can be measured

by
The consumption of the reactants
(HO or CH3Cl) or
The appearance of the products
Concentration, M
Graphically
Rate =
[CH3Cl]
[CH3OH]
Time, t
[CH3Cl]
t
[CH3Cl]t=t [CH3Cl]t=0
Time in seconds
Concentration, M
Initial Rate
[CH3Cl]t=0
[CH3Cl]t=t
[CH3Cl]
Time, t
[CH3Cl]t=t [CH3Cl]t=0
Initial Rate
=
(from slope)
t
Example:
HO + Cl CH3
[OH]t=0
60oC
H2O
[CH3Cl]t=0
HO CH3 + Cl
Initial rate
mole L-1, s-
Result
1.0 M
0.0010 M
4.9 10-7
1.0 M
0.0020 M
9.8 10-7 Doubled
2.0 M
0.0010 M
9.8 10-7 Doubled
2.0 M
0.0020 M
19.6 10
-7
Quadruple
d
Conclusion:
HO + Cl CH3
60oC
H2O
HO CH3 + Cl
The rate of reaction is directly

proportional to the
concentration of either
reactant.
When the concentration of
either reactant is doubled, the
rate of reaction doubles.
The Kinetic Rate Expression

HO + Cl CH3
60oC
H2O
HO CH3 + Cl
Rate [OH][CH3Cl]
Rate = k[OH][CH3Cl]
k=
Initial Rate
[OH][CH3Cl]
= 4.9 10-7 L mol-1 s-1

5B. What is the Order of This

Reaction?
This reaction is said to be second
order overall
We also say that the reaction is
bimolecular
We call this kind of reaction an SN2
reaction, meaning substitution,
nucleophilic, bimolecular
. A Mechanism for the SN2

Reaction
H
HO
Br
H
H
HO
Br
C
H
transition state (T.S.)
negative HO
OC bond
brings an e
partially
pair to +C; Br
formed; CBr
begins to move bond partially
away with an
broken.
Configuration
e pair
ofWileyC& begins
toreserved.
2014 by John
Sons, Inc. All rights
OC bond
formed; Br
departed.
Configuratio
n of C
inverted
7. Transition State Theory:

Free-Energy Diagrams
A reaction that proceeds with a
negative free-energy change
(releases energy to its
surroundings) is said to be
exergonic
A reaction that proceeds with a
positive free-energy change
(absorbs energy from its
surroundings) is said to be
At 60oC (333 K)
Go = -100 kJ/mol
This reaction is highly
exergonic
Ho = -75 kJ/mol
This reaction is exothermic
Its equilibrium constant (Keq) is

ln Keq
Go = RT ln Keq
Go
=
RT
=
(100 kJ/mol)
(0.00831 kJ K-1 mol-1)(333 K)
= 36.1
Keq = 5.0 x 1015
A Free Energy Diagram for a Hypothetical

SN2
Reaction That Takes Place with a
Negative Go
The reaction coordinate indicates

the progress of the reaction, in terms
of the conversion of reactants to
products
The top of the energy curve
corresponds to the transition state
for the reaction
The free energy of activation (G)
for the reaction is the difference in
energy between the reactants and the
transition state
The free energy change for the
reaction (Go) is the difference in
A Free Energy Diagram for a Hypothetical

Reaction with a Positive Free-Energy
Change
7A.Temperature & Reaction

Rate
Distribution of energies at two

different temperatures. The
number of collisions with
energies greater than the free
energy of activation is indicated
by the corresponding shaded
area under each curve.
A 10C increase
in temperature
will cause the
reaction rate to
double for
many reactions
taking place
near room
temperature
The relationship
between the rate
constant (k) and
G is
G
/RT
exponential
:
k = k0 e
e = 2.718, the base of

natural logarithms
k0 = absolute rate
constant, which equals
the rate at which all
transition states
proceed to products
(At 25oC,
12

A reaction with a
lower free energy
of activation (G)
will occur
exponentially
faster than a
reaction with a
higher G, as
dictated byG/RT
k = k0 e
Free Energy Diagram of SN2

Reactions
Free Energy
T.S.
G
HO- + CH3Br
Go
G = free energy of
activation
Go =free energy
change
CH3OH + Br-
Reaction Coordinate
Exothermic (Go is negative)

Thermodynamically favorable
process
The Stereochemistry of SN2

Reactions
Inversion of configuration
HO
CH3
+
C Br
H
CH2CH3
(R)
(inversion)
CH3
HO
H
(S) CH2CH3
+ Br
Example:
CH3
Nu attacks from the TOP

face.
I +
OCH3
(inversion of configuration)
CH3
OCH3 +
I
Example:
Nu attacks from the BACK
side.
(inversion of
configuration)
The Reaction of tert -Butyl

Chloride with Water:
An SN1 Reaction
The rate of SN1 reactions depends

only on concentration of the alkyl
halide and is independent of
concentration of the Nu
Rate = k[tBuCl]
In other words, it is a first-order
reaction
unimolecular nucleophilic
substitution
9A.Multistep Reactions & the

Rate-Determining Step
In a multistep reaction, the rate of

the overall reaction is the same
as the rate of the SLOWEST step,
known as the rate-determining
step (r.d.s)
Fork1example:
Reactant
k2
Intermediate
(slow)
(fast)
1
k3
Intermediate
(fast)
2
k1 << k2 or
Product
Fig. 6.5
A
B
C
The opening A is
much smaller than
openings B and C
The overall rate at
which sand
reaches to the
bottom of the
hourglass is
limited by the rate
at which sand falls
through opening A
Opening A is
analogous to the
rate-determining
step of a multistep
reaction
0.A Mechanism for the SN1

Reaction
A multistep process
slow
r.d.s.
Energy Diagram of SN1 Reactions
intermediate
Step (2)
CH3
(k2)
CH3 C +H2O
fast
CH3
CH3 H
CH3 C O
CH3 H
intermediate
Step (2)
CH3
(k2)
CH3 C +H2O
fast
CH3
CH3 H
CH3 C O
CH3 H
fast
intermediate
Step (2)
CH3
(k2)
CH3 C +H2O
fast
CH3
CH3 H
CH3 C O
CH3 H
k1 << k2 and
k3
fast
2 intermediates and 3 transition

states (T.S.)
The most important T.S. for SN1

reactions is T.S. (1) of the ratedetermining step (r.d.s.)
CH3
CH3
Br
CH3
11.Carbocations
11A. The Structure of
Carbocations are
Carbocations
H3C
H3C
trigonal planar
The central carbon
atom in a
carbocation is
electron deficient; it
C
CH3
has only six e in its
valence shell
The p orbital of a
carbocation
contains no
electrons, but it can
accept an electron
pair when the
2014 by John Wiley & Sons, Inc.carbocation
All rights reserved.
11B. The Relative Stabilities of

Carbocations
General order of reactivity

(towards SN1 reaction)
3o > 2o >> 1o > methyl
The more stable the carbocation

formed, the faster the SN1 reaction
Stability of cations
most stable (positive inductive
effect)
R
H
R
R
>
>
>
R R
H
H H
H H
Resonance stabilization of allylic
and benzylic cations
CH2
CH2
etc.
Stereochemistry of SN1 Reactions

Ph
CH3
Ph
CH3OH
Br
CH2CH3
(S)
CH3OH
CH3 CH2CH3
50:50
chance
CH3
OCH3
CH2CH3
(R) and (S)
racemic mixture
(trigonal planar)
CH3OH
attack from left
Ph
CH3OH
attack from right
(1 : 1)
racemic
mixture
(R)
( 1 : 1 ) (S)
Example:
(R)
Br
H2O
(SN1)
(one
enantiomer)attack from
slow
TOP face
r.d.s
H2O
.
(carbocation)
OH
OH
H2O
H2O
H2O attack from
BOTTOM
face
Example:
I
Bu
Me
OMe
Me MeOH tBu
Me +tBu
OMe
MeOH
slow
r.d.s
.
t
Bu
Me
t
MeOH
Bu
MeOH
Me
Me
CH3
MeOH
Bu
trigonal planar
O
Me
Factors Affecting the Rates of

SN1 and SN2 Reactions
The structure of the substrate
The concentration and reactivity

of the nucleophile (for SN2
reactions only)
The effect of the solvent
The nature of the leaving group

. The Effect of the Structure of

the Substrate

Methyl > 1o > 2o >> 3o > vinyl or
aryl
DO NOT
undergo
SN2 reactions
For example:
R Br +HO
R OH + Br
Relative Rate (towards SN2)

CH3 Br
methyl
6
CH3
Br CH3 C CH2Br
CH3CHo2 Br CH3CH
o
neopent
1
2
CH3
CH3
2 10 4 10
Most
reactiv
e
500
yl
1
CH3
CH3 C
o Br
3CH3
<1
Least
reactiv
e
Compare
H
HO
C
H
H
HO
C
CH3
Br
faster
HO
C
H
Br
+ Br
slower
HO
+ Br
CH3
CH3
CH3
HO
Bu
C
CH3
Br
CH3
HO
CH3
very
slow
Br
HO
extremely
slow
CH3
+ Br
C
CH3
CH3
Note NO SN2 reaction on sp2 or sp

carbons
sp2
sp2
sp
Reactivity of the Substrate in

SN1 Reactions

3o > 2o >> 1o > methyl
The more stable the carbocation

formed, the faster the SN1 reaction
Stability of cations
R
most stable (positive inductive

effect)
>
R
>
H H
>
H
Allylic halides and benzylic halides

also undergo SN1 reactions at
I
reasonable rates
Br
an allylic bromide
a benzylic iodide
Resonance stabilization for allylic

and benzylic cations
13B. The Effect of the

Concentration
& Strength of the
For Nucleophile
SN1 reaction
Recall: Rate = k[RX]
The Nu does NOT participate
in the r.d.s.
Rate of SN1 reactions are NOT
affected by either the
concentration or the identity
of the Nu
For SN2 reaction

Recall: Rate = k[Nu][RX]
The rate of SN2 reactions
depends on both the
concentration and the
identity of the attacking Nu
Identity of the Nu
The relative strength of a Nu
(its nucleophilicity) is
measured in terms of the
relative rate of its SN2 reaction
rapid
with a given
substrate
Good Nu
Poor Nu:
Very
slow
The relative strength of a Nu can

be correlated with 3 structural
features
A negatively charged Nu is always
a more reactive Nu than its
conjugate acid
e.g. HO is a better Nu than
H2O and RO is better than ROH
In a group of Nus in which the
nucleophilic atom is the same,
nucleophilicities parallel basicities
e.g. for O compounds,
Wiley & Sons, Inc. All rights

reserved.
2014 by John
When the nucleophilic atoms

are different, then
nucleophilicities may not
parallel basicities
e.g. in protic solvents HS,
NC, and I are all weaker
bases than HO, yet they
are stronger Nus than HO
HS > NC > I > HO
13C. Solvent Effects in SN2 & SN1

Reactions
SN2 reactions are favored by polar

aprotic solvents (e.g., acetone,
DMF, DMSO)
SN1 reactions are favored by polar

protic solvents (e.g., EtOH,
MeOH, H2O)
Classification of solvents
Non-polar solvents
(e.g. hexane,
benzene)
Solvents
Polar
solvent
s
Polar protic solvents

(e.g. H2O, MeOH)
Polar aprotic solvents
(e.g. DMSO, HMPA)
SN2 Reactions in Polar Aprotic

Solvents
The best solvents for SN2
reactions are
Polar aprotic solvents, which
have strong dipoles but do
not have OH or NH groups
O
Examples
O
CH
3
O
CH3
CH3
(DMSO)
N
CH3
(DMF)
P NMe
Me2N NMe2 2
(HMPA)
CH3CN
(Acetonitrile)
Polar
aprotic solvents tend

to solvate metal cations
rather than nucleophilic
anions, and this results in
naked anions of the Nu
and makes the e pair of the
Nu more available
DMSO
CH3O Na
CH3O + DMSO Na
"naked anion"
Tremendous
acceleration in
SN2 reactions with polar
aprotic solvent
CH3Br + NaI
CH3I + NaBr
Solvent
Relative
Rate
MeOH
DMF
106
SN2 Reactions in Polar Protic

Solvents
In polar protic solvents, the Nu
anion is solvated by the
surrounding protic solvent
which makes the e pair of the
Nu less available
OR and thus less
H
reactive in SN2 reactions
RO H Nu H OR
H
OR
Halide Nucleophilicity in Protic

Solvents
OR
RO
I > Br OR
> Cl > F
H
H
H
RO H
H OR
RO
OR
(strongly solvated)
RO H
OR
(weakly solvated)
Thus, I is a stronger Nu in protic

solvents, as its e pair is more
available to attack the substrate in
the SN2 reaction.
Halide Nucleophilicity in Polar

Aprotic Solvents (e.g. in DMSO)
F > Cl > Br > I
Polar aprotic solvents do not

solvate anions but solvate the
cations
The naked anions act as the

Nu
Since F is smaller in size and

the charge per surface area is
larger than I, the
Solvent plays an important role in

SN1 reactions but the reasons are
different from those in SN2
reactions
Solvent effects in SN1 reactions

are due largely to stabilization or
destabilization of the transition
state
Polar protic solvents stabilize the

development of the polar
transition state and thus
accelerate this rate-determining
step (r.d.s.):
The Nature of the Leaving Group
Leaving groups depart with the

electron pair that was used to
bond them to the substrate
The best leaving groups are those

that become either a relatively
stable anion or a neutral molecule
when they depart
The better a species can stabilize

a negative charge, the better the
LG in an SN2 reaction
SN1 Reaction:
C X
slow
r.d.s.
SN2 Reaction:
Nu:

C
X
slow
C X
r.d.s.
Nu C
Nu C
+X
Examples of the reactivity of some

XCH
: 3O + CH3X CH3OCH3 +
Relative
X Rate:
Best
X
Worst X
HO ,
H2N,<<F < Cl < Br < I < TsO
RO
~0
200
10,00 30,00 60,00

0
0
0
Note: Normally RF, ROH, R

NH2, ROR do not undergo SN2
reactions.

a poor
leaving group
R O
Nu
a good
a strong
basic anion
R Nu
leaving group
H2O
weak
base
Other weak bases that are good

leaving groups:
Organic Synthesis: Functional

Group Transformation Using
SN2 Reactions
OH
HO
CN
Br
MeS
MeO
HS
SMe
SH
Me
Me C C
Me
NMe3
Br
I
Br
N3
MeCOO
Me3N
N3
Examples:
NaOEt,??DMSO
Br
NaSMe,
?? DMSO
SMe
Examples:
??
I
CN
(optically active, chiral)
Need SN2 reactions to control

stereochemistry
But SN2 reactions give the inversion
of configurations, so how do you
get the retention of configuration
here??
Solution:
double inversion retention
??
I
CN
NaBr
DMSO
NaCN
DMSO
(SN2 with
inversion)
Br
(SN2 with
inversion)
(Note: Br is a stronger Nu
than
I in polar aprotic solvent.)
The Nonreactivity of Vinylic and

Phenyl Halides
X
C
X
vinylic halide
phenyl halide
Vinylic and phenyl halides are

generally unreactive in SN1 or SN2
reactions
Examples
Br
NaCN
DMSO
NaSMe
HMPA
No Reaction
No Reaction
Elimination Reactions of Alkyl

Halides
Substitution
Elimination
Substitution reaction (SN) and

elimination reaction (E) are
processes in competition with
each other
e.g.
I
BuOK
BuOH
O Bu +
SN2: 15%
E2: 85%
15A. Dehydrohalogenation
hydrogen
carbon
Br
LG
H
C
carbon
C
X halide as LG
BuOK
t
o
BuOH, 60 C
+ KBr + BuOH
hydrogen
OtBu
5B. Bases Used in Dehydrohalogenation

Conjugate base of alcohols is often
used as the base in
dehydrohalogenations
Na
RO + Na + H2
ROH
NaH
RO + Na + H2
16.The E2 Reaction
Br
EtO +
+ EtOH + Br
Rate = k[CH3CHBrCH3][EtO]
Rate determining step involves

both the alkyl halide and the
alkoxide anion
A bimolecular reaction
Mechanism for an E2 Reaction

Et O
CH3
C C H
H
Br
H
H
Et O
CH3
C C H
H
Br
H
H
H
H
C C
+
CH3
H
Et OH + Br
EtO removes Partial bonds in

C=C is fully
the transition
a proton;
formed and
state: CH and
CH breaks;
the other
CBr bonds
new bond
products are
break, new
forms and Br
EtOH and
CC bond
begins to
forms
depart
Br
e Energy Diagram of E2 Reaction

Free Energy
T.S.
E2 reaction has ONE

G transition state
CH3CHBrCH3
+ EtO-
CH2=CHCH3
+ EtOH + Br-
Reaction Coordinate
Rate = k[CH3CHBrCH3][EtO]
Second-order overall
bimolecular
17.The E1 Reaction
E1: Unimolecular elimination

CH3
CH3
CH3
H2O
CH3 C Cl
CH3 C OH+CH2 C
CH3
CH3
CH3
slow
(major (SN1)) (minor (E1))
r.d.s
H2O as
CH3
nucleophile
CH3 C
CH3
H2O as
base
Mechanism of an E1 Reaction
carbon
hydrogen
H
H2O
slow
fast (E1 product)
r.d.s
. fast H O
2
O
H HO
2
H
H3O
OH + H3O
(SN1 product)
Step (1):
CH3
CH3 C Cl
CH3
H2O
(k1)
slow
r.d. step
CH3
CH3 C + Cl
CH3
Produces relatively
stable 3o
carbocation and a
Cl. The ions are
solvated (and
stabilized) by
surrounding H2O
2014 by John Wiley & Sons, Inc. All molecules
rights reserved.
Aided by the
polar solvent,
a chlorine
departs with
the e pair
that bonded it
to the carbon
Step (2)
H3C
H
C C H +H2O
H3C
(k2)
H3C
fast
H3C
CH2
H
H2O molecule removes

+ H O
one of the hydrogens
H
which are acidic due to
the adjacent positive
charge. An e pair moves Produces alkene
and hydronium ion
in to form a double bond
between the and
carbon atoms
How To Determine Whether

Substitution or Elimination Is
Favoured
All nucleophiles are potential
bases and all bases are potential
nucleophiles
Substitution reactions are always
in competition with elimination
reactions
Different factors can affect which
type of reaction is favoured
18A. SN2 vs. E2
(b)
Nu
(a)
H C
C X
(a)
H C
SN2
Nu C
(b)
E2
+X
+ Nu H + X
Primary Substrate
With a strong base, e.g. EtO

Favor SN2
NaOEt
Br EtOH
OEt
SN2: 90%
+
E2: (10%)
Secondary Substrate

Favor E2
+
Br
NaOEt
EtOH
E2: 80%
+
OEt
SN2: 20%
Tertiary Substrate

E2 is highly favored
Br
NaOEt
EtOH
+
E2: 91%
OEt
SN1: 9%
Base/Nu: Small vs. Bulky
Unhindered small base/Nu

NaOMe
Br MeOH
+
OMe
SN2: 99%
E2: 1%
Hindered bulky base/Nu

t
KO Bu
Br t
BuOH
+
O Bu
SN2: 15% E2: 85%
t
Basicity vs. Polarizability

O
O
O
CH3
CH3 C O
(weak base)
Br
EtO
(strong base)
SN2: 100%
E2: 0%
OEt
+
SN2: 20%
E2: 80%
ertiary Halides: SN1 vs. E1 & E2
Br
EtO
OEt
+
(strong
base) E2: 100% SN1: 0%
EtOH
OEt
+
heat
E1 + E2: 20% SN1: 80%
19.Overall Summary
SN1
SN2
E1
CH3X
RCH2X
R'
RCHX
R'
RCX
R"
Very fast
Mostly
Very little;
Mostly SN2 with
Solvolysis possible;
weak bases;
e.g. with H2O;
e.g. with CH3COO
MeOH
Very favorable
with weak bases;
e.g. with H2O;
MeOH
E2
Hindered bases give

mostly alkenes;
e.g. with tBuO
Very little
Strong bases
promote E2;
e.g. with RO, HO
Strong bases
Always competes
promote E2;
with SN1
e.g. with RO, HO
Review Problems
CN
t
SN2 with inversion
Bu
(2)
I
NaH
Et2O
H
I
Intramolecular SN2
(3)
CH3
OH
HCl
Bu
Cl attacks
from top face
Bu
CH3
H
O
H
CH3
t
Bu
SN1 with racemization
Cl attacks
from bottom
face
sp2 hybridized
carbocation
END OF CHAPTER 6

CH 06

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Chapter 6

About The Authors

In this chapter we will consider:

What groups can be replaced (i.e.,

The various mechanisms by which

The conditions that can promote

An alkyl halide has a halogen

The carbonchlorine and carbon

Iodine does not have a permanent

Iodine is a good leaving group due

2014 by John Wiley & Sons, Inc. All rights reserved.

Halogens are more

2014 by John Wiley & Sons, Inc. All rights reserved.

Different Types of Organic

Vinyl halides (Alkenyl halides)

Acetylenic halides (Alkynyl

Different reactivity than alkyl

2014 by John Wiley & Sons, Inc. All rights reserved.

Timing of The Bond Breaking &

Two types of mechanisms

transition state (T.S.)

2014 by John Wiley & Sons, Inc. All rights reserved.

2nd type: SN1 (stepwise

A reagent that seeks a positive

Nucleophile nucleus loving

phile derived from the Greek

2014 by John Wiley & Sons, Inc. All rights reserved.

Has an unshared pair of e

This is the positive

2014 by John Wiley & Sons, Inc. All rights reserved.

To be a good leaving group, the

The rate of the substitution

2014 by John Wiley & Sons, Inc. All rights reserved.

5A.How Do We Measure the

The rate of reaction can be measured

2014 by John Wiley & Sons, Inc. All rights reserved.

2014 by John Wiley & Sons, Inc. All rights reserved.

9.8 10-7 Doubled

9.8 10-7 Doubled

2014 by John Wiley & Sons, Inc. All rights reserved.

The rate of reaction is directly

The Kinetic Rate Expression

= 4.9 10-7 L mol-1 s-1

5B. What is the Order of This

2014 by John Wiley & Sons, Inc. All rights reserved.

. A Mechanism for the SN2

transition state (T.S.)

7. Transition State Theory:

2014 by John Wiley & Sons, Inc. All rights reserved.

Its equilibrium constant (Keq) is

(0.00831 kJ K-1 mol-1)(333 K)

A Free Energy Diagram for a Hypothetical

2014 by John Wiley & Sons, Inc. All rights reserved.

The reaction coordinate indicates

2014 by John Wiley & Sons, Inc. All rights reserved.

A Free Energy Diagram for a Hypothetical

2014 by John Wiley & Sons, Inc. All rights reserved.

7A.Temperature & Reaction

Distribution of energies at two

2014 by John Wiley & Sons, Inc. All rights reserved.

e = 2.718, the base of

2014 by John Wiley & Sons, Inc. All rights reserved.

Distribution of energies at two