Acid-Catalyzed and Base-Catalyzed Esterification of Vanillin

Alexander, S.
University of Nevada, Las Vegas

Objectives:
The goal of this lab was to synthesize vanillin acetate by acylation of vanillin. The goal
of this lab was to use spectroscopic methods, namely, 13C NMR, 1H NMR, and IR in
addition to melting point (mp) to determine the difference between the product formed
when the reaction is acid-catalyzed and when the product is base-catalyzed. Additionally,
the goal of this lab was to utilize the aforementioned methods to propose a mechanism
for the acid-catalyzed reaction.
Reaction Mechanisms:
Base-Catalyzed Mechanism

Figure 1. Mechanism for the base-catalyzed esterification of vanillin

Acid-Catalyzed Mechanism

Figure 2. Mechanism for the acid-catalyzed esterification of vanillin

Experimental Procedure:
Base-Catalyzed Reaction
0.30 g (0.002 moles) of vanillin were dissolved into 5 mL of a 10%, by weight, NaOH
solution in a flask. Roughly 6 g of crushed ice was added to the flask, then 0.8 mL of
acetic anhydride (0.008 moles). After adding the acetic anhydride a white precipitate
formed, as expected. The stoppered reaction continued for roughly 30 minutes, with
occasional shaking, every 5-10 minutes.
The product was filtered using a Hirsch funnel and the precipitate washed with cold
water. The solid was then recrystallized using 95% ethanol and then allowed to dry over a
week, collected, and then characterized.
Acid-Catalyzed Reaction
A spin vane was in a 3 mL conical vial, 0.15 g vanillin (0.001 moles) and 1 mL(0.01
moles) of acetic anhydride were then added to the vial. This was stirred at room
temperature until the vanillin dissolved, roughly 10 minutes. Once the vanillin was
dissolved, one drop of 1 M sulfuric acid was added. This solution continued to stir at
room temperature for 1.5 hours. The solution changed to a light orange during this hour, a
light purple or orange was expected.
After the solution was done stirring it was transferred to a centrifuge tube and capped.
The solution was cooled in an ice bath for a few minutes, then the centrifuge tube
vigorously shaken. While shaking, a white product precipitated out of solution, the tube
was shaken until precipitation was complete. Once precipitation was complete, the
precipitate was collected via Hirsch funnel and washed 4 times with cold water. After the
sample was washed well, it was recrystallized with 95% ethanol. The crystals were
allowed to dry for a week then harvested and characterized.
Results:
Table 1. Yield and melting point of products.
Mass (g)
Base-Catalyzed
Acid-Catalyzed

Moles

% Yield

MPexp

MPtheo

0.228 g

0.0012 moles

59.42 %

71-81 C

77-79 C

0.225 g

0.0008 moles

77.02 %

91-93 C

90-91 C

Figure 3. H-NMR spectrum of product from base-catalyzed esterification of vanillin

Figure 4. H-NMR spectrum of product from acid-catalyzed esterification of vanillin

Figure 5. IR spectrum of product from base-catalyzed esterification of vanillin

Figure 6. IR spectrum of product from acid-catalyzed esterification of vanillin

Discussion:
First it is important to note the differences between the melting points of the acid and
base-catalyzed reactions, Table 1. The melting points are within the theoretical ranges,
the acid-catalyzed product had a much smaller range than the base-catalyzed product.
The variation of ranges indicates impurities present in the base-catalyzed reaction,
potentially from the step at which ice is added to the flask, the ice is not made from DI
water and likely contained impurities.
The mp of the acid-catalyzed reaction is higher, this is indicative of a larger molecule or
molecule with more or stronger bonds and may be a useful indicator of what they product
may be. The product may be a tri-ester; this data supports the higher molecular weight
and increased hydrogen bonding.
The IR spectra in figures 5 and 6 show the absorptions of the acid and base-catalyzed
reactions, respectively. Both contain a strong peak near 1750 cm-1 that corresponds to a
C=O stretch, however the acid product has what appears to be a greater signal for the
C=O peak, indicating an increased abundance of C=O bonds and the possibility of a
triester. Both also show the aromatic C-H stretching of the 1600cm-1 range and a 3500
cm-1 range. The stretch at 3500 cm-1 is indicative of N-H stretching due to contamination;
it must be from contamination because no nitrogen containing compounds were used in
either reaction. This N-H stretch may have also contributed to the inaccurate melting
point values in Table 1.
Figure 1 and Figure 2 show the H-NMR spectra for the base and acid-catalyzed
reactions, respectively. Both show a peak at 3.8 PPM that corresponds to the ether group
and they both show, at 7.5 PPM and 7.1 PPM, the aromatic hydrogen(s). There is a
prominent difference between the two spectra; Figure 1 shows a peak at 10 PPM that
corresponds to an aldehyde group. The peak at 10 PPM is present only in the basecatalyzed product. Different from Figure 1, Figure 2 showing the H-NMR of the acidcatalyzed product has a small peak at 7.7 PPM. The peak at 7.7 PPM is from the
hydrogen on the carbon where the aldehyde group was on the vanillin, normally this
would show up at about 1.1 PPM, but it is likely that it is downshifted. The downshift of
this peak is likely because of the hydrogens proximity to two ester groups and an

aromatic ring. Figure 2 also has two more peaks the acid-catalyzed product does not
have. The peak at 2.1 PPM corresponding to the hydrogen(s) near the two esters on the
side where the aldehyde was on vanillin and the peak at 2.3 PPM is from the other ester
groups hydrogen(s).
Conclusion:
The data from spectroscopic analysis and melting point measurements shows that the
catalyst used in the esterification of vanillin, if it is acidic or basic, produces different
products. It appears that the acid-catalyzed product produces a triester that the basecatalyzed reaction does not, or perhaps may in very small quantities undetectable by the
methods available in this lab. The yield for the reactions were 59% and 77% for the base
and acid-catalyzed reactions, respectively. The yield may be somewhat inflated due to
impurities detected in the measurements.
References:
Pavia, D.L.; Lampman, G.M.; Kriz, G.S.; Engel, R.G. Introduduction to Organic
Laboratory Techniques: A Small Scale Approach, 3rd ed.; Brooks/Cole Thomson
Learning: Belmont, 2012; pp. 507-509.