Demonstration

pubs.acs.org/jchemeduc

Regioselective Hydration of an Alkene and Analysis of the Alcohol

Product by Remote Access NMR: A Classroom Demonstration
Maureen E. Smith, Sara L. Johnson, and Douglas S. Masterson*
Department of Chemistry and Biochemistry, The University of Southern Mississippi, Hattiesburg, Mississippi 39406, United States
*
S Supporting Information

ABSTRACT: A two-part demonstration was conducted in our first-

semester organic chemistry course designed to introduce students to the
formation of alcohols, regioselective reactions, and analysis of organic
products by NMR analysis. This demonstration utilized the oxymercura-
tion−demercuration sequence to prepare an alcohol from an alkene in a
Markovnikov manner because the reaction is easy to execute and has a
dramatic, observable color change during the transformation. The alcohol
product produced was then utilized in a classroom demonstration of 1H
NMR using a remote accessible NMR spectrometer.

KEYWORDS: Second-Year Undergraduate, Demonstrations, Organic Chemistry, Hands-On Learning/Manipulatives,

Constitutional Isomers, NMR Spectroscopy

H ydration of an alkene to produce an alcohol, by addition

of water across a double bond, is a fundamental reaction
taught in organic chemistry courses. Students learn that
hydration reactions can be completed in a regioselective
manner. One regioselective method is the hydroboration−
oxidation sequence. This reaction has been carried out
successfully as an undergraduate laboratory experiment.1−3
However, the reaction is not a feasible reaction for an in-
classroom demonstration because it must be carried out under
a nitrogen atmosphere, requires a long reaction time (>30
min), and does not produce any visible changes during the
reaction progress. A second regioselective method of hydration
is the oxymercuration−demercuration sequence. This reaction
lends itself well to the classroom, as it proceeds quickly without
side products and provides clear color changes that are easily
observable as the reaction progresses. Additionally, workup is
rapid and straightforward, allowing for quick characterization of
the product by NMR. Therefore, for this demonstration, a
modified undergraduate organic laboratory oxymercuration−
demercuration experiment was chosen for use in the class-
room.4
This reaction takes place in two stages, the oxymercuration
with mercuric acetate, followed by the in situ reduction of the
organomercurial intermediate with sodium borohydride. In the
oxymercuration step, 1-octene is reacted with a solution of
mercuric acetate in deionized water/tetrahydrofuran (THF).
The solution of mercuric acetate in H2O/THF begins opaque
yellow, and immediately becomes clear and colorless as it reacts
with the 1-octene, indicating the formation of the organo-
mercurial intermediate. The intermediate is reduced in situ by
treatment with sodium borohydride in basic medium,
© 2012 American Chemical Society and
Division of Chemical Education, Inc.
producing a secondary alcohol. Metallic mercury is formed in
this reaction sequence and is recovered from the mixture by
simple decantation (Scheme 1).
The oxymercuration−demercuration sequence is an example
of a regioselective reaction where the formation of one bond is
preferred over other possible locations. Two possible products
may arise from the hydration of 1-octene, 1-octanol or 2-
octanol. In this reaction, Markovnikov’s rule allows one to
predict which product will be formed by stating that in the
addition of water to a double bond, the nucleophile will be
added to the more substituted carbon of the double bond.
Therefore, using Markovnikov’s rule, students should predict
that the product of this reaction will be 2-octanol. However,
formation of this product may not be intuitive to a novice
organic chemist, as a student can use correct arrow pushing
formalisms to arrive at either product. The two products are
structurally different, but there is no difference between their
physical properties that would allow for easy identification by
the students in a classroom setting. Because the product
requires further analysis, the situation presents an opportunity
to demonstrate region-specificity, Markovnikov’s rule, and the
use of NMR spectroscopy in structural identification.
Organic chemistry students are exposed to NMR spectros-
copy through both lecture and laboratory; however, because of
time and resource limitations, very few students experience
more than a theoretical education in the introductory organic
course sequence. Unless a student participates in undergraduate
research, most student experience is limited to analysis of
hypothetical spectra based on the predicted product of a
Published: November 2, 2012
99 dx.doi.org/10.1021/ed300053z | J. Chem. Educ. 2013, 90, 99−101
Journal of Chemical Education
Scheme 1. Oxymercuration−Demercuration Reaction and Corresponding Color Changes
laboratory reaction or analysis of samples produced and
purified by the instructor. These spectra do not give students
an accurate impression of NMR spectroscopy or the scientific
process because hypothetical spectra do not take into account
side products, and instructor-prepared samples are less likely to
include contaminants and unreacted materials. Therefore,
although students learn to interpret spectra, they do not
become familiar with the nature of science. Likewise, students
gain no experience with the instrument or the processes by
which spectra are obtained.
Students’ lack of experience is due largely to the cost of
NMR spectrometers and their maintenance. Such instrumenta-
tion is too costly for most colleges to maintain for the sole
purpose of education. NMR spectrometers are common to
research universities, but access to these instruments by
students is limited by their location and availability.
Spectrometers are often located in research departments
where it is not feasible for inexperienced undergraduate
chemistry students to have open access on an individual basis
without major safety concerns. In addition, the increase in
traffic would disrupt researchers and place an unnecessarily
high demand on persons responsible for maintaining the
instrument.
In an effort to expand the use of research instrumentation,
the National Science Foundation has awarded funds to
universities interested in purchasing multiuser cyber-accessible
instruments. The remote network infrastructure allows for
instrumentation in one location to be accessed by users in a
different location. This feature increases the research
accessibility of the instrument and creates a new opportunity
for educational outreach. Sharing of the instrument allows
instructors on the same or nearby campuses to incorporate
NMR spectroscopy into their classroom. The remote network
infrastructure increases use of the instrument and enriches the
educational experience of students involved without increasing
safety or traffic concerns.
In recent years, several examples of networked NMR
spectrometer arrangements have been published.5−8 We
describe an organic chemistry demonstration that makes use
of remote access to a networked NMR spectrometer equipped
with Web camera to demonstrate the identification of the
product obtained from the hydration of 1-octene by the
oxymercuration−demercuration sequence.
■
DEMONSTRATION
The oxymercuration−demercuration reaction took place in a
single reaction flask. Mercuric acetate was placed in an
Erlenmeyer flask and dissolved in deionized water. After the
100
Demonstration
mercuric acetate was dissolved, THF was added with
continuous swirling. This resulted in the solution turning an
opaque yellow color and the formation of a fine precipitate.
Next, 1-octene was added to the flask with continuous swirling.
As the 1-octene was added, the solution quickly changed colors
from bright opaque yellow to clear and colorless, indicating that
the organomercuric intermediate has been formed (Scheme 1).
The organomercurial intermediate was then reduced by slowly
adding an aliquot of NaBH4 in NaOH solution to the
Erlenmeyer flask. The reaction was exothermic, so the flask
was placed in a cool water bath to avoid excessive boiling of the
THF. During the addition of the NaBH4/NaOH solution to the
flask, the solution turned an opaque gray that separated with
time to a clear colorless liquid and a mercury precipitate. After
typical workup, a sample was prepared for NMR analysis. A
proton NMR spectrum was acquired using a spectrometer that
was accessed by remote connection. Students observed the
instrument demonstration by a Web camera.
Workup of product, setup of the remote network infra-
structure, sample preparation, details of NMR data acquisition,
and spectra can be found in Supporting Information.
■
HAZARDS
Safety glasses, gloves, and laboratory coat were all worn during
this demonstration. Mercuric acetate is toxic and can cause skin
irritation, eye, and lung damage and should be handled with
extreme care. The alkene, 1-octene, can cause skin, respiratory
tract, and eye irritation and damage. Sodium borohydride and
sodium hydroxide are caustic and can cause burns of the skin,
eye, and respiratory tract. Tetrahydrofuran can cause skin and
eye irritation. Dichloromethane can cause skin and eye
irritation and is harmful if swallowed. Deuterated chloroform
is a suspected carcinogen and should be handled with care. The
dichloromethane and deuterated chloroform were both handled
in a well-ventilated hood.
■
DISCUSSION
This demonstration was presented in two classes of first-
semester introductory organic chemistry: a larger regular
lecture section and a smaller honors section. Each demon-
stration was presented using two people, the instructor and the
presenter, over two class periods. The demonstrations were
scheduled to coincide with the instructor’s lessons on
regioselectivity and NMR spectroscopy, but they were not
presented in consecutive classes. In between the two
demonstrations, the product was worked up and prepared for
NMR analysis. Each demonstration used approximately 15 min
dx.doi.org/10.1021/ed300053z | J. Chem. Educ. 2013, 90, 99−101
Journal of Chemical Education Demonstration

of the beginning of class. This left the rest of the class period
for the instructor to cover class content.
The group presentation dynamic worked well, as the
presenter was able to focus on presenting the demonstration
while the instructor was able to talk about the related course
content. This also prevented any downtime when issues arose
with the demonstration. In general, most chemistry questions
were directed to and addressed by the instructor. However,
during the NMR analysis, students did ask the presenter
questions about how the instrument was maintained. A number
of students were interested in the technical details of the
instrument and acquisition process. They asked questions about
the sample tubes, the strength of the magnet, and the
temperature of fluids inside the magnet.
When students compared the acquired spectrum to the two
possible products, they were able to identify peaks indicating
the presence of 2-octanol. Students also mentioned that a
number of other peaks were present (slight amount of 1-octene
and trace solvents). This was due to the fact that the product
had been worked up, but not purified. Students discussed what
these peaks’ presence meant about the reaction and, in the
honors section, some students even assigned the peaks to the
starting materials.

■
*
ASSOCIATED CONTENT
S Supporting Information

Product workup, setup of the remote network infrastructure,

sample preparation, details of NMR data acquisition, and
spectra. This material is available via the Internet at http://
pubs.acs.org.

■ AUTHOR INFORMATION
Corresponding Author
*E-mail: Douglas.Masterson@usm.edu.
Notes
The authors declare no competing financial interest.

■ ACKNOWLEDGMENTS
D.S.M. would like to thank the National Science Foundation
for a CAREER award (MCB 0844478). M.E.S. would like to
thank the National Science Foundation for providing her with a
GK-12 Fellowship (0947944). S.L.J. would like to thank the
National Science Foundation for the instrumentation grant
providing equipment and funding used in this work (CHE
0840390). We would also like to thank Gary Cook for his help
in the initial setup of the remote network infrastructure.

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