UNIVERSITI TEKNOLOGI MARA (UiTM) ORGANIC CHEMISTRY (CHM557)

SEMESTER 20224
OCTOBER 2022 - FEBRUARY 2023

EXPERIMENT 3:
Esterification Reactions of Vanillin

NAME : AHMAD ZAKWAN BIN KASSIM

STUDENT ID : 2021886994
GROUP : AS2533A2
DATE : 08 NOVEMBER 2022

Objective (1M)

Introduction (2M)

Procedure in flowchart (2M)

Calculation (5M)

Discussion (3M)

Conclusion (1M)

Questions (6M)

TOTAL

OCT2022-FEB2023
 OBJECTIVE
1. To synthesize esterification products of vanillin with acetic anhydride under basic and
acidic conditions.
2. To determine the melting point of the esterification products of vanillin.
3. To characterize the esterification products of vanillin using IR and 1H NMR spectroscopy.

INTRODUCTION
Vanillin is a phenol aldehyde, with the molecular formula C 8H8O3. Aldehyde, hydroxyl and
ether are some of the functional groups. It is synthetic and made from petrochemical waste and
paper. C10H10O4 is the molecular formula of vanillyl acetate, a flavoring ingredient. The
simplest isolated carboxylic acid anhydride is acetic anhydride. It is a colorless liquid with a
strong acetic acid odor, the result of the interaction of acetic acid with moisture in the air.
Acetic anhydride is a flammable substance that causes skin irritation. Alcohol or carbon dioxide
foams are preferred for fire fighting due to their reaction with water. Acetic anhydride vapor is
extremely dangerous. Esterification is a chemical reaction that leads to the formation of an ester
as a reaction product. We used sodium hydroxide as the basic solution and sulfuric acid as the
acidic solution in this experiment. Under acidic and basic conditions, the reaction product
between vanillin and acetic anhydride will have different structures on IR and NMR spectra.
The chemical equation for esterification of vanillin under basic and acidic conditions is shown
below:
 PROCEDURE
A. BASIC CONDITION
a) Preparation of Product
1. Vanillin (1.50g) was dissolved in sodium hydroxide (10%, 25mL) in a
250mL. Erlenmeyer flask. A bright yellow green solution was
obtained.
2. Crushed ice (30g) and acetic anhydride (4.0mL) were added then. A
cloudy, milky white precipitate was formed immediately on adding
acetic anhydride.
3. The flask was stoppered with a clean PTFE stopper and it was shake
several times over a 20 minutes period.
4. The precipitate was filtered using a Hirsch funnel or a small Buchner
funnel and the solid was washed with ice-cold water (5mL). The
washing process was repeated three times with the ice-cold water
(5mL). For the setup of a filtration apparatus, figure 3.1 was referred.
5. The product (white solid) was transferred to the small beaker (50mL).
b) Recrystallization of the Product
1. The solid was recrystallized from 95% ethanol. 95% ethanol (15mL)
was transferred in a 100mL conical flask/beaker and the mixture was
heated in a hot plate at 60ºC.
2. The mixture was stirred and heated until the entire solid dissolves in
the boiling solution. More solvent (ethanol) was added slowly and the
heating was continued if there was still insoluble solid in your hot
mixture until it completely dissolve.
3. The mixture was cooled in room temperature for one minute and the
cooling was continued in an ice bath. Crystallization was induced by
scratched up and down the inside of the flask with a glass rod if no
crystals formed.
4. The crystals was filtered using a clean Buchner or Hirsch funnel under
reduced pressure (see Figure 3.1). All the crystals from the flask was
transferred to the funnel using a spatula at this stage. The crystals was
washed with a small amount of cold solvent (95% ethanol). The
crystals were allowed to dry by sucking air through them. The dried
crystals obtained were transferred into a weighed labelled sample
bottle. Melting point of the product was below 100ºC. The product was
not placed in oven to dry.
5. The melting point of the product (literature value is 77-79ºC) was
determined.
6. The IR and 1H NMR (in CDCl3) spectra of the product as well as IR
spectra for vanillin were determined.
B. ACIDIC CONDITION
a) Preparation of Product
1. Vanillin (1.50g) was dissolved in acetic anhydride (10mL) in a 250mL
Erlenmeyer flask.
2. A magnetic stir bar was placed in the flask and the mixture was stirred
at room temperature until the solid dissolves. The flask was stoppered
with PTFE stopper.
3. Sulfuric acid (1.0M, 10 drops) were added drop by drop to the reaction
mixture while continuing to stir the mixture.
4. The flask was stoppered with PTFE stopper and stirred at room
temperature for 1 hour. The solution turned purple or purple-orange in
colour during the period.
5. The flask was cooled in an ice-water bath for 4-5 minutes after 1 hour.
6. Ice-cold water (35mL) was added to the mixture in the flask. The
mixture turned to a pale light green in colour.
7. The flask was stoppered tightly with a clean PTFE stopper and the
flask was shake vigorously-almost hard as you can shake while holding
your thumb on the stopper.
8. The flask was continued to cool and shake to induce crystallization.
9. Crystallization has occurred when you can see small solid clumps
separated from the cloudy liquid and settling to the bottom of the flask.
10. The solid or crystal was filtered using a Hirsch funnel or a small
Buchner funnel and the solid was washed with ice-cold water (5mL).
The washing process was repeated three times with the ice-cold water
(5mL). For the setup of a filtration apparatus, Figure 3.1 was referred.
11. The product (white solid) was transferred to the small beaker (50mL).
b) Recrystallization of the Product
1. The solid from 95% ethanol was recrystallized. 95% ethanol (15mL)
was transferred in a 100mL conical flask/beaker and the mixture was
heated in a hot plate at 60ºC.
2. The mixture was stirred and heated until the entire solid dissolves in
the boiling solution. More solvent (ethanol) was added slowly and it
was continued to heat until completely dissolve if there is still insoluble
solid in your hot mixture.
3. The mixture was cooled in room temperature for one minute and it was
continued to cool in an ice bath containing a little bit of salt.
Crystallization can be induced by scratched up and down the inside of
the flask with a glass rod if no crystals formed.
4. The crystals were filtered using a clean Buchner or Hirsch funnel under
reduced pressure (see Figure 3.1). All the crystals were transferred
using a spatula from the flask to the funnel at this stage. The crystals
was washed with a small amount of cold solvent (95% ethanol). The
crystals was allowed to dry by sucking air through them. The dried
crystals obtained were transferred into a weighed labelled sample
bottle. Melting point of the product was below 100ºC. The product was
not placed in oven to dry.
5. The melting point of the product (literature value is 90-91ºC) was
determined.
6. The IR and 1H NMR (in CDCl3) spectra of the product as well as IR
spectra for vanillin were determined.
 RESULT
DATA
A. BASIC CONDITION
1. Weight of Product: 0.8898g
2. Melting Point of the Product: 80°C
3. Appearance of the product: White crystal solid form
4. IR data (in Table):
i. Vanillin

Wavenumber (cm-1) Type of Bond (Group)

3200-3600 O-H
1670-1760 C=O
1090-1400 C-O

ii. Product

Wavenumber (cm-1) Type of Bond (Group)

1599.6 C=C
1750.5 C=O
1209.6 C-O
2848.0 C-H

5. 1H NMR data of the Product (in Table)

Chemicals Multiplicity Number of Type of Proton

Shift, δ (ppm) Hydrogen
9.96 Singlet 1

2.36 Singlet 3

3.92 Singlet 3

7.40–7.60 Singlet 3
OBSERVATIONS

Steps Observations
Reaction of vanillin A bright yellow green solution obtained.
with 10% NaOH
Addition of acetic A cloudy, milky white precipitate formed.
anhydride
B. ACIDIC CONDITION
1. Weight of Product: 2.1584g
2. Melting Point of the Product: 90°C
3. Appearance of the product: White solid
4. IR data (in Table):
i. Vanillin

Wavenumber (cm-1) Type of Bond (Group)

3200-3600 O-H
1670-1760 C=O
1090-1400 C-O

ii. Product

Wavenumber (cm-1) Type of Bond (Group)

1522.6 C=C
1753.2 C=O
1200.2 C-O
2984.3 C-H

5. 1H NMR data of the Product (in Table)

Chemicals Multiplicity Number of Type of Proton

Shift, δ (ppm) Hydrogen
7.63 Singlet 1

3.84 Singlet 3

7.00-7.60 Singlet 3

2.0-2.5 Singlet 9
OBSERVATIONS

Steps Observations
In esterification of vanillin in The solution turns to purple orange after 1 hour.
the presence of acid
CALCULATION
A. BASIC CONDITION

B. ACIDIC CONDITION
 DISCUSSION
The percent yield of the pure product in this experiment 3 was 46.31% in the basic condition
and 73.33% in the acidic condition. Since the substance was lost when we moved it from filter
paper to the plastic bag during weighing process, the efficiency seems to be very low in the
basic condition. The melting points of the reactions for both basic and acidic conditions are
within the literature (base:80°C ; acid:90°C). Acetic anhydride acts as an electrophilic in the
base condition, subject to nucleophilic attack by alcohol when anhydride reacts with alcohol
under both acidic and basic conditions. Alcohol, ether and aldehyde functional groups are all
present in the vanillin molecule. Since esterification stops only at the ester, the base-catalyzed
reaction is a direct esterification reaction that yields no other significant products. Esters are not
the only result of acid-catalyzed esterification. It forms an ester, but since there are other
functional groups in the molecule that can react with the anhydride under basic or acidic
conditions, the ester continues to react. Under acidic conditions, vanillin reacts with acetic
anhydride to give vanillin triacetate, while under basic conditions vanillin gives vanillin acetate.
The formation of these products was verified by IR and NMR. NMR shows that the base
product is vanillin acetate and the acidic product is vanillin triacetate. The presence of
hydrogen under basic conditions is 9.96ppm, indicating that the substance produced is
composed of aldehydes. This value is absent in the acid product, indicating that the substance
formed does not contain an aldehyde group. The products of both reactions also show a peak in
the NMR spectrum at about 2.5ppm-2.1ppm indicating -OCH3 bonding. Both basic and acidic
have three hydrogen atoms at 7.6-7.0ppm. The presence of hydrogen with an aromatic ring was
demonstrated by these results.
The FTIR test results show that the two conditions have many functional groups in common.
The C=O bonds of aldehydes and esters between 1670cm -1 and 1760cm-1 are functional groups.
The C-O bond of an ester occurs at wavelengths between 1160cm-1 and 1400cm-1. These two
functional groups have sharp peaks. At wavelengths 1600cm -1-1500cm-1, a weak peak form
appears, indicating a C=C bond in the aromatic ring. The C-H bond of the aromatic ring is
suggested by the average peak shape in both compounds and it appears at a very small and
weak peak in the spectrum.

CONCLUSION
In conclusion, the reaction between vanillin and acetic anhydride has been successfully studied
under two conditions. Comparison of IR, NMR and melting point were used to evaluate the
products formed. The product forming process has been successfully designed. The melting
points of both products produced under acidic and basic conditions are within the range of the
theoretical melting points by reference. The theoretical melting point of the product under
acidic conditions is between 90°C and 91°C while the theoretical melting point of the product
under basic conditions is between 77 and 79°C. The percentage yield of the product under basic
conditions is 46.31%, while it is 73.33% under acidic conditions. The objectives of the
experiment were achieved.
 QUESTIONS
1. Under different reaction media, vanillin undergoes esterification with
acetyl chloride yielding two different products.

a) Based on the IR spectrum of vanillin, at what range should you

observe the absorption signal of the hydroxyl group?

It should be in range of 3200cm-1– 2600cm-1 with broad peak.

b) Based on its 1H NMR spectrum, what is the expected chemical shift

value for the methoxy group (OCH3)? What is its multiplicity?

According to OCH3 bond, it will be between 2.5ppm-2.1ppm and have singlet

multiplicity.

c) Draw the structures of the major products for the esterification of

vanillin with acetyl chloride in:
i. 10% NaOH solution

ii. 1.0M H2SO4 solution

2. Write the mechanism for the reaction between vanillin and acetyl chloride
in 10% NaOH solution.
 REFERENCES
1. Solomon, Fryhle, Snyder (2016). Organic Chemistry Twelveth Edition, Wiley, United
State Of America.
2. Gallage, Nethaji J., & Møller, Birger L. (2015). Vanillin–Bioconversion and
Bioengineering of the Most Popular Plant Flavor and Its De Novo Biosynthesis in
the Vanilla Orchid. Molecular Plant, 8(1), 40-57.
doi:https://doi.org/10.1016/j.molp.2014.11.008
3. Pavia, Lampman, Kriz and Engel, Introduction to Organic Laboratory Techniques 3rd
Edition (2011). page 863-865.