Chemistry 20

Organic Laboratory
Procedures

Lab Manual and Supplement for

Teaching Fellows

Harvard University
Chemistry and Chemical Biology
Science Center 210

Spring 2014
 Table of Contents
TF Supplement
TF Responsibilities .................................................................................................5
Summary of Emergency Procedures .......................................................................10
TF Notes..................................................................................................................14

Student Lab Manual

Introduction .............................................................................................................37
1. Separation of an Unknown Mixture ................................................................65
2. Purification of Organic Compounds ................................................................75
3. The Grignard Reaction ....................................................................................85
4. Electrophilic Addition and E2 Elimination .....................................................91
5. Friedel-Crafts Acylation and Chromatography ...............................................100

Appendices
1. Laboratory Map ...............................................................................................115
2. Glassware and Common Equipment ...............................................................116
3. How to Clean Up Your Bench .........................................................................118
4. Sample Lab Report ..........................................................................................120
5. Some Data on Common Solvents ....................................................................123
6. Rotovap Instructions ........................................................................................124
7. Infrared Spectrometer Instructions .................................................................127
8. Table of Characteristic Infrared Absorptions .................................................130
9. Periodic Table of the Elements ........................................................................131
TF Supplement
TF Responsibilities
Head Lab TF
Matt Patton [email protected] 828-335-5942

Please call me in case of emergency

Many of the laboratory operations and safety procedures are described in the Organic Laboratory
Procedures section included in this manual. The information below is a supplement to this
material.

Outside of the Lab

Teaching fellows should arrive at the lab a minimum of fifteen minutes before their scheduled
teaching period. (The only exception to this policy is the very first lab session, when you will
need to arrive 30 minutes early.) At this time you will not only prepare and set up for the
experiment, but also receive any last-minute instructions, procedural notes/modifications, etc.
Additional notes on experiments will sometimes be emailed.

While you do not have to establish office hours, you are strongly encouraged to make yourselves
accessible to your students. Check your email often, and respond in a timely fashion.

Pre-Lab
In the first scheduled lab session (Lab 0), the Head Lab TF will introduce students to the lab,
discuss safety and waste disposal, and briefly run through emergency procedures. Students will
then go upstairs and you will give them a tour of the lab space. Point out common equipment,
locations of chemicals, solvents, and safety devices. Coordinate with other TFs so you don’t
bump into each other! The Head Lab TF will provide guidelines for this tour at the introductory
TF meeting.

The first thing you should do in every subsequent lab session is check your students’ pre-lab
write-ups while they come in. Assign them each a pass (adequate preparation, correct format) or
incomplete score. This will not correlate with a numerical grade, but it will serve as feedback for
them for the next lab report. You can probably just write your feedback directly in their lab
notebooks and take it into account when you are grading the lab report as an overall Pass or
Rewrite. Students who are given an incomplete pre-lab score must correct the deficiencies you
indicated in their final write-up. Students who come to lab without having prepared a suitable
pre-lab will not be permitted to participate in that day’s lab session and they will have to
finish the pre-lab and make up the lab in the next available section to earn a passing score.

You will be responsible for giving a brief (no longer than 10 minutes or so) pre-lab talk to your
section. The students will have already attended or watched the lab lecture associated with the
experiment, so try and tailor your talk to be very practical (point out safety issues and/or
procedural changes, reagent locations, etc.). Try to make the discussions interactive – ask
students questions and try to get them to think about what they are doing. For many labs,
including an example of the glassware setup will help students work more efficiently.

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In the Laboratory
You are required to attend every laboratory session to which you are assigned. If for any reason
you absolutely cannot make a session (class, religious conflict, sudden emergency, swallowed by
the earth, etc.), you are required to notify the Head Lab TF as soon as you can. It is absolutely
unacceptable under any circumstances to miss a lab session without notification or to arrange for
a sub without notifying the Head Lab TF!

There should be a TF in the lab at all times. If you have to leave the lab for an emergency, you
must notify the Head Lab TF so he can cover for you until you get back. You may ask him or
another TF to cover for you if you just need to run to the restroom during lab.

The labs will be 5 hours long. At 12:45 PM or 10:45 PM, have all students stop working and
start cleaning up. There should be more than enough time to complete most of the experiments,
especially since they are working in pairs.

Please encourage your students to "multitask" and be efficient with their time. Many
experiments are designed to make the students do multiple things at one time; they need to learn
early that efficiency is very important, or they will never complete the later experiments.

Make sure that you are familiar with every aspect of the experiment being performed that week.
If you are unsure about anything, ask. The students will be looking to you for help and guidance,
and automatically assume you are familiar with the lab. You are not expected to be omniscient,
but you are expected to be completely prepared. Never hesitate to consult the Head Lab TF for
help!

Be sure the equipment such as the balances, rotovaps, and IRs are well maintained. These are
expensive pieces of equipment. If there is any problem with the equipment, let the Head Lab TF
know so it can be fixed promptly.

Every TF is responsible for cleaning up if the students don’t. Remember, if you have to clean
up after them, they should not receive all clean-up points! The lab should be returned to a
state of organization and cleanliness at the end of each section. If the lab is found to be in
disarray after lab (e.g., glassware is filthy, balance areas are covered with spilled chemicals,
center bench hood is strewn with used pipets), that entire lab section will lose a group clean-up
point for the day. You probably don’t want to have to face your students if this should happen…

All TFs must conform to safety standards just like students: i.e., no eating or drinking in the lab,
proper attire is to be observed (including wearing lab coats), and safety goggles, not safety
glasses, must be worn at all times. Normal glasses are NOT acceptable in the lab. Even if your
lenses are made of impact-resistant plastic, if they do not have hard plastic full side shields on
them, you must wear safety goggles over them. The cleaning service that launders our lab coats
comes to pick them up and deliver new ones on Friday morning each week.

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Whenever any reagent or solvent container is opened for the first time, write the month/day/year
it was opened on the container. This is especially important for ethers. The Head Lab TF will
usually take care of this, but it is important to know just in case.

A quick word on making up labs: students should be strongly encouraged at every opportunity
not to miss their regularly scheduled lab. There are simply too many students with too many
conflicts to allow any of them to reschedule. If a student has to miss a lab for a medical or other
emergency, they must contact the Head Lab TF as early as possible so they can arrange to attend
another lab section. Just e-mailing you to ask to make up a lab in completely unacceptable! If a
student emails you about an emergency, please let the Head Lab TF know. We simply cannot get
ourselves into the situation of having to arrange a “make-up lab” session at the end of the term.

After the Lab Session

Closing Procedures - When leaving at the end of the day you must shut off the hood lights (all
other lights in the lab and TF rooms are on automatic switches, so don’t bother them), close all
hoods, and shut off the coolers, mel-temps, UV lamps, and rotovaps. Again, you are also
responsible for cleaning up anything that your students didn't clean up! Save yourself the trouble
and make sure they all earn their clean-up points before leaving. You will want to divvy up end-
of-lab tasks between all of your students.

Grading
You will be given answer keys and grading rubrics for the quizzes. Each quiz question is worth
3 points. The Head Lab TF will provide grading guidelines to ensure consistency between
sections – do not deviate from these guidelines. Students may have questions about the quizzes,
and you should make an effort to answer these by e-mail, but if any students ask you to
essentially check over their answers for the quiz, you must reply to them indicating that this is
not acceptable, and if they have any specific questions about the quiz you will be happy to help;
be sure to CC me on your reply. There are a total of 18 points associated with the lab each
session: 14 from the quiz, 2 points for individual safety/clean-up, and 2 points for group clean-
up. Before each student leaves, in order to get their individual clean-up points, they need to ask
you to examine their work area and determine whether it is clean enough to warrant the points.
The points, if earned, should be noted in the student’s lab notebook and initialed by you before
they turn in their write-up. The students can see what they need to do in Appendix 3 of the lab
manual. Grade the quizzes, record the grades, and return them to your students with the lab
reports at the beginning of the next lab session. Again, you may NOT leave graded work lying
around, as this is contrary to Harvard’s academic confidentiality policy. You should keep an up-
to-date Excel spreadsheet of your quiz grades and clean-up points, and send the Head Lab TF a
copy every week. Do NOT grade quizzes during lab time – your responsibility is to supervise the
students, not sit and grade or check your e-mail!

You must return graded lab reports (Pass or Rewrite) in the very next lab session so that those
students who did not pass will have the opportunity to revise their report and hand in an
acceptable copy. Rewrites are due back to you by the following lab section. ALL lab reports
are due 24 hours after the first lab!

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Include written comments and feedback (both positive and negative) on the lab reports. Be
especially detailed for the first two lab reports.

Report any low grades and missing or unprepared students to the Head Lab TF ASAP.

Treat all students fairly and equally.

Laboratory Safety
It is extremely important that you follow safety protocol and make sure that your students are
doing the same. Let the Head TF know about any potentially dangerous spills, incidents,
accidents, or anything else. Even if it seems minor, it should at least be reported so a decision
can be made about whether or not to issue an incident report. You should also report “near miss”
incidents even if there wasn’t anything to deal with afterwards. Although there may not be an
actual incident, the report will be useful to the Lab Planning Group. There will be periodic and
unscheduled audits by the Head TF, lab coordinator, EHS, and others throughout the semester.
Any messy areas or safety problems during lab need to be addressed by students immediately.
Any safety violations are recorded for the Head TF and department/course safety personnel. As a
result, please check that students are being clean and safe throughout the lab.

There are three major safety responsibilities of the TFs:

1. Enforce that students are working personal protective equipment at ALL TIMES, even when
sitting down and writing up reports. This includes goggles, lab coat, closed shoes, and pants.
2. Set a good example by wearing PPE at ALL TIMES. Your lab coats will be blue and located
in the TF room.
3. Ensure that students have been provided all the relevant safety information before they begin
working.

Any instances of noncompliance are to be addressed immediately.

In the case of shorts or open-toed shoes, offenders will be allowed to participate in pre-lab
activities, but should be sent out immediately afterwards to put on acceptable clothing for lab.
We are no longer providing these students scrubs or shoe covers. Any student who repeatedly
fails to adhere to the dress policy, as well as his TF, will have to deal directly with the Head Lab
TF! Please err on the side of caution!

Do not be afraid to be the "bad guy" when enforcing safety!

Enforcing safety is for students' benefit and will aid in creating safe laboratory habits. You can
always point out that (1) otherwise both you and the student can be kicked out of lab, (2) it will
be reflected in evaluations which will be part of any recommendation letters, and/or (3) the Head
TF will deduct points from them and give lengthy lectures.

Look for responsible students.

In case of emergency, there is no guarantee that you will be able to do everything all at once to
address it. Some of the Chem 20 sections have only one TF and one Head TF, and in
emergencies, there will be many necessary actions all at once. Your Head TF should act as a

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point person for delegation, but be on the lookout for students who seem like they would be
particularly well-prepared to help in an emergency. The ideal student is responsible and
knowledgeable but not skittish.

Department Policy on Safety Violations in the Teaching Labs

Safety is of the utmost importance in chemistry lab courses. All students and teaching fellows are
expected to follow course safety policies at all times and to address safety issues immediately
when they are observed.
Response to safety violations by students
Students will receive verbal warnings for first occurrences of minor safety violations and have
points deducted from their safety points. Serious or repeated violation will result in a written
warning, and the student will be made to leave the lab immediately. Written warning will include
warning of exclusion from the course (see Handbook for Students, Exclusion from a Course).

A student who commits a safety violation after written warning must appeal to the DUL (Dr.
Spoering) and co-DUS (Dr. Tucci) to remain in the course and normally will be recommended to
the Administrative Board for exclusion.

Response to failure to enforce safety policies by a teaching fellow

Teaching fellows are expected to ensure that their students are in compliance with safety policies.
If a teaching fellow fails to address safety violations, they must meet with the DUL (Dr.
Spoering) and co-DUS (Dr. Tucci) to discuss the incident. The second time this occurs, the
teaching fellow will normally be replaced.

Instances of severe neglect or unsafe behavior by a TF may lead to immediate dismissal.

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 Summary of Emergency Procedures
You must read and understand the safety policy and procedures at the beginning of the student
lab manual (see “Lab Zero”). In addition, you must read and understand all of the information in
this section – always be prepared to deal with emergency situations – know where to find help if
it is needed!

Emergency Telephone: A red emergency phone is located just to the left of the entrance to the
lab. This is a regular phone and can be used to dial any number in case of emergency. To report
emergencies that require paramedics or fire fighters, call 911. To report security or crime related
issues, call the Harvard Police at (617) 495-1212. There is an emergency response guide flipchart
hanging near the phones that has additional emergency information and contact numbers.

Operations Center Telephone: Next to the emergency phone is a white telephone that
automatically connects to the Operations Center. Regular phone calls cannot be made from
this phone. The Harvard University Operations Center is a communications, dispatch and
response center providing 24-hour per day, 365-days per year. Use this phone to report after
hours facilities problems, spills, or if you don’t know what to do. The Head TF will be the
one who typically uses this phone, however you should be aware of its function. In addition
to emergencies (detailed below), you can call the Control Center for any of the following
problems:
Flooding: If a pipe is leaking and starts flooding the lab, call the Control Center; they will
send someone over from Facilities to help repair or manage the leak.
Power outages: If the power goes out, or if you had to cut the power with the Emergency
Electrical Disconnect, call the Control Center.
Failed heating or cooling: If the heat isn't working, call the Control Center.
Hoods aren't on: Call the Control Center

When you call the Control Center, tell them who you are, where you are (Science Center 210, the
organic teaching labs), and the nature or cause of the problem (busted pipe, spilled/broken jug of
methylene chloride, fire, serious injury, etc.) The Control Center will call the appropriate
authorities (fire department, police, facilities maintenance, etc.) as necessary. If the lab needs
any sort of minor (non-urgent) repairs, notify the Head Lab TF, who will in turn notify the
appropriate maintenance people. You should NEVER call the Control Center without speaking
to the Head TF first except in the case of life-threatening emergency!

Student Injuries/Incidents: Detailed information about specific types of injuries and incidents
can be found in the sections following:

Minor injuries (cuts or burns treatable by supplies in laboratory first aid kits):
Help student administer first aid; clean wound and bandage if necessary.
If student chooses to continue working, make sure that the wound is securely covered, and
have the student put on a pair of fresh gloves so that no chemicals are allowed to come into
contact with broken or irritated skin.
Inform the Head TF so that an incident report can be prepared.

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Chemicals on skin, small exposures:
Wash immediately with water for at least 15 minutes.
For large quantities of strong acids or bases, rinse well with water for at least 15 minutes. Do
NOT attempt to neutralize acid or base spills on skin!
Inform the Head TF.

Deep Cuts (requiring medical attention/stitches):

Using a gauze pad (found in lab first aid kits), apply pressure to slow or stop bleeding.
You can accompany the student to UHS for treatment, or if the student is not comfortable
walking over (or is too woozy from the blood!), call the Control Center to have them
dispatch HUPD to give the student a ride to UHS.
IMPORTANT NOTE: Whenever a student goes to UHS, two things must occur: first, you
must call them ASAP (the number is found on the red flip chart under the control center
phone) to let them know a student is coming over from the organic teaching labs. They
will want to know the specifics of the injury, the circumstances under which it occurred,
and whether chemicals were involved (you may have to spell the exact names of the
chemicals). Remember to remain calm and keep a clear head when explaining the
situation, so that exactly what happened is communicated in a lucid fashion. Second, you
will need to fill out a UHS Visit Form with the same important information, which will
be brought with you and given to the UHS staff on call when you arrive with the student.
This form should be filled out as quickly and completely as possible and approved by the
Head TF before you leave the Science Center. Keep in mind that HUPD will not
transport students who have been injured by a chemical exposure, due to concerns of
contamination – the only options are either walking the student over, or calling 911 for an
ambulance and fire rescue response.
Inform the Head TF.

Chemicals on skin, large exposure:

Escort student to safety shower and assist in removing contaminated clothing. You may wish
to shield the student from view with your own lab coat to preserve his or her modesty as much as
possible, but only if doing so will not present a contamination hazard for you. In the meantime,
yell to alert other TFs, who should assist in diverting student attention away and procuring a
replacement lab coat for the affected student.
Accompany student to UHS (remember to call ahead and fill out a visit form) or call the
Control Center for an ambulance to transport the student in the case of a serious
exposure.
Inform the Head TF.

Chemical exposures of the eye:

Flush eyes with water at eyewash station (remove contact lenses!) immediately and
continuously for 15-20 minutes. The student must forcibly hold his or her eyelids open to ensure
sufficient exposure to the streams of water, blink repeatedly, then repeat during this entire
timeframe. Supervise the student to ensure correct decontamination procedure is followed.
Remember, his or her eyesight may depend on it!
Accompany student to UHS for eye examination (remember to call ahead and fill out a visit
form). Inform the Head TF.

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Life-threatening injury:
If a student needs urgent medical attention, they will need to be transported to the hospital,
not UHS. Calling for an ambulance is the only option.
Call the Control Center immediately. Calmly and clearly give your name and location
(Science Center 210) and explain the nature of the emergency.
Know beforehand that the Control Center operator will be able to transfer your call directly
to the Cambridge Fire/Rescue dispatch closest to campus, who will know where you are and
arrive in very short order; calling 911 on a cell phone will require a couple of extra transfers, and
may not end up connecting you to the closest dispatch center.
Do not hang up until told to do so.
Inform the Head TF as soon as you can, or have another TF do so while you are on the line
with the Control Center. Remember, for life-threatening emergencies, you do NOT need to
check with the Head TF or anyone else before calling for help!

Laboratory fires:
If the fire is small, you can close the hood and allow it to burn out (or cover it if it is safe to
do so without risk of personal harm).
Official Harvard CCB policy is that researchers, students, and TFs are not responsible for
attempting to extinguish fires. You should only attempt to put out a fire if you are trained to do
so, if you feel comfortable doing so, and if doing so would pose no threat to the health and
safety of you or anyone else.
The extinguishers at the ends of the benches are all CO2. In case of a magnesium fire, use the
dry chemical extinguisher near the door.
In case of a large fire, evacuate the lab immediately and pull the fire alarm.
Call the Control Center if it is safe to do so. They will call the fire department. Provide
information on the nature, location within the lab, and cause of the fire (what types of
chemicals are involved, how large, etc.) If the nature of the fire is such that you cannot
remain in the lab (sheer size, noxious fumes or smoke), leave the lab and pull the fire alarm.
You should know two emergency exits from the lab – one is the main lab entrance, and the
other is the door to the general chemistry lab. In either case, depart the labs and exit the
Science Center to the left and down the stairs. The rendezvous point is located across Oxford
Street between Lowell and Mallinckrodt.
Inform the Head TF immediately.

Toxic fumes:
Evacuate the lab and call the Control Center if it is safe to do so – otherwise leave the
vicinity (close the laboratory doors if it is safe to do so) and call 911.
Inform the Head TF immediately.

Chemical spills:
You must use your chemical judgment to determine whether a given spill is minor or major.
To this end, you must read and understand sections E through J of the CCB Chemical
Spill Policy, found here: www.chem.harvard.edu/safety/labsafety.php -- this is required
reading!
In case of a minor spill, clean it up as appropriate (dilute acids or bases with water, and wipe
up, don't throw oxidizing agents on reducing agents, etc.); ask the Head TF for assistance.

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 In case of a large spill, a spill of a particularly dangerous or noxious chemical, or an organic
that can’t be neutralized or diluted as above, evacuate the lab, and call the Control Center
and tell them what was spilled and the location of the spill. If it is not possible to call the
Control Center without exposing yourself to the spill (or any fumes issuing from it), be
safe – leave the affected area and call 911 instead.
Please be judicious of your use of the phrase “chemical spill” – this means something very
different to laymen, even trained EHS personnel, than it does to chemists, and could set
off a very serious response. If in doubt, consult the Head TF first, but never hesitate to
evacuate the lab in the event of a spill you judge to be potentially harmful.

Mercury spills:
Students never use mercury thermometers, so we should never have to deal with this. Just in
case a student manages to find and break a mercury thermometer, we do have mercury
spill kits in the lab. One is in the TF room and one is in the waste room. Get one and
follow instructions in case of a small spill. A minor mercury spill is defined as a broken
thermometer or manometer. Notify the Head TF. In the very unlikely event of a large
mercury spill, evacuate the lab and call the Control Center or EH&S (number found on
the red flip chart below the Control Center phone) for assistance.

Ether:
Always check the date on cans of ether before using them. Do not open a can of ether older
than 3 months. Carefully place it in the hood in the TF room and inform the Head TF.
If you suspect some ether of having gone to peroxides, CLEARLY LABEL the peroxidic
ether, and place it in a hood and away from heat sources. Clearly label the hood
containing the affected ether.
NEVER ATTEMPT TO QUENCH PEROXIDES! Notify the Head TF, who will arrange
for safe removal of the peroxidic ether.

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Lab 3 TF Lab Notes
Prelab Talk:

 Demo the reflux setup for Part I, including how to add reagents to the flask through the
addition funnel. Leave the demo up for their reference. Clamps should be at the top and
bottom of the condenser plus a ring to hold up the sep funnel. Most just hold in the three neck
RB with a Keck clip. Include a lab jack so they can suspend their setup when they swap out
the stir plate and the steam bath.

Safety concerns:

 Make sure they have an ice/water bath on hand. It is very easy for this reaction to get out of
hand/react too fast. Many students will add the bromobenzene too fast, causing a vigorous
reflux and a lot of darkening. This is bad, as it leads to lots of biphenyl and benzene side
products.

 Keep an eye on their reactions, and have them cool them down if the reflux is anything more
than a gentle reflux. The condensation ring should not ride too high up in the condenser!

 They should not be using heating plates to heat anything – they should be using steam baths.

 They will have an open neck, but they have to close it for safety reasons because hot liquid
might come shooting out.

Practical notes and reminders:

 Remind them that there are steps to a reaction: do the reaction, work up the reaction, purify
products, in an endless loop.

 Adding excess iodine to start with made the reaction initiations a lot more reliable, but you
lose a color change step. If you would like, you can just go around to hoods to give a crystal
to groups when you check their setups.

 If they clean their glassware with acetone, make sure the flask is DRY before they start!

 Bromobenzene, anhydrous ether, and methyl benzoate should be dispensed from the center
bench hood. Make sure you label ether bottles with the date when first opening them.
Magnesium turnings are next to the balances.

 The Drierite is pre-mixed and on the shelves. If we run out of mixed Drierite, you will need to
mix some blue in with the white before students use it.

 When they get their drying tubes, encourage them to find ones that are blue/white and not
purple. If there aren’t enough charged ones, just toss the used Drierite into the solid waste and
add some more premixed Drierite from the white shelves.

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 For the IRs, just wait until the first group is ready to demo it for everyone. Tell them that they
should probably clean instruments such as this every time BEFORE and AFTER they use it
unless they are there to watch it being well-cleaned before them. It will save more time in the
long run. Remind them to not contaminate the computer keyboards or mice with their gloves.
Also, make sure that when they are done they close their file but not the program because it
takes a bit for the program to boot up. Login is chem135 with no password.

 Remind them to recap containers to keep them anhydrous.

 Students need to submit one IR per partner, not per pair.

Experimental notes:

 Check their setups before students turn on the heat.

 Expect about half the students' reactions not to start right away if they aren't initiated
somehow. This reaction is actually very robust, but occasionally doesn't start due to wet/dirty
glassware (they won't be doing anything to dry their glassware.) If they clean their glassware
with acetone, make sure the flask is DRY before they start!

 All four methods of jump-starting the reaction work: 1) add a small-scale Grignard reaction,
2) add initiator, 3) heat gently, 4) carefully grinding turnings in bottom. If you want to start a
small-scale reaction, do it in a medium or large test tube; add the reagents but DON'T grind
until the last possible moment. Once you grind the Mg with a stir rod in the presence of the
other reagents, the reaction takes off! One medium-large test tube can start three or four
student reactions or one particularly stubborn reaction. Students tend to like the small-scale
Grignard because it looks cool to have a boiling test tube in your hands.

 You can also use a reaction from another group to jumpstart another.

 They should make careful note of the color changes going on in the reaction. This reaction
gives a whole range of different colors and goes between clear and cloudy a number of
different times. Make sure they also record their errors, i.e., “bromobenzene solution added
too fast; reaction became too vigorous and shot through top of condenser,” etc.

 If they have a lot of solids remaining, they probably just have to add more ether to make the
chunks dissolve.

 I2 (brown) reacts with Mg to form MgI2 (colorless) so it is usually apparent when the
activation is complete (i.e. the solution turns from brown to clear). MgI2 can act as the
“bridging halide” in the addition which speeds the reaction along.

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 The formation of Ph-MgBr turns the solution brown. As a result, if using iodine, the solution
may never turn clear because the Ph-MgBr may begin forming before all of the iodine is
consumed, making it difficult to tell what is going on in the flask. To avoid this problem, it
may be best to simply activate everybody’s Mg with iodine before adding any bromobenzene.
Once the solution clears, start adding the bromobenzene drop-wise. This may be overly
cautious but will minimize any difficulty with getting people's reactions going. You could
also add 1,2-dibromoethane to initiate – it seems this sometimes works better than iodine.
You can decide how you want to do it in your section.

 The initiators consume an equal amount of Mg, and it may be a good idea to weigh out the
initiator and add an equimolar amount of Mg so as not to diminish yield.

 Once they have transferred their reaction to the sep funnel, make sure that they wash with
water a couple of times before washing with bicarb. This is because if there are any residual
salts around, our observation has been that they crash out in bicarb. You want to wash them
away completely before neutralizing.

 The 100-mL 3-necked flask the reaction is run in is often difficult to clean (magnesium salts
often remain). A lot of their glassware will be caked with white streaks. Some 6M HCl should
do the trick – just make sure that it is clean before they put it into the bins.

Useful Figures from Zubrick:

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Student Lab Manual

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36
 Chemistry 20 Laboratory General Information

Head Lab TF

Matt Patton [email protected]

Laboratory TFs

Nare Janvelyan [email protected]

Cristin Juda [email protected]

Locations

The organic chemistry laboratory is located in Science Center 210 (across from the elevator). TF
Mailboxes are on the second floor of the Science Center. A Teaching Fellow (TF) must be
present for you to enter the laboratory.

Lab lectures will tentatively take place in Science Center Lecture Hall D at 11 am Fridays before
A lab sections.

Overview

This laboratory course is designed to introduce you to the basic analytical and synthetic
techniques employed in the practice of organic chemistry.

A passing grade for all experiments is required to pass the course.

Any announcements related to lab will be posted on the Chem 20 website

(http://isites.harvard.edu/icb/icb.do?keyword=k101517) on the Laboratory page. Here you will
also find pre-lab quizzes, lab lecture videos, and the lab calendar.

Scheduling

Laboratory sessions are scheduled for five consecutive hours (1 pm – 6 pm or 6 pm – 11 pm), on

an approximately biweekly basis. Pre-lab quizzes must be completed prior to coming to lab or
you will not be allowed to begin the experiment. Any student who is late to lab for any reason
will receive a zero for the quiz and will not be allowed to complete the lab, as these experiments
often take the whole lab period.

You will section for the laboratory using the FAS Online Sectioning tool (you must section
separately for lab and section). Before the first lab, there will be a required two-hour lab
orientation that will cover important safety information as well as introduce you to the lab space.
The mandatory safety orientation and walkthrough will tentatively take place Tuesday, February
4 or Wednesday, February 5 from 2 pm – 4 pm, you will have your choice as to which session to
attend.

37
You will work with one other person to complete each experiment, but must submit all written
work individually. Each student pair will be assigned their own chemical fume hood during the
first laboratory session, and all chemical work must be performed in this hood.

Important Lab Safety Rules

The primary goal for the instructors of this laboratory is for each and every person (both students
and TFs) to safely make it through the semester. Never endanger the safety of yourself or others
for any reason. Detailed safety policies are outlined in the lab manual and covered in training
sessions. However, the following items are so important that they will be stressed from the
outset:

• Safety goggles (available for purchase at the Harvard COOP) must be worn in the lab at all
times. They must be worn from the second you walk in until the second you leave, even if you
are not doing chemistry. The correct type of goggles will be shown at the first lecture, and
photos are posted on the course website. Although we may have extra goggles on hand from
time to time, failure to show up to lab with your own goggles will automatically incur a
safety/clean-up point penalty. Furthermore, any student who arrives at lab without goggles is at
risk of being barred from that lab session altogether if there are no extra pairs to wear – always
bring your goggles!

• You must wear proper attire to lab. This means no shorts or shoes that expose ANY part of
the foot or leg are permitted in the laboratory. You will be immediately sent home to change if
you attempt to enter the lab wearing shorts, capri pants, short dresses or skirts, sandals, flip-
flops, “ballerina” flats, Toms, “boat” shoes, high-heeled footwear, etc. – you will also receive a
safety/clean-up point penalty to your grade for that lab. You will not receive a warning before
incurring this penalty. The best way to comply with policy and protect yourself from exposure
is to ALWAYS wear long pants (a sturdy pair of jeans is best) and sneakers or boots that cover
the entire foot and ankle.

• You must wear one of the provided lab coats over your clothing at all times while working in
the lab. Neither gloves nor lab coats should ever be worn outside the laboratory – they are
contaminated!

• A Teaching Fellow (TF) must be present for you to enter the laboratory.

• Make-up labs will NOT be arranged for any students who miss a lab due to failure to adhere to
our proper laboratory attire policies!

38
Preparation

Nothing less than complete preparation prior to arriving in the organic chemistry laboratory is
acceptable. Lack of preparation will retard your progress through the experiments, and will also
result in danger to yourself, your TF, and your labmates. Contact your TF or the Head Lab TF if
you have any questions about an experiment.

The lab lecture for each experiment will help you prepare for each lab and for the online lab
quiz. You must attend the lab lecture (recommended) or thoroughly view the video online before
coming to lab.

Required Materials

Text

The Organic Chem Lab Survival Manual: A Student’s Guide to Techniques, 8th ed. by James W.
Zubrick. This book is available at the Harvard COOP. You may come across other editions,
which are acceptable, but you are responsible for figuring out the appropriate pages to read in
any other editions, and some older editions may actually lack entire chapters assigned for
reading, so be careful if you decide to purchase them.

Notebook

Your lab notebook must be the kind that makes carbon copies, so that a copy of your notes can
be submitted to your TF at the end of each lab session. These research lab notebooks are
available for purchase at the Harvard COOP, but you can buy them anywhere you wish. Students
who arrive to lab without the proper laboratory notebook will be provided with a temporary
replacement notebook on a one-time basis, but will incur a penalty to their grade for that lab, and
will be refused participation in subsequent labs unless a satisfactory lab notebook has been
procured. Students who arrive at lab without having completed the pre-lab write-up in its entirety
present a danger to themselves and others and will be barred from participating in that lab.
Always come to lab prepared!!!

Lab manual

Available for purchase from FlashPrint, 99 Mount Auburn St.

Lab Safety Goggles

The proper indirectly vented safety goggles are available from the Harvard COOP, and other
types will not be allowed. You must purchase your own and bring them to every scheduled
laboratory session. These goggles will be appropriate for other chemistry lab courses that you
may take as well. Any student who shows up to lab without goggles will be dismissed from lab
to fetch his or her goggles.
 

39
Attendance

You must attend every one of your assigned laboratory sessions. The number of students
enrolled in the course and our unwavering commitment to safety in the laboratory make it
impossible for us to permit attendance of non-assigned laboratory sections without explicit
permission from the Head Lab TF. Should a serious illness or family emergency arise, please
notify the Head Lab TF and your own Lab TF as soon as possible, so we can work with you to
help you complete all the experiments. If you have a religious conflict during the semester,
please notify the Head Lab TF at least two weeks prior.

Grading

Your lab score will be calculated as follows:

5 Lab Reports Pass/Rewrite
5 Labs with 2 Individual Clean-Up points each 10
5 Labs with 2 Group Clean-Up points each 10
5 Pre-lab Quizzes @ 14 points each 70
1 Orientation Safety Quiz 10
–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
Total 100 points

Lab Reports

See the lab manual for a description of how to write good lab reports. Appendix 4 also shows an
example of a passing report. Your TF will let you know of any more specific expectations he or
she might have for your reports either prior to an experiment by e-mail or in the pre-lab talk. You
will turn in your completed lab report before you leave each lab session. Your TF will then
return your report in the next lab session with a grade of either Pass (an acceptably written
report) or Rewrite (if any part of the report is unsatisfactory or incomplete). Should you receive
a grade of Rewrite, you will have until the next lab session to satisfactorily revise your report and
turn it back in to your TF for regrading in order to pass that lab (and ultimately the course).

Failure to complete all of the lab experiments and pass all of the write-ups will result in a
failing grade for the course.

Pre-lab Quizzes

The pre-lab quizzes are designed to test practical understanding of the procedures, safety
considerations, and fundamental chemical concepts as explained in lab lectures, your lab manual,
your textbook/lecture notes, and in Zubrick. The pre-lab quizzes can be found on the Chem 20
website and should be completed at least 30 minutes prior to your scheduled lab section. Failure
to complete the pre-lab quiz for a lab will result in a zero for the quiz. You must correctly
complete the safety questions on the quiz to enter the lab. The quizzes require that you attend (or
watch) lab lectures, do all required reading and think about the lab in advance. Be certain to have
any questions answered BEFORE coming to lab! Your TF is always available by e-mail to help

40
you with the quiz material. If you have questions about the quiz material for Lab 1, please e-mail
the Head Lab TF.

Personal Clean-Up/Safety Points

You will earn up to two points in each lab session for obeying all safety regulations and leaving
your fume hood, bench-top, sink, and drying rack in immaculate condition at the end of each lab.
In order to earn these points, it is your responsibility to have your TF initial your notebook at the
end of the lab period to verify that you did in fact leave your work area clean. For a description
of exactly what is expected of you, refer to Appendix 3 of the lab manual. Failure to adhere to
ANY rules and regulations of the laboratory could result in losing your personal safety/clean-up
points for that session, at your TF’s discretion and as mentioned above. Please note that your TF
may assign groups to handle additional clean-up tasks, and failure to complete these tasks could
also result in personal safety/clean-up point deductions.

Group Clean-Up/Safety Points

Each lab section will earn up to two points as a group each week for properly following waste
disposal rules, handling reagents responsibly, and keeping all common areas in the lab clean.
These include the waste disposal hoods, center bench reagent dispensing areas, balances and
melting point apparatus areas, glassware room and bins, white shelves, and the instrument room.
Failure to keep these areas spotless will result in the entire laboratory section losing up to two
points for that lab session, at the Head Lab TF’s discretion. The easiest way to avoid this is to
always be sure to clean up after yourself!

41
 Chemistry 20 Laboratory
Spring 2014 Syllabus

Lab # Lab Description

 
Orientation and Safety Walkthrough
Feb 3 – 4 0

Separation of an Unknown Mixture

Feb 10 – 26 1 Acid-Base Extraction

Purification of Organic Compounds

Mar 3 – Mar 12 2 Recrystallization and Distillation

The Grignard Reaction

Mar 24 – Apr 2 3 Preparation of a Grignard Reagent
Synthesis of Triphenylmethanol

Electrophilic Addition and E2 Elimination

Apr 7 – Apr 16 4 Synthesis of Diphenylacetylene
Reactivity of α-Pinene

Friedel-Crafts Acylation
Apr 21 – 30 5 Friedel-Crafts Acylation of Ferrocene
Thin-Layer and Flash Chromatography

Note 1: Unexcused absences from lab are not permitted. Contact Matt Patton, Head Lab TF
(e-mail: [email protected]) in case of a medical emergency. The attendance policy is
detailed in the lab manual.

42
 2014  Chemistry  20  Lab  Calendar
February  2014
Sunday Monday Tuesday Wednesday Thursday Friday Saturday
1

2 3 4 5 6 7 8
Orientation  and   Orientation  and  
Lab  Lecture  1
Safety   Safety  
11-­‐1PM
Walkthrough Walkthrough  
9 10 11 12 13 14 15
Lab  1  
Monday  A
1-­‐6PM
16 17 18 19 20 21 22
Lab  1 Lab  1
Presidents  Day Tuesday  A Wednesday  A
1-­‐6PM 6-­‐11PM
23 24 25 26 27 28
Lab  1   Lab  1 Lab  1
Lab  Lecture  2
Monday  B Tuesday  B Wednesday  B
11-­‐1PM
1-­‐6PM 1-­‐6PM 6-­‐11PM

March  2014
Sunday Monday Tuesday Wednesday Thursday Friday Saturday
1

2 3 4 5 6 7 8
Lab  2 Lab  2 Lab  2
Monday  A Tuesday  A Wednesday  A
1-­‐6PM 1-­‐6PM 6-­‐11PM
9 10 11 12 13 14 15
Lab  2 Lab  2 Lab  2
Lab  Lecture  3
Monday  B Tuesday  B Wednesday  B
11-­‐1PM
1-­‐6PM 1-­‐6PM 6-­‐11PM
16 17 18 19 20 21 22

Spring  Break Spring  Break

23 24 25 26 27 28 29
Lab  3 Lab  3 Lab  3
Monday  A Tuesday  A Wednesday  A
1-­‐6PM 1-­‐6PM 6-­‐11PM
30 31
Lab  3
Monday  B
1-­‐6PM

April  2014
Sunday Monday Tuesday Wednesday Thursday Friday Saturday
1 2 3 4 5
Lab  3 Lab  3
Lab  Lecture  4
Tuesday  B Wednesday  B
11-­‐1PM
1-­‐6PM 6-­‐11PM
6 7 8 9 10 11 12
Lab  4 Lab  4 Lab  4
Monday  A Tuesday  A Wednesday  A
1-­‐6PM 1-­‐6PM 6-­‐11PM
13 14 15 16 17 18 19
Lab  4 Lab  4 Lab  4
Lab  Lecture  5
Monday  B Tuesday  B Wednesday  B
11-­‐1PM
1-­‐6PM 1-­‐6PM 6-­‐11PM
20 21 22 23 24 25 26
Lab  5 Lab  5 Lab  5
Monday  A Tuesday  A Wednesday  A
1-­‐6PM 1-­‐6PM 6-­‐11PM
27 28 29 30
Lab  5 Lab  5 Lab  5
Monday  B Tuesday  B Wednesday  B
1-­‐6PM 1-­‐6PM 6-­‐11PM

43
The Lab Notebook and Your Lab Report
Reading
Zubrick, Chapter 2 (Keeping a Notebook). Lab manual: Appendix 4.

Introduction
Your purpose in writing a lab report is to communicate your procedure, results, and analysis
to others in a concise and well-organized format. Lab reports should be written in three parts as
outlined below. You must complete each section in this format to receive a passing grade. Refer
to Appendix 4 as you read through this section for an example lab report.

Pre-Lab (Written Before Lab)

In order to prepare for each lab, you must understand both the theory behind the techniques
you will be using and the procedure that you will carry out (from this manual and described in
the Zubrick book).

The pre-lab’s purpose is to collect all of the necessary information in one place so you can
work more efficiently and safely in lab. For these reasons, you will not be allowed to begin the
lab unless you have a satisfactorily written pre-lab.

A complete pre-lab consists of:

A. Header: Preface each experiment with a title, your name, the date, your lab TF’s name, and
the day/time of your lab section and your lab partner’s name.
B. Purpose: Write a brief statement outlining your experimental objective(s).
C. Safety Information: Briefly describe the important safety information. This should include
both the standard safety information that you follow every week as well as any specific
safety information particular to that week’s lab. You do not have to use complete sentences.
D. Materials: Write a list of glassware and chemicals you’ll need for the experiment. Include
concentrations and other necessary descriptors. It will be helpful to split this up for multi-
part experiments.
E. Reagent Table: (if applicable): Copy relevant data from the table that is provided for each
experiment in the lab manual. This is especially important for synthetic experiments. You
do not have to copy any information that will not be useful.
F. Pre-lab Write-Up: This may include theoretical yield calculations, mechanisms, laboratory
techniques, etc. Please try to keep these organized for clarity.
G. Procedure: Outline the procedure in a way that you can understand and repeat it. This does
not mean that you should transcribe the manual word for word. Summarize it, make notes to
yourself, and use pictures and abbreviations.

It is HIGHLY recommended that you use a two-column format when writing your
procedure; an example of this can be found in Appendix 4. Outline the procedure in the left
column before coming into lab, and fill in the right column with your corresponding
observations. This will help you organize things neatly.

44
Observations (written during lab)
You will record all of your important laboratory operations and observations as they happen.
A stepwise sequence of short phrases is often sufficient for this purpose. Include enough detail so
that you or someone “skilled in the art of organic chemistry” could repeat the experiments with
only your lab notes. Record any interesting observations even if they are not explicitly
mentioned in the manual.

It is not necessary to describe standard lab glassware or basic techniques. Familiarity with
the form and function of commercially available equipment is presumed. It is also not necessary
to record successful completion of steps written in your procedure.

Typical observations/recordings include:

 Exact masses and volumes used in reaction ( “3.02 g unknown”)
 Characteristics: color, smell, phase, clarity, shape of crystals, homogeneity of a solution
(“red, crumbly solid”, “clear, colorless liquid with an alcohol smell”)
 Labeled layers of a solution (“Organic ether layer above aqueous layer”)
 Accidents and errors (“Spilled approx. 5 mL of the solution”)
 Deviations from the procedure (“Washed with additional 25 mL brine”)
 Duration (“stirred 1 hr”)

Results and conclusions (written before leaving the lab)

A. Product data: Report the yield in g or mL, percent yield based on amounts used, melting
point, boiling point, etc. using proper units. Make sure to label what these
calculations/values/pictures are. Show calculations.
B. Interpretation and explanation: Results obtained in your experiment, including spectral data
if relevant. Include an analysis of the likely sources of error in your experimental results for
recording boiling/melting points, yields, and spectra. Common types of error include
accidents, instrumental error, and theoretical error/flawed assumptions. Do not include
generic (“human error”, “loss in transfer”) or speculative sources of error (“IR probably
dirty”). It is understood that there will always be some small errors in all laboratory
techniques, so they do not need to be stated.
C. Any additional information specified for the experiment under Lab Write-Up.

Lab report tips

 Work in parallel and use down time efficiently.
 Ensure that the duplication mechanism your lab notebook employs is in place and working
before you begin writing.
 Always include the units of any number you record (mg, g, mL, L, mmol, mol, °C, %, etc.)
 All laboratory data, observations, and calculations must be recorded directly in the lab
notebook at the time they are obtained. The use of scratch paper or rough drafts is not
permissible.
 Use ink, never pencil.
 Don’t erase or scribble out entries. Simply draw a line through the erroneous text and add the
new information.
 Each new experiment should begin on a new page. Leave yourself space. It is better to write
too little on a page than too much.

45
 Lab 0: Orientation and Safety Walkthrough
Reading

Zubrick: Chapters 1 (Safety First), Chapter 2 (Keeping a Notebook) , 4 (Jointware), and 9 (Clean
and Dry). Lab manual: all material under Introduction, Lab 0, Appendices 1-4. Orgolabs
website: the ACS Student Safety Guidelines.

Introduction

On your first day of lab you’ll be whisked away on a tour of the Louis and Mary Fieser
Laboratory of Organic Chemistry (a.k.a. Science Center 210). The labs are named after the
husband and wife team that pioneered the synthesis of 1,2,3,4-tetraphenylnaphthalene, which
you will carry out at the end of next term. Your preparation and attention this week will help
ensure that the long road to that final synthesis is a safe one.

Lab 0 will be an experience to introduce you to the format of the lab course and will be
structured just like every other lab (except you will have no pre-lab assignment or report write-
up). Please make sure that you are intimately familiar with the content below, read assigned
readings (which will help you in the in-lab quiz), and wear appropriate attire as explained below.
The graded portion of your lab experience will begin on Lab 0 – there is never an acceptable
time to have unsafe behavior in a lab environment. As you read, keep in mind any questions you
may want to ask.

This orientation will also consist of an introduction to course policies, safety information, a
tour of the lab, and a short in-lab assignment. The only preparation necessary is the assigned
reading, looking over the pre-lab questions, and wearing lab-appropriate clothing.

The Beginning-of-Lab Routine

As with every other lab, you should be prepared and settled by seven minutes after the hour
and wear acceptable clothing! As you enter the room, please have your goggles on. TFs will help
direct you to opposite sides of the room to hang up coats/bags and put on a lab coat. This is a
good opportunity to figure out your size. The TFs will also point out where the nitrile gloves are
located; please put on gloves from the white shelves.

For one time only, the TFs will not start the pre-lab quizzes immediately in order to give you
time to put on personal protective equipment. When you are done putting on PPE, please pick up
a pre-lab quiz and take a seat at any stool. Later on, you will find your partners and be assigned
hoods during Lab 1. If you had a pre-lab assignment, you would have it open and ready for the
TFs to check off, and your manuals would be closed. The TFs will write the three selected
questions on the board, and you can begin answering the chosen questions. After turning your
quizzes in, please assemble near the entrance for the lab tour.

46
A Tour of the Lab

Take a look at Appendix 1 of this manual. It is a map of the lab where you’ll spend many
hours in the coming weeks. Pay particular attention to the location of safety equipment; the Head
TF will point it out as we go along.

Teaching fellows
Soon you will meet your lab TFs, the primary mentor and guide in the lab. He or she will
give you a short introduction to each lab, administer the pre-lab quizzes, and solve most of the
problems that inevitably arise in the laboratory during the semester. Your section assignments
will be emailed to you automatically, and you will determine your TF at Lab 1.

Science Center 210 entrance

The entrance to the lab is also an emergency exit. Slightly in front and to the left of the
entrance as you enter, you will see a row of hoods and benches that have ice machines on the
near end and yellow solvent cabinets on the far side. Historically, this has been called the “center
bench” even though it is not exactly in the center of the laboratory.

Center bench
The center bench area is composed of four fume hoods, an ice machine, and yellow flame
cabinets. The four fume hoods are used as a place to dispense the liquid reagents used for each
lab; dispense silica gel for column chromatography; and store the containers for chemical waste.
Note that both sides of the center bench contain different waste containers. The ice machines
supply the laboratory with ice for cold baths. The yellow flammable solvent cabinets should
never be opened by students. Any special solvents you need will be set out for you before you
arrive in lab.

White shelves
The walls to the right and left of the entrance contain a series of white cabinets with black
shelves, which are called the “white shelves”. Most standard laboratory supplies you need to
conduct experiments are here, including glass pipets, rubber bulbs, filter paper, pH paper, drying
agents, disposable nitrile gloves, office supplies, and various other things. Feel free to take what
you need from these shelves, but be sure to return materials back to where you found them.

TF prep rooms
In between the white shelves on both sides of the lab are TF rooms where chemicals are
stored. These rooms are off-limits to students.

Glassware storage room

Just past the white shelves is a glassware storage room. In here, you will find specialty
glassware, rubber tubing, adapters, and many other implements you will need in your
experiments. You can also find extra tubing or clamps if your common bench items are
lacking/broken. Feel free to enter this room and borrow any items you may need for an
experiment. You must thoroughly clean and return all borrowed glassware to the dirty glassware
bins or the glassware room. Nothing that you obtain from this room is disposable.

47
Dirty glassware bins
When you’re finished with glassware (and other implements) from the glassware room, it
should be thoroughly cleaned and placed in the plastic bins located in front of the glassware
washing room. There should be no visible chemicals on any glassware in these bins. At the end
of the laboratory session, professional technicians will remove any recalcitrant contamination
from the glassware and return it to the glassware storage room for the next lab session. If dirty
glassware is found after the lab, the entire lab section will have group cleaning points deducted.

Note that disposable scintillation vials, test tubes, disposable Pasteur pipets, rubber pipet
bulbs, TLC chambers/lids/plates, and Tygon tubing NEVER go into the glassware bins!

Backpack and coat storage area

The backpack and coat storage areas are located on the far right wall and the far left wall of
the lab. Please keep your coat and bags there so that the lab will not be cluttered with things to
trip over and so your personal items will remain clean. We cannot ensure the safety of any items
left in this area, so if you have something that’s valuable or important to you, it would be best to
leave it at home.

Lab coat racks

Located next to the backpack and coat storage areas on the far right wall and the far left wall
of the lab are metal racks with white lab coats. When you arrive at lab, take a white lab coat from
the rack to wear during the lab period. The lab coats come in a variety of sizes, so try to find a
size that will fit you. Wearing a lab coat will provide protection while you are working in lab. At
the end of the lab period, hang your lab coat up neatly on the metal rack in the correct size
section.
If you spill something on your lab coat during the lab period, notify your TF and hand your
dirty lab coat to your TF. Get a clean lab coat from the metal rack to wear for the remainder of
the lab period.

Exits/entrances to Science Center 212

There are two sets of doors on the right-hand wall, both of which lead into the general
chemistry labs. These doors also serve as emergency exits.

Melting point apparatus area

Melting point apparatuses (Mel-Temps) are located along the walls opposite the entrance.
Please clean up any spills you make, throw out used capillary tubes in the blue cardboard
glassware disposal boxes, and turn off the instruments when not in use. A melting point
apparatus will explode if left on and unattended (no joke)! Additionally, UV visualization boxes
are located in this area. Heating plates will also be stored here when not in use.

Balance area
Between the Mel-Temps along the wall are analytical balances. These balances are extremely
expensive pieces of equipment; passing breezes, water, and spilled chemicals drastically shorten
their lifetimes. It is very important that you close the doors to the balances when you are done
weighing and that you immediately clean up any spilled chemicals with the brushes located
nearby. This is also the area where solid reagents are usually dispensed. Again, immediately
clean up any spilled chemicals that you find in this area, even if you were not the one to make
the mess. If a mess is left here at the end of lab, your entire section could lose their clean-up
point for the day!

48
Solvent dispensing hoods
Located beside the balance and Mel-Temp areas are fume hoods with metal solvent
dispensers. Common organic solvents such as acetone, ethyl acetate, hexanes, methylene
chloride, methanol, and ethanol can be obtained here. Please cover your solvents to avoid fumes
and evaporation. Let your TFs know if any of these solvents are running low or having problems
dispensing. Note that the solvent taps have variable flow so you can adjust the rate of solvent
flow based on how much solvent you need.

Common aqueous solutions

In the middle of the back wall is a bench with carboys (large plastic jugs) containing
commonly used aqueous solutions (3M NaOH, 3M HCl, etc.) Notice that there are plastic
buckets beneath each of them. These buckets catch the drips; make sure they’re under the carboy
you’re using, so you don’t drip sulfuric acid etc. onto your shoes! Don’t take more solution than
you need, and don’t put unused solutions back into the carboys.

Waste hoods
There are fume hoods in the lab dedicated to housing buckets for collecting chemical waste.
See the Waste Disposal Guidelines section in your manual for a description of our waste policies.
Please keep this area clean, and don’t overfill the containers. Close the lid after you dispose of
your waste. If a waste container is full or nearly full, please alert a TF immediately.

Instrument room
The instrument room is to the far left of the lab entrance. It is equipped with infrared
spectrometers (IRs) and a polarimeter. There will be instructions on how to use these instruments
in your lab manual when appropriate, but don’t ever try to use them without the assistance of
your TF. Take off your gloves when you are using the computer. One partner can use the
computer and the other can handle chemicals to help protect our electronics from contamination.

At your bench
You and your partner will be assigned a sink, fume hood, and bench top area to use
throughout the course. The only liquids (No solids!) going into your sink should be
uncontaminated ice from ice baths and soapy water used in washing your hands. Do not put
chemically contaminated glassware in the sinks. All chemical work should be carried out in your
fume hood.
Materials for cleaning your glassware (acetone and distilled water squirt bottles, brushes, and
waste beakers) are located at the back of your assigned hood. Each bench is also supplied with a
set of equipment (see Appendix 2) that is stored in the cabinets under the sinks and under the
rotary evaporators (rotovaps). Each bench should also have a pink plastic container with
additional items. Notify your TF if you are missing any equipment or your equipment stops
functioning. Don’t raid other benches for common-bench supplies. Each bench area also has
convenient a pull-out board above the drawers that can be used as a writing desk.

You and your partner are responsible for the cleanliness of your assigned hood, sink, and
bench top. All glassware must be washed, dried, and returned to the dirty glassware bins by the
end of the lab period. Refer to Appendix 3 for glassware washing instructions. Additionally,
please push your chairs in and keep the areas between benches uncluttered to prevent any
accidents.

49
Important Safety Considerations

General safety considerations

A chemistry lab can be a dangerous place to work. There are flammable solvents, toxic and
corrosive chemicals, electrical equipment, delicate glassware, and more. The potential for injury
from these dangers can be minimized if you are aware of and follow proper safety procedures.
The most important safety precaution you can take is to come to lab prepared and to think
about what you are doing. The most dangerous thing in a lab is an unprepared student trying to
carry out a procedure he or she does not understand.

Many of our laboratory safety guidelines are described below and also in your manual’s
section on Safety Guidelines. You should also closely read Zubrick Chapter 1 and the ACS
Student Safety Guidelines posted on the website. Both the Head TF and your lab TF are
authorized to deduct points or remove you from the laboratory without warning if you fail to
follow any of these guidelines.

You will all be required to read the safety information provided in this manual
and sign the Chemistry Course Safety Policy Agreement before you are allowed
to participate in any lab experiments.

Violations of safety and laboratory policy

The department has instituted a simple three-step escalation for any students who do not
adhere to safety regulations and laboratory policies in general, as follows:

A first offense will garner a verbal warning and loss of clean-up points for that experiment.
The course will follow up with a written warning in the case of particularly serious offenses.

A second offense will result in the student being dismissed from the lab, as well as a zero for
that particular experiment. The student may petition to be allowed to make up the lab on a case-
by-case basis. The course will also follow up with a final written warning.

Subsequent offenses will result in dismissal from the course, necessitating a formal petition
to the Director of Undergraduate Laboratories for readmittance.

50
Personal Protective Equipment

Clothing
Wear long pants (preferably something sturdy such as jeans) and closed shoes. No exposed
legs or exposed feet are permitted in the laboratory. You will be sent away to change and
have points deducted if you enter the lab wearing shorts, skirts, sandals, flip-flops, open-toed
pumps, etc. Through some combination of pants, socks, and shoes, you must fully cover your
legs and feet. Leggings or tights do not count as pants. Rather than shielding your legs from a
splash as sturdy pants might, they will only hold chemical spills next to your skin.
No leniency will be given for any clothing that attempts to circumvent the rules. Please
understand that these rules are intended to eliminate exposed skin and reduce safety risks, and
you will be expected to apply these principles to your clothing choices. Not every unacceptable
piece of clothing can be explicitly listed, so use your best judgment.
If you have long hair, tie it back to avoid the possibility of dipping it into chemicals, solvents,
or flame.

Lab coats
You are also required to wear one of the provided white lab coats available on the metal
racks. The possibility of ruining your clothing exists, so do not wear clothes you cannot live
without.
If you need to leave the lab for any reason (going to the bathroom, etc.), you should take off
your lab coat and any other protective gear to avoid contaminating areas outside of the lab.

Your TFs will be wearing blue lab coats so they can be easily identified.

Eye protection
The American Chemical Society has determined that only safety goggles, not safety glasses,
provide adequate protection for students in a chemistry laboratory. Check that your safety
goggles are UV protective. There will be goggle defogger provided in the labs.
Bring your safety goggles to lab with you every week. Safety goggles must be worn in the
lab at all times. They must be worn from the second you walk into the laboratory space until the
second you leave, even if you are not doing chemistry. There are absolutely no exceptions. If
you forget your safety goggles, a pair will be provided to you with a point deduction. Otherwise
you will not be permitted in the laboratory. Repeated failure to wear your safety goggles will
result in permanent dismissal from the lab, necessitating a formal petition to the course instructor
and Director of Undergraduate Laboratories for readmittance.

The American Chemical Society has determined that contact lenses, when worn in
conjunction with safety goggles, are permissible in a chemistry laboratory. We have adopted
their recommendation as our policy. Should you get something in your eyes while wearing
contacts, make sure to tell your TF and medical personnel that you are wearing contacts.

51
Gloves
You must wear gloves whenever you are working in the lab. You will find latex-free
disposable nitrile gloves (XS, S, M, L, XL) on the white shelves. They are only designed to
protect you from splashes and other incidental contact with chemicals. Acids, bases, and organic
solvents will penetrate quickly through these gloves, so you should not continue to wear a pair of
gloves if you have spilled anything on them. Changing gloves periodically will prevent you from
spreading these chemicals onto your lab book and everything else you touch. Never rub your
eyes while you are wearing gloves. In rare instances, the nitrile gloves may irritate your skin. Let
your TF know if this happens.

There are thick rubber gloves available that will give you more chemical protection than the
nitrile ones. These gloves can resist even concentrated acids and bases for a time. They are a bit
awkward to work with and are usually only used when working with strong acids or bases,
especially nasty chemicals, and any other time your TF instructs you to do so. Even though the
gloves are resistant, you should wash them off if anything spills on them. Ask your TF where
you can find these gloves if necessary. You may wish to wear a pair of the nitrile gloves
underneath the orange gloves for greater protection and comfort.

You should wash your hands several times while in lab, especially just before leaving.

Safety Equipment

Know where the nearest safety equipment is at all times. You never know when you or your
neighbor will need it. In case of any incident, notify a TF immediately.

First aid kits

There are two first aid kits: one on the wall right near the main entrance and another by the
exit to the general chemistry laboratory. In these you will find bandages, burn ointments, pain
relievers, antacids, antibiotic creams, eye drops, etc.

Eye washes
There are emergency eye washes along both the front and back walls of the room. If you get
a chemical in your eyes, hold your head such that your eyes are in the streams of water and blink
for at least 15 minutes. If you notice your neighbor has gotten something in their eyes, calmly
escort them to the eyewash and help them rinse out their eyes. It is not the end of the world if
you need to use the eye wash station; if you feel a burning sensation in your eyes, you may want
to give them a rinse for a few minutes just to be safe.

If you wear contact lenses, please wash your eyes first. The lenses can be removed during or
after a wash. Contaminated contact lenses should be discarded.

Safety showers
Safety showers are located in three places along the back wall of the lab, directly opposite
three of the eyewashes. To operate, pull the handle down. The shower puts out a massive deluge
of really cold water, so be prepared. Immediately strip off any contaminated clothing while under
the shower. Don’t be modest, be safe. The shower is not self-locking, so you’ll have to pull the
handle down every 20 seconds or so.

52
Fire blankets
Fire blankets are located in three places along the front wall of the room. If someone’s
clothing is on fire, either douse him with water under a shower or wrap them in a fire blanket as
he or she rolls around on the floor.

Electrical disconnect
Do not touch or strike a person in contact with a live electrical circuit. Disconnect the power
first by pressing the closest “Emergency Electrical Disconnect” red button located along the
front, back, and right-hand walls. These buttons cut off power to nearby (not all!) outlets and
fixtures in the lab in the case of fire, flammable chemical spill, or other emergencies.

Fire extinguishers
Fire extinguishers are located along the front wall and attached to the sides of the rows of
benches that face the front/back wall. In case of fire, notify a TF immediately. The TFs are
trained to use a fire extinguisher if it is necessary. Note that fires fueled by combustible metals or
substances that react with carbon dioxide must be extinguished with a class D fire extinguisher.
Multipurpose (class A, B, C) fire extinguishers will fuel any fire that involves combustible
metals or substances that can react with carbon dioxide.

Spill control kits/pillows

Any spills should be reported to your TF immediately. They will supervise the cleanup or
obtain professional assistance if deemed necessary. Large spills of relatively non-volatile or non-
toxic chemicals can be contained using the absorbent pillows and spill kits, which are located
throughout the lab. Minor spills of acid or base solutions can be cleaned up with the use of
sodium bicarbonate (for acids) or Hazorb (for acids or bases). Hazorb is in the white cardboard
cartons right next to the bulk aqueous solutions.

Fire alarm
A fire alarm is located on the wall just outside the entrance to the lab. It is there for a reason.
If you need to pull it, you should be on your way out of the lab!

Operations center telephone

A telephone that automatically connects to the Operations Center is located just to the left of
the entrance to the lab. The Harvard University Operations Center is a communications, dispatch
and response center providing 24-hour, 365-day Standard and Emergency Response Services to
the Harvard community. Regular phone calls cannot be made from this phone. The Operations
Center can be called to dispatch police, fire, ambulance, and facilities maintenance personnel.
The TFs will be the ones who typically use this phone; however, you should be aware of its
function.

53
Accidents and Emergencies

In case of any emergency, please notify your TF immediately.

Injuries
If you are injured, no matter how small the injury, tell your TF. In the case of minor injuries
(small cuts, minor burns, splinters, etc.), first aid can be given on-site with laboratory first-aid
kits. In the case of anything worse than a minor injury, you will be escorted to UHS by a TF or
police officer. Never leave for treatment without notifying your TF! After treatment of any
injury, you will be asked if you wish to continue that day. You will not be penalized if you are
unable to finish that day, even if it’s because you simply feel uncomfortable returning to the
bench.

Spills
If you spill anything on your skin, immediately wash the area with water and notify your TF
who will give you further instruction. If you spill a chemical in your hood or on the floor, tell
your TF. Small spills are easily contained, and your TF can tell you how to deal with them. If the
spill looks large or is something particularly nasty, notify your TF and move away from the area.

If you spill a large amount of chemical or a particularly dangerous chemical on your body
and/or your clothes, you will need to use a safety shower. Get your TF’s attention by yelling and
proceed directly to a safety shower and pull the chain. Remove the affected clothing (trust us,
modesty should be the last thing on your mind if you ever need the safety shower). The TFs will
direct other students’ attention away from you and provide a lab coat and clothing for you when
the rinsing is done. We also have eyewashes for rinsing spills out of your eyes or face.

Fires
The dangers from fire and spills can be minimized and effectively handled by careful
handling and following procedures outlined in the manual. If a fire does occur, immediately step
away from it and notify a TF. Most fires occur inside of a fume hood and will burn themselves
out on their own. The TFs are trained to use a fire extinguisher if it is necessary. Do not try to be
a hero – you are not responsible for putting out any fire. There is also a fire alarm on the wall
outside the main entrance if a fire gets out of hand. You should also be aware of the evacuation
paths.

Evacuation
If the fire alarm goes off, immediately walk out of the lab and exit the Science Center. The
Head TF will inform you of the best evacuation route, and there is a diagram in the lab that
illustrates the available evacuation routes. If any TF tells you to get out of the lab or a certain
area, do it! In years past we have had a number of students continue to work in areas where there
were fires and chemical spills. Dedication is a valuable asset to have in the laboratory, but we
would much prefer to have you safe than finished ten minutes early!

54
Additional Safety Topics

Chemicals
Wash your hands thoroughly before you leave the lab. There is soap at each sink. Constantly
washing your hands and wearing gloves can take a toll on your skin, so we can provide hand
cream as well.

Put all chemical waste in the appropriate waste containers. Waste Disposal Guidelines are
outlined in this manual. If you have any questions, please ask.

Material Safety Data Sheets (MSDS) are available for every chemical that you will be using
in the lab. They can be accessed online via the home page. MSDS give toxicity information, safe
handling, and information on what to do in case of exposure. A sample MSDS summary sheet is
included in Appendix 10 for a common laboratory solvent, DMF. Look it over. In general, it is
often difficult to ascertain how harmful chemicals actually are. Err on the side of caution. Your
exposure is well under the suggested limits if you use safety procedures.
A note about chemical warning labels: It is an unfortunate fact that in order to cover
themselves in case of lawsuits, chemical companies have sometimes become a bit overzealous
when labeling chemicals. For example, the warning label on sand states, “Chronic inhalation
hazard. Overexposure may cause lung damage. Suspect cancer hazard. May cause cancer.” It
also suggests you wear “protective eyewear, hand protection, and standard lab clothing” when
handling sand. Imagine how that would feel on the beach! So what should you believe? Use your
head, and err on the side of caution. If you have any questions about the chemicals with which
you are working, ask your TF or the Head TF. The lab was designed and the procedures were
written so that your contact with hazardous chemicals is minimized. You simply cannot do
chemistry without chemicals, but you can think about what you are doing to stay safe.

Glassware
Be aware of the dangers of handling glassware. The most common laboratory injuries are
cuts received from a piece of broken glass. Be especially careful when connecting pieces of
glassware together and taking them apart. Don’t force anything. If you can’t get two pieces of
glassware together or apart, ask your TF for help.

If you break any glassware, please notify a TF to help you clean it up. Our primary concern is
your safety and the safety of others. Do not dispose of broken glass improperly! Nobody wants
improperly cleaned-up broken glass to end up accidentally hurting someone.

Cell phones
Do not use your cell phone in lab. We will have wall clocks, and you should have separate
calculators. Not only are cell phones a distraction, but you do not want to contaminate your
phone with chemicals.

55
Fume hood safety and energy conservation
Fume hoods protect researchers from inhaling chemicals by constantly pulling air into the
hood and exhausting it out of the building. However, they will only protect you if operated
properly. A lowered sash provides much higher protection against contamination or injury.
Because they constantly pull air from the room when their sashes are open, fume hoods use an
enormous amount of energy. A single open fume hood can use as much energy in a year as 3.5
houses! By simply closing the sash when you are not using the hood, you can reduce energy
consumption by 60% or about $3000+ a year. Here are the basic instructions:

 Use the fume hood for all chemical manipulations.

 Keep everything at least six inches back from the hood face.
 Don’t lean into the hood or put your head into it when contaminants are present.
 Try to keep the sash lower than the level of the yellow arrow sticker. The lower the sash, the
greater the protection and energy savings.
 Close the sash entirely when you have finished with your work.

The Campus Energy Reduction Program, a part of the Harvard Green Campus Initiative, is
working hard to reduce energy consumption in FAS labs. You can help by keeping the sash
down as much as possible.

Food and drink

It is important to eat before coming to lab. You’ll be on your feet for up to five hours and
without providing energy for your body, you may become tired and/or light-headed. Food or
drink in the laboratory is prohibited. Smoking is not allowed in the Science Center, especially in
the laboratory. If you start to feel ill during lab and think some food or a drink may be the
remedy, let your TF know, and you may go down to the Science Center Greenhouse Cafe.

56
 Chemistry Laboratory Course Safety Policy Agreement
I have read the Safety Information in the Laboratory Manual in its entirety, have attended the
Safety Training conducted by the course staff, and I understand this information.

I realize that the Laboratory Manual and Safety Trainings do not contain comprehensive
information regarding every hazard I may encounter in the laboratory. I recognize that I must
proactively inform myself about the hazards associated with every task and experiment I
undertake and every substance I employ.

I agree to follow the safety policies and principles described in the Laboratory Manual while
conducting experiments in the Chemistry Teaching Laboratories.

_________________________________________
NAME (printed)

_________________________________________
SIGNATURE

_________________________________________
DATE

57
58
Waste Disposal Guidelines
Please ask your TF if you have ANY questions regarding cleaning or disposal that are
not addressed in this manual.

Massachusetts and federal laws require Harvard to adhere to strict regulations for the
identification, storage, and disposal of hazardous wastes. Operations that do not meet regulatory
requirements can result in substantial penalties including fines of up to $27,500 per day, per
violation. Students are the most important element of our laboratory’s hazardous waste
management system. Proper handling of waste will keep you, your colleagues, and the
environment safe. Adhere to the following guidelines, and always ask a TF when you have a
question regarding the disposal of waste in the laboratory.

No organic chemicals, including acetone, should ever get poured down the sink.

This includes any water or acetone used to wash glassware because it is likely contaminated
with residual chemicals. Occasionally, aqueous solutions of inorganic acids or bases (e.g. HCl or
NaOH) can be disposed of down the sink if the pH is in the range of 5 - 9. Your TF will provide
explicit instructions when this is a possibility.

Standard Disposal Options

Reusable materials
Students should always ask their TFs if there is any question about whether or not certain
materials or tools are disposable. Nothing from the glassware room is disposable, but the white
shelves contain both disposable and non-disposable items. Read further to see where items can
be properly disposed.

Disposable:
 Glass scintillation vials  Gloves
 Weight boats  Used boiling chips
 Filter paper  Drierite (if no longer dry)
 Weighing/wax paper  Label tape

Regular trash
Paper towels, paper, etc. that are not contaminated with organic chemicals can be disposed
of in the regular trash barrels at the end of each row of benches. Please do not put any glass or
needles in the regular trash!

Acceptable for regular trash:

 Uncontaminated paper towels  Tissues
 Uncontaminated paper  Outside material
 Uncontaminated disposable gloves

59
Glass disposal boxes
It is important for the safety of our students, course staff, and members of the Science
Center community to dispose of glass properly. All glass, broken or unbroken, should be
disposed of in the blue and white cardboard glass disposal boxes at the end of each row of
benches. These boxes help prevent the Science Center staff from being cut when disposing of the
regular trash. Only glass that is largely clean can be disposed of in these boxes; ask your TF if
there are any questions. Pipettes, vials, test tubes, bottles, and broken glassware are the most
common items disposed. Glass disposal boxes are not trash cans and should not be treated as
such!

Acceptable for glass waste:

 Cleaned pipettes  Broken glassware
 Cleaned scintillation vials  Used Mel-Temp capillary tubes
 Cleaned test tubes  Used TLC plates
 Cleaned empty reagent containers  Used TLC spotters

Chemical Waste Disposal

There are several waste hoods throughout the lab that contain five-gallon buckets for
chemical waste. The different types of chemical waste generated in the laboratory are segregated
to facilitate proper disposal, thus you should dispose of any chemical waste you generate in the
appropriately labeled bucket. Please notify your TF if these containers are full or almost full.
These waste containers are located on both sides of the center bench.

Solid waste
All chemically contaminated solid materials (including chemicals themselves) should be
disposed of in the solid waste container. Please ensure that you are not disposing of materials
that belong in standard disposal options or silica waste.

Acceptable:
 Paper towels, weigh boats, filter paper, etc. contaminated with chemicals
 Used drying agents such as magnesium sulfate and sodium sulfate
 Used Drierite
 Chemicals that are in a solid physical state
 Contaminated disposable gloves

Aqueous waste
Aqueous waste includes all solutions containing water and alcohol that may be contaminated
with any chemicals. Please do not dispose of any contaminated aqueous solution down the sink,
even when used in cleaning.

Acceptable:
 Aqueous solutions contaminated with organic material
 Alcohol-based solutions (e.g., methanol and ethanol)
 Aqueous rinse solutions: when washing glassware, collect any distilled water rinses
contaminated with chemicals in the aqueous rinse beaker and dispose of them in this
container.

60
Recyclable acetone waste
In general, dispose of used acetone in the recyclable acetone waste. Please do not dispose of
any contaminated acetone down the sink, even when used in cleaning. If you are performing a
lab that may contaminate the acetone, your TF will instruct you of how to dispose of it.

Acceptable:
 Acetone rinse solutions: when washing glassware, you must collect acetone rinses in the
beaker provided in each hood for this and dispose of them in this waste container.

Non-halogenated organic waste

Organic solvents that are not contaminated with halocarbons (which are halogenated and
organic!) should be disposed of in non-halogenated organic waste.

Acceptable:
 Non-halogenated organic solvents such as ether, ethyl acetate, hexane, toluene, etc.
 Solutions of non-halogenated organic compounds dissolved in non-halogenated organic
solvents
 Solutions of halogen compounds lacking any halogen-carbon bonds (ions, etc.)

Halogenated waste (provided as necessary)

Although the name of this waste refers to halogens in general, halogenated waste is intended
for the disposal of halocarbon compounds. Halocarbons or halogenated organic compounds are
often extremely hazardous materials to both organisms and the environment and must be
disposed of with care into the correct disposal option. Non-organic compounds containing
halogens (halogen ions, metal halides, etc.) can be disposed of in other appropriate containers.

Acceptable:
 Chlorinated solvents such as methylene chloride and chloroform
 Halogenated organic compounds (fluorides, chlorides, bromides, iodides)
 Any mixture of solvents or organic compounds that contain a halogenated organic component

Strongly acidic waste and strongly basic waste

There is a separate waste bucket for strongly acidic aqueous waste (pH < 5) and a separate
waste bucket for strongly basic aqueous waste (pH > 9). Never mix acidic and basic waste
together because dangerous exothermic reactions can occur! These will be located on the
opposite side of the center bench.

Acceptable:
 Strong acids/acidic solutions
 Strong bases/basic solutions

Silica gel waste

Although silica is a solid material, it is a serious inhalation hazard that should be disposed of
separately from the solid waste.

Acceptable:
 Used and dried-out silica from column chromatography
 Sand used in column chromatography

61
62
Experiments

63
64
 Lab 3: The Grignard Reaction
Reading

Zubrick: Chapters 23 (Reflux and Addition) and 34 (Infrared Spectroscopy).

Lab manual: Appendices 7 (IR Instructions) and 8 (Table of Characteristic IR Absorptions).
Review IR interpretation in the organic textbook you use in lecture.

Summary

In this experiment, you will prepare a Grignard reagent (phenylmagnesium bromide) from
bromobenzene and magnesium metal. You will then add the Grignard reagent to methyl benzoate
to afford triphenylmethanol.

Introduction

In 1912, the Nobel prize in chemistry was awarded to Victor Grignard for his study of
organomagnesium compounds which behave as if there is a negative charge on the carbon and a
positive charge on the magnesium. These “carbanion salts” are excellent nucleophiles and are
used extensively to form a wide variety of compounds such as alcohols, carbonyl compounds,
and other organometallic reagents.

In this experiment, you will prepare phenylmagnesium bromide from bromobenzene and
magnesium. This Grignard reagent adds to methyl benzoate, converting the ester to the
magnesium salt of triphenylmethanol. Hydrolysis yields the tertiary alcohol.

Mg0 1. Ph OMe
Br MgBr OH
anhyd. ether 2. H3O+
2 equiv 2 equiv

Grignards can be tricky to handle, and yields are often less than 100% due to various side
reactions that Grignards undergo, such as dimerization (Wurtz coupling), protonation
(quenching), and disproportionation. For example, a propyl Grignard's reactions:

MgBr + Br coupling

MgBr + Br + disproportionation

MgBr + H2O protonation

In addition, sometimes a small amount of black sludge can be seen at the bottom of the
reaction vessel during Grignard reactions, perhaps due to polymerization.

85
Part I. Preparation of the Grignard Reagent

Reagent Table

bromobenzene magnesium ether methyl benzoate triphenylmethanol

MW (g/mol) 157.01 24.305 74.12 136.15 260.34
mp (°C) -31 - -116 -12 164.2
bp (°C) 156 - 34.5 198-9 380
density (g/mL) 1.495 - 0.714 1.094 -
g 7.85 1.22 - 2.7 -
mL 5.25 - - 2.5 -
mol 0.05 0.05 - 0.02 -
equiv 2.5 2.5 - 1 -

Safety Precautions

 All chemical work should be carried out in the hood.

 Wear the required personal protective equipment at all times – appropriate shoes, adequate leg
coverage, lab coat, gloves, and goggles!
 This lab involves the heating of solvents and requires caution when handling hot solvents and
hot glassware. Also be careful of hot steam from the steam bath.
 Ether is flammable! Use a steam bath or hot water bath.

Odds and Ends

 Many Grignard reactions require rigorously anhydrous conditions: flame- or oven-dried

glassware, inert atmosphere, etc. This reaction tends to work well without employing
rigorously anhydrous conditions.
 Water quenches Grignard reagents! It is imperative that all glassware be dry for the Grignard
reaction. If the glassware is wet, rinse it with a little acetone and allow it to dry for a few
minutes.
 Recap the ether containers so that they stay anhydrous.
 Good magnesium is shiny; oxidized (deactivated) magnesium is white.
 Use anhydrous ether, not the ether from the hoods. Do not use the ether from the taps in the
solvent hoods (i.e., technical grade ether) for the reaction; you must use anhydrous ether.
 Aim your sep funnel at the back of the hood, away from yourself and your neighbor.

86
Procedure

The glassware setup for addition and reflux that you will
use is shown on the right: a 100 mL three-necked round-
bottom flask fitted with a reflux condenser, addition funnel,
a drying tube filled with Drierite, and a rubber septum as a
stopper. Make sure your setup is well-clamped. After your
glassware is set up, add 0.05 mol of magnesium turnings
then 10 mL of anhydrous diethyl ether. Prepare an ice bath
in case cooling of the reaction becomes necessary.
Pour a solution of 0.05 mol bromobenzene in 15 mL
anhydrous ether into the addition funnel. Be prepared to
record all the following observations! Slowly add about one
quarter of this solution to the reaction vessel. Stir the
mixture, and look for evidence that the reaction has begun.
Cloudiness, a slight darkening, warming, or small bubbles
forming on the magnesium are indications that the reaction
has started. If the glassware and reagents are dry, the
reaction should begin within minutes. You should use a stir
plate and stir bar to mix the solution for this step, but
you must use a steam bath to heat the reaction mixture later.
This is a safety precaution—ether has a low flash point and
would catch on fire if an unwary student accidentally turned
a variac up too high. Steam has a safe upper temperature
limit.

If the reaction does not start within 5-10 minutes, consult with your TF to see which of the
following procedures should be followed.

1) Gently crush some of the magnesium turnings to expose unoxidized metal surfaces. Gently
grind the turnings with a dry glass rod against the bottom of the flask under the surface of the
liquid, giving a twisting motion to the glass rod. If done properly, the liquid should become
slightly cloudy, and bubbles should form where the new magnesium surface has been
exposed. If done improperly, you may push the glass rod through the bottom of the flask and
have a hazard on your hands.
2) Start a small-scale Grignard reaction in a test tube, and add this to your reaction flask.
3) Heat gently (with hands or heating mantle on low).
4) Add a small crystal of iodine or a small amount of 1,2-dibromoethane to initiate the reaction.

Once the reaction has started, the ether will begin to reflux, and the flask will become slightly
warm. The rest of the bromobenzene-ether solution should now be added dropwise (over 15-30
minutes) with stirring at a rate just barely fast enough to maintain a gentle reflux. As the reaction
proceeds, note that a light precipitate begins to form, a coating appears on the magnesium, and
the solution turns dark. If the bromobenzene is added too quickly, the reaction may reflux too
vigorously, and cooling with an ice/water bath may be necessary. If the reaction proceeds too
quickly, the yield may be reduced due to increased Wurtz coupling. After the addition is
complete, stir the mixture until the refluxing stops.

87
Part II. Synthesis of Triphenylmethanol

Safety Precautions

 All chemical work should be carried out in the hood.

 Wear the required personal protective equipment at all times – appropriate shoes, adequate leg
coverage, lab coat, gloves, and goggles!
 This lab involves the heating of solvents and requires caution when handling hot solvents and
hot glassware. Also be careful of hot steam from the steam bath.
 This lab involves the use of concentrated sulfuric acid, a strong acid. Use extra caution when
handling strong acids such as sulfuric acid.
 Remember to turn off the Mel-Temp when it is not in use!

Procedure

Allow the phenylmagnesium bromide solution to cool to room temperature. Then add a
solution of 0.02 mol of methyl benzoate in 25 mL anhydrous ether dropwise (through the
addition funnel) at such a rate that the reaction mixture refluxes gently. When the addition is
complete, reflux the reaction mixture on a steam bath for 30 minutes. Allow the solution to cool
to room temperature, and carefully transfer the solution into a 150 mL beaker equipped with a
stir bar. If there are a lot of solid chunks on the bottom of the flask, break them up with a spatula,
and rinse them with ether.
Chill 17 mL of deionized water and 17 mL of 3M sulfuric acid separately in an ice bath.
Carefully add the cold water to the stirring solution drop-by-drop, and then slowly add the 3M
sulfuric acid. This is the “H+ workup” step. Watch for a color change or cloudiness/precipitate to
appear or disappear; these traits are characteristic of quenching Grignard reactions. Make sure to
record any observations! If too much precipitate forms and stirring is impossible, stir with a glass
rod, rinse the flask with a bit of water, and continue the workup. A fair amount of solid may
form, and it may be necessary to add some more water or ether.
Once the acid has been added, let the solution stir for about 5 minutes, and test the pH of the
aqueous layer. You’ll need to pipet some out—don’t try and shove the pH paper through the
ether into the aqueous layer. Slowly add more acid, if necessary, until the reaction has been
completely quenched (acidified). Pour the acidified reaction mixture into a 250-mL separatory
funnel, rinsing the flask with a small amount of ether. You may need to add some more ether
(~20 mL) to ensure that all of your product remains dissolved in the organic layer. Remove the
aqueous layer.
Wash the organic layer first with water (3 x 25 mL), then with 5% aqueous sodium
bicarbonate (1 x 25 mL) to neutralize residual acid. Follow this with an aqueous saturated
sodium chloride wash (1 x 25 mL) to “dry” the ether layer. A saturated NaCl wash is typically
used to “dry” an organic layer or break up an emulsion because the charged sodium and chloride
ions render the organic and aqueous layers even less miscible. This series of washes removes
residual acid, bicarbonate, and water from the organic layer. It is very important that you vent
your sep funnel frequently while working up the reaction (acidifying, extracting, washing, etc.).
In years past, we have had a few sep funnels blow their tops and spew their contents all over.

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 After removing the aqueous layer, dry the organic layer further with anhydrous sodium
sulfate. Unlike magnesium sulfate, you will know when it is dry when the large grains no longer
form clumps. Filter the solution into a pre-weighed round-bottom flask, and remove the ether on
the rotovap. Collect the solid, and recrystallize the crude triphenylmethanol from methanol.
Record the yield, melting point, mass, and product appearance, and include an IR spectrum. (Be
sure to read Appendix 7: IR Instructions.) Don’t forget to show your product to your TF before
discarding it!

Cleanup

 Aqueous layers go into aqueous waste.

 Any unused magnesium can go into solid waste.
 Put organics into the appropriate waste buckets: bromobenzene is halogenated, so it goes in
the halogenated waste. Triphenylmethanol goes in solid waste.
 Dispose of leftover solids, contaminated gloves, and filter paper in the solid waste buckets.
 Dispose of paper towels and clean gloves in the trash.
 All acetone rinses must go into recyclable acetone waste.
 Aqueous (water) and ethanolic solutions of organic chemicals go in the aqueous waste bucket.
 Wipe off your benchtop with paper towels. Water and acetone can be used if needed.
 Wash your hands well before you leave.

Pre-Lab Write-Up

 Write a balanced equation and an arrow-pushing mechanism. For those of you who aren’t
familiar with a mechanism for the formation of the Grignard reagent, a simplified version is
given below.

Br Mg MgBr MgBr

 Calculate theoretical yield, showing your calculations.

 Summarize the procedure for setting up a refluxed reaction. Include a picture of the setup.

Lab Write-Up

Include the following in your Results and Conclusions:

 Record all observations, masses, percent yield, and melting point. Include percent yield for
both initial crude product and the recrystallized product. Attach your IR spectrum; each
person needs to attach their own IR.
 Discuss how the IR spectrum of your product proves that the reaction was successful. A
standard IR spectrum for the methyl benzoate starting material has been provided after this
lab for comparison.
 Interpretation and explanation of results obtained in your experiment. Include an analysis of
the likely sources of error that may have led to unexpected results in your mp, bp, percent
recovery, etc. Do not include generic (“human error”, “loss in transfer”) or speculative
sources of error (“IR probably dirty”).

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