CHEM 2380

Grignard Reagents: Synthesis of Triphenylmethanol

Shilton & Co.

4 Quayside, Beach Head, FL 38283

Robert Moore
School of Chemistry and Biochemistry
Georgia Institute of Technology
Atlanta, Georgia 30332-0400

Dear Dr. Moore:

It was good to meet you last month at the International
Conference on Organic Radicals. As we discussed, Shilton & Co.
markets standards for scientific, engineering and biomedical
diagnostic instrumentation. We have been asked to supply a
customer with a material which is a stable carbon radical. Our
review of the .scientific literature suggests that triarylmethane
radicals, Ar3C , are relatively stable. Accordingly, we need to
acquire a material from which we can generate these radicals so
that we can assess their stability.
Is it possible to prepare triarylmethanols in your research
laboratories? These could then be converted to the corresponding
halides, from which we believe that we can abstract halogen atoms
to prepare the radicals.
Triphenylmethanol would certainly be a useful first attempt for
us to prove whether this is a feasible route.
Please provide a detailed report for inclusion in our
applications newsletter,Organichimica Acta.
Regards,
Hal Jorgensen

Shilton & Co.

INTRODUCTION
Grignard reagents are particularly useful to prepare new carbon-carbon bonds by addition to
carbonyl compounds (Solomons 10e, 12-6,8). Grignard reagents are made by reaction of alkyl
or aryl bromides with magnesium. Besides being nucleophilic, Grignard reagents are strong
bases: they react with water, requiring that they be handled with extreme care.
In this experiment, you will carry out the reaction of bromobenzene with magnesium to
afford phenylmagnesium bromide, and them perform an addition of the Grignard reagent to
benzophenone, a ketone. Aqueous work-up will give the tertiary alcohol, triphenylmethanol.
MgBr

Br
Mg
Et2 O

MgBr
O

1.

OH
Me-O-tBu
2. H3 O+

The procedure provided for the synthesis of triphenylmethanol from bromobenzene and
benzophenone is taken from the research literature. This demonstrates how abbreviated
experimental sections are in the scientific literature relative to the detailed procedure provided.

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Experiment: Educational Objectives

Reaction

Preparation of Grignard Reagent

Arylbromide + Magnesium Grignard reagent
Grignard addition to ketone
Ketone + Grignard reagent 3 Alkoxide
Protonation of Alkoxide
3 Alkoxide + Acid 3 Alcohol
Overall, this is a nucleophilic addition to a carbonyl.

New techniques

Handling water sensitive reagents

Trituration
Infrared spectroscopy of solids
using single-crystal attenuated total reflectance

Other techniques

Extraction

Other concepts

Organometallic chemistry

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SECTION________________

NAME_______________________

PRE-LAB EXERCISES (due at beginning of lab)

1. Read the entire procedure and cited sections of the Techniques Manual, and view the appropriate web
video clips. Transfer a written procedure to your notebook. You will not be allowed to take copies of
the experiment or manual into the laboratory. Thus, the procedure in your notebook should be
sufficiently detailed for you to take the pre-lab quiz and to perform the experiment in the absence of
other information.

2. Provide a detailed procedure for the synthesis of triphenylmethanol from the Grignard reagent
(phenylmagnesium bromide) in the space provided. Include in this procedure the following quantities
to be used: i) mass of 2.0 mmol of magnesium metal, ii) volume of bromobenzene (as specified in
Procedure 11.1B) , iii) mass of benzophenone (as specified in Procedure 11.2) and iv) theoretical
yield of triphenylmethanol. [Remember, yields are quoted relative to the moles of limiting reagent]

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PROCEDURE

You will (Period 9 or 10):

1. Prepare phenylmagnesium bromide (30 minutes).
2. React phenylmagnesium bromide with benzophenone and quench the reaction (120
minutes).
4. Characterize the product by melting point (30 minutes).
3. Characterize the product by infrared spectroscopy. (5 minutes).
1. Preparing Phenylmagnesium Bromide
Safety
1. Minimize your exposure to organic solvents
2. Grignard reactions are extremely reactive and should be handled with care to avoid
exposure to water.
3. Glassware taken from the oven will be hot!
4. Be careful with syringes and needles. The Laboratory Instructor will demonstrate transfer
of diethyl ether using a syringe.
Procedure
A. LITERATURE PROCEDURE

Triphenylmethanol, 12c. Bromobenzene (55 mL, 0.52 mmol) was

added slowly to a mixture of magnesium (12.2 g, 0.50 mmol) and
anhydrous diethyl ether (250 mL). After consumption of the
magnesium, the solution was added slowly to a solution of
benzophenone (91 g, 0.50 mmol) in anhydrous methyl tert-butyl ether
(250 mL). The mixture was stirred for 30 min and 3 M hydrochloric
acid (500 mL) was added. The product was extracted into methyl tertbutyl ether (3 x 200 mL). The organic portion was washed with
saturated aqueous sodium chloride (300 mL), dried over CaCl2, filtered
and the solvent was removed to afford triphenylmethanol as an offwhite solid (98.8 g, 76%). mp 160-163 C. 1H NMR (CDCl3, 300
MHz) 2.82 (s, 1 H, -OH), 7.2-7.3 (m, 15 H, aromatic).

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B. DETAILED PROCEDURE
All equipment and reagents used in this procedure must be absolutely dry. The glassware to
be used (reaction tubes, and a stirring rod) can be dried in a 110 C oven for 30 min, along with
the magnesium. The plastic and rubber ware should be rinsed with acetone and blown
completely dry in a flow of air. Do not place plastic ware in the oven. New, sealed packages of
syringes can be used without prior drying.
Remove a reaction tube from the oven, and immediately cap it with a septum. In the
operations that follow, keep the tube capped except when it is necessary to open it. Allow the
tube to cool to room temperature and then add about 2.0 mmol of magnesium powder. Record
the weight of magnesium used to the nearest milligram. Crush the magnesium powder in the
bottom of the reaction tube with a glass stir bar before recapping the tube. This will create a
fresh surface of the metal, free of oxide and grease, at which the reaction will begin. Anhydrous
diethyl ether (0.5 mL ) is obtained and added to the magnesium. Place an empty syringe needle
through the septum for pressure release.
Obtain 0.7 mL of anhydrous diethyl ether in a second dry, capped reaction tube and a 15%
molar excess of bromobenzene. Swirl this tube to mix the diethyl ether and bromobenzene.
Using a syringe, inject approximately 0.1 mL of the bromobenzene solution into the reaction
tube containing magnesium and diethyl ether. Mix the contents by vigorously flicking the tube.
The reaction will ordinarily start at this point. If the reaction does not start at this point, hold
the tube on the bench-top, remove the septum briefly and crush the magnesium with a glass stirrod. The reaction should start within seconds. Immediately replace the septum, syringe and
needle. Once the Grignard reaction starts, it will continue. The solution will become cloudy and
begin to boil as the magnesium metal reacts with the bromobenzene to form phenylmagnesium
bromide.
Once the reaction has started bubbling, or gently boiling, add the remainder of the solution of
bromobenzene one or two drops at a time, over a period of several minutes, shaking the tube
vigorously between each addition. The reaction is complete when the boiling subsides and none
(or a very little) of the magnesium remains. If diethyl ether has evaporated form the mixture,
add anhydrous tert-butyl methyl ether to make the volume up to 1.5 mL, prior to starting the next
step.
Cleaning up
Dispose of all wastes in appropriate containers.
2. Reaction of Phenylmagnesium Bromide with Benzophenone
Safety
1. Phenylmagnesium bromide is extremely reactive: handle with caution.
2. Minimize exposure to organic solvents.
Procedure
Dissolve 2.0 mmol [Mass?] of benzophenone in 1.0 mL of anhydrous tert-butyl methyl ether
in a capped reaction tube by gentle shaking. Pull the solution into a dry syringe and add it dropwise through the septum to the solution of the Grignard reagent over 10 minutes with shaking
after addition of every second drop. Rinse the last traces of benzophenone out of the vial with a

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few drops of anhydrous tert-butyl methyl ether, and add this solution to the reaction tube.
Remove the syringe but leave the needle in the septum. Mix the contents of the tube thoroughly
using a stirring rod and recap the tube. Allow the mixture to stand at room temperature. The
reaction is complete when the red color fades and an off-white solid remains.
Upon completion of the reaction, remove the septum, cool the tube in an ice-bath and add 2
mL of 3 M hydrochloric acid to the mixture dropwise, with stirring. Verify that the aqueous
solution is acidic with litmus. Allow sufficient time for any leftover magnesium to react with the
hydrochloric acid. Transfer the solution to a centrifuge tube using 2 mL of methyl tert-butyl
ether (this does not have to be anhydrous) to complete the transfer. Shake the tube to extract the
triphenylmethanol. Two clear (though not necessarily colorless) liquid layers will separate upon
standing. Remove the aqueous layer with a Pasteur pipette. Shake the ether layer with an equal
volume of saturated aqueous sodium chloride solution to remove water and any remaining acid.
Remove the aqueous layer again, and then dry the methyl tert-butyl ether layer by adding
anhydrous CaCl2 pellets to the tube.
Using a Pasteur pipette, remove the solution from the drying agent and place it in a
preweighed, labeled dry Erlenmeyer flask. Wash off the CaCl2 with 1 mL of methyl tert-butyl
ether, and add this to the solution in the Erlenmeyer flask. Place a boiling stick in the solution in
the Erlenmeyer flask and heat the mixture to gentle boiling on a steam bath to remove the solvent
Use trituration to purify the product. Add 0.5 mL of petroleum ether in an ice bath and
grinding up the solid with a stirring rod. Collect the product by vacuum filtration on the Hirsch
funnel, using a few mL of cold petroleum ether to complete the transfer.
Cleaning up
Dilute the acidic aqueous layer and the saturated sodium chloride with water and flush it
down the drain. Discard methyl tert-butyl ether in the non-halogenated organic waste container.
3. Characterization of Product
Procedure
Obtain a melting point of your product.
Obtain the infrared spectrum of the isolated triphenylmethanol using attenuated total
reflectance (ATR).

Smart MIRacle ATR

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PREPARING YOUR REPORT (due Period 10 or 11)

Prepare a technical report with accompanying cover letter to Mr. Jorgensen as requested,
your report should include:
1. A detailed description of the procedure and results of the synthesis of
triphenylmethanol.
Attach the following:
1. Tables of data indicating quantities of reagents used, mass of product, yield.
2. Infrared spectrum of triphenylmethanol and spectral analysis.

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REPORT COVER PAGE

NAME

Experiment: Grignard Reagent

Experiment completed Period 9: report due Period 10
or, completed in Period 10: report due Period 11

SECTION

1. Answers to prelab questions

(submitted prior to performing experiment)

(5)

2. Pre-lab Quiz

(5)

3. Report (procedure, discussion, results, grammar,

spelling, style)

day

am/pm

(25)

4. Data requested (in report and sample submitted)

Discussion of procedure and results

(15)

5. Raw Data (attachments)

Data Tables

(15)

6. Answers to Questions

(10)

TOTAL

(75)

CHEM 2380 Grignard Reagent

Report Cover Sheet

QUESTIONS (due Period 10 or 11, attach to Report)

Provide complete answers to the following questions in the spaces provided. Hand in this page attached
to your report.
1. Triphenylmethanol also can be prepared from the reaction of methyl benzoate with phenylmagnesium
bromide. Write the stepwise reaction mechanisms for this reaction.

2. If the m ethyl benzoate used to pre pare triphenylmethanol in question 1 is wet, what byproduct is
formed?

CHEM 2380 Grignard Reagent

Questions