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
*[email protected]

Students taking their first organic chemistry course often do different oxidation states depending on the substituents on
not recognize oxidation-reduction reactions. When students carbon. Most organic textbooks concede that oxidation and
learn about oxidation-reduction in general chemistry, they are reduction (as defined in terms of electron gain or loss) has little
introduced to it in terms of the loss or gain of electrons. But the meaning in organic chemistry, yet the authors use several pages
notion of gaining or losing electrons becomes less pertinent to describing algorithms to determine whether a given reagent is
organic chemistry. When students are given an organic synthesis, oxidized or reduced.
they rarely think about reagents that will act as either oxidizing or
reducing agents and they tend to lump these reagents with the
A Simpler Approach to Oxidation and Reduction
many other reagents that they memorize. If students are to apply
oxidation states when analyzing the products of organic reac- A relatively simple approach to teach students how to view
tions, the concept needs to be taught in a relevant form. oxidation and reduction is to add the total number of heteroatoms,
Oxidation and reduction has been written about extensively π-bonds (triple bonds count as two), and rings in each organic
in this Journal. Many articles explain oxidation numbers as they reactant and then do the same for each organic product. A higher
are taught in general chemistry courses (1-3) and one article number for the organic product compared to a given organic reac-
explored oxidation numbers in biochemistry (4). Different tant indicates oxidation, whereas a lower number signifies reduction.
approaches have been examined in organic chemistry. One Two examples of organic reactions that demonstrate the approach
approach proposed using electron density as a way of helping are shown in Figures 1 and 2.
students gain more theoretical understanding of oxidation and A slightly more complicated transformation is exemplified
reduction (5). Another article explained the topic with reference in the synthesis of hirsutene shown in Figure 3. From the decrease in
to an “average oxidation number” for carbon (6). oxidation number, it is clear that the transformation requires a
The variety of approaches proposed for introducing oxida- reducing agent, which in this case was tributyltinhydride. (Organo-
tion and reduction in the literature is paralleled by the variety of metallic hydrides are considered to be variants of metal hydride
approaches used in organic textbooks. Many textbooks treat reducing agents. Although they are oxidized in the process of
oxidation-reduction reactions in a cursory manner and often do reducing organic reactants, the focus in this article is on the organic
so with vague or fairly complicated heuristics. The approach reactants or products.) The approach also has application to a group
described in this article is conceptually straightforward so that of compounds related to folic acid (Figure 4).
students can quickly assess an organic reaction in terms of Consideration of oxidation levels is also useful in cases
oxidation and reduction. Because of the simplicity of this where neither oxidation nor reduction occurs because the
approach, instructors could use oxidation and reduction as an alteration of the molecule does not involve an oxidizing or
organizing framework for teaching organic chemistry. The reducing agent. A simple example of this conversion is shown by
concept could be introduced with the very first reactions that the pinacol rearrangement (Figure 5) in which the product is at
are presented such as the halogenation of an alkane or an alkene. the same oxidation state as the starting material. The approach is
The approach described in this article provides students with a also applicable to a more complex situation involving the
simpler approach to oxidation and reduction that can be utilized tautomers of pterin (Figure 6) in which all tautomers have the
for many organic reactions. same oxidation state.
This approach to understanding oxidation-reduction re-
Textbook Treatment of Oxidation and Reduction 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
Textbooks take a variety approaches to discuss oxidation products. For this to be true, one must add an additional
and reduction (7-20). A summary of 11 textbooks is provided in consideration: the total oxidation numbers on both sides of
the supporting information. Although most textbooks still the equation involves the difference in the number of molecules
mention oxidation in terms of a loss of electrons (perhaps as a reacting and the number of molecules formed in the balanced
tie into general chemistry), they often describe oxidation as a equation. For example, in the case of the formation of benzopi-
decrease in hydrogen atoms or an increase in oxygen, nitrogen, or nacol from benzophenone (Figure 7), three reactants are in-
halogen atoms. The more complicated approaches involve a volved (two benzophenone molecules and one isopropanol
calculation of the oxidation state of each carbon atom involved in molecule) and two products are obtained (one benzopinacol
the reaction. Such an approach requires determination of formal molecule and one acetone molecule). The difference between the
charge or a multistep procedure with several subsets to determine number of reactants and the number of products is one, and thus,
the oxidation state of carbon. Similar oxidation levels may have 1 needs to be added to the total oxidation number on the side of

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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 1351
10.1021/ed100457z Published on Web 10/08/2010
 In the Classroom

Figure 5. Application to a rearrangement that is neither an oxidation

nor a reduction: the pinacol rearrangement.

Figure 1. Oxidation of toluene demonstrating the oxidation-reduction

approach.

Figure 6. Examples of compounds with the same oxidation state: tauto-

mers of pterin.

Figure 2. Oxidation of 1-phenyl-1-propene.

Figure 3. Reductive synthesis of hirsutene.

Figure 7. Oxidation numbers for reactants and products for a reaction in

Figure 4. Relative oxidation levels of compounds related to folic acid. which a bond is formed: formation of benzopinacol from benzophenone.

the equation having the smaller number of molecules, in this case, the total oxidation number on the side of the equation that has
the products. An example involving bond breakage is shown by the smaller number of molecules, in this the reactants.
the decarboxylation reaction in Figure 8. The number of pro- Although there does not seem to be any simple corollary
ducts formed is two (cyclohexane carboxlic acid and carbon of the oxidation-reduction approach to inorganic oxidizing or
dioxide) and the number of reactants is one (1,1-cyclohexane reducing agents in general chemistry, the formalization of utiliz-
dicarboxylic acid) so the difference of one needs to be added to ing electron half-reactions can still be applied. Every increase in

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1352 Journal of Chemical Education Vol. 87 No. 12 December 2010 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 Figure 11. Synthesis of progesterone.
lost, the single bonded dihalogen intermediate is at the proper
oxidation state for the desired product. The final elimination student to supply reasonable reagents. A consideration of the
step remains and is neither an oxidation nor a reduction. The oxidation-reduction levels would be a significant help in solving
approach is shown in Figure 10 for the synthesis of phenylace- the problem.
tylene from styrene. Once the student has determined the nature of the transfor-
The oxidation-reduction approach could be employed in mation (oxidation, reduction, or neither), he or she is ready to
the more challenging synthetic problem involving the analysis of choose the reagent needed to bring about the transformation. The
the Johnson progesterone synthesis (21). An examination of the number of oxidizing and reducing reagent that students encounter
oxidation levels for the first step indicates that the reaction is in beginning organic chemistry is rather limited and fall into distinct
neither an oxidation nor reduction but is basically a complex categories. As shown in the table of oxidizing agents (Table 1 in the
intramolecular rearrangement catalyzed by acid (Figure 11). An supporting information), the categories of reagents are halogens,
examination of the oxidation levels for the second step indicates halogens attached to a heteroatom, transition-metal oxides, and
an oxidation and ozone, a reagent that students encounter early group 6A oxides. The categories of reducing agents (Table 2 in the
in organic courses, is employed. The last step is neither an supporting information) consist of catalytic hydrogenations, group
oxidation nor a reduction as indicated by the oxidation levels 3A metal hydrides, organometallics, solvated electrons, and metals
and is an intramolecular aldol cyclization. It is not uncommon in acid. Clearly there are differences in specificity and reactivity of
for problems such as this to leave out the reagents and to ask the 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 7. Jones, J., Maitland Organic Chemistry, 3rd ed.; W. W. Norton:
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1354 Journal of Chemical Education Vol. 87 No. 12 December 2010 pubs.acs.org/jchemeduc r 2010 American Chemical Society and Division of Chemical Education, Inc.