UNIVERSITI TEKNOLOGI MARA SARAWAK

FACULTY OF APPLIED SCIENCES

CHM557

Organic Chemistry

DRY LAB 3

LAB REPORT EXPERIMENT 3:

Esterification Reactions of Vanillin: The Use of NMR to Determine a Structure

PREPARED FOR:
MDM WONG MUI HUNG

PREPARED BY:

ASLA MARLEENA BINTI NAZERIE

2020994865

DATE OF SUBMISSION:

20𝑡ℎ APRIL 2020

GROUP:
AS222 3A
Objective

The objectives of this experiment are:

1. To study the mechanism in esterification reaction of vanillin in acidic and basic condition
2. To identify the product in acid and basic condition using IR spectrum
3. To identify the product in acid and basic condition using proton-NMR spectrum
4. To calculate the percentage yield of product formed in acid and basic condition.

Apparatus

Erlenmeyer flask, stopper, Buchner funnel, rubber stopper, magnetic stirrer, analytical balance.

Chemicals

Vanillin, acetic anhydride, sodium hydroxide, ethyl alcohol, sulfuric acid

Introduction

Vanillin is a commonly used flavoring compound and it is provided from variety of

source. Vanillin is a polyfunctional compound where it has three functional group attached
with an aromatic ring. The three functional group that attached to the aromatic ring are aldehyde
group, hydroxyl group and methoxy group. Besides that, vanillin is a white crystalline
compound that can be isolated from vanilla plant (Isac-Garcia, 2016). Vanillin is the common
name for 4-hydroxy-3-methoxybenzaldehyde. The structure below is Vanillin:

4-hydroxy-3-methoxybenzaldehyde (vanillin)

Esterification is a reaction occur when two reactants to make an ester. For example, the
reaction between an alcohol and carboxylic acid will form an ester. Besides that, carboxylic
acid derivative also can form an ester with alcohol. For example, acyl chloride or acid chloride
and acid anhydride. In this experiment, the vanillin will react with acid anhydride to make an
ester (Esterification, 2020).
 The vanillin gives different product depending on which state their where react
with. So, in this experiment, we will identify the product formed in acidic and basic condition.
Both products will be identified using the IR spectrum and proton NMR spectrum. Based in
the experiment 2, IR spectroscopy is an instrument to detect the functional group of an
unknown product or confirming the functional group that present in a compound. IR
spectroscopy can detect functional group because it has the fingerprint region. Any vibrations
that are found in the region are used to confirm the identity of an organic compound or
functional group (Infrared Spectroscopy, 2019). Meanwhile, NMR spectroscopy allows to
characterize the new products. Basically, NMR spectroscopy use the magnetic resonance to
detect or to characterize the product (Nuclear Magnetic Resonance Spectroscopy, 2020).

Procedure

For acidic condition:

1. 1.50 g of vanillin was dissolved with 10 ml of acetic anhydride in a 125 ml of Erlenmeyer

flask.
2. Then, a magnetic stirrer was placed in the flask and the mixture was stirred at room
temperature until the solid dissolved.
3. 10 drops of 1.0 M sulfuric acid were added to the reaction mixture while it was stirred.
4. The flask was stopped with a stopper and was stirred at room temperature for 1 hour.
5. During the time, the colour of the solution had changed to purple or purple-orange in
colour.
6. The, the flask was cooled in an ice-water bath for 4 to 5 minutes.
7. Next, 35 ml of ice-cold water was added to the mixture in the flask.
8. After that, the flask was stopped tightly using a clean rubber stopper and was shaken
vigorously.
9. Next, the mixture was cool and shaken to induce crystallization.
10. The crystal was filtered using Buchner funnel and the solid was washed with three 5-ml
portion of ice-cold water.
11. The crystal was recrystallized from hot 95% ethanol and was allowed to dry. Then, the dry
crystal was weighed, and the percentage yield was calculated.
12. The IR spectrum of the product was determined using the dry-film method. Meanwhile,
for the Proton-NMR spectrum, the product was determined using a CDCL3 solution.
13. The structure of the product was confirmed using the spectrum data.
For basic condition:

1. 1.50 g of vanillin was dissolved with 25 ml of 10 % sodium hydroxide in a 250 ml

Erlenmeyer flask.
2. Next, 30 g of crushed ice and 4.0 ml of acetic anhydride was added into the Erlenmeyer
flask.
3. The flask was closed with a clean rubber stopper. Then, it was shaken several times for 20
minutes. A cloudy, milky white precipitate was formed immediately.
4. After that, the precipitate was filtered using a Buchner funnel and was washed using a
three 5ml portion of ice-cold water.
5. The solid was recrystallized from 95% ethyl alcohol and the mixture was heated in a hot-
water bath at 60℃.
6. After the crystal was dried, it was weighed, and the percentage yield was calculated.
7. The IR spectrum of the product was determined using the dry-film method. Meanwhile,
for the Proton-NMR spectrum, the product was determined using a CDCL3 solution.
8. The structure of the product was confirmed using the spectrum data.

Result and observation

i. Observation: Solution change to purple-orange colour in acidic solution.

: Both acidic and basic solution formed a white crystalline product.
ii. Task 2

1. From the data provided in the procedure section (Laboratory Techniques, A Small-
Scale Approach, 3rd Edition by Engel, Kriz, Lapman and Pavia, page 863), calculate
the theoretical yield for the product in Acidic and Basic condition. Provide the
chemical equations and calculation for both reaction conditions. State the limiting
reagent for the reactions.

Mass, g of vanillin Melting point, ℃

Acid condition 1.5 g 90-91

Basic condition 1.5 g 77-79

Theoretical yield = mass of vanillin acetate and vanillyl alcohol

𝑚𝑎𝑠𝑠,𝑔
• No of mole vanillin = 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠,𝑔/𝑚𝑜𝑙
1.5 𝑔
= 152 𝑔/𝑚𝑜𝑙 = 9.86 X 10-3 mol.
 1.08,𝑔 102 𝑔
• No. of mole acetic anhydride (acid ) = 10ml X ÷
1 𝑚𝑙 1 𝑚𝑜𝑙
= 0.105 mol.
1.08,𝑔 102 𝑔
• No. of mole acetic anhydride (base) = 4ml X ÷
1 𝑚𝑙 1 𝑚𝑜𝑙
= 0.042 mol.

• In acid, 1 mol of vanillin react with 1 mol of acetic anhydride and produce 1 mol
vanillyl alcohol.
No. mol vanillin acetate= (9.86x10-3 + 0.105)÷2 = 0.057 mol
Find mass of vanillin alcohol (theoretical mass) = mole X molar mass
= 0.057 mol X 152g/mol
= 8.664g

• In basic, 1 mol of vanillin react with 1 mol of acetic anhydride and produce 1 mol
vanillyl acetate.
No. mol vanillin acetate= (9.86x10-3 + 0.042)÷2 = 0.026 mol
Find mass of vanillin acetate (theoretical mass) = mole X molar mass
= 0.026 mol X 152g/mol
= 3.952g
• the limiting reactant is vanillin since vanillin has smaller mol compared to acetic
anhydride, vanillin will used up early.

2. Calculate the percentage yield if

a. the yield obtained in acidic condition is 0.02g
𝑎𝑐𝑡𝑢𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
percentage yield = 𝑋 100
𝑡ℎ𝑒𝑜𝑟𝑖𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
0.02𝑔
= 𝑋 100
8.664
= 0.23%

b. the yield obtained in basic condition is 0.04g

𝑎𝑐𝑡𝑢𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
percentage yield = 𝑋 100
𝑡ℎ𝑒𝑜𝑟𝑖𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
0.04 𝑔
= 𝑋 100
3.952𝑔
= 1.01%
iii. Task 3
1. a. Draw the mechanism reaction of vanillin with acetic anhydride in the presence
of NaOH.

b. Draw the product obtained from a reaction of vanillin with acetic anhydride in the
presence of NaOH.
c. Provide the expected 1H NMR shifting value in ppm for all the H for the product.

➢ H for aldehyde = 10 ppm and H for ester = 6 ppm.

d. Provide the expected IR spectrum for the product.
➢ To detect vanillin acetate, we find and C=O bond for ester which is 1758.36 cm-1.
2. a. Draw the mechanism reaction of vanillin with acetic anhydride in the presence
of HCl.
b. Draw the product obtained from a reaction of vanillin with acetic anhydride in the
presence of HCl.

c. Provide the expected 1H NMR shifting value in ppm for all the H for the product.

➢ The chemical shift for alcohol is 3.9 ppm and the chemical shift for ester is 6
ppm
 d. Provide the expected IR spectrum for the product.

➢ To detect 4-acetoxy-3-methoxybenzylalcohol, we find and C=O bond for ester which

is 1758.36 cm-1 which is the same with C=O in 4-acetoxy-3-methoxybenzaldehyde.
Another functional group that can be detected is alcohol which is 2984.64 cm-1.

Discussion

In this dry lab, we are discussing about the esterification of vanillin. Vanillin is a
polyfunctional compound where it has three functional group attached with an aromatic ring.
The three functional group that attached to the aromatic ring are aldehyde group, hydroxyl
group and methoxy group. Based on what I have searched and learned, when the vanillin react
with acetic anhydride in the presence of NaOH or base, the OH ion will attack the hydroxy
group that attached at the aromatic ring causing the OH group to react with the acetic anhydride
and eventually formed an ester. While, for the reaction of vanillin with acetic anhydride in the
presence of H2SO4, an ester was formed same as the ester in basic condition. However, the
reaction was said to continue reacting to produce a final product. After the ester was formed,
this product will react with a weak nucleophile and it attacked the aldehyde group where the
final product was formed. The aldehyde will eventually become an alcohol group. As the final
product, 4-acetoxy-3-methoxybenzaldehyde was formed in the presence of base and, 4-
acetoxy-3-methoxybenzylalcohol was formed in the presence of acid (What is the product in
an esterification of vanillin with acetic anhydride, 2020).

As for the observation, in the acid-catalyzed reaction, the solution turn into purple-
orange colour. After the crystal for both products are formed, it was identified using the IR and
NMR spectrum. For IR spectrum, we can distinguish vanillin acetate and vanillyl alcohol. In
the IR spectrum of vanillin acetate, we can detect the C=O for ester at 1758.36 cm-1 while for
the vanillyl alcohol, we can detect the O-H bond at 2984.64 cm-1.In the H NMR spectrum both
products show the chemical shift of H for the ester group at 6 ppm. to distinguish the product,
vanillin acetate has a chemical shift at 10 ppm where the H ion for aldehyde is shifted.
Meanwhile, for vanillyl alcohol, the chemical shift for H of alcohol is at 3.9 ppm.

As for the percentage yield for the product, I get 0.23% for vanillyl alcohol and 1.01%
for vanillyl acetate. The limiting reactant is vanillin as vanillin are used up early than the acetic
anhydride. 1 mol of vanillin react with 1 mol of acetic anhydride to produce 1 mol of vanillin
acetate and 1 mol of vanillyl alcohol.

Lastly, for precaution that need to be remembered when conducting this experiment is
to always take the measurement in the measuring cylinder at the eye level to avoid parallax
error. Other than that, we must be careful when pouring the solution into a beaker or other
apparatus because some of the chemicals can evaporated easily such as methylene chloride.
Besides that, always use a proper attire when doing experiment such as wearing lab coat, gloves
and mask so that any unwanted accidents or injuries can be avoided.

Conclusion

There are two products formed, one for the product formed in acidic condition and the
other are in basic condition. In acidic condition the product formed is 4-acetoxy-3-
methoxybenzylacohol while in basic condition, the product formed is 4-acetoxy-3-
methoxybenzaldehyde. Both of the products were identified using the IR and NMR spectrum.
Besides that, the percentage yield for both product was calculated where 0.23% for the acidic
and 1.01% for the basic condition. The mechanism of the reaction was also studied.

Questions

1. Under different reaction media, vanillin undergoes esterification with acetyl chloride
yielding two different products.

Basic or
?
acidic medium

Vanillin

a) Based on the IR spectrum of vanillin, at what range should you observe the absorption
signal of the hydroxyl group?
From the IR spectrum of vanillin, the signal absorption for the hydroxyl group in
vanillin is form the range 3580 – 3650.

b) Based on its 1H NMR spectrum, what is the expected chemical shift value for the
methoxy group (OCH3)? What is its multiplicity?
From the 1H NMR spectrum of vanillin, the expected chemical shift value for methoxy
group is 3.8 ppm. The multiplicity for the methoxy group is 2 or duplet because the at
the adjacent carbon is 1. So, 1 + 1= 2.
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.
3. Task 4 :
1
4. 1. Figure 1 shows the H-NMR (400 MHz, CDCl3) spectra of 4-ethoxy-3-methoxy
benzaldehyde (top) and 4-ethoxy-3-methoxy benzyl alcohol (bottom). Label the major peak
and fill in expected integration values of the 1H NMR.

C=O

O-H

Figure 1
a) For basic condition: 4-acetoxy-3-methoxybenzaldehyde
The major peak is C=O where the chemical shift is 10ppm.
b) For acidic condition: 4-acetoxy-3-methoxybenzylacohol
The major peak is O-H where the chemical shift is 3.9 or 4 ppm.
2. Figure 2 shows the IR spectra of 4-ethoxy-3-methoxybenzaldehyde (top) and 4- ethoxy-3-
methoxy benzyl alcohol (bottom). Assign the functional groups to the IR spectra.

Figure 2

c) For basic condition: 4-acetoxy-3-methoxybenzaldehyde

Functional group Wavenumber, cm-1

Ester , C=O – R 1735 – 1750

Aldehyde, C=O 1670 – 1740

Ether/ methoxy group 1400 – 1090

d) For acidic condition: 4-acetoxy-3-methoxybenzylacohol

Functional group Wavenumber, cm-1

Ester , C=O – R 1735 – 1750

Alcohol, O – H 3200 – 3550

Ether/ methoxy group 1400 – 1090

References

websites
Esterification. (2020, April 19). Retrieved from chemguide :
https://www.chemguide.co.uk/organicprops/alcohols/esterification.html

Infrared Spectroscopy. (2019, June 3). Retrieved from Chemistry LibreText:

https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbo
ok_Maps/Supplemental_Modules_(Physical_and_Theoretical_Chemistry)/Spectrosco
py/Vibrational_Spectroscopy/Infrared_Spectroscopy

Isac-Garcia, J. (2016). Vanillin. Retrieved from ScienceDirect:

https://www.sciencedirect.com/topics/chemistry/vanillin

Nuclear Magnetic Resonance Spectroscopy. (2020). Retrieved from Chemistru MSU:

https://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Spectrpy/nmr/nmr1.htm

What is the product in an esterification of vanillin with acetic anhydride. (2020, April 18).
Retrieved from Study.Com: https://study.com/academy/answer/what-is-the-product-
in-an-esterification-of-of-vanillin-with-acetic-anhydride-in-the-presence-of-base-
what-is-the-product-in-the-presence-of-acid-if-these-products-are-the-same-explain-
why-the-base.html
Pre- Laboratory preparations