Nguyen 1

Experiment #7: A Green Synthesis of Camphor

Introduction
The new-age herbalist Basil Wormwood explores the composition and uses of natural
products from plants. One of phenomena that puzzled him is while Basil was away, his lab
assistant spilled some vinegar in a batch of peppermint oil. He removed the vinegar by extraction
when he returned, but the aroma of the oil had changed markedly. The assignment is to find out
what happens when menthone from peppermint oil is treated with acid.
Experimental Method
Peppermint oil is a mixture of several optically active components, including (-)-menthol,
and (-)-menthone, the corresponding ketone. Menthone can exist as (-)-menthone and (+)menthone, which are enantionmers of each other. Menthone can also exist as (-)-isomenthone
and (+)-isomenthone; they are enantionmers of each other, but diasteriomers of (-) and (+)menthone.
The configuration at the stereocenter next to its carbonyl group of aldehyde or ketone
may change under acidic or basic conditions. (-)-menthone has two stereocenters, so that the
changing of the configuration at just one of them will yield a diastereomer of (-)-menthone. If the
configuration at the carbon next to the carbonyl group changes, the product will be the (+)isomenthone. The product will be analyzed by polarimetry to determine whether or not
isomerization has taken place and the percentage of the (-)-menthone has isomerized if so. If one
enantiomer of menthone rotates polarized light in a clockwise (+) direction, the other will rotate
light by the same amount in a counterclockwise (-) direction.

Nguyen 2
CH3

CH3
+

O
H3C

CH3

H3C

CH3

(+ ) - is o m e n th o n e

(-)-m e n th o n e

Specific Optical rotation using D line of a sodium lamp in degree and a 1.00dm tube, 25oC:
25

[ ]D =

cl

the observed optical rotation in degree; (+) for R or (-) for L

c:

mass recovered over 10mL ethanol (g/mL)

l:

cell length (dm); l = 1

Optical rotation of Menthone: []menthone = -30o; []isomenthone = +92o

menthone + isomenthone =1

[ ]25D =[ ] menthone menthone + [ ] isomenthone isomenthone

[ ]menthone menthone + [ ]isomenthone( 1 menthone )
menthone( [ ] menthone [ ] isomenthone ) + [ ] isomenthone
menthone(30o 92o ) +92o
122o menthone +92o
25

menthone =

[ ]D 92
122

; isomenthone =1 menthone

Nguyen 3
Isomerization of (-)-menthone Experiment
Under the hood, 2.004 mL of (-)-menthone was poured into 50-mL round bottom flask,
then added 10.0mL of glacial acetic acid, and 10.0mL of HCl. Under stirring, heating and reflux
for one hour, the mixture was left to cool down to room temperature before transferring into a
beaker. In order to neutralize the mixture, 6.0M NaOH solution was used until it turned red
litmus into blue color. A strange solid was formed on top layer.
The extraction used 75mL of solvent grade diethyl ether. MgSO4 was used to dry the
combined ether. After evaporate by a rotary evaporator, the recovery mass was 1.154g. The
optical rotation offset was -0.45; the is +2.00. Therefore, the optical rotation is:
25

[ ]D =

=
cl

+2.000.45
+1.5510
o
=
=13.43
1.154 g
1.154
1 dm
10 mL absolute ethanol
menthone

o
[ ] 25
13.43o92o
D 92
=
=
=0.644 ;

122o

122o

isomenthone =1 menthone =10.644=0.356

The starting material had 100% (-)-menthone. Under acidic condition, (-)-methone
isomerized to (+)-isomenthone at 1:1 ratio. The final solution had the mole fraction of
isomenthone equal to 0.356. Because of the 1:1 ratio that (-)-menthone isomerized to (+)isomenthone, the percentage of (-)-menthone that changed to (+)-isomenthone is 35.6%
Discussion

Nguyen 4
Since axial and equatorial bonds are non-equivalent, there are differences of energies
between two non-equivalent positions in which to place any substituent. Equatorial substituent is
lower energy than axial substituent. When the ring flip occurs as above, it converts axial
substituent to equatorial, and via versa. The two conformations are in equilibrium at room
temperature, however, it has tendency to be at more stable state. Therefore, the equatorial
conformation is favored in the equilibrium. The substituents prefer to occupy the less sterically
hindered equatorial position. In this case, di-substituted cyclohexane, the substituents will
move until the isomer will be at the most stable in which it has maximum number of
substituents at the equatorial positions.
(-)-menthone should be the more stable diastereomer due to its stable chair conformation
has substituents at equatorial position. The composition of the isomerization mixture consistent
with this conclusion since the percentage of (-)-menthone that changed to (+)-isomenthone is
only 35.6%. The mixture remains the larger amount of (-)-menthone, which is more stable.