X-13

Oral Report

You will have a 20-30 minute oral laboratory report the week following the laboratory. Your TA will
schedule the report time with you during the lab and give you further information.

1. Why would an emulsion form between THF and water? Explain how brine helps separate the
layers.

Emulsion may form when mixing THF and water because THF is highly miscible in most
aqueous solutions. Brine will increase the ionic strength of the aqueous layer and help separation
by forcing the surfactant-like molecule to separate into one phase or the other.

2. Why is this reaction run under inert atmosphere? Write chemical equations for the two reactions
which would produce hazardous products if the synthesis was run under ambient conditions.

This reaction was run under an inert atmosphere of N2 because lithium and
dichlorodiphenylsilane are air sensitive reagents.

Li + H2O → LiOH + H2 (g)

3. Write the reaction mechanism for the formation of HPS.

Diphenylacetylene + THF(tetrahydrofuran) + Lithium <dark blue> -> +
Dichlorodiphenylsilane -> HPS(heycaphenylsilole) <blown>

4. Define aggregation induced emission (AIE) and aggregation caused quenching (ACQ). Compare
and contrast AIE vs. ACQ. How does the structure of a molecule dictate whether AIE, ACQ, or
neither process will occur? Provide the name and structure of a molecule that exhibits ACQ in
solution. The TA may request the reference for the molecule you provided as an example.

Aggregation induced emission (AIE) : the photophysical phenomenon in which

non-luminescent molecules in solutions are induced to show bright emission upon
aggregate formation

Aggregation caused quenching (ACQ) :a known phenomenon responsible for low

emission of dyes when in the form of solid state

5. AIE is partially responsible for the fluorescence properties of HPS in CIL containing solutions.
Explain how.
 6. Based on your IR analysis, is there evidence to support a change from starting material to
product? Briefly explain.

7. Reference 3 obtained a similar plot of Fluorescence Intensity vs. CIL Fraction as the one obtained
in this laboratory (Figure 3.a). The researchers suggested this setup may be used as a “Fluorescent
Chemosensor for Detection and Quantitation of Carbon Dioxide Gas”. Do you agree with this
claim? Explain why or why not.

8. Provide two experimental observations (not including IR data) that support the formation of CIL
from DPA and CO2.

9. Compare the intensity of your stock solution to your 1000ppm 0% CIL solution. Name and
explain two factors causing this trend.

10. The reaction used to form the CIL in this laboratory is reversible. Using the chemicals and
equipment available to you in both lab periods, design an experiment to convert the CIL back to
DPA.

11. Generate a question which has NOT been asked in questions 1-10. Present the question and your
answer in 2 minutes or less. Your question must be similar in length and scope to those above.
The TA may ask follow-up questions if needed.

O-007D - Oral Report

Q. Explain the theory of H-NMR

H-Nuclear Magnetic Resonance spectroscopy studies molecules by analyzing the interaction of

electromagnetic radiations with the nuclei inside a strong magnetic field, where nuclei behave
like microscopic magnetics. They spin in the main magnetic field.
The spinning frequency is proportional to the magnetic field strength. Electron density also
affects the spinning frequency. A molecule with higher electron density results in more shielding,
and thus a lower local field energy and lower spinning frequency. The frequency of the spins is
measured from the electric current.

Each spin can have 2 states: along and against the magnetic field. The difference in energy of
the spin states influences its neighbor nuclei, hence we see splitting signals in groups (ie.
multiplet).

The difference in energy between each nuclei is the chemical shift. Each nuclei can influence
neighbor nuclei via sharing of electrons through chemical bonds (ie. j coupling).

Q. Briefly explain what you did for this experiment.

The goal of this experiment is to synthesize ethyl 4-aminobenzoate (benzocaine) from ethyl 4-
nitrobenzoate via a chemoselective reduction reaction (ie. catalytic hydrogenation) in an inert
system. This reaction has three states of matter present: solid (pd/c), liquid (solution containing
ethyl 4-nitrobenzoate) and gas (hydrogen gas).

Overall procedure:
1. First reacted ethyl 4-nitrogenzoate and ethyl acetate (solvent), then with pd/c.
2. Replaced oxygen with nitrogen (via the three-way stop clock and balloon partially filled
with nitrogen gas)
3. Replaced nitrogen gas with hydrogen gas.
4. Had the reaction stir for ~1hr and filtered through the celite sandwich.
5. Rotary vapped the crude and prepared the H- NMR sample
6. Re-dissolved crude in diethyl ether and washed with HCl, NaOH, water and then brine
(recrystallization).
7. Dried the product with anhydrous sodium sulfate and vacuum filtered.

Q. What is the purpose of HCl and NaOH washes?

Since the product is dissolved in diethyl ether, HCl wash does the first separation by protonating
the amine which dissolves it into the aqueous layer. Then NaOH wash neutralizes the amine
and brings it back into the organic layer.