CHM 556

ORGANIC CHEMISTRY II
EXPERIMENT 3: ESTERIFICATION REACTION OF VANILLIN: THE USE
OF NMR TO DETERMINE A STRUCTURE

NAME
AMAR SAFWAN BIN MOHD ALI HANAPIAH (2015272222)
LAB PARTNER
SALMA IZZATI BINTI SINAR MASHURI (2015839778)
NURUL SHAZREENA BINTI ZULKAFLY (2015258246)
CLASS: AS2453D1
LECTURES NAME: PN. NUR VICKY BIHUD

LABORATORY REPORT MARKING SCHEME

Objective of the Experiment

Introduction
Experimental Procedure
Results and Observations
Calculations
Discussion
Conclusion
Answers to Questions
References
Pre-laboratory preparations
Laboratory techniques
Total Marks

Full
Marks
Mark(s) (to be filled by lecturer)
1.0
2.0
1.0
3.0
3.0
2.0
1.0
3.0
1.0
2.0
1.0
20

Objective
To investigate the esterification reaction between vanillin and acetic anhydride under two
conditions, basic and acidic conditions, then measure the melting points, obtains NMR and IR
spectra.
Introduction
Vanillin (4-hydroxy-3-methoxybenzaldehyde), a pleasant smelling aromatic compound,
occurs naturally in vanillin beans. Vanillin is used widely as a flavouring additive for beverages,
cooking and aromatic addictive for candles, incense, potpourri, fragrances, perfumes, and air
fresheners. The product of reaction between vanillin and acetic anhydride under acidic condition
and basic condition will give different product that will be determined by using FTIR and NMR
spectrum. Base used in this experiment is sodium hydroxide while acid used is sulphuric acid.
The reaction of vanillin with acetic acid anhydride in the presence of base is an example of
the esterification of phenol. The product, which is a white solid, can be characterize easily by its
infrared and NMR spectra.
When vanillin is esterified with acetic with acetic anhydride under acidic conditions,
however, the product that is isolated has a different melting point and different spectra.

Procedure
1. Acidic condition:
i.

1.5g of vanillin was added into a conical flask containing 10ml of acetic acid.

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 about 4
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 60oC) 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 tested.

2. Basic condition:
i.

1.5g of vanillin was added into a conical flask with 25ml of 10% NaOH
solution.

ii.

4ml of acetic acid anhydride and 30g of crushed ice were added into the
solution.

iii.

The mixture then was shaken for 20 minutes and cloudy, milky white
precipitate will form.

iv.

The mixture then was filtered by using Buchner funnel with washing of 3
portions of 5ml ice cold water.

v.

For recrystallization, 15ml warm ethanol (below 60oC) was added with the
crystal collected from 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 tested.

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.

RESULT AND OBSERVATION:

i.

Fourier Transform Infrared result:

Bond

Theoretical
wavenumber, cm-1

Experimental 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 turn 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.

Mass of product (acidic condition) = 2.2139g

Mass of product (basic condition) = 1.4761g
Melting point of product (acidic condition) = 94C
Melting point of product (basic condition) = 79C
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%
Acidic condition

Basic condition

Mass of product (g)

2.2139

1.4761

Theoretical yield (g)

2.9211

1.9145

Percentage yield (%)

75.78

77.10

Melting point (C)

94

79

Discussion
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 when filter. 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 wont tear off. The
person in charge also must make sure that the solid that want to dissolve must be completely
dissolve before proceeding to the next step. The melting point was done by using the melting
apparatus. The theoretical melting point of product for acidic condition is between 90-91oC while
for the basic condition is between 77-79oC. The melting point that get in the experiment is in the
acidic condition is 94oC and for the basic condition is 79oC. Thus its prove that the melting point
for the compound in the acidic and basic condition follow the theoretical melting point.

From the FTIR test, 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 wavenumber. 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 wavenumber 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.
The structures of the products were tested by using the Nuclear Magnetic Resonance. Some
of 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 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.

Conclusion:
The percentage yield under acidic condition is 75.78% and the percentage yield in basic
condition is 77.10%. The melting point of product under acidic condition is 94C and the melting
point of product under basic condition is 79C. Both products show the functional groups of
ester and aldehyde from the result of Infrared Spectroscopy and from the NMR result the
structure of the products resulting:

References:
1. Acetic anhydride, 27/10/2014, http://en.m.wikipedia.org/wiki/acetic_anhydride
2. CHM 556 Organic Chemistry 2 lecture notes prepared by Prof. Faujan.
3. Department of Chemistry and Biochemistry University Delaware, Synthesis of Vanilin,
24/10/2014, http://valhalla.chem.udel.edu/vanilin.html
4. T.W. Graham Solomons, Craig B. Fryhle, Organic Chemistry, Asia, John Wiley and Sons,
2011.