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Act 8 Procedure

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44 views

Act 8 Procedure

Uploaded by

tep45
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Activity 8: Procedure

Activity 8: Alkene Addition Reactions:


Selective Markovnikov Hydrohalogenation
of Carvone

The Experiment

Lab Activity Goal


Verify experimentally the structural factors governing the chemo- and
regioselectivity of alkene addition reactions in the context of the
hydrochlorination of carvone.

Pre-Laboratory Assignments
See the Activity 8 Pre-Lab Preparation and Outline document in Labflow.
Activity 8: Procedure

Experimental Procedure1

Part 1. Carvone Hydrochlorination


1. Weigh a 50-mL round bottom flask.
2. Using a clean plastic pipette, add 2 mL of carvone to the weighed 50-mL
flask. Note that plastic pipettes have a 1 mL volume graduated into 0.25
mL increments.
3. Weigh flask again to obtain the exact mass of carvone.
4. Add 1 mL of H2O to the carvone.
5. Add a stir bar to the flask. Clamp the flask to the monkey bars on top of a
stir plate.
6. Obtain ~75 mL of saturated NaHCO3(aq) in a beaker. Set a plastic pipette in
the beaker and place in your hood for later use to quench/rinse glassware
with acidic reagents.

• Note: Designate another beaker to serve as an aqueous waste that will


later be transferred to the aqueous waste in the back of the laboratory.
Activity 8: Procedure

7. Obtain TMSCl (chlorotrimethylsilane) according to the directions below.

Note that TMSCl is corrosive. Carefully follow directions below and from your
instructor. As always, wear goggles and gloves. If TMSCl comes in contact with
your gloves or clothing, they must be immediately removed.

• Set a dry 10-mL graduated cylinder in a 250-mL beaker. Invert a 50-mL


beaker on top of the graduated cylinder to serve as a lid. Take the
assembly to the TMSCl dispensing location.
• Your instructor will add ~6 mL of TMSCl to your graduated cylinder.
Holding the assembly with both gloved hands and being careful not to
trip or bump into anyone, carefully take the TMSCl back to your hood.

8. Add the TMSCl to the stirring carvone/water mixture. Use a funnel to


ensure that all the TMSCl is added to the inside of the flask. If a pipette is
used to transfer the TMSCl, be sure to hold it vertically (not holding the
pipette vertically can cause pipette contents to unexpectedly squirt out).
9. Record the time that you finish adding the TMSCl.

• Note: As always, make sure that you are wearing gloves for step 10.
TMSCl reacts with water to make hydrochloric acid in the reaction flask.

10. To clean up the residual TMSCl, pull the hood sash down as far as possible.
Place the funnel on the graduated cylinder and rinse the funnel and the
graduated cylinder with saturated NaHCO3(aq) using the pipette. Place the
(probably fizzing) grad cylinder in the back of your hood. Once fizzing
stops, place the rinse from the graduated cylinder into your designated
aqueous waste beaker.
11. Be sure to dispose of your gloves properly. Get new gloves before you
handle chemicals again.
Activity 8: Procedure

Part 2. Monitoring the Reaction Using TLC Analysis


Note: Use ~20 mL of the already prepared 30% EtOAc (ethyl acetate) in hexanes
as the TLC developing solvent. A single TLC chamber can be used to run all of
your TLC plates.

1. Prepare a UV-active TLC plate with 3 lanes.

• Lane 1 should be the carvone standard starting material (S), lane 2 should
be a co-spot (C), and lane 3 should be the reaction aliquot (R). The co-spot
is made by spotting both the starting material and the reaction aliquot in
the co-spot lane. Be sure to use a clean capillary tube for the reaction
aliquot. Dispose of any used capillary tubes in the glass waste. If your
capillary tube has liquid in it, gently tap out the excess liquid onto a paper
towel before disposal.
• For a reaction aliquot, use a pipette to obtain one drop of the reaction
mixture. Add this drop to a small vial and dilute with two to four drops of
TLC eluent. Use the diluted reaction aliquot for TLC analysis.

2. Do your first TLC analysis as soon as you have your plate prepared. Record
the elapsed time of your reaction.
3. Monitor the progress of the reaction by doing a TLC analysis every 15 min.
Repeat the TLC analysis until carvone is no longer observed in the reaction
aliquot. The total reaction time is expected to be between 15-60
minutes. Record the time when the reaction is observed (by TLC) to be
complete. Make sure you dispose of any used capillary tubes in the glass
waste before you move on to Part 3.
Activity 8: Procedure

Part 3. Reaction Work-Up


1. Once TLC indicates that no carvone remains, add 5 mL of H2O and 10 mL
of diethyl ether to the reaction mixture.
2. Transfer the mixture to a clamped 250-mL Erlenmeyer flask. Via pipette
carefully add ~5 mL NaHCO3(aq). Gently stir using stir bar and stir plate. If
there is still observable fizzing, then carefully add more NaHCO3(aq) in 5 mL
portions until there is no fizzing, which should indicate the mixture is
neutralized. Test the pH of the mixture with Congo red paper to ensure
the mixture is no longer strongly acidic. A blue Congo Red test result
means the mixture is still strongly acidic.
• You can test the pH multiple times on a single strip of Congo Red
paper. Set the Congo Red test strip on a paper towel, then lightly dip a
stir rod into the mixture. Gently transfer a drop of the mixture on the
filter paper. Repeat as often as necessary until the mixture is
neutralized.
3. Transfer the quenched reaction mixture to the 125-mL separatory funnel.
Let the layers separate. Drain the aqueous (denser) layer.
4. Wash the organic layer that remains in the separatory funnel with
aqueous NaHCO3 (10 mL). Once the layers separate and the aqueous layer
is once again drained, wash the remaining organic layer with 10 mL of
brine, i.e. saturated aqueous sodium chloride (10 mL). Let the layers
separate and drain the brine.
5. Transfer the washed organic layer from above into an appropriately-sized
Erlenmeyer flask and add a small scoop of MgSO4 to dry. You will know
the organic solution is dry when the some of the MgSO4 flows freely upon
swirling (see figure below).
Activity 8: Procedure

When the solution is dry (i.e. has no water remaining), not all of the MgSO4 will settle at
the bottom. Some MgSO4 will stay suspended in solution and appear as a "snow
globe".

6. Add 3 boiling stones to a 50-mL beaker. Weigh and record its mass.
7. Use gravity filtration to transfer the dried organic extract into the weighed
beaker containing the boiling stones. Evaporate the ether from your
carvone addition product using a steam bath.

• Note that placing the steam bath on top of a lowered lab jack, rather
than leaving it on the bench top, helps condensed water to drain into
the cup sink (water runs downhill).

8. Once all the ether has evaporated, cool the beaker, and then record its
mass.

Part 4. Product Characterization and Spectroscopic


Analysis
1. Finishing Activity 7: obtain an IR spectrum, melting point range, and mass
of your recrystallized Grignard reaction product.
2. Obtain an IR spectrum of both your reaction product and carvone.
Activity 8: Procedure

3. Your instructor will give you guidance on the analysis of the carvone starting
material NMR spectrum so that you can complete the Activity 8 Post-Lab
Assessment.

NOTE: The NMR spectrum of the carvone addition product (Spectrum A) is


embedded in the Activity 8 Post-Lab Assessment. You will analyze this spectrum.
Remember that methyl groups, like methylene hydrogens, can be diastereotopic
even if they seem equivalent.
Activity 8: Procedure

Clean-Up and Waste Disposal


Activity 8 Specific Clean-Up
• Organic Liquid Waste:
o Acetone rinse from glassware washing (includes the final product)
o TLC eluent
• Aqueous Waste:
o NaHCO3 solution waste (from quenching excess TMSCl and reaction
mixture)
• Solid Waste:
o MgSO4
o Used Congo Red paper
o Used filter paper
o Used gloves
• Glass Waste:
o Acetone-rinsed vials used for TLC monitoring
o Used capillary tubes

Routine Clean-Up
• Clean up your hood space of all trash, spilled chemicals, etc. Don’t leave a
mess for the people who share this hood at other time slots. Up to 24 other
people are sharing this space at various time slots throughout the week.
Clean up your mess!
• No dirty or clean glassware should be left in the sink. No used filter paper or
wadded up dirty paper towels should be left in the sink.
• Dirty paper towels go into the REGULAR TRASH, not the red solid waste
trash. This saves the university a lot of waste disposal money!
• Dispose of dirty filter paper in the red solid waste container.
o Do NOT deposit filter paper in the liquid waste eco-funnel as this will
cause a clog which will lead to a messy overflow of waste .
o Do NOT leave filter paper in the sink as this is poor lab etiquette and
rude.
Activity 8: Procedure

• Used gloves should be disposed of into the red solid waste.


• Ask your instructor if you are in charge of cleaning up the balance area
for this week. If you are in charge do the following:
o Be sure all reagent bottles are properly capped.
o Use the small brush to clean off balances.
o Use small broom and dustpan (located on the wall surrounding the
balance area) to remove excess solid from counter. Dispose of excess
solids in red solid waste container. Return broom and dustpan to proper
location.
o Wipe down the counter with a moist paper towel.
• Ask your instructor if you are in charge of making sure the sink area is
presentable for the next lab group.
o Wash any dirty glassware rudely left in the sink. Let clean glassware air
dry on rack or window sill area.
o Dispose of any paper towels, filter paper, or cotton rudely left in the sink.
o Do not remove broken glass from the drain or the sink. Rather, tell your
instructor and fill out a blue "something wrong form" located in the
cabinet above the solid waste containers. Be sure to record room number
and the Left/Right location of the sink. Give the form to your instructor
who will pass it to the appropriate person.

Post-Lab Assignment
The Activity 8 Post-Lab Assessment is posted on Labflow and is due before the
deadline posted on Labflow.

References
1
Boudjouk, P.; Kim, B.-K.; Han, B.-H. J. Chem. Educ. 1997, 74, 1223-1224.

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