Alkenes:
Synthesis
&
Reactions
Preparing
Alkenes
Elimination
Reactions
1. Dehydrohalogenation
Reaction
of
an
alkyl
halide
with
a
strong
baseHX
acid
is
neutralized
by
base
2. Dehydration
Treatment
of
an
alcohol
with
a
strong
acidOH
is
neutralized
by
strong
acid
3. Halogenation
of
Alkenes:
Addition
of
X2
If
halogenation
reaction
is
carried
out
on
a
cycloalkane,
only
the
trans
isomer
is
formed
(Anti)
If
you
see:
Just
a
halogen
pair
Bromonium
ion
accounts
for
anti
formation
because
the
Bromine
protects
one
side
of
the
cycloalkene
so
that
the
other
bromine
can
only
attach
from
the
other
side
4. Halohydrins
from
Alkenes:
Addition
of
HOX
Reaction
of
alkenes
with
hypohalous
acids
(HO-CL
or
HO-Br)
to
make
1,2-halo
alcohols,
called
Halohydrins
Before,
we
saw
that
the
prescence
of
a
nucleophile
(Br-)
in
front
of
a
bromonium
ion
makes
the
halogenation,
but
if
there
are
two
nucleophiles
(halogen
+
water,
etc.),
the
water
nucleophile
is
stronger
and
reacts
with
the
bromonium
ion
to
make
a
bromohydrin.
This
other
nucleophile
is
also
added
to
the
other
side
of
the
bromonium
If
you
see:
A
halogen
and
another
nucleophile
(H2O,
H2O2,
etc.)
NBS
is
a
source
of
bromine
instead
of
using
actual
bromine
5. Hydration
of
Alkenes:
Addition
of
H2O
by
Oxymercuration
Water
is
added
to
an
alkene
to
yield
an
alcohol,
a
process
called
hydration.
The
halogen
is
added
to
the
side
with
the
least
groups
If
you
see:
Water
and
a
strong
acid
catalyst
6. Oxymercuration-Demercuration
Oxymercuration
involves
electrophilic
addition
of
Hg(OAc)2
in
THF
solvent.
Intermediate
then
treated
with
NaBH4
to
cause
demercuration
and
produce
an
alcohol
If
you
see:
Hg(OAc)2
and
THF
Very
similar
to
halohydrin
formation:
Hg
is
at
the
top
of
the
triangle.
Water
attaches
to
the
other
Carbon,
and
loses
a
proton
(See
halohydrin
diagram)
The
OH
group
attaches
to
more
highly
substituted
carbon
and
H
attaches
to
less
(Markovnikov),
but
Hydrogen
that
replaces
mercury
can
be
on
either
side
of
the
molecule
7. Hydration
of
Alkenes:
Addition
of
H2O
by
Hydroboration
This
is
a
complementary
method
to
oxymercuration-demercuration
that
produces
the
non-Markovnikov
product.
Involves
the
addition
of
a
B-H
bond
to
an
alkene
to
yield
RBH2.
Oxidation
with
H2O2
then
yields
an
alcohol
If
you
see:
BH3
and
H2O2
In
this
reaction,
boron
attaches
to
the
less
highly
substituted
carbon,
and
both
B
and
H
attach
on
the
same
side
of
the
molecule.
During
oxidation,
the
B
is
replaced
with
an
OH
with
the
same
stereochemistry,
and
the
overall
molecule
is
syn
non-Markovnikov.
This
happens
because
there
is
no
intermediate
form,
and
the
C-H
and
C-B
bonds
form
at
the
same
time
and
at
the
same
face
8. Reduction
of
Alkenes:
Hydrogenation
Alkenes
react
with
H2
in
the
presence
of
a
metal
catalyst
like
Pd
or
Pt.
As
a
result,
the
double
bond
has
been
hydrogenated
or
reduced
Reduction:
Creating
C-H
bonds
or
breaking
C-X
If
you
see:
H2,
Pt
or
Pd
Takes
place
on
the
surface
of
solid
catalyst
particles
(homogeneous
solution)
Usually
syn
hydrogens
add
to
the
double
bond
from
same
face
Hydrogenation
begins
with
adsorption
of
H2
onto
the
catalyst
surface.
Vacant
orbital
on
the
metal
interacts
with
the
filled
alkene
pi
orbital.
Hydrogen
is
then
inserted
into
the
double
bond
and
saturated
product
diffuses
away
from
catalyst
The
catalyst
usually
only
approaches
the
more
accessible
face
of
an
alkene,
so
there
is
usually
only
a
single
product
9. Oxidation
of
Alkenes:
Epoxidation
and
Hydroxylation
Oxidation:
Form
C-X
or
break
C-H
Alkenes
are
oxidized
to
give
epoxides
on
treatment
with
a
peroxyacid
such
as
meta-
chloroperoxybenzoic
acid.
If
you
see:
meta,
or
any
other
peroxyacid
Peroxyacids
transfer
oxygen
atoms
to
alkene
with
syn
stereochemistry
through
a
one
step
mechanism.
The
oxygen
farthest
from
the
carbonyl
group
on
the
peroxyacid
is
transferred
to
the
alkene.
Other
method:
Use
halohydrins
and
then
treat
with
base:
HX
is
eliminated
and
epoxide
produced.
Epoxides
then
undergo
ring-opening
reaction
with
water
(hydrolysis)
to
give
a
diol.
The
whole
process
is
called
hydroxylation.
The
product
is
trans
Other
Method:
Hydroxylation
can
be
carried
out
directly
without
an
intermediate
epoxide
with
OsO4.
The
reaction
is
syn
and
creates
an
intermediate
cyclic
osmate.
It
is
then
cleaved
with
NaHSO3
If
you
see:
OsO4,
NaHSO3,
or
NMO
With
NaHSO3:
With
NMO
and
catalytic
OsO4:
10. Oxidation
of
Alkenes:
Cleavage
to
Carbonyl
Compounds
Ozone
adds
rapidly
to
C-C
double
bonds
to
give
cyclic
molozonide
intermediate,
which
then
spontaneously
rearranges
to
form
an
ozonide.
The
ozonide
is
then
treated
with
zinc
to
convert
it
to
carbonyl
compounds
If
you
see:
O3,
Zn
If
an
alkene
with
a
tetrasubstituted
double
bond
is
ozonized,
two
ketone
fragments
result;
if
an
alkene
with
a
trisubstituted
double
bond
is
ozonized,
one
ketone
and
one
aldehyde
result
Other
method:
Use
KMnO4
to
cleave;
if
hydrogens
on
double
bonds,
carboxylic
acids
are
produced;
if
two
hydrogens
are
present
on
one
carbon,
CO2
is
formed
If
you
see:
KMnO4
Other
method:
Initial
hydroxylation
to
a
1,2-diol,
then
treatment
of
diol
with
HIO4.
If
two
OH
groups
are
in
an
open
chain,
two
carbonyl
compounds
result.
If
two
OH
groups
are
on
a
ring,
a
single,
open-chain
dicarbonyl
compound
is
formed.
11. Addition
of
Carbenes
to
Alkenes:
Cyclopropane
Synthesis
This
reaction
is
an
addition
of
a
carbene
to
yield
a
cyclopropane.
Carbenes
are
usually
only
intermediates.
To
make
them:
a
common
method
is
the
use
of
chloroform,
CHCl3
with
a
strong
base
If
you
see:
R2C
If
creation
of
the
dichlorocarbene
is
made
in
the
presence
of
an
alkene,
addition
to
the
double
bond
occurs
and
a
product
is
formed.
If
you
are
starting
from
a
trans
alkene,
you
get
a
trans
product,
and
vice
versa
