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Introduction
Vanillin (4-hydroxy-3-methoxybenzaldehyde), a pleasant smelling aromatic compound, occurs
naturally in vanilla beans. Vanillin is used widely as a flavouring additive for beverages, cooking
and aromatic additive for candles, incense, potpourri, fragrances, perfumes, and air fresheners.
Vanilin is a phenolic aldehydes, an organic compound with the molecular formula C8H8O3.
Vanillin is also a multifunctional compound that reacted with acetic anhydrite under acidic
or basic condition to formed different products that is ester 1 and ester 2 as shown in the figure
above. The reaction of vanillin with acetic anhydride in the presence of base is an example of the
esterification of a phenol. The product, which is a white solid, can be characterized easily by its
IR and NMR spectra. It is expected to get the same compound in base reaction but the spectrum
shows different compound formed when reacted under acidic condition.
FTIR Results :
Compound (C=O-OR) / cm-1 (C=O) / cm-1 (O-H) / cm-1
Basic condition
Acid condition -
Observations
When preparing vinyllyl acetate, cloudy white and milky precipitate of product was
formed.
On the other hand, in esterification of vanillin in the presence of acid, the solution turns to
purple orange after 1 hour.
Calculations
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛
Mole of vanillin : 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑣𝑎𝑛𝑖𝑙𝑙𝑖𝑛
1.5061 g
= 152.15g/mol
= 0.2649 mol
1.7996
= × 100 %
1.9204
= 93.71 %
(𝑇ℎ𝑒𝑜𝑟𝑒𝑐𝑡𝑖𝑐𝑎𝑙−𝑎𝑐𝑡𝑢𝑎𝑙 𝑦𝑖𝑒𝑙𝑑)
Percentage error of basic reaction = × 100
𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
(1.92014− 1.7996)
= × 100 %
1.9204
= 6.29 %
For the reaction with acidic product,
Theoretical yield : mole of limiting reactant × molar mass of product
= 9.8988 x 10-3 mole × 296 g/mole
= 2.9300 g
Actual yield : 2.4563 g
𝐴𝑐𝑡𝑢𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
Percentage yield : × 100%
𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
2.4563
= × 100 %
2.9300
= 83.83 %
(𝑇ℎ𝑒𝑜𝑟𝑒𝑐𝑡𝑖𝑐𝑎𝑙−𝑎𝑐𝑡𝑢𝑎𝑙 𝑦𝑖𝑒𝑙𝑑)
Percentage error of acidic reaction = × 100 %
𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
2.9300−2.4563
= × 100 %
2.9300
= 16.17 %
Discussion
Aldehydes can react with alcohols to form hemiacetals and acetals by an equilibrium reaction. The
essential structural features of hemiacetals are –OH and –OR attached group on the same carbon
atom. An acetal has two –OR group for each carbon. If we take some alcohol solution and pass
into small amount of gaseous HCl a hemiacetals formed and the hemiacetal react with a second
molar equivalent of the alcohol to produce an acetal.
For the mechanism of the basic condition, the acetic anhydride plays the part of the electrophile,
undergoing nucleophile attack by the alcohol when an anhydride reacts with an alcohol for both
acidic and basic conditions. The vanillin molecule has several functional groups, among them
alcohol, ether, and aldehyde. The base-catalyzed reaction is a straightforward esterification and
does not produce any other significant products because esterification stops at the ester. However,
the acid-catalyzed esterification does not form only the ester. It forms the ester, but this ester
continues to react because there are other functional groups present in the molecule that can react
with the anhydride under base or acid conditions.
For esterification reaction of vanillin under acidic condition, vanillin react with acetic anhydride
to produce vanillin triacetate while under basic condition, it produce vanillin acetate. These
product formed was supposed confirmed by using IR and NMR. Unfortunately, the NMR
instrument showed incorrect data as the instrument needed to be service first.
The functional group for both acid and basic product has been determined using IR spectrum. From
the basic IR spectrum, there are (C=O-OR) group which present at the peak of cm-1
(Ester) and for acidic condition is cm-1 (Ester). Besides, there are also (C=O) group
-1
which at frequency cm (Aldehyde) for basic and cm-1 (Aldehyde) in acidic
condition. In addition, there is present in O-H group but only for basic condition.
Conclusions
The reaction between vanillin and acetic anhydride under two conditions are successfully
investigated. The products formed is determined using IR, NMR and melting point comparisons.
The compound in acidic and basic condition was identified. The melting point of the acidic product
is 92˚C while the melting point of the basic product is 78˚C. The percentage yield of the basic
product is 93.71 % while the percentage yield of the acidic product is 83.83 %.
Questions
1. Under different reaction media, vanillin undergoes esterification with acetyl chloride yielding
two different products.
Basic or
?
acidic medium
Vanillin
a) Based on the IR spectrum of vanillin, at what range should you observe the absorption
signal of the hydroxyl group?
b) Based on its 1H NMR spectrum, what is the expected chemical shift value for the
methoxy group (OCH3)? What is its multiplicity?
c) Draw the structures of the major products for the esterification of vanillin with acetyl
chloride in:
2. Write the mechanism for the reaction between vanillin and acetyl chloride in 10% NaOH
solution.
References
Laboratory textbook: Pavia, Lampman, Kriz and Engel, Introduction to Organic
Laboratory Techniques 3rd Edition, Page 49
Vanillin, http://en.wikipedia.org/wiki/Vanillin , retrieve on 7 April 2013
Acetic anhydride, http://en.wikipedia.org/wiki/Acetic_anhydride , retrieve on 7 April 2013
Esterification reaction of vanillin,
http://www.lhup.edu/mmaresch/Chem430/CH430Lab/vanillin.htm , retrieve on 7 April
2013