MAPUA UNIVERSITY

School of Chemical, Biological, and Materials Engineering and Sciences

Experiment No. 2.3

Electrophilic Addition: Explore Reactions of Hydrocarbons and Nucleophilic Addition:

Explore the Grignard Reaction

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Date Performed:

Date Submitted:

Faculty In-charge
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I. Introduction

Addition reactions are important in producing raw materials and complex

substances which are used for drug synthesis in the pharmaceutical industry
and for insecticide development in the manufacturing industry (Huang & Li,
2017). With this, the experiment aims to use the knowledge on electrophilic
addition reactions to identify hydrocarbons, and to study the principle of
nucleophilic addition reactions and Grignard reactions to synthesize an organic
molecule. To achieve this, the following sub-objectives are assigned: (1) to
understand the reactions of alkanes, alkenes, and alkynes with electrophiles,
and of carbonyl groups with nucleophiles (2) to provide a detailed and
mechanistic understanding of electrophilic and nucleophilic addition reactions,
(3) to describe a Grignard reaction and the sensitivity of its conditions, (4) to
discuss the role of reagents in a Grignard reaction, (5) to learn about
Markovnikov’s Rule and carbocation stability, (6) to predict the products of
different addition reactions, and (7) to practice essential laboratory techniques
like air-sensitive synthesis, reflux reactions, and synthesis and use of reagents.

II. Theory

Addition reactions, whether electrophilic or nucleophilic addition reactions,

involve the process of transforming sp hybridized carbon atoms into sp 2 or sp3
atoms, or sp2 hybridized carbons into sp3 carbons (Smith, 2017). In electrophilic
addition, an electrophile attacks the double or triple bond of a molecule and
then bonds with the molecule by donating the electron of the pi bond to the
electrophile (Smith & March, 2006). The electrophile used in the reaction does
not have to be a cation, but it can also be the positive region of a dipole or an
induced dipole (Smith & March, 2006). Russian chemist Vladimir Markovnikov
observed in 1870 that electrophiles react to asymmetrical alkenes in a certain
way which he states under Markovnikov’s rule that a molecule H-X reacts to a
double bond so that hydrogen bonds with the unsaturated carbon with the
highest number of hydrogen atoms bonded directly to the carbon atom
(Ouellette & Rawn, 2019).

While in nucleophilic addition, a nucleophile attacks a carbon atom in a

double or triple bond in order to form a carbanion, the mechanism in this
reaction is the same as the electrophilic addition except the charges of the
molecules are reversed (Patai & Rappoport, 1964). However, if an alkene has
a good leaving group, then a substitution reaction may occur as a side reaction
(Patai & Rappoport, 1964). Additionally, Grignard reactions refer to the addition
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of aldehydes and ketones to organomagensium compounds (RMgX) or

Grignard reagents, which are formed from the reaction of magnesium metals
and alkyl, aryl, or vinyl halides in ether or water solvents under certain
conditions (Smith & March, 2006). Lastly, hydrocarbons are the simplest
compounds which contain only hydrogens and carbons arranged in branched
or straight chains, with some containing the same empirical formula but having
different structure and properties (Speight, 2011).

III. Methodology

Identifying Simple Hydrocarbons Using Bromine Test

The chemicals or reagents required for this experiment were bromine water
(Br2 (aq)), hex-1-ene (C6H12), pentane (C5H12), and two unknown water samples.
Meanwhile, the equipment and apparatus used in the experiment were
pipettes, stoppers, test tubes, and a test tube rack. In Figure 1, the
experimental procedure for identifying simple hydrocarbons using the bromine
test was presented.

Figure 1. Process Flow Diagram for Identifying Simple Hydrocarbons

Using Bromine Test

Addition of HBr

The chemicals or reagents required for this experiment were but-1-ene in

dissolved pentane, but-2-ene in dissolved pentane, and hydrogen bromide
(HBr) gas. On the other hand, the equipment and apparatus used in the
experiment were 2 pcs. of funnels, 2 pcs. of graduated cylinders, a gas tank, 2
 School of Chemical, Biological and Materials Engineering and Sciences

sets of ice baths, and 2 pcs. of Schlenk flasks. In Figure 2, the experimental
procedure for the addition of HBr is illustrated.

Figure 2. Process Flow Diagram for Addition of HBr

Synthesis of Organic Compounds through Grignard Reactions

The chemicals or reagents required for this experiment were anhydrous

diethyl ether ((C2H5)2O), bromobenzene (C6H5Br), ketone (LAB-2409),
magnesium, and sulfuric acid (H2SO4). On the other hand, the equipment and
apparatus used in the experiment were an analytical balance, beakers, a
Claisen adapter, a reflux condenser, a 250 mL volumetric flask, an addition
funnel, a glass funnel, a 50 mL graduated cylinder, pipettes, and a spatula. In
Figure 3, the experimental procedure for the synthesis of organic compounds
through Grignard reactions is shown.

Figure 3. Process Flow Diagram for Synthesis of Organic Compounds

through Grignard Reactions
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IV. Results

The resulting data observed and recorded from the experiment are shown
below. In Figure 4, the outcomes of the bromine tests on hex-1-ene, pentane,
and the water samples were presented. The unknown water sample 2 and
pentane did not undergo color change, while hex-1-ene and the unknown water
sample 1 went into a color change from orange to clear or colorless.

Figure 4. Results of the Bromine Tests

Figure 5 demonstrates the graph of the products formed when the HBr gas
reacted with but-1-ene and but-2-ene. The products of reaction of but-1-ene
and HBr have a graph with 2 peaks, while for but-2-ene, the graph has only 1
peak.

Figure 5. Results of the Reactions of HBr and but-1-ene and but-2-ene

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Lastly, in Figure 6, it shows the chemical structure of the reactant ketone,

the Grignard reagent, and the organic compound synthesized through the
Grignard reaction of a Grignard reagent and the ketone.

Figure 6. The Organic Structure of the Product of the Grignard Reaction

V. Discussion

Bromine tests are used to identify whether hydrocarbons possess pi bonds

or unsaturated carbon-carbon bonds in their chemical structure. The bromine,
which is usually orange to brownish in color, breaks the unsaturated carbon
bonds and bonds with each of the two carbon atoms as seen in Figure 7. As it
attaches to the carbons, it loses its original color into a clear or colorless liquid
substance. Looking at the results of the experiment, bromine did not change its
color when mixed with pentane or the unknown water sample 1 (or alkane
hexane). It is because neither compound contains double or triple bonds that
would react with bromine. On the other hand, it turned colorless when hex-1-
ene or the unknown water sample 2 (or 2-methyl-1-butene) was combined with
bromine because both compounds have pi bonds in their chemical structures.

Figure 7. Electrophilic Addition Reaction of Ethene and Bromine

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In this part of the experiment, the resulting solution underwent

chromatography analysis. It is observed from the analysis that the reaction of
HBr and but-1-ene produced a graph with 2 peaks, while the graph for but-2-
ene had only 1 peak. The number of peaks in the graphs indicate the number
of compounds formed which were detected in the chromatography analysis.
With that, 2 compounds were formed when HBr gas was reacted with but-1-
ene, but only 1 compound when reacted with but-2-ene. It is because when
more than one intermediate is possible in the electrophilic addition reaction, the
most stable intermediate is the most likely to be favored in the reaction. And
since but-1-ene is asymmetrical, the reaction could go into two ways, with one
being favored most in the reaction which was observed in the graph. While for
but-2-ene, the compound is symmetrical and could only result into a single
product which was also observed in the chromatography analysis.

Lastly, a Grignard reagent was created from magnesium, bromobenzene,

and anhydrous diethyl ether in the experiment. The resulting product was a
phenylmagnesium bromide (C6H5MgBr) which will be the Grignard reagent for
the succeeding reaction. After that, the sample ketone or LAB-2409 was
reacted with the Grignard reagent, then the solution was poured into the sulfuric
acid in order to break the transition complex and for the alcohol to form in the
product. Looking at the Grignard product, the carbonyl group in the ketone was
replaced with a phenol and alcohol groups.

After this experiment, the knowledge on electrophilic and nucleophilic

addition reactions was applied to identify hydrocarbons and synthesize
compounds using Grignard reaction, respectively. Also, electrophilic addition
reactions regarding alkanes, alkenes, and alkynes, and carbonyl groups for
nucleophilic addition were detailed and understood. The experiment was then
able to predict the products of the electrophilic and nucleophilic addition
reactions. Moreover, the role of reagents and the sensitivity conditions in
Grignard reactions and the carbocation stability in Markovnikov’s Rule were
explored in the laboratory activity. Finally, essential laboratory techniques like
air-sensitive synthesis, reflux reactions, and synthesis and use of reagents
were practiced.
 School of Chemical, Biological and Materials Engineering and Sciences

VI. References
a

Huang, G., & Li, X. (2017). Applications of Michael addition reaction in organic
synthesis. Current Organic Synthesis, 14(4), 568-571.
doi:10.2174/1570179414666161121124846
Ouellette, R. J., & Rawn, J. D. (2019). Alkenes: Addition Reactions. In R. J.
Ouellette, & J. D. Rawn, Organic Chemistry: Structure, Mechanism,
Synthesis (2nd ed., pp. 167-193). Cambridge: Academic Press.
doi:10.1016/B978-0-12-812838-1.50006-2
Patai, S., & Rappoport, Z. (1964). Nucleophilic attacks on carbon–carbon
double bonds. In S. Patai (Ed.), The Chemistry of the Alkenes (Vol. I,
pp. 469-584). Hoboken: John Wiley & Sons.
doi:10.1002/9780470771044.ch8
Smith, M. B. (2017). Acids, Bases, and Addition Reactions. In M. B. Smith,
Organic Synthesis (4th ed., pp. 61-95). Cambridge: Academic Press.
doi:10.1016/B978-0-12-800720-4.00002-7
Smith, M. B., & March, J. (2006). March's Advanced Organic Chemistry:
Reactions, Mechanisms, and Structure (6th ed.). Hoboken: John Wiley
& Sons. doi:10.1002/0470084960
Speight, J. G. (2011). Chemical and Physical Properties of Hydrocarbons. In
J. G. Speight, Handbook of Industrial Hydrocarbon Processes (pp.
325-353). Houston: Gulf Professional Publishing. doi:10.1016/B978-0-
7506-8632-7.10009-X