Vous êtes sur la page 1sur 3

Discussion for Lab #5: Macrocyclic Synthesis

Diels-Alder (DA) reaction is a concerted [4+2]-cycloaddition reaction, in which all bonds


are broken and formed in the same step reaction since it takes place in a single step cyclic
redistribution (syn-addition). It is also classified as pericyclic, which leads to a ring formation
and involves a cyclic rearrangement of bonding electrons; which means, that the bonds are
broken and formed simultaneously. Aside from that, it is also stereospecific because the
substituents do not have the ability to change around and switch. Most of the time, DA reaction
is usually thermodynamically favored (products are favored over reactants) because it converts
two -bonds into two stronger -bonds.
A DA reaction is consists of a diene (a molecule that contains two double bonds) and a
dienophile (a molecule that loves a diene). In a DA reaction, acyclic compounds form a cyclic
compound. A good example is the experiment performed; which is to synthesize 4,5-dimethyl-
cis-cyclohex-4-ene-1,2-dicarboxylic anhydride from maleic anhydride (diene) and 2,3-
dimethylbutadiene (dienophile). In a classic DA reaction, a good diene is locked in the s-cis
confirmation and is nucleophilic (electron rich) while a dienophile is electrophilic (electron
poor). The reason why it is not in s-trans is because the ends of the diene are much far apart to
interact and overlap with the p orbitals of the dienophile. It is stated that a [4+2] concerted
reaction is thermodynamically allowed which means that simultaneous cyclic reaction that
involves four electrons of one reactant and two electrons of the other, is possible. However, a
concerted [2+2] cycloaddition is thermodynamically unfavorable because the formation of
cyclobutadiene cannot proceed via concerted reaction without involving an intermediate step.
In order to synthesize 4,5-dimethyl-cis-cyclohex-4-ene-1,2-dicarboxylic acid from the
cyclic anhydride, a process called hydrolysis was performed. Hydrolysis is the decomposition
of a chemical compound with the addition of water. In hydrolysis, a part of a certain molecule is
split into two parts with the addition of water (

). One of the groups collects hydronium ion


Discussion for Lab #5: Macrocyclic Synthesis

(

), while the other collects the hydroxyl group (

. In the presence of

(an acid
catalyst which speeds the reaction and lowers activation energy), the carbonyl group (C=O)
becomes protonated, and leads to an easier nucleophilic attack. Since the cyclic anhydride
contains CO-O group, it is converted with two carboxylic acid groups (-CO-OH).
In order to get the desired products, two work-up procedures involve the process of
crystallization. Crystallization is the process of forming solid crystals from the precipitate of the
solution. In order to get the cyclic anhydride, the reaction mixture was poured into a beaker that
contains water because water will react with the anhydride to produce precipitate. With the use
of vacuum filtration, the original product was then obtained. On the hydrolysis work-up, the
solvent used was 25% acetone/water instead of 100% water due to the fact that the anhydride
melts faster in the reaction mixture of 25% acetone/water solution, because its boiling point will
be lower than the b.p of pure water. The hydrolyzed product is very insoluble in water and has a
great tendency to crystallize after it cools down and is purified by performing crystallization.
The IR spectrum for product obtained after the DA reaction, shows significant peaks at
~1797.12 which is the peak for anhydride (-CO-O) and ~1472.78 for carboxylate (-COO). Since
the significant peaks for the cyclic anhydride were identified, this signifies that the product was
indeed the cyclic anhydride. After the hydrolysis, the product obtained showed significant peaks
at ~3446.24, which is the hydroxy-OH, ~1842.43

for the anhydride (RCO-O), ~1712.29


for the carboxylic acid COOH, ~1558.50 for the phenyl group (C=C), and ~1780, which is the
peak for anhydride for the first product obtained. Although the hydrolyzed product can still be
identified, one of the reasons why theres an excess peak, may be because while the mixture was
being dissolved, the presence of the oil drops had not completely disappeared, resulting in a
lower melting point at 201C, and some impurities. If the reaction was heated a little longer,
maybe a better IR result and higher melting point can be obtained.
Discussion for Lab #5: Macrocyclic Synthesis


References
Bruice, P. Organic Chemistry, 7
th
ed.; Pearson: New Jersey, 2013.
Padias, A. Making The Connections, 2nd ed.; Hayden-McNeil Publishing: Plymouth, MI, 2013.
Padias, A. Organic Chemistry Laboratory Manual, 4th ed.; Hayden-McNeil Publishing:
Plymouth, MI, 2013.