Kenta Sueyoshi

3/17/14
CHEM 346 AA
LAB 8
Multi-step Tetraphenylnapthalene Synthesis
Purpose:
In this lab, four steps were
taken to produce
tetraphenylnapthalene from
benzaldehyde. This was the first
lab in which multiple steps were
taken to produce the final product,
which emphasizes the importance
of a high yield of purified
compound in each step. To make
sure the right compound was
obtained in each step, melting point,
1

H NMR, IR, and Rf values were taken.

Figure 1: The steps taken to produce tetraphenylnapthalene from

benzaldehyde is shown above

Description of Experimental Approach:

In the first step, 5 mL of benzaldehyde was mixed and heated in a water bath under reflux
with thiamine hydrochloride, ethanol, and NaOH, then recrystallized with ethanol to theoretically
produce 10.400 g of benzoin. Using 5 mL of benzaldehyde would also give a theoretical yield of
21.6275 g of tetraphenylnapthalene. In the second step, 1.000 g of benzoin produced in the first

step was mixed with glacial acid and nitric acid to be heated on a steam bath, then mixed with
water in a flask to produce the yellow benzil crude, which was then recrystallized with ethanol to
produce a theoretical amount of 0.991 g. 0.300 g of benzil was mixed with dibenzyl ketone and
ethanol, and heated under reflux with a water bath in step three. The solution was then mixed
with KOH and ethanol and cooled in an ice water bath after 15 minutes of running under reflux
to produce 0.549 g of tetraphenylcyclopentadienone. In the final step, 0.200 g of the
tetraphenylcyclopentadienone was reacted with DME, anthranilic acid, and isopentyl nitrite
under reflux to create a yellow-orange solution. This solution was mixed with water and
methanol precipitating out a solid, which was then recrystallized with 2-propanol to produce
0.225 g of the final product, tetraphenylnapthalene.
Summary of Findings:
Overall, the four steps were a success, and 0.124 g of tetraphenylnapthalene was obtained,
giving a 0.57% yield. The first step gave a 20.90% yield with 2.174 g of benzoin. It was seen that
benzoin was produced because the IR spectrum showed an OH peak that benzaldehyde would
not have. In the second step, 0.544 g of benzyl was produced, giving a 55.03% yield. The
transformation was visible because the OH peak in the IR spectrum had disappeared, while the
C=O peak remained. 0.434 g, or a 79.05% yield of tetraphenylcyclopentadienone was produced
in the third step, which was confirmed from the sum of the integral values in the 1H NMR
spectra of tetrapehnylcyclopentadienone. The change in the integral values and peaks in the 1H
NMR spectrum confirmed the final steps reaction. Ultimately, 0.124 g of the final product was
obtained, giving a 55.11% yield for the last step.

Data and Analysis:

Benzoin

Benzil

Tetraphenylcyclopentadienone Tetraphenylnapthalene

Mass (g)

2.174

0.544

0.434

0.124

Yield (%)

20.90

55.03

79.05

55.11

M.P. (oC)

129.2-131.8

93.3-94.7

218.8-220.4

201.2-203.4

Rf value

0.69

0.76

0.88

0.96

Table 1: Listed is the mass, percent yield, melting point, and Rf values of each of the products from each step

Peaks (cm-1)
1400-1300
1500-1400
2800-2700
3000-2900
3400-3300

Benzoin
Strong
Strong
Weak
Strong
Strong

Benzil
Strong
Strong
Strong
Strong
No

Table 2: The peaks from the IR spectrum are listed and assigned

Dienone
Strong
Strong
Strong
Strong
No

Integral Value
0.23
0.43
0.88
1.00
6.45
1.01

Napthalene
Strong
Strong
Very weak
Strong
No

Assignment
Mineral Oil
Mineral Oil
Carbonyl
Mineral Oil
Alcohol

Chemical Shift (ppm)

1.240
1.603
4.548
5.943
7.259
7.322
7.525

Multiplicity
4
1
2
2
1
12
9

Assignment
Impurity
CH next to alcohol
Para on benzene ring
Para on benzene ring
CHCl3 impurity
Ortho and Meta on benzene rings
Alcohol

Chemical Shift (ppm)

1.586
7.516
7.670
7.974

Multiplicity
1
8
9
6

Integral Value
0.17
2.03
1.00
1.87

Assignment
Water impurity
Meta on benzene ring
Para on benzene ring
Ortho on benzene ring

Chemical Shift (ppm)

6.918
7.168
7.233

Multiplicity
6
4
4

Integral Value
1.00
0.79
3.56

Assignment
Meta on phenyl
Para on phenyl
Ortho on phenyl

Table 3: The peaks and their characteristics from Benzoin's NMR spectrum is listed above.

Table 4: The peaks and their characteristics from Benzil's NMR spectrum is listed above.

Table 5: The peaks and their characteristics from Tetraphenylcyclopentadienone's NMR spectrum is listed above.

Chemical Shift (ppm)

1.546
6.846
7.226
7.260
7.418
7.671

Multiplicity
1
1
3
1
4
4

Integral Value
0.58
1.00
1.50
0.20
0.28
0.26

Assignment
Water impurity
Ortho on phenyls
Meta and Para on phenyls
CHCl3 impurity
Napthalene H
Napthalene H

Table 6: The peaks and their characteristics from Tetraphenylnapthalene's NMR spectrum is listed above.

When converting the starting material, benzaldehyde to benzoin in the first step, 2.174 g

or a 20.90% yield was recovered. Based on the melting point, the measured 129.2-131.8 oC is
very similar to the literature value of 132 oC with a small range, so the benzoin was purified well.
Based on the IR spectrum, the product had a strong OH peak around 3400cm -1, which it should
have. It also had a weak carbonyl peak around 2800cm-1, which it also should have, so both
functional groups were spotted. Looking at the 1H NMR spectrum, the integral values give a sum
of about 24, with a ratio of 1:2.5:2.5:2.5:16.25:2.5, which is twice the amount of hydrogen atoms
in benzoin. Each of the peaks was assigned protons as listed in Table 3.
In the second step, benzoin was converted into benzil, which has a literature melting
point of 94-96 oC, and was measured to have a melting point of 93.3-94.7 oC. The melting point
clearly overlapped the literature value, and had a small range of 1.4 oC, so it could be assumed
from the melting point that the conversion was successful, and that the purification step was also
well done. However, since only 0.544 g, or a 55.03% yield was obtained, the efficiency of the
conversion was not very good. Looking at the IR spectrum, the benzil spectra lost the alcohol
peak that the benzoin had, but the carbonyl peak became stronger like it should have. From this,
it can also be concluded that the conversion from benzoin to benzil was successful. In the NMR
spectrum of benzil, there are only three large peaks because the hydrogen atoms on the left
benzene ring and the hydrogen atoms on the right benzene ring are equivalent. The sum of the
integrals also add up to about 5, which accounts for one of the benzene rings. The peak at 7.670

ppm represents the hydrogen on the opposite side of the methylene group because there is only
one on each benzene ring, and the integral value is half of the others. The peak at 7.974 ppm
represents the hydrogen closest to the carbonyl bond because the electronegativity of the oxygen
in the carbonyl group will make the chemical shift of the hydrogen higher than it should be. The
last one left is the peak at 7.516 ppm, which represents hydrogen in the middle of the other two.
This can be determined other than elimination by the fact that the multiplicity is larger than the
other two peaks. Since the middle hydrogen will couple with the two around it, it will have a
larger multiplicity than the other two hydrogen atoms. There was an extra peak at 1.586ppm with
an integral value of only 0.17, so it was concluded that it was an impurity of water. This
probably occurred because the product wasnt dried sufficiently before the NMR spectrum was
taken.
Benzil was then reacted to produce tetraphenylcyclopentadienone in the third step. The
yield for this step was 0.434 g, or 79.05%, which is a very high yield compared to the steps. The
purity of the product was also very good, seeing that the literature value melting point is 219-220
C, and the measured melting point was 218.8-220.4 oC. The measured melting point clearly

overlapped the literature value, and even had a small range of 1.6 oC. For this step, it is hard to
tell by the IR spectrum if the reaction occurred because both the benzil and
tetraphenylcyclopentadienone only has a carbonyl group and benzene rings. The functional
groups in both molecules are the same, so it makes sense that the IR spectra of the two
compounds are very similar. However, the NMR spectra are different because the number of
hydrogen atoms and the symmetry of the molecule changed. In the NMR spectrum of
tetraphenylcyclopentadienone, the integral values of the peaks add up to 6, which represent the
number of different hydrogen atoms on the molecule. The peak at 7.168 ppm can be determined

to be the hydrogen farthest away from the cyclopentene from the same logic used for the peak in
benzil. Since there are the least number of hydrogen atoms on the opposite side of the benzene
ring compared to the others, this hydrogen should have the smallest integral value at its peak.
The peak with the smallest integral value in this case would be the peak at 7.168 ppm. Next, the
peak at 6.918 ppm should represent the hydrogen in between the other two hydrogen atoms
because it has the largest multiplicity. From process of elimination, the peak at 7.233 ppm must
represent the hydrogen closest to the 5-membered ring. Just like one of the hydrogen atoms on
benzil, the chemical shift of this hydrogen is higher than the others because the electronegativity
of the oxygen atom de-shields the hydrogen. This also happens to the meta-hydrogen but in the
opposite manner. Instead of making the chemical shift higher, it makes the chemical shift lower
than the others. This fits with the chemical shift of each of the hydrogen atoms. Since there are
three different hydrogen atoms on a phenyl, and there are two different phenyls in this molecule,
there should be six different peaks to represent the six different hydrogen atoms. However, this
isnt seen, and instead, the integral value of the peak at 7.233 ppm is larger than it should be. The
ratios should be 1:2:2, because thats the ratio in which they appear in the molecule. This
difference in integral value could have been caused because the integral of the CHCl 3 peak is
included in the integral value. However, it doesnt make sense for the impurity to have an
integral of about 2. Another possible cause of the large integral peak could be because the
oxygen atom has very little affect on the hydrogen atoms on the phenyl farther away from the
oxygen. If the oxygen has very little shielding effect, and the hydrogen atoms originally have a
chemical shift near 7.233 ppm, it could have overlapped and made it seem like there was only
one peak with a multiplicity of 4.

The last step was the synthesis of tetraphenylnapthalene from

tetraphenylcyclopentadienone. Based on the melting point of 201.2-203.4 oC and the small range
of 2.2 oC, the 0.124 g, or 55.11% yield was successfully produced and purified. Looking at the IR
spectrum, the carbonyl peak that the last three compounds had is now gone, which means that
tetraphenylnapthalene was produced successfully. The product doesnt have any functional
groups except C=C, it makes sense that no other peaks in the IR spectrum are present. The NMR
spectrum is very similar to that of tetraphenylcyclopentadienone because the only difference is
that there was a benzene ring attached, and the oxygen atom is lost. The symmetry is still kept,
so the final product has eight distinct hydrogen atoms. Starting with the peak at 6.846 ppm and
an integral value of 1.00, this peak can be assumed to be the ortho hydrogen atoms. This is
because the other large peak at 7.226 ppm has an integral value of 1.50, which is 1.5 times that
of the 6.846 ppm peak. This means that there are 1.5 times more hydrogen atoms represented in
the 7.226 ppm than there is in the 6.846 ppm peak. The only hydrogen atom that is half in
abundance as another hydrogen atom is the para hydrogen atom on the phenyls. It was concluded
that the other hydrogen represented in the 7.226 ppm is the meta hydrogen because it would have
a more similar chemical shift to the para hydrogen than the ortho hydrogen would. The two
peaks at 7.418 ppm and 7.671 ppm were determined to be the two hydrogen atoms on the
naphthalene because they are the least abundant hydrogen atoms in the molecule, which fits with
the small integral value of 0.26 and 0.28. The large multiplicity created by the two hydrogen
atoms could be a cause of the neighboring hydrogen atoms, and possibly because the hydrogen
atoms on the other side of the naphthalene are electromagnetically different. The first impurity
peak at 1.546 ppm was determined to be the cause of water. Water may have been in the sample

when the NMR spectrum was taken because the product wasnt dried enough. The second
impurity peak at 7.260 ppm would be the solvent, or CDCl 3 peak.
Lastly, the Rf values that were measured for each of the products in each step makes
sense because as the compound becomes more like tetraphenylnapthalene, it becomes less polar,
making the Rf value increase. The first product, benzoin, has the smallest R f value of 0.69
because it has an OH group, making it very polar. Next, benzil has a larger R f value because it
loses the OH group to a carbonyl, which is less polar. OH is more polar than a carbonyl because
it can have hydrogen bonding. The third product, tetraphenylcyclopentadienone, has even a
larger Rf value because it loses one of the carbonyls and adds more phenyl groups, making the
polarity of the molecule delocalized. The final product, tetraphenylnapthalene has the largest R f
value, because along with losing the carbonyl group, it doesnt have any sites to be polar, and the
molecule is aromatic, making the Rf value very close to 1.