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CHM 556

ORGANIC CHEMISTRY (II)


EXPERIMENT 3 :
ESTERIFICATION REACTIONS OF VANILIN :
THE USE OF NMR TO DETERMINE A
STRUCTURE
Lab group : ASB3Ag
Lecturers name : Prof Assoc. Zurina Binti Mahmud
Date of the experiment : 16 October 2014
Date of submission : 27 November 2014

Objectives :

1. To investigate the reactions between vanillin and acetic anhydride under two
conditions, basic and acidic condition.
2. To propose mechanism that will explain why the reaction proceeds differently under
basic and acidic conditions.
3. To determine the melting points and the structure of product by using NMR and IR
spectra.

Introduction :

Figure 3.0 : product when reacted in acidic and basic condition

Vanillin, (4-hydroxy-3-methoxybenzaldehyde), 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 3.0. One of the product is a monoester, formed by reaction at the
phenol OH group in vanillin. The other is a triester, with one ester forming at the phenol OH
group and two esters forming at the aldehyde group. 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.
Apparatus :
1.
2.
3.
4.
5.

250 ml Erlenmayer flask


Rubber stopper
Buchner funnel
Vacuum filtration
Measuring cylinder

Chemicals :
1.
2.
3.
4.

1.50 g vanillin
25 ml 0f 10% NaOH
30g crushed ice
4 ml acetic anhydride

5.
6.
7.
8.

5 ml ice-cold water
95% ethyl alcohol
Hot-water bath
1.0 M sulphuric acid

Procedure :
4- Acetoxy- 3- Methoxybenzaldehyde (Vinillyl Acetate) was prepared by 1.5g of vanillin was
dissolved in 25 ml of 10% sodium hydroxide in a 250 ml Erlenmeyer flask.Then 30g of crushed
ice and 4 ml of acetic anhydride are added. After that, stopper the flask with a clean rubber
stopper, and the mixture was shaked several times for 20 minutes. After adding acetic anhydride,
it was noted that a cloudy, milky white precipitate was formed immediately.In addition, the
precipitate formed was filtered using Buchner funnel and the solid was washed with three 5 ml
portions of ice-cold water. The solid was recrystallize from 95% ethyl alcohol. The solid was
dissolved by adding small portions of hot 95% ethyl alcohol. If the solid dissolves, no more
solvent is added. But if the solid has not dissolved, another portion of boiling solvent is added, as
before, and the process is repeated until the solid dissolves. After all the solid have been
dissolved, the solution was filtered into another conical flask. The flask that contains crystal was
put in a beaker that had ice water bath for 10-15 minutes at room temperature. The flask was
scratched with a glass rod. The crystal was collected by vacuum filtration using a Buchner
funnel. The crystal was rinsed with a small portion of cold solvent. The crystals were dried,
weight, and the percentage yield was calculated. The melting point, IR and NMR were obtained.
In esterification of vanillin in the present of acid site, 1.5g of vanillin was dissolved in 10
ml of acetic anhydride in a 125 ml Erlenmeyer flask. Magnetic stir bar was placed in the flask,
and the mixture was stirred at room temperature until the solid dissolves.Then, 10 drop of 1.0M
sulphuric acid was added to the reaction mixture.Stopper the flask, and the mixture was stirred at
room temperature for 1hour. The flask was cooled in an ice water bath for 4-5 minutes at the end
of reaction. 35 ml of ice-cold water was added to the mixture in the flask. The flask was stopper
tightly and shake the flask vigorously. The product was filtered and washed with three 5 ml icecold water. The crude product was recrystallizing from hot 95% ethanol. The recrystallization
step was repeated as mention in above procedure. The crystal was allowed to dry. The dried
crystals was weighed and the percentage yield was calculated. The melting point, IR, and NMR
were obtained.

Result :
Basic condition :

Mass of vanillin
Mass of empty petri dish
Mass of petri dish + crystal
Mass of crystal
Melting point of crystal

1.5061 g
17.4340 g
18.1991 g
0.7651 g
79.0oC

Acid condition :
Mass of vanillin
Mass of empty petri dish
Mass of petri dish + crystal
Mass of crystal
Melting point of crystal

1.5009 g
16.9932 g
18.5114 g
1.5182 g
91.0oC

FTIR result :
Compound

(C=O-OR) /cm-1

(C=O)/ cm-1

(O-H)/ cm-1

Basic condition

1750.99(Ester)
1207.21 (Acetate)

1691.09(Aldehyde)

3422.43(Alcohol)

Acid condition

1751.60 (Ester)
1206.74 (Acetate)

1690.32 (Aldehyde)

Observation :
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.

Calculation :
Mole of vanillin : mass of vanillin/molar mass of vanillin
=1.5061 g/152.15g/mol
=9.8988 x 10-3 mol

Mole of acetic anhydride : (volume x density) / molar mass of acetic anhydride


=(10 ml x 1.082 g/ml) /102.09 g/mol
=0.1058 mol
So, the limiting reactant is vanillin

For the reaction with basic product,


Theoretical yield : mol of limiting reactant x molar mass of product
=9.8988 x 10-3 mol x 194 g/mol
=1.9204 g
Actual yield : 1.0056 g
Percentage yield : (Actual yield/ Theoretical yield) x 100%
=(1.0056 g/1.9204 g) x 100%
=52.36%
Percentage error of acidic reaction =

(theoretical yieldactual yield )


theoretical yield

1.92041.0056

=
1.9204

X 100

= 47.64%

For the reaction with acidic product,


Theoretical yield : mol of limiting reactant x molar mass of product
=9.8988 x 10-3 mol x 296 g/mol
=2.9300 g
Actual yield : 1.5182 g

X 100

Percentage yield : (Actual yield/ Theoretical yield) x 100%


=(1.5182 g /2.9300 g) x 100%
=51.82%

Percentage error of acidic reaction =

(2.93001.5182)
2.9300

= 48.18%

Discussion :
In this experiment,

(theoretical yieldactual yield )


theoretical yield

X 100

X 100

In this experiment 3, the percentage yield of pure product in basic condition is 52.36% and for
the acidic condition is 51.82%. The yield seems very small because the product was lost when
we transferred it into filter paper during filtration. Another error is because we did not scratch the
flask with carefully to initiate crystallization. The melting point for reaction under basic
condition is 79C while under acidic condition is 91C. These melting points is under literature
range values (base is 77C-79C) and (acid is 90C-91C).
For the mechanismof 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 confirmed by using IR and NMR. The NMR showed that product
formed under basic is vanillin acetate and under acidic is vanillin triacetate. For basic condition,
one hydrogen is present at 10 ppm and this showed that the product formed consist of aldehyde.
In acidic, this value is absent, means that product formed does not contain aldehyde group. In
basic, there are present in hydrogen but three hydrogen at 2.3 ppm while in acidic is nine
hydrogen.So, base contain only one ester while acid contain three ester groups. At 3.9 ppm,
products in base and acid contain same number of hydrogen which is three hydrogen. These
showed that the presence of OCH3. At 7.5 ppm, there are three hydrogen present both in basic
and acidic. These showed that the presence of hydrogen with aromatic ring. Based on the
spectrum, we can conclude that the functional group of the product that produced is ester.
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
1750.99cm-1(Ester) and 1207.21cm-1 (Acetate) and for acidic condition is 1751.60 cm-1 (Ester)
and 1206.74 cm-1 (Acetate).Besides, there are also (C=O) group which at frequency 1691.09 cm 1
(Aldehyde) for basic and 1690.32cm-1 (Aldehyde) in acidic condition.In addition, there is
present in O-H group but only for basic condition that is 3422.43cm-1.

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 mechanism for products formed is successfully drawn. The percentage yield of product
under basic condition is 52.36% and for the acidic condition is 51.82%. The experiment goals
were achieved.

References:
[1] Laboratory textbook: Pavia, Lampman, Kriz and Engel, Introduction to Organic Laboratory
Techniques 3rd Edition, Page 49
[2]Vanillin, http://en.wikipedia.org/wiki/Vanillin ,retrieve on 7 April 2013
[3]Acetic anhydride, http://en.wikipedia.org/wiki/Acetic_anhydride,retrieve on 7 April 2013
[4]Esterification reaction of vanillin,
http://www.lhup.edu/mmaresch/Chem430/CH430Lab/vanillin.htm, retrieve on 7 April 2013
[5]Experiment 2 , http://www.chem.moravian.edu/~rdlibby/_211-212ChemPDF/Laboratory/Experiments/212-08Lab/Expt2-AcylSub/_Expt_2_AcylSub-Handout-wk1.pdf ,
retrieve on 7 April 2013

Mechanisms: