Objective

 To investigate the reaction of vanillin with acetic anhydride under two condition, basic and
acidic condition
 To identify the melting point of the product

Introduction

Vanillin is a phenolic aldehyde, an organic compound with the molecular formula

C8H8O3. Vanillin is an organic crystal that forms outside the vanillin bean and the extraction
of naturally occurring vanillin is not only expensive but highly inefficient. Although the
chemical structure of synthetically produced vanillin are identical, it is cheap and alternative
for the real thing. The functional group in this molecule is ether, aldehyde and phenol.
Synthesis vanillin was used in food flavouring agent.

Carboxylic acids react with alcohols to form esters through a condensation reaction
which is known as esterification. Fischer esterification proceed very slowly in absence of
strong acids, but they still reach the equilibrium when an acid and an alcohol are refluxed
with a small amount of concentrated sulphuric acid and sodium hydroxide. Ester synthesis
also can be accomplished by the reaction of an alcohol with an anhydride. By using
anhydride, we do not used strong acid because strong acid may cause side effect reaction.
Esters undergo saponification which refluxing an ester with aqueous sodium hydroxide
which produces an acetate.
Apparatus

250mL conical flask

Stopper

Small Buchner funnel

Hot water bath

125mL conical flask

Magnetic stirrer

Ice water bath

Chemicals

Vanillin

10% NaOH solution

Crushed ice

Acetic anhydride

Ice-cold water

95% ethanol

CDCL3
Procedure

Acidic condition:

i. 1.5g of vanillin was added into a conical flask containing 10mL of acetic anhydride.
ii. 10 drops of 1.0M H2SO4 was added slowly into the solution with stirring.
iii. The mixture then was stirred for 1 hour by using magnetic stirrer at room
temperature.
iv. After the stirring was done, the mixture was placed in cool ice bath for about4
minutes.
v. 35mL of ice cold water was added into the mixture, and was shaken to induce the
crystallization.
vi. The mixture was filtered by using Buchner funnel to collect the crystal.
vii. The crystal was washed with 3 portions of 5mL ice cold water.
viii. For recrystallization, 15mL warm ethanol (below 60°C) was added with the crystal
collected from the filtration until it dissolved.
ix. The mixture was put in ice bath to initiate the recrystallization.
x. The mixture was filtered again until dry crystal was obtained.
xi. The weight of product was recorded and the melting point, NMR and also IR spectra
were determined.

2. Basic condition:

i. 1.5g of vanillin was added into a conical flask with 25mL of 10% NaOH solution.
ii. 4mL of acetic anhydride and 30g of crushed ice were added into the solution.
iii. The mixture was shaken for 20minutes and cloudy, milky white precipitate will form.
iv. The mixture then was filtered by using Buchner funnel with washing of 3portions of
5mL ice-cold water.
v. For recrystallization, 15mL warm ethanol (below 60°C) was added with the crystal
collected from the filtration until it dissolved.
vi. The mixture was put in ice bath to initiate the recrystallization.
vii. The mixture was filtered again until dry crystal was obtained.
viii. The weight of product was recorded and the melting point, NMR and also IR spectra
were determined.
Result and Observation

Basic condition Acid condition

Mass of vanillin (g) 1.5002 1.5006
Mass of beaker (g) 35.0320 35.0405
Mass of beaker + crystal (g) 37.1664 37.4968
Mass of crystal (g) 2.1334 2.4563
Melting point of crystal 78°C 92°C

Calculation

Mass of vanillin = 1.5006g

Molar mass of vanillin = 152g/mol

Mol of vanilin = 1.5006g / 152g/mol = 0.009872mol

Molar mass of vanillin in acid condition = 296.275g/mol

Molar mass of vanillin acetate = 194.186g/mol

Theoretical yield of acidic condition = 296.275g/mol × 0.009872mol= 2.9248g

Percentage yield in acidic condition = 2.4563 × 100% = 83.98%

2.9248

Theoretical yield of basic condition = 194.186g/mol × 0.009872mol= 1.917g

Percentage yield in basic condition = 2.1334 × 100%= 111.28%

1.917
Discussion
In this experiment, reaction of vanillin with acetic anhydride had been done in acid
and basic condition. The percentage yield for acid condition is 83.98% and for basic
condition is 111.28%. The loss of the mass of the product may occur during the filtration
done by using the Buchner funnel and some of it may be left in the container during the
transfer into the Buchner funnel set. In order to get the higher mass of the product, the
process of adding solution must be done slowly and always stir the solution. The person
incharge also must make sure that the solid that want to dissolve must be completely
dissolve before proceeding to the next step.

The melting point test was done by using the melting point apparatus. The melting
point of both products that was done under acidic and basic condition lies in the range of the
theoretical melting point by references which is under acidic condition is between 90-91°C
while under basic condition is between 77-79°C. The melting obtained from the experiment
for acid condition is 92°C and for basic condition is 78°C.

From the FTIR test, 5 peaks were obtained in acid condition which is at 1752.68cm1,
1369.52 cm-1, 1199.80 cm-1, 1160.41 cm-1 and 1014.03 cm-1. Some peaks were also
obtained in basic condition. The result obtained showed that both of the products have the
same several functional groups. The functional groups are C=O bond from aldehyde and
ester that lies between 1670-1760cm-1. The C-O bond of ester appears at wavenumber that
lie between 1090-1400cm-1. Both of these functional groups have a sharp shape of peak.
Weak shape of peaks appears in several at 1500, 1600cm-1 that indicate the C=C bond in
aromatic ring. The medium shape of peak indicated in both of the compounds is the C-H
bond for aromatic ring and it appears in a very small and not strong peak in the spectrum.
C=C bond in aromatic and C-H bond for aromatic ring did not appear in IR spectrum for acid
condition. This might due to error while doing the esterification of vanillin in acid condition
and the pellet that had been made are too thick or too thin.

The structures of the products were tested by using the Nuclear Magnetic
Resonance. The peaks are not separated well, so that adjustment must be done to know the
exact number of hydrogen at a certain signal. The higher the concentration of the signal, the
lesser the electron density around it. Both of them used to have the benzene ring with 3
hydrogen atoms around, that appear around 7ppm in the spectra. For the product under
basic condition, it should has 2 same signals that are 3H, singlet that lie at different
concentration.The first signal with less concentration has high electron density than
the second signal that move to the lowfield of the spectrum.
Question
1. Under different reaction media, vanillin undergoes esterification with acetyl chloride
yielding two different products.

Basic or
+
?
acidic medium

a) Based on the IR spectrum of vanillin at what range should you observe the
absorption signal of the hydroxyl group?
At 3590-3650cm-1 and 3200-3550cm-1

b) Based on its 1H NMR spectrum, what is the expected chemical shift value for the
methoxy group (OCH3)? What is its multiplicity?

c) Draw the structure of the major products for the esterification of vanillin with acetyl
chloride in:
i. 10% NaOH solution

ii. 1.0 M H2SO4 solution

2. Write the mechanism for the reaction between vanillin and acetyl chloride in 10% NaOH
solution.

Conclusion

In conclusion, we can study the reaction of vanillin with acetic anhydride under basic and
acidic condition. We also can identify the percentage yield of product which is in acid 83.98%
and basic 111.28%

References

Idayu Razali. Esterification Reaction of Vanillin. [Online]

http://www.academia.edu/11982344/Esterification_reactions_of_vanilin (accessed on Oct
23, 2018)
Amirul Azhar. Esterification Reaction of Vanillin (The use of NMR and IR Spectroscopy to
Determine the Structure). [Online] Dec 06 2014.
https://www.scribd.com/doc/249342029/ESTERIFICATION-REACTION-OF-VANILIN-THE-
USE-OF-NUCLEAR-MAGNETIC-RESONANCE-AND-INFRARED-SPECTROSCOPY-TO-
DETERMINE-THE-STRUCTURE (accessed on Oct 23, 2018)