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A solvent-free oxidation of 1-pentanol to pentanoic acid for the undergraduate

organic laboratory

Article  in  The Chemical Educator · January 2004

DOI: 10.1333/s00897040751a

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 Chem. Educator 2004, 9, 1–2 (web)1

A Solvent-free Oxidation of 1-Pentanol to Pentanoic Acid for the

Undergraduate Organic Laboratory

Jaclyn A. Barrett, John J. Esteb,* Geoffrey C. Hoops, and Jeremy M. Richter

Butler University, Clowes Department of Chemistry, 4600 Sunset Avenue, Indianapolis, Indiana 46208,
jesteb@butler.edu.
Received August 30, 2003. Accepted September 19, 2003.

Abstract: Herein we present an oxidation experiment for a first-year organic chemistry class. This oxidation
utilizes a solid mixture of CuSO4•5 H2O and KMnO4 prepared by the students using a mortar and pestle. The
oxidation takes place under solvent-free conditions and a good yield is obtained for the reaction. This experiment
provides for the simple oxidation of a primary alcohol to a carboxylic acid using a relatively nontoxic oxidizing
agent under solvent-free conditions. Furthermore, students are able to utilize acid–base extraction techniques for
purification of the final product.

Introduction mixture of KMnO4 and CuSO4•5H2O as the oxidizing agent

Oxidation reactions are a part of any organic chemist’s
repertoire [1], and they are thus included in introductory
organic chemistry textbooks as a matter of course. Given the
synthetic importance of these reactions, they should also be
featured in the typical instructional laboratory as well;
however, relatively few experiments have been developed for
the undergraduate laboratory involving the chemical oxidation
of alcohols [2]. Among the published procedures, most involve
the use of hypochlorite solutions [2b–d] as the oxidizer or Cr
(VI) based supported oxidizing reagents [2e–g]. This lack of
experiments is most likely due to the inherent toxicity and
disposal costs of most of the oxidizing reagents used to
accomplish these transformations.
The use of organic solvents in chemical reactions, while
convenient in terms of thermal control and mixing of reagents,
does introduce several undesirable features. Organic solvents
raise the cost of running a reaction, both in terms of purchase
and perhaps even more so in terms of appropriate disposal.
Many organic solvents are highly flammable, providing an
obvious hazard and requiring specialized storage conditions.
The use of organic solvents as a medium for chemical
reactions certainly remains a valuable technique in synthetic
chemistry, and thus some exposure to such procedures for
undergraduate students is warranted; however, training
aspiring young chemists to run reactions only in organic
solvent may also unintentionally introduce a bias that all
reactions require solvents in order to proceed in measurable
yield, thus helping to perpetuate the automatic use of organic
solvent when not really required. In response to these
problems, more attention has recently been given to the
development of solvent-free exercises for the undergraduate
laboratory [2a, 3]. In fact, many modern research laboratories
have begun to move in the direction of solvent-free operations,
as evidenced by an explosion of literature in the area of green
chemistry and solvent-free reactions [4]. Thus, solvent-free
oxidation reactions that can be run easily by students would be
a valuable asset to the organic instructional laboratory.
We have previously published a solvent-free oxidation of
secondary alcohols to their ketones that employs a ground
[2a]. This previous work, based upon the demonstration of the
utility of this oxidizing agent by Shaabani and Lee [5],
provided an excellent example of a solvent-free, relatively
nontoxic oxidation reaction that could be safely and
reproducibly run by undergraduate students. Shaabani and Lee
[5] described solvent-free oxidations of a wide variety of
functional groups, including alcohols, aromatic primary
amines, thiols, and sulfides; however, they did not explore the
use of their oxidation systems for the synthesis of carboxylic
acids from primary alcohols (they were able to synthesize
aldehydes from primary alcohols using a modified oxidant
mixture of KMnO4/Al2O3). We describe herein an extension of
this work involving the oxidation of primary alcohols to their
carboxylic acids employing the same oxidant. While this
reaction proceeds in lower isolated yields than the
corresponding production of ketones, the experiment does
provide students with a concrete example of the utility of a
common oxidation agent for multiple reactions. The workup
for the isolation of the carboxylic acid also serves as a classic
example of the use of acid–base extraction techniques for
product purification.
In this experiment, a ground mixture of KMnO4 and
CuSO4•5 H2O was used to oxidize 1-pentanol (1) to pentanoic
acid (2) under solvent-free conditions (Scheme 1). 1-Pentanol
was selected as a suitable alcohol due to its low cost, low
toxicity, and for its ability to be oxidized in a one-and-a-half-
hour time period. Furthermore, students are able to obtain
enough material to characterize their product by NMR,
GC/MS, or IR. Lastly, the scale of the reaction was carefully
chosen to prevent a violent reaction from occurring due to the
solvent-free nature of the procedure. As with any experiment,
unauthorized scale-up should not be performed.
O
KMnO4 / CuSO4
HO 1.5 h HO
(1) (2)
Scheme 1

© 2004 The Chemical Educator, S1430-4171(04)0xxxx-x, Published on Web 1/9/2003, 10.1333/s00897040751a, xxxxxxaa.pdf
2 Chem. Educator, Vol. 9, No. X, 2004
Experimental Procedure
A powdered mixture of the oxidant was prepared by grinding 1.58
g (10 mmol) of KMnO4 with 2.50 g (10 mmol) of CuSO4•5 H2O with
a mortar and pestle until the mixture was visually homogeneous. 1-
Pentanol (1) (0.42 g, 4.82 mmol) was added to a 25-mL round-bottom
flask, followed by the addition of ca. 4 g (10 mmol) of the oxidant
mixture. The resulting reaction mixture was stirred vigorously for 1
min with a spatula as the flask began to become warm indicating
initiation of the exothermic reaction. A reflux condenser was
immediately attached and the flask was placed in a preheated hot
water or steam bath at ca. 100 °C. After 1.5 h, the reaction was
stopped [6]. The mixture was cooled to room temperature and
desorbed from the solid reaction byproduct [7] with 2 × 10 mL
portions of diethyl ether. Decantation of the suspension yielded an
ether solution which was in turn acidified with ca. 15 mL of 6 M HCl
at 0 °C to produce a light green biphasic solution. The colorless ether
layer was collected and the aqueous layer was extracted with two
additional 10 mL portions of diethyl ether. Drying of the combined
ether extracts with MgSO4, followed by gravity filtration, and
evaporation of the solvent produced 0.20 g of the desired pentanoic
acid (2) [8] in 41% isolated yield (81% conversion by GC, the
remaining 19% consisted mainly of a mixture of 1-pentanol and
pentanal). Comparison was made between the infrared spectra of the
starting material and that of the product to confirm formation of the
carboxylic acid.
Hazards
Potassium permanganate is a potent oxidizing agent. Care
should be taken when used in conjunction with organic
materials and strong acids. Thermal decomposition may yield
toxic fumes of manganese oxides. Keep reaction temperature at
100 °C or below to help to avoid thermal decomposition.
Diethyl ether is a highly flammable solvent. Hydrochloric acid
is corrosive and may cause burns. Scale-up of the reaction
conditions should not be attempted as the reaction may become
violent.
Acknowledgment. The authors would like to thank Butler
University’s 2003 Summer organic chemistry classes for
helping assist with the preparation and testing of this
laboratory. The authors would also like to thank Dr. Stacy
O’Reilly for helpful discussion.
© 2004 The Chemical Educator, S1430-4171(04)0xxxx-x, Published on Web 1/9/2003, 10.1333/s00897040751a, xxxxxxaa.pdf
View publication stats
Esteb et al.
Supporting Materials. A laboratory handout out for
students is available (DOI 10.1333/s00897040751a)
References and Notes
1. For books on oxidation reactions, see (a) Hudlicky, M. Oxidations in
Organic Chemistry; American Chemical Society: Washington, 1990;
(b) Haines, A. H. Methods for the Oxidation of Organic Compounds,
2 vols.; Academic Press: New York, 1985, 1988; (c) Chinn, L. J.
Selection of Oxidants in Synthesis; Marcel Dekker: New York, 1971;
(d) Augustine, R. L. Oxidation, 2 vols.; Marcel Dekker: New York,
1969, 1971.
2. (a) Esteb, J. J.; Schelle, M. W.; Wilson, A. M. J.Chem. Educ. 2003,
80, 907; (b) McDonald, C. E. J. Chem. Educ. 2000, 77, 750–751; (c)
Shadwick, S. R.; Mohan, R. S. J. Chem. Educ. 1999, 76, 1121–1122;
(d) Hill, J. W.; Jenson, J. A.; Henke, C. F.; Yaritz, J. G.; Pederson, R.
L. J. Chem. Educ. 1984, 61, 1118; (e) Luzzio, F. A.; Fitch, R. W.;
Moore, W. J.; Mudd, K. J. J. Chem. Educ. 1999, 76, 974–975; (f)
Taber, D. F.; Wang, Y.; Liehr, S. J. Chem. Educ. 1996, 73, 1042–
1043; (g) Buglass, A. J.; Waterhouse, J. S. J. Chem. Educ. 1987, 64,
371–372; (h) Crouch, R. D.; Holden, M. S.; Burger, J. S. J. Chem.
Educ. 2001, 78, 951–952; (i) Yohe, G. R.; Louder, H. U.; Smith, G.
A. J. Chem. Educ. 1933, 10, 374–375; (j) Hart, H.; Reilly, J. L. J.
Chem. Educ. 1978, 55, 120–121; (k) Hulce, M.; Marks, D. W. J.
Chem. Educ. 2001, 78, 66–67.
3. Esteb, J. J.; Stockton, M. B. J. Chem. Educ. 2003, 80, 1446–1447.
4. For some recent reviews see (a) Tanaka, K.; Toda, F. Chem. Rev.
2000, 100, 1025–1074. (b) Tanaka, K. Solvent-free Organic
Synthesis; Wiley-VCH: Weinheim, 2003; pp 1–433.
5. Shaabani, A.; Lee, D. G. Tetrahedron Lett. 2001, 42, 5833–5836.
6. We have optimized the conditions for what could be reasonably
performed at most undergraduate universities and colleges. Using a
1.5 hour reaction time allowed for the greatest conversion while still
allowing students a reasonable amount of time to perform the
reaction workup in a 3-hour time period.
7. Decomposition of any excess KMnO4 can be performed by gently
heating the residue in 10 mL of ethanol. Alternatively, we have
found that treating the residue with a solution consisting of two 500
mg vitamin C tablets in 500 mL of water is an effective means of
both decomposing excess KMnO4 and cleaning the glassware used in
the reaction.
8. Pentanoic acid possesses an unpleasant odor. Care should be taken
not to unnecessarily leave the product uncapped outside of the hood.