NUCLEOPHILIC ACYL SUBSTITUTION: THE SYNTHESIS OF

ESTERS

N.D. SILAVA

INSTITUTE OF BIOLOGY, COLLEGE OF SCIENCE

UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY, PHILIPPINES

DATE PERFORMED: FEBRUARY 8, 2011

ABSTRACT

This experiment aimed to synthesize 2-Pentyl Acetate, an ester that emits the fragrance of a
Banana. An excess of 2- pentanol and Acetic acid were made to react by nucleophilic acyl substitution,
catalyzed by H2SO4 in a reflux setup and the organic layer of the resulting solution was made to undergo
purifying steps to produce a sweet-smelling ester. Le Chatelier’s principle was used to ensure a
reasonable yield and the percentage yield of 76.45% deemed the experiment successful.

INTRODUCTION

Esters compose the distinct fragrances was used.

of fruits and flowers. They could also be used as
pesticides and they can be spun into fibers. They
are colorless and water-insoluble. [1] The process
of synthesizing an ester is called Esterification.
[4]
There are several ways to prepare esters. They Figure I. Fischer Esterification
can be from
It involves heating a mixture of an
1. Carboxylic acids and alcohols alcohol and a carboxylic acid in the presence of
2. Acyl Chlorides and alcohols a strong mineral acid catalyst [1] like
3. Anhydrides and alcohols [1] concentrated H2SO4 or dry HCl [3] to yield an
ester and water as end product. [4] The reaction
In this experiment, Direct Esterification is reversible and the position of equilibrium can
(no. 1), also known as Fischer Esterification be made favorable by using an excess of the
alcohol or the carboxylic acid [3] [4] to favor the
 formation of the ester. Another way of driving METHODOLOGY
the reaction towards the right is by removal of
the water by distillation or by use of a 6.57 ml of 0.06 ml 2-pentanol and 3.43
dehydrating agent or molecular sieve. [2] ml of acetic acid were mixed in a round bottom
Conversely, addition of water to the reaction, a flask with porcelain boiling chips. Concentrated
process of hydrolysis, would drive the reaction H2SO4 was then added to acidify the solution [3]
towards the left or towards the reactants. [1] The and the solution was put in a reflux setup for 1
same catalyst, hydrogen ion, that catalyzes the hour and was cooled to room temperature after.
forward reaction necessarily would catalyze the The solution was then transferred to a
reverse reaction, hydrolysis. [3] separatory funnel and cold H2O was used to
The structures of both the alcohol and collect the washings and add them to the funnel
the acid are important in affecting the rate of until the aqueous layer was twice the volume of
Esterification. [1] Steric hindrance or the the organic layer then NaCl was added to
presence of bulk groups near the site of facilitate separation of the layers. NaHCO 3 was
reaction, whether in the alcohol or in the acid, then added slowly to the solution until the
slows down esterification. [3] Tertiary alcohols effervescence stopped. The top layer or the
and acids with several alkyl groups on the α- Organic Layer was then separated from the
carbon are almost completely unreactive in an bottom aqueous layer and it was put in an
esterification reaction. [1] The order of reactivity Erlenmeyer flask and was dried with anhydrous
of alcohols and acids from the most reactive to Na2SO4. The ester was already clear however
the least reactive is shown below. distillation was not performed due to lack of
time.
Acids: HCOOH > CH3COOH > RCH2COOH >
R2CHCOOH > R3CCOOH

Alcohols: CH3OH > R-CH2OH > R2CHOH > RESULTS AND DISCUSSION
R3COH

In this experiment, 2-pentanol was chosen as the The reaction between 2-pentanol and
alcohol and Acetic acid was chosen as the Acid acetic acid started with the protonation of the
to synthesize 2-Pentyl acetate [1] which emits a carboxyl group of acetic acid by the acid
banana-like odor. catalyst, H2SO4, making the carboxyl carbon
O [1]
positive
CH3 – C + H+
OH
OH
CH3 – C +
OH
Figure II. 2-Pentyl acetate

Thus, it was the objective of the group 2-pentanol then attached via
experiment to synthesize an ester through a nucleophilic substitution to the positively
reversible acid-catalyzed reaction of 2-Pentanol charged carboxyl carbon. A tetrahedral
and Acetic acid. intermediate was then formed. [4]

OH (CH2)2CH3
CH3 – C + + CHCH3OH
OH
 The Reflux setup was necessary since
the carboxylic acid was converted directly to an
ester when it was heated with an alcohol in the
OH
CH3 – C – O + H presence of an acid catalyst. [3] It made possible
OH (CH2)2CH 3 the boiling of a solution and the condensation of
CHCH3 the distilled product vapors so that the solution
would not evaporate. [7]

Le Chatelier’s principle states that “in a

The hydrogen ion was then transferred system in equilibrium, the addition of reactants
from alcohol moiety to one of the OH groups of shifts the equilibrium such that the forward
the tetrahedral intermediate. [1] [4] reaction is favoured until equilibrium is
established.” [5]
CH2 CH2 OH
OH CH(CH3)2 At equilibrium point, a substantial
CH3 – C – O amount of ester, water, alcohol, and carboxylic
CH3 – C – O+ CH2 CH2
O+ acid was present in the round bottom flask. So to
H CH(CH3)2
OH H H ensure a reasonable yield of the ester, an excess
of the alcohol, 2-pentanol was used, to drive the
forward reaction faster. [1] [2] The limiting reagent
Water was then eliminated and the ester,
was the acetic acid. Removal of the aqueous
2-pentyl acetate was formed. [1] The steps in the
layer was necessary to prevent hydrolysis, which
mechanism may be viewed as a combination of
would push the reaction in the direction of the
two stages. The first stage dealt with the
reactants. [1] Na2SO4 was used as a drying agent
formation of a tetrahedral intermediate and the
to make sure that any trace of water would not
second stage dealt with the dissociation of the
remain in the crude ester. [2] Another method that
tetrahedral intermediate. [4]
would favor the formation of esters was removal
of water by the azeotropic distillation. [2]

NaHCO3 was preferred over NaOH

since NaHCO3 gives less moles of H2O
stoichiometrically compared to NaOH when
it reacted with H2SO4. An excess of water
would push the reaction backwards, towards
This intermediate had a change in
the formation of reactants and lesser of the
hybridization at the carboxyl carbon from sp2 in
ester. It can be seen that 2 mol of NaHCO3
the carboxylic acid form to sp3 in the produced 1 mol of H2O whereas 2 mol of NaOH
intermediate before returning back to sp2 in the produced 2 mol of H2O. [3]
ester. It could be noticed that carbonyl oxygen of
the carboxylic acid was protonated during the 2NaHCO3 + H2SO4 → Na2SO4 + 2H2CO3
first step, not the hydroxyl oxygen. It is because H2CO3 → H2O + CO2 (gas)
the species formed by the former is more stable Figure III. Reaction of NaHCO3 with Na2SO4
since it is stabilized by electron delocalization.
2NaOH(aq) + H2SO4 (aq) → Na2SO4 (aq) + 2H2O(l)
The positive charge is shared equally by both Figure IV. Reaction of NaOH with Na2SO4
oxygen atoms. [4]
 esters for acid chloride should be done to give
After drying the crude ester, distillation an irreversible reaction that goes to completion.
was necessary in order to purify the substance
further by eliminating 2-pentanol since they
have different boiling points. Esters can also be
prepared with different alcohols. As said in this REFERENCES
report, less bulky alcohols with lesser steric
[1]
hindrance react more completely. [1] So when Zimmerman, Isaak, Organic Chemistry.
ethanol is used to prepare an ester, it would be Benziger Bruce & Glencoe, Inc. 1977
necessary to use pure ethanol since presence of
water would push the reaction backward and [2]
March, Jerry, Advanced Organic Chemistry,
make it slow. 4th ed. John Wiley & sons. 1992
[3]
Morrison, R.T. & Boyd, R. N. Organic
Chemistry, 6th ed. Prentice-hall, inc. 1992
[4]
Carey, Francis A. Organic Chemistry, 3rd
Table I. Experimental Results edition. McGraw-Hill Companies, inc. 1996
Theoretical yield 7.81 g [5]
Whitten, ET. Al. General Chemistry, 8th ed.
Actual yield 5.97 g Thomson, Brooks and Cole.
% yield 76.45%
[6]
Clark, Jim,
http://www.chemguide.co.uk/physical/catalysis/
Results show that the actual yield of
esterify.html, 2002. (Accessed on feb. 16, 2011)
5.97 grams is close to the theoretical yield of
7.81 grams, giving a percentage yield of [7]

76.45%. This would mean that the Fischer http://en.citizendium.org/wiki/Reflux_(distillatio

Esterification gives a high yield. n) (accessed on feb 16, 2011)
However, the loss in the yield may be
attributed to the unreacted acetic acid and 2
pentanol. Distillation of the crude ester was not APPENDIX
done due to the lack of time. Had the distillation
Properties 2-Pentyl Acetate
pushed through, % yield would be significantly
lower due to other impurities dissolved in the Structure:
ester.

CONCLUSION AND RECOMMENDATION Weight/volume 9.08 ml

Molecular weight 130.19 ml
The experiment was a success, based on
the quantity of ester synthesized and the banana- Density 0.86 ml
like smell surrounding it. The experiment also Boiling Pt. 130-135°C
obtained a 76.45% percentage yield, which
could be considered as good enough. However,
Experimental Results
improvement is needed for the time allotted for
this experiment. The distillation was skipped Theoretical yield 7.81 g
due to time constraint. Also, preparation of Actual yield 5.97 g
 % yield 76.45%

Calculations:

Theoretical Weight of ester:

Mol limiting reagent * Molecular Wt=

.05998 mol * 130.19 (g/mol) =

7.81 g.

* convert to volume:

7.81 g/0.86(g/ml) = 9.08 ml

% Yield:

Actual yield/Theoretical yield =

5.97 g/7.81 g = 76.45%