SIC2019

LAB REPORT EXPERIMENT 2: PREPARATION OF

TRIPHENYLCARBINOL VIA GRIGNARD REACTION

PREPARED FOR: DR CHENG SIT FOON

NAME SUMAYYAH BINTI LOKMAN

MATRIC NO. 22003285/1

SESSION 2023/2024

SEMESTER 1

OCCURANCE 2
TITLE:
Preparation of triphenylcarbinol via Grignard reaction
INTRODUCTION
Triphenylcarbinol or triphenylmethanol can be synthesised by Grignard reaction. The addition
of organomagnesium halide (Grignard reagent) to a ketone or aldehyde will form tertiary or
secondary alcohol respectively while reaction with formaldehyde leads to a primary alcohol.
On the other hand, the addition of an excess Grignard reagent to an ester or lactone will give
tertiary alcohol which the two alkyl groups are the same and a reaction of Grignard reagent
with nitrile produces unsymmetrical ketone via metalloimine intermediate. In this experiment,
Grignard reagent reacts with an ester which is methyl benzoate to produce triphenylcarbinol;
a tertiary alcohol.

OBJECTIVE:
1) To synthesis a Grignard reagent
2) To prepare triphenylcarbinol using Grignard reaction

PROCEDURE
Part A: Preparation of Grignard Reagent
1. About 1.4 g of Magnesium turnings and about 10 mL sodium-dried ether are placed
in a dry 250 mL two-neck flask fitted with a 50 mL dropping funnel and a reflux
condenser.
2. A drying tube filled with Calcium Chloride is placed at the top of the condenser.
3. A mixture of 6.2 mL of bromobenzene and 30 mL dry ether are placed into the
dropping funnel.
4. A small amount of the mixture (about 5 mL) is released slowly into the reaction flask
and the flask is shaken gently.
5. One or two iodine crystals are added as catalyst to initiate the reaction.
6. If the reaction does not start after 2-3 minutes where iodine colour disappears, cloudy
solution is formed and the ether solution starts to boils, the reaction flask is warmed
gently using water bath until the reaction starts on its own.
7. If the reaction still does not start, ultrasonic is used or 1 mL of Grignard reagent is
added.
8. When the reaction starts, the rest of bromobenzene mixture is added into the
reaction flask slowly to avoid vigorous reaction.
9. When the addition is completed, the solution is refluxed on water bath for 15 minutes.
10. The reaction mixture is cooled to room temperature.
Part B: Grignard reaction
1. 3.5 g of methyl benzoate in 10 mL dry ether is added to the Grignard solution via the
dropping funnel at slow rate.
2. The flask is shaken gently to ensure the mixture mix thoroughly.
3. The mixture is refluxed on water bath for 10-15 minutes after the addition is
completed.
4. The reaction mixture is cooled in an ice bath.
5. 30 mL of 10% aqueous sulfuric acid is added to a beaker containing 74 g cracked
ice.
6. The cooled reaction mixture is poured slowly into the mixture of cracked ice and
aqueous sulfuric acid.
7. The mixture is stirred until all solid has dissolved.
8. Additional ether may be added if the amount is insufficient to dissolve all the product.
9. The ether layer is transferred into a separating funnel and the aqueous layer is
removed.
10. The organic layer is washed with 15 mL 10% aqueous sulfuric acid, 12 mL water and
1g sodium bisulphite in 12 mL water sequentially and remove the aqueous layer from
the separating funnel.
11. The organic layer is transferred into a dry conical flask and anhydrous Na2SO4.
12. The dried organic layer is filtered into a dry conical flask and 15 mL of petroleum
ether (60-80℃) is added to the solution.
13. The solution is concentrated gently on a steam bath until triphenylcarbinol precipitate
out.
14. The mixture is left to cool to room temperature.
15. The flask is placed into an ice bath to maximize precipitation of triphenylcarbinol
solid.
16. The crude product of triphenylcarbinol solid is recrystallised with methylated sprits
17. The recrystallised triphenylcarbinol is collected using suction filtration and washed
using cold methylated spirits.
18. The dried crystals are weighed, the melting point is taken and the total yield of
triphenylcarbinol is obtained.

Reaction scheme:
RESULTS AND CALCULATIONS

Compound Volume Density Mass (g) Molecular Moles

(mL) (g/mL) mass (mol)
(g/mol)
- - 1.45 24.31 0.0596
Magnesium
6.2 1.491 9.2 157.01 0.0586
Bromobenzene

Methyl 3.2 1.094 3.5 136.15 0.0257

benzoate

Table 1: Amount of reactant used

Limiting reagent = methyl benzoate

0.0257 mol methyl benzoate = 0.0257 mol triphenylcarbinol

Theoretical yield

Molecular mass triphenylcarbinol= 260.33 g/mol

Mass of triphenylcarbinol = 0.0257 mol × 260.33 g/mol
= 6.69 g

Actual yield

Mass of triphenylcarbinol obtained= 2.21 g

2.21 𝑔
Percentage yield = × 100%
6.69 𝑔
= 33.03 %

Melting point of compound (triphenylcarbinol) obtained = 162-163℃

Compound Melting point (℃) colour

Theoretical triphenylcarbinol 161-164 Milky white

Experimental 162-163 Milky white/ off white

triphenylcarbinol

Table 2: Comparison theoretical and actual data

DISCUSSION
This experiment consists of two part which is preparation of Grignard reagent and
synthesis of triphenylcarbinol via Grignard reaction. In the first part of the experiment,
it is required to make sure the apparatus is dry because the Grignard reagent will
readily react with protic solvents such as water or functional groups with acidic protons
like alcohol and amines. Therefore, if atmospheric water is present, it will not react with
methyl benzoate and the product; triphenylcarbinol yield will decrease. In order to
prevent such situation, extra precautions should be made which is to dry the glassware
inside the oven before use, use calcium chloride drying tube and also use cotton wool
to cover the end of the two-neck flask. Calcium chloride is highly hygroscopic.
Therefore, it is used to absorb moisture from the air and preventing it from entering the
reaction flask. It is not encouraged to use glass stopper to cover the end of the flask
as the built-up pressure can cause it to explode when heated. Iodine is used in this
step as an indicator. Change of iodine colour from dark brown to colourless indicate
the magnesium is activated. In addition, iodine also acts as an activator. Iodine helps
to remove the oxidised surface on the magnesium which is MgO in order for
magnesium to react with bromobenzene. This reaction is exothermic so the flask will
be warm when the reaction occurred.

For the second part which is the preparation of triphenylcarbinol via Grignard reaction,
the sulfuric acid is used to react with the anion and unreacted magnesium. As this
reaction is exothermic, the ice is used to absorb the heat. The anion is protonated in
order to obtain neutral organic alcohol product which will appear as the organic ether
layer. As the magnesium salt is ionic, it should partition into the aqueous layer. The
aqueous layer is discarded from the bottom of the separating funnel and the organic
layer is removed from the upper part of separating funnel to avoid mixing with the
aqueous layer. Anhydrous sodium sulphate is then added to the organic layer to
absorb any water present in the solution and forms sodium sulphate hydrate. The
addition of anhydrous sodium sulphate is stopped when the sodium sulphate stopped
clumping up indicating all the water in the solution has reacted. After that, the solution
is filtered using cotton wool to trap the solid sodium sulphate. The solution is then put
on a steam bath. In this process, the solvent is evaporated and the solution is
concentrated to make crystallisation process easier. The concentrated solution is then
put in an ice bath to maximise crystallisation. Recrystallisation is a process to purify
solid compound. Before recrystallisation, the compound is yellowish in colour but after
recrystallisation, the compound is milky white/ off white and shiny. The solvent used
for recrystallisation process is methylated spirit. It is chosen as the solvent as the
compound dissolve in methylated spirit at high temperature but does not dissolve at
low temperature.

The yield of the compound is low probably because of the magnesium does not fully
reacted in the first part to produce Grignard reagent. However, the reaction is
proceeded due to lack of time. Therefore, less Grignard reagent is obtained to react
with methyl benzoate to produce triphenylcarbinol. Secondly, there is also a possibility
of atmospheric water or oxygen entering the reaction flask and protonate the Grignard
reagent during the drying tube is removed to add solvents and other reagent and
decrease the reactivity of Grignard reagent and lead to low yield of triphenylcarbinol.
Some products are also lost during recrystallisation process and suction filtration due
to the product being stuck on the filter paper.

CONCLUSION
The product which is triphenylcarbinol is obtained successfully via Grignard reagent
with yield 2.21 g and melting point of 161-164℃. The product is milky white/ off white
in colour which matched the theoretical physical properties.

SAFETY PRECAUTIONS

1. Keep the apparatus dry to avoid Grignard reagent being protonated.

2. Do the experiment in fume cupboard.
3. Discard the chemicals in appropriate waste bottle.
4. Avoid shaking the separating funnel too strongly to avoid excessive pressure.
5. Wash hands before leaving the lab.

REFERENCES
Chemistry 211 Experiment 2. (n.d.). http://home.miracosta.edu/dlr/211exp2.htm

Experiment 12 Grignard Reaction; Preparation of Triphenylcarbinol. (n.d.). Retrieved

November 26, 2023, from https://myweb.liu.edu/~nmatsuna/che122/exp12.pdf

Grignard Reaction. (n.d.). https://www.organic-chemistry.org/namedreactions/grignard-

reaction.shtm#:~:text=Grignard%20Reagents,leads%20to%20a%20primary%20alcoh

ol.

Grignard Reaction: Synthesis of Triphenylmethanol. (n.d.). Retrieved November 26, 2023,

from

https://www.cerritos.edu/chemistry/chem_212/Documents/Lab/4_GrignardReaction.p

df

Grignard Synthesis of Triphenylmethanol. (n.d.). Retrieved November 26, 2023, from

https://web.mnstate.edu/jasperse/chem365/grignard.pdf