Background:

The Diels-Alder reaction is a cycloaddition reaction between a diene and an alkene. Typically
this alkene is substituted and is termed a dienophile. (Synthesis in the hydroaromatic series, IV.
Announcement: The rearrangement of malein acid anhydride on arylated diene, triene and
fulvene, Diels, O.; Alder, K. Ber. 1929, 62, 2081 & 2087.) Although there is no electrophile and
nucleophile in this reaction, and all bonds form simultaneously, resonance structures show us
that there are partial positive and negative charges that give rise to faster reactions between the
dienophile and the diene. To observe the fastest reaction, the diene has to be very electron rich.
Maximal orbital overlaps as a result of electron withdrawing groups on the dienophile also help
to move the reaction forward faster. The reaction is initiated by heat and always form new 6membered rings. (Smith, Janice G. "The Diels-Alder Reaction." Organic Chemistry. 3rd ed. New
York, NY: McGraw-Hill, 2011. 58889. Print.)
Purpose:
The purpose of this reaction is to make a cyclohexane product utilizing the Diels-Alder reaction.
The product made is cis-norbornene-5,6-endo-dicarboxylic acid anhydride and will be
characterized by TLC, IR and melting point.
Reaction Scheme:

Reagents:

Compound

mol. wt. (g
mol-1)

m.p. or b.p.
(C)

SAFETY

Maleic anhydride

98.06

5156 (m.p.)

Toxic, corrosive, irritant,

health hazard

Ethyl acetate

88.11

76.577.5
(b.p.)

Flammable, toxic

Hexanes

86.18

69 (b.p.)

Flammable, acute and

chronic toxicity,
environmental hazard

Dicyclopentadiene

132.2

35 (m.p.)
170 (b.p.)

Flammable, acute toxicity,

environmental hazard

Pet. Ether

--

60-80 (b.p.)

Flammable, chronic toxicity

Procedure:
cis-norbornene-5,6-endo-dicarboxylic acid anhydride. Dissolve maleic anhydride (0.20 g) in
ethyl acetate (1 mL) and add hexanes (1 mL). Add cyclopentadiene (0.20 ml, 0.160 g) and mix the
reactants together. Let tube cool to room temperature. If crystallization does not occur, start
nucleation by scratching the bottom of the tube. If crystallization occurs too quickly, redissolve the
crystals by heating the mixture, and cool more slowly. Remove solvent and wash crystals with pet.
ether. Evaporate excess solvent and allow product to dry.