Department of Chemistry

Organic Chemistry Laboratory

(Chem 2018)

First Semester Lab. Manual

2022

Thursday Session: 2:30 – 5:30

Supervisor: Dr. C. S. Lee

Technicians/Demonstrators: Ms. April Lau

Postgraduate Student: Mr. JIANG Yanxin
Mr. YEUNG Yik Hoi
 Table of Contents

General Information 3
Safety Precautions in Laboratory 4
Instructions on report writing 9
Glassware for Organic Chemistry Laboratory ------------------------------ 12
Locker Apparatus List 14
Chemical Waste Disposal For Organic Chemistry Laboratory------------15
Laboratory Schedule 16
Experiment 1 Liquid-liquid Extraction ------------------------------------ 17
Experiment 2 A Facile Solvent-Free Cannizzaro Reaction ------------- 21
Experiment 3 Resolution of (+/-) –1-phenylethyl amine ---------------- 22
Experiment 4 Synthesis of Aspirin (Microscale) -------------------------25
Experiment 5 Solvolysis of Alkyl Halide ---------------------------------- 29
Experiment 6 Williamson Synthesis ---------------------------------------- 30
Experiment 7 Diels Alder Reaction ---------------------------------------- 33
Experiment 8 A Green, Guided-Inquiry Based Electrophilic Aromatic
Substitution 35

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General Information
Performing experiments with chemicals in the laboratory is one of the most important and
exciting aspects of organic chemistry. This one-year organic laboratory course is scheduled in two
parts. The first part is to be taken in the first semester of the first year while the second half of the
laboratory course is taken after students have completed the first-year organic chemistry lecture. The
purpose of this laboratory course, in the first part, is to teach the basic skills required to manipulate
and purify of organic compounds and to introduce simple organic syntheses. Afterwards, experiments
are arranged in such a way to enable students to gain experience in natural product isolation and
structure determination as well as multi-step synthesis.

Throughout the entire year, fundamental skills of experimental organic chemistry should be
acquired. In addition, the need for planning ahead and being well organized in the laboratory will be
obvious.

In order to maximize the learning experience, students are required to read through the manual
and related chemical principles beforehand. Pre-laboratory writing of acceptable standard is also
needed. For a brief period, the excitement and the frustration of practical organic chemistry willbe
encountered.

Late

Students should reach the laboratory before the lesson starts. Performance marks will be
deducted if a student is late for more than 10 minutes. No mark will be given to that laboratory report
if a student is late for more than half an hour.

Make ups

No make-up labs will be given. Arrangement can be made to do a lab in another section doing
the same experiment. However, you must have a signed approved form. Approval must be obtained
in advance.

Prelab Quiz

The prelab quiz will be arranged later. The quiz will cover materials from the laboratory
experiments and reading assignments.

Grade Distribution

Grades will be assigned on the basis of the quality of your prelab exercises, lab reports, a final
exam, and on a subjective evaluation of your performance (including improvement). Points for the
course are divided as follows (this may be subject to slight revision as the semester proceeds):

Reports 55%
Performance 15%
Prelab quiz 30%

3
Safety Precautions in Laboratory
1. Personal Protection

1) All students must wear safety goggles, laboratory apparel, and leather shoes in the laboratory.
Short trousers and non-leather shoes are prohibited.
2) It is advised that students should have their own gloves available. Gloves are preferably worn in
transferring corrosive or toxic chemicals.
3) Each student should have his/her own cloth for cleaning and holding hot objects.
4) Never work alone in the laboratory.
5) Never undertake any unauthorized experiments.

2. Chemical Toxicity

1) Never taste any chemicals.

2) Keep any volatile chemicals 15 cm from your head.
3) In determining the odor of a compound, bring the stopper of the bottle cautiously toward the nose;
do not inhale. Alternatively, you may hold the substance away from you and waft the vapors
toward you with your hand.
4) Use a fume hook insofar as possible when pouring and handling volatile substances and for
carrying out reactions in which noxious gases are released. If this is not feasible, affix appropriate
gas-traps to your apparatus.
5) Avoid contact of any chemicals with the skin.
6) Never eat or drink in the laboratory.
7) Always wash your hands with soap before leaving the laboratory.

3. Fire Hazard

1) Flame use is not recommended in laboratory except in special cases. Flammable chemicals should
be heated with a hot plate but avoid spilling any of those chemicals in the laboratory. Theheated
flammable chemicals should then be contained in an Erlenmeyer flask or test tubes in a beaker of
water.
2) Before lighting a flame, check to see that volatile liquids are not being poured or evaporated in a
distance of 3 meter from you.
3) Conversely, before pouring or evaporating a volatile liquid, be certain that none of your neighbor
is using a flame.
4) When refluxing or doing distillation, be certain that the set-up is tightly fitted.
5) Always turn a burner off as soon as you are finished using it.
6) As a general practice, and particularly if a burner is in use, avoid loose-fitting long sleeves and
cuffs; long hair should be tied back during laboratory work.
7) Smoking is not permitted in the laboratory.
8) Familiarize yourself with the properties of a solvent before using it, particularly its toxicity and
flammability. Alternatively, you may check the properties from the label of the original bottle.

4. Cleaning of Spilled Chemicals on Bench

1) Spilled chemicals must be cleaned at once. Water should be mopped up as soon as possible,
particularly that on the floor.
2) It is safe for you to wear gloves in cleaning hazardous chemicals and wash the cleaning cloth
thoroughly with water afterwards or just dispose it.
3) For acid or alkaline, wash with a liberal quantity of water.
4) For organic chemicals, wash with acetone or detergent and then a large amount of water.
4
5) Do not wipe any solid on the bench to the floor. Receive the solids on a paper, wrap it and put in
a litter bin.

5. Laboratory Accidents and First Aid

1) In case of any hazardous situation, report to the instructor or to the Department Office
immediately, whichever is more convenient.
2) In the event of an injury to someone in the laboratory:
a) Notify the instructor immediately,
b) Abrasion, burn, or minor cut should be treated in preparation room or,
c) If more serious in nature, the student should be escorted to the First-Aid Station or the
University Nurse should be called, and
d) If the injuries are obviously very serious (requiring the attention of a physician), then Dial
999 for an ambulance and the University Nurse, and
e) Do not leave a seriously injured person alone unless absolutely necessary, and for severe
burns, cuts and shock (elevate feet, loosen clothing, keep warm).

6. Burns

Thermal Burns

-Small burns
1) Soak a sterile gauze pad or clean cloth in a lacing soda solution (24-30 g of sodium bicarbonate in
1 liter of water, lukewarm if possible).
2) Place the pad over the burn, and bandage loosely. (Do not disturb or open blisters.)
3) If the skin is not broken, immerse burned part in clean cold water or apply clean ice to relieve
pain.

-Extensive burns
1) Have the victim lie down, place the cleanest available cloth material over all burned body areas to
exclude air, call an ambulance and the university nurse.
2) If the victim is conscious and can swallow, give him water, tea, coffee or other non- alcoholic
beverages.

-Chemical Burns
1) Acids on the skin
a) Wash immediately and thoroughly with liberal quantity of water,
b) Then with 0.5% sodium bicarbonate solution, and finally
c) With water for 10 to 15 minutes.

2) Alkalis on the skin

a) Wash immediately with a large volume of water, then
b) With 2 % acetic acid, and finally
c) With water for 10 to 15 minutes.

3) Bromine on the skin

a) Wash with soap and warm water, and the
b) Thoroughly soaked with 0.6 M sodium thiosulfate, or cover with a wet sodium thiosulfate
dressing for at least 3 hours
c) Call the university nurse and see a doctor.

4) Sodium on the skin

5
a) If a small solidified fragment of sodium can still be seen, remove if carefully with forceps
b) Wash with water thoroughly, then
c) With 2% acetic acid, and finally
d) With water for 10 to 15 minutes.

5) Phosphorus on the skin

a) Wash well with cold water and
b) Treat with 1% silver nitrate solution.

6) Methyl sulfate on the skin

a) Wash immediately and liberally with concentrated ammonia solution, and then
b) Rub gently with wads of cotton wool soaked in concentrated ammonia solution.

7) Organic substances on the skin

a) Wash freely with ordinary ethanol, followed by
b) Washing with soap and warm water.
c) If the skin is burned (as by phenol), soak the injured part in water for at least 3 hours.
d) Remove all clothing that is contaminated (best in a shower or stream of water).

8) Extensive Chemical Burns

a) Have the victim lie down and call for an ambulance and the college nurse at once.
b) If the victim is conscious and can swallow, give him plenty of non-alcoholic beverages to drink.
(Do not apply ointment, grease, sodium carbonate, or other substances to extensive burns. All burns,
except those where the skin is reddened in small area only, should be seen by a physician)

7. Shock

Every burn, either thermal or chemical, can be complicated by shock. The signs of shock are a
pale face, shallow breathing, cold or clammy skin with beads of perspiration on the forehead and
palms of hands, and chills or complaint of chilled feeling. Frequently shock is accompanied by nausea
of vomiting. In shock resulting from burns the liquid part of the blood flows into the burned areas;
there may not be enough blood volume left to keep the brain, heart, and other organs functioning
normally.

1) To treat shock, keep the victim lying down (preferably with feet elevated), keep his air-way open,
keep him warm if the weather is cold, and
2) Give water or other non-alcoholic beverage if he can swallow. (Never give alcoholic beverages.)
3) Call the university nurse.

8. Cut

-Minor cuts
1) Allow the cut to bleed for a few seconds, see that no glass remains.
2) Rinse with soap and water.
3) Cover with a bandage or a sterile dressing and keep dry.

-Serious cuts
1) Attempt to stop the bleeding with compresses and pressure. (Tourniquet should be applied only
by those who have received first-aid training.) Continuous pressure should not maintain for more
than 5 minutes.
2) Keep the victim seated.
3) Call for an ambulance and the university nurse.
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9. Eye Accidents

1) Abundant but not high-pressure stream of water is directed from a tap fitted with a rubber tube
onto the area about the eyeball.
2) Continue washing for 15 minutes, then
3) Take the victim to the university nurse and a doctor.

10. Glass in Eye

1) Wash with water in an eye bath.

2) Call for a doctor and the university nurse immediately.

11. Fires

-Burning Clothing
Do not run. Roll on the floor to smother the fire and to help keeping the flames away from your head.
Your neighbors can help to extinguish the flames by using:
1) Fire blankets, laboratory coats, or other items that are immediately available, or
2) A laboratory shower, if close by, or
3) A carbon dioxide extinguisher if used with care only until the flames are extinguished and if the
flames are not near the head. (A carbon tetrachloride extinguisher should not employ.)

-Burning reagents and/or fire from electrical socket

1) Remove yourself from any danger.
2) If it is possible to do so without submitting yourself to danger; turn out all gas burners and the
main gas tap and
3) Switch off all electric hot plates in the vicinity;
4) Remove objects, which might ignite.
5) If the electrical socket is burned, turn off all electrical switches.

-Small fire
Extinguished by covering the opening of the vessel with wet cloth, watch glass, asbestos wire gauze,
or a nonflammable container.

-Medium fire
Extinguished by:
1) Sand, or
2) Fire extinguisher directing its nozzle toward the base of the flame.
Burning oil may be extinguished with sand and/or powdered sodium bicarbonate (never water).
Smother sodium fires with dry sand.
Fire from electrical socket should never be extinguished with water.

-Large fire
If the fire shows any sign of getting out of hand, sound the fire alarm. Ventilate the room after using a
fire extinguisher.

12. Poisons

Solids or liquids
-In the mouth but not swallowed
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1) Spit out at once and
2) Wash repeatedly with water.

-If swallowed
1) Call a doctor and the university nurse immediately.
2) In the meantime, give an antidote according to the nature of the poison:

-Acids (including oxalic acid)

1) Dilute by drinking much water, followed by lime water or milk of magnesia.
2) Milk then be given but no emetics.

-Caustic alkalis
1) Dilute by drinking much water,
2) Followed by vinegar, lemon or orange juice, solutions of lactic acid or citric acid.
3) Milk may then be given but no emetics.

-Salt of heavy metals

1) Give milk or white of an egg.

-Arsenic of mercury compounds

1) Give an emetic immediately, e.g. one teaspoonful of mustard, or one tablespoonful of salt or zinc
sulfate, in a tumbler of warm water.

-Gas
1) Remove the victim to the open air, and
2) Loosen clothing at neck.

-To counteract chlorine or bromine fumes if inhaled in only small amounts,

1) Inhale ammonia vapor or gargle with sodium bicarbonate solution.
2) Afterwards the patient should suck eucalyptus pastille, or drink warm dilute peppermint or
cinnamon essence, to soothe the throat and lungs.
If breathing has stopped, apply artificial respiration.

8
Instructions on report writing

All reports must be handed in the next laboratory session. Additional time may be permitted if
melting points and/or masses are required to finish your report. However, it is expected that all
questions, with the exception of those requiring addition data, will be answered before you arrive.
Marks will be deduced for late reports, 0.5 mark per day for short report, 1mark per day for long
report.

Grading of your lab reports will be based on your write-ups (completeness, clarity, brevity,
sentence structure, style, and format), observations, conclusions, calculations, and yield and purity of
products.
Hints: (How to avoid point loss on your reports)
Correct number of significant figures including accuracy of measurements
Conclusion to each experiment recorded in lab notebook
Clear sample calculations

Use formal language when writing your reports, especially in the Discussion/Conclusion
section. Sentences such as “I spilled some of the stuff” should not appear in the discussion. Usage of
first person singular (“I” or “My”) should be avoided. For example, “2.0 grams of sodium chloride
was added to the reaction flask.” Good report writing skill is a major requirement in almost every
professional field you may get into the future. This is a good time to develop this skill.

Pre-lab Sheet
Pre-lab sheet should be done before each laboratory session. It should contain the following
items: Name, Student No., Session No., Locker No., Date, Title, Equation and Procedure in point
form.

Short Report Format

Short report forms are provided and students need to complete the form ONLY. No additional
page is required.

Long report format

Reports should be presented on foolscap papers suitably fastened together.

Every report should bear the number and title of the experiment and the date on which it is
performed

Long report data sheets are provided and students are required to write a long report according
to the ‘Long report format’ in computer format. At the end of semester, students are needed to
hand in softcopies of long report in CD or upload to BUmoodle.

(Section : Name: Student No: Locker No: )

1. Date and title: The date and title should be at the top of a new page

2. Objectives: Prepare a brief statement regarding the work to be done.

3. Balanced Chemical Equations: Should show the formulas, the names and the amount of the
reactants and products. (gram/ml, mole, mole ratio)

4. Physical constant in table form (check handbook):

9
Chemical name
Structural formula
Mol. Wt.
Color
Phase
Melting point
Boiling point
Density
(You can usually find physical constants of chemicals in the CRC Handbook of Chemistry and
Physics, the Aldrich Catalog, or the Merck Index. Be sure to include all the chemicals used in the
experiment if possible.)

5. Theory: methodology/mechanism/possible side reactions/product isolation and purification

scheme.

6. Procedure and observation: should be written with your own word in PAST tense and PASSIVE
voice. Use common sense to include meaningful observations (color of phase changed, gas
evolved, precipitate or crystalline solid appeared, heat released etc.). Record as much
observation as possible. It may be useful when you need to find out what went wrong in an
experiment.

Example of procedure:
a) n-Butyl alcohol (15 ml), glacial acetic acid (17 ml) and conc. sulfuric acid (2 ml) were refluxed in
a 100 ml R.B. flask for 75 minutes.
b) After the reaction mixture was cooled slightly below boiling, the condenser was removed and set
downward for simple distillation.

Example of observation:
a) The ethanol solution was yellow.
b) Approximate 5 ml of the reaction mixture was spilled and lost while being transferred to a
separation funnel.

7. Calculation:

8. Results: Including the main product weight, % yield, m.p./b.p., color, crystalline form (solvent)

9. Discussion/Conclusion: This section should be written like an essay that can stand on its own. It
needs to have meaningful introductory statements, a brief summary of the experiment, and a
discussion of the results. You may need to address some of these questions if appropriate: Do the
results make sense? Do they agree with the theories behind the experiments? What is learned
from the experiments? You should also discuss the factors that may have caused errors in the
results. For experiments involving a synthesis of a compound, you should discuss the purity of the
product and how you confirm its identity.

10. References: This section consists of a numbered listing of literature references that were used to
perform the experiment and that were used to write the lab report. The reference numbers must
correspond to the reference citations used in the text of the report.

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Marks Distribution

Short report – full mark is 5

Objective 0.5
Balanced Equation 0.5
Observations 1
Table of reactants 0.5
Calculation 1
Result 0.5
Question 1

Long report – full mark is 10

Objective 0.5
Balanced Equation 0.5
Table of reactants 0.5
Theory 1
Procedure & observation 1
Calculation 0.5
Result 1
Discussion 3
Question 1
Reference 0.5
Conclusions 0.5

Points will be deducted if the report is difficult to follow, read, or understand. Neatness,
organization, completeness, grammar, and clarity of writing are important elements of a lab report.

Short reports include: exp. 1,2,4,5,6,7,8

Long reports include: exp.3

11
 Glassware Commonly Used in the
Organic Chemistry Laboratory
Distillation and Reaction glassware

Round bottom flask Stillhead Vacuum adapter

Water Condenser Thermometer adapter Claisen adapter

Reduction adapters Air condenser TLC chamber

Bench Glassware

Beaker Conical flask Suction flask

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 Separatory funnel Glass rod Vials

Test tubes Thermometer Watch glass

Graduated cylinder Filtering funnels Drying tube

Bench equipment

Spatula Stir bar Forceps

O-ring Water bath Yellow and blue clips

13
 Glassware Check List for Organic Chemistry Laboratory

Check In No. Items Check Out

1 Graduated Cylinder, 100ml
1 Graduated Cylinder, 10ml
8 Beakers, any sizes
5 Conical Flasks, any sizes
1 Funnel, Stemless
1 Funnel, 75mm
1 Buchner funnel, 90mm
2 Glass Rod
1 Spatula, Iron Cast
2 Watch Glasses
1 Water Bath, Iron Cast
1 Adapter Receiver, RA 1/11
1 Adapter Reduction, DA 12
1 Adapter Screw, ST 51/13
1 Round Bottom Flask, 100ml, FR100/2S
1 Still head, SH 4/1
1 Stopper, SB 14
1 Water Condenser, C1/11
1 TLC Chamber
2 Stirrer Bars
1 Microscale Kit
1 50 ml Boiling Tube

Name: Name: _____________________

Signature: _______________ Signature: __________________

Locker No: Locker No: _________________

Check out Date:___________ Check in Date: ______________

Check in Date: Signature: _________________

14
Chemical Waste Disposal For Organic Chemistry Laboratory

Solvent Wastes:

Solvent wastes are not be poured down the drain. Organic waste bottle will be available in the
laboratory to contain the waste solvents that you generate. Aqueous solution that does not contain
heavy metals can probably be discarded in the drain. Additional information will be provided during
the laboratory period. If you are in doubt, ask the technician for assistance.

Solid Wastes:

Most of the solid wastes you will generate during the semester are non-toxic and can be
disposed of in the trash. Solids should be wrapped with papers before disposal. Some of your products
will be collected. Heavy metal precipitates and similar toxic solids will be collected in special
container that will be appropriately labeled.

Broken glass:

Special receptacles are available for broken glass (a large box). DO NOT put anything into the
broken glass box except glass.

Organic Waste Bottles are available in Fume Hood.

15
 Lab Schedule

Exp. No. Title Thursday Carey & Other

Reference
1 Check in Sept 8

2 Liquid-liquid Extraction Sept 15

3 A Facile Solvent-Free Cannizzaro Reaction Sept 22

Resolution of (+/-) –1-phenylethyl amine (part one)

4 Resolution of (+/-) –1-phenylethyl amine ( part two ) Sept 29 Carey 9th

(long report) P290-293

5 Synthesis of Aspirin (Microscale) Oct 6 Carey

P932-933
6 Solvolysis of Alkyl Halide Oct 13

7 Williamson Synthesis Oct 20 Carey

P657-659
8 Diels Alder Reaction Oct 27 Carey
391-396
9 A Green, Guided-Inquiry Based Electrophilic Nov 3 Carey
Aromatic Substitution 456-509

References:

‘Macroscale and Microscale Organic Experiments’, Williamson, Third Edition,

Allen M. Schoffstall, Barbara A., ‘Microscale and miniscale organic chemistry laboratory
experiments’, 2004

Lutz F. Tietze , ‘Reactions and syntheses in the organic chemistry laboratory’, 2007

16
 Experiment 1
Solvent Extraction: An Example of the Separation of an Acid, a Base,
and a Neutral Substance
Expected learning outcomes:
1. Able to acquire the technique of liquid–liquid extractions and solid filtration.
2. Able to develop an appropriate separation protocol and identify the components of a mixture.
3. Able to determine the solubility characteristics of pure substances in a variety of solvents.
4. Able to use the developed procedure to separate each component, and assess the success of their
protocol through the characterization and possible further purification of each component.

Introduction

Liquid-liquid extraction is commonly used in the organic laboratory. It is a very powerful method for
the separation and isolation of materials encountered at the microscale and the macroscale level. In
most extractions, a capped centrifuge tube, or a 10 x 75mm test tube, or a conical vial is used as the
container. In other case, a separating funnel is employed as the mixer and the container. It is essential
that complete mixing of the two immiscible solvents is achieved.

Theory

The components of the mixture to be separated in this experiment are benzoic acid (an acid), ethyl 4-
aminobenzoate (a base) and 9-fluoreone (a neutral compound). The solubility characteristics of
organic acids in water can be shown to be highly dependent on the pH of the solution. By extending
the extraction approach to include organic bases, it has been possible to develop a general procedure
for the separation of mixtures of organic acids, bases and neutral substances.

COOH NH2 O

CO2C2H5

Benzoic Acid Ethyl 4-aminobenzoate 9-Fluorenone

m.p. 121-1230C m.p. 88-900C m.p. 82-850C

Materials

Benzoic Acid 0.5g

Ethyl 4-aminobenzoate 0.5g
9-Fluorenone 0.5g
Diethyl Ether 50mL
3M HCl 30mL
3M NaOH 30mL
6M NaOH 20mL
6M HCl 20mL

17
Procedure

1. Weigh out 0.5g of Benzoic acid, 0.5g of Ethyl 4-aminobenzoate and 0.5g of 9-Fluorenone into a a
125mL Erlenmeyer flask.

2. Use a 100mL measuring cylinder to transfer 50mL of diethyl ether to the flask to dissolve all the
substances.

Separation and Isolation of the Basic Component – Ethyl 4-aminobenzoate

1. Transfer the resultant solution to a separating funnel. Place a large enough beaker under the
funnel. Add 20ml of 3M HCl slowly into the separating funnel with swirling.

2. Cap and thoroughly mix the resulting two-phase system for several minutes. Vent carefully.

3. Remove the bottom layer (aqueous) into a labeled 125mL Erlenmeyer flask.

4. Repeat step 1 to 3 with an additional 10mL 3M HCl. Collect all aqueous fractions in the
125mL Erlenmeyer flask.

5. Save the ether solution in the separating funnel and leave it on an O-ring.

6. Add 6M NaOH slowly to the cooled acidic solution in the 125mL Erlenmeyer flask till the
solution is distinctly alkaline to litmus paper.

7. Cool the flask in ice bath for 15 minutes.

8. Collect the solid precipitate by reduced pressure filtration using a Buchner funnel. Wash the
filter cake with two 3ml portions of cold water.

9. Air dry the solid by spreading out on the watch glass.

10. Weigh the material and calculate the percent recovery next period. Obtain the melting point of
dry ethyl 4-aminobenzoate and compare your result to the literature value.

 A separating funnel is used to separate immiscible liquid phases. The size of the funnel should be
chosen so that the contents do not exceed three –quarters of its capacity (approximately).

Separation and Isolation of the Acidic Component – Benzoic Acid

1. Add 20mL of 3M NaOH to the ether solution that was left inside the separating funnel.

2. Mix the two layers thoroughly. Vent carefully.

3. Transfer the bottom layer (aqueous) to a labeled 125mL Erlenmeyer flask.

4. Repeat step 1 to 3 with an additional 10mL 3M NaOH. Collect all aqueous fractions in the
125mL Erlenmeyer flask.

5. Save the ether solution in the separatory funnel. Cap the funnel and put into an O-ring.

6. Add 6M HCl dropwise to the cooled alkaline solution till the solution becomes distinctly
18
 acidic to litmus paper.

7. Cool the flask in ice bath for 15 mins.

8. Collect the solid precipitate by reduced pressure filtration using a Buchner funnel. Wash the
filter cake with two 3mL portions of cold distilled water.

9. Air dry the solid by spreading out on the watch glass.

10. Weigh the material and calculate the percent recovery next period.

Separation and Isolation of the Neutral Component – 9-Fluorenone

1. Wash the ether solution with two 10mL portions of water. Keep the aqueous layer till the end of
the period.

2. Transfer the ether layer into a conical flask. Dry the wet ether with anhydrous granular
magnesium sulfate.

3. Filtered the dried ether solution into a tared 100mL round bottomed flask.

4. Rinse the magnesium sulfate with another portion of 5mL ether. Combine the washing into the
100mL round bottomed flask.

5. Remove the solvent with the rotor-evaporator.

6. A yellow residue will be left inside the round-bottomed flask.

7. Determine the yield of 9-fluorenone next period.

 Drying is required as small amounts of water generally remain suspended and/or dissolved in the
organic phase. A dry organic solvent is one with no traces of water present.

Questions:

1. Why is it necessary to remove the stopper from a separatory funnel when liquid is being drained
from it through the stopcock?

2. Each of the solvents listed bellowed are used in experiments in this text to extract organic
compounds from aqueous solutions. Will the organic phase be the upper or lower layer when each
of these solvents is mixed with water? Explain your answer for each case.

a) Methylene chloride b) Pentane c) Toluene d) Diethyl ether

19
 Experiment 2
A Facile Solvent-Free Cannizzaro Reaction: Synthesis of
2-chlorobenzoic acid
Expected learning outcomes
1. Able to understand the basic concept and principle of Cannizzaro Reaction.
2. Able to learn green chemistry concepts.
3. Able to carry out experimental work independently.

Introduction

The Cannizzaro reaction is an example of a disproportionation reaction. The disproportionation

reaction is fascinating because a single reactant gives rise to two products. Strong bases are used to
catalyze the disproportionation reactions of some aldehydes to their corresponding alcohols and
carboxylic acids.

In recent year, green chemistry has become an important focus in the chemical industry and teaching
laboratories because of environmental, health and economic concerns. Most organic chemical
reactions in the laboratory take place in organic solvent. These solvents account for a great proportion
of the waste material generated in a laboratory.

In this experiment, the reaction can be accomplished starting only with 2-chlorobenzaldehyde and
solid potassium hydroxide without solvent. Liquid 2-chlorobenzaldehyde was converted by grinding
with KOH pellets, into equimolar quantities of solid 2-chlorobenzoic acid and solid 2-chlorobenzyl
alcohol. Isolate the two products using the solubility properties of the formed products.

Reference: Rajviroongit,S., et al., J. Chem. Ed., 86(1), 2009, p85

20
Materials

potassium hydroxide 1.5 g

2-chlorobenzaldehyde 2 mL

Precautions

1. Avoid in contact with caustic potassium hydroxide

2. 2-chlorobenzaldehyde has bad smell, cover its container.

Procedure

1. In a fume hood, 2-chlorobenzaldehyde (17.8mmol, 2mL) and potassium hydroxide (26.7mmol,

1.5g) are added to the mortar.

2. The mixture is ground with a pestle. If solid materials begin to coat the mortar or the pestle,
dislodge them with a spatula and put back into the mixture.

3. About 30 minutes of grinding are required for completion of the reaction at which point the
gummy mixture turns into a paste.

4. To the mixture add 20ml of water. Carefully pour the mixture into the Buchner funnel. Wash the
mortar twice with 10ml of water. Solvents flows rapidly through the Buchner funnel into the flask
whereas the solid remains in the funnel. Wash the solid with another 10ml of water.

5. Transfer the filtrate in the Buchner flask into a conical flask. Carefully add 3M HCl dropwise to
the solution in the conical flask kept cooled in an ice-bath until turbidity is observed.

6. Swirl the mixture thoroughly and check the pH of the solution.

7. Continue adding 3M HCl until the solution becomes acidic to the pH paper.

8. Collect the precipitate by vacuum filtration. Leave the funnel under vacuum for a few minutes to
get rid of most of the solvent. When the solid dries, disconnect the hose, turn off the water
aspirator and use a spatula to transfer the product into a watch glass.

9. Report the % yield and melting point range.

 During the acidification step, even though the filtrate is acidic to the pH paper, it is advised to add
more drops of HCl until there is no more precipitate.

Questions:

1. Why is the Cannizzaro Reaction limited to aldehyde that does not contain alpha hydrogens?

2. If the Cannizzaro reaction is carried out in D2O solution, no deuterium becomes attached to
carbon in the alcohol produced. How does this support the mechanism?

21
 Experiment 3
Resolution of (+/-)-1-phenylethylamine

Expected learning outcomes

1. Able to understand the techniques of liquid-liquid extraction, reflux, and rotary evaporation.
2. Able to resolve the enantiomers of phenylethylamine and to learn the technique of measuring
optical rotation with a polarimeter.

Introduction

Configurational isomers are those in which the different spatial arrangements of the isomeric
molecules cannot be produced by rotation about single bonds but require that bonds be broken and
remade. There are two kinds of configurational isomers (i.e. optical and geometrical isomers). For a
chiral molecule with at least one asymmetric carbon, they may exist in two forms of
nonsuperimposable mirror image molecules which known as enantiomers.

Theory

A pair of enantiomers exhibits the same physical and chemical properties, with two exceptions: the
direction in which they rotate the plane polarization of plane-polarized light and reactions in a chiral
environment. Hence, a pair of enantiomers cannot be separated from each other by any of the
common physical separation procedures used in the laboratory. However, racemic mixture (1:1
enantiomeric mixture) can be resolved, or separated by converting the enantiomers to diastereomers.
In this experiment, (  )--phenylethylamine is partially resolved by the isolation of the (S)-(-)-1-
phenylethylamine from the racemic mixture. Optically active L(+)-tartaric acid, which is found in
grapes and other fruits, will be used to carry out this partial resolution. When the racemic amine is
treated with L(+)-tartaric acid, two diastereomers will be formed.
O

CO2H + -
CO
NH2 NH3
H OH H OH
Ph C CH + Ph CH3
H 3 OH H OH H

H
-
+ -1-phenylethylamine CO2H CO2H
(+)-tartaric acid
O
+ -
CO
NH3

H OH
+ H3 C Ph
OH H
H
CO2H

Note that the product amine salts are not enantiomeric. They are diastereomers that differ in their
solubilities in methanol. The less-soluble diastereomeric salt can be crystallized and separated from
the other salt, which remains soluble in methanol. After separation, the enantiomeric amine is
isolated from this salt by treatment with base.
H2O
R+NH3-O2CR’ + OH- ⎯ ⎯⎯→ RNH2 + -O2CR’ + H2O
22
Chiral molecules are optically active; that is, they have a rotational effect on the plane of polarized
light as it passes through the substance.

The observed angle of rotation depends on many factor: (1) the nature of the compound, (2) its
concentration, (3) the length of the sample through which the light must pass (the path length), (4)
temperature, (5) solvent, and (6) the wavelength of light.

In fact, the optical rotation is one of the most characteristics of a chiral compound. Therefore it is
common practice to report the specific rotation rather than the observed rotation to unit concentration
and path length with the following equation:

23
It is found that the concentration and the solvent used have some effects to the specific rotation for
certain compounds. So when report specific rotation, the concentration and the solvent used must be
stated. For example, the expression of the specific rotation of (+)-Glucose is [a]D = +52.5 (c=3 in
water). (Note: here, C = g/100mL)

Reference: Ault, A. J. Chem. Educ. 1965, 42, 269.

Materials

L(+)-Tartaric acid 21 g
Methanol 300 mL
DL(  )--Methylbenzylamine 18 mL
[(+/-)1-Phenylethylamine]
Sodium hydroxide 10% solution 60 mL
Diethyl ether 3 x 25 mL
Anhydrous sodium sulfate 4g

Precautions

1. Methanol is toxic, avoid breathing its vapour.

2. Phenylethylamine has bad smell, always cover its container, wash its residue in fumehood.

3. Diethyl ether ( b.p. 34.5 C ) is a highly flammable liquid. Distillation of diethyl ether must be in
a no flame environment, a hot-water bath (50-70 C) is applicable in most case.

Procedure

Week 3

1. Completely dissolve 21 g tartaric acid in 300 mL methanol in a 500 mL conical flask with
swirling.

2. Add 18mL racemic amine slowly to the tartaric acid solution.

3. Once the addition is complete, cover the flask with parafilm or plastic wrap and put it on shelf
without disturbing! When the solution returned to room temp., ask technician for seeding. Store
the labeled solution in your locker. (The solution must be left to slowly crystallize until next
week.)

Week 4

4. Examine the crystalline form, record it accordingly (prism? needle? or mixture of both?
crystalline size)

5. Filter the crystals in a Buchner funnel under reduce pressure.

6. Wash the crystals with 8 mL cold methanol 2 times. Return the filtrate to the waste bottle.

7. Dissolve the salt into 50 mL of 10% sodium hydroxide. Check the pH to ensure that the solution is
still basic. If not, add more sodium hydroxide. Extract this mixture with 3 portions of 20 mL of
diethyl ether. (Remember to release the pressure built up inside of funnel.)
24
8. Dry the organic layer (Upper Layer) with anhydrous magnesium sulfate for about 10 minutes.

9. Rota-evaporate the ether layer off. Set up simple distillation for the amine.

10. Distill the amine off into a pre-weighed dry small conical flask with a sand bath.

Week 5

11. Weigh the amine. Make up 10 mL methanol solution for the optical rotation testing: Weigh
accurately 0.8 g to 1.0 g amine in a 10 mL volumetric flask, fill with methanol to the mark.
Measure optical rotation of the solution as instructed.

12. Discard the amine solution in the waste bottle.

13. Report the crystalline form, the size, the degrees of rotation, and the “specific rotation” as the
above example. calculate the approximately percentage of (+) and (-) enantiomer in your sample
according to following formula:

Optical purity = (Observed specific rotation / Specific rotation of pure substance) x 100
= x (%)
Suppose the predominant form in the optically impure mixture is the (+)- enantiomer, thus
%(-) enantiomer = (100-x) / 2 = y
%(+) enantiomer = 100-y
Report these data.

 Diethyl ether will form H-bonds with water, so there is more water in the ether layer. We have to
add more drying agent to remove water.

Question: Suppose you had prepared a racemic organic acid and it was necessary to resolve it. How
could this be done?

25
 Experiment 4
Synthesis of Aspirin (Acetylsalicyclic Acid)
Expected learning outcomes
1. Able to understand the basic concept and principle of microscale chemistry.
2. Able to carry out a microscale organic reaction.
3. Able to acquire the skills for a small scale preparation.
4. Able to carry out experimental work independently.

Introduction

Aspirin is an analgesic (painkiller), an antipyretic (fever reducer), and an anti-inflammatory agent. It

is the premier drug for reducing fever, a role for which it is uniquely suited. As an anti-inflammatory
agent, it has become the most widely effective treatment for arthritis. Patients suffering from arthritis
must take so much aspirin (several grams per day) that gastric problems may result. For this reason，
aspirin is often combined with a buffering agent.

Theory

Salicylic acid is a compound with two functional groups. Both the hydroxyl and the carboxylic acid
group can undergo esterification reaction. After reacted with acetic anhydride, acetylsalicyclic acid or
aspirin will be resulted. This process is known as acylation or acetylation.

O
OH OCCH3
+ H
(CH CO) O
3 2

COOH COOH

Salicylic Acid Acetic Anhydride Acetylsalicyclic Acid

MW 138.12, m.p. 159 0C MW 102, b.p. 140 0C MW180.2, m.p. 138-140 0C

Thin-layer chromatography (TLC)

TLC is a sensitive, fast, simple, and inexpensive analytical technique that will be used repeatedly in
carrying out organic experiments. It is a micro technique, as little as 10-9g of material can be detected,
although the usual sample size is from 1 to 100 x 10-6g.

In TLC analysis, about 10 L of a diluted unknown solution is spotted on a pencil line drawnnear one
end of the TLC plate, using the capillary tube. The plate is then developed with appropriatesolvent or
mixed solvent system. Through capillary action, the components of the sample move up together
with the solvent. Different components in the sample are carried at different rates up the plate due to
variations in their adsorption on the adsorbent coating. Because silica gel is a rather polarstationary
phase, less polar compounds tend to move towards the top of the silica gel coated aluminum plate.

26
The retention factor (Rf) of each component with respect to a particular solvent system is defined as
following:

Rf = Distance Travelled by Component

Distance Travelled by Solvent

If two components have the same Rf value with a particular developing solvent system, they are
likely to be the same compound. However, if a second comparison with another solvent system
resulted in different Rf values, the two components are then different from each other.

Thin Layer Chromatography (TLC) can be used:

1. to determine the number of components in a mixture

2. to determine the identity of two substances
3. to monitor the progress of a reaction
4. to determine the effectiveness of purification
5. to determine the appropriate solvent system for a column chromatographic separation

27
Steps for Thin Layer Chromatography

Eluting Solvent
1. An eluting solvent is already prepared on the bench.
2. Use a clean beaker to take approximately 5 mL of the eluting solvent to your working station.

Developing Chamber
1. In the Pyrex jar provide, measure 5mL of the eluting solvent into it.
2. Add a piece of small filter paper so that one end of the filter paper is dipped into the thin layer of
the solvent.

3. Capped the Pyrex jar and let the air inside became saturated with solvent vapor.
4. Do not shake or move the jar while developing a TLC plate.

Sample Preparation
1. Prepare the sample solution by dissolving the crude product in the dichloromethane (methylene
chloride).
2. The sample solution (0.1% w/v) is ready for TLC analysis.

Spotting the TLC Plate

1. Use the capillary tube provided to spot the TLC plate. Spot both your raw sample and pure
caffeine standard side by side.
2. The spots should be made as small as possible to allow good separation.
3. Let the spots dry up before putting into the TLC developing chamber.
4. Draw a line at the top of the plate with a pencil when the solvent front is 0.5cm from the top of
the plate.
5. Use tweezers, remove the plate from the developing jar and let it air dry.

TLC Plate Visualization

1. Put the TLC plate under the UV lamp affixed to a dark chamber.
2. Turn the UV lamp on. Do not look into the UV lamp with BARE EYES.
3. Dark or purple spots will be seen on the plate.
4. Circle each spot with pencil. Identify and compare each spot with the standard.
5. Calculate the Rf values for all spots. Hand in your TLC plate as part of the lab report.

Materials

Salicylic Acid 0.5g

Conc. H2SO4 1 Drop
Acetic Anhydride 1 mL

Procedure

1. Weigh 0.5 g of salicylic acid into a 10 mL round bottom flask.

2. Add 1 mL of acetic anhydride and 1 drops of concentrated sulphuric acid into the flask.
3. Put a small magnetic stirrer bar into the flask.
4. Connect a condenser to the round bottom flask and heat the solution mixture in a hot water bath for
20 minutes while maintain a steady stirring.
5. Pour the reaction mixture into a 50 mL beaker.
28
6. Add 10 mL water and swirl the solution mixture to ensure complete mixing.
7. Leave the solution mixture in an ice-bath for 10 minutes. Aspirin should crystallize from the
solution at this stage. (Ask for help if you don’t get the solid)
8. Filter off the white solid under vacuum.
9. Wash the product with cold water
10. Store the product in locker for drying.
11. Weigh the dried aspirin and calculate the percentage yield. Measure the melting point range of
your dried product next week.

melting point range =

Thin Layered Chromatography

1. Spot both your sample and the starting material (provided by the technicians) side by side on a

TLC plate.

2. Put your TLC plate in the developing chamber.

3. Remove the TLC plate when the solvent front is 0.5cm from the top of the plate.

4. Air-dry your plate and view under a short wavelength UV lamp.

EA = Ethyl Acetate
AA = Acetic Acid
Solvent system: 99:1 (EA : AA)

Questions:

1. Hydrochloric acid is about as strong a mineral acid as sulfuric acid. Why would it not be a
satisfactory catalyst in this reaction?

2. How do you account for the smell of vinegar when a used bottle of aspirin is opened?

29
30
 Experiment 5
A Flexible Solvolysis Experiment for the Undergraduate Organic Laboratory

Expected learning outcomes:

1. Able to understand the concept and principle of Solvolysis.
2. Able to design an experiment for the synthesis of ether.
3. Able to monitor the experiment and isolate the product by laboratory techniques.

Theory
Substitution reactions represent an important class of reactions in organic chemistry. One of the better
methods of preparing mixed ethers is the Williamson ether synthesis. However, there are times when
such an SN2 reaction will not take place, and an S N1 reaction is the only way to effect a substitution
reaction. In such reactions, all the key components must be in place for the transformation to take
place.

The choice of substrate is essential for the SN1 reaction. In this case, the substrate, triphenylmethyl
bromide, is optimal for this reaction as the leaving group is attached to a tertiary carbon and the
resulting carbocation will be resonance stabilized. The leaving group is a bromide ion, a very stable
ion in ionizing solvents.

Materials
triphenylmethyl bromide 0.5 g
Alcohols 20 mL Water, Methanol, Ethanol

Reference: Esteb, J.; Magers, J.; McNulty, L.; Morgan, P.; Tindell, K.; Wilson, A. J. Chem.
Educ. 2009, 86, 853.

Procedure
For water, methanol and ethanol
1. To a 100 mL round bottom flask (r.b.f) equipped with a stir-bar, add 10 mL acetone.
2. Add 0.5 g triphenylmethyl bromide (trityl bromide) into the solution. The solid should have
dissolved. Then add 20 mL of water/alcohol and stir the reaction mixture using a stir-plate
for 30
minutes.
3 After the reaction is complete, pour the reaction mixture over approximately 15 g of ice in a
100 mL beaker. Rinse the r.b.f with about 5 mL cold water and add this to the beaker.
4 Swirl the beaker until all of the ice has melted. Collect the crude triphenylmethyl ether
product by suction filtration. Rinse the beaker with approximately 5 mL cold water and add
this to the Büchner funnel.
5. Calculate a percent yield and determine a melting point range for the product.

Questions
1. Typically, SN1 reactions compete with E1 reactions, why are no E1 products observed in this
reaction.
31
 Experiment 6
Williamson Synthesis
Expected learning outcomes
1. Able to understand the basic concept and principle of Williamson synthesis.
2. Able to acquire the technique of refluxing and crystallization.
3. Able to acquire the technique of melting point determination.

One of the better methods of preparing mixed ethers (i.e., those with two different
hydrocarbon groups) is the Williamson ether synthesis. In this synthesis, a phenoxide ion acting as a
nucleophile reacts with a primary alkyl halide in an SN2 reaction. The alkyl halide should always be
primary to minimize the formation of alkene by-products.

Theory

In this experiment, a phenol (being acidic) is readily converted to a phenoxide ion. The
bromide ion of the alkyl halide is easily displaced, and it enables the reaction to proceed rapidly and
in high yield. The final product is a commercial odor enhancer used in perfumes.

-
RO
- R' X ROR' + X

Alkoxide Ion Alkyl Halide Ether Halide Ion

OH OCH2CH3
+ CH3CH2Br + KOH + H2O

2–Naphthol Ethyl Bromide 2-Ethoxynaphthalene

m.p. 122-1230C

Materials

Potassium Hydroxide 1.3g

2-Naphthol 2g
Ethyl Alcohol (absolute) 18mL
Ethyl Bromide 4mL

Precautions

1. Potassium hydroxide is strongly caustic. Avoid contacting with skin, eyes, and clothing.

2. Phenols, alkyl halides and methanol are toxic. Avoid contacting with skin and breathing vapors.
32
3. Collect all organic wastes in the waste bottle.

Procedure

1. Place 1.3g of potassium hydroxide and 8mL of absolute ethanol in a 100mL round-bottomed
flask. Add a stir bar.

2. Stir the solution until all the potassium hydroxide has dissolved.

3. Place 2.0g of 2-naphthol and 10mL of absolute ethanol in a 50mL beaker. Stir the solution until
all the phenol has dissolved.

4. Add the 2-naphthol solution to the potassium hydroxide solution in the 100mL R.B. flask.

5. Add 4mL of ethyl bromide to the same flask. Wipe off chemicals inside the neck of the round
bottom flask with tissue.

6. Attach the reaction vessel to a reflux condenser, and heat the reaction mixture on a water bath
( metal basin ) for 1 hour.

Water Out

Water In

Reflux withWater Bath Set Up

7. After refluxing for 1 hour, turn off the heat. Cool down the reaction mixture, while waiting,
perform the TLC to check the completeness of the reaction (see instruction below). Pour the
reaction mixture to about 70ml of ice chips solution in a 250ml beaker.

8. Stir until all the ice chips have completely melted.

9. Collect the solid on a Buchner funnel. Wash the product with 150ml of tap water. Air-dry the
product in locker. Report the % yield and melting range in next lab period

Thin Layered Chromatography

1. Spot both your sample and the starting material (provided by the technicians) side by side on a
TLC plate.

2. Put your TLC plate in the developing chamber.

33
3. Remove the TLC plate when the solvent front is 0.5cm from the top of the plate.

4. Air-dry your plate and view under a short wavelength UV lamp and record your observation.

PE = Petroleum Ether
EA = Ethyl Acetate
Solvent system: 1:4 Ethyl acetate : Petroleum ether

Questions:

1. Explain why phenols, including the β-naphthol used in the current experiment, would be acidic,
and easily react with base.

2. What problem will likely occur if too much pure sample is put in the melting point capillary?

34
 Experiment 7
(microscale)
Diels - Alder Reaction :
Preparation of 9, 10 - Dihydroanthracene - 9, 10 - endosuccinic
Anhydride
Expected learning outcomes:
1. Able to understand the basic concept and principle of microscale chemistry
2. Able to acquire the skill for a small scale preparation
3. Able to carry out experiment work independently

Theory

The Diels - Alder reaction is the reaction of a diene with a dienophile to form a cyclic system.

In this experiment, maleic anhydride serves as the dienophile and the double bonds in the
central ring of anthracene function as the diene to prepare 9, 10 - Dihydroanthracene - 9, 10 -
endosuccinic anhydride. The reaction is shown. (Scheme 1)

O O
O

O O O
+

anthracene maleic anhydride

9, 10 - dihydroanthracene -
9, 10 - endosuccinic anhydri

Scheme 1

Conventional Synthesis

Materials

Anthracene 450 mg
Maleic anhydride 250 mg
Dry xylene 3.5 ml

Procedure

Weigh 450 mg anthracene and place in a 10 ml round bottom flask. Add 250 mg maleic
anhydride to the flask. Measure 3.5 ml dry xylene using 10 ml measuring cylinder and add to the
flask. Add a stirrer bar. An air-cooling condenser is attached to the round bottom flask. Place the send
up in a sand bath. Reflux the mixture inside the fumehood for 30 minutes. The setup is shown in the
next page.

35
 Cool the solution to room temperature and then cool in ice bath. Filter the crystals by suction
on a Hirsch funnel. Wash the product with 1.5ml of xylene and two 2.5-ml cold methanol. Air-dry the
product in locker. Weigh the product and determine the melting range.

Questions:

1. Why is xylene a good solvent?

2. The product of this reaction can be hydrolyzed by water. Show the product of the hydrolysis
reaction. Write the relevant equation.

36
 Experiment 8
A Green, Guided-Inquiry Based Electrophilic Aromatic Substitution

Expected learning outcomes:

1. Able to understand the concept and principle of green chemistry
2. Able to learn about the principle of electrophilic iodination
3. Able to interpret experimental results, perform calculations on these results and draw
appropriate and accurate conclusions

Theory

There are several methods available to perform electrophilic iodination on aromatic rings. Most
methods involve using iodine and an oxidizing agent, such as nitric or periodic acids, and are not very
environmental friendly. One method, which is potentially more environmental friendly, uses NaI and
bleach in an alcoholic solvent (K. M. Doxsee and J. E. Hutchinson, Green Organic Chemistry,
Brooks-Cole, 2004, 182-188). The bleach oxidizes the iodide to iodine (or iodonium ion), which then
reacts with the aromatic ring to iodinate it.

In this experiment, we will study the directing effects of a pair of substituent on a single aromatic
ring. Salicylamide is a component of some analgesics. The hydroxyl group on the ring is a strongly
activating, electron donating substituent, which the amide group is electron withdrawing.

O NH2 O NH2
NaI
OH OH
NaOCl

I
The electrophile that we will use is formed in the reaction of sodium hypochlorite (NaOCl, bleach)
with iodide ion. The I+ ion formed in this reaction is a strong electrophile that reacts quickly in an
electrophilic aromatic substitution reaction.

+
NaOCl + NaI I

37
Materials

Salicylamide 1g
Absolute ethanol 20 ml
Sodium iodide 1.2 g
6% Sodium hypochlorite solution 10 ml
10% Sodium thiosulfate 10 ml
10% HCl 10 ml

Precautions: Bleach is approximately 5.25% by weight NaOCl in water, which also contains some
NaOH. Therefore, it is corrosive, so wear gloves, and if you spill any on you, wash it off quickly with
water. Ethanol is flammable. Hydrochloric acid is also corrosive.
Procedure

1. Measure out about 1 g of salicylamide and record the mass to the nearest 0.10 g.

2. Place the salicylamide into a 100 mL round-bottom flask. Dissolve the salicylamide in 20 mL
of absolute ethanol.

3. Once the salicylamide is completely dissolved, add 1.2 g of sodium iodide to the reaction
mixture, stir until the mixture is homogeneous with a magnetic stirrer. Place the 100 mL
round-bottom flask containing the reaction mixture into an ice bath.

4. When the reaction is cooled to 0oC (about 10 min.), remove the reaction vessel from the ice
bath and quickly add 10 mL of 6% sodium hypochlorite solution (bleach).

5. Stir the reaction mixture vigorously. The solution will change colors from the initial clear
reaction mixture to a dark red-brown to increasingly lighter shades of yellow. When the
solution reaches a faint, pale yellow-green color, the reaction is complete. (Typically this
takes around 30 minutes.)

6. Allow the reaction vessel to sit on the benchtop undisturbed for 10 minutes. Add 10 mL of
10% sodium thiosulfate solution to the reaction mixture and swirl the flask until the contents
are thoroughly mixed.

7. Next, acidify the reaction solution by slowly adding 10% HCl. You will notice a white solid
beginning to form in the reaction vessel. At this time, the pH of the solution is nearing the
desired acidity. Continue adding 10% HCl, but carefully monitor the acidity.

8. Once the mixture is acidic (blue to red litmus), filter using vacuum filtration and a Buchner
funnel. Allow the crystals to remain in the funnel (break up clumps) with air being drawn over
them for 5 min to speed up the drying process. Air-dry the product in locker.

9. Report the % yield and melting point range in the next lab period.

38
Questions:

Use your knowledge of electrophilic aromatic substitution and the directing effects of substituents on
an aromatic ring to answer the following questions.

1. What are the possible sites of iodination of the salicylamide ring? Briefly explain.

2. Predict the most likely site of iodination of the salicylamide ring and explain your prediction.

39