Shannon Gu

TA Patrick Shelton

CHEM 346

12 March 2018

Multi-Step Tetraphenylnaphthalene Synthesis

I. Purpose
The purpose of this lab was to convert benzaldehyde into tetraphenylnaphthalene in four

synthesis steps, to determine the yield of the products at each step, and to characterize each product

using melting points, TLC, 1H NMR, and IR.

II. Experimental Approach

In the first synthesis, 0.049 mol of benzaldehyde was converted to benzoin, in a reaction

catalyzed by thiamine hydrochloride [1]. In the second synthesis, benzoin was converted to benzil

via nitric acid oxidation, and the crude product was recrystallized in ethanol [1]. The third synthesis

involved reacting benzil with dibenzyl ketone under basic conditions to create

tetraphenylcyclopentadienone [1]. Lastly, the fourth synthesis was a Diels-Alder reaction in which

tetraphenylcyclopentadienone, anthranilic acid, and isopentyl nitrite reacted to form

tetraphenylnaphthalene [1]. 152 mg of crude tetraphenylnaphthalene was then recrystallized in

isopropyl alcohol [1]. The yield of each synthesis product was measured, and the products were

characterized using melting points, TLC, 1H NMR, and IR [1].

III. Findings
The first synthesis of benzaldehyde to benzoin yielded a highly impure product with a

percent yield of 71.2%. 3.004 g of stock benzoin was used for the second synthesis and produced

benzil with a percent yield of 85.5%. From there, tetraphenylcyclopentadienone was synthesized

with a percent yield of 85.7%, and crude tetraphenylnaphthalene was synthesized with a percent

yield of 96.0% and recrystallized with a percent yield of 13.6%. The overall yield of

tetraphenylnaphthalene prior to recrystallization was 70.3% and after recrystallization was 9.57%.

Melting points, TLC, 1H NMR, and IR confirmed that each synthesis was carried out successfully.

IV. Data and Analysis

Table 1: Yields of Synthesis Products

Starting
Theoretical Actual Yield
Reactant Amount Product Percent Yield (%)
Yield (g) (g)
(g)
Benzaldehyde 5.194 Benzoin 5.194 3.697 71.2*
Benzoin 3.004 Benzil 2.976 2.543 85.5
Tetraphenyl-
Benzil 2.247 4.070 3.489 85.7
cyclopentadienone
Tetraphenyl- Tetraphenyl-
3.496 3.933 3.775 96.0
cyclopentadienone naphthalene
Crude Recrystallized
tetraphenyl- 0.154 tetraphenyl- 0.154 0.021 13.6
naphthalene naphthalene
Pre-recrystallization:
Overall
70.3
Percent
Post-recrystallization:
Yield (%):
9.57
*The percent yield of benzoin was not considered in the overall yield calculation due to starting
the second synthesis with stock benzoin.
 Calculation of theoretical yield:
1 mol benzoin 212 g
0.049 mol benzaldehyde (2 mol benzaldehyde) (1 mol benzoin) = 5.194 g benzoin
1 mol benzoin 1 mol benzil 210 g
3.004 g benzoin ( )( )( ) = 2.976 g benzil
212 g 1 mol benzoin 1 mol benzil
1 mol benzil 1 mol dienone 384 g
2.247 g benzil ( )( )( ) = 4.070 g tetraphenylcyclopentadienone
210 g 1 mol benzil 1 mol dienone
1 mol dienone 1 mol naph. 433 g
3.496 g dienone ( 384 g
) (1 mol dienone) (1 mol naph.) = 3.933 g tetraphenylnaphthalene

Table 2: Rf Values of Synthesis Products

Product Observed Rf Standard Rf

Benzoin DCM: 0.19 DCM: 0.19
Benzil DCM: 0.76 DCM: 0.8
DCM: 0.93
Tetraphenylcyclopentadienone DCM: 0.93
50/50 hexane/acetone: 0.83
Tetraphenylnaphthalene 50/50 hexane/acetone: 0.92 N/A

Table 3: Melting Points of Synthesis Products

Source for Literature Values: Sigma-Aldrich

Observed Melting Points Literature Value Melting Points

Product
(°C) (°C)
Benzoin 128 - 130 134 - 138
Benzil 85.5 - 88.1 94 - 95
Tetraphenylcyclopentadienone 210.8 - 216.7 217 - 220
Tetraphenylnaphthalene 198.6 - 203.4 199 - 201

Table 4: 1H NMR for Benzoin

Literature
Chemical Shift Integral (# Coupling Constants Spectra
Multiplicity Identity
(ppm) Protons) (Hz) Chemical Shift
(ppm)
0.000 Singlet 2.649 -- TMS --
1.664 Singlet 0.085 -- H2O --
2.163 Singlet 1.150 -- Acetone --
4.582 Doublet 0.828 JGJ = 6 -OH (HG) 6.120
5.957 Doublet 1.000 JJG = 6 HJ 6.090
JBA = 1.2
Aromatic H
JBC = 7.3
7.409 Multiplet 7.975 (HB, HC, HD, 7.242 – 7.560
JCA (ortho) = 7.6
HE, HF)
JCA (para) = 1.6
Doublet of JAB = 2.2 Aromatic H
7.912 2.010 8.024
Triplets JAC = 7 (HA)
 Figure 1: Benzoin

Table 5: IR for Benzoin

Literature Spectra
Wavenumber (cm-1) Identity
Wavenumber (cm-1)
1260.7 Alcohol C-O (stretch) 1263
1448.3 Aromatic C=C (stretch) 1450
1594.5 Aromatic C=C (stretch) 1595
1675.6 Ketone C=O (stretch) 1679
3376.2 O-H (stretch) 3379

Benzoin:
0.049 g of benzaldehyde was mixed with thiamine hydrochloride, ethanol, and NaOH to

produce a yellow solution, which then stood in the dark for four days. After four days, my solution

was the only one in the class to have a crystalline product. While the yield was fairly high (71.2%),

the product was highly impure (Table 1). My product was a light yellow while pure benzoin is

white, and my product also smelled distinctly of almonds which is characteristic of benzaldehyde.

This product was neither recrystallized nor characterized; instead, stock benzoin was used for

characterization. Benzoin’s Rf value was 0.19, the lowest of the four synthesis products (Table 2).

Because benzoin is the most polar of the four synthesis products due to its hydroxyl group, it will

have the highest affinity for the polar silica gel of the TLC and travel the shortest distance.

Benzoin’s melting point was determined to be 128 – 130 °C, which is 4 °C lower than the literature

melting point value (Table 3). Even though stock benzoin should be pure, its melting point suggests
that impurity was present. Stock benzoin may naturally have small quantities of impurities which

could affect the melting point measurements.

Benzoin has eight distinct proton environments. In its 1H NMR spectrum, however, there

were only four distinct signals (Table 4, Appendix Figure 1). The first signal was a doublet with

an integration of 0.828 and a chemical shift of 4.58 ppm; based on the multiplicity and the

integration, this signal is produced by the proton on the hydroxyl group (HG) (Figure 1). It is only

adjacent to one proton—the proton on the same carbon as the hydroxyl group—so based on the

n+1 rule, it is a doublet (Table 4). The literature spectrum, however, places HG at a chemical shift

of 6.120 ppm, and it does not have any signals that are below 6 ppm (Table 4, Appendix Figure

2). The discrepancy between the obtained spectrum and the literature spectrum can be explained

by hydroxyl group protons having variable chemical shifts, ranging anywhere from 2.2-5 ppm [2].

As such, a chemical shift of 4.58 ppm would not be unreasonable for a hydroxyl group proton. The

splitting between HG’s doublet peaks was 6 Hz, and because HG is adjacent to only one proton,

this splitting must correspond to JGJ (Table 4).

The next signal downfield was also a doublet, with an integration of 1.000 and a chemical

shift of 5.96 ppm, and it corresponds to the proton on the same carbon as the hydroxyl group (HJ)

(Table 4). It has a high chemical shift due to its proximity to both the hydroxyl group and the

carbonyl group, which are electron-withdrawing and thus have de-shielding effects (Figure 1).

Since HJ is only adjacent to HG, the coupling constant of HJ’s doublet should equal the coupling

constant of HG’s doublet. As expected, the splitting between HJ’s peaks was 6 Hz, which matches

JGJ (Table 4).

The second-most downfield signal was a multiplet with an integration of 7.975 and

centered at 7.41 ppm (Table 4). Based on literature spectra, this multiplet corresponds to protons
HB, HC, HD, HE, and HF (Table 4, Appendix Figure 2). As these protons are all aromatic, their

signals would have similar chemical shifts and overlap. Within the multiplet, at least two signals

can be discerned: a triplet of triplets on the left side of the multiplet and a doublet of triplets right

next to it (Appendix Figure 2). Based on literature spectra, the triplet of triplets corresponds to HB

due to it being split by the two protons ortho to it (HC) and the two protons meta to it (HA), while

the doublet of triplets corresponds to HC due to it being split by HB and the two HA (Figure 1). The

coupling constants from HB and HC were determined to be JBA = 1.2 Hz, JBC = 7.3 Hz, JCA (ortho)

= 7.6 Hz, and JCA (para) = 1.6 Hz. Ortho protons have coupling constants of 6-9 Hz, meta protons

have coupling constants of 2-3 Hz, and para protons have coupling constants of 0-1 Hz [3]. HB and

HC are ortho to each other, and their coupling constant falls within the 6-9 Hz range (Table 4).

Meanwhile, HB and HA are meta to each other, so their coupling constant is much lower as expected

(Table 4). HC is also ortho to HA, making JCA = 7.6 Hz; however, it also has a smaller coupling

constant of 1.6 Hz, which most likely corresponds to the HA that is para to HC (Table 4, Figure 1).

The peaks in the rest of the multiplet were not clearly identified based on literature spectra, so

coupling constants for HD, HE and HF were not determined.

The last signal in the NMR spectrum was a doublet of triplets with an integration of 2.010

and a chemical shift of 7.91 ppm, corresponding to the aromatic protons H A (Table 4, Figure 1).

HA has the highest chemical shift of the aromatic protons due to its proximity to the carbonyl

group, which has a strong de-shielding effect. In addition, it is a doublet of triplets due to it being

split by the two HC ortho to it as well as the HB meta to it (Figure 1). Its coupling constants were

JAB = 2.2 Hz and JAC = 7 Hz, which support the coupling constants determined from HB’s and HC’s

signals as well as HB’s and HC’s positions relative to HA (Table 4).

 As for benzoin’s IR spectrum, the key peaks were the O-H stretch at 3376.2 cm-1 as well

as the C-O stretch at 1260.7 cm-1, which neither benzaldehyde nor the other synthesis products

have (Table 5). Other important peaks include aromatic C=C stretches at 1448.3 cm -1 and 1594.5

cm-1, and the ketone C=O stretch at 1675.6 cm-1. The literature IR spectrum for benzoin

corroborated the obtained IR spectrum (Table 5).

Table 6: 1H NMR for Benzil

Literature
Chemical Shift Integral (# Coupling Spectra
Multiplicity Identity
(ppm) Protons) Constants (Hz) Chemical Shift
(ppm)
0.000 Singlet 7.678 -- TMS --
7.200 Singlet 0.077 -- CHCl3 --
JBA (ortho) = 7.4
Triplet of H meta to ketone
7.517 3.582 JBC = 7.4 7.502
triplets (HB)
JBA (para) = 1.3
Triplet of JCB = 7.2 H para to ketone
7.670 2.000 7.649
triplets JCA = 1.4 (HC)
Doublet of JAB = 7 H ortho to ketone
7.983 3.738 7.981
triplets JAC = 1.6 (HA)

Figure 2: Benzil

Table 7: IR for Benzil

Literature Spectra
Wavenumber (cm-1) Identity
Wavenumber (cm-1)
1577.9 Aromatic C=C (stretch) 1578
1591.4 Aromatic C=C (stretch) 1595
1656.2 Ketone C=O (stretch) 1658
1675.1 Ketone C=O (stretch) 1679
Benzil:
3.004 g of stock benzoin was reacted with nitric acid to produce benzil, which had an actual

yield of 2.543 g and a percent yield of 85.5% (Table 1). The reaction was monitored with TLC

until the reaction mixture only showed the presence of benzil. The reaction mixture’s benzil had a

Rf of 0.76, while the benzil standard had an Rf of 0.8 (Table 2). Benzil’s Rf is higher than benzoin’s

because benzil is less polar, having another carbonyl in place of the hydroxyl group on benzoin

(Figure 2). After recrystallizing benzil from the reaction mixture, its melting point was determined

to be 85.5 – 88.1 °C (Table 3). This melting point is around 6 °C lower than that of the literature

value, suggesting that the benzil was impure (Table 3). Recrystallization should have removed

most impurities from the benzil in the reaction mixture, so impurities most likely came from

ethanol not being evaporated enough. After drying the benzil crystals for a longer time, however,

the melting point did not increase from the original measurement.

In the 1H NMR spectrum for benzil, three distinct signals were present (Table 6, Appendix

Figure 5). The first signal was a triplet of triplets with an integration of 3.582 and a chemical shift

of 7.52 ppm (Table 6). This signal is from the protons meta to the carbonyl group (HB), with two

on each aromatic ring (Figure 2). HB’s signal is a triplet of triplets, but it was expected to be a

doublet of triplets because HB is split by one HC and two HAs (Figure 2, Table 6). Based on the

splitting between the peaks, HB has coupling constants of 7.4 Hz and 1.3 Hz. Since HB is ortho to

both HA and HC, the 7.4 Hz coupling constant must be JBA (ortho) and JBC (Table 6). HB is also

para to the other HA, so the 1.3 Hz coupling constant must be JBA (para) (Table 6). The second

signal was also a triplet of triplets, and it had an integration of 2.000 and a chemical shift of 7.67

ppm (Table 6). Based on its integration, this signal must come from the two protons para to the

two carbonyl groups (HC) (Table 6, Figure 2). As expected, HC’s signal is a triplet of triplet because

HC is split by two HBs and two HAs (Figure 2). Its coupling constants were 7.2 Hz and 1.4 Hz,
which correspond to JCB and JCA, respectively; JCB’s value corroborated the JBC obtained from HB’s

signal (Table 6). The final signal was a doublet of triplets with an integration of 3.738 and a

chemical shift of 7.98 ppm, corresponding to the protons ortho to the carbonyl groups (HA) (Table

6). HA is a doublet of triplets because it is split by two HB and one HC, and it is the most de-shielded

proton due to its proximity to the carbonyl group (Figure 2). Its coupling constants were

determined to be JAB = 7 Hz and JAC = 1.6 Hz, which support the coupling constants obtained from

HB and HC (Table 6).

The IR spectrum confirmed that the conversion of benzoin to benzil was successful, as it

lacked a O-H peak at around 3300 cm-1 (Appendix Figure 7). Benzil’s most important IR peaks

were the ketone C=O stretches at 1656.2 cm-1 and 1675.1 cm-1 (Table 7). It also contained two

aromatic C=C peaks at 1577.9 cm-1 and 1591.4 cm-1 (Table 7). The literature IR spectrum for

benzil supported the obtained benzil IR spectrum well (Table 7, Appendix Figure 8).

Table 8: 1H NMR for Tetraphenylcyclopentadienone

Literature
Chemical Shift Integral (# Coupling Constants Spectra
Multiplicity Identity
(ppm) Protons) (Hz) Chemical Shift
(ppm)
0.000 Singlet 11.453 -- TMS --
1.560 Singlet 0.318 -- H2O --
2.169 Singlet 2.297 -- Acetone --
Doublet of JCB = 6.4
6.924 3.999 HC 6.923
Triplets JCA = 1.8
JBC (ortho) = 6.4
CHCl3, HA,
7.188 Multiplet 16.893 JBA = 6.4 7.156, 7.230
HB
JBC (para) = 2.4
 Figure 3: Tetraphenylcyclopentadienone

Table 9: IR for Tetraphenylcyclopentadienone

Literature Spectra
Wavenumber (cm-1) Identity
Wavenumber (cm-1)
Peak 1 1596.1 Aromatic C=C (stretch) 1496
Peak 2 1709.8 Ketone C=O (stretch) 1710

Tetraphenylcyclopentadienone:
Of the 2.976 g of benzil produced, 2.247 g was used to synthesize tetraphenyl-

cyclopentadienone (Table 1). The theoretical yield of tetraphenylcyclopentadienone was 4.070 g

while the actual yield was 3.489 g, resulting in a percent yield of 85.7% (Table 1). The reaction

was carried out in a reflux apparatus; at one point the mixture was heated too quickly, causing the

mixture to reflux too vigorously and making the product cover the entire inner surface of the round-

bottom flask. The product was difficult to remove from the flask, and as a result, some product

was lost. However, the yield was more than enough for characterization and carrying out the next

synthesis.

The Rf value for tetraphenylcyclopentadienone was 0.93 (Table 2). This Rf value is much

higher than that of benzil’s and benzoin’s, which is expected given how nonpolar tetraphenyl-

cyclopentadienone is compared to benzil and benzoin; tetraphenylcyclopentadienone has only one

carbonyl group and four phenyl groups (Table 2, Figure 3). The melting point was 210.8 – 216.7

°C (Table 3). While the upper value of the melting point was very close to the literature value, the

range of the melting point was very wide, which may be a result of impurity from unevaporated

ethanol (Table 3).

The 1H NMR spectrum had two signals of interest: a doublet of triplets and a multiplet

(Table 8, Appendix Figure 9). The doublet of triplets has an integration of 3.999 and a chemical

shift of 6.92 ppm, and based on the literature spectrum, it comes from the ortho protons on the two

phenyls closest to the carbonyl (HC) (Table 8, Figure 3). On a monosubstituted ring, protons that

are ortho to the substituent tend to have the highest chemical shifts, but this trend is not observed

here (Table 8). The doublet of triplets yielded coupling constants of 6.4 Hz and 1.8 Hz (Table 8).

According to typical aromatic proton coupling constants [3], the 6.4 Hz must be JCB because HC is

ortho to HB, and the 1.8 Hz must be JCA because HC is meta to HA (Table 8, Figure 3).

Meanwhile, the multiplet has an integration of 16.983 and a chemical shift of 7.19 ppm,

and its large integration indicates that it corresponds to all the remaining protons on the molecule

(HA, HB) (Table 8, Figure 3). Interestingly, the literature spectrum marks all the protons on the two

inner phenyl rings as identical, despite that substitution on aromatic rings produces unequal proton

environments (Figure 3, Appendix Figure 10). The signals may overlap significantly, or resolution

may not be high enough to discern between the protons on those phenyl groups. In addition, the

integration of 16.983 is higher than the expected integration of 16, due to the CHCl 3 signal

overlapping with the multiplet—the tallest peak is at 7.23, which corresponds to CHCl3 (Appendix

Figure 9). Tetraphenylcyclopentadienone’s literature spectrum shows that CHCl3 specifically

overlaps with HA’s signals, making coupling constants difficult to determine (Appendix Figure

10). Coupling constants can, however, be determined from HB’s peaks in the multiplet, which are
upfield from CHCl3’s peak. From HB’s signal, coupling constants were calculated as JBC (ortho) =

JBA = 6.4 Hz, due to HB being ortho to both HC and HA, and JBC (para) = 2.4 Hz (Table 8).

The IR spectrum for tetraphenylcyclopentadienone only contained two prominent peaks

outside of the nujol mull peaks—a ketone C=O stretch at 1709.8 cm-1 and an aromatic C=C stretch

at 1596.1 cm-1 (Table 9, Appendix Figure 11). While the peaks were discernible, they were not

resolved well due to the tetraphenylcyclopentadienone being dilute in the nujol. The literature IR

spectrum’s C=O stretch was at 1710 cm-1, which is very close to my obtained IR spectrum, but it

placed the C=C stretch at 1496 cm-1 (Table 9, Appendix Figure 12).

Table 10: 1H NMR for Tetraphenylnaphthalene

Literature
Integral
Chemical Shift Coupling Spectra
Multiplicity (# Identity
(ppm) Constants (Hz) Chemical Shift
Protons)
(ppm)
0.000 Singlet 131.74 -- TMS --
1.548 Singlet 3.610 -- H2O --
Inner phenyl protons
6.845 Singlet 11.159 -- 7.01
(HF, HG, HH)
CHCl3, outer phenyl
7.244 Multiplet 15.782 JCE = 3.4 7.39
protons (HC, HD, HE)
Doublet of JAB (meta) = 3.4 Aromatic ring outer
7.393 2.060 7.560
doublets JAB (ortho) = 6.6 protons (HA)
JBA (meta) =
Doublet of Aromatic ring inner
7.640 2.000 3.25 7.82
doublets protons (HB)
JBA (ortho) = 6.6

Figure 4: Tetraphenylnaphthalene
 Table 11: IR for Tetraphenylnaphthalene
Literature Spectra
Wavenumber (cm-1) Identity
Wavenumber (cm-1)
1442.8 Aromatic C=C (stretch) 1463.4
1493.9 Aromatic C=C (stretch) 1463.4
2852.7 Aromatic C-H (stretch) 2957.3
2923.0 Aromatic C-H (stretch) 2957.3

Tetraphenylnaphthalene:

In the final synthesis, 3.496 g of tetraphenylcyclopentadienone reacted with 1.1 molar

equivalent of anthranilic acid and 3.3 molar equivalents of isopentyl nitrite to produce 3.775 g of

tetraphenylnaphthalene, a percent yield of 96.0%. The lab manual originally called for 1.5 moles

of isopentyl nitrite per mole of anthranilic acid [1]; however, after adding the first 1.5 moles and

refluxing for 15 minutes, the reaction did not turn orange as expected. To speed up the reaction,

another equivalent of isopentyl nitrite was added, and the reaction mixture began to turn orange.

After isolating the crude solid, 42 mg was used for recrystallization in 25 mL of isopropyl alcohol.

Crystals did not form after twenty minutes of the solution being at room temperature, and only

began to form after evaporating the isopropyl alcohol with an air stream. To ensure that enough

product was obtained, another 112 mg of tetraphenylnaphthalene was recrystallized. The percent

yield of recovery from both recrystallizations was only 13.6% (Table 1). Considering how slow

recrystallization was, recovery would have been improved if there were more time to allow crystals

to form, and if less solvent were used to dissolve the tetraphenylnaphthalene. The recrystallization

brought down the overall yield of the multi-step synthesis considerably: the overall yield of the

crude tetraphenylnaphthalene was 70.3%, but the overall yield of recrystallized tetraphenyl-

naphthalene was only 9.57% (Table 1).

Due to tetraphenylnaphthalene being highly nonpolar, a solvent of 50/50 hexane/acetone

was used for TLC instead of DCM. There was no tetraphenylnaphthalene standard, so the
recrystallized product was compared to tetraphenylcyclopentadienone. Tetraphenylnaphthalene

yielded an Rf value of 0.92, while tetraphenylcyclopentadienone had an Rf value of 0.83 (Table 2).

As expected, tetraphenylnaphthalene’s Rf value is higher than that of tetraphenyl-

cyclopentadienone, as tetraphenylnaphthalene lacks highly electronegative atoms and is thus more

nonpolar. As a result, tetraphenylnaphthalene has a higher affinity for the mobile phase of the TLC

and will travel further up the plate. The melting point of tetraphenylnaphthalene was 198.6 – 203.4

°C, which overlaps with the literature value of 199 – 201 °C (Table 3). While the lower and upper

values for the melting point are very close to the literature values, suggesting high purity, the range

of the melting point is also wide, suggesting some impurity. A different explanation for the wide

range is that the temperature readings were increasing very quickly at the time the product began

to melt, and thus the readings are not fully representative of the product’s true melting point.

Tetraphenylnaphthalene is expected to contain eight signals in its 1H NMR spectrum, as it

contains eight distinct proton environments [1]. However, only four signals were observed (Table

10, Appendix Figure 13). The most upfield signal is a singlet with an integration of 11.159 and a

chemical shift of 6.84 ppm, and it corresponds to all the protons on the two inner phenyl groups

(HF, HG, HH) (Table 10, Figure 4). These protons have the lowest chemical shift because they are

the furthest away from the central aromatic ring (Figure 4). The signal is a singlet, which suggests

that the 10 protons comprising it are identical, but the resolution may be too low to distinguish

more complicated splitting patterns (Table 10). As a result, coupling constants could not be

determined for those protons (Table 10).

The protons on the outer phenyl groups (HC, HD, HE) comprise the next signal, a multiplet

with an integration of 15.782 and a chemical shift of 7.24 ppm (Figure 4, Table 10). The integration

of 15.782 is significantly higher than the integration of 10 because the signal for CHCl3 overlaps
with the phenyl protons’ signal; a large peak corresponding to CHCl3 can be seen at 7.23 ppm

(Appendix Figure 13). Aside from the CHCl3 peak, only two other peaks are visible, and the

splitting between them is 3.4 Hz (Table 10). Given that a coupling constant around 2-3 Hz is

characteristic of meta protons, the 3.4 Hz likely corresponds to JCE (Table 10). Once again, due to

low resolution, more complex splitting patterns were not observed.

The final two signals are both doublet of doublets (Table 10). The upfield doublet of

doublets has an integration of 2.060 and a chemical shift of 7.39 ppm, and it corresponds to the

outer protons on the central aromatic ring (HA) (Table 10, Figure 4). The downfield doublet of

doublets has an integration of 2.000 and a chemical shift of 7.64 ppm, and it corresponds to the

more de-shielded inner protons on the central aromatic ring (HB) (Table 10, Figure 4). The two HA

and two HB are adjacent to each other, so based on the n+1 rule, the expected splitting pattern

would be a triplet for both HA and HB. They are doublets of doublets, however, suggesting that

each HA is split by the HB ortho to it, then by the HB meta to it (Figure 4). The coupling constants

derived from HA’s signal were JAB (meta) = 3.4 Hz and JAB (ortho) = 6.6 Hz, and the coupling

constants from HB’s signal are expected to be very close to that; indeed, the coupling constants

from HB were JBA (meta) = 3.25 Hz and JBA (ortho) = 6.6 Hz (Table 10).

On an IR spectrum, a successful synthesis of tetraphenylnaphthalene would be represented

by a lack of a ketone C=O stretch between 1750 cm-1 and 1650 cm-1. Indeed, the obtained IR

spectrum for tetraphenylnaphthalene demonstrated no such C=O stretch (Table 11, Appendix

Figure 15). The main peaks in tetraphenylnaphthalene were from the aromatic C-H stretches at

2852.7 cm-1 and 2923.0 cm-1, as well as the aromatic C=C stretches at 1442.8 cm-1 and 1493.9 cm-
1
(Table 11). The literature spectrum places the C-H stretch at 2957.3 cm-1 and the C=C stretch at

1463.4 cm-1, which does not align well with my obtained spectrum (Table 11, Appendix Figure
16). The differences in peaks may be due to the differences in the solvents used; the literature

spectrum appears to use nujol mull, while my spectrum used DCM. Regardless, the key peaks of

tetraphenylnaphthalene can be observed in both spectra (Appendix Figure 15, Appendix Figure

16).

Conclusion:

In the first synthesis, 0.049 mol of benzaldehyde was converted to benzoin; however, the

conversion was unsuccessful due to large amounts of unreacted benzaldehyde. 3.004 g of stock

benzoin was used to initiate the second synthesis, which produced benzil with a percent yield of

85.5%. In the third synthesis, benzil was converted to tetraphenylcyclopentadienone and had a

percent yield of 85.7%. In the fourth and final synthesis, tetraphenylcyclopentadienone was

converted to crude tetraphenylnaphthalene, which was then recrystallized. The crude

tetraphenylnaphthalene had a percent yield of 96.0%, but the recrystallized tetraphenylnaphthalene

had a percent yield of only 13.6%. Thus, the overall percent yield of recrystallized

tetraphenylnaphthalene was 0.855*0.857*0.96*0.136 = 9.57%.

TLC and IR confirmed that each synthesis was performed correctly, with TLC showing

that the synthesis products became increasingly nonpolar and IR showing the loss or gain of key

functional groups between each synthesis product. Melting point measurements determined the

purity of each product; each product apart from tetraphenylnaphthalene demonstrated some degree

of impurity. Lastly, 1H NMR was a means to further characterize each product and confirm the

completion of each synthesis step.

 Sources

[1] Chemistry 346 Lab Manual. (2018).

[2] Overview of Chemical Shifts in H-NMR. (n.d.). Retrieved March 8, 2018, from
http://www2.ups.edu/faculty/hanson/Spectroscopy/NMR/HNMRshift.htm
[3] NMR Aromatic Proton Coupling. (n.d.). Retrieved March 1, 2018, from
http://www.sas.upenn.edu/~genette/NMRcoupling.pdf
Appendix Figure 1: Obtained 1H NMR Spectrum for Benzoin
Appendix Figure 2: Literature 1H NMR Spectrum for Benzoin
Source: Spectral Database for Organic Compounds
Appendix Figure 3: Obtained IR Spectrum for Benzoin
Source: Ethan Knight, CHEM 346 AB
Appendix Figure 4: Literature IR Spectrum for Benzoin
Source: Spectral Database for Organic Compounds
Appendix Figure 5: Obtained 1H NMR for Benzil
 Appendix Figure 6: Literature 1H NMR Spectrum for Benzil
Source: Gazi, S. & Ananthakrishnan, R. (2012). Bromodimethylsulfonium bromide (BDMS) as a
Potential Candidate for Photocatalytic Selective Oxidation of Benzylic Alcohols Using Oxygen
and Visible Light. The Royal Society of Chemistry, 2, 7781-7787. doi: 10.1039/C2RA20553J
Appendix Figure 7: Obtained IR Spectrum for Benzil
 Appendix Figure 8: Literature IR for Benzil
Source: Spectral Database for Organic Compounds
Appendix Figure 9: Obtained 1H NMR for Tetraphenylcyclopentadienone
Appendix Figure 10: Literature 1H NMR for Tetraphenylcyclopentadienone
Source: Spectral Database for Organic Compounds
Appendix Figure 11: Obtained IR Spectrum for Tetraphenylcyclopentadienone
Appendix Figure 12: Literature IR Spectrum for Tetraphenylcyclopentadienone
Source: Spectral Database for Organic Compounds
Appendix Figure 13: Obtained 1H NMR Spectrum for Tetraphenylnaphthalene
 Appendix Figure 14: Literature 1H Spectrum for Tetraphenylnaphthalene
Source: Cant, A., Roberts, L., & Greaney, M.F. (2010). Generation of benzyne from benzoic acid
using C–H activation. The Royal Society of Chemistry, 46, 8671-8673. doi:
10.1039/C0CC02547J
Appendix Figure 15: Obtained IR Spectrum for Tetraphenylnaphthalene
 Appendix Figure 16: Literature IR Spectrum for Tetraphenylnaphthalene
Source: Shashidher, B., Bajjuri, R., & Guguloath, V. (2011). Formation and Trapping of
Benzyne. Pharmaceutica Analytica Acta, 02(07). doi:10.4172/2153-2435.1000137