Synthesis of Artificial Flavoring Agent

Muhammad Noor Wali

Contribution from Department of Chemistry, LUMS Syed Babar Ali School of Science and
Engineering, Opposite U Block, 54792, DHA Lahore
Received 4th March 2020; Email: [email protected]

ABSTRACT: Benzyl Acetate, which is an artificial flavoring agent was synthesized using the
process of esterification by reacting benzyl alcohol with acetic acid in the presence of sulfuric
acid under reflux. The reaction was monitored using TLC by calculating the Rf value of the
reactants and the product. After the completion of the reaction, the mixture was neutralized, and
the product was extracted using separation funnel. Finally, using rotary evaporator, the solvent
used for extraction was removed and ester in liquid form was obtained in low yield-59%. The
presence of the ester was confirmed using FTIR by assigning major peaks.

INTRODUCTION and their derivatives with alcohols/halo

hydrocarbons are reliable methods for the
Over the years there has been quite a lot of
preparation of esters. However, these
use of artificial flavoring agents. Artificial
protocols require the pre-functionalization of
flavors are usually organic compounds
substrates and often suffer from harsh
which are volatile and they produce some
reaction conditions.2 Aromatic esters are
flavor. These organic compounds include
very important chemicals having wide
ketones, aldehydes and ethers. But artificial
applications in a variety of areas in chemical
compounds mostly contain esters which are
industry such as perfumes, flavors,
produced by a reaction called esterification
pharmaceuticals, plasticizers, solvents and
in which alcohols are reacted with
intermediates.3 Esters are also present in
carboxylic acids in the presence of a strong
natural products such as orange whose
acid (usually concentrated sulfuric acid) as a
flavor contains octyl acetate
catalyst to produce ester and water. This
(CH3COOC8H17), Isoamyl acetate
reaction belongs to a very important class of
(CH3COOC5H11) is the component of the
reactions, especially physiologically referred
banana flavor. Similarly, many other fruits
to as a condensation/dehydration reaction. It
such as raspberry, pear, pineapple etc. all
is similar to the reactions used to produce
contain esters which give them their flavor.
proteins, DNA and RNA.1 This acid
In this experiment, Benzyl acetate which is a
catalyzed reaction is the simplest reaction to
constituent of essential oils from flowers
prepare esters and is known as the Fischer
such as jasmine, tobira and ylang-ylang was
Reaction. In this reaction the reactants and
synthesized using Fischer reaction. Benzyl
the products are in an equilibrium and the
acetate is a fragrance ingredient used in
position of the equilibrium can be changed
many compounds. It may be found in
by removing the product from the reaction
fragrances used in decorative cosmetics, fine
mixture or adding excess of the reactants.
fragrances, shampoos, toilet soaps, other
However, Fischer reaction has some
toiletries, and non-cosmetic products such as
problems associated with it. In general, the
household cleaners and detergents.4 It is
nucleophilic reactions of carboxylic acids
used in the perfume industry as well as in
the flavorings industry to stimulate the for this purpose is known as IR
flavors of apple, banana, strawberry and spectrometer.1
pear flavors. It is used as a solvent as well in
EXPERIMENTAL SECTION
plastics, resin, cellulose acetate, nitrate, oils,
lacquer, polishes and inks. For this Chemicals and Materials Glacial acetic
esterification reaction to occur using the acid, benzyl alcohol, sulfuric acid, diethyl
principles of the Fischer reaction, benzyl ether, sodium hydrogen carbonate and
alcohol has to be reacted with an acid in the anhydrous magnesium sulphate.
presence of few drops of concentrated
sulfuric acid under reflux. The reaction Glassware and Equipment A round bottom
scheme of this experiment is given in the flask (100 mL), a pipette, a pipette sucker, a
figure below. magnetic bar, a reflux condenser, a heating
mantle, TLC plates, TLC tank, pH papers, a
O
HO O H2SO4
O
separating funnel, filter papers, beaker (250
+ Few Drops H2O
OH
+
mL), stem funnel, an Erlenmeyer flask (100
benzyl alcohol acetic acid benzyl acetate
mL), a glass rod, a graduated cylinder, and
Fig 1. Reactions involving the synthesis of an iron ring stand with ring clamp, etc.
benzyl acetate Procedure 20mL of acetic acid was pipetted
The progress of the reaction will be into a 100ml round bottom flask. 10 mL of
measured using TLC. To obtain a neutral benzyl alcohol was added in the same round
product, the mixture should be neutralized bottom flask. 2-3 drops of sulfuric acid were
and should pass through separation funnel to added using a pasture pipette into the same
remove water produced during esterification flask as a catalyst. Magnetic stir bar was
and neutralization to obtain the ester in pure added to the flask and the assembly was set
and dry form. Finally, rotary evaporation has up for reflux. The progress of the reaction
to be done to remove the organic layer was measured using TLC for which the
(solvent) in which the product is present. solvent was n-hexane: ethyl acetate (3:1). A
Rotavap is used to dry a product by sample of mixture from the flask was taken
removing the solvent under reduced and was introduced onto the TLC plate
pressure. This allows us to achieve which was kept in the solvent. The reaction
evaporation at lower temperatures. FTIR was considered complete when the mixture
will be used to confirm the presence of spot of benzyl alcohol (which was one of the
benzyl acetate. It is a technique that deals reactants) diminished and stopped travelling
with the outcome of interaction of matter and the mixture spot of the product travelled
with infrared region of the electromagnetic ahead. The reaction continued for an hour
radiations i.e., light with a wavelength range and thirty minutes. The reaction was stopped
higher than visible light and shorter than that after the confirmation of completion and
associated with microwaves i.e. 0.8 - 1000 was allowed to cool at room temperature.
μm. IR spectroscopy is used to identify the The excess acetic acid was removed using
chemical compounds by recognizing the rotary evaporator, and then the remaining
nature of chemical functional groups present mixture was added to a beaker containing
in the molecule and the spectrometer used 60mL of distilled water. The resulting
solution was neutralized using sodium
bicarbonate. The neutrality of the solution 10.4
= =0.09617
was confirmed by using pH paper. The 108.14
solution was transferred to a separating
Molecular weight of benzyl acetate=150.18
funnel. Diethyl ether was added to the
g/mol
separating funnel and after shaking and
venting for 2-3 minutes, the oily layer Theoretical yield of benzyl acetate=
containing the ester was extracted and 0.09617*150.18=14.44g
drained into another beaker. After this,
2. Calculation of experimental yield
anhydrous magnesium sulfate was added
into the organic layer as a dehydrating agent Mass of empty 52.965
and the mixture was allowed to settle for 5 round bottom flask
minutes. Next, gravity filtration of the Mass of flask + 61.484
mixture was performed to separate the Ester
magnesium sulfate from the mixture. Then, Mass of Ester 8.519
an empty and dry round bottom flask was produced
weighed and the filtrate from the gravity Table 1. Recordings of masses in grams to
filtration was added to this flask. The calculate the mass of ester produced.
solvent was removed using rotary 3. Percentage yield calculation
evaporation and we obtained ester in liquid
form. The flask was then reweighed to Percentage yield=
calculate the amount of product produced. Experimental yield 8.519
∗100= ∗100=58.99 %
The product was confirmed by using FTIR Theoretical yield 14.44
and by assigning major peaks.
For the calculation of percentage yield, we
RESULTS AND DISCUSSION must first know which of the reactants is
limiting because the amount of the limiting
Percentage yield calculation reactant determines the amount of product
The percentage yield calculation involves produced. By calculating the number of
three steps: moles of each reactant or simply by looking
at their volumes used, it is evident that
1. Calculation of theoretical yield benzyl alcohol was the limiting reactant.
Volume of benzyl alcohol used=10ml The number of moles of benzyl alcohol were
calculated by using its density. As it can be
Density of benzyl alcohol=1.04 g/ml seen in Fig 1, the molar ratio of benzyl
Mass of benzyl alcohol used alcohol to benzyl acetate is 1:1. These
results helped us calculate the percentage
=Density of benzyl alcohol * Volume of yield of benzyl acetate produced. The
benzyl alcohol used percentage yield appeared to be low because
= 1.04*10=10.4g of some reasons. Firstly, during shaking and
venting of the separation funnel, the
Molecular weight of benzyl alcohol=108.14 pressure built up in the funnel was so high
g/mol that the stop cock of the funnel was pushed
out which resulted in some loss of the
Moles of benzyl alcohol used
organic layer containing the product. Also,
 during the gravity filtration some of the the standard IR wavenumbers provided by
product was stuck with anhydrous the website of the Department of Chemistry
magnesium sulfate which might have UCLA. The standard values are quoted in
resulted in the decrease of percentage yield. Table 2.
This could have improved if we used
vacuum filtration instead of gravity filtration
which would have separated all of the TLC
organic layer.
Solvent Front
Characterization of the product using Rf = 0.76
FTIR
9 0 1 00
50 60 70 80
Tran smi tta nc e [%]
40
30
20

3089. 14
3065. 83
3033. 50
2952. 71

1734. 72

1497. 47
1455. 39
1362 .21

1221 .76

1080. 47
1024. 31
964. 17
920. 88
903. 35
836. 39
735. 86
696. 00
611. 23

400 0 3 500 300 0 2 500 2 000 150 0 1 000 500

Wa ven umbe rc m-1

Rf = 0.28

R Base Line
P

Fig 3. TLC of the reaction mixture

Rf value calculation:
Distance travelled by the product=22 mm
Distance travelled by the reactant= 8mm
C:\PROGRAM FILES\OPUS_65\MEAS\22100069-OL-EX5-2020.0 22100069-OL-EX5-2020 ATR platinum Diamond 1 Refl 05/03/2020

Page 1/1 Solvent Front= 29mm

Fig 2. IR Spectrum of the product Rf value of the product
Type of
Standard Experimental DistanceTravelled by the product
Phenomeno
Wavenumber Wavenumber = =
Solvent front
(cm-1)
n (cm-1) 22
C=O Ester
1750-1720 1734.72 =0.759
29
(strong)
C-O-C 1250-1050 1221.78 Rf value of the reactant
(strong)
DistanceTravelled by the reactant
Benzene ring 1600-1400 1497.47 = =
Solvent front
(weak)
Table 2. IR Spectrum of Benzyl acetate 8
=0.28
29
For confirming the functional groups of
Benzyl Acetate, IR spectroscopy of the TLC was done to monitor the reaction
product produced was carried out. FTIR progress. For this a spot of benzyl alcohol
Spectrum (Fig 2.) shows the presence of the was introduced on the plate and was labelled
functional groups of benzyl acetate. The as R. Simultaneously, a spot was taken from
spectrum indicates the presence of a C=O the reaction mixture and was introduced on
ester bond (1734.72 cm-1), a C-O-C group the plate and labelled as P. The TLC plate
(1221.78 cm-1) and a benzene ring (1497.47 was kept in a solvent for which n-hexane:
cm-1). All these values were compared with ethyl acetate was 3:1. The set up was kept in
a beaker which was covered to prevent the Sulfuric acid is a dehydrating agent as well
evaporation of the solvent. The plate was and might assist in the removal of small
monitored under UV and the spot of the amount of water produced during the
reactant diminished and did not travel much. reaction. As a result higher yield may be
But the spot of the product was visible and achieved. Acetic acid was used in excess
travelled along the plate. This can be seen and was removed using rotary evaporator.
from the Rf values as well where benzyl Sodium bicarbonate was added to neutralize
acetate as a Rf value of 0.759 as compared the aqueous solution containing the organic
to benzyl alcohol which has a Rf value of product and water. During the extraction of
0.28. our product from the aqueous layer, we
added diethyl ether because our product is
Improvements for the experiment Since
an ester which is non-polar and won’t be
water is produced in this reaction, therefore,
soluble in the aqueous layer. Therefore, by
to achieve a higher yield it must be removed
using diethyl ether, which is non-polar as
to shift the position of the equilibrium
well, we can isolate our product from the
towards the forward side. In this experiment
aqueous phase. Since the separated organic
we could have introduced Dean Stark
layer might contain a little amount of water
apparatus which removes water produced in
and water takes a lot of time to be removed
organic reactions carried out under reflux. In
if we use rotary evaporator. Therefore,
the Dean’s Stark apparatus, the water
anhydrous magnesium sulfate was added as
produced during the reaction is collected in
a dehydrating agent to remove any sort of
the burette and it can be removed using its
water droplets left in the organic layer.
tap. Since we’re removing one of the
products the equilibrium shifts towards the CONCLUSION
forward side according to Le Chatelier’s
Synthesis of benzyl acetate by reacting
principle. As a result, we can achieve a
benzyl alcohol and acetic acid, in the
higher yield of benzyl acetate.
presence of strong acid, under reflux was
Uses of the reagents used in the reaction successful. A yield of 59% was produced.
and workup Since we performed the The benzyl acetate formed was separated
Fischer Reaction of esterification, we from the aqueous solution using separating
needed an alcohol and a carboxylic acid to funnel with the addition of diethyl ether. The
produce ester and, in this experiment, we solvent of the organic layer was removed
produced benzyl acetate so we needed using rotary evaporator to obtain ester. The
benzyl alcohol and acetic acid. The reaction presence of the compound was confirmed by
took place in the presence of few drops of using FTIR and analyzing the IR spectrum
concentrated sulfuric acid, which was added of the functional groups by assigning major
to the reaction mixture as a catalyst since peaks. Although the yield came out to be
under acidic conditions the carbonyl group around 60% which was less than it should
of the acid becomes protonated and thus have been which was due to the loss of
allows quicker nucleophilic substitution. By materials during the pressure built in the
protonating the carbonyl oxygen, it reduces separating funnel while shaking and venting.
the energy gap between HOMO and LUMO
Post Lab Questions
of the oxygen. Hence, acting as a catalyst.
 1. Comprehend the strategies to 3. Mechanism of condensation
improve yield of the product under reaction between carboxylic acid
milder conditions using acid and alcohol
derivatives O HO
1
1
6
5
OH
The Fischer Reaction is a simple reaction to 2
1 OH
H+ OH
2
3
4 OH
H3C OH
OH
perform. However, it requires strong acetic acid

conditions such as high temperatures, usage

of catalysts and requires a lot of time as H2SO4
HSO4-1

well. Similarly, carboxylic acid derivatives

such as acyl halides, acid anhydrides and O OH OH2
OH
OH
amides can be used for the production of O HSO4-1
O H3C O OH
H H3C O

esters as well. These acid derivatives allow H2SO4

the reaction to occur at milder conditions.

Reacting acyl halides with alcohols is a Fig 4. Mechanism of condensation
time-efficient reaction (requires 1 hour). The reaction between acid and alcohol
reaction can happen at room temperature The mechanism of the reaction is shown in
with excellent yields and high efficiency. 5 Fig 4. The addition of sulfuric acid results in
Furthermore, it is also well known that a the protonation of the carbonyl oxygen of
mixed-anhydride method using acetic acid resulting in a lower energy
trifluoroacetic anhydride is sometimes very difference between HOMO and LUMO,
convenient for the generation of bulky allowing the nucleophilic acyl substitution.
carboxylic esters.6 The oxygen of the alcohol attacks the
2. Working and advantages of Dean- electrophilic carbon of the acid. The
stark apparatus. hydrogen of the alcohol will be removed and
The synthesis of many organic compounds will protonate the OH group of the acid
results in the production of water. According making water a good leaving group. After
to Le Chatelier’s Principle the position of the removal of water, a protonated carbonyl
the reaction moves towards the forward side oxygen is formed again. The proton is then
if the amount of the reactants is increased or removed to form H2SO4 from HSO4-1 which
if the product is removed from the reaction shows that sulfuric acid is used a catalyst in
mixture. Therefore, in organic reactions or this reaction.
any type of a chemical reaction where water REFERENCES
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