CHEM 2120 W23 1

CHEM 2120 Experiment 4

Diels-Alder Cycloaddition Reaction with Anthracene

Objective

1. To synthesize the Diels-Alder adduct 9,10-dihydroanthracene-9,10-,β-succinic acid

anhydride (1):

2.
To

1
characterize the product (1) by m.p. and NMR spectroscopy

Introduction

The Diels-Alder reaction is arguably the most elegant of the fundamental organic
chemistry reactions. It is a much used reaction type since it involves carbon-carbon
bond formation with a wide variety of substituted alkene reagents and forms the very
useful cyclohexene ring. Specifically, the reaction is a concerted [4 + 2] cycloaddition
reaction (4  electrons + 2  electrons) between a conjugated 1,3-diene and an alkene,
called the dieneophile (“cycloaddition” means "ring forming"; “concerted” means
“together”, i.e. in one step).
Unsubstituted alkenes, such as ethylene, are poor dieneophiles and react with
anthracene only at high temperature and pressure. The reaction is facilitated by the
presence of an electron-withdrawing group (EWG) and/or conjugation on the
dieneophile. The diene component must be in the s-cis conformation to yield the cyclic
product (where "s" refers to the C-C single bond in C=C-C=C). For this reason, cyclic
dienes usually react more readily than acyclic species. For example, 1,3-
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cyclopentadiene, which is locked in the s-cis conformation, reacts with maleic anhydride
about 1000 times faster than 1,3-butadiene, which prefers an s-trans conformation.

s-cis 1,3-cyclopentadiene s-trans-1,3-butadiene

The Diels-Alder reaction is highly stereospecific and the orientation of the groups
on the dienophile are retained in the product. Thus, the addition must be suprafacial-
suprafacial1, i.e. both new bonds are formed on the same side of the dienophile. This
means that two groups that are cis on the dienophile will be cis in the product (and a
trans dienophile will give a trans product) as seen in the reactions of cis vs. trans
dimethylfumarate:

The reaction of cyclopentadiene with maleic anhydride demonstrates the further

stereochemical consequence of the relative orientation of the reactants in Diels-Alder
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reactions. In this situation, there are two possible ways in which the reactants may
bond. This reaction leads to the formation of two products: the "endo" and "exo"
stereoisomers:

In this lab, the Diels-Alder reaction between anthracene and maleic anhydride will be
performed in order to assess the effectiveness of the reaction, i.e. the yield and the
nature of the product(s) that forms.
1
see Wikipedia “Antarafacial and suprafacial” article; or the University of Liverpool “The
Woodward Hoffman description of the Diels-Alder reaction”
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Prelab Preparation
NOTE: For this and all subsequent labs, students will not be allowed to perform the lab
unless they have entered into their lab notebook all that is asked for in the prelab prep
section of the lab procedure and submitted the Introduction/reagent data table to their
instructor; there will be a 50% penalty for rescheduling due to unpreparedness (students need
to be prepared in order to finish the lab in time and it is also a safety issue, students who have
not prepared are much more likely to cause a serious accident)

1. Reading and Theory.

i. Read sections section 20.3.1.2 (pp. 1022 – 1027) Olgilvie textbook (and course
notes; or LibreText Diels-Alder Reaction) which discuss the mechanism, substituent
effects and stereochemistry of the Diels-Alder reaction. Note that the write-up
instructions ask for the mechanism and p-orbital overlaps in the introduction. Learn
the definition of endo vs. exo product isomers.

ii. Read the “reflux” section of the LibreText “Book: Organic Chemistry Lab Techniques
contributed by professor Lisa Nichols (Butte Community College)

iii. View the ON Tech “Reflux Reaction - Phenacetin” video on the Canvas Expt4 page.

(optional) below is a list of YouTube videos from other institutions, the MIT video is very
good quality.
YouTube videos (active 2023)
https://www.youtube.com/watch?v=fHEk2WFgmXQ (reflux technique, MIT dig lab tech)
https://www.youtube.com/watch?v=b6xFAEkjmGg (“ChemSurvival” good detailed
explanation)

iv. Identify the number of different (i.e. symmetrically inequivalent) hydrogens in the
reactant and product molecules which is also the number of peaks expected in the
1
H-NMR spectrum. Familiarize yourself with the ppm regions in the 1H-NMR for
aromatic, alkene and alkane hydrogens (see Chap 13 Olgilvie or the Expt5b “Tut
Overheads NMR 2120 lab” file; or Lehman's Student Companion 2 nd ed., p. 301 -
302 (note: for figure G-41, p. 301 Lehman's Lab companion, the chemical shift units
at the bottom of that figure should have 10 ppm on the left side and 0 ppm on the
right, it shows the reverse which is the old  "tau" system of units used in the 1960's
and 1970's)).
Identify the number of different (i.e. symmetrically inequivalent) carbons in the
reactant and product molecules which is also the number of peaks expected in the
1
H-NMR spectrum.
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1. Lab notebook / Reagents and Safety.

Enter the following in your Lab Notebook:

1. A point form list or flowchart of the procedural steps

2. For each of the compounds/solvents to be used (Aldrich links given below), relevant
chemical properties are provided below (table 1); you must look up the missing data
for anthracene and hand write it into your lab notebook (printouts of the complete
data table will be provided in the lab so it is not necessary to write the data for the
other compounds)
Sigma-Aldrich catalog entries for compounds/solvents used in this lab:
SDS of anthracene (Aldrich website):
http://www.sigmaaldrich.com/catalog/product/aldrich/a89200?lang=en&region=CA

SDS of maleic anhydride (Aldrich website):

http://www.sigmaaldrich.com/catalog/product/aldrich/m188?lang=en&region=CA

SDS of xylenes (Aldrich website):

https://www.sigmaaldrich.com/catalog/product/aldrich/214736?lang=en&region=CA

SDS of ethyl acetate (Aldrich website):

https://www.sigmaaldrich.com/catalog/product/sigald/319902?lang=en&region=CA

Table 1. Physical Properties of compounds/solvents to be used in Exp4

(source: the SDS sheets from Aldrich links above) ; for further detail on GHS classes/categories: WHMIS 2015 Hazard
Classes ; United Nations GHS Presentations ; ChemSafetyPro UNPurpleBook pdfs and GHS Classification Criteria ;
compound colour state m.p. b.p. density vapour
(rm (rm temp) pressure
temp)
anthracene °C °C
maleic
white solid 51-56 °C 200 °C N/A 0.2 mmHg
anhydride
xylenes colourless liquid < 0 °C 137-140 °C 0.86 g/mL 18 mmHg
ethyl acetate colourless liquid -84 °C 76.5-77.5 °C 0.90 g/mL 73.0 mmHg

3. For each of the compounds / solvents to be used (Aldrich links given above),
relevant chemical safety data from the Aldrich SDS sheets is provided below (table
2); you must look up the missing safety info for anthracene and hand write it into
your lab notebook (printouts of the complete data table will be provided in the lab so
it is not necessary to write the data for the other compounds)
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Table 2. Safety Hazards and Precautions of compounds/solvents to be used in Expt5

(source: the SDS sheets from Aldrich links above)
compound Hazards Identification (SDS section 2)
anthracene
maleic anhydride Acute toxicity, Oral; Skin corrosion ; Harmful to aquatic life
xylenes Flammable liquid; Toxic Material Causing Other Toxic Effects; Chronic toxicity
Flammable liquid ; Toxic Material Causing Other Toxic Effects ; Specific target organ toxicity -
ethyl acetate
single exposure (Category 3), Central nervous system
compound Potential Health Effects (Inhalation, Skin, Eyes, Ingestion) (SDS section 2)
anthracene Inhalation “” ; skin: “” ; Eyes: “” ; Ingestion: “” ;
Inhalation “May cause allergy or asthma symptoms or breathing difficulties if inhaled; Causes
damage to organs (Respiratory system) through prolonged or repeated exposure if inhaled”; skin:
maleic anhydride
“Causes severe skin burns and eye damage; May cause an allergic skin reaction”; Eyes: “Serious
eye damage” ; Ingestion: “Harmful if swallowed” ;
Inhalation “May cause respiratory irritation” ; skin: “Causes skin irritation” ; Eyes: “Causes serious
eye irritation” ; Ingestion: “May be harmful if swallowed”; May be fatal if swallowed and enters
xylenes
airways; May cause damage to organs (Central nervous system, Liver, Kidney) through
prolonged or repeated exposure if inhaled
Inhalation “May be harmful if inhaled. Causes respiratory tract irritation. Vapours may cause
ethyl acetate drowsiness and dizziness” ; skin: “May be harmful if absorbed through skin. Causes skin
irritation” ; Eyes: “Causes eye irritation” ; Ingestion: “May be harmful if swallowed” ;
compound Precautions for Safe Handling (SDS section 7)
anthracene
Avoid contact with skin and eyes. Do not breathe dust/ fume/ gas/ mist/ vapours/ spray. Avoid
formation of dust and aerosols. Provide appropriate exhaust ventilation at places where dust is
maleic anhydride
formed. Wash skin thoroughly after handling. Avoid release to the environment; Contaminated
work clothing should not be allowed out of the workplace
Avoid contact with skin and eyes. Avoid inhalation of vapour or mist. Keep away from sources of
xylenes ignition; Keep container tightly closed in a dry and well-ventilated place. Containers which are
opened must be carefully resealed and kept upright to prevent leakage
Avoid contact with skin and eyes. Avoid inhalation of vapour or mist ; Keep away from sources of
ethyl acetate
ignition - No smoking
compound Respiratory / Hand / Eye / Skin Protection (SDS section 8)
Respiratory: fumehood; respirator where risk assessment shows appropriate Hand: “Handle with
anthracene gloves.” ? rubber min thickness ?mm Eye: Face shield and safety glasses ; Skin: Complete suit
protecting against chemicals according to concentration and amount
Respiratory: fumehood; respirator where risk assessment shows appropriate Hand: “Handle with
maleic anhydride gloves.” nitrile rubber min thickness 0.11 mm Eye: Face shield and safety glasses ; Skin:
Complete suit protecting against chemicals according to concentration and amount
Respiratory: fumehood; respirator where risk assessment shows appropriate Hand: “Handle with
xylenes gloves.” nitrile rubber min thickness 0.4 mm Eye: Face shield and safety glasses ; Skin: Complete
suit protecting against chemicals according to concentration and amount
Respiratory: fumehood; respirator where risk assessment shows appropriate Hand: “Handle with
gloves.” butyl rubber min thickness 0.3 mm Eye: Face shield and safety glasses ; Skin: impervious
ethyl acetate clothing, Flame retardant antistatic protective clothing ; The type of protective equipment must be
selected according to the concentration and amount of the dangerous substance at the specific
workplace
compound Flammability and Flashpoint* (for liquids) (SDS section 9)
anthracene Flammability: ; Flashpoint: “”
 CHEM 2120 W23 7

maleic anhydride Flammability: “No data available” ; Flashpoint: “No data available”
xylenes Flammability: lower explosion limit: 1.2 %(V) | upper explosion limit: 7 %(V) ; Flashpoint: 4 °C
ethyl acetate Flammability: lower explosion limit 2.2 %(V) | upper explosion limit 11.5 %(V) ; Flashpoint: -2.99 °C
compound Chemical Stability and Reactivity (SDS section 10)
anthracene stability: reactivity:
stability: Stable under recommended storage conditions; reactivity: No data available;
maleic anhydride Incompatible materials: Strong oxidizing agents, Strong acids, Strong bases, Strong reducing
agents, Alkali metals, Amines
stability: Stable under recommended storage conditions; reactivity: Vapours may form explosive
xylenes
mixture with air ; Incompatible materials: Strong oxidizing agents
stability: Stable under recommended storage conditions; reactivity: Vapours may form explosive
ethyl acetate
mixture with air ; Incompatible materials: Strong oxidizing agents
*FYI: see Wikipedia Flashpoint article for definition, “The flash point of a volatile material is the lowest
temperature at which vapours of the material will ignite, when given an ignition source”

2. Make up a complete Reagent Data table and Write the Introduction for the lab
report before the lab and submit them in a WORD document to Turnitin before your
lab begins (there will be a separate Turnitin submission for “Expt3 Reagent Data
and Intro” due before the start of the lab);
Note re Reagent Data Table: this version of the reagent data table will be marked
by the TA as part of the report mark. For your report, edit the table to give the
“actual” amounts used for the lab; no other changes from the originally submitted
version will be marked (e.g. correcting the MW or #equiv’s of a compound).
You must either:
(i) hand write the reagent data table into your lab notebook then take a pic and put
it in the WORD file submitted to Turnitin
(ii) make the reagent data table in the WORD file submitted to Turnitin then print it
and staple into your lab notebook.
Note re Introduction: only this version of the Introduction will be marked by the TA
and included in the report mark, ie. any changes made to the Introduction after the
lab will not be marked. Details on what to include in the Introduction are given in
the Lab Report section of the Lab Outline file and also specific comments in the
write-up instructions below.
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Procedure Work Individually in the fumehood

Reaction (in the fumehood, rxn uses high heat and xylenes are too smelly!)
Weigh and add 400 mg of anthrancene and 200 mg of maleic anhydride to a 10 mL
round bottom flask containing a magnetic stir vane and equipped with a water
condenser protected by a calcium chloride drying tube. In the fumehood, add 5.0 mL of
xylene (dried over molecular sieves) to the solid mixture.

Heat the reaction mixture at reflux for 30 minutes in a sand bath at about 185 - 190 °C
(heat setting of 8 on hot plate); your instructor will check the reaction temp with a high
temp thermometer. Use aluminum foil to cover the sand bath to help achieve this level
of heat. During this time the initial yellow color of the reaction mixture gradually
disappears. After 30 min, but while the reaction solution is still hot, keep the finger
clamp on the neck of the rb flask and, while holding the clamp (not the hot rb flask),
pour the reaction solution into a 50 mL beaker; this mitigates the problem of product
precipitating out in the rb flask and sticking to the glass. Allow the reaction solution to
cool to room temperature and then place it in an ice bath for 10 minutes to complete the
crystallization of the product. If the solid freezes into a “hard puck”, let it sit at room
temp. for ~ 5 min to warm up to a slurry that can be more easily filtered. If it remains
solid puck, a small addition of ~ 0.5 mL ethyl acetate often helps it form a slurry.

Isolation of Product (in the fumehood, xylenes are too smelly!)

Collect the product 1 crystals by suction filtration using a Hirsch funnel and wash the
filter cake with two 1 mL portions of cold ethyl acetate; if the product still looks a little
“ugly”, try a couple more cold ethyl acetate washes to remove more impurities. Transfer
product to a filter paper to complete the drying. The product is usually of sufficient
purity for direct characterization at this point. Note that the product can be further
purified by recrystallization from ethyl acetate, however it is difficult dissolve all the
solids in the short time available, therefore it is not recommended.
 CHEM 2120 W23 9

Characterization
Weigh the dried Diels-Alder product and calculate the percent yield. Show your product
to your instructor. Determine the melting point (Mel-temp setting of 6.5 recommended,
adjust as appropriate) and compare your result with the product 1 literature value (m.p.
= 261-262 °C). One or two student samples will be selected for NMR analysis and
posted to Canvas.

Write-up
Full report (with abbreviated Introduction) as per the "Lab Outline" file ("Laboratory
Reports" section) and note the following additional instructions.

Introduction: Do only the following for your Introduction.

1. Draw and discuss the mechanism (with arrows to show electron movements) of the
Diels-Alder reaction between anthracene and maleic anhydride. Draw the
orientation and phases of the reacting p-orbitals showing how they overlap in a
“suprafacial” geometry to form product (Olgilvie Section 20.3.1, pp1020-1021; or
LibreText Diels-Alder Reaction).

2. Why does the diene need to be in the s-cis conformation to yield the cyclic product?

3. Why do the anhydride groups of the maleic anhydride reactant help the Diels-Alder
reaction go faster?

4. For this particular reaction, are the exo and endo forms of product 1 different
stereoisomers or are they the same molecule? If the 1,4-adduct of anthracene and
maleic anhydride had formed, would it have different exo and endo isomers?

5. Give the reaction conditions, ie. what apparatus, solvent, temperature and time will
be used. How will the product be isolated from the reaction mixture and how will it
be characterized?

Procedure: as per the "Lab Outline" file.

Data and Results: as per the "Lab Outline" file.

A reagent data and yield table is required; if, for some reason, the yield was not
obtained, you must give an example yield calculation.
 CHEM 2120 W23 10

Discussion: as per the "Lab Outline" file; in addition. Include the following items:

briefly discuss the yield and m.p.

IR spectra:
Why is IR not a good method for distinguishing product (1) from the reactant maleic
anhydride?

NOTE: the following NMR questions are worth 5 marks for the Expt4 report but most
students will need the benefit of the NMR tutorial explanation, therefore the answers to
these questions are not due to be handed in until the second week of the NMR/IR
tutorial.

NMR spectra:

Note that the 1H-NMR of the product has aromatic multiplet patterns that do not follow
the n+1 rule because the molecule has a rigid conformation which does not allow free
rotation around the C-C bonds; likewise the non-aromatic H’s do not couple with each
other which violates the n+1 rule. In these cases, the 13C-NMR is preferred for
identification because the peaks do not have splitting patterns (a special irradiation
technique is used to prevent the C-H coupling interactions), each different carbon in the
molecule gives one singlet peak.

i. The 1H-NMR of product (1) shows four aromatic multiplet signals (two multiplets are
overlapped at 7.2 ppm) and two non-aromatic peaks; explain how this spectrum is
consistent with the product (1) molecule and not with either of the reactants.

ii. Draw the structure of the product (1) molecule and indicate which carbons are unique
and which are chemically (symmetrically) equivalent; identify the planes of symmetry
and/or rotations that exchange equivalent carbons. How many peaks are expected in
the 13C-NMR spectrum? Which peak(s) are assignable to a C=O carbon?

note: the three closely spaced peaks at 77.0 ppm in the 13C-NMR spectrum are
caused by the CDCl3 solvent that the sample is dissolved in, thus they have nothing
to do with the product and should be ignored.

iii. Compare the student sample from this year with the “1H/13C NMR student product
W11” which is pure (1H NMR has only a small impurity at 2.3ppm and a bit of water
at 1.5 ppm; 13C NMR shows no impurities as they are so small they are covered by
the noise in the baseline); are there significant side product or impurities in the
student sample? Note that the chemical shift of maleic anhydride (not given in the
Aldrich spectrum) is 7.048 ppm (1H-NMR) and 164.58 ppm, 136.76 ppm (13C-NMR).

Bonus 3 marks: discuss something noteworthy about the lab, e.g. something
noteworthy that you observed and/or discuss the effectiveness of the reaction and
 CHEM 2120 W23 11

procedure; was there a low yield and, if so, do you think it was just because the reaction
did not go to completion or do you think there was enough product but that some or a lot
was lost in the work-up, and what could you try next time to solve the problem? Or did
something else not work as well as it should or take longer than necessary to do, if so,
what would you do different next time in an attempt to improve the outcome or improve
the efficiency? If you don’t think any improvement is needed, support your opinion by
summarizing how the steps worked well.