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Experiment 7

CHEM 613
Experimental Organic Chemistry
2013
Anastazija Ristovska

Post-Lab
Haloform Reaction

The purpose of this experiment was to prepare benzoic acid from acetophenone using
NaOCl, sodium hypochlorite, HCl, and NaOH. Acetophenone has the structural formula of an
acetyl functional group attached to a benzene ring. The purpose of the reaction is to substitute
the methyl group of acetophenone with a hydroxyl group. Therefore the experiment procedure
will have the hard task of breaking only one carbon bond while leaving the rest intact, and then
creating a carbon-hydrogen bond. The reaction is called a haloform reaction even though a
halogen element is not present anywhere in the final desired product (benzoic acid) because a
CHX3, in this case CHCl3 gas is released during a halogenation of a methyl ketone in the
presence of base.
The procedure consisted of adding 20ml 5% NaOCl solution to 560mg acetophenone.
This step produced replaced the methyl group of acetophenone with covalently bound sodium
monoxide NaO- unit. This step successfully severs the carbonyl carbon methyl C-C bond and
creates a carbon-oxygen bond. The reaction is C6H5-CO-CH3 + 3NaOCl C6H5-COONa +
CHCl3 + 2NaOH. Chloroform is released. The sodium hypochlorite solution is not miscible
with acetophenone, and in order for this reaction to take place they must be heated while
swirling in a heat bath. It took 42min for acetophenone to dissolve in sodium hypochlorite at
90C. After it had dissolved completely, 30 drops of acetone were added in order to destroy any
remaining sodium hypochlorite by forming sodium acetate with it (which was removed during
purification). The next step is acidulation with hydrochloric acid; 37% HCl was added slowly
until it was observed using litmus paper that the solution has turned acidic. Every drop of HCl
added formed a white-yellowish precipitate. The container of the solution was moved to an ice
bath to form even more of this precipitate which was then isolated using vacuum filtration. What
happened during this step is a salt metathesis reaction: C6H5COONa + HCl C6H5COOH +
NaCl. The theoretic yield of benzoic acid was 514mg, and only 20mg were obtained. The percent
yield was therefore 3.9%. There can be many theories why the reaction had such low yield, one
of which is, in the first step which was the rate determining step, and was indeed a very slow
step, the reaction was either carried out for too short, or the temperature was too low. The
temperature was precisely controlled using thermometer, but perhaps increasing the temperature
even more could have both increased the reaction rate as well as increased the yield.
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The MS analysis of the starting organic reactant shows the molecular ion peak at
120m/z, and the strongest peak is at 105m/z. The 105m/z peak is due to the breaking off of the
methyl group, leaving only a benzene ring (phenyl group) attached to a C=O carbonyl group.
The second strongest peak is at 77m/z and this is the peak of the benzene ring ion by itself.
Theres also a peak at 43m/z from the fragment that occurs when only the benzene ring is
removed from the molecule, leaving behind only the carbonyl and methyl groups bound
together.

The first absorption we should be looking for in the IR spectral analysis of acetophenone
is the characteristic carbonyl peak in the 1665-1760cm-1 area, and we do see it at 1695cm-1. At
3000-3100cm-1 we see the aromatic C-H stretches, and at 1600cm-1 the aromatic C=C- in-ring
stretches can be noticed. At 1760cm-1 the aromatic C-H oop stretch is seen.

The molecular ion peak in the benzoic acid mass spectrum appears at 122cm-1, whereas
the strongest peak is at 105cm-1 and it comes from the fragment left over when the methyl
group carbonyl group bond is severed and the methyl group is cleaved off from the molecule.
The third strongest peak is at 77m/z and it comes from the ion fragment that contains only a
benzene ring with nothing else attached to it other than the five phenyl protons of benzoic acid.

The benzoic acid carbonyl peak is seen at 1695cm-1, the same position as in
acetophenone. The aromatic C-H oop peak is seen at 705cm-1 and in that area there is now only
one peak as opposed to thee that were seen for acetophenone, so we assume that the two
additional peaks in acetophenone came from the methyl group C-H bond vibrations. This time
the aromatic C-H stretches in the 3000-3100cm-1 region are overlapped by a broad carboxylic
acid O-H bond stretch from 2500cm-1 to 3200cm-1.
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