Exp't 42

Two Easy Diels-Alder Puzzles

Adapted by Selembo, Sun, Underwood, Watson, Woycechowsky, Jennifer Woelker & R. Minard from Pickering, M., "Three Easy Puzzles based on the Diels-Alder
Reaction, J.Chem. Educ., 67, 524 (1990 ). Revised 3/17/01
Introduction:
The Diels-Alder reaction is a pericyclic [4+2] cycloaddition, in which a conjugated diene and an isolated alkene add together in
a single step without intermediates by a cyclic redistribution of bonding electrons (1). This process is very useful in organic
synthesis because it forms two carbon-carbon bonds in one step and is one of the few methods available for forming cyclic
molecules (1). (For a more detailed description of the reaction see McMurry, Organic Chemistry, 2nd Ed., Brooks & Cole,
1988 p. 466-471 and p. 1094-1098.)
cyclic product dienophile diene
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
+
+
.
.
.
.
.
.
2
3
4
1
1'
2'
.
. .
.
.
.
Starting diene & "ene"
all carbons sp
2
hybridized
cyclic transition state
.
.
sp
2
hybridized
carbons
sp
3
hybridized
carbons
cyclic product with
two new bonds formed
When both the diene and dieneophile are cyclic, it is possible to form two products with different geometries, called exo and
endo, as shown below:
H
H
H
H
Which
product,
exo or endo,
is favored?
electrons more or less
in this transition state
than in this one?
Is the overlap of p
Exo-isomer
minor product
endo-isomer
major product
The objectives of this experiment are:
1) to perform two different Diels-Alder reactions:
a) furan and maleic anhydride.
O
O
O
O
endo or exo Diels-Alder product????
+
maleic anhydride:
a dienophile
furan:
a diene
b) 1,3-cyclohexadiene and maleic anhydride.
O
O
O
endo or exo Diels-Alder product????
maleic anhydride:
a dienophile
1,3-cyclohexadiene:
a diene
+
2) to identify which of the possible structures, the endo or exo form, the products have by melting point determination.
Adduct exo product endo product
furan/maleic anhydride 114C 80C
1,3-cyclohexadiene/maleic anhydride 157C 147C
Prelaboratory Exercise:
1. Complete the equations above showing both the endo and exo products for each reaction. Predict which one is favored, exo
product or endo product; refer to your textbook if necessary.
2. How could you synthesize compound 1 (shown below) using a Diels-Alder reaction?
Caution:
Maleic anhydride and the Diels-Alder adducts are intense skin irritants - Wear gloves! 1,3-cyclohexadiene has a
noxious odor so work in a hood. Furan is very low boiling.
Synthesis:
Prepare 5 mL of a 4M solution of maleic anhydride in CH
2
Cl
2
. (Show your calculations in your lab notebook).
Filter off the insoluble maleic acid using a Hirsch funnel and suction filtration.
Mark two reaction tubes and measure 0.5 mL furan into one and 0.25 mL 1,3-cyclohexadiene into the other
(be careful with these reagents - they are expensive!). The 1,3-cyclohexadiene reactions is very exothermic, so
cool this reaction tube in an ice bath before adding the maleic anhydride. (And after the addition, if necessary!)
Add the appropriate equimolar amount of maleic anhydride to the reaction tubes (show calculations). The
cyclohexadiene reaction turns yellow, the furan reaction does not. (The nature of this yellow color is still a topic of
research.)
Cork the test tubes, seal the corks with Parafilm, and set them in your locker until the next laboratory period
because the reaction takes 24 - 48 hours to reach completion.
Isolation and Purification:
If crystals haven't formed, insert a clean stirring rod or boiling stick into the reaction tube, remove the wet rod or
stick, and allow it to dry, forming seed crystals. When reinserted, crystallization should be instantaneous. Pipet off

O
OCH
3
1
Exp't 42
the remaining liquid (Pasteur pipet method), wash the crystals with ice-cold CH
2
Cl
2
or 1:1 (V/V) CH
2
Cl
2
:hexane, let
the crystals dry, and determine the yield and melting point.
Recrystallize the 1,3 cyclohexadiene adduct in about 1.9 mL of a 5:2 mixture of hexane:ethyl acetate.
Take the melting point of the furan adduct before recrystallization. The furan adduct requires much more "finesse"
to recrystallize because it undergoes a reverse or retro Diels-Alder reaction at the melting point. Use a hot water
bath adjusted to a temperature just below the melting point you obtained to dissolve the adduct. Use the same
solvent mixture as above, but use only part of the crude product. Alternatively, you can try acetone and induce
crystallization by dripping hexane into the acetone solution. Obtain melting points of all recrystallized products.
Cleanup:
Dispose of leftover maleic anhydride/CH
2
Cl
2
solution in the Halogenated Organics container and the solids and
left-over recrystallizing solvents in Nonhalogenated Organics container.
Analysis:
Obtain melting points of all recrystallized products.
Final Report:
Determine which of the possible products you have, exo or endo by comparing your melting points with the literature
values.
Answer these questions at the end of your report:
1. Explain why the 4M solution of maleic anhydride is made in CH
2
Cl
2
and not in water. Show the reaction between
maleic anhydride and water.
2. Give structures for the major Diels-Alder product of the following reactions:
1,3-cyclohexadiene and tetrachloroethene
1,3-cylcohexadiene and fumaric acid, the trans isomer of maleic acid
Synthetic Experiment PreLab Grading Sheet
Name(s):
TA:
Date:
PreLab For Exp't #:42
Title: Two Easy Diels-Alder Puzzles
Possible Missed
Points Points
Date, Name, Desk #, Experiment # & Title(abbreviated after 1
st
pg), Section &
TA Name
4
Summary 12
Goals 12
Reactions, structures, conditions, diagrams 14
Completeness of Chemical Data Table(s) 6
PreLab Exercise 16
Chromatographic Behavior Comparison 12
Spectral Features Comparison 12
Work-up isolation and recrystallization 12
TOTAL FOR PRELAB
100
Date Handed in:
General Comments: Total Points:
Synthetic Experiment Final Report Grading Sheet
Name:
TA:
Date:
Final Report For Exp't #:42
Title: Two Easy Diels-Alder Puzzles
Possible Missed
Points Points
Name, Date, Experiment Title (abbreviated after 1st page) and every page
numbered
4
OBSERVATION and DATA - Overall organization, readability, completeness 8
Data: Weighing data, molecular weights, moles, d, & v of necessary
compounds.
12
Yield: Show % yield & wt. calculations with limiting reagent.
Purity: Give pure and impure melting points.
12
RESULTS AND DISCUSSION - Overall organization, readability, completeness 8
Results; Achievement of goals 16
Product Analysis Data: Quality and Interpretation Structure(s) drawn on
each Spectrum or Chromatogram
Assignment and discussion of any spectral data.
Mp data and its meaning
24
POSTLAB QUESTIONS
16
TOTAL POINTS 100
Date Handed in:
General Comments: Total Points: