In the Laboratory
edited by
Green Chemistry
Solvent-Free Conversion of α-Naphthaldehyde
to 1-Naphthoic Acid and 1-Naphthalenemethanol:
Application of the Cannizzaro Reaction
John J. Esteb,* Keith M. Gligorich, Stacy A. O’Reilly, and Jeremy M. Richter
Clowes Department of Chemistry, Butler University, Indianapolis, IN 46208; *jesteb@butler.edu
The base-catalyzed oxidation–reduction of aromatic al-
dehydes, commonly referred to as the Cannizzaro reaction,
is a useful synthetic reaction (1) that is routinely covered in
organic chemistry textbooks. However, illustrating the reac-
tion in an undergraduate teaching laboratory in a simple, yet
impressive manner is often difficult to achieve. As a result,
there has been only one exercise developed for the under-
graduate laboratory involving the Cannizzaro reaction (2).
In the published procedure, 4-chlorobenzaldehyde is con-
verted to 4-chlorobenzoic acid and 4-chlorobenzyl alcohol.
Although this procedure works well, it suffers from the draw-
backs that the reaction must run for 1.5 hours and since it is
run in solvent, the quantity of halogenated waste generated
can be problematic.
Recently, Yoshizawa, Toyota, and Toda (3) reported a
solvent-free modification to the general procedure utilized
in the Cannizzaro reaction. The relatively low toxicity and
availability of the reagents used (4) coupled with the sim-
plicity and cleanliness of their procedure led us to investi-
gate the possibility of converting this synthetic process into
a form applicable to the teaching laboratory. The base-cata-
H O K O O OH
KOH
+ Using a mortar and pestle, 2.7 g (48.1 mmol) of KOH
2 heat
1 3
HCl
HO O
+ KCl
2
Scheme I. Reaction of potassium hydroxide and α-naphthaldehyde
(1) under solvent-free conditions to produce 1-naphthoic acid (2)
and 1-naphthalenemethanol (3).
1794 Journal of Chemical Education • Vol. 81 No. 12 December 2004
Mary M. Kirchhoff
ACS Green Chemistry Institute
Washington, DC 20036
W
lyzed oxidation or reduction of aldehydes under solvent-free
conditions has not yet been utilized in the undergraduate
teaching laboratory. The laboratory exercise that we have de-
veloped offers several advantages over many of the existing
exercises including the ease of reaction workup, shorter reac-
tion time, relative environmental friendliness of the reagents,
ability to reduce the quantity of waste generated and hazard-
ous materials used, and overall cost effectiveness of the reac-
tions. All of these advantages are important considerations
in the development and implementation of a new experiment
for the teaching laboratory (5).
Experimental Overview
In this experiment, a mixture of potassium hydroxide
and α-naphthaldehyde (1) are heated under solvent-free con-
ditions to produce 1-naphthoic acid (2) and 1-
naphthalenemethanol (3) (Scheme 1). α-Naphthaldehyde was
selected as a suitable starting material owing to its low cost,
low toxicity, and rapid conversion to the desired products.
Furthermore, this reaction offers the added advantage that
the students are able to isolate two separate products, both
of which are solids, that can be easily isolated from the reac-
tion mixture and purified through acidic workup and crys-
tallization. Lastly, since the reaction yields are very good, the
students obtain enough material to characterize their prod-
uct by NMR, GC–MS, or IR if desired.
Experimental Procedure
are ground into a fine powder and transferred to a 50-mL
round-bottom flask. Next, 4.1 mL (30.2 mmol) of α-
naphthaldehyde are slowly added while the resulting mixture
is stirred with a spatula until the contents appear homoge-
neous. A reflux condenser is attached and the flask is placed
in a preheated hot water or steam bath at ca. 100 ⬚C. The
mixture is stirred briefly at 5 min intervals. After 0.5 h, the
flask is removed from the heat source and the mixture cooled
to room temperature. Upon cooling, 30 mL of water are
added to the reaction mixture and the contents transferred
to a separatory funnel. Since a considerable quantity of ma-
terial will remain in the flask, a second 30-mL portion of
water is used to extract any remaining potassium salts from
the reaction mixture still contained in the flask. This extract
is combined with the first aqueous portion in the separatory
• www.JCE.DivCHED.org

funnel. The reaction flask is finally rinsed with 10-mL of ether
and the ether washing is also added to the separatory fun-
nel.1 The aqueous solution is extracted with 2 × 25-mL por-
tions of ether. The organic and aqueous layers are separated
and treated independently. The aqueous layer is slowly acidi-
fied with 3 M HCl (ca. 15 mL) producing a white precipi-
tate. Suction filtration of the product affords 2.25 g (86%)
of 1-naphthoic acid (mp 160–162 ⬚C). The combined or-
ganic extracts are dried with MgSO4, filtered, and the sol-
vent removed by rotary evaporation. Solidification of the oily
residue is accomplished by cooling in an ice bath,2 yielding
1.89 g (79%) of 1-naphthalenemethanol (mp 61–63 ⬚C) as
an off-white solid.3 Purity of the product is assessed through
melting point determinations and 1H NMR. Typical student
yields are in the 60–85% range for each product.
Hazards
Potassium hydroxide is caustic and can cause severe
burns. Care should be taken when handling this chemical.
Ether, toluene, and hexanes are flammable liquids; there
should be no open flames in the laboratory. Hydrochloric
acid is corrosive and may cause damage to the skin. α-
Naphthaldehyde is a lachrymator and an irritant. 1-
Naphthoic acid is an irritant. Magnesium sulfate is
hygroscopic. Further health and safety notes may be found
in the Supplemental Material.W In general, solvent-free reac-
tions can become violent if the scale of the reaction is in-
creased. Modification to this experimental procedure is not
recommended.
Acknowledgments
The authors would like to thank Butler University’s 2003
summer organic chemistry classes for helping with the prepa-
ration and testing of this lab. The authors would also like to
thank Anne Wilson for helpful discussion.
www.JCE.DivCHED.org • Vol. 81 No. 12 December 2004
In the Laboratory
W
Supplemental Material
Instructions for the students and notes for the instruc-
tor are available in this issue of JCE Online.
Notes
1. It may be necessary to stir the mixture with a glass rod or
a spatula to completely transfer all of the contents of the reaction
flask to the separatory funnel.
2. A few students may have difficulty getting their oil to so-
lidify. This is usually due to the incomplete removal of solvent. We
have found that oils that refuse to solidify quickly will usually do
so by allowing the product to sit open in a hood overnight. Char-
acterization of the oil can be accomplished through the use of GC–
MS, 1H NMR, or other analytical techniques if so desired.
3. It is possible to recrystallize 1-naphthalenemethanol from
a toluene–hexane mixture but we have found that the students tend
to produce oils instead of crystals owing to their lack of experience
in the use of a mixed-solvent system.
Literature Cited
1. For a review of the Cannizzaro reaction, see: Geissman, T. A.
Org. React. 1944, 2, 94.
2. Gilbert, J. C.; Martin, S. F. In Experimental Organic Chemis-
try a Miniscale and Microscale Approach, 3rd ed.; Harcourt Col-
lege Publishers: Orlando, Fl, 2002; pp 513–519.
3. Yoshizawa, K.; Toyota, S.; Toda, F. Tetrahedron Lett. 2001, 42,
7983.
4. Gosselin, R. E.; Hodge, H. C.; Smith, R. P.; Gleason, M. N.
Clinical Toxicology of Commercial Products, 5th ed.; Williams
& Wilkins: Baltimore, MD, 1976; Section II, pp 1–459.
5. (a) Esteb, J. J.; Stockton, M. B. J. Chem. Educ. 2003, 80, 1446.
(b) Esteb, J. J.; Schelle, M. W.; Wilson, A. M. J. Chem. Educ.
2003, 80, 907. (c) Barrett, J. A.; Esteb, J. J.; Hoops, G. C.;
Richter, J. M. Chem. Educator [Online] 2004, 9, 30–31; DOI
10.1333/s00897040751a.
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