Synthesis of Camphor

Camphor is a bicyclic ketone with a molecular formula of C10H16O. A solid at room temperature,
camphor is white, waxy, and has a strong odor. It is used as an ingredient in cooking, as a topical
decongestant and cough suppressant, as well as a component in fireworks and explosives. The
aim of our experiment was to synthesize camphor in a three-step process beginning with
camphene (C10H16).

The process first involves the acid-catalyzed electrophilic addition of camphene to give isobornyl
acetate. The alkene group on camphene undergoes electrophilic addition by a proton in the
presence of acid. This forms a tertiary carbocation, which then undergoes nucleophilic attack by
the sigma bond between the bridgehead carbon and the carbon adjacent to it. This forms a
secondary carbocation where the bridgehead once was. The alcohol on acetic acid is
deprotonated, and the resulting alkoxy attacks the secondary carbocation, forming isobornyl
acetate. In the presence of aqueous hydroxide ion, the partial-positive carbon on the carbonyl is
attacked by the base and the carbonyl pi electrons shift to the oxygen. The electrons shift back
and then sigma electrons shift to the other oxygen, and the isobornyl group leaves, leaving a
carboxylic acid The oxygen on the isobornyl group then deprotonates the alcohol on the
carboxylic acid and the result is isoborneol. In the final step, the alcohol nucleophilically attacks
a chlorine atom on hypochlorous acid. Water abstract a proton from the positively charged
oxygen. Water then abstracts another proton from the carbon bonded to the oxygen, and the
electrons shift to form a carbonyl between the carbon and oxygen. Chlorine leaves, resulting in
the ketone camphor.

Methods
A 1.36-gram sample of camphene was dissolved in 3 mL of acetic acid. After solvation, 0.50 mL
of 8 M sulfuric acid was added to the mixture and heated to 85 deg. C. The mixture was further
heated for 15 minutes and then cooled for approximately 5 minutes in an ice bath. The mixture
was transferred to a seperatory funnel in which the organic contents were extracted using two 4mL portions of water. The aqueous layer was drained after each addition. Sodium bicarbonate
was added last and the aqueous layer was once again drained. The mixture was dried with
anhydrous calcium pellets after which the product was extracted using a rotary evaporator. An IR
spectrum was obtained.
This product was mixed with 1.1 molar equivalents of 2.5 M potassium hydroxide in 75:25
ethanol:water. The mixture was then heated under reflux for one hour after which it was poured
onto 15 grams of cracked ice. The product solidified and was extracted via vacuum filtration. IR
spectrum and melting point was obtained.
A 1.6 molar equivalent of glacial acetic acid was added dropwise to this product while being
stirred. A 1.1 molar equivalent of sodium hypochlorite was obtained, then a one-tenth portion of
that was added to the mixture. After waiting three minutes, the rest was added dropwise over a
10-minute period. The mixture was then stirred for 30 minutes and then cooled in an ice bath for
approximately 5 minutes. The mixture was transferred to a seperatory funnel where the aqueous
component was drained using one portion of 8 mL methyl tert-butyl ether followed by one
portion of 10 mL saturated bicarbonate. Anhydrous calcium chloride pellets were added to the
organic layer, then a rotary evaporator was used to extract the camphor. IR spectrum and melting
point was obtained.

Result
Part 1: Isobornyl acetate

Product mass: 1.3 g

Theoretical yield: 0.010 mol x (196 g/mol) = 1.96 g (1.3g / 196g/mol)

Yield: 1.3g / 1.96g = 66%

Figure 1. IR spectrum for the synthesized isobornyl acetate product.

Figure 2. Literature IR spectrum of isobornyl acetate. Obtained from the Spectral Database for
Organic Compounds.
Part 2: Isoborneol

Product mass: 0.8 g

Overall theoretical yield: 0.010 mol x (154 g/mol) =1.54 g isoborneol
Overall yield: 0.8g / 1.54g = 52%
Theoretical yield based on isobornyl acetate yield: [1.3g / (196 g/mol)] x 154 g/mol =

1.02 g
Yield based on isobornyl acetate yield: 0.8g / 1.02g = 78%
Observed melting point: 153.8 deg. C
Literature melting point: 210 deg. C (Robertson & Hussain 1969)

Figure 3. IR spectrum for the synthesized isoborneol product.

Figure 4. Literature IR spectrum of isoborneol. Obtained from the Spectral Database for Organic
Compounds.

Part 3: Camphor

Product mass: 0.045 g

Overall theoretical yield: 0.010 mol x (152 g/mol) = 1.52 g
Overall yield: 0.045 g / 1.52 g = 3%
Theoretical yield based on isoborneol yield: [0.8g / (154g/mol)] x 152 g/mol = 0.8 g
Yield based on isoborneol yield: 0.045g / 0.8 g = 6%
Observed melting point: 132.2 deg. C
Literature melting point: 178 deg. C (Robertson & Hussain 1969)

Figure 5. IR spectrum for the synthesized camphor product shown at the top. Lab standard for
camphor shown at the bottom (Bard 2015).

Figure 6. Literature IR spectrum for camphor. Obtained from the Spectral Database for Organic
Compounds.
Discussion
The IR spectrum obtained for the isobornyl acetate product was consistent with the spectrum
provided by SDBS[1]. Absorptions at 2963.80 cm-1 and 2878.60 cm-1 correspond to sp3
hybridized C-H bonds, and their proportions are almost identical to the literature spectrum. A
strong absorption at 1733.62 cm-1 is indicative of an ester carbonyl stretch, and an unlabeled peak
at roughly 3000 cm-1 corresponds to a C-O stretch. All in all, the IR spectrum confirms the
presence of isobornyl acetate. For isoborneol, the results were not as clear. In the experimental
isoborneol IR, there is reason to believe an alcohol is present due to the broad absorption at
3430.87 cm-1 . Absorptions at 2951.27 cm-1 and 2873.11 cm-1 are indicative of C-H stretch. Both
of these functional groups are represented on the literature IR spectrum according to SDBS[2].
However, the experimental IR clearly contains a 1741.46 cm-1 absorption that indicates an ester
carbonyl, which is not present in the structure of isoborneol, but is present in isobornyl acetate.
Further, there is significant melting point depression in the isoborneol product at 153.8 deg. C

compared to the literature value at 210 deg. C (Robertson & Hussain 1969), indicative of the
presence of impurities. The O-H stretch may be due to the presence of water in the sample, rather
than the alcohol in isoborneol, and the C-H stretches in the experimental and literature IR spectra
of both isoborneol and isobornyl acetate are interchangeable save for variations in strength. On
the other hand, the experimental IR of isoborneol lacks the strong C-O stretch of an ester present
in isobornyl acetate. All of this most likely means there was a mixture of unreacted isobornyl
acetate and isoborneal on the sample. This likely occurred because the mixture was not heated
under reflux for a long enough period of time. The mixture was taken out of the condenser about
12 minutes before the full hour.
The results for the final product, camphor, were similarly puzzling. The experimental IR showed
a weak O-H stretch at 3435.62 cm-1 and a moderately strong C-O stretch at 1069.88 cm-1 .
Neither of these ought to be present in camphor, and were not present in the literature IR as
shown by SDBS[4] or the lab standard obtained by Bard[5]. The strong carbonyl stretch at
1734.13 cm-1 is consistent with the literature spectra and the actual structure of camphor, but it
was present in the experimental spectra of isoborneol and isobornyl acetate as well. This could
mean that some isobornyl acetate remained in the sample. As for the weak O-H stretch, it could
be representing water or the alcohol in isoborneol. There was, once again, significant melting
point depression. The difference between the observed melting point of 132.2 deg. C and the
literature melting point of 178 deg. C indicated the presence of impurities in the sample. These
could be previous reactants, products, and reagents.
The yields left much to be desired: 66% for isobornyl acetate, 52% for isoborneol, and 3% for
camphor. This meant that significant amounts of product were lost along the way, or that
reactants were not fully consumed. When yields were calculated so that the expected number of
moles equaled the product yield in the previous step, the actual yields changed: 78% for
isoborneol, and 6% for camphor (isobornyl acetate remained at 66%). This indicates that the
amount of product lost from camphene to isobornyl acetate, and from isobornyl acetate to
isoborneol was mild in comparison to what was lost between isoborneol and camphor. Errors in
measuring reactants and reagents, transfers between containers, and inadequate conditions to
allow the reaction to fully consume all the reactants could have all contributed to these poor
yields in all three steps. The camphor yield was particularly striking, and was likely due to two

mishaps: loss of camphor product during an aborted attempt at vacuum filtration and multiple
rounds of liquid-liquid extraction involving imprecise draining.
Conclusion
The purpose of this experiment was to synthesize camphor in a multistep synthesis beginning
with camphene. The initial step was the acid-catalyzed electrophilic addition of camphene to
give isobornyl acetate, followed by saponification to give isoborneol, and finally oxidation with
sodium hypochlorite to form camphor. Isobornyl acetate was successfully synthesized with an IR
spectrum that matched the literature, although only two thirds of the expected amount of product
resulted. The IR spectrum of following product, isoborneol, was questionable due to the presence
of a carbonyl stretch indicative of isobornyl acetate. The significant melting point depression
meant an impurity was present, and given the IR spectrum, meant that this impurity was likely
unconsumed isobornyl acetate with or without water. Camphor's IR spectrum was similar to the
literature but indicated some water or alcohol as well as a C-O bond. A melting point depression
further led to the conclusion that were impurities present, possibly water, isoborneol, isobornyl
acetate, or a combination of all three with camphor. Low yields, especially for camphor, were
likely due to spills, multiple liquid-liquid extractions, errors in measurement, and incomplete
reactions. Better handling of chemicals and tighter experimental procedures would help to avoid
significant losses of products in multistep reactions such as these in the future.
References
1. Spectral Database for Organic Compounds (SDBS); IR spectrum; SDBS No.: 7147; RN
125-12-2; http://riodb01.ibase.aist.go.jp/sdbs/ (accessed February 15, 2016).

2. Spectral Database for Organic Compounds (SDBS); IR spectrum; SDBS No.: 6804; RN
124-76-5; http://riodb01.ibase.aist.go.jp/sdbs/ (accessed February 15, 2016).

3. Robertson, J.S.; Hussain, M. Metabolism of Camphors and Related Compounds.

Biochem J., 1969 113(1): 57-65.

4. Spectral Database for Organic Compounds (SDBS); IR spectrum; SDBS No.: 5925; RN
21368-68-3; http://riodb01.ibase.aist.go.jp/sdbs/ (accessed February 15, 2016).

5. Bard, R.S. Reference IR spectrum of (-)-camphor purchased from Sigma Aldrich.

Recorded October, 2015.