SPRING 2016 CHEM 2924/2214

Modifications for Expt 16: Grignard Reaction with a Ketone Part 1:Triphenylmethanol
More so than any other reaction that you will run this semester, the Grignard reaction requires
strict adherence to the experimental procedure. . Maintaining anhydrous reaction conditions is
essential due to the basicity of Grignard reagents and reactivity with water.
**You will not be preparing your Grignard Reagent in this lan** A commercial 3 M solution of this
reagent from Aldrich will be provided to you by your instructor/TA. The instructor/TA will measure out the
reagent for you using an Argon balloon to keep the atmosphere inert within the reagent bottle and
your syringe. Note: you have to have your reaction apparatus completely built and equipped
with drying tube and fresh septa before you receive the syringe. This is similar to the procedure
we used when doing the first part of the hydroboration-oxidation lab procedure last semester. You must
learn the Grignard Formation Procedure for PreLab Quiz 7 as I want you to know how its done.
Each student will use three syringes and needles to carry out the Grignard reaction. Please
handle them very carefully, both at your lab bench and while transporting through the lab.
One of the three syringes will be dedicated for use with anhydrous ether ONLY (see the
next two bullet points). An ADP will NOT be used to dispense anhydrous ether, as directed
in the lab textbook procedure.
Label each of your syringes. Make sure the anhydrous ether syringe is used to dispense anhydrous
ether, and that only anhydrous ether, is used from the appropriate reagent bottles. If cross
contamination avoided, this syringe may be re-used throughout the procedure as needed.
Another of the three syringes will be dedicated for use with Commercial Grignard Reagent ONLY
(see the next two bullet points). Dont get this syringe until your complete apparatus is built.
The last syringe will be used for quenching your Grignard Reaction with aqueous acid .
Your instructor or TA will provide a solution of Methanol to quench your syringe after the reagent
is dispensed into your reaction.
Note that two grades of diethyl ether will be available in the reagent hood: anhydrous (dry)
ether, and ether (or ether for workup). The former is used in all cases during the reaction,
and the latter (not anhydrous) during the aqueous workup. Please be sure to select the
correct type of ether at each step.
Dispose of all syringes and needles in the sharps waste containers only. If any syringes
and/or needles are found elsewhere by any TA or the lab coordinator, the entire lab section will
be penalized with point deductions.
In this first part, you will complete the procedure through and including Isolation of Product.
For the pre-lab quiz, you are responsible for all portions of the experimental procedure written
in the lab manual including prepration of the Grignard Reagent.
Please incorporate the below modifications/clarifications to the procedure from the textbook for your PreLab
Report indicated below. Dont forget for the PreLab Quiz you will learn all the theory including the regular
phenylmagnesium bromide preparation procedure. The quiz will not the written Alternate Procedure.
NOTE: The alternate procedure begins at the bottom begins at the bottom of page 279
but continues with the first sentence on page 280. The regular procedure resumes with the
second sentence on page 280, In a dry, screw-capped vial

1. Reagents and Equipment

Your TA will instruct you about any necessary glassware drying steps. There are ovens in
the labs but no Bunsen burners.
You will substitute Drierite (anhydrous calcium sulfate) for calcium chloride in the drying
tube
Note: For the PreLab/PostL:ab report, there is no need to measure out 76 uL of bromobenzene
and 18 mg of Mg as these are redundant as the commercial Grignard Reagent is suppled to you.
You will weigh out 105 mg (0.58 mmol) of benzophenone solid in this first part. You quickly transfer that
solid into the vial removed from from your dried apparatus using weighing paper and then quickly reconnect
that vial to the apparatus to keep everything dry.
You will then measure out 1.6 mL instead of 1.3 mL of Ethyl Ether by syringe and then dispense that
through the septum in your apparatus. You will stir suspension until it is in solution.
You will give your Grignard Syringe to your instructor/TA and they wll dispense out 300 uL (0.90 mmol) of the
Grignard Reagent and give it back to you. You will add that solution through the septum at the top of apparatus
slowly dropwise while stirring over 5-10 minutes. If reaction starts gentle refluxing, that is fine, just make sure
you dont add at a rate where the reflux rate is too vigorous as there is no reflux condensor connected.
You will stir reaction for 30 minutes after addition has been completed
The actual procedure you will have done will be the following (write in your own words please).
A 3 mL vial, claisen adaptor with septa and drying tube with adaptor were dried and put into a dessicator
by your instructor or TA. A reaction apparatus was quickly built on the benchtop to match the picture on page
279 in the lab textbook. A total of 105 mg (0.58 mmol) of benzopheneone was weighed out on weighing paper
and quickly placed into the vial by quick disconnection and reconnection to the apparatus. A total of 1.6 mL of
anhydrous ether was added via syringe-1 through the septum on top and the resulting suspension stirred going
into solution over a 1-2 minute period. To this reaction solution was added 300 uL (900 mmol) of 3M PhMgCl
PhenylMagnesium Chloride solution slowly dropwise via syringe-2 over a 5-10 minute period to enable a
gentle reflux. The reaction mixture was stirred for a total of 30 minutes; afterwhich, a beaker of ice water was
placed under the vial and a solution of 0.4 mL (1.2 mmol) of 3 M HCl solution was added via syringe-3 and the
mixture stirred until homogeneous bilayer was observed.
Note: You will then follw the rest of the procedure as written under the caption Isolation of Product on page 281
and beyond in your lab textbook.
2. Isolation of Product
In the very last part of this section of the procedure, you will NOT transfer the dried ether
solution to a Craig tube.
Instead, transfer the dried ether solution to a tared, screw-cap test tube. Label the test
tube with your name, TAs name, section number, and chemical name of the product
(either use a white label or write directly on the vial with a Sharpie pen). Do not cap the vial.
Be sure to weigh the empty vial + label.
In contrast to the typical procedure of concentrating the product solution by warming in a
heater block, the ether will simply be allowed to evaporate over the course of the week. A
crude product weight will be obtained next week.
Place the labeled test tube, containing your crude product solution, in a test tube rack in the
3rd lab hood. Your TA will direct you to the correct location. Do not cap the tube.
The concentrated crude product will be used next week in Part 2 of the Grignard
experiment.
You wil TLC the crude reaction mixture this week using the below procedure and will then make note
The results in you observations/results section in your electronic notebook:

Thin-Layer Chromatography
Obtain two TLC plates and one microcapillary pipet (to spot your sample). You will use the
same pipet for both of your samples. Obtain a small amount of acetone in a small beaker
or Erlenmeyer flask.
Prepare the TLC plates for the application of (at least) four spots. Feel free to add a cospot lane, if there is room.
Spot the same four spots on each TLC plate:
Biphenyl standard / crude product / purified product / triphenylmethanol standard
Standard solutions of biphenyl and triphenylmethanol will be provided. Use ONLY the
microcapillary pipets attached to the standards.
Between applications of your two samples, rinse the microcapillary pipet 2x with acetone.
Spot the acetone on a paper towel or Kimwipe.
Elute one plate using 1:9 ethyl acetate in hexanes as the elution solvent system, and the
other plate using 1:4 ethyl acetate in hexanes. Do NOT use methylene chloride as directed
in the book.
Using a UV lamp, visualize and circle the spots with a pencil. Measure distances (in mm,
with at least two significant figures) and calculate Rf values for all spots.
Sketch the TLC plates in your lab notebook, paying attention to the relative sizes and
intensities of all spots.
If some or all of your spots are too big and/or too faint, you may repeat the TLC analysis.
There should be ample time to do so.

Grignard Reaction Modifications

page 2