You are on page 1of 4

ALDOL REACTION.

SYNTHESIS OF TRANS-p-ANISALACETOPHENONE

1. Weigh 1 g of sodium hydroxide1 and place it in a test tube. Add 1 mL of water, stopper the
test tube, and gently swirl the tube until complete dissolution of solid is achieved. As sodium
hydroxide dissolves, the solution may become hot. Allow the solution to cool to room
temperature.
2. Place 1.0 mL of p-anisaldehyde and 1.0 mL of acetophenone in a 25 mL pear shape flask,
and add 3 mL of 95% ethanol. Place a stir bar in the flask and stir the solution for 1 min. Using
a Pasteur pipet, add to the flask 5-7 drops of the 50% sodium hydroxide solution. Stir the
resulting mixture for 30 min at room temperature (Fig. A).

A.

B.

3. Transfer the solution into a 25 mL Erlenmeyer flask and cool it in an ice bath. If crystals do
not form, scratch the liquid-air interface with a spatula to induce crystallization. It can take up
to 20 min for crystals to form. Collect the product by vacuum filtration, wash it with 1-2 mL of
cold ethanol, and air-dry the crystals (Fig. B).

Sodium hydroxide is hygroscopic, so avoid unnecessary exposure of the pellets to air.

4. Transfer the crude product into a clean, dry 25 mL Erlenmeyer flask, add 5-6 mL of methanol
and heat the mixture to just below boiling point. All solid should dissolve upon heating (Fig.
C).

C.

D.

5. Cool the solution in ice. Isolate the obtained crystals by vacuum filtration on a Hirsch funnel
and rinse them with 1.5-2 mL of cold methanol. Air-dry the product, calculate the percent yield,
and determine the melting point (Fig. D).
6. Perform the test for unsaturation using bromine in dichloromethane and the Baeyer test.
Obtain IR spectrum for the product. To prepare the IR sample, dissolve a few milligrams of the
product in dichloromethane (about 0.5 mL), load 2-3 drops of this solution onto Teflon tape,
and allow the solvent to evaporate.

The following is to be included in your laboratory report, along with your response to the
exercises below:

IR Exercise

On the IR spectrum of the product provided below (Fig. 1), identify the following signals:
C=C stretching of aromatic rings;
C=O carbonyl stretching (hints: Carbonyl group signal is one the most intense. C=O absorption
occurs at lower frequency in conjugated systems);
Ar-O stretching.

105
%T
90

75

15
3500
FTIR Measurement

3000

2500

2000

1750

1500

1250

1170.71
1153.35

1211.21

1591.16

30

1510.16

1571.88

1658.67

45

1257.50

60

1000

750

500
1/cm

Figure 1. IR-spectrum of trans-p-anisalacetophenone.

NMR Exercise
Below is a 400 MHz 1H NMR spectrum of the expected product of your aldol reaction (Fig. 2).
1) On the spectrum, label the signals arising from the alkene protons. Calculate the J
coupling constant for the signals. Does the calculated coupling constant meet with your
predictions?
2) On the spectrum, label the signals arising from the protons on the para-disubstituted
phenyl ring of the product. Calculate the J coupling constant for the signals.
You should be able to identify the signals using the integration trace on the spectrum, and from
your prediction of splitting patterns.
Equation for calculating coupling constant:
J = distance between split peaks (in ppm) times 400 Hz/ppm

MeO

9.5

9.0

8.5

8.0

7.5

11.10
7.0

8.040
8.021
7.825
7.786
7.617
7.595
7.579
7.561
7.521
7.502
7.452
7.413
6.951
6.929
6.5

Figure 2. 1H NMR Spectrum of trans-p-anisalacetophenone.

6.0

5.5
5.0
4.5
Chemical Shift (ppm)

3.841
4.0

3.00
3.5

3.0

8.040
8.021
8.018
8.0

7.825
7.786
2.5

7.521
7.502
7.452
7.413

7.617
7.595
7.579
2.0

1.5

7.5
Chemical Shift (ppm)

11.10

1.0

7.0

0.5

6.951
6.929