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
producing a secondary alcohol. Metallic mercury is formed in
this reaction sequence and is recovered from the mixture by
simple decantation (Scheme 1).
hydration reactions can be completed in a regioselective The oxymercuration−demercuration sequence is an example
manner. One regioselective method is the hydroboration− of a regioselective reaction where the formation of one bond is
oxidation sequence. This reaction has been carried out preferred over other possible locations. Two possible products
successfully as an undergraduate laboratory experiment.1−3 may arise from the hydration of 1-octene, 1-octanol or 2-
However, the reaction is not a feasible reaction for an in- octanol. In this reaction, Markovnikov’s rule allows one to
classroom demonstration because it must be carried out under predict which product will be formed by stating that in the
a nitrogen atmosphere, requires a long reaction time (>30 addition of water to a double bond, the nucleophile will be
min), and does not produce any visible changes during the added to the more substituted carbon of the double bond.
reaction progress. A second regioselective method of hydration Therefore, using Markovnikov’s rule, students should predict
is the oxymercuration−demercuration sequence. This reaction that the product of this reaction will be 2-octanol. However,
lends itself well to the classroom, as it proceeds quickly without formation of this product may not be intuitive to a novice
side products and provides clear color changes that are easily organic chemist, as a student can use correct arrow pushing
observable as the reaction progresses. Additionally, workup is formalisms to arrive at either product. The two products are
rapid and straightforward, allowing for quick characterization of structurally different, but there is no difference between their
the product by NMR. Therefore, for this demonstration, a physical properties that would allow for easy identification by
modified undergraduate organic laboratory oxymercuration− the students in a classroom setting. Because the product
demercuration experiment was chosen for use in the class- requires further analysis, the situation presents an opportunity
room.4 to demonstrate region-specificity, Markovnikov’s rule, and the
This reaction takes place in two stages, the oxymercuration use of NMR spectroscopy in structural identification.
with mercuric acetate, followed by the in situ reduction of the Organic chemistry students are exposed to NMR spectros-
organomercurial intermediate with sodium borohydride. In the copy through both lecture and laboratory; however, because of
oxymercuration step, 1-octene is reacted with a solution of time and resource limitations, very few students experience
mercuric acetate in deionized water/tetrahydrofuran (THF). more than a theoretical education in the introductory organic
The solution of mercuric acetate in H2O/THF begins opaque course sequence. Unless a student participates in undergraduate
yellow, and immediately becomes clear and colorless as it reacts research, most student experience is limited to analysis of
with the 1-octene, indicating the formation of the organo- hypothetical spectra based on the predicted product of a
mercurial intermediate. The intermediate is reduced in situ by
treatment with sodium borohydride in basic medium, Published: November 2, 2012
© 2012 American Chemical Society and
Division of Chemical Education, Inc. 99 dx.doi.org/10.1021/ed300053z | J. Chem. Educ. 2013, 90, 99−101
Journal of Chemical Education Demonstration

Scheme 1. Oxymercuration−Demercuration Reaction and Corresponding Color Changes

laboratory reaction or analysis of samples produced and mercuric acetate was dissolved, THF was added with
purified by the instructor. These spectra do not give students continuous swirling. This resulted in the solution turning an
an accurate impression of NMR spectroscopy or the scientific opaque yellow color and the formation of a fine precipitate.
process because hypothetical spectra do not take into account Next, 1-octene was added to the flask with continuous swirling.
side products, and instructor-prepared samples are less likely to As the 1-octene was added, the solution quickly changed colors
include contaminants and unreacted materials. Therefore, from bright opaque yellow to clear and colorless, indicating that
although students learn to interpret spectra, they do not the organomercuric intermediate has been formed (Scheme 1).
become familiar with the nature of science. Likewise, students The organomercurial intermediate was then reduced by slowly
gain no experience with the instrument or the processes by adding an aliquot of NaBH4 in NaOH solution to the
which spectra are obtained. Erlenmeyer flask. The reaction was exothermic, so the flask
Students’ lack of experience is due largely to the cost of was placed in a cool water bath to avoid excessive boiling of the
NMR spectrometers and their maintenance. Such instrumenta- THF. During the addition of the NaBH4/NaOH solution to the
tion is too costly for most colleges to maintain for the sole flask, the solution turned an opaque gray that separated with
purpose of education. NMR spectrometers are common to time to a clear colorless liquid and a mercury precipitate. After
research universities, but access to these instruments by typical workup, a sample was prepared for NMR analysis. A
students is limited by their location and availability. proton NMR spectrum was acquired using a spectrometer that
Spectrometers are often located in research departments was accessed by remote connection. Students observed the
where it is not feasible for inexperienced undergraduate instrument demonstration by a Web camera.
chemistry students to have open access on an individual basis Workup of product, setup of the remote network infra-
without major safety concerns. In addition, the increase in structure, sample preparation, details of NMR data acquisition,
traffic would disrupt researchers and place an unnecessarily and spectra can be found in Supporting Information.

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high demand on persons responsible for maintaining the
instrument. HAZARDS
In an effort to expand the use of research instrumentation,
the National Science Foundation has awarded funds to Safety glasses, gloves, and laboratory coat were all worn during
universities interested in purchasing multiuser cyber-accessible this demonstration. Mercuric acetate is toxic and can cause skin
instruments. The remote network infrastructure allows for irritation, eye, and lung damage and should be handled with
instrumentation in one location to be accessed by users in a extreme care. The alkene, 1-octene, can cause skin, respiratory
different location. This feature increases the research tract, and eye irritation and damage. Sodium borohydride and
accessibility of the instrument and creates a new opportunity sodium hydroxide are caustic and can cause burns of the skin,
for educational outreach. Sharing of the instrument allows eye, and respiratory tract. Tetrahydrofuran can cause skin and
instructors on the same or nearby campuses to incorporate eye irritation. Dichloromethane can cause skin and eye
NMR spectroscopy into their classroom. The remote network irritation and is harmful if swallowed. Deuterated chloroform
infrastructure increases use of the instrument and enriches the is a suspected carcinogen and should be handled with care. The
educational experience of students involved without increasing dichloromethane and deuterated chloroform were both handled
safety or traffic concerns. in a well-ventilated hood.

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In recent years, several examples of networked NMR
spectrometer arrangements have been published.5−8 We DISCUSSION
describe an organic chemistry demonstration that makes use
of remote access to a networked NMR spectrometer equipped This demonstration was presented in two classes of first-
with Web camera to demonstrate the identification of the semester introductory organic chemistry: a larger regular
product obtained from the hydration of 1-octene by the lecture section and a smaller honors section. Each demon-
oxymercuration−demercuration sequence. stration was presented using two people, the instructor and the

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presenter, over two class periods. The demonstrations were
scheduled to coincide with the instructor’s lessons on
DEMONSTRATION regioselectivity and NMR spectroscopy, but they were not
The oxymercuration−demercuration reaction took place in a presented in consecutive classes. In between the two
single reaction flask. Mercuric acetate was placed in an demonstrations, the product was worked up and prepared for
Erlenmeyer flask and dissolved in deionized water. After the NMR analysis. Each demonstration used approximately 15 min
100 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.

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*
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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