6309

2/19/2014
AMDG

Grignard Reaction: Preparation of

Benzoic Acid

Figure 1. Reaction Mechanism showing the preparation Benzoic Acid with a Grignard
Reagent.

Abstract
Synthesis of Benzoic Acid using a Grignard reagent and dry ice with an acidic
workup was the focus of this experiment. Anhydrous reaction conditions were used to
favor the product and to eliminate the possibility of quenching the Grignard reagent. The
product was purified and isolated by extraction and vacuum filtration. Melting point and
13

C NMR analysis was done to confirm the identity and purity of the product and it was

concluded that Benzoic acid was synthesized.

Results and Discussion

The reaction mechanism shown in Figure 1 depicts the the magnesium inserting

itself into the bromobenzene to form the Grignard reagent. In lab the bromobenzene and

6309
Grignard Reaction: Preparation of
2/19/2014
Benzoic Acid
AMDG
ether solution was added in small aliquots to the magnesium turning. This prevented the
reaction mixture from getting too hot. Due to the exothermic nature of the reaction, the
solution was added slowly to maintain control of the heat of the reaction. An ice bath
was also kept just in case the reaction go too hot.

Table 1. Melting Point and Percent Yield of the product

After the sample was allowed to dry for 24 hours, the melting point was taken and
13

C NMR was taken. Given that the actual melting point of benzoic acid is 120C the

melting point observed is conclusive with that of benzoic acid and the synthesized
product is very pure. The percent yield was calculated from the moles of magnesium
used in the experiment. Not all of the turnings reacted and it was calculated to be the
limiting reagent, however not factoring in the amount of magnesium that did not react
could throw off the calculation of the percent yield.
The 13C NMR displayed 5 peaks which is would correlate with the structure of
Benzoic Acid. The most downfield peak at 171.11 ppm is indicative of the carbon
bearing the carboxyl group. The peak at 133.56 ppm is indicative of the carbon on the
aromatic ring that is furthest from the carboxyl group. The peaks at 129.94ppm and
128.22ppm are indicative of the 2 sets of equivalent carbons on either side of the ring
and the peak at 128.98ppm is indicative of the carbon adjacent to the carboxyl group

carbon. All the peaks together give the predicted peaks for benzoic acid and give
conclusive data to the identity of the product. If 1H NMR were done to further confirm the
identity and structure of the product, there would be 4 peaks. One broad singlet (1H)
downfield around 10ppm for
the H on the carboxyl group.
There would be complex
splitting between 7.5 and
8.5ppm to represent the peaks associated with the hydrogens on the aromatic ring to
display a total of four signals.

Conclusion
The Grignard reagent was successfully prepared slowly by adding
bromobenzene to magnesium turnings in an anhydrous ether to maintain control over
the heat of the reaction. The preparation of the Grignard to be done in an anhydrous

solvent to prevent protonation of the reagent to yield benzene, so a solvent like ethanol
would not be ideal for this experiment.

Figure 2. Reaction Mechanism depicting the formation of the biphenyl impurity formed
as a result of double addition of the Grignard reagent.
Grignard reagents are very reactive and will add to electrophilic sites twice if
possible. The mechanism in Figure 2 shows the formation of the possible biphenyl
impurity that is removed in extraction. Upon obtaining the crude product an acid-base
reaction was done with the use of sodium bicarbonate to cause the product to be
soluble in water and thus a part of the aqueous layer when dichloromethane was added.
Sodium bicarbonate is not a strong enough base to deprotonate the alcohol on the
biphenyl impurity so it does not become soluble in the aqueous layer. This technique
allowed for a successful extraction of the biphenyl impurities and undesirable organic
product that may have been in the reaction mixture. In order to improve the accuracy of
the percent yield calculation it would have been ideal to weigh the amount of the
magnesium turnings that did not react to subtract them from the mass of the magnesium
used to calculate the yield. After completing the experiment and allowing the compound
to dry, the melting point and 13C NMR data gave conclusive data to the identity of the
compound as benzoic acid.