Mikey Zhitnitsky6BL, Alex LillExperiment 17B Lab Report (Part 1) Overall, this lab

is the first part in a four step synthesis to create hexaphenylbenzene. The first
step includes the formation of stilbene from benzaldehyde and diethyl-
benzylphosphonate, with parts 2 and 3 creating diphenylacetlene and benzil,
respectively. These parts are then combined as the intermediates to create the
final product in part 4: hexaphenylbenzene. Specifically, part 1 results in the
creation of stilbene from Horner-Wadsworth-Emmons addition of a benzaldehyde.
The mechanism first begins with aqueous NaOH pulling of a hydrogen and
creating the carbanion intermediate in addition to a negatively charged oxygen (in
the diethyl-benzylphosphonate molecule of the nonpolar phase) (Discussion Question
3). Next, the oxygen�s electrons reform the double bond, initiating the
nucleophilic attack of the carbonyl carbon of the benzaldehyde. The newly formed
negatively charged oxygen from the benzaldehyde then attacks the phosphorus group
to form a highly strained 4-membered heterocyclic ring. Once the bonds rearrange to
release the phosphonate molecule, the E isomer of stilbene is formed. The Z isomer
is much less common because if both benzene groups were near each other, steric
hindrance would cause the molecule to be extremely strained (unfavorable). For
the experiment, benzaldehyde, Aliquat 336, diethyl benzylphosphonate, hexanes, and
NaOH were added to a vial. This mixture was heated and stirred vigorously for an
hour. The hexane solvent was used to dissolve the solid phosphonate and
benzaldehyde compounds, but the NaOH is not soluble in the nonpolar solution and
thus, will not be able to form the carbanion intermediate. However, the addition of
Aliquat 336, a phase transfer catalyst, will be able to catalyze the movement of
hydroxide into the organic layer through its positively charged nitrogen and long
aliphatic side chains. This process repeats to allow more phosphate to be exchanged
for hydroxide ions. Additionally, the reason for vigorous stirring is because it
maintains homogeneity and allows Aliquat 336 to diffuse quickly across the hexane
and the polar layers (Discussion Question 1). In order to check the progress of the
reaction, a TLC analysis was taken and examined for the absence of the starting
material, benzaldehyde, and the presence of the product, stilbene through the
various Rf values. Next, the vial was cooled and ether was added to separate
the layers into an organic and aqueous layer. Here the organic layer consists of
hexanes and ether, while the aqueous layer consists of NaOH. In order to continue
the extraction, the organic layer was washed with water and brine. This allows
impurities such as benzylphosphonate (another starting material) to be pulled into
the aqueous layer and taken out by a pipette. After the solution is dried with
Na2SO4 and filtered through a cotton plus, the E isomer of stilbene is finally
created. The cis isomer of other compounds is usually more polar, allowing a higher
melting point and a more solid crystalline structure. However, cis-stilbene is a
liquid because pi-pi stacking forces, which occur when aromatic rings are planar,
do not occur in the slightly twisted cis isomer. Thus, the trans-isomer of stilbene
can successfully stack and form a more solid crystalline structure (Discussion
Question 2). The results of the spectroscopy showed that the IR had peaks at
3090cm-1, 1720cm-1, and 750cm-1. These peaks are indicative of bonds such as sp2 C-
H, C=C, and C-H bending. The HNMR showed a 2H singlet, 2H triplet, 4H doublet, and
4H triplet, with the CNMR showing 5 different carbons. Overall the experiment
had a yield of 11%, proving some errors had occurred. For example, if the reaction
had not yet gone to completion or if some product become caught in the filter or
cotton plugged pipette, then both the percent yield and spectroscopy of the product
would be skewed. Experiment 18B (Part 2) In the second step of the 4-part lab,
stilbene, the product of part 1, was made into dibromide, and finally, into
diphenylacetylene. Here, we use retrosynthesis (converting the molecule into a more
simple structure), convergent synthesis, and linear synthesis to show how percent
yield can be increased in multistep reactions. When a compound is made through
linear synthesis (assuming a yield of 90% each time), there is a 59% yield overall.
However, when a compound is made through convergent synthesis, where two products
are brought together to form a new one, there is a 72% overall yield. This proves
that a convergent synthesis, the pathway we are using to create hexaphenylbenzene,
is much more efficient to getting more yield of the same compound. If in a
convergent synthesis scheme, one product yield was only 25% and the rest were 90%,
the total yield would be 20%, not 72% (Discussion Question 1). The mechanism to
create diphenylacetylene is initiated by nucleophilic attack of a bromine group (in
pyridinium perbromide) by the central double bond in stilbene (Sn2 reaction). This
allows the formation of a positively charged bromonium ion. Next, a second bromine
attacks one of the two central carbons of stilbene to neutralize the positively
charged bromine and finally form the dibromide molecule. After, two E2 elimination
reactions with KOH result in diphenylacetylene, because the hydroxide pulls off
each central hydrogen and allows bromine to act as a good leaving group, forming a
double, then triple bond. For the experiment, E-stilbene and acetic acid were
added and refluxed until a homogenous solution formed. Next, pyridinium perbromide
was added and the solution was refluxed again for 10 more minutes. Pyridinium
perbromide is used instead of liquid bromine because of bromine�s toxic qualities,
such as its ability to quickly cause burns. Thus, pyridinium perbromide delivers
the 1 equivalent of bromine needed without its deleterious effects (Discussion
Question 3). After dibromide is formed and filtered, triethylene glycol is
added, along with 85% potassium hydroxide. This mixture is then heated for 10 more
minutes at 160-170�C. Here, triethylene glycol is used as a solvent with a high
boiling point. This type of solvent is needed because dibromide�s Newman projection
shows the phenyl groups next to each other, a very sterically unfavorable position
that requires a high temperature. Thus, traditional solvents such as hexanes or
ethers will no be suitable, as their boiling points are too low and will evaporate
before refluxing (Discussion Question 2). After filtering the crystals and
washing them with 70% ethanol, they were dried under a vacuum and recrystallized to
remove further impurities. Lastly, IR, MP (60 degrees C), and NMRs were taken. The
spectroscopy results show peaks at 3070cm-1, 1570cm-1, and 750cm-1, proving Sp2 C-
H, C=C, and C-H Bending bonds respectively. Additionally, the HNMR showed a 4H
doublet, 4H triplet, and 2H doublet, with the CNMR showing 5 different carbons.
Overall, the experiment resulted in diphenylacetylene with a percent yield of
61%. Some sources of error, such as not allowing the refluxing to finish, or not
adequately drying the diphenylacetylene crystals in the Buchner funnel, altered the
percent yield and purity of the product. If refluxing did not finish, then both the
percent yield and the quality of the IR would be decreased. If the crystals were
not completely dry before weighing, then the percent yield might be deceptively too
high. Experiment 19B (Part 3) In the third part of this 4-step process, benzil is
synthesized from benzoin with co-oxidation. The product of this experiment, along
with the product from part 2, diphenylacetylene, will act as reactants and
intermediates to form the final product, hexaphenylbenzene. The mechanism is
initiated by the copper (II) acetate catalyst, which removes an electron from the
carbonyl bond. While the now reduced Cu+ ion stabilizes the negatively charged
oxygen, acetate removes the hydrogen across from the hydroxyl group, forming a
central double bond. This bond can have resonance with the negatively charged
oxygen to reform the carbonyl bond. In this case, a newly oxidized Cu2+ ion will
remove the single electron from the carbon with the hydroxyl group and create a
positively charged oxygen. Lastly, another acetate ion removes the hydrogen from
the hydroxyl group, forming the second carbonyl bond in the benzil molecule. In
this mechanism, ammonium nitrate acts as a co-oxidant because it continuously re-
oxidizes the catalytic copper ion, reducing itself to N2 and H2O (Discussion
Question 2, Mech on notebook paper). For the experiment, benzoin, copper
acetate acetic acid solution, and ammonium nitrate were added to a vial and heated
to 150�C for 45 minutes. The heat allows copper to react with benzoin and initiate
the removal of an electron. After 45 minutes, a TLC was taken to ensure the
reaction went to completion and no reagent is left in the solution. After cooling
to room temperature, the reaction mixture was put into an ice bath and the yellow
crystals were filtered with an H2O wash. After, the filtrate must be neutralized
with NaHCO3 because it contains harmful acetic acid. Next, the benzil was
recrystallized from hot ethanol to remove any impurities, and the presence of
unoxidized benzoin was tested. To do this, purified benzil was dissolved in ethanol
and 1 drop of NaOH. A purple color will appear is benzoin is present. This occurs
because hydroxide will remove the hydroxyl proton, allowing resonance
delocalization of the new negatively charged oxygen, creating the purple color
(this does not happen with benzil). Upon completion of this step, no purple color
was observed, indicating a complete reaction (Discussion Question 4). Other
reducing agents, such as NaBH4, can also reduce benzoin.
If starting with an enantiomerically pure sample of benzoin, the hydroxide ion can
add to each side equally, allowing a mixture of diasteroemers. If starting with a
racemic mixture, there can be four products, specifically, 2 sets of enantiomers
where they share similar meso compounds (Discussion Question 3). After checking for
purple, we calculated a 90.5% after recrystallization (Discussion Question 1) and
analyzed spectroscopy values. The IR for Benzil showed a small peak at 3070cm-1
indicating sp2 C-H, and a large peak at 1700cm-1, indicating a C=O. The IR for
Benzoin showed a large broad peak at 3400cm-1, indicating OH, and another large
peak at 1700cm-1, indicating C=O. The HNMR for benzil had a 4H triplet, 4H doublet,
and a 2H triplet, with the CNMR showing 5 different carbons. The HNMR for benzoin
showed 1H doublet, 2H doublet, 1H doublet, 2H doublet, 2H triplet, 1H singlet, and
1H singlet, while the CNMR showed 9 different carbons. Overall, possible sources of
error include not allowing the reaction to go to completion, not drying the
solution from water adequately enough, all of which would greatly decrease percent
yield and IR values.