Experiment 1: Oxidation of (1S)-(-)-borneol to

(1S)-(-)-camphor

Garrett Decker
Objective:

The goal of the experiment was to perform an oxidation of (1S)-(-)-borneol to (1S)-(-)-

camphor by using sodium hypochlorite and glacial acetic acid. Afterwards the reactions product
was purified through washes and the techniques of: IR, TLC, and melting point was used to test
purity. The purity was important to determine as the product will be used in a reduction reaction
in the next lab.

Overall Reaction:
Mechanism:
Stoichiometry table:
Compound Formula Amount MW mmol Molar Density
(g/mol) Equivalent (g/cm3)
(1S)-(-)- C10H18O 0.378g 154.25 2.45 1.0 1.01
borneol
Glacial CH3COOH 0.30mL 60.052 5.25 1.0 1.05
acetic acid
Sodium NaOCl 7.0mL 74.4 104.4 1.0 1.11
hypochlorite
(bleach)
Acetone C3H6O 1.0mL 58.08 13.5 1.0 0.784

Limiting reagent: (1S)-(-)-borneol

Procedures/observations:

Procedure Observations
0.360g of borneol, 1 mL of reagent  0.378g borneol was added
grade acetone, and 0.30 mL of glacial  1 mL acetone added
acid was put into a 10mL round bottom  0.30 mL glacial acid added
flask. Reflux condenser was attached, Setup:
and flask was immersed in sand bath.

Solution was heated to 45C +/- 5C.  Solution was clear after dissolution of borneol
External thermometer to was used to
monitor the temp. and it was
maintained for the full reaction. Stirred
reaction until all borneol dissolved.
While stirring, 6.0 ml of bleach  Bleach solution murky tan color before addition
solution was added dropwise slowly to reaction
over 30 mins through top of the reflux  Condensation of solution formed at the top of
condenser. the round bottom flask
 Solution in round bottom flask turned murky
white as bleach solution was added
Mixture was stirred for another 5 min.  The paper did not turn color when the solution
then starch iodide paper was used to was transferred to it.
test for completion. A glass stir rod was
used to transfer a small amount of
solution to the iodine paper.
There was no change in color, so 5  After adding 8 drops of bleach and waiting 4
drops of bleach were added slowly and mins. the iodine paper changed to a blue-black
stirred for 1-2 minutes while heating. color.
Retested with indicator paper until a
color change was noted. When a color
change was noted, an additional 2-3
drops of bleach was added and then
stirred with heat for 2 more minutes to
assure the reaction was complete.
When the reaction was complete, the  1mL dichloromethane was used to rinse the
mixture was allowed to cool to room vessel
temperature and then transferred to a  The solution looked cloudy
centrifuge tube. The reaction vessel  The bottom layer was clear while the top layer
was rinsed with 0.5-1.0 mL of
was a murky white color.
dichloromethane and the rinse was
transferred to the same centrifuge tube.
1.0-2.0 mL of dichloromethane was
added to the centrifuge tube; a Pasteur
pipet was used to pull the contents of
the centrifuge tube in and out several
times to mix up the layers.
The lower layer was extracted by pipet
and transferred to another centrifuge
tube. The extraction of the aqueous
layer was repeated with another 1.0-2.0
mL of dichloromethane. The lower
organic layer was transferred each time
and combined with the
dichloromethane solution already
saved.
The dichloromethane solution was  Organic solution was still a milky white color
washed with 2.0 mL of saturated after all the washes
sodium bicarbonate solution. A stir rod  Lots of CO2 bubbles formed as solution was
was used to agitate until the bubbling agitated
of CO2 gas had slowed considerably or
stopped. Again, the dichloromethane
layer was transferred to a clean
container and the aqueous layer was
discarded from the centrifuge tube.
The dichloromethane was returned to
the centrifuge tube and washed with
2.0 mL of 5% sodium bisulfite
solution. The organic layer was
transferred to another container, the
bisulfite solution was discarded, and
the dichloromethane solution was
returned to the centrifuge tube. Then
another wash with deionized water was
done.
Using a clean, dry pipet, the  Weight of tared flask = 55.470g
dichloromethane solution was
transferred to a small, clean beaker.
The organic layer was dried thoroughly
with anhydrous sodium sulfate and
then filtered (filter pipet) into a 25- or
50-mL TARED round-bottom flask.
Evaporate the dichloromethane with  Took a long time for solid to appear
mild (hand) warming using an  As the solution dried it started to form a white
aspirator. Remove from heat as soon as solid
solid begins to appear, since the
camphor may sublime and be lost. If
handwarming, discontinue warming
when approximately 1 mL of solvent
remains for the same reason. Continue
to remove the solvent with the
aspirator until solid camphor is dry.
Weigh the flask containing the
camphor and calculate the percent  Flask with product weight= 55.651g
yield.  55.651g – 55.470g= 0.181g
 Percent yield= (0.181g/0.373g) x100 = 48.5%

Characterization: a. Obtain a melting Camphor RF= 39mm/54mm = 0.72

point range in a sealed capillary tube. Borneol RF = 34mm/54mm = 0.63
b. Obtain an IR spectrum of the Melting point: 175-177℃
camphor and make assignments. c. Do IR peaks: 2957 corresponding to CH stretch
a TLC of the product and starting
1738.8 corresponding to C=O stretch
material (dissolve each of them in
acetone in a separate vial. Use 10:1
1390.3 corresponding to CH3 stretch
hexanes/EtOAc to develop the silica
plate then place the plate in an iodine
chamber (to be provided by the TA).
Remove the silica plate and circle the
spots.
Seal the flask containing the camphor
with parafilm until the reduction
session.
Results:
Compound Amount mol Theoretical % yield Melting
used/obtained yield point (℃)
(1S)-(-)-borneol 0.378g 0.00245 ------- --------- 206-208
(1S)-(-)-camphor 0.181g 0.00119 0.373g 48.5% 175-177

Wavenumber cm-1 Fumctional group Strong, weak, Broad or sharp

medium, peak
1738.80 Carbonyl C=O Strong sharp
2957.64 Csp3-H medium sharp
1390.30 C-H Medium sharp
Calculations:
Discussion:
The goal of this experiment was to perform an oxidation of borneol to camphor changing
the alcohol group of borneol into the ketone group present in camphor, and then use IR, TLC,
and melting point to identify the reaction was successful and the product was pure. The reducing
agent in this reaction was Borneol because it reduced(gave electrons to) Sodium hypochlorite
which acts as the oxidizing agent. This is a type of β-elimination reaction that takes place at the
C2 while unaffecting C1 or C4.
Throughout the reaction NaOCl reacted with the glacial acetic acid initially added to
create hypochlorous acid(HOCl) in the solution. The reaction lasted about 35 minutes on a heat
of 45℃ +/- 5℃ during this time the added heat and HOCl worked to oxidize (1S)-(-)-borneol at
the C2 carbon. The reaction was tested for completion by putting a drop of the solution on
starch-iodine paper. The reaction on the starch-iodine paper (Cl2 + 2I- (aq)  I2 + 2Cl-) produces
a starch-iodine complex causing the paper to have a blue-black coloration as the reaction makes
Iodine.
After the starch-iodine paper was used to test completion of the reaction the product was
washed with dichloromethane, sodium bicarbonate, sodium bisulfate, and deionized water.
During each wash the lower organic layer was taken and transferred as it was denser due to
dichloromethane. The sodium bicarbonate helped extract acid from the product, while sodium
bisulfate got rid of the excess bleach present in the solution.
(1S)-(-)-borneol and (1S)-(-)-camphor have a 1:1 stereometric molar ratio allowing for
theoretical yield for camphor to be calculated directly by the amount of (1S)-(-)-borneol initially
used as it was the limiting factor. There was 0.00245 mol of (1S)-(-)-borneol used in the reaction
this means the theoretical yield of camphor was 0.373g. After the reaction was completed, the
washes were done, and the product was dried only 0.181g of camphor was acquired. This equals
out to a percent yield of 48.5%. The TLC analysis showed that borneol had an Rf of 0.63 while
camphor had an Rf of 0.72. This distribution of Rf values makes sense as borneol is polar due to
the OH alcohol group it has causing it to not travel as far up the polar silica sheet compared to
camphor that has a less polar ketone group in comparison. The melting point for the product was
not taken as there was not enough time to do so. It is likely that a lower melting point than the
literature value 175-177℃ of camphor would have been seen since the product was likely still a
slightly wet. An IR spectrum was also taken to show that camphor had been obtained from the
reaction. The peaks seen in the spectrum are representative of camphor and shows the product
was pure. The strong peak at 1738.8 cm-1 identifies camphor’s most differentiating characteristic
as it identifies a carbonyl group (C=O stretch) present in the ketone. The CH2 bend has a medium
peak around 1470 cm-1 and the CH3 has a medium peak around 1390.3 cm-1. The sp3 hybridized
C of the C-H stretch has a medium peak around 2957.6 cm-1. All these analytic tests show that
camphor was obtained through the reaction.
Post lab questions:
1. Enantiomerically pure starting material was used in the Oxidation of Borneol experiment.
Stereochemical relationships are important in this lab and the next lab. More importantly,
stereochemistry plays a significant role in biology and medicine. Draw the enantiomer of
the camphor isomer shown below. 2 pt

2. How has camphor been used in everyday life? List two uses
Camphor is often used in topical lotions and ointments to help reduce irritation, pain, and
inflammation. It is also known to be used as a decongestant and cough suppressant and is found
in Vicks VapoRub.
3. Sodium bisulfite was used in the experiment. Write the reaction that occurred with the
sodium bisulfite.

4. What is the stereochemical relationship (enantiomers, diastereomers, or not related)

between the molecule you drew in #1 and (1R)-(+) borneol? 2 pt
Not related, the molecule drawn in #1 is (1S)-(-)-camphor which has a different chemical
formula than that of (1R)-(+) borneol.