A Greener Wittig Reaction

Purpose

In
this experiment, we performed a Wittig reaction using benzyltriphenylphosphonium
and 4-methylbenzaldehyde in order to determine the stereochemistry of the major
alkene product using gas chromatography.

Results
The mass of the purified product was approximately 0.72 grams. The expected yield
can be calculated using the mass of the triphenylphosphonium because that is the
limiting reagent. Approximately 1.8 grams of the starting material was used which
translates to 0.0046 moles of starting material. Since all of the reactions are in a
one-to-one ratio, the resulting yield should also be 0.0046 moles. The molar mass of
the product should be 210.27 grams which means that the mass of the expected
yield is 0.97 grams. Using a simple yield calculation,

Actual Yield
0.72 g
=
=0.74=74 yield . The melting point of the purified product
Expected Yield 0.97 g
was measured to be about 121.5 to 126.1 degrees Celsius.
In the crude gas chromatography, it is evident that there are multiple peaks with
each peak representing a different compound. The ones towards 0 minutes are the
solvents such as water and dicholormethane. The next fastest compound is at 2.7
minutes. This is the aldehyde that was added in excess to ensure the reaction was
only limited by the other starting material. At the other end of the spectrum at
around 8 minutes is the leftover byproduct of the reaction, the triphenylphospine
oxide. Both of these match with their respective reference chromatograms as shown
on the course webpage. This leaves only 2 other significant peaks one at 4.4 and
one at 5.1 minutes. It is known that the Z isomer elutes faster than the E isomer
because of van der Waals forces. Therefore, the peak at 4.4 min is the Z isomer and
the peak at 5.1 min is the E isomer. In the purified gas chromatography, it can be
observed that the peaks in general are much smaller, and that peaks of the
extraneous material i.e. extra starting material and reaction byproduct is
significantly reduced. In addition, the height of the Z-isomer peak is also reduced
well below the peak of the E-isomer.
The E/Z ratio is calculated by dividing the area under the curve of the E isomer and
dividing it by the area under the curve of the Z isomer. The E/Z ratio of the crude

product is calculated as

calculated as

128034
=0.84 , and the ratio of the purified product is
153148

65564
=6.04 .
10847

Discussion
1. Based on your purified melting point as well as the chromatogram of your
purified product, how successful was the recrystallization?
The recrystallization was very successful at removing the impurities of the
product. While in the crude product chromatography, the height of the peaks
of the byproduct and reagent rivaled that of the desired product, they were
negligible compared to the product peaks in the purified sample. The melting
point of the product was not as accurate. The melting point of Emethoxystilbene is approximately 135o-138oC. The melting point obtained in
this experiment is about 126o to 130o C so they are slightly different. This
may be due to an error in taking the melting point either heating too fast or
not having the temperature set correctly.
2. What was the major alkene isomer in your product mixture? Do you think that
sterics plays a large part in this outcome?
In the crude product, the alkene isomers seemed to be approximately
equivalent, but after recrystallization, the trans or E configuration became the
majority. An interesting observation is that the ratio of E to Z changes
drastically after recrystallization. It goes from being approximately equal to
being heavily in favor of the E isomer this is because during the purification
process, the cis isomer also got removed from the system. Benzene is an
electron donating group so it will push the reaction to form a non-stabilized
ylide which leads to Z-alkenes. In the crude product it can be seen that there
is a slightly higher amount of Z-alkene than E-alkene. However, benzene is a
very weak electron donating group so it will not significantly affect the E/Z
ratio, only push it slightly towards the Z-isomer.

3. Compare the changes between this greener Wittig reaction and the
normal Wittig reaction described in the background section. Comment of
the change in environmental impact that each change made.
In the greener reactions, the strong base changes from nBuLi to NaOH. nBuLi
is very dangerous and is highly flammable and reactive. It will catch fire
spontaneously if exposed to air specifically the water in the air. It may also
cause reproductive toxicity. The solvent that is used for this compound, N,Ndimethylformamide is very toxic to humans that can cause damage to organs
as well as to the health of an unborn child. While using these compounds may
improve yield, they are very harmful to humans and if mixed with the water
supply, cause drastic environmental damage.
4. What principles of green chemistry were followed in this experiment? Which
were not?
There are twelve principles of green chemistry: prevent waste, maximize
atom economy, design less hazardous chemical syntheses, design safer
chemicals and products use safer solvents and reaction conditions, increase
energy efficiency, use renewable feedstocks, avoid chemical derivatives, use
catalysts, not stoichiometric reagents, design chemicals and products to
degrade after use, analyze in real time to prevent pollution, and minimize the
potential for accidents. In this experiment, most of these principles were
followed. Atom economy is efficient, very little excess chemicals was used.
The much more dangerous chemicals were replaced by NaOH and water.
While NaOH is somewhat hazardous, it is much less so than the other bases
used in Wittig reactions. Energy efficiency was definitely observed, in a
normal Wittig reaction, the compound is heated, but in this experiment the
reaction occurred under room temperature. In this experiment, no catalysts
were used and the reactant was calculated in stoichiometric amounts which

goes against one of the chemicals. Also, the compounds used in the
experiment are not designed to degrade after use as a yield calculation is
needed and having the chemicals degrade could affect the experiment. Some
principles didnt have too much relevance to this experiment such as the
analysis of pollution and avoiding temporary modifications of chemicals.