UNIVERSITI TEKNOLOGI MARA (UiTM) ORGANIC CHEMISTRY (CHM556/557)
SEMESTER 20224
OCTOBER 2022 - FEBRUARY 2023
EXPERIMENT 3:
ESTERIFICATION REACTIONS OF VANILLIN:
THE USE OF NMR TO DETERMINE A STRUCTURE
NAME :
STUDENT ID :
GROUP :
DATE :
Objective (1M)
Introduction (2M)
Procedure in flowchart (2M)
Calculation (5M)
Discussion (3M)
Conclusion (1M)
Questions (6M)
TOTAL
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UNIVERSITI TEKNOLOGI MARA (UiTM) ORGANIC CHEMISTRY (CHM556/557)
YOUR WRITTEN REPORT MUST HAVE:
Objective: (1M)
Introduction: (2M)
Summarize the experiment briefly, add mechanism here
Procedure in flowchart: (2M)
Calculation: (5M)
Discussion: (3M)
Summarize the IR spectrum briefly.
Conclusion:(1M)
Questions: (6M)
References:
Appendix 1:
IR spectrum in Acid Condition
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UNIVERSITI TEKNOLOGI MARA (UiTM) ORGANIC CHEMISTRY (CHM556/557)
Appendix 2:
IR spectrum in Basic Condition
Appendix 3:
NMR Spectrum for Acid Condition
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UNIVERSITI TEKNOLOGI MARA (UiTM) ORGANIC CHEMISTRY (CHM556/557)
Appendix 4:
NMR Spectrum for Basic Condition
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UNIVERSITI TEKNOLOGI MARA (UiTM) ORGANIC CHEMISTRY (CHM556/557)
EXPERIMENT 3
ESTERIFICATION REACTIONS OF VANILLIN:
THE USE OF NMR TO DETERMINE A STRUCTURE
DURATION
3 hours x 2 weeks
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
In this experiment, you will investigate the reactions between vanillin and acetic anhydride
under two conditions, basic and acidic conditions. These reactions will produce different
products. You are given two lab sessions to complete this experiment. The first session should
be used to conduct the reaction under basic condition. The second session should be used to
conduct the reactions under acidic condition. Chemical equation of the esterification of vanillin
under basic and acidic conditions is shown below:
O C
H
C
H3C O
O NaOH OCH3
C O O
H
CH3 C O C CH3 O
HO
OCH3 O C CH3
H2SO4
Acetic anhydride O C H
Vanillin
C O C CH3
H3C O O
OCH3
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UNIVERSITI TEKNOLOGI MARA (UiTM) ORGANIC CHEMISTRY (CHM556/557)
A. BASIC CONDITION
(3 HOURS x 1 SESSION)
Watch the video by the following link:
https://www.youtube.com/watch?v=aYAVxfclNGI&t=198s
APPARATUS
Stainless steel spatula
Glass rod
PTFE stopper
Bulb pipette (if any)
Glass pasteur pipette
Hirsch funnel
Hirsch flask
Rubber tubing
Rubber bung or rubber filter adapter
Bosshead for retort stand
Retort stand
Retort stand clamp
Erlenmeyer flask with a 29/32 socket size (250 mL)
Conical flask (100 mL)
Beaker
Filter paper
Measuring cylinder (5 mL, 50 mL)
Hot plate
Thermometer
Glass rod
Sample bottle
Melting point apparatus
Aspirator vacuum pump
IR Spectrometer
NMR Spectrometer
CHEMICALS
Vanillin
10% sodium hydroxide (NaOH)
Acetic anhydride
95% ethanol
Ice
Salt
Distilled water
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UNIVERSITI TEKNOLOGI MARA (UiTM) ORGANIC CHEMISTRY (CHM556/557)
PROCEDURE
a. Preparation of product
1. Dissolve vanillin (1.50 g) in sodium hydroxide (10%, 25 mL) in a 250 mL
Erlenmeyer flask. A bright yellow green solution is obtained.
2. Then, add crushed ice (30 g) and acetic anhydride (4.0 mL). On adding acetic
anhydride, a cloudy, milky white precipitate forms immediately.
3. Stopper the flask with a clean PTFE stopper and shake it several times over a
20 minutes period.
4. Filter the precipitate using a Hirsch funnel or a small Buchner funnel and wash
the solid with ice-cold water (5 mL). Repeat the washing process three times
with the ice-cold water (5 mL). Refer to the Figure 3.1 for the setup of a
filtration apparatus.
5. Transfer the product (white solid) to the small beaker (50 mL).
b. Recrystallization of the product
1. Recrystallize the solid from 95% ethanol. Transfer 95% ethanol (15 mL) in a
100 mL conical flask/beaker and heat the mixture in a hot plate at 60ºC.
2. Stir the mixture and heat it until the entire solid dissolves in the boiling solution.
If there is still insoluble solid in your hot mixture, slowly add more solvent
(ethanol) and continue heating until completely dissolve.
3. Cool the mixture in room temperature for one minute and continue cooling in
an ice bath. If no crystals formed, crystallization can be induced by scratching
up and down the inside of the flask with a glass rod.
4. Finally, filter the crystals using a clean Buchner or Hirsch funnel under reduced
pressure (see Figure 3.1). At this stage, use a spatula to transfer all the crystals
from the flask to the funnel. Wash the crystals with a small amount of cold
solvent (95% ethanol). Allow the crystals to dry by sucking air through them.
Transfer the dried crystals obtained into a weighed labelled sample bottle.
Melting point of the product is below 100ºC. Do not place the product in oven
to dry.
5. Determine the melting point of the product (literature value is 77-79ºC).
6. Determine the IR and 1H NMR (in CDCl3) spectra of the product as well as IR
spectra for vanillin.
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UNIVERSITI TEKNOLOGI MARA (UiTM) ORGANIC CHEMISTRY (CHM556/557)
Figure 3.1: Setup of a Filtration Apparatus
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UNIVERSITI TEKNOLOGI MARA (UiTM) ORGANIC CHEMISTRY (CHM556/557)
B. ACIDIC CONDITION
(3 HOURS x 1 SESSION)
Watch the video by the following link:
https://www.youtube.com/watch?v=glmLkDQC7hk&t=21s
APPARATUS
Erlenmeyer flask with a 29/32 socket size (250 mL)
Measuring cylinder (10 mL, 50 mL)
Magnetic stir bar
Bulb pipette (if any)
Glass pasteur pipette or plastic pasteur pipette
PTFE stopper (size: 29/32)
Beaker
Stainless steel spatula
Hirsch funnel
Hirsch flask
Rubber tubing
Rubber bung or rubber filter adapter
Bosshead for retort stand
Retort stand
Retort stand clamp
Filter paper
Glass rod
Conical flask (100 mL or 250 mL)
Thermometer
Sample bottle
Hot plate stirrer
Melting point apparatus
Aspirator vacuum pump
IR Spectrometer
NMR Spectrometer
CHEMICALS
Vanillin
1.0 M sulfuric acid
Acetic anhydride
95% ethanol
Ice
Distilled water
OCT 2022-FEB 2023_COVID19
UNIVERSITI TEKNOLOGI MARA (UiTM) ORGANIC CHEMISTRY (CHM556/557)
PROCEDURE
a. Preparation of product
1. Dissolve vanillin (1.50 g) in acetic anhydride (10 mL) in a 250 mL Erlenmeyer
flask.
2. Place a magnetic stir bar in the flask and stir the mixture at room temperature
until the solid dissolves. Stopper the flask with PTFE stopper.
3. While continuing to stir the mixture, add drop by drop sulfuric acid (1.0 M, 10
drops) to the reaction mixture.
4. Stopper the flask with PTFE stopper and stir at room temperature for 1 hour.
During the period, the solution will turn purple or purple-orange in colour.
5. After 1 hour, cool the flask in an ice-water bath for 4-5 minutes.
6. Add ice-cold water (35 mL) to the mixture in the flask. The mixture will turn to
a pale light green in colour.
7. Tightly stopper the flask with a clean PTFE stopper and while holding your
thumb on the stopper, shake the flask vigorously-almost hard as you can shake!
8. Continue to cool and shake the flask to induce crystallization.
9. Crystallization has occurred when you can see small solid clumps separating
from the cloudy liquid and settling to the bottom of the flask.
10. Filter the solid or crystal using a Hirsch funnel or a small Buchner funnel and
wash the solid with ice-cold water (5 mL). Repeat the washing process three
times with the ice-cold water (5 mL). Refer to the Figure 3.1 for the setup of a
filtration apparatus.
11. Transfer the product (white solid) to the small beaker (50 mL).
b. Recrystallization of the product
1. Recrystallize the solid from 95% ethanol. Transfer 95% ethanol (15 mL) in a
100 mL conical flask/beaker and heat the mixture in a hot plate at 60ºC.
2. Stir the mixture and heat it until the entire solid dissolves in the boiling solution.
If there is still insoluble solid in your hot mixture, slowly add more solvent
(ethanol) and continue heating until completely dissolve.
3. Cool the mixture in room temperature for one minute and continue cooling in
an ice bath containing a little bit of salt. If no crystals formed, crystallization
can be induced by scratching up and down the inside of the flask with a glass
rod.
4. Finally, filter the crystals using a clean Buchner or Hirsch funnel under reduced
pressure (see Figure 3.1). At this stage, use a spatula to transfer all the crystals
from the flask to the funnel. Wash the crystals with a small amount of cold
solvent (95% ethanol). Allow the crystals to dry by sucking air through them.
Transfer the dried crystals obtained into a weighed labelled sample bottle.
Melting point of the product is below 100ºC. Do not place the product in oven
to dry.
5. Determine the melting point of the product (literature value is 90-91ºC).
6. Determine the IR and 1H NMR (in CDCl3) spectra of the product as well as
IR spectra for vanillin.
OCT 2022-FEB 2023_COVID19
UNIVERSITI TEKNOLOGI MARA (UiTM) ORGANIC CHEMISTRY (CHM556/557)
RESULTS AND OBSERVATIONS
A. BASIC CONDITION
Results:
a. Weight of product : ______________
b. Melting point of the product : _______________ ºC
c. Appearance of the product : _______________
e. IR data (in Table):
i. Vanillin
ii. Product
Wavenumber (cm-1) Type of bond (group)
1
f. H NMR data of the product (in Table):
Chemical shift, δ Multiplicity Number of Type of proton
(ppm) hydrogen
Observations:
Write the observations such as colour changes, colour of the precipitate etc during the
period of experiment.
Steps Observations
Calculations/Task:
a. Calculation of theoretical yield of product.
b. Percentage yield of product.
c. Discuss the IR and NMR spectrums given with regard to the structures (Table
e and f).
d. Name the products and draw their reaction mechanisms.
OCT 2022-FEB 2023_COVID19
UNIVERSITI TEKNOLOGI MARA (UiTM) ORGANIC CHEMISTRY (CHM556/557)
B. ACIDIC CONDITION
Results:
a. Weight of product : _______________
b. Melting point of the product : _______________ ºC
c. Appearance of the product : _______________
e. IR data (in Table):
i. Vanillin
ii. Product
Wavenumber (cm-1) Type of bond (group)
1
f. H NMR data of the product (in Table):
Chemical shift, δ (ppm) Multiplicity Number of Type of
hydrogen proton
Observations:
Write the observations such as colour changes, colour of the precipitate etc during the
period of experiment.
Steps Observations
Calculations/Task:
a. Calculation of theoretical yield of product.
b. Percentage yield of product.
c. Discuss the IR and NMR spectrums given with regard to the structures (Table
e and f).
d. Name the products and draw their reaction mechanisms.
OCT 2022-FEB 2023_COVID19
UNIVERSITI TEKNOLOGI MARA (UiTM) ORGANIC CHEMISTRY (CHM556/557)
QUESTIONS
1. Under different reaction media, vanillin undergoes esterification with acetyl chloride
yielding two different products.
O
O
H Basic or acidic medium
Cl ?
HO
OCH3
Vanillin
a. Based on the IR spectrum of vanillin, at what range should you observe the
absorption signal of the hydroxyl group?
b. Based on its 1H NMR spectrum, what is the expected chemical shift value for
the methoxy group (OCH3)? What is its 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.
REFERENCE
Pavia, Lampman, Kriz and Engel, Introduction to Organic Laboratory Techniques 3 rd Edition
(2011). page 863-865.
OCT 2022-FEB 2023_COVID19
