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INTRODUCTION
This experiment is designed both as a preparative and an investigative project. Two
outcomes are expected: preparation of benzoic acid from bromobenzene and analysis of
the by-products of a Grignard reaction, an integral part of the synthetic procedure.
GC/MS analysis of the organic layer, generated in the reaction of a Grignard reagent
with CO2, will provide experimental evidence for the nature of the by-products. The
mechanism of the Grignard reaction has been provided in this hand-out, and students
will provide the structure of the by-products in the Pre-Lab assignment. Additionally,
students will propose refinements of the experimental procedure designed to minimize
the amount of by-products. The knowledge of the side products will help students
understand how side reactions affect the yield of the desired material. For example, if
you are an R&D scientist in a company, you would want to minimize the amount of byproducts. The latter reduce the yield of desired compound, therefore increasing the
cost of the product. By-products may contaminate the final material, thus further
increasing cost due to need for additional purification steps.
bromobenzene
+ Mg
anhydrous ether
MgBr
(1)
Phenyl magnesium bromide will then be allowed to react with CO2, followed by
hydrolysis, to give benzoic acid [equation (2)].
1
MgBr
+ CO2
O
O
H+
(MgBr)
OH
(2)
benzoic acid
Ar-----MgBr
MgBr
(MgBr)
(3)
H+
O
OH
+ Mg2+ + Br -
benzoic acid
that may be present. Inorganic ions, such as Mg , Br , H3O , and Cl , remain in the
aqueous layer. The ether layer is removed from the aqueous layer, and the ether is then
extracted with several portions of aqueous NaOH solution. This converts the benzoic
acid into its water-soluble sodium salt, which is now contained in the basic aqueous layer.
Several NaOH extractions are done to help ensure complete removal of benzoic acid
from the ether layer, and the other organic by-products. Note that you must retain
the organic (ether) layer for the optional Part II of this experiment.
3
The combined aqueous sodium hydroxide layers are then boiled gently to remove
traces of ether, which is slightly soluble in water. If the basic solution is not boiled
before acidification, traces of ether will be present in the aqueous layer and thus
dissolve some of the benzoic acid. If the benzoic acid stays dissolved, it will not fully
crystallize upon acidification that would then decrease the amount of benzoic acid
recovered. Decolorizing charcoal is added before boiling to remove any colored
impurities that may be present. The basic solution is then cooled and made distinctly
acidic with HCl to precipitate benzoic acid. Upon protonation of the anion, the ionic
sodium salt becomes an uncharged organic compound, insoluble in a polar solvent like
water. After cooling this mixture in an ice bath, the benzoic acid is collected by vacuum
filtration and allowed to air dry. If your instructor desires, it may be recrystallized
from hot water.
[Note: The ether layer may be analyzed by gas chromatography and mass spectral
analysis for the presence of by-products. See Part II for this discussion.]
REAGENT/PRODUCT TABLE:
Reagents
bromobenzene
Mg
Dry Ice (CO2)
diethyl ether
MW (g/mol) MP (C)
BP (C)
Density
157.02
-31
156
1.491
24.3
Used in Excess - not the limiting reagent
74.12
-166
34.6
Product
benzoic acid
MW (g/mol) MP (C)
122.12
122-123
BP (C)
249
EXPERIMENTAL PROCEDURE:
Preparation of Phenyl Magnesium Bromide
1.
Obtain the following items that have been pre-dried in an oven for you: 1 small
sample vial and cap, 1 large sample vial and cap, one 5" Pasteur pipette, one
Claisen adapter, and one 5 mL conical vial without cap containing a spin vane.
2.
3.
Obtain a drying tube packed with indicating silica gel desiccant pellets, and set up
the apparatus as described in Section A.5 and shown in Figure A.5A. Place the vial
in the aluminum block on the stirring hot plate.
4. Take the large, dry sample vial to your instructor who will fill it about two-thirds
full of anhydrous ether. Tightly cap it, and label it as ether vial.
5.
(a)
For use in Step 6, clean the syringe in the Microscale Kit by drawing several
portions of acetone into it (with needle attached). Carefully remove the
plunger and place the barrel end of the syringe over the heavy-walled tubing
attached to the house vacuum, and pull air through the syringe for a minute to
remove the acetone. Carefully reinsert the plunger.
Using the clean, dry syringe (Step 5a), transfer all the bromobenzeneether
mixture to the conical vial containing the Mg turnings. This may be done by drawing
the bromobenzeneether mixture into the syringe, inserting the needle through the
rubber septum on the reaction apparatus, and injecting the mixture. It will be
necessary to refill the syringe several times to get all the bromobenzeneether
mixture into the conical vial, and this should be done as quickly as possible.
7.
Turn on the magnetic stirrer (no heat), and stir the mixture gently. The reaction
has started when the solution turn light yellow (or darker) color; another indication
that the reaction has started is the formation of a brownish-gray, cloudy solution
and sometimes even a trace of white precipitate (magnesium hydroxide). If none of
these changes are observed after 510 min, consult your instructor.
8.
As soon as the reaction has started, use the syringe and add about 1 mL of ether
from the ether vial to the conical vial. If the reaction becomes too vigorous, as
evidenced by vigorous boiling, place the conical vial in a beaker of cold tap water
until the boiling has subsided some but do not cool it until the boiling stops. The
volume of the reaction mixture should be about 4 mL that can be estimated from
the volume markings on the conical vial. If not, add more ether from the ether
vial to the reaction mixture using the syringe so the volume is at least 4 mL.
9. Allow the reaction mixture to stir for an additional 510 min, during which time most
or all of the magnesium metal should be gone. If traces of Mg metal are left, they
will dissolve when HCl is added in Step 11.
For adding this 1-mL of ether, you may use the syringe without cleaning and drying it.
17. Repeat Step 16 two more times with 4 mL portions of 5% NaOH. Combine all the
NaOH extracts in the same beaker. Save the upper ether layer remaining in a vial
labeled ether layer.
2
18. Add a little decolorizing charcoal to the beaker containing the basic NaOH layers
and heat it gently on the hot plate, with stirring or swirling, for about 2 minutes to
remove traces of ether dissolved in the aqueous layer. The solution does not have
to, and should not boil, although the bubbles of escaping ether fumes will be
observed initially.
19. Using a glass funnel and filter paper, gravity filter the contents of the beaker into
another clean, small beaker. Add about 2 mL of water to this beaker that contained
the NaOH layers from Step 18, swirl around, rinsing the inside of the beaker as
best as possible. Pour this through the filter paper as well. The filter funnel does
not have to be pre-warmed because the product is contained in solution as its watersoluble sodium salt and thus will not crystallize in the funnel.
20. Cool the beaker containing the filtrate from Step 19 to room temperature by
placing it on the bench for a couple minutes. With stirring, add about 4 mL of 6 M
HCl to the beaker. This converts sodium benzoate into benzoic acid, and you should
observe the formation of a white precipitate of benzoic acid. Use pH paper to
determine that the solution is pH ~ 1. (Check the pH by adding a drop of solution on
the tip of a stirring to a piece of pH paper. DO NOT dip the pH paper in the
solution.) If the solution is not pH 1, add HCl dropwise and with stirring until the
solution is the proper acidity.
21. Cool the beaker in an icewater bath. Collect the benzoic acid by vacuum filtration
on a Hirsch funnel (Section A.2, Figure A.2). Add 1 mL of ice water to the beaker,
swirl to rinse, and pour over the solid on the funnel. Repeat with a second 1 mL
portion of ice-water. Support the funnel in a beaker and allow it to dry until the
3
22. Transfer the dry benzoic acid to a dry, pre-weighed sample vial, and determine the
weight and percent yield of the product. Determine the mp range (reported mp of
benzoic acid: 122C) and hand in the product in properly labeled vial.
WASTE DISPOSAL
1.
Place the acid layer from Step 15 and the filtrate from Step 21 in the aqueous acid
waste bottle.
2.
Place the organic layer remaining in the large vial (Step 17) in the organic waste
container.
3.
Filter paper and other paper waste belong in the trash can.
The mechanism for the formation of a Grignard reagent, and of some of the byproducts, is shown below. Notice that the reaction is initiated at the surface of the
metal by an electron transfer to the aryl halide. This reduction process results in the
formation of a bromide anion and a phenyl radical, a highly energetic, reactive
intermediate. This molecule results when the bromide anion is removed from the
2
bromobenzene radical anion. The resulting unpaired electron remains in the vacant sp
hybrid orbital. This free-radical is very similar to the familiar alkyl radical such as
3
methyl, with an unpaired electron in the sp orbital. It is the phenyl radical that reacts
+1
with Mg to generate phenyl magnesium cation that then traps a bromide anion to form
the Grignard reagent, 1.
Phenyl radical may undergo side reactions typical of organic radicals, such as
reaction with another phenyl radical. This occurs when the localized concentration of
8
radicals is too high. The resulting possible by-products will be identified by the GC/MS
analysis of the ether layer saved from Step 17, which was used in Steps 23-25. Recall
that the Pre-Lab exercise asked that you make some suggestions as to the nature of
these by-products based on your understanding of radical reactions. Now you can use
GC/MS data to validate or refute your previous hypothesis.
Note that the
understanding of these side reactions will help you in planning your experimental
synthetic procedure. Obviously, minimizing the former will increase the yield of the
desired Grignard reagent and ultimately the desired product.
Br
Br
+ Mg+1
radical anion
By-Product A
+ Br-1 + Mg+1
phenyl radical
By-Product B
H2O
MgBr
CO2
OH
The results of the GC/MS analysis will be given to you in either of two ways: as a
chromatogram file, stored on one of the NT Windows computers as described in the
general hand-out for the discovery-based experiments, or as an output of the GC/MS
instrument. In the latter case, you will receive a gas chromatogram printout of the
GC/MS with mass spectra of each of the by-products.
90
85
80
75
70
65
60
%Transmittance
55
50
45
40
35
30
25
20
15
10
5
-0
4000
3500
3000
bromobenzene
2500
2000
Wavenumbers (cm-1)
1500
1000
100
95
90
85
80
75
70
%Transmittance
65
60
55
50
45
40
35
30
25
20
15
10
4000
3500
3000
2500
2000
Wavenumbers (cm-1)
1500
1000
O
OH
0.07
0.14
10
0.21
6
PPM