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of
Tetraphenylcyclopentadienone
Becky
Ortiz
Introduction
In the first step in the formation of TPCPD, an intermolecular proton transfer, the oxygen of
hydroxide
from
the
base
will
accept
a
hydrogen
bonded
to
one
of
the
carbons
bonded
to
the
carbonyl
of
1,3
diphenylacetone.
The
hydrogen
will
in
turn
donate
its
electrons
to
that
carbon
to
create
a
partial
negative.
In
a
nucleophilic
addition,
one
of
the
double
bonds
of
the
carbonyl
in
benzyl
will
break
and
the
electrons
will
move
to
the
oxygen
to
create
a
partial
negative
charge
on
the
oxygen.
The
partial
negative
carbon
of
1,3-diphenylacetone
will
donate
electrons
to
form
a
bond
to
the
carbon
that
is
now
single
bonded
to
the
oxygen.
The
partial
positive
oxygen
will
then
accept
a
hydrogen
from
water
in
an
intermolecular
proton
transfer
and
that
hydrogen
will
donate
its
electrons
to
the
oxygen
of
the
water
to
create
a
partial
negative
oxygen
in
hydroxide.
In
an
E2
elimination,
the
oxygen
of
hydroxide
will
accept
the
hydrogen
bonded
to
the
carbon
of
1,3-diphenylacetone
bonded
to
benzyl.
That
hydrogen
will
donate
its
electrons
to
form
a
double
bond
between
the
carbons
bonding
benzyl
and
1,3-
diphenylacetone.
The
bond
of
the
alcohol
will
break
and
the
electrons
forming
the
bond
will
be
accepted
by
the
oxygen
of
the
alcohol
to
form
a
partial
negative
charge
on
the
oxygen.
In an intermolecular proton transfer, the oxygen of the hydroxide will accept a hydrogen from
the
carbon
bonded
to
the
carbonyl
of
the
1,3-diphenylacetone
portion.
The
electrons
from
the
hydrogen
will
then
be
donated
to
the
carbon
to
form
a
partial
negative
charge.
The
double
bond
of
the
carbonyl
of
benzyl
will
break
and
donate
the
electrons
to
the
oxygen
to
form
a
partial
negative
charge.
The
partially
negative
carbon
will
then
donate
electrons
to
form
a
bond
between
itself
and
the
carbon
bonded
to
the
partial
negative
oxygen
in
a
nucleophilic
addition.
The
partial
negative
oxygen
will
then
accept
a
hydrogen
from
water
and
the
hydrogen
will
in
turn
donate
its
electrons
to
the
oxygen
of
the
water,
an
intermolecular
proton
transfer.
The
last
step,
an
E2
elimination,
the
oxygen
of
hydroxide
will
accept
the
hydrogen
of
the
carbon
bonded
to
the
carbonyl
which
will
donate
its
electrons
to
form
a
bond
between
the
carbon
and
carbon
of
the
alcohol
group.
The
bond
of
the
alcohol
group
will
break
and
the
electrons
of
the
bond
will
be
accepted
by
that
oxygen,
creating
a
partial
negative
charge
on
the
oxygen
of
the
leaving
hydroxide
group.
The purpose of this experiment is to synthesis TPCPD, monitor this aldol condensation reaction
by
TLC,
purify
by
recrystallization,
and
analyze
the
product.
TLC
will
be
used
to
monitor
the
reaction
progression
towards
production
formation.
Recrystallization
will
then
be
utilized
to
purify
the
product
after
determining
the
reaction
is
over
using
TLC.
To
measure
the
efficiency
of
the
synthesis
and
purification
techniques,
percent
yield
of
the
crude
TPCPD
and
percent
recovery
of
the
pure
TPCPD
were
calculated.
In
the
analysis
of
the
products
purity
and
characterization,
melting
point
range,
infrared
spectroscopy,
and
nuclear
magnetic
spectroscopy
were
used.
Experimental
In the synthesis of TPCPD, benzyl (0.432g, 2 mmoles) was reacted with 1,3-diphenylacetone
(0.435
g,
2
mmoles)
in
95%
ethanol
(5mL,
)
for
40
minutes.
A
solution
of
potassium
hydroxide
(0.175g,
)
and
95%
ethanol
(1.5
mL,
)
was
added
to
the
reaction
mixture
during
this
time.
The
reaction
was
monitored
by
TLC
(2:1
mixture
of
dichloromethane:hexanes).
The
dark
purple
crude
TPCPD
was
isolated
by
vacuum
filtration
and
washed
with
ice
cold
95%
ethanol
(5
mL,
).
The
crude
TPCPD
was
purified
by
recrystallization
using
a
mixture
of
95%
ethanol
(20
mL,
)
and
toluene
(20
mL)
as
the
solvent.
The
pure
TPCPD
crystals
were
then
isolated
by
vacuum
filtration.
Rf
values
obtained
from
the
reaction
mixture
monitored
by
TLC
at
time
0
Benzyl,
spot
1
Benzyl,
spot
2
Reaction
mixture
1,3-diphenylacetone,
spot
1
1,3-diphenylacetone,
spot
2
Rf
value
0.21
0.56
0.63
0.12
0.56
Rf
values
obtained
from
the
reaction
mixture
monitored
by
TLC
at
time
10
minutes
Benzyl,
spot
1
Benzyl,
spot
2
Reaction
mixture,
spot
1
Reaction
mixture,
spot
2
Reaction
mixture,
spot
3
Reaction
mixture,
spot
4
1,3-dipheylacetone,
spot
1
1,3-diphenylacetone,
spot
2
Rf
value
0.20
0.51
0.18
0.37
0.57
0.63
0.082
0.49
Rf
values
obtained
from
the
reaction
mixture
monitored
by
TLC
at
time
20
minutes
Benzyl,
spot
1
Benzyl,
spot
2
Reaction
mixture,
spot
1
Reaction
mixture,
spot
2
Reaction
mixture,
spot
3
Reaction
mixture,
spot
4
1,3-dipheylacetone,
spot
1
1,3-diphenylacetone,
spot
2
Rf
value
0.17
0.48
0.31
0.44
0.54
0.65
0.13
0.48
Rf
values
obtained
from
the
reaction
mixture
monitored
by
TLC
at
time
40
minutes
Benzyl,
spot
1
Benzyl,
spot
2
Reaction
mixture,
spot
1
Reaction
mixture,
spot
2
Reaction
mixture,
spot
3
Reaction
mixture,
spot
4
1,3-dipheylacetone,
spot
1
1,3-diphenylacetone,
spot
2
Rf
value
0.13
0.47
0.18
0.47
0.62
0.69
0.11
0.49
Chemical
shift
ppm
observed
6.892-7.221
Chemical
shift
ppm
theoretical
6.5-8.0
2.151
2.1-2.5
multiplicity
integral
d
m
m
d
m
m
s
19.45
1.38
IR
data
of
TPCPD
Functional
group
C-H,
aromatic
C=O
C=C,
aromatic
Absorption
frequency
theoretical
(cm-1)
3100-3000
1760-1665
1600,
1580,
1500,1450
Results
and
Discussion
In the synthesis of crude TPCPD, the reaction was monitored by TLC. In the standard spots of all
the
TLC
plates
for
benzyl
and
1,3-diphenylacetone,
there
are
two
spots.
This
is
most
likely
because
both
started
to
decompose.
The
second
spot
is
most
likely
the
benzyl
and
1,3-diphenylacetone.
Since
benzyl
has
a
higher
ratio
of
electronegative
atoms
to
carbons
and
hydrogens,
it
is
the
most
polar
and
will
have
the
lowest
Rf
value.
TPCPD
will
have
the
highest
Rf
value
as
it
is
the
least
polar
and
has
a
much
lower
ratio
of
electronegative
atoms
to
carbons
and
hydrogens
due
to
only
one
carbonyl
and
four
aromatic
rings.
1,3-diphenylacetone
will
have
an
Rf
value
closer
to
benzyl,
but
slightly
higher
since
it
has
one
less
carbonyl
and
a
lower
ratio
than
benzyl,
but
still
a
higher
ratio
compared
to
TPCPD.
The
reaction
lane
only
has
one
large
spot
with
a
higher
Rf
value,
0.63,
than
the
second
spot
of
the
benzyl
lane,
0.53,
and
the
1,3-diphenylacetone,
0.56.
This
indicates
that
the
product
could
be
already
forming
since
the
Rf
value
is
close
to
those
of
the
product
spot
Rf
values
of
0.63,
0.65,
0.69.
Since
there
are
numerous
intermediates
in
the
synthesis
of
TPCPD,
it
will
be
difficult
to
determine
whether
the
starting
material
is
present
as
a
spot,
or
if
it
is
an
intermediate.
The
focus
will
be
on
the
size
and
color
intensity
of
the
spots
in
the
reaction
lane.
At 10 minutes, the reaction turns from a clear liquid to a dark purple liquid. On the TLC plate, all
four
spots
were
equal
in
intensity
with
the
three
first
intermediate
spots
being
of
slightly
larger
size
compared
to
the
last
spot,
of
the
TPCPD
spot.
This
indicates
the
reaction
is
moving
toward
product
formation,
but
is
primarily
intermediates.
At
20
minutes,
the
TPCPD
spot
has
the
darkest
intensity
and
is
slightly
larger
than
the
intermediate
spots.
This
indicates
the
reaction
is
almost
over.
At
40
minutes,
the
reaction
is
over.
All
the
spots
are
very
faint,
but
the
intermediate
spots
are
slightly
smaller
than
the
last
TPCPD
spot.
The
faintness
of
the
spots
could
be
due
to
a
light
spotting
of
the
lane.
The
reaction
produce
a
dark
purple
powder
solid.
The
crude
TPCPD
had
a
melting
point
range
of
220.4-222.2C.
Since
the
melting
point
range
is
slightly
higher
than
its
melting
point
range
of
217-220C5,
this
could
be
a
result
of
heating
the
sample
too
fast.
The
percent
yield
was
calculated
to
be
88.3%.
Since
this
is
slightly
high,
it
is
possible
there
is
still
some
ethanol
present
from
the
wash
to
create
a
higher
than
expected
percent
yield.
It
is
also
possible
synthesis
techniques
were
properly
carried
out.
After recrystallization of the crude TPCPD, dark purple crystals were formed. The melting point
range
was
determined
to
be
220.4-222.2C
which
is
the
same
as
the
crude
melting
point.
This
could
be
a
result
of
toluene
present
after
recrystallization.
This
is
most
likely
the
result
since
toluene
has
a
high
boiling
point
and
as
the
sample
began
to
melt,
it
appeared
to
be
evaporating
as
it
melted.
The
percent
recovery
of
TPCPD
was
calculated
to
be
41.5%.
This
is
a
little
low,
especially
compared
to
the
percent
yield,
this
indicates
poor
purification
techniques.
This
could
be
due
to
loss
of
product
that
stuck
to
the
flask,
filter
paper,
or
stirring
rod
during
vacuum
filtration.
The NMR spectrum (figure 3) obtained also helps to support the purity of the crystals. NMR
displays
the
peaks
of
hydrogen
groups
present
in
the
tested
compound.
Hydrogen
groups
unique
to
TPCPD
will
help
identify
the
product.
Any
peaks
that
are
not
unique
to
TPCPD
indicates
an
impurity
and
a
potential
error
in
the
synthesis
or
purification
of
the
product.
The
integral
values
will
also
indicate
how
many
hydrogens
are
present
in
the
peak.
There
are
6
distinct
hydrogen
groups
in
TPCPD.
However,
they
are
all
aromatic
hydrogens
so
their
theoretical
range
is
6.5-8.0
ppm.
The
integral
value
of
the
aromatic
hydrogens
was
19.45,
which
is
close
to
the
actual
integral
value
of
20.
The
20
aromatic
hydrogens
appeared
in
a
range
of
6.892-7.221
ppm
which
is
within
its
expected
range.
However,
there
was
a
singlet
at
2.151
ppm
which
is
most
likely
acetone.
While
the
NMR
shows
the
product
is
pure
from
starting
material
or
intermediates,
there
is
an
acetone
impurity.
This
could
be
the
result
of
acetone
left
over
in
the
NMR
tube
or
not
having
fully
evaporated
after
cleaning
glassware.
The
NMR
can
still
support
that
TPCPD
was
properly
purified.
The IR spectrum (figure 4) also helps to determine the purity of the compound as it will absorb
different
types
of
bonds
between
functional
groups
at
different
wavelengths.
In
the
observed
IR
spectrum,
the
C-H
bond
of
the
aromatic
ring
was
absorbed
at
3053.4
cm-1
and
was
within
the
theoretical
range
of
3100-3000
cm-1.
The
C=O
bond
of
the
carbonyl
was
absorbed
at
1704.8
cm-1
and
was
within
its
theoretical
range
of
1760-1665
cm-1.
The
C=C
of
the
aromatic
ring
was
observed
at
a
range
of
1596.1
to
1351.1
cm-1
and
is
close
to
its
theoretical
range
of
1600-1450
cm-1.
Since
the
absorption
frequencies
were
fairly
similar,
this
can
support
that
TPCPD
product
is
pure.
Conclusion
After analyzing the NMR scan and the IR scan, it can be concluded that the TPCPD is pure. Even
though
the
NMR
had
an
acetone
peak,
the
TPCPD
was
still
pure
from
starting
material
and
other
compounds
used
in
the
process
of
synthesis
and
recrystallization.
It
does
indicate
there
was
some
error
in
producing
the
sample
for
the
NMR
like
not
letting
cleaned
glassware
evaporate
the
acetone
completely.
The
melting
point
also
indicates
there
were
some
poor
techniques
in
determining
the
melting
point,
even
though
it
was
close
to
its
melting
range
of
218-220C.5
However,
since
the
percent
yield,
88.4%,
was
a
little
high,
and
percent
recovery,
41.5%,
was
a
little
low,
it
indicates
there
were
some
errors
during
the
synthesis
and
purification
process.
These
errors
include
ethanol
not
being
completely
evaporated
before
weighing
the
crude
TPCPD
and
not
collecting
all
of
the
crystals
after
recrystallization.
In
order
to
improve
this
experiment,
it
is
suggested
that
the
techniques
of
recrystallization,
determining
melting
point
range,
and
filtration
be
practiced.
Signs
of
a
more
complete
synthesis
would
be
a
more
fitted
percent
recovery,
a
higher
percent
yield,
and
a
more
accurate
melting
point
range.
References
1
Zhi, L., Wu, J., Li, J., Stepputat, M., Kolb, U., & Mullen, K. (2005), DielsAlder Reactions of
Fieser, L.F. & Fieser, M. Topics in Organic Chemistry. Reinhold Pub. Corp., New York,1963.