Chem 35.

1 – TEG

Espiritu, Walter Aljhon March 18, 2014

Silong, Rafaelle
Tumimbang, Glenn Vincent

I. Abstract
Chemical reactions vary and are different in nature. One of which is the oxidation-reduction
reaction, where a substance is being oxidized while another is being reduced. Organic compounds
behave the same way. In organic chemistry, redox reactions are focused on the carbon atom.
Oxidation of carbon means that there is an increase in number of carbon-oxygen bonds or a
decrease in number of carbon-hydrogen bonds; and reduction is the total opposite. In this
experiment, a reaction involving both oxidation and reduction on benzaldehyde will be observed
called Cannizzaro reaction.

II. Keywords: oxidation-reduction reaction, Cannizzaro reaction, base-catalyzed reaction

III. Introduction
One of the notable organic reactions
in chemistry is the Cannizzaro reaction,
named after its discoverer, Stanislao
Cannizzaro. It is limited to aldehydes lacking
alpha hydrogen centers. It produces an
alcohol and carboxylic acid at minimal
amounts, accounting only 50% to the yield
even under ideal conditions. It is a base-
catalyzed reaction, which begins with the
nucleophilic attack of OH- on the carbonyl
center. The resulting anion attacks another
molecule of aldehyde, transferring a hydride
ion. In the final step, the acid and alkoxide
ions formed exchange a proton. All in all, the
discovery of Cannizzaro has proven to be one
of the most important reactions in synthetic
organic chemistry.
assemble the apparatus for heating under
reflux.
Major Step 2: Reaction Process
First, place the base of the 25 mL
flask in a heating bath, preheated to ~75
degree celsius, and heat the reaction mixture
with stirring for 1.5 hour. Then, remove the
flask from the bath and cool the mixture to
room temperature. Then, add 2.5 mL of water
and transfer the mixture in a small separatory
funnel. Extract the aqueous mixture with 3
separate 1.0 mL portions of dichloromethane
and collect the organic layer. Combine all the
organic extracts in a centrifuge tube. Save
both prgamoc and aqueous layers.
Major Step 3: Isolation and Purification of
Products

IV. Methodology Wash the combined dichloromethane

Major Step 1: Cannizzaro Reaction Setup
First, dissolve 1.0g of KOH in 1 mL
distilled H2O in a test tube. Then, weigh 200
mg of 4-chlorobenzaldehyde and transfer it to
a 25 mL distilling flask, add 0.5 mL of
methanol and stir to dissolve the 4-
chlorobenzaldehyde. Then, using a Pasteur
pipette, transfer 0.3 mL of the 50% aqueous
KOH sol’n to the flask (note: do not get any of
the solution on the ground glass joint). Finally,
extracts with two separate 0.5 mL portions of
saturated aqueous sodium chloride. Then,
transfer the dichloromethane layer to a dry
centrifuge tube and add several tips full of
anhydrous sodium sulfate. Swirl the tube
occasionally for ~10-15 minutes. Using a
small filter pipette, transfer the dried solution
in a clean 5 mL test tube and rinse the sodium
sulfate with ~0.2 mL dichloromethane and
transfer the rinse to the test tube. Remove the
dichloromethane by steam bath. The crude for
4-chlorobenzylalcohol may be recrystallized

Expt. 7: Base-Catalyzed Oxidation – Reduction of Aldehydes by the Cannizzaro Reaction Page 1

Chem 35.1 – TEG
from 4% acetone in hexane in a Craug tube
and air dry the product. Then cool the
aqueous phase saved from the initial
dichloromethane extraction in an ice-water
bath, acidify the solution by slowly adding
0.5mL of concentrated HCl. Finally, collect the
precipitate via vacuum filtration and wash the
filter cake with ~1-2 mL water and collect the
air dry product, the crude 4-chlorobenzoic acid
may be recrystallized from methanol in a
Craig tube.
V. Results and Discussion
The general equation of the reaction is:
Figure 1. Cannizzaro Reaction of benzaldehyde
In this chemical reaction, two moles of
benzaldehyde are treated hydroxide, a
reaction in which one mole of benzaldehyde is
oxidized to form benzoic acid while the other
one is reduced to form benzyl alcohol.
The mechanism is believed to be as follows:
Figure 2. Cannizzaro Reaction Mechanism
A hydroxide ion serves as a
nucleophile and attacks the carbonyl group of
Expt. 7: Base-Catalyzed Oxidation – Reduction of Aldehydes by the Cannizzaro Reaction
benzaldehyde, generating a tetrahedral
intermediate. This tetrahedral intermediate
then functions as a hydride reducing agent by
giving off a hydride ion to another molecule of
benzaldehyde. In this manner, one molecule
of benzaldehyde is oxidized (by the hydroxide
ion) and forms a benzoic acid molecule; and
another is reduced (by the hydride ion) and
forms benzyl alcohol molecule.
The products are then separated by
liquid-liquid extraction through their distinctive
properties. Benzoic acid is polar, which make
it soluble to polar solvents such as water by
generating ions.However, benzyl alcohol is
nonpolar, making it soluble to nonpolar
solvents such as dichloromethane.
VI. Guide Questions
1. Write the mechanism for the reaction.
2. After separating the organic and aqueous
layers, the dichloromethane layer is first
washed with two portions of saturated
aqueous sodium chloride prior to the drying
with anhydrous sodium sulfate. What is the
purpose of these washes?
The saturated aqueous sodium
chloride will wash away traces of water and
KOH in the dichloromethane, it will also
decrease the benzyl alcohol’s solubility in
water so the washings will not wash away the
product. The sodium sulfate also removes
traces of water from the solvent so that it will
evaporate and the product won’t be sticky wet
in the end.
3. The Cannizzaro reaction much more slowly
in dilute than in concentrated KOH solution.
Explain.
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Chem 35.1 – TEG
The overall Cannizzaro reaction is
third order kinetics, that is, rate =
k[RCHO]2[OH-]. It is second order on the
aldehyde and first order on the hydroxide.
Dilute solutions provide less concentrations of
OH- ions to the reaction, and therefore, the
reaction proceeds much slower than in
concentrated solutions.
4. A carbon-based hydride reducing agent in
biological systems is nicotine amine adenine
dinucleotide, NADH, which reduces carbonyl
compounds by a mechanism similar to the
Cannizzaro reaction. Using curved arrows to
symbolize the flow of electrons, write the
mechanism for the hydride transfer from
NADH to a carbonyl compound. Your
mechanism should show how NADH becomes
NAD+. What is the driving force for this
reaction?
5. Discuss the differences observed in the IR
and NMR spectra of benzaldehyde, benzyl
alcohol, and benzoic acid that are consistent
with the formation of the two products from
benzaldehyde by the Cannizzaro reaction.
They all have overtones at 1650 to
2000 cm -, indicating the presence of an
aromatic ring, as well as peaks at 1600-1700
cm-. On the H-NMR spectra, they all have
peaks at 7 to 7.5 ppm, indicating the presence
of a hydrogen in aromatic ring.
In the IR spectra of benzaldehyde,
there is a strong peak at 1750 cm -, indicating
a carbonyl moiety and peaks at 2750 cm-,
Expt. 7: Base-Catalyzed Oxidation – Reduction of Aldehydes by the Cannizzaro Reaction
indicating the presence of aldehyde moiety. In
H-NMR, a strong stretch is observed at 10.5
ppm, indicating an aldehydic moiety.
However, in IR spectra of benzoic
acid, a broad peak at 3400cm- is observed,
which confirms a hydroxyl group; and a
carbonyl peak at 1750 cm-. On its H-NMR
peak, it also has a chemical stretch at 10 ppm,
indicating a carboxylic acid moiety.
On the other hand, the IR spectra of
benzyl alcohol, there is also a broad band at
3300 cm- to 3600 cm-, confirming the
presence of an alcohol. Also, there is a peak
at 1450 cm-, which is due to an aliphatic
carbon bond. On H-NMR, there is a peak at 4
ppm, indicating a C-O bond and at 2.5 ppm,
which depicts the presence of an allylic
hydrogen.
VII. Conclusion
In the experiment conducted to
observe Cannizzaro reaction, it was observed
that the reaction is done under basic
conditions. The base acts as the nucleophile
that will attack the carbonyl group, resulting
into benzoic acid (carboxylic acid) and benzyl
alcohol (alcohol). The order of kinetics also
affect the speed of the reaction, that is, at
higher base concentrations, it proceeds faster
than in dilute concentrations of base.
VIII. References
Carey, F. (2006). Organic Chemistry,
6th Edition
Klein, D. (2012).Organic Chemistry.
Cannizzaro reaction. Retrieved from:
http://www.britannica.com/EBchecked/
topic/92753/Cannizzaro-reaction
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I hereby certify that I substantially contribute

to this report.

_____________________
Walter Aljhon Espiritu

_____________________
Rafaelle Silong

_____________________
Glenn Vincent Tumimbang

Expt. 7: Base-Catalyzed Oxidation – Reduction of Aldehydes by the Cannizzaro Reaction Page 4