Exercise 11 Synthesis of Aspirin (Aceylsalicylic Acid From Salicylic Acid)

EXERCISE 11
SYNTHESIS OF ASPIRIN
(Aceylsalicylic Acid from Salicylic Acid)
VI. Results and Discussion

In this experiment, the first part involves synthesizing aspirin ( acetylsalicylic
acid) by mixing 1g salicylic acid with 3ml acetic anhydride, then followed by 5
drops of phosphoric acid. Salicylic acid acts as the limiting reactant in this
experiment. The phosphoric acid acts as a catalyst, protonating the C=O of the
acetic anhydride, thus making it positive and more susceptible to nucleophilic
attack. Excess acetic anhydride was used to drive the formation of product forward
that will increase the amount of product. As stated in the introduction, acetic
anhydride also acts as an alcohol to provide an ester. Thus the process involves
esterification. Esterification is a reaction between a carboxylic acid and an alcohol
wherein the hydroxyl group turns into an ester ( R-OH to R-OCOCH3). Since salicylic
acid is a phenol, it undergoes esterification through subjecting it to reactive
reagent, unlike acetic acid which will not undergo the reaction (Carman,2008). In
general, it is nucleophilic acyl substitution wherein a nucleophile attacks the
carbonyl carbon of an acyl derivative creating an intermediate with the leaving
group and the nucleophile both attached to the carbonyl carbon (McMurry, 2012).
Figure 11.1. shows the mechanism.
Figure 11.1. Mechanism involved in the formation of aspirin.

The mixture of salicylic acid, acetic anhydride, and phosphoric acid was
mixed and heated in a steam bath for 15 minutes making the mixture clear. Heating
the system would hasten the rate of solubility of the salicylic acid to acetic
anhydride since it increases the surface area exposed to reactants (Petrucci,

Herring, Madura & Bissonnette, 2011). Adding dH2O after heating will induce further
esterification of acetylsalicylic acid and decomposition of unreacted acetic
anhydride after the complete formation. Acetic anhydride plus water will produce
acetic acid (CH3COOH). Transparent swirls in the mixture were seen during this
process (Table 11.3). The next steps involve adding 20ml ice cold water after the
vigorous reaction has ended, placing it to room temperature and ice cold bath. The
addition of cold water is vital in recrystallization since acetylsalicylic acid is
insoluble in water, it would precipitate out as solid, crystals of crude aspirin. Cold
water must be used since esters have low melting point (as seen in MSDS part of
this paper). It will make the crude aspirin less soluble. Placing it into an ice cold bath
prevents the hydrolysis (reverse reaction) once the products start to form
(University of Sydney ,nd). If hot water was used, it would favor the reverse reaction
that will cause low % yield (Bruice, 2013).
RCOOH + R'OH
RCOOR' + H2O
Suction filtration and washed with ice-cold dH2O was done after. As seen in
table 11.8, 1.73 g of crude aspirin was obtained during this process. The filtrate was
observed to be a little cloudy. The residue was white and crystalline, the expected
physical properties of aspirin. A theoretical yield of 1.30g acetylsalicylic acid was
computed knowing that only 1g of salicylic acid , the limiting reagent, was used.
The percent yield
in the preparation of aspirin is 135 percent. The calculated
percent yield for the aspirin is high and the reason for this is that either the crude
aspirin can still have impurities contributing to its total mass or was not properly air
dried. The melting point ranges from 110-142 Celsius.
Sample
Mass of crude aspirin (g)
Mass of filter paper + watch glass(g)
Mass of filter paper + aspirin +watch
glass (g)
Percent recovery
Data
1.73
0.22 +24.50=24.77
26.45
135%
Table 11.8. Recovery data for crude aspirin.
The next step is recrystallization. The purpose of recrystallization is to get rid

of contaminating substances that would affect the yield product, such as salts. The
impurities stay in the solution. The dried crude aspirin was dissolved using minimal
amounts of 95% ethanol. Minimal amounts were used because the aim is to make
the mixture saturated as much as possible. Adding too much decreases percent
recovery of the desired aspirin. Cold distilled H2O was then added to allow the
insoluble aspirin to recrystallize then placed in cool bath. This process needs not be
hurried, as recrystallization itself is a slow process unlike precipitation. Similar
process such as separation through suction filtration and cooling in cold bath in
crude aspirin is also done with recrystallized aspirin.As seen in table 11.9,
1.27
grams of recrystallized aspirin was obtained from the 1.76 grams crude aspirin. The
computed value for the % recovery was 72.2 percent. Errors in this part could be
due to the incomplete recrystallization of aspirin or because of some of the initial
crude aspirin was not properly suction flask-ed leaving some of the aspirin in the
filtrate.
Sample
Mass of recrystallized aspirin (g)
Mass of filter paper & watch glass (g)
Mass of filter paper+ watch glass +
aspirin
Percent recovery
Data
1.27
0.24 + 24.50
26.01
72.7 %
Table 11.9. Recovery data for recrystallized aspirin.
The last part of the experiment is determining the melting point. This is done
to assess if the recrystallized aspirin is impure or not. A large difference in the
melting point ranges of crude aspirin and synthesized aspirin indicates impurity
since compounds have uniform structures. It implies that specific compounds, if
pure, should melt at a specific temperature. The theoretical melting point of aspirin
as indicated in the MSDS is 139 degree Celcius. It was determined that the crude
aspirin have a melting point range of 110-142 degree Celcius. The recrystallized
aspirin on the other hand have a melting point range of 120-134 degree Celcius.
Although the synthesized aspirin is relatively shorter in range than crude aspirin, its
range did not pass through the theoretical melting point of 139 C. The wide range
of crude aspirin tells that there are still impurities. The observed values indicate
that the obtained aspirin (crude and synthesized) are both impure.
In characterizing salicylic acid(starting material) to acetylsalicylic acid

(product), chemical tests were performed. The first test involves potassium
permanganate. It is used to determine the presence or absence of primary or
secondary alcohol groups. Loss of violet color and precipitation of brown particles
would indicate positive results. The expected or theoretical result should be positive
for salicylic and negative in synthesized aspirin. As seen in table 11.10, it is
observed that negative results are concluded from salicylic and synthesized aspirin
observations. The reaction in salicylic acid produced yellow mixture while in
synthesized aspirin, it produced yellow orange liquid.
The next test is the FeCl3 test which is commonly used to determine the
presence of phenols. FeCl3 reacts with phenols and produces violet/purple colored
complexes. In the experiment, a purple complex was observed in salicylic acid since
it had a phenol group. The observed results agreed with the theoretical results.
Salicylic acid is positive and synthesized aspirin is negative.
Salicylic
+/-
OBERVATIONS
Synthesized
KMnO4
Acid
Yellow
Aspirin
Yellow
FeCl3
mixture
Turned dark
liquid
Light
Test
purple
mixture
+/-
Acetic
+/-
orange
Anhydride
Pink
purple
yellow
liquid
Light
with
yellow
liquid
white
precipitates
Figure 11.10. Revised table on characterization of aspirin from starting
material.
Determining the presence of starch in commercialized aspirin and in the
synthesized aspirin is the last test. The iodine solution reacts with starch to form a
dark blue/violet colored complex. As seen in Table 11.7, although the mixture is
translucent white, there were purple precipitates in the mixture of commercially
available aspirin that would still indicate positive result. The possible reason for still
having white mixture is that the iodine solution was not thoroughly reacted with the
starch. On the other hand, there was a negative result upon reaction with the
synthesized aspirin. There was no evident reaction as the aspirin did not dissolve
and the mixture remained clear. The results of this experiment imply that
commercial aspirin is not pure and that there are added ingredients to it such as
starch.
VII. Summary and Conclusion

As stated earlier, organic synthesis is a very useful process in chemistry. It
allows the further study of building complex compounds and substances which may
not be common or naturally-occurring.
In this experiment, aspirin or acetylsalicylic acid was synthesized through the
reaction of salycilic acid (starting material) and acetic anhydride with phosphoric
acid serving as a catalyst. The reaction mechanism involved was esterification or
others would say nucleophilic acyl substitution in general sense. The first part
involves preparation of acetylsalicylic acid specifically steam bath, ice cold bath,
and suction filtration. 135% yield was obtained in crude aspirin. This crude product
underwent recrystallization and 72.7 % was recovered.
The synthesized aspirin underwent characterization tests such as potassium
permanganate, FeCl3, and differentiation from commercially available aspirin. The
results coincided with the expected observations except for the potassium
permanganate which resulted negative from salicylic acid and synthesized aspirin. It
is revealed that commercial aspirin is not pure since it is positive for the starch test.
VIII. References
Bruice, P. (2013) Organic Chemistry (7th Edition) pp. 688, 694-696. Pearson
Education.
Division of Organic Chemistry and Natural Products. (2004). Basic Organic
Chemistry Laboratory
Manual. 7th edition. UPLB : Institute of Chemistry, College of Arts and Sciences.
Carman,S. (2008). Esterification: The Synthesis of Aspirin (ASA). Retrieved from

http://www.drcarman.info/kem220lb/01lab220.pdf
McMurry, R.S. 2012. 8TH Ed. Organic Chemistry. USA: Prentice Hall, 332-345.
Petrucci, R., Herring, G., Madura, J., Bissonnette, C. (2011). General Chemistry:
Principles
and Modern Applications (10th Edition). p. 677. Toronto. Pearson
Canda.
University of Sydney (n.d.). E29 ESTERIFICATION. Retrieved from

https://scilearn.sydney.edu.au/fychemistry/prelab/e29.pdf
IX. REMARKS AND RECOMMENDATIONS

It is recommended that the execution of suction filtration should be more
careful. There should be incidence of pushing the air inside that will cause the
displacement of the filter paper. It will cause the entering of aspirin inside the
Erlenmeyer flask without being filtrated resulting to a lower percent recovery.

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EXERCISE 11

VI. Results and Discussion

Figure 11.1. Mechanism involved in the formation of aspirin.

anhydride since it increases the surface area exposed to reactants (Petrucci,

in the preparation of aspirin is 135 percent. The calculated

The next step is recrystallization. The purpose of recrystallization is to get rid

In characterizing salicylic acid(starting material) to acetylsalicylic acid

VII. Summary and Conclusion

Carman,S. (2008). Esterification: The Synthesis of Aspirin (ASA). Retrieved from

and Modern Applications (10th Edition). p. 677. Toronto. Pearson

University of Sydney (n.d.). E29 ESTERIFICATION. Retrieved from

IX. REMARKS AND RECOMMENDATIONS

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