Chemistry Lab Report : III

Formation and use of an organometallic reagent : Synthesis of

triphenylmethanol.
The Grignards Reaction
Aim:
This experiment is split into two parts.
Part 1 aims at formation of phenylmagnesium bromide by reacting bromobenzene with magnesium
turnings in the presence of an aprotic solvent, i.e. ether. The reaction adopts a SN2 mechanism.
Part 2 aims at synthesising triphenylmethanol utilising methyl benzoate and phenylmagnesium
bromide as reactants.
These reactions are commonly called Grignard reactions

Introduction:

In 1912, Victor Grignard was awarded the Nobel Prize in Chemistry for the discovery of these novel
reactions. In essence, Grignard reactions involve the synthesis of new carbon-carbon bonds.
It first involves the formation of an organometallic reagent followed by the nucleophilic attack onto
an electrophilic alpha carbon in a carbonyl group resulting in a new carbon - carbon bond.
The general scheme of the experimental reaction can be seen in Fig. (1)

Fig (1): General scheme of a) formation of Grignard Reagent b) Formation of Triphenylmethanol

Part 1. - Formation of an organometallic reagent
The chemical reaction between the organic halide bromobenzene and a magnesium metal
produces an aryl free radical and a magnesium free radical. The two subsequently covalently bond.
This covalent bond is highly polarized because the magnesium is bonded to bromine which is an

electron withdrawing group. This causes the formation of a partial positive charge and partial
negative charge on the magnesium atom and the phenyl group respectively. Fig. (2)

Fig. (2): Mechanism of formation of phenyl magnesium bromide

Part 2. - Synthesising triphenyl methanol
The basicity of the Grignard reagent, phenyl magnesium bromide, allows it to react with the
electrophilic carbonyl carbon of the ester, methyl benzoate. This reaction takes place two times and
results in the formation of a ketone intermediate The final step of the synthesis is involving
hydrolysis of the magnesium alkoxide by using a mineral acid, sulphuric acid (10 %). As a result,
the reaction synthesizes an alcohol, triphenylmethanol, and magnesium salt (water soluble).
Fig. (3)

Fig. (3): Mechanism of formation of Triphenylmethanol

Experimental Procedure:
Prior to beginning the experiment, all apparatus was confirmed to be completely dry.
Part 1:
Magnesium turnings ( 0.6 g ) were taken in 100 ml round bottom flask. Sodium dried ether ( 10 ml )
was added to the flask. A reflux condenser was set up, and the round bottom flask was placed in
an Aluminium heating block which in turn was placed on a hot plate.
Bromobenzene ( 4 g; 2.7 ml; 0.025 mol ) was collected from a stock bottle and approximately 1 ml
was added down the condenser to the reaction flask. No sign of reaction was noted. The
apparatus was disassembled and the Magnesium turnings were vigorously stirred using a glass
rod to break the oxide film that had formed due to exposure of the metal to oxygen in the air.

The solution soon turned cloudy white, confirming the start of the reaction. The apparatus was
reassembled. (Care was taken to reduce the amount of time ether came in direct contact with the
air due to its tendency to form hydroperoxides when reacting with oxygen.) The reaction that
transpired was an exothermic reaction. No other heat source was required to facilitate the forward
reaction. An additional volume of ether (10 ml) followed by the remainder of the bromobenzene (~
1.7 ml) was added down the condenser.
When the reaction no longer boils without supplementary heating, the hot plate was switched on
and the products formed meant to reflux to enable appropriate mixing for 15 minutes. Since ether
boils at 34.5o C care was taken to reflux at ~ 40oC as excessive heat can either decompose the
product or form undesirable /side products.
Part 2:
To phenyl magnesium bromide, in the round bottom flask, methyl benzoate ( 3.3 g ; 3 ml ; 0.024
mol ) in ether ( 10 ml ) was added down the condenser in such a manner as to maintain a gentle
reflux. An exothermic reaction took place. A complication ( fire alarm ) caused us to a deficit of
time, hence further refluxing was not done and the contents of the flask having turned into a thick
suspension were brought back into solution by adding excess ether ( ~ 3 ml ) and then cooled in an
ice bath.
The resultant solution was poured into a conical flask containing sulphuric acid ( 10% ; 25 ml ) to
hydrolyse the salts and form triphenylmethanol (impure). The solution was then separated in a
separating funnel, with the clear light yellowish-green layer of product dissolved in ether collected
on top and the water below. The layer of ether was washed with saturated sodium chloride solution
( 2 x 10 ml ) to make the separation more efficient by drawing the polar water molecules into the
lower layer.
The product collected, was further dried by the addition of MgSO4 ( 2 g ) and then purified by
recrystallisation from a mixture of ethyl acetate and hexane. The crystals obtained were initially
yellow. On addition of hexane turned white.
The percentage yield was calculated, however the determination of the melting point was cut short
o

due to a shortage of time. It was noted however that the product had not melted at 120 C.

Results:
Amount of triphenyl methanol obtained post recrystallisation = 1.37 g
Molecular weight of triphenyl methanol = 260.33 g/mol
No. of moles of product ( Actual yield ) = 1.37 / 260.33 = 5.26 x 10-3 moles.
Theoretical yield.
No. of moles of bromobenzene reacting = 4 [g] / 157.0069 [g/mol] = 0.025 moles.
No. of moles of methyl benzoate used = 3.3 [g] / 136.15 [g/mol] = 0.024 moles.

Since 2 moles of bromobenzene reacts with one mole of methyl benzoate stoichiometrically,
bromobenzene is the limiting factor.
Therefore, theoretical yield of triphenyl methanol = 0.0125 moles = 12.5 x 10-3 moles
Percentage yield = (Actual / Theoretical) x 100 = 42.08 %
Melting point of triphenyl methanol = 164.2 C. (Literary reference : Jean-Claude Bradley Open
Melting Point Dataset obtained from the RSC website at http://www.chemspider.com/ChemicalStructure.6215.html)

Discussion:
From the results section, a relatively low percentage yield (42.8 %) was noted. This is most
probably due to the fact that efficient mixing of the reactants was not possible due to insufficient
refluxing, This can be attributed to the delay (fire alarm) during the day of the experiment.
Whilst forming the organometallic reagent, phenyl magnesium bromide, care was taken to ensure
all apparatus coming in contact with the the Grignard reagent was thoroughly dried.The partial
negative charge on the carbon atom that bonded to magnesium exhibits a very basic property. The
water molecule destroys the nucleophilic property of Grignard reagent. This is why several
precaution steps are taken in the procedure to avoid the Grignard reagent reacting with water [Fig.
(4) ]

Fig. 4: Reaction of Grignard reagent with water

On reaction with water it will decompose to form benzene and Mg(OH)Br.
Additionally, whilst preparing the phenyl magnesium bromide, care was taken to seal the reflux
condenser well and reduce the amount of time the reaction solution came in contact with oxygen in
the air. Grignard reagents react with oxygen to form hydroperoxides, thus highly unstable when
exposed to the air. Vapours from the highly volatile solvent (ether) help to prevent oxygen from
reaching the reaction solution.
Another reason why ether is a good solvent to perform this reaction in is because the oxygen
atoms on the ether molecule coordinate with the Mg metal in the Grignard Reagent to stabilise it
as depicted in Fig. (5)

Fig. (5): Ether molecules forming a coordinate complex and stabilising the Grignards Reagent.
Lastly, the addition of NaCl to the separating funnel is done due to its high ionic strength. Water is a
very polar molecule, therefore due to ionic interaction with NaCl, it gets drawn out of the organic
solvent and hence is beneficial for separation of moisture from the organic layer.

Conclusion:
Overall, the reaction was a success. 42.08 % was the percentage yield. The low yield can be
accounted for by the lack of sufficient reflux done due to the circumstantial shortage of time ( fire
alarm ).
In terms of techniques used, clarity was obtained on the theory of the reflex condenser and
separating funnel.
Precautions were taken to keep all apparatus away from water and also from excess heat due to
the flammable nature of diethyl ether.
Lastly, synthesis of the Grignard reagent was practiced and practically understood, one of the most
synthetically useful and versatile classes of reagents available to the organic chemist.