SEMESTER 20214

OCTOBER 2021 – FEBRUARY 2022

EXPERIMENT 3:
ESTERIFICATION OF VANILLIN

NAME : SITI NUR AFIQAH BINTI MAHAZAN

STUDENT ID : 2020897786
GROUP : AS2533A1
DATE : 19TH NOVEMBER 2021

Objective (1M)

Introduction (2M)

Procedure in flowchart (2M)

Calculation (5M)

Discussion (3M)

Conclusion (1M)

Questions (5M)

References (1M)

TOTAL (20M)
OBJECTIVES

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 can be found both naturally and artificially. It is used in flavourings, foods,
perfumes, and pharmaceuticals. Vanillin is used as a chemical intermediate in the production
of several important drugs and other products. Vanillin is ingested by humans through
dermal contact with perfumes and ingestion of food products that contain vanillin as a
flavour additive. Vanillin has a low potential for bioaccumulation in aquatic organisms. It is
generally regarded as safe for use as a flavouring agent in foods and beverages. Vanillin is
an acid in solution and may irritate the eyes and respiratory mucous membranes. It is also
used in medicine as an anticlastogenic and antimicrobial agent.

Esterification occurs when carboxylic acids react with alcohols to form esters via a
condensation reaction. In the absence of strong acids, Fischer esterification proceeds slowly,
but it still achieves equilibrium when an acid and an alcohol are refluxed with a small
amount of concentrated sulphuric acid and sodium hydroxide. The reaction of an alcohol
with an anhydride can also be used to synthesise ester. Acetic anhydride was used instead of
strong acid because strong acid can cause side effects. Esters are saponified by reacting an
ester with aqueous sodium hydroxide, which results in the formation of acetate.

Carbonyl compound reactions can be catalysed by either an acid or a base. Under both acidic
and basic conditions, acetic anhydride readily undergoes acyl substitution reactions with a
wide range of nucleophiles. Phenolic OH groups, such as those found on vanillin, are
commonly used as effective nucleophiles in acetic anhydride reactions. However, as the
reaction indicates, the reaction of vanillin with acetic anhydride produces different products
under basic and acidic conditions. Chemical equation of the esterification of vanillin under
basic and acidic conditions is shown below:
To determine the functional group of the product in this experiment, infrared spectroscopy
was used. The identification of organic compounds capable of bonding is one of the most
common applications of infrared spectroscopy. Infrared energy is absorbed by vibrating
bonds at a frequency that corresponds to the frequency of the bond's vibration. The bond will
absorb the radiation if the frequency of the radiation matches the vibrational frequency. The
vibration's amplitude will grow. The vibrational energy of molecules' bonds is quantized.
Only at certain permitted frequencies can the bonds stretch and bend.

Nuclear Magnetic Resonance (NMR) spectroscopy was also used to determine the structure
of the product. The nuclei of some isotopes of many elements, including H, absorb
electromagnetic radiation in the radiofrequency (Rf) region of the spectrum when placed in a
strong magnetic field, according to the NMR theory. The number of signals in an NMR
spectrum is proportional to the number of different types of hydrogen atoms in a molecule.
A hydrogen nucleus's NMR signal is not split by other hydrogen atoms that are the same as
itself.

A. BASIC CONDITION

APPARATUS

Stainless steel spatula Conical flask (100 mL)

Glass rod Beaker
PTFE stopper Filter paper
Bulb pipette (if any) Measuring cylinder (5 mL, 50 mL)
Glass Pasteur pipette Hot plate
Hirsch funnel Thermometer
Hirsch flask Glass rod
Rubber tubing Sample bottle
Rubber bung or rubber filter adapter Melting point apparatus
Bosshead for retort stand Aspirator vacuum pump
Retort stand IR Spectrometer
Retort stand clamp NMR Spectrometer
Erlenmeyer flask with a 29/32 socket size (250
mL)
CHEMICALS

Vanillin
10% sodium hydroxide (NaOH)
Acetic anhydride
95% ethanol
Ice
Salt
Distilled water

Figure 3.1: Setup of a Filtration Apparatus

PROCEDURE
RESULTS AND OBSERVATIONS
A. BASIC CONDITION
Results:
a. Weight of product : 1.1123 g

b. Melting point of the product : 79.0℃

c. Appearance of the product : white solid precipitate of vanillin acetate

(4-Formyl-2-methoxyphenyl acetate)
d. IR data (in Table):

i. Vanillin
ii. Product
IR data Wave number (𝐜𝐦−𝟏 ) Type of bond (group)
Vanillin 1758.36 C = O (aldehyde)
e. Product (Vanillin acetate) 1396.96 C − O (ester)
1H NMR data of the product (in Table):

Chemical shift, δ Multiplicity Number of Type of proton

(ppm) hydrogen
9.97 Singlet 1H −CHO
7.20 - 7.52 Singlet 3H

3.92 Singlet 3H −OCH3

1.64 - 2.37 Singlet 3H −COOCH3

Observations:

Write the observations such as colour changes, colour of the precipitate etc.
during the period of experiment.
Steps Observations
Basic Reaction between 1.5 g vanillin with 25 mL of 10% NaOH
produce a bright yellow green solution
Bright yellow green solution turns to milky white precipitate after
the addition 4 mL of acetic anhydride with 30 g of crushed ice
The solid become shiny after the crystallization process with a
small amount of cold solvent (95% ethanol)
Calculations/Task:

Volume of acetic anhydride = 4 mL

Density of acetic anhydride = 1.08 g mL−1
Mass of acetic anhydride = Volume of acetic anhydride × Density
= 4 mL × 1.08 g mL−1
= 4.32 g
Mass of acetic anhydride
No. of moles of acetic anhydride =
Molar mass of acetic anhydride
4.32 g
=
102.09 g mol−1
= 0.04232 mol (available)
Mass of vanillin = 1.50 g
Molar mass of vanillin = 152.15 g mol−1
Mass of vanillin
No. of moles of vanillin =
Molar mass of vanillin
1.50 g
=
152.15 g mol−1
= 9.85869 × 10−3 mol (available)
From stoichiometry, 1 mol of acetic anhydride ≡ 1 vanillin
0.04232 mol of acetic anhydride ≡ 0.04232 mol of vanillin (required)
Since the no. of moles for available vanillin (9.85869 × 10−3 mol) is less than required
(0.04232 mol), thus the limiting reactant is vanillin.

a. Calculation of theoretical yield of product.

Actual yield = 1.1123 g

Molar mass of vanillin acetate (product) = 194.186 g mol−1
Theoretical yield = No. of moles of limiting reactant × Molar mass of product
= 9.85869 × 10−3 mol × 194.186 g mol−1
= 1.9144 g
b. Percentage yield of product.

Actual yield
Percentage yield = × 100%
Theoretical yield
1.1123 g
= x 100%
1.9144 g
= 58.10%
 Theoretical yield − Actual yield
Percentage error of basic reaction = × 100%
Theoretical yield

1.9144 g − 1.1123 g
= × 100%
1.9144 g

= 41.90%

c. Discuss the IR and NMR spectrums given regarding the structures (Table e and f).

The IR spectrum was used to determine the functional group of the basic product.
There was (RCOOR′) group which present at the peak of 1758.36 cm−1 for aldehyde
and 1396.96 cm−1 for ester. For 1H NMR spectrums of basic conditions, one
hydrogen was present at 9.97 ppm, indicating that the product formed was aldehyde.
At 2.37 ppm, there were three hydrogens present in basic. This shows that the base
only contains one ester. At 3.92 ppm, products in base contained the same number of
hydrogens, which were three hydrogens. This revealed the presence of −OCH3 . At
7.20 – 7.52 ppm, there were three hydrogens present in the basic condition,
indicating the presence of hydrogen with an aromatic ring. Based on the 1H NMR
spectrum, the functional group of the product produced can be identified as ester.

d. Name the products and draw their reaction mechanisms.

Name of the product: 4-Acetoxy-3-methoxybenzaldehyde (Vanillin acetate)

DISCUSSION

Vanillin is a phenolic aldehyde, an organic compound with the molecular formula C8H8O3.
The goal of this experiment is to investigate the reactions between vanillin and acetic
anhydride under basic conditions using the esterification technique. For the base solution,
sodium hydroxide was used. An equilibrium reaction occurs when aldehydes react with
alcohols to form hemiacetals and acetals. The –OH and –OR attached groups on the same
carbon atom are essential structural features of hemiacetals. For each carbon in an acetal,
there were two –OR groups. When an alcohol solution was passed through a small amount
of gaseous HCl, a hemiacetal was formed, and the hemiacetal reacts with a second molar
equivalent of the alcohol to form an acetal.
In the basic condition, the reaction of 1.50 g vanillin with 25 mL of 10% sodium hydroxide
produced a bright yellow green solution. After 30 g of crushed ice and 4.0 mL of acetic
anhydride were added, the bright yellow green solution turned to milky white precipitate.
The solid product became shiny after the recrystallization process with warm 95% ethanol.
This product yielded a 58.10% of percentage yield. In basic conditions, it is not purely
vanillin acetate because it should melt between 77 and 79 degrees Celsius.

In the mechanism of the basic condition, acetic anhydride acts as an electrophile, undergoing
nucleophile attack by the alcohol when an anhydride reacts with an alcohol under both acidic
and basic conditions. The vanillin molecule contains several functional groups, including
alcohol, ether, and aldehyde. The base-catalyzed reaction is a straightforward esterification
that produces no other significant products because esterification terminates at the ester.
Vanillin reacts with acetic anhydride to form vanillin acetate during the esterification
reaction under basic conditions. The formation of these products was confirmed using
infrared (IR) and nuclear magnetic resonance (NMR) techniques. Vanillin acetate was
discovered by 1H NMR spectroscopy to be the product formed under basic conditions.

The IR spectrum was used to determine the functional group of the basic product. There was
(RCOOR′) group which present at the peak of 1758.36 cm−1 for aldehyde and 1396.96 cm−1
for ester. For 1H NMR spectrums of basic conditions, one hydrogen is present at 9.97 ppm,
indicating that the product formed was aldehyde. At 1.64 – 2.37 ppm, there are three
hydrogens present in basic conditions. This shows that the base only contains one ester. At
3.92 ppm, products in base contain the same number of hydrogens, which is three
hydrogens. This revealed the presence of −OCH3 . At 7.20 – 7.52 ppm, there are three
hydrogens present in the basic condition, indicating the presence of hydrogen attached to an
aromatic ring. Based on the 1H NMR spectrum, the functional group of the product
produced can be identified as ester which was 4-Acetoxy-3-methoxybenzaldehyde or better
known as vanillin acetate.

There might be some error that occurred while handling the experiment as the product's
mass may be lost during the filtration process using the Buchner funnel, and some of the
product may be left in the container during the transfer. To obtain a higher mass of the
product, the solution should be added slowly and continuously stirred. Furthermore, the solid
to be dissolved must be completely dissolved before proceeding to the next step. A melting
point apparatus was used to perform the melting point test. The melting point of the product
made under basic conditions is in the range of the theoretical melting point by reference,
which is around 77 − 79 ℃ for basic conditions.

CONCLUSION

The percentage yield of product under basic condition obtained was 58.10% The reaction
between vanillin and acetic anhydride under basic conditions was successfully
experimented. The products formed was determined using IR, 1H NMR, and melting point
comparisons. The mechanism for the product formed was successfully drawn. The
experiment goals 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?

The absorption signal of the hydroxyl group could be observed at the range of
3300 − 3600 cm−1 as a broad U-shape peak

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

The expected chemical shift value for the methoxy group (OCH3) is between 3.0 −
4.0 ppm and the multiplicity is 3H singlet

c. Draw the structures 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.

REFERENCES

Pavia, Lampman, Kriz and Engel, Introduction to Organic Laboratory Techniques 3rd
Edition (2011). page 863-865.

Jenkins, A., & Erraguntla, N. K. (2014). Vanillin. Encyclopedia of Toxicology, 912–914.

https://doi.org/10.1016/b978-0-12-386454-3.00544-3

U.S. National Library of Medicine. (n.d.). Vanillin. National Centre for Biotechnology
Information. PubChem Compound Database. Retrieved November 11, 2021, from
https://pubchem.ncbi.nlm.nih.gov/compound/Vanillin.

Libretexts. (2020, August 5). 21.4: Experiment 65 reactions. Chemistry LibreTexts.

Retrieved November 11, 2021, from
https://chem.libretexts.org/Ancillary_Materials/Laboratory_Experiments/Wet_Lab_Ex
periments/Organic_Chemistry_Labs/Lab_II/21%3A_Experiment_65-
_Esterification_of_Vanillin/21.04%3A_Experiment_65_Reactions.
APPENDIX 1:

IR Spectrum in Basic Condition

C − O stretch (ester)

C = O stretch (aldehyde)

APPENDIX 2:

NMR Spectrum for Basic Condition