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Chem 210 CH 07 SN1 SN2 E1 E2 PDF
Chem 210 CH 07 SN1 SN2 E1 E2 PDF
210
[CHAPTER
7:
SUBSTITUTION
AND
ELIMINATION
REACTIONS
OF
ALKYL
HALIDES
Make sure that if you are going to do an E2 or E1 process that you have a β -‐hydrogen to react!
Example:
Even
though
the
benzyl
carbocation
is
as
stable
as
a
3o,
the
example
on
the
left
can
only
undergo
SN1
as
there
are
no
β -‐hydrogens;
the
example
on
the
right
there
are
β -‐hydrogens
and
we
would
show
both
SN1
and
E1
products:
1
Fall
2011
CHEM
210
[CHAPTER
7:
SUBSTITUTION
AND
ELIMINATION
REACTIONS
OF
ALKYL
HALIDES
2. The
Reagent:
Nucleophilicity
vs.
Basicity
After
we
know
what
is
possible
for
a
substrate,
we
now
inspect
the
nucleophile/base
to
see
what
will
happen.
We
can
divide
nucleophiles/bases
into
categories:
Once we know what category we are in, we can now decide on the course of the reaction:
For “Nucleophile (only)” do not use ANY of these for E2. They lack the basicity needed to lower the EA.
2
Fall
2011
CHEM
210
[CHAPTER
7:
SUBSTITUTION
AND
ELIMINATION
REACTIONS
OF
ALKYL
HALIDES
For
“Strong
Nuc/Strong
Base”
the
bimolecular
mechanisms
dominate.
As
the
substrates
get
more
hindered,
SN2
slows
down
and
E2
speeds
up.
For
“Weak
Nuc/Weak
Base”
the
unimolecular
mechanisms
predominate
and
are
always
in
competition.
For
primary
substrates
that
cannot
form
carbocations,
the
reaction
will
have
to
be
SN2
and
it
will
be
very
slow.
3. Stereochemistry
If
the
reaction
proceeds
by
SN2
or
E2
reaction,
inspect
the
substrate.
If
it
is
written
in
a
stereochemical
form,
you
probably
have
to
consider
stereochemistry
to
determine
the
outcome
of
the
reaction.
If
the
reaction
is
SN1/E1
remember
that
stereochemistry
is
usually
lost
(SN1)
or
will
allow
all
possible
E1
reactions
to
occur.
4. The
Sovlent
Polar
aprotic
solvents
are
used
for
SN2
and/or
E2
reactions
of
2o
and
3o
substrates.
Primary
or
methyl
substrates
can
have
any
solvent
for
SN2.
Remember
that
nucleophilicity
of
elements
within
a
group
on
the
periodic
table
increases
going
upward
(stronger
base).
Polar
protic
solvents
are
used
for
SN1/E1
reactions
and
the
solvent
itself
may
become
the
nucleophile/base.
Remember
that
Nucleophilicity
of
elements
within
a
group
increases
going
downward
(weaker
bases).
3
Fall
2011
CHEM
210
[CHAPTER
7:
SUBSTITUTION
AND
ELIMINATION
REACTIONS
OF
ALKYL
HALIDES
Mixed
Problems
1. Identify
the
mechanism
when
1-‐bromobutane
is
treated
with
the
following:
2. Identify
the
mechanism
when
2-‐bromopentane
is
treated
with
the
following:
3. Identify
the
mechanism
when
2-‐bromo-‐2-‐methylpentane
is
treated
with
the
following:
4. When
2-‐chloro-‐1,1,2,3,3-‐pentamethylcyclohexane
is
treated
with
sodium
hydroxide
neither
SN2
nor
E2
products
are
formed.
Explain.
5. Complete
the
following
reactions
(treat
the
OTs
group
as
a
bromide!):
4
Fall
2011
CHEM
210
[CHAPTER
7:
SUBSTITUTION
AND
ELIMINATION
REACTIONS
OF
ALKYL
HALIDES
6. Complete
the
following
reactions:
a.
b.
c.
d.
e.
f.
g.
h.
i.
j.
k.
5
Fall
2011
CHEM
210
[CHAPTER
7:
SUBSTITUTION
AND
ELIMINATION
REACTIONS
OF
ALKYL
HALIDES
7. Complete
the
following
reactions
indicating
the
MAJOR
product:
a.
b.
c.
d.
e.
f.
g.
h.
i.
6
Fall
2011
CHEM
210
[CHAPTER
7:
SUBSTITUTION
AND
ELIMINATION
REACTIONS
OF
ALKYL
HALIDES
KEY
–
Mixed
Problems
1. 1-‐bromobutane
is
primary:
a)
NaOH
is
a
strong
nucleophile
and
strong
base.
The
substrate
in
this
case
is
primary.
Therefore,
we
expect
SN2
(giving
the
major
product)
b)
NaSH
is
a
strong
nucleophile
and
weak
base.
The
substrate
in
this
case
is
primary.
Therefore,
we
expect
only
SN2
c)
When
a
primary
alkyl
halide
is
treated
with
t-‐BuOK,
the
predominant
pathway
is
expected
to
be
E2.
d)
DBN
is
a
weak
nucleophile
and
a
strong
base.
Therefore,
we
expect
only
E2.
e)
NaOMe
is
a
strong
nucleophile
and
strong
base.
The
substrate
in
this
case
is
primary.
Therefore,
we
expect
SN2
2. 2-‐bromopentane
is
secondary:
a)
NaOEt
is
a
strong
nucleophile
and
strong
base.
The
substrate
in
this
case
is
secondary.
Therefore,
we
expect
SN2
with
a
possible
minor
E2
b)
NaI
is
a
strong
nucleophile
and
weak
base.
DMSO
is
a
polar
aprotic
solvent.
The
substrate
is
secondary.
Under
these
conditions,
only
SN2
can
occur.
c)
DBU
is
a
weak
nucleophile
and
a
strong
base.
Therefore,
we
expect
only
E2.
d)
NaOH
is
a
strong
nucleophile
and
strong
base.
The
substrate
in
this
case
is
secondary.
Therefore,
we
expect
SN2
e)
t-‐BuOK
is
a
strong,
sterically
hindered
base.
Therefore,
we
expect
only
E2.
3. 2-‐bromo-‐2-‐methylpentane
is
tertiary:
a) EtOH
is
a
weak
nucleophile
and
weak
base.
The
substrate
in
this
case
is
tertiary.
Therefore,
we
expect
both
SN1
and
E1.
b) b)
t-‐BuOK
is
a
strong,
sterically
hindered
base.
Therefore,
we
expect
only
E2.
c) c)
NaI
is
a
strong
nucleophile
and
weak
base.
The
substrate
in
this
case
is
tertiary.
Therefore,
we
expect
only
SN1.
d) d)
NaOEt
is
a
strong
nucleophile
and
strong
base.
The
substrate
in
this
case
is
tertiary.
Therefore,
we
expect
only
E2.
e) e)
NaOH
is
a
strong
nucleophile
and
strong
base.
The
substrate
in
this
case
is
tertiary.
Therefore,
we
expect
only
E2.
4. The
substrate
is
tertiary,
so
SN2
cannot
occur
at
a
reasonable
rate.
There
are
no
beta
protons,
so
E2
also
cannot
occur.
7
Fall
2011
CHEM
210
[CHAPTER
7:
SUBSTITUTION
AND
ELIMINATION
REACTIONS
OF
ALKYL
HALIDES
5. Complete
the
following
reactions
(treat
the
OTs
group
as
a
bromide!):
8
Fall
2011
CHEM
210
[CHAPTER
7:
SUBSTITUTION
AND
ELIMINATION
REACTIONS
OF
ALKYL
HALIDES
k)
9
Fall
2011
CHEM
210
[CHAPTER
7:
SUBSTITUTION
AND
ELIMINATION
REACTIONS
OF
ALKYL
HALIDES
6. Complete
the
following
reactions:
a.
b.
c.
d.
e.
f.
g.
h.
i.
j.
k.
10
Fall
2011
CHEM
210
[CHAPTER
7:
SUBSTITUTION
AND
ELIMINATION
REACTIONS
OF
ALKYL
HALIDES
7. Complete
the
following
reactions
indicating
the
MAJOR
product:
a.
b.
c.
d.
e.
f.
g.
h.
i.
11
Fall
2011