LABORATORY REPORT

ORGANIC CHEMISTRY
(CHM557)

NAME OF STUDENT : IRFAN NURHADI BIN AZAHAR

STUDENT NUMBER : 2020819572
GROUP MEMBERS : 1. IRFFAN NURHADI BIN AZAHAR
2.
3.
GROUP : AS2223A1
NUMBER AND TITLE OF EXPERIMENT : EXPERIMENT 3: Esterification of Vanillin: The
Use of NMR to a Structure
DATE OF EXPERIMENT : 14 DISEMBER 2021
DATE OF REPORT SUBMISSION : 3 JANUARI 2022
NAME OF LECTURER : DR. NOR AKMALAZURA JANI
Introduction
Vanillin (4-hydroxy-3-
methoxybenzaldehyde), an aromatic compound with a good scent, occurs naturally in vanilla
beans. Vanillin is commonly used as an aromatic agent for candles, incense, potpourri, fragra
nces, perfumes and flavour for drinks and cooking. Vanilin is an organic compound with the
molecular formula C8H8O3, a phenolic aldehyde.
Vanillin is also a multifunctional compound that has reacted to various products that are
ester 1 and ester 2 with acetic anhydrite under acidic or basic condition. An example of
the esterification of a phenol is the reaction of vanillin with acetic anhydride in the
presence of the base. Its IR and NMR spectra can easily characterize the product, which
is a white solid.

Procedure Flow Chart

A. Basic Condition
a. Preparation of product

In a 250 mL Erlenmeyer flask,

dissolve vanillin (1.50 g) into
sodium hydroxide (10 percent, 25
mL). It produces a vivid yellow-
green solution.
Crushed ice (30 g) and acetic
anhydride (4.0 mL) added into the
flask. A cloudy, milky white
precipitate forms instantly upon
adding acetic anhydride.

Using a clean PTFE stopper to

stop the flask and shake it several
times over a period of 20 minutes.

Using a Hirsch funnel or a small

Buchner funnel, filter the
precipitate and wash the solid with
ice-cold water (5 mL). With the
ice-cold water (5 mL) repeats the
washing process three times. For
the set up of a filtration
apparatus, refer to Figure 3.1.
Transfer the product (white solid)
to the small beaker (50 mL).
 b. Recrystallization of the product.

Recrystallize 95 % ethanol from

the solid. In a 100 mL conical
flask/beaker, pass 95 % ethanol
(15 mL) and heat the mixture at
60⁰C in a hot dish
Stir the mixture and heat it in the
boiling solution until the whole
solid dissolves. If your hot
mixture still contains insoluble
solids, add more solvent (ethanol)
slowly and continue to heat until
completely dissolved.

Cool the mixture for one minute at

room temperature and proceed to
cool in an ice bath. Crystallization
can be caused by scratching up
and down the inside of the flask
with a glass rod if no crystals have
been formed.

Finally, under reduced pressure,

Determine the product's melting
point (77-79⁰C is the literature
value) and determine the product's
IR and 1H NMR (in CDCl3)
spectra as well as vanillin IR
spectra.
filter the crystals using a clean
Buchner or Hirsch funnel (see
Figure 3.1). Using a spatula at this
point to move all of the crystals
from the flask to the funnel. Wash
the crystals (95 % ethanol) with a
small amount of cold solvent.
Enable them to dry up by sucking
air through the crystals. Move the
collected dried crystals into a
labeled weighed sample bottle.
The product's melting point is
below 100⁰C. Do not set the
product to dry in the oven.
Figure 3.1: Setup of a Filtration Apparatus
 B. Acidic Condition
a. Preparation of Product.

In a 250ml Erlenmeyer flask, dissolve vanillin

(1.50g) in acetic anhydride(10ml) and put a
magnetic stick bar in the flask and stir the
mixture at room temperature until the solid
dissolved. Stop the flask using PTFE stopper.

Add drop by drop sulfuric acid (1.0M, 10

drops) to the reaction mixture while
continuing to stir the mixture, and stop the
PTFE stopper flask and stir for 1 hour at room
temperature. The solution will turn purple or
purple-orange in colour through the time.

Cool the flask for 4-5 minutes in an ice-water

bath after 1 hour and add ice-cold water (35ml)
to the mixture in the flask. The mixture turns
green in colour to a pale light.

Tightly stop the flask with a clean PTFE

stopper and shake the flask vigorously,
almost hard as you would shake while putting
your thumb on the stopper, then proceed to
cool and shake the flask to induce
crystallization

When you can see tiny firm clump separating

from the cloudy liquid and settling at the bottom
of the flask, crystallization has occurred, using
Hirsch funnel or a small Buchner funnel. Filter
the solid or crystal and wash the solid with ice-
cold water (5ml). the ice-cold water repeats the
washing process three times. For the setup of a
filtration system refer to figure3.1 and then pass
the product (white solid) to small beaker
(50ml).
b. Recrystallization of the Product.

Recrystallize 95% ethanol from

the solid. In a 100ml conical flask,
pass 95% ethanol (15ml) and heat
the mixture at 60℃ in a hot dish.
Stir the mixture and heat it in the
boiling solution until the whole
solid dissolves. If the hot mixture
still contains insoluble solids, add Cool the mixture for one minute at
more solvent (ethnol) slowly and room temperature and proceed to
continue to heat until completely cool in an ice bath that has a little
dissolved. bit of salt in it. Crystallization can
be caused by scratching up and
down the inside of the flask with a
glass rod if no crystals have been
formed.

Finally, under decreased pressure,

filter the crystals using a clean
Buchner or Hirsch funnel (see
Figure 3.1). Using a spatula at this
point to move all of the crystals
from the flask to the funnel. Wash
the crystals (95 % ethanol) with a
small amount of cold solvent.
Enable them to dry up by sucking
air through the crystals. Move the Determine the product melting
collected dried crystals into a point (literature value is 90-91⁰C)
labeled weighed sample bottle. and determine the product IR and
The product's melting point is 1H NMR (in CDCl3) and vanillin
below 100oC. Do not set the IR spectra.
product to dry in the oven
Results and Observations

A. Basic Condition

Results:

a. Weight of product : 1.1123 g

b. Melting point of the product : 77-79ºC

c. Appearance of the product : White crystal solid form

e. IR data (in Table):

i. Vanillin
ii. Product

Wavenumber (cm-1) Type of bond (group)

2968 C-H
1758 C=O

1
f. H NMR data of the product (in Table):

Chemical shift, δ Multiplicity Number of Type of proton

(ppm) hydrogen
9.96 Singlet 1 ROCH
2.38 Singlet 3 OOCH3
4.04 Singlet 1 OH

Observations:

Write the observations such as colour changes, colour of the precipitate etc during
the period of experiment.

Steps Observations
Dissolve vanillin in Bright yellow green solution
sodium hydroxide
Added acetic Cloudy, milky white precipitate
anhydride
Final product form White crystal formed
Calculations and Task:

a. Calculation of theoretical yield of product.

Mass of vanillin = 1.5g
Mass of product = 1.1123g
Molecular mass vanillin = 152 g/mol
Molecular mass product = 194 g/mol
No. mol vanillin = 1.5/152
= 9.87 x 10-3
Theoretical yield product = 9.87x10-3 x 194 = 1.9148

b. Percentage yield of product

(1.1123/1.9148) x 100
=58.09%
c. Name the products.
4-formylphenyl acetate/ vanillyl acetate
B. Acidic Condition

Results:

a. Weight of product : 2.3979 g

b. Melting point of the product : 90-91ºC

c. Appearance of the product : White solid crystal form

e. IR data (in Table):

i. Vanillin
ii. Product

Wavenumber (cm-1) Type of bond (group)

1753 C=O
1160 C-O

1
f. H NMR data of the product (in Table):

Chemical shift, δ (ppm) Multiplicity Number of Type of proton

hydrogen
4.00 Singlet 1 OH
2.23, 2.34 Doublets 3 OOCCH3
7.24, 7.27 Doublets 1 Benzene ring

Observations:

Write the observations such as colour changes, colour of the precipitate etc during
the period of experiment.

Steps Observations
Stir mixture under Colorless to purple/purple orange
room temperature for
1 hour
Added ice-cold water Purple/purple-orange to pale green
Final product form White color formed
Calculations and Task:

a. Calculation of theoretical yield of product.

Mass of vanillin = 1.5g
Mass of product = 2.3979g
Molecular mass vanillin = 152g/mol
Molecular mass product = 296g/mol
No. mol vanillin = 9.87x10-3mol
Theoretical yield product = 9.87x10-3 x 296 = 2.9215g
b. Percentage yield of product
(2.3979/2.9215)x100
=82.08%
c. Name the products and draw their reaction mechanisms.
(4-Acetoxy-3-methoxyphenyl) methylene diacetate
Discussion
In this experiment, the primary aim was to be accomplished by specifying each compound
for acidic and basic conditions. The reaction will generate tri-ester basis on the theoretical
in acidic condition. The reaction will produce 4-Acetoxy-3-Methoxybenzaldehyde
(Vanillyl Acetate) whilst in basic condition. Analysis of the functional group and product
structure was performed using IR spectroscopy and NMR spectroscopy. The performance
structure is shown below.
The mass of the basic product collected was 1.1123 g from the mass theoretical product
capable of producing is 1.9148 g, of which only 58.09%. Due to the loss of the substance
during transition between procedures, the percentage yield was lower than the theoretical
mass and could also induce incompleteness in the reaction. While the mass of the product
obtained for acid condition was 2.3979 g of theoretical mass product capable of 2.9215 g
of product, of which only 82.08%. The percent of yield is more than half percent means
the yield of product was successful.
There were variations between the acid melting points and the reactions that were
basecatalyzed. Based on the theoretical fact, the variety of melting points for basic
condition product is 77-79 ⁰C. Although the theory-based range of melting points for the
acid condition product is 90-91 ⁰C, the range variance shows impurities present in the
product. The molecular weight and structure bonding present in the product can affect the
melting point of the product. Based on the theoretical proof, the molecular weight of the
acidic condition product was 296 g/mol higher than the reaction product of the basic
condition, 194.18 g/mol. The greater the compound's molecular weight, the greater the
compound's melting point. The impurity of the product from the reaction may also be
triggered by it. Even, recrystallize has been done.
The resulting IR spectra illustrate the absorption of the acid and base-catalyzed reactions,
respectively. Both contain a high peak that corresponds to a C=O stretch around 1750 cm-
1
. The presence of C=O bonds in the compound has been indicated. Ester fictional group
was represented the product. In acid condition product, IR spectrum also show the peak at
1160 cm1 to indicate C-O. The NMR showed that the basic product is vanillin acetate and
the acidic product is vanillin triacetate. One hydrogen is present at 9.97 ppm for basic
conditions, and this showed that the substance produced consists of aldehyde. This value
is absent in the acidic product, indicating that the substance formed does not contain an
aldehyde group. Product for both reactions also give NMR spectrum peak at range 4.00
ppm which is indicate the -OH bond.

Conclusion
Throughout the experiment, it was possible to recognize the commodity. The acid or base
esterification reaction produces various products. The acid-catalysed product tends to
produce (4-Acetoxy-3-methoxyphenyl) methylene diacetate while basic reaction produces
4-Acetoxy3-Methoxybenzaldehyde. For the base and acid catalysed reactions, the percent
yield of product for the reactions was 58.09% and 82.08% respectively.
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
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 3300 – 2500 cm-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 2.1-2.5 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. 1.0 M H2SO4 solution

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