Organic Chemistry Lab Report 13: Multistep Synthesis of Hexaphenylbenzene

April 22, 2014

Purpose/ Reactions:

The purpose of this step was to perform the multistep parallel synthesis of
Hexaphenylbenzene. We began with the synthesis of meso-dibromostilbene and
then produced diphenylacetylene. We also synthesized
tetraphenylcyclopentadienone, which we reacted with the diphenylacetylene to
produce the Hexaphenylbenzene.
















Results:

1. YIELDS
a. Synthesis of meso-Stilbene Dibromide
i. Final mass: 3.05 g
ii. Starting materials: 1.0 g trans-stilbene , 2.0 g pyridinium
tribomide
1. 1.0g/180.25 = 0.0055 mol ; 2.0 g/319.82 = 0.0063 mol
2. 0.0055 mol trans-stilbene is limiting reagent
3. 0.0055 mol trans-stilbene * (1 mol meso-Stilbene
Dibromide/ 1 mol trans-stilbene) * (340.05 g/ 1 mol
meso-Stilbene Dibromide) = 1.89 g meso-Stilbene
Dibromide theoretical yield
4. Yield = (3.05 g)/(1.89)*100 = 161.4% yield
b. Synthesis of diphenylacetylene
i. Final mass: 1.3 g
ii. Starting Material: 3.05 g meso-Stilbene Dibromide; KOH
1. 3.05 g meso-Stilbene Dibromide * (1 mol/ 340.05 g
meso-Stilbene Dibromide) = 0.0090 mol meso-Stilbene
Dibromide is limiting reagent
2. 0.0090 mol meso-Stilbene Dibromide * (1 mol
diphenylacetylene/ 1mol meso-Stilbene Dibromide) *
(178.23 g/ mol) = 1.60 g diphenylacetylene theoretical
yield
3. Yield = (1.3 g)/(1.6 g)*100 = 81.3% yield
c. Synthesis of tetraphenylcyclopentadienone
i. Final mass: 0.15 g
ii. Starting materials: 200 mg 1,3-diphenylacetone; 200 mg
benzil; 200 L benzyltrimethylammonium hydroxide
1. 0.2 g 1,3-diphenylacetone/ 210.27 = 9.512E-4 mol; 0.2 g
benzil/ 210.23 = 0.9513E-4 so the 1,3-diphenylacetone
is the limiting reagent but not by much
2. (0.9512E-4 mol 1,3-diphenylacetone) * (1 mol
tetraphenylcyclopentadienone/ 1mol 1,3-
diphenylacetone) * (384.47 g/mol) = 0.65 g
tetraphenylcyclopentadienone theoretical yield
3. Yield = (0.15 g)/(0.65 g)*100 = 23.1% yield



2. OVERALL YIELD
a. With a 23.1% yield, tetraphenylcyclopentadienone was the limiting
reagent for the overall reaction.
i. 0.15 g tetraphenylcyclopentadienone * (1 mol/ 384.47 g) =
3.90E-4 mol tetraphenylcyclopentadienone ; 1.3 g
diphenylacetylene * (1 mol /178.23 g) = 0.0073 mol
ii. 3.90E-4 mol tetraphenylcyclopentadienone is the limiting
reagent
iii. 3.90E-4 * (1 mol hexaphenylbenzene/ 1mol
tetraphenylcyclopentadienone) * (534.69 g/ mol
hexaphenylbenzene) = 0.21 g hexaphenylbenzene
iv. Yield = (0.13 g)/(0.21 g)*100 = 62.0% yield
hexaphenylbenzene

3. IR SPECTRA
a. tetraphenylcyclopentadienone
i. I had key peaks at 3054 cm
-1
and 2986 cm
-1
representing the
aromatic C-H bonds, 1265 cm
-1
representing the C-O double
bond of the ketone carbonyl, and 738 cm
-1
representing the C-C
bonds of the phenyl groups. These all fall in accordance with
the literature values for each of these respective bonds.
b. hexaphenylbenzene
i. I had key peaks at 3054 cm
-1
representing the C-H bonds in the
aromatic phenyls, 2963 cm
-1
representing the weak overtones,
1700 cm
-1
, 1670 cm
-1
, and 1595 cm
-1
representing the C-C
bonds in the aromatics and 693 cm
-1
representing the aromatic
C-H bonds.


Discussion:

1. PURITY
a. meso-Stilbene Dibromide
i. The literature value melting point for this molecule is 241C
and my recorded melting point range was 234C-236C,
indicating a very pure product. In addition, the literature
describes the appearance of his compound as a white power,
which I also recorded.
b. tetraphenylcyclopentadienone
i. The literature value melting point for this molecule is 219C-
220C and I recorded a melting point range of 216.8C-
219.3C. The literature describes
tetraphenylcyclopentadienone as a dark purple crystalline
solid. I had similar observations as I described the compound
as a dark purple crystalline solid. Therefore, my product was
also very pure.
c. diphenylacetylene
i. The literature value melting point for this molecule is 62.5C
and I recorded a melting point range of 59.5C-62C. The
literature describes diphenylacetylene as a clear crystalline
solid. I had similar observations as I described the compound
as a clear, crystal-structured solid. Therefore, my product for
diphenylacetylene was pure.
2. The key difference between the tetraphenylcyclopentadienone and the
hexaphenylbenzene should be the absence of the carbonyl (ketone) peak in
the latter molecule. Upon the addition of diphenylacetylene and heat,
tetraphenylpentadienone will lose a Carbon and Oxygen atom and will form
the hexaphenylbenzene, which itself is compromised of only the phenyl
groups surrounding a benzene ring. My IR spectra show this analysis to be
true as I observed a peak at 1265 cm
-1
representing the C-O double bond of
the ketone carbonyl in the tetraphenylcyclopentadienone and no peak at this
value for the hexaphenylbenzene. A lack of the carbonyl group illustrates the
success of this reaction because it shows that the ketone was removed
completely.
3. All the melting points in this synthesis are relatively high (the melting point
of the meso-stilbene dibromide is around 240C) so activation energy for the
reaction must be reached for the reaction to commence specifically, in the
synthesis of the hexaphenylbenzene, all of the diphenylacetylene and the
tetraphenylcyclopentadienone need to react for a good yield since we are
already in parallel synthesis and will only get a 73% yield. Therefore, the
temperature needs to be above 260C so that the activation energy of the
individual components is reached and they can react to form
hexaphenylbenzene. Furthermore, both the reagents in the synthesis of the
hexaphenylbenzene are solids so there would need to be a high temperature
to get the two substances to dissolve and to mix together to react.
4. The cyclopentadienone is itself very unstable but when the four phenyl
groups are added to it, they serve to protect the carbonyl core from any
external reagents and reactants. The phenyl groups repulse each other so
that they spread around the carbonyl group at four of the five Carbons on the
cyclopentadienone and therefore, due to their large size relative to the
carbonyl, sterically prevent other reactants from approaching the oxygen.
5. You can test the hexaphenylbenzene for optical rotation and see if it
illustrates both R and S characteristics. If the optical rotation shows zero
degree rotation than the mixture is racemic since the R and S cancel each
other out.
6.