EXPERIMENT 3 – ESTERIFICATION REACTION OF VANILLIN : THE USE OF

NMR TO DETERMINE A STRUCTURE

Objective of the Experiment

 To investigate the reactions between vanillin and acetic anhydride under two conditions,
basic and acidic conditions, measure the melting points, obtain NMR and IR spectra.

Introduction
Vanillin (4-hydroxy-3-methoxybenzaldehyde), a pleasant smelling aromatic compound, occurs
naturally in vanilla beans. Vanillin is used widely as a flavouring additive for beverages, cooking
and aromatic additive for candles, incense, potpourri, fragrances, perfumes, and air fresheners.
Vanilin is a phenolic aldehydes, an organic compound with the molecular formula C8H8O3.

Vanillin is also a multifunctional compound that reacted with acetic anhydrite under acidic
or basic condition to formed different products that is ester 1 and ester 2 as shown in the figure
above. The reaction of vanillin with acetic anhydride in the presence of base is an example of the
esterification of a phenol. The product, which is a white solid, can be characterized easily by its
IR and NMR spectra. It is expected to get the same compound in base reaction but the spectrum
shows different compound formed when reacted under acidic condition.

List of Apparatus and Chemicals

 250 ml Erlenmayer flask  30g crushed ice
 Rubber stopper  4 ml acetic anhydride
 Buchner funnel  5 ml ice-cold water
 Vacuum filtration  95% ethyl alcohol
 Measuring cylinder  Hot-water bath
 1.50 g vanillin  1.0 M sulphuric acid
 25 ml 0f 10% NaOH
Experimental procedures
Acidic condition :
1. 1.5 g of vanillin was added into a conical flask containing 10 mL of acetic acid.
2. 10 drops of 1.0M H2SO4 was added slowly into the solution with stirring.
3. The mixture then was stirred for 1 hour by using magnetic stirrer at room temperature.
4. After the stirring was done, the mixture was placed in cool ice bath for about 4 minutes.
5. 35 mL of ice cold water was added into the mixture, and was shaken to induce the
crystallization.
6. The mixture was filtered by using Buchner funnel to collect the crystal.
7. The crystal was washed with 3 portions of 5 mL ice cold water.
8. For recrystallization, 15 mL warm ethanol (below 60°C) was added with the crystal
collected from the filtration until it dissolved.
9. The mixture was put in ice bath to initiate the recrystallization.
10. The mixture was filtered again until dry crystal was obtained.
11. The weight of product was recorded and the melting point, NMR and also IR spectra were
tested.
Basic condition :
1. 1.5g of vanillin was added into a conical flask with 25mL of 10% NaOH solution.
2. 4mL of acetic anhydride and 30g of crushed ice were added into the solution.
3. The mixture was shaken for 20minutes and cloudy, milky white precipitate will form.
4. The mixture then was filtered by using Buchner funnel with washing of 3 portions of 5mL
ice-cold water.
5. For recrystallization, 15mL warm ethanol (below 60°C) was added with the crystal
collected from the filtration until it dissolved.
6. The mixture was put in ice bath to initiate the recrystallization.
7. The mixture was filtered again until dry crystal was obtained.
8. The weight of product was recorded and the melting point, NMR and also IR spectra were
tested.
Results
Basic condition Acid Condition
Mass of vanillin (g) 1.5002
Mass of empty beaker (g) 35.0320
Mass of beaker + crystal (g) 36.8316

Basic condition Acid Condition

Mass of product (g) 1.7996 2.4563
Theoretical yield (g) 1.9204 2.4563
Percentage yield (%) 93.71 83.83
Melting point of crystal (°C) 78 92

FTIR Results :
Compound (C=O-OR) / cm-1 (C=O) / cm-1 (O-H) / cm-1
Basic condition
Acid condition -

Observations
 When preparing vinyllyl acetate, cloudy white and milky precipitate of product was
formed.
 On the other hand, in esterification of vanillin in the presence of acid, the solution turns to
purple orange after 1 hour.
Calculations

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛
Mole of vanillin : 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛

1.5061 g
= 152.15g/mol

= 9.8988 × 10-3 mol

(𝑣𝑜𝑙𝑢𝑚𝑒 × 𝑑𝑒𝑛𝑠𝑖𝑡𝑦)
Mole of acetic anhydride : 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑐𝑒𝑡𝑖𝑐 𝑎𝑛ℎ𝑦𝑑𝑟𝑖𝑑𝑒

(25 ml × 1.082 g/ml)

= 102.09 g/mol

= 0.2649 mol

So, the limiting reactant is vanillin.

For the reaction with basic product,

Theoretical yield : mole of limiting reactant × molar mass of product
= 9.8988 × 10-3 mole × 194 g/mole
= 1.9204 g
Actual yield : 1.7996 g
𝐴𝑐𝑡𝑢𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
Percentage yield : × 100%
𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑

1.7996
= × 100 %
1.9204

= 93.71 %
(𝑇ℎ𝑒𝑜𝑟𝑒𝑐𝑡𝑖𝑐𝑎𝑙−𝑎𝑐𝑡𝑢𝑎𝑙 𝑦𝑖𝑒𝑙𝑑)
Percentage error of basic reaction = × 100
𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑

(1.92014− 1.7996)
= × 100 %
1.9204

= 6.29 %
For the reaction with acidic product,
Theoretical yield : mole of limiting reactant × molar mass of product
= 9.8988 x 10-3 mole × 296 g/mole
= 2.9300 g
Actual yield : 2.4563 g
𝐴𝑐𝑡𝑢𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
Percentage yield : × 100%
𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑

2.4563
= × 100 %
2.9300

= 83.83 %
(𝑇ℎ𝑒𝑜𝑟𝑒𝑐𝑡𝑖𝑐𝑎𝑙−𝑎𝑐𝑡𝑢𝑎𝑙 𝑦𝑖𝑒𝑙𝑑)
Percentage error of acidic reaction = × 100 %
𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑

2.9300−2.4563
= × 100 %
2.9300

= 16.17 %
Discussion
Aldehydes can react with alcohols to form hemiacetals and acetals by an equilibrium reaction. The
essential structural features of hemiacetals are –OH and –OR attached group on the same carbon
atom. An acetal has two –OR group for each carbon. If we take some alcohol solution and pass
into small amount of gaseous HCl a hemiacetals formed and the hemiacetal react with a second
molar equivalent of the alcohol to produce an acetal.

For the mechanism of the basic condition, the acetic anhydride plays the part of the electrophile,
undergoing nucleophile attack by the alcohol when an anhydride reacts with an alcohol for both
acidic and basic conditions. The vanillin molecule has several functional groups, among them
alcohol, ether, and aldehyde. The base-catalyzed reaction is a straightforward esterification and
does not produce any other significant products because esterification stops at the ester. However,
the acid-catalyzed esterification does not form only the ester. It forms the ester, but this ester
continues to react because there are other functional groups present in the molecule that can react
with the anhydride under base or acid conditions.

For esterification reaction of vanillin under acidic condition, vanillin react with acetic anhydride
to produce vanillin triacetate while under basic condition, it produce vanillin acetate. These
product formed was supposed confirmed by using IR and NMR. Unfortunately, the NMR
instrument showed incorrect data as the instrument needed to be service first.

The functional group for both acid and basic product has been determined using IR spectrum. From
the basic IR spectrum, there are (C=O-OR) group which present at the peak of cm-1
(Ester) and for acidic condition is cm-1 (Ester). Besides, there are also (C=O) group
-1
which at frequency cm (Aldehyde) for basic and cm-1 (Aldehyde) in acidic
condition. In addition, there is present in O-H group but only for basic condition.

Conclusions
The reaction between vanillin and acetic anhydride under two conditions are successfully
investigated. The products formed is determined using IR, NMR and melting point comparisons.
The compound in acidic and basic condition was identified. The melting point of the acidic product
is 92˚C while the melting point of the basic product is 78˚C. The percentage yield of the basic
product is 93.71 % while the percentage yield of the acidic product is 83.83 %.
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?

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.
References
 Laboratory textbook: Pavia, Lampman, Kriz and Engel, Introduction to Organic
Laboratory Techniques 3rd Edition, Page 49
 Vanillin, http://en.wikipedia.org/wiki/Vanillin , retrieve on 7 April 2013
 Acetic anhydride, http://en.wikipedia.org/wiki/Acetic_anhydride , retrieve on 7 April 2013
 Esterification reaction of vanillin,
http://www.lhup.edu/mmaresch/Chem430/CH430Lab/vanillin.htm , retrieve on 7 April
2013