VI.

Results and Discussions

In this experiment the synthesis of acetylsalicylic acid became possible
through the induction of an acetyl functional group into a chemical compound or
simply acetylation. In this particular synthesis, the acetylation used acetic
anhydride as the acetylating agent which readily reacts with the free hydroxyl
group. The mechanism in the acetylation of salicylic acid begin when hydroxyl
group attached in the salicylic acid protonates the -carbon in the carbonyl group of
the acetic anhydride(also known as ethanoic anhydride) which will eventually yield
the acetylated product due to the displacement of acetate and loss of proton during
the reaction.

Figure 11.1 Mechanism for the reaction involved in the synthesis of acetylsalicylic
acid from

salicylic acid. (Image retrieved from:

http://alevelchem.com/img/aspirin_preparation.gif)
The first part of the synthesis was the preparation of the acetylsalicylic acid,
in which 1 g of the starting material which is the salicylic acid was dissolved in a 3
mL acetic anhydride and 5 drops of 85% phosphoric acid. The used of acetic
anhydride instead of acetic acid as an acetylating agent in this synthesis was one of
the relevant point in this experiment because the speed of reaction between
salicylic acid and acetic anhydride is faster compared to the reaction between acetic
acid and salicylic acid also the used of acetic anhydride in the synthesis gives a
higher yield compared with the used of acetic acid. Addition of 5 drops 85%

phosphoric acid in during the experiment was also relevant because it hastens the
dissolving of salicylic acid also it makes acetic anhydride more electrophilic. If in the
case an acetyl chloride was used as an electrophile during the synthesis addition of
phosphoric acid in the reaction will definitely not be needed because acetyl chloride
is electrophilic enough.
After the mixing/dissolving the salicylic acid with acetic anhydride and
85%phosphoric acid, the mixture then was subjected into heat for about 15
minutes. Heating the mixture turned the heterogeneous white colored mixture into
a homogeneous colorless liquid solution. This observed change in the color of
mixture upon heating indicates that the salicylic acid becomes more soluble or it
completely was dissolved due to the increased in temperature. Upon heating the
mixture, addition of 2 mL distilled water followed, in this step a heterogeneous
thickened mixture was observed with presence of slightly formed white precipitate.
Thus adding of water in the mixture upon heating slight formed the desired product
which is the aspirin. The visibility of aspirin upon adding water is due to the fact that
aspirin does not readily dissolve in water. Also, adding water upon heating the
mixture decomposes the excess acetic anhydride used to react with the salicylic
acid. Next upon adding 2 mL distilled water, addition of 20 mL ice-cold water in the
mixture and placing it in an ice-bath further made the desired product aspirin more
visibly formed. Upon cooling the mixture, suction filtration comes next, in which
white powdered substance was obtained during isolation. After suction filtration the
precipitate in the filter paper was allowed to dry using a steam bath and after drying
some traces of small bits of sugar like crystalline solids became visible.
Next part of the experiment was the purification of the crude product/aspirin
obtained during the preparation of acetylsalicylic acid from salicylic acid or simply
the recrystallization of the aspirin. To start with the recrystallization process, 0.85 g
of crude aspirin from a total of 0.89 g of crude product obtained during the
preparation of acetylsalicylic acid was allowed to dissolve in a 95% ethanol
dropwise until all the crude aspirin completely dissolves.
After completely dissolving the crude aspirin, addition of cold distilled water
dropwise follows and then the mixture was allowed to cool in an ice bath both this
step gave an observable reappearance of sugar like crystals which was first
observed during the preparation of acetylsalicylic acid. After the observed
reappearance of the desired recrystallized/purified aspirin suction filtration follows

and in this step more visible crystals left in the filter paper was observed. Upon
suction filtration the filter paper together with the more visible crystals was again
allowed to dry under the steam bath and after drying much more visible fine
crystals was observed.
Aspirin was recrystallized in this experiment using 95% ethanol and not with
hot water because knowing that aspirin undergoes reactions as of esters once hot
water was used during the recrystallization there would be a great tendency that
the aspirin will be hydrolysed and may yield back into carboxylic acid.
After the preparation of acetylsalicylic acid, recrystallizing/purifying the crude
aspirin the last part of the synthesis was the characterization of aspirin or simply
distinguishing the differences between a pure salicylic acid, commercialized
acetylsalicylic acid & the laboratory synthesized acetylsalicylic acid using various
characterization tests. Three various tests namely, FeCl 3 test which tests the
presence of impurities specifically the presence of unreacted salicylic acid in the
synthesized aspirin, KMnO4 test which detects the presence of 1 alcohols, 2
alcohols and phenols in the compounds and lastly the Starch test which utilized an
I2/KI solution or simply iodine solution to detect the presence of starch in between
the commercial and synthesized aspirin. In the FeCl 3 test only the synthesized
aspirin yields a positive result in which the mixture turned into a bright purple
solution which indicated that the synthesized aspirin still contains unreacted
salicylic acid in this case, we must consider using more amount of excess acetic
anhydride to completely utilized the limiting reagent which is the salicylic acid. Next
test was the KMnO4 test, in this particular test only the salicylic acid again yields
into a positive result because in its structure it contains a benzene ring with
attached OH group or simply the sturucture of phenol. Last characterization test
conducted was the Starch test in which the commercial aspirin yield a positive
result because it contains starch in its composition.
As for the quantitative analysis in this experiment the percent yield of the
crude aspirin was 68.3% in which the acetylated 1.0 g of salicylic acid only yields to
0.89 g of crude aspirin somehow far from the theoretical yield which was 1.304 g of
crude aspirin supposedly. This discrepancy in the percent yield may be attributed to
the incomplete acetylation of salicylic acid by acetic anhydride thus much more
excess reagent must be used to completely consume the limiting reagent which is
the salicylic acid to have a higher yield of the desired product. And for the percent

recovery of the crude aspirin it yielded 58.8% pure aspirin meaning that the
synthesized aspirin was almost pure but not perfectly pure this may because of the
experimental error occur during weighing, filtration (improper washing of crystals,
using warm/hot solvent in washing/ rapid crystallization which may trapped some
impurities), transfer, drying and other unknown factor that greatly affects the purity
of the aspirin
And lastly for the melting point determination of the crude and recrystallized
aspirin, the crude aspirin got a MP range (102C-104C) and for the synthesized
aspirin it got a MP range (112C-139C). Compared with the literature value of the
MP of a pure aspirin which is 136C, the MP range of the crude aspirin seems very
far this may be due to presence of some impurities during the first part of the
experiment specifically the presence of unreacted salicylic acid and for the
synthesized aspirin though it has the literature value of the MP of pure aspirin it is
still not enough to conclude that the synthesized aspirin is pure enough because the
MP range of synthesized aspirin is quite wide meaning it might have loose, uneven
packing of crystals resulting in the wide MP range.
VII. Summary and Conclusion
As for the summary, the synthesis was of acetylsalicylic acid from a
commercially available compound which is salicylic acid was indeed a useful
process in organic chemistry. Through simple preparation of acetylsalicylic acid by
acetylation of salicylic acid, and recrystallization a much more safer and useful
organic compound was obtained from a highly strong compound which is salicylic
acid.
In this experiment, a successfully synthesized aspirin was obtained yet it may
not be useful enough because of some impurities that is present in the compound.
VIII. References
Moore, William. Laboratory Manual for Organic Chemistry: A Microscale Approach.
New York:
McGraw-Hill, c1996. Print.
Jones [et al.]. Laboratory Manual to accompany World of Chemistry: Extended
Version.

Orlando, Florida: Sanders College Publishing, c1991. Print.

Szafran, Zsi. Microscale general chemistry laboratory : with selected macroscale

experiments.

New York: Wiley & Sons, Inc.,c1993. Print.

Division of Organic Chemistry and Natural Products. Laboratory Manual for a course
in Basic

Organic Chemistry (Chem 40.1). Institute of Chemistry, College of Arts

and Sciences,

University of the Philippines Los Baos, College, Laguna: Ninth

Printing, c2013. Print.

Henrickson [et al.]. A Laboratory for general, organic, and biochemistry. 5th ed. New
York, USA: McGraw-Hill,c2007. Print

IX. Remarks and Recommendations

A much more useful and safe aspirin might be synthesized during this
experiment if the Institute of Chemistry may have provide a much more clean
laboratory materials, much precise and accurate laboratory equipments and such
materials needed in a full synthesis of aspirin.