In the Classroom
Oxidation and Reduction Reactions in Organic
Chemistry
Ivan A. Shibley Jr., Katie E. Amaral,* David J. Aurentz, and Ronald J. McCaully
Division of Science, Penn State Berks, Reading, Pennsylvania 19610, United States
*kea12@psu.edu
Students taking their first organic chemistry course often do
not recognize oxidation-reduction reactions. When students
learn about oxidation-reduction in general chemistry, they are
introduced to it in terms of the loss or gain of electrons. But the
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notion of gaining or losing electrons becomes less pertinent to
organic chemistry. When students are given an organic synthesis,
they rarely think about reagents that will act as either oxidizing or
reducing agents and they tend to lump these reagents with the
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many other reagents that they memorize. If students are to apply
oxidation states when analyzing the products of organic reac-
tions, the concept needs to be taught in a relevant form.
Oxidation and reduction has been written about extensively
in this Journal. Many articles explain oxidation numbers as they
are taught in general chemistry courses (1-3) and one article
explored oxidation numbers in biochemistry (4). Different
approaches have been examined in organic chemistry. One
approach proposed using electron density as a way of helping
students gain more theoretical understanding of oxidation and
reduction (5). Another article explained the topic with reference
to an “average oxidation number” for carbon (6).
The variety of approaches proposed for introducing oxida-
tion and reduction in the literature is paralleled by the variety of
approaches used in organic textbooks. Many textbooks treat
oxidation-reduction reactions in a cursory manner and often do
so with vague or fairly complicated heuristics. The approach
described in this article is conceptually straightforward so that
students can quickly assess an organic reaction in terms of
oxidation and reduction. Because of the simplicity of this
approach, instructors could use oxidation and reduction as an
organizing framework for teaching organic chemistry. The
concept could be introduced with the very first reactions that
are presented such as the halogenation of an alkane or an alkene.
The approach described in this article provides students with a
simpler approach to oxidation and reduction that can be utilized
for many organic reactions.
Textbook Treatment of Oxidation and Reduction
Textbooks take a variety approaches to discuss oxidation
and reduction (7-20). A summary of 11 textbooks is provided in
the supporting information. Although most textbooks still
mention oxidation in terms of a loss of electrons (perhaps as a
tie into general chemistry), they often describe oxidation as a
decrease in hydrogen atoms or an increase in oxygen, nitrogen, or
halogen atoms. The more complicated approaches involve a
calculation of the oxidation state of each carbon atom involved in
the reaction. Such an approach requires determination of formal
charge or a multistep procedure with several subsets to determine
the oxidation state of carbon. Similar oxidation levels may have
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r 2010 American Chemical Society and Division of Chemical Education, Inc. pubs.acs.org/jchemeduc Vol. 87 No. 12 December 2010
10.1021/ed100457z Published on Web 10/08/2010
different oxidation states depending on the substituents on
carbon. Most organic textbooks concede that oxidation and
reduction (as defined in terms of electron gain or loss) has little
meaning in organic chemistry, yet the authors use several pages
describing algorithms to determine whether a given reagent is
oxidized or reduced.
A Simpler Approach to Oxidation and Reduction
A relatively simple approach to teach students how to view
oxidation and reduction is to add the total number of heteroatoms,
π-bonds (triple bonds count as two), and rings in each organic
reactant and then do the same for each organic product. A higher
number for the organic product compared to a given organic reac-
tant indicates oxidation, whereas a lower number signifies reduction.
Two examples of organic reactions that demonstrate the approach
are shown in Figures 1 and 2.
A slightly more complicated transformation is exemplified
in the synthesis of hirsutene shown in Figure 3. From the decrease in
oxidation number, it is clear that the transformation requires a
reducing agent, which in this case was tributyltinhydride. (Organo-
metallic hydrides are considered to be variants of metal hydride
reducing agents. Although they are oxidized in the process of
reducing organic reactants, the focus in this article is on the organic
reactants or products.) The approach also has application to a group
of compounds related to folic acid (Figure 4).
Consideration of oxidation levels is also useful in cases
where neither oxidation nor reduction occurs because the
alteration of the molecule does not involve an oxidizing or
reducing agent. A simple example of this conversion is shown by
the pinacol rearrangement (Figure 5) in which the product is at
the same oxidation state as the starting material. The approach is
also applicable to a more complex situation involving the
tautomers of pterin (Figure 6) in which all tautomers have the
same oxidation state.
This approach to understanding oxidation-reduction re-
actions also follows the rule that the sum of the oxidation levels
of the reactants must equal the sum of the oxidation levels of the
products. For this to be true, one must add an additional
consideration: the total oxidation numbers on both sides of
the equation involves the difference in the number of molecules
reacting and the number of molecules formed in the balanced
equation. For example, in the case of the formation of benzopi-
nacol from benzophenone (Figure 7), three reactants are in-
volved (two benzophenone molecules and one isopropanol
molecule) and two products are obtained (one benzopinacol
molecule and one acetone molecule). The difference between the
number of reactants and the number of products is one, and thus,
1 needs to be added to the total oxidation number on the side of
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Journal of Chemical Education 1351
 In the Classroom
Figure 1. Oxidation of toluene demonstrating the oxidation-reduction
approach.
Figure 2. Oxidation of 1-phenyl-1-propene.
Figure 3. Reductive synthesis of hirsutene.
Figure 4. Relative oxidation levels of compounds related to folic acid.
the equation having the smaller number of molecules, in this case,
the products. An example involving bond breakage is shown by
the decarboxylation reaction in Figure 8. The number of pro-
ducts formed is two (cyclohexane carboxlic acid and carbon
dioxide) and the number of reactants is one (1,1-cyclohexane
dicarboxylic acid) so the difference of one needs to be added to
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1352 Journal of Chemical Education Vol. 87 No. 12 December 2010
Figure 5. Application to a rearrangement that is neither an oxidation
nor a reduction: the pinacol rearrangement.
Figure 6. Examples of compounds with the same oxidation state: tauto-
mers of pterin.
Figure 7. Oxidation numbers for reactants and products for a reaction in
which a bond is formed: formation of benzopinacol from benzophenone.
the total oxidation number on the side of the equation that has
the smaller number of molecules, in this the reactants.
Although there does not seem to be any simple corollary
of the oxidation-reduction approach to inorganic oxidizing or
reducing agents in general chemistry, the formalization of utiliz-
ing electron half-reactions can still be applied. Every increase in
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pubs.acs.org/jchemeduc r 2010 American Chemical Society and Division of Chemical Education, Inc.
 In the Classroom

Figure 8. Oxidation numbers for reactants and products for a reaction

in which a bond is broken: 1,1-cyclohexane dicarboxylic acid to
cyclohexane carboxlic acid.

Figure 10. Conversion of styrene to phenylacetylene.

Figure 9. Half reaction for the oxidation of toluene.

oxidation level of one unit is equivalent to the loss of two electrons.

The general chemistry method of writing half reactions for
inorganic reagents can then be applied to balancing reactions. An
example of the oxidation of toluene to benzoic acid is shown in
Figure 9.

Oxidation-Reduction Approach Applied to Synthesis

Early in the study of organic chemistry students are faced
with the sequence of reactions involving the conversion of an
alkene to an alkyne. There seems to be reluctance by students to
proceed from a double bond to a single-bond intermediate when
they are trying to generate a triple bond. If the process is viewed
from the point of view of oxidation and reduction, the process
becomes clearer. For example, the student can reason that the
synthesis involves an oxidation, that is, going from one π-bond to
two π-bonds. Reaction of the alkene with a halogen (bromine)
brings about the oxidation. Even though the original π-bond is
lost, the single bonded dihalogen intermediate is at the proper
oxidation state for the desired product. The final elimination
step remains and is neither an oxidation nor a reduction. The
approach is shown in Figure 10 for the synthesis of phenylace-
tylene from styrene.
The oxidation-reduction approach could be employed in
the more challenging synthetic problem involving the analysis of
the Johnson progesterone synthesis (21). An examination of the
oxidation levels for the first step indicates that the reaction is
neither an oxidation nor reduction but is basically a complex
intramolecular rearrangement catalyzed by acid (Figure 11). An
examination of the oxidation levels for the second step indicates
an oxidation and ozone, a reagent that students encounter early
in organic courses, is employed. The last step is neither an
oxidation nor a reduction as indicated by the oxidation levels
and is an intramolecular aldol cyclization. It is not uncommon
for problems such as this to leave out the reagents and to ask the
Figure 11. Synthesis of progesterone.
student to supply reasonable reagents. A consideration of the
oxidation-reduction levels would be a significant help in solving
the problem.
Once the student has determined the nature of the transfor-
mation (oxidation, reduction, or neither), he or she is ready to
choose the reagent needed to bring about the transformation. The
number of oxidizing and reducing reagent that students encounter
in beginning organic chemistry is rather limited and fall into distinct
categories. As shown in the table of oxidizing agents (Table 1 in the
supporting information), the categories of reagents are halogens,
halogens attached to a heteroatom, transition-metal oxides, and
group 6A oxides. The categories of reducing agents (Table 2 in the
supporting information) consist of catalytic hydrogenations, group
3A metal hydrides, organometallics, solvated electrons, and metals
in acid. Clearly there are differences in specificity and reactivity of
the reagents in the various categories that the student will need to

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r 2010 American Chemical Society and Division of Chemical Education, Inc. pubs.acs.org/jchemeduc Vol. 87 No. 12 December 2010 Journal of Chemical Education 1353
 In the Classroom
consider, but familiarization with the general nature of oxidizing
and reducing reagents should eliminate a considerable amount of
memorization.
Benefits to Students
Students often think of organic chemistry as a collection of reac-
tions that they need to commit to memory. The underlying similari-
ties among reactions are sometimes lost. Each textbook author takes a
slightly different approach to create unifying themes. However, none
of the books rely on oxidation-reduction reactions as extensively as
they could. A teacher wishing to provide additional coherence to
organic chemistry could utilize the approach suggested above to lead
learners through reactions by continually referring to oxidation levels.
Because the procedure is relatively simple, an instructor no longer
needs to introduce a reaction with a title such as “reduction of
alkenes” but can write a reaction and then ask students whether the
reaction is reduction or oxidation, which can lead them to start
classifying reagents as either oxidizing or reducing agents.
The use of oxidation levels to help understand organic
chemistry could be used as a unifying theme in the course. Even if
an instructor chooses not to focus on oxidation or reduction, the
simplified protocol for determining whether an organic molecule
has been oxidized or reduced should clarify a topic that some-
times seems mysterious to students. As Gregg argued in 1945,
“The student might be able to appreciate many organic reactions
more fully if he [or she] recognized these reactions as oxidation-
reduction reactions.” (22)
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Supporting Information Available
Table of oxidizing agents; table of reducing agents; table of organic
textbooks and a summary of the oxidation-reduction treatment. This
material is available via the Internet at http://pubs.acs.org.
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pubs.acs.org/jchemeduc r 2010 American Chemical Society and Division of Chemical Education, Inc.