Experiment 6

CHEM 613
Experimental Organic Chemistry
2013
Anastazija Ristovska

Post-lab
Benzopinacolone Synthesis

Pinacol rearrangements are important reactions because they are an efficient method of
synthesizing ketones that are difficult to synthesize through other conventional methods.
The mass of benzopinacol obtained in Experiment 1 was
0,2990g. The purpose of Experiment 6 was to convert the
bezopinacol obtained in experiment 1 to benzopinacolone. Since
we only needed 100mg of benzopinacol to conduct experiment 6,
and we had 300mg, this amount was enough for the experiment to
be replicated three times.
The benzopinacolone synthesis is a pinacol rearrangement reaction. A
pinacol rearrangement is an acid catalyzed dehydration of 1,2-diols i.e.
glycols, which converts them to aldehydes or ketones. The most famous
example of this type of rearrangement is the pinacol-pinacolone
rearrangement. In pinacol there are four methyl groups attached to the two carbon atoms of
ethylene glycol; in benzopinacol there are four phenyl groups attached to the two carbon atoms
of ethylene glycol. The mechanism of the reaction involves a transfer of one phenyl group from
one carbon atom to another. In order for this to be induced, it was needed that glacial acetic acid
and solid iodine be added to the benzopinacol, heating the mixture in a water heat bath. The
iodine is used as catalyst. Alternatively, the reaction can be carried out in very strong acids if
iodine is not to be used.
The first step of the pinacol rearrangement happens when a proton from the solution
protonates one of the hydroxyl OH groups. Once the OH2+ group is formed, it is suitable for
the water to leave, because once it leaves it will leave as a neutral water molecule and will transfer
its positive charge to the carbon atom it was attached to, now making it a positive cation. It was
preferred that the positive charge be located on the carbon atom (instead of the water molecule)
because it formed a tertiaty carbon cation. The next step is a methide shift in the pinacolpinacolone reaction, and a phenide shift in the benzopinacole-benzopinacolone reaction.
1

Once the methide or phenyde group shifts from the carbon atom that is still bonded to
an oxygen to the carbon atom that has just lost a water molecule, the positive charge transfers to
the carbon bonded to the oxygen molecule. The C-O bond is a lower LUMO, and the reason
why its lower is because of the oxygen. The oxygen is withdrawing electrons from the carbon
because of its high electronegativity, bestowing slight positive charge on the carbon. Therefore it
is counterintuitive to think that the positive charge of the tertiaty carbon would prefer to transfer
to the neighboring carbon that is already slightly positive and destabilized by the oxygen
electrons for purposes of this rearrangement. The reason why that process is favorable anyways
and it is desirable to have the oxygen attached to the carbon receiving the oxygen charge is
because electrons are actual particles with positive charge, and they get stabilized by mingling in
the low vacant orbital associated with the positive charge. Thus, when the positive charge gets
transferred to the carbon atom attached to the oxygen, it is the electrons on the oxygen that get
lower in energy. Once this happens the electrons from the O-H bond are likewise attracted
towards the positive carbon atom, so they lower their energy by forming the double carbonyl
bond. The proton leaves, and the product is formed.
The condition for this reaction to take place is that the migrating group be positioned
trans- to the leaving OH group. The reaction is concerted, or otherwise it would have been
hard for the phenide, which is a bulky group, to make the migration properly.
The theoretical yield of benzopinacolone was 99,44mg benzopinacolone based on these
calculations: 0,1045g/366.16g/mol = 2,854*10-4mol 384,42; 2,854*10-4mol*384,42g/mol =
0,09944g = 99,44mg. 57,5mg were obtained which means that the percent yield was 57,8%. The
limiting reagent was benzopinacol, since acetic acid was added in excess, and acetic acid and
iodine were catalysis and were thus not wasted in the process. The proton that was donated by
acetic acid to the OH group that leaves the first carbon atom as water is later regained from the
OH groups that transforms into a carbonyl group by any negatively charged acetic acid
conjugated base molecule.
The experimental procedure was commenced by adding 104,5mg benzopinacol to a test
tube, to which 1ml glacial acetic acid was added also, and the test tube was swirled. It was
observed that the benzopinacol did not dissolve immediately. One crystal of solid iodine was
added to the test tube, and the tube was placed over a water heat bath; it was left to heat on the
water vapor of the bath. The solution was immediately colored bright red from the iodine. After
several minutes, when it could be observed that all the benzopinacol had dissolved in the acetic
acid, the test tube was removed from the water heat bath and was left on the bench to cool. The
test tube was then transferred to an ice bath. Crystal formation was observed. A vacuum filter
apparatus was set up, and the crystals were isolated through vacuum filtration. Benzopinacolone
was observed to be a white crystalline substance.

243

100

50

165
O

27

39

51

62

77
74

105
91 98

115 125

139 150

174 183191 202

215

228 239

250

270

332

348

20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300 310 320 330 340 350 360
(mainlib) Acetophenone, 2,2,2-triphenyl-

The mass spectrum shows two major peaks, one for m/z=243, and one for m/z=165,
also two smaller ones at m/z=105 and m/z=77; the molecular weight peak is at m/z=348. The
m/z 243 peak is due to the three phenyl groups attached to the carbon atom at center, which has
been divided from the keto-carbon atom. The 105 peak is due to the phenyl group plus the
carbon atom bonding the carbonyl oxygen. The peak at 165 is due to two phenyl groups bonded
to the central (non-keto) carbon atom, whereas the peak at 77 is due to a single phenyl group not
bonded to anything else.

The IR spectra of benzopinacolone had one sharp peak at 3050-3100cm-1, another shorter sharp
peak at 1700cm-1, a long sharp peak at 700cm-1, one peak at 1200cm-1, and another one yet
shorter at 1500cm-1. A carbonyl stretch at 1710-1665 cm-1 indicates that the carbonyl group is
,-unsaturated, which is true, the -carbon belongs to a benzene ring. A C-H stretch coming
from aromatic rings usually appears at 3000-3100cm-1, which is consistent with the peak we
notice at 3050-3100cm-1 and comes from the C-H bonds in the four benzene rings of
benzopinacolone. The C-H aromatic bonds have also created an C-H oop stretch at 700cm-1,
which could have as well been found anywhere in the range 625-900cm-1. The 1500cm-1 peak is
indicative of the C-C bond stretches of the aromatic phenyl groups, and it could had been
expected that it appears anywhere in the range between 1400-1500cm-1. The peak at 1200cm-1
comes from a ketone C-(C=O)-C stretching of the C-C bonds. In the bezopinacol IR we can
clearly see an OH stretch that is not noticed in the benzopinacolone IR.