Objective:

The objective of this experiment was to reduce pinacolone to pinacolyl alcohol using sodium
borohydride in the presence of methanol.

Mechanism of Sodium Borohydride Reduction

Mechanism of Pinacolone by Sodium Borohydride

Materials:
2-necked 250 ml round bottom flask
Lab jack
Solid dropping funnel
Separatory funnel
Ice bath
50 mL methanol
25 mL pinacolone

Thermometer
1 g sodium borohydride
Balance
Weighing bottle
Clamps
Glass grease
1 L separatory funnel
250 mL MTBE
Long stem funnel
200 mL saturated sodium chloride
500 mL Erlenmeyer flask (with stopper)
2.03 grams anhydrous sodium sulfate
Boiling chips
400 mL beaker
25-50 mL round bottom flask
Vacuum side arm
Condenser
IR spectroscopy interface
Intro:
Reduction reactions are one of the main type of reactions in organic chemistry.
Reduction refers to a reaction in which the oxidation state of a molecule decreases. It can also
be generalized to a reaction in which the net number of C-O bonds decreases or the number of
C-H bonds increases. In this experiment, pinacolone will be reduced to pinacolyl alcohol.
Pinacolyl alcohols chemical formula is C6H15OH. It is not known for its industrial use, but it is
known for being a precursor the nerve agent Soman (1).
The reduction reaction will take place using sodium borohydride. Sodium borohydride
exists as a solid at room temperature, usually as a powder. It will act as a reducing agent and
donate a proton to the pinacolone. Methanol will be used as because it slows down the reaction
and does not react violently with water. MTBE will be used as a solvent for the reaction to take
place. The organic mixture with MTBE and pinacolyl alcohol will then undergo fractional
distillation. Fractional distillation takes advantage of the different boiling points of compounds in
a mixture to separate them. The mixture is heated, one of the compounds will vaporize, and
then get recondensed into another flask for collection.
Analysis will take place using infared (IR) spectroscopy. IR spectroscopy uses photons
that cause vibrations of bonds, and then analyzes these bond vibrations using a
spectrophotometer. This is useful because it not only tells us what bonds are unique to a
sample, but also tell us what bonds are not present, and allows us to differentiate between two
different samples. The latter is what we will be employing in this experiment.

Methods:
A. Reaction.

1. Use a 2-necked 250 ml round bottom flask. Fix in position on top of lab jack. Place a
solid dropping funnel in one of the necks positioned vertically.
2. Prepare an ice bath that can fit between the flask and the lab jack. Note: an ice bath
consists of a little ice and lots of water.
3. Add 50 ml of methanol to the 2 necked flask. Then add 25 ml of pinacolone. In the
second neck place a thermometer that is NOT in a fixed position. It will be used to stir
and determine the temperature of the reaction.
4. To weigh out 1 g of sodium borohydride, take the balance to your hood. Weigh the
sodium borohydride in a weighing bottle with a capped end in the hood. Only an
approximate weight is needed.
5. Addition of sodium borohydride to ketone can produce a large amount of heat. If the
heat is accumulated, sodium borohydride can cause fire.
6. ADD SODIUM BOROHYDRIDE SLOWLY TO THE FLASK. IT SHOULD TAKE AT
LEAST 1 HOUR. If the temperature rises above 20 degrees, cool with ice-WATER bath.
If the temperature is below 15 degrees it will rise because the reaction is exothermic.
Lower the ice-WATER bath.
7. See the instructor after you added all sodium borohydride.

B. Workup
1. Fix a 1 liter separatory funnel in a ring clamp (as shown below)

2. Add 250 ml of MTBE through a long stem funnel.

3. MTBE is extremely flammable. The flash point (the lowest temperature at which it can
form an ignitable mixture in air) of MTBE is -10C. MTBE is possible a carcinogen. It is
harmful by inhalation, ingestion or through skin contact.
4. Add your reaction mixture through the long stem funnel.
5. Add 200 ml of saturated sodium chloride solution through the long stem funnel. The
reason to add saturated sodium chloride is to prevent for formation of emulsions. The
sodium ion is hydrated by the water therefore there is no emulsion. That is termed the
salting-out effect. So you can shake vigorously but you must vent frequently because
the heat transferred from the palm of your hand is sufficient to cause the MTBE to boil.
6. The sodium chloride may precipitate because it is initially present at its solubility limit.
You will see this occur if the aqueous phase becomes cloudy. Add water and shake to
dissolve the salt.
7. Shake about 2 minutes, venting frequently.
8. Discard the bottom aqueous layer in the sink as an ordinary waste.
9. Drain the organic extract from the separatory funnel into a 500 ml Erlenmeyer flask
fitted with a cork stopper.
10. Add 2.03 g. of anhydrous sodium sulfate to the organic extract. Swirl 2 times.

C. Purification

1. To the 500 ml round bottom flask, add boiling stones.

2. Insert thermometer into thermometer adapter. Need to read up to 125 degrees.
3. Collect first distillate in a 400 mL beaker. It is MTBE.
4. Continue heating: Remove 400 mL beaker with first distillate when temperature
reaches 95 degrees. Discard first distillate in organic waste. Replace the 400 mL beaker
with a 25-50 mL round bottom flask attached via an adapter with a vacuum side arm to
the condenser.
5. Collect second distillate until 500 ml round bottom flask is almost dry. Do not let the
flask completely dry. 6. Save the product for the next lab session.
Potential sources of error:
- Re-did the distillation because first flask was not removed at the proper
temperature
- Leakage in long separatory funnel stopper, MTBE fell out and was lost

Results:
Temperature vs time measurements for boiling point of MTBE
Temperature

Time (Seconds)

51

250

52

100

53-55

35

56

15

57

40

58-60

30

61

14

62

14

63

11

64

13

65

12

66

15

67-70

22

71-72

11

73-75

16

Standard IR curve for pinacolone:

IR curve for pinacolyl alcohol after reduction with sodium borohydride:

Superimposed IR Spectra of Pinacolone Standard (gray) vs. Sample (yellow)

Conclusion:

From the superimposed graph of pinacolone and pinacolyl alcohol, it is obvious that there is a
distinct difference in these two compounds. There is a peak in the 3600-3300 region in the
pinacolyl alcohol graph, but not in the pinacolone graph. This 3600-3000 cm^-1 peak is
indicative of a OH stretch, which confirms that the reduction was successful. Also, the
difference in the right side (fingerprint region) shows that the two compounds are not the same.
The C double bonded to O missing in the pinacolyl alcohol is probably the reason for this
change, along with possible impurities in the sample.
Post Lab Questions:
1. If the reaction proceeded, then the IR graph for the product would have different peaks than the
IR graph for the reactant. Each IR graph is specific to the compound used to generate it.
2. For a reduction reaction using LAH, potential solvents can be tetrahydrofuran or an ether.
3. The added NaCl prevents emulsions by increasing the polarity of the aqueous layer, which
prevents the organic compounds from dissolving in the aqueous layer.
References:
"IPCS INCHEM." IPCS INCHEM. Chemical Safety Information from Intergovernmental
Organizations, n.d. Web. 19 Oct. 2015.
<http://www.inchem.org>