EXPERIMENT 3

ESTERIFICATION REACTIONS OF VANILLIN: THE USE OF NMR TO

DETERMINE A STRUCTURE
INTRODUCTION

Vanillin (4-hydroxy-3-methoxybenzaldehyde) is a phenolic aldehyde. It is an organic

compound with molecular formula C8H8O3. Vanillin is used widely as a flavouring additive
for cooking, beverages, perfumes, candles and many more. The functional group in vanillin is
aldehyde, phenol and ether. The structure of vanillin is

The product of reaction between vanillin and acetic anhydride under acidic and basic
condition will give different product. The product that is isolated has different melting point
and different spectra. The product will be determined by using NMR and FTIR spectrum. In
this experiment, the acid used is sulphuric acid and sodium hydroxide as a base.

OBJECTIVE

1. To investigate the esterification reaction between vanillin and acetic anhydride under
two condition, basic and acidic conditions.
2. To measure the melting points, obtain NMR and IR spectra.

CHEMICALS

1. 1.5g of Vanillin
2. 10 ml acetic acid
3. 10 drops 1.0M Sulphuric acid
4. Ice cold water
5. 15 ml warm ethanol
6. 25 ml of 10% Sodium hydroxide solution
7. 4 ml acetic anhydride
8. 30g of crushed ice
APPARATUS

1. 100ml beaker
2. Magnetic stirrer
3. Buchner funnel
4. Measuring cylinder
5. Conical flask

PROCEDURE

Acidic condition:

1. 1.5g of vanillin was added into a conical flask containing 10 ml of acetic acid.
2. 10 drops of 1.0M H2SO4 was added slowly into the solution with stirring.
3. The mixture the was stirred for 1 hour by using magnetic stirrer at room temperature.
4. After the stirring was done, the mixture was placed in cool ice bath for about 4
minutes.
5. 35 ml of ice-cold water was added into the mixture and was shaken to induce the
crystallization.
6. The mixture was filtered by using Buchner funnel to collect the crystal.
7. The crystal was washed with 3 portions of 5 ml ice cold water.
8. For recrystallization, 15ml warm ethanol (below 60 ºC) was added with the crystal
collected from the filtration until it dissolved.
9. The mixture was put in ice bath to initiate the recrystallization.
10. The mixture was filtered again until dry crystal was obtained.
11. The weight of the product was recorded, and the melting point, NMR and IR spectra
were tested.

Basic Condition:

1. 1.5g of vanillin was added into a conical flask with 25ml of 10% NaOH solution.
2. 4ml of acetic anhydride and 30g of crushed ice were added into the solution.
3. The mixture was shaken 20 minutes and cloudy, milky white precipitate will form.
4. The mixture then was filtered by using Buchner funnel with washing of 3 portions of
5ml ice-cold water.
 5. For recrystallization, 15ml warm ethanol (below 60 ºC) was added with the crystal
collected from the filtration until it dissolved.
6. The mixture was put in ice bath to initiate the recrystallization.
7. The mixture was filtered again until dry crystal was obtained.
8. The weight of the product was recorded, and the melting, NMR and IR spectra were
tested.

RESULT AND OBSERVATIONS:

i. Fourier Transform Infrared result:

Bond Theoretical Experimental wavenumber, cm-1

wavenumber, cm-1
Acidic Basic
C=O (aldehyde, ester) 1760-1670 (s) 1771.41 1758.07
C-O (ester) 1400-1090 (s) 1369.63 1396.28
C=C (aromatic) 1600,1500 (w-several) 1611.11,1522.87 1599.18,1508.16
C-H (aromatic) 3100-3000 (m) 3018.41
*(b)-broad peak, (s)-sharp peak, (w)-weak.

ii. Nuclear Magnetic Resonance result:

1. Acidic condition

Signal Concentration, ppm

1H, singlet 7.69
3H, singlet (benzene) 7.16
3H, singlet 3.88
9H, singlet 2.1-2.4

2. Basic condition
Signal Concentration, ppm
1H, singlet 10.01
3H, singlet (benzene) 7.3-7.6
3H, singlet 3.96
3H, singlet 2.41
 iii. Observation
1. Acidic condition
 Colour change from colourless to brick red after the addition of 1.0M
of H2SO4 (10drops).
 The brick red colour turns to milky white after the addition of 35mL of ice
cold
water.
 The solid become shiny after the recrystallization process with
warm 95% ethanol.
2. Basic condition
 Reaction between 1.5g vanillin with 25mL of 10% NaOH
produce yellow solution.
 Yellow solution turns to milky white mixture after the addition of 4mL
acetic
anhydride and 30g crushed ice.
 The solid become shiny after the recrystallization process with
warm 95% ethanol.

CALCULATION

Mass of vanillin = 1.5g

Molar mass of vanillin = 152g/mol

Molar mass of vanillin acetate (product) = 194g/mol

Mol of vanilin =

= 0.009868mol

Volume of acetic anhydride = 4mL = 4cm3

Density of acetic anhydride = 1.08g/cm3

Mass of acetic anhydride = 1.08g/cm3 × 4cm3

= 4.32g
Mol of acetic anhydride =

= 0.04235mol

Limiting reactant: vanillin.

Mass of product (acidic condition) = 2.2139g

Mass of product (basic condition) = 1.4761g

Melting point of product (acidic condition) = 94°C

Melting point of product (basic condition) = 79°C

Percentage yield = (actual / theoretical) × 100%

Theoretical yield of acidic condition = 296g/mol × 0.009868mol = 2.9211g

Percentage yield in acidic condition = 2.2139/2.9211 × 100% = 75.78%

Theoretical yield of basic condition = 194g/mol × 0.009868mol = 1.9145g

Percentage yield in basic condition = 1.4761/1.9145 × 100% = 77.10%

DISCUSSION
In this experiment, we performed the reactions between vanillin and acetic anhydride
under two conditions, which were basic and acidic conditions. We conducted the reaction
under acidic condition first because the reaction took 1 hour of stirring. While waiting for the
reaction to stir, we proceed to the reaction under basic condition.
The melting point was done by using the melting apparatus. The theoretical melting
o
point of product for acidic condition is between 90-91 C while for the basic condition is
o
between 77-79 C. The melting point that we get in the experiment is in the acidic condition
o o
is 94 C and for the basic condition is 79 C. Thus, it’s proven that the melting point for the
compound in the acidic and basic condition follow the theoretical melting point. The
percentage yield both of under acidic condition and basic condition lies above 70% of the
theoretical yield.
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. This is because the filter was tear off little bit that make the compound
when filter is loss. In order to get the higher mass of product, the process of adding solution
must be done slowly and always stir the solution so that the filter paper won’t tear off. We
also must make sure that the solid that want to dissolve must be completely dissolve before
proceeding to the next step.
The result obtained from the FTIR test showed that both products have the same
several functional groups. The functional groups are C=O bond from aldehyde and ester
-1
that lies between 1670-1760cm wavenumber. The C-O bond of ester appears at
-1
wavenumber that lie between 1090-1400cm . Both functional groups have a sharp shape
-1
of peak. Weak shape of peaks appears in several at 1500, 1600cm wavenumber that
indicate the C=C bond in aromatic ring. The medium shape of peak indicated in both
compounds is the C-H bond for aromatic ring and it appears in a very small and not strong
peak in the spectrum.
The structures of the products were tested by using the Nuclear Magnetic Resonance
(NMR). Some of the peaks are not separated well, so that adjustment must be done to know
the exact number of hydrogens at a certain signal. We all know that, the higher the
concentration of the signal, the lesser the electron density around it. Both 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 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 low field of the spectrum. The product that we got at
the end of the experiment was 4-acetyloxy-3-methoxyphenyl methanediyl diacetate under
acidic condition while the product under basic condition was 4-formylphenyl acetate.

CONCLUSION
We able to perform the experiment successfully. The percentage yield under acidic
condition is 75.78% while the percentage yield in basic condition is 77.10%. The melting
point of product under acidic condition is 94°C and the melting point of product under basic
condition is 79°C. Both products show the functional groups of ester and aldehyde from the
result of FTIR and from the NMR result. The product that we got at the end of the
experiment was 4-acetyloxy-3-methoxyphenyl methanediyl diacetate under acidic condition
while the product under basic condition was 4-formylphenyl acetate
REFERENCES
1. Acetic anhydride. (n.d.). Retrieved May 25, 2019, from
http://en.m.wikipedia.org/wiki/acetic_anhydride
2. Acetic anhydride. (n.d.). National Library of Medicine National Center for
Biotechnology Information Retrieved May 30, 2019, from
https://pubchem.ncbi.nlm.nih.gov/compound/UN1715U.S.
3. Www.d.umn.edu. (n.d.). Retrieved May 25, 2019, from
http://www.d.umn.edu/chemistry/faculty/carlson/downloads/Handouts/Corrected_My
stery_Experiments.pdf