CHE2623 Experiment 2

May 12, 2024

Directive effect when brominating Vanillin.

Christell Stoltz
Student no: 67952259

Lab partner: Audrey Choshi (45123446)

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1 Objective
The aim of this experiment was to brominate Vanillin and determine whether
the substituents are meta or ortho-para directing.

2 Introduction
Vanillin is an aromatic compound with a mehoxyl, and two hydroxyl sub-
stituents. The methoxyl (-OCH3 ) and hydroxyl (-OH) groups are activating
groups due to their unshared pairs of electrons, the resonance effect of the
unshared electrons direct the incoming electrophile towards the ortho-para
positions. The second methoxyl (-CHO) group is a deactivating group and
withdraws electrons away from the ring leaving the ortho-para positions with
a positive charge and directing the incoming electrophile to the meta posi-
tions [2].
Brominating the aromatic compound with Hydrobromic acid in the pres-
ence of Potassium bromate and acetic acid produced the Bromine ions insitu,
to reduce the risk that toxic liquid bromine poses.

3 Reaction Mechanism

Figure 1: The resonance mechanism for ortho-para directing groups.

Figure 2: The resonance mechanism for meta directing groups.

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 Figure 3: The reaction mechanism for the bromination of Vanillin.

4 Experimental Method
1.52g of Vanillin and 0.75g of Potassium bromate was weighed into an Erlen-
meyer flask. The flask was moved to the fumehood and 20mL of Acetic acid
and 2mL of 48% of Hydrobromic acid was added. The reaction was stirred
for 45 minutes and then 150mL of cold water was added. The reaction was
allowed to stir for a further 20 minutes. 10% Sodium Thiosulfate solution
was added until the orange colour turned yellow. The crystals that precip-
itated was filtered and then dissolved in Ethanol-water while heating. The
product was recrystallized by cooling the mixture.

5 Results
The melting point range obtained from the products were 167.2°C - 170.2°C.
The average melting point was 168.7°C.
The percentage yield can be calculated by considering the balance equa-
tion and determining the limiting reagent.

3C8 H8 O3 + CH3 COOH + HBr + KBrO3 →

3C8 H7 BrO3 + C2 H3 O2 K + 3H2 O
m
n= (1)
M
The formula used to calculate moles(n) using the mass (m) and molar mass
(M) (Eq.1).

m=p×V (2)

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The formula used to convert the volume (V) of a reagent to a mass (m) using
the density (p) in g/cm3 . The density of Acetic acid is 1.049g/cm3 and of
48% Hydrobromic acid is 1.49g/cm3 (Eq. 2).

Figure 4: A table to compare the moles of each chemical present that can
react.

According to the table above (Fig.?? Potassium bromate is the limiting

reagent. The moles of Potassium bromate is proportional to 3 moles of
5-Bromovanillin theoretically produced thus 0.013 moles can be produced.
Using Eq.1 to calculate the theoretical yield = 2.05g 5-Bromovanillin.
The actual yield was found to be = 1.9482g 5-Bromovanillin.

Actual yield(g)
% yield = × 100 (3)
T heoretical yield(g)
According to Eq. 3 the % yield = 95%.

6 Discussion
The average melting point (168.7°C) of the products obtained correspond to
the melting point of 5-Bromovanillin or m-Bromovanillin (166.0°C) the 8.7°C
difference can be due to a negligible amount of impurities still present in the
product.
The %yield at 95% is high and acceptable for the synthesis of a organic
compound. Loss in yield can be due to the transfer of the product to a
watch-glass for drying.

7 Conclusion
The objective of this experiment was achieved by confirming that the meta-
directing aldehyde substituent of Vanillin dominates to form 5-Bromovanillin.
The aldehyde blocks the ortho-para positions by withdrawing electron den-
sity.

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8 Answers to Questions
2) The reaction turned a bright orange color and a precipitate formed.
3) Hydrobromic acid was added in excess and the Sodium thiosulfate
neutralises the Hydrobromic acid to eliminate it as an impurity.
4) No organic solvents were used and an operative utilization of the Hy-
drobtomic acid byproduct leads to zero organic waste.
5)

7) To synthesise Vanillin commercially from guaiacol it needs to react

with glyoxylic acid. Starting with condensation promoted by a base and
followed by catalyzed oxidative decarboxylation of the vanillylmandelic acid
to vanillin at a temperature of 80–130°C. The reaction mechanism sourced
from [1] is as follows:

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References
[1] Dr. Rosaria Ciriminna et al. “Vanillin: The Case for Greener Production
Driven by Sustainability Megatrend”. In: National Library of Medicine
(2019). url: https : / / www . ncbi . nlm . nih . gov / pmc / articles /
PMC6547943/#: ~ :text=The%20latter%20acid%20and%20guaiacol,
of%2080%E2%80%93130%20%C2%B0C..

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[2] An Explanation of Substituent Effects. [Online; accessed 2023-07-13].
2022.