Acid-Catalyzed Fisher Synthesis and

Purification of Methyl Salicylate and

Isobutylpropionate

Ristovska, Anastazija*
Wang, Sam
Chemistry Department, Rice University, Houston,
Texas 77005, USA

phosphoric acid aiming to achieve 10 molepercent H3PO4 solution; in the second flask
32.3mL of propanoic acid and 20mL of isobutyl
alcohol were added along with the same amount
of phosphoric acid. We began heating the roundbottom flasks at 70-80C for the one containing
the salicylic acid and methanol, and 60-70C for
the one containing the propanoic acid and
butanol. We refluxed for 1hr. The reflux system
was then dismantled and the flasks were left to
cool on the bench.
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ar24@rice.edu
April 4, 2013

Abstract. Fisher esterification was carried out by

refluxing carboxylic acid with alcohol with the
addition of phosphoric acid as catalyst. Two
reactions were carried out using the esterification
pairs of salicylic acid and methanol, and
propanoic acid and isobutyl alcohol to obtain
methyl salicylate and isobutyl propionate
respectively. The products were isolated via
separation extraction and were then purified by
distillation. The separation extraction of methyl
salicylate was performed in dichloromethane,
whereas that of isobutyl propionate was carried
out using deionized water.

Figure1. Reflux System Diagram

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Background. As a typical alcohol-carboxylic
acid acid-catalyzed esterification reaction, the
phosphoric acid protonated the carbonyl of the
salicylic and propanoic acids, making them more
electrophilic and susceptible to the nucleophilic
attack by the methanol and isobutanol oxygen
atoms.

Scheme 1. Fisher Esterification

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Two reflux systems were set up using 300-mL
round-bottom flasks. In one of the flasks 3.00g
salicylic acid and 32.5mL of methanol were
added along with 1mL of concentrated

Two 50-mL separatory funnels were set up and

the mixtures from the round-bottom flasks were
added to them. Methyl salicylate was extracted
using three 20-mL portions of dichloromethane
and was retained in the organic phase of the
separation extraction. The isobutylpropinoate
containing solution was rinsed with three 20-mL
washes of deionized water and the ester was
retained in the organic phase of the funnel
separation. Once the organic phases were
extracted they were purified using a distillation
set-up similar to the one shown in Figure 2. A
single distillation system was set up that was
used to run the distillations of both esters
separately. The methyl salicylate containing
dichloromethane solution was poured into a 250mL round-bottom flask and the dichloromethane
was evaporated using rotary evaporation at 5060C. After this, the round-bottom flask was
connected to the distillation apparatus and was
heated at 220C. The product dripping on the
other side of the condenser was collected in a 50-

mL round-bottom flask. Once the product

stopped dripping at the temperature of 220C,
the distillation process was stopped. The
isobutylpropinoate was then transferred to a 250mL round-bottom flask and the flask was
connected to the distillation apparatus. The
second ester was heated at 130C and the
dripping purified product on the other side of the
condenser was collected in another 50-mL
round-bottom flask.

Figure 2: Distillation Apparatus

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Supporting Information Available: For complete
tables of physical properties of the chemicals used,
please visit http://pubchem.ncbi.nlm.nih.gov.
Acknowledgements. We are grateful to Mr. F.
Robert, Ms. M.G Melisa, Mr. V. Farrukh, and Ms. W.
Amanda for lab manuals data.
References. An example of the General Chemistry
Experiment for the synthesis of methyl salicylate can
be found at http://tinyurl.com/ca6kvua. For reference
on the synthesis of isobutyl propionate please refer to
http://tinyurl.com/cd98kts.