Chem 35.

1
 –
 TEG
Expt. 7: Base-Catalyzed Oxidation
 –
 Reduction of Aldehydes by the Cannizzaro Reaction Page 1
Espiritu, Walter Aljhon March 18, 2014Silong, RafaelleTumimbang, Glenn Vincent
I. Abstract
Chemical reactions vary and are different in nature. One of which is the oxidation-reductionreaction,
where a substance is being oxidized while another is being reduced. Organic compoundsbehave 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 adecrease in number of
carbon-hydrogen bonds; and reduction is the total opposite. In thisexperiment, a reaction involving
both oxidation and reduction on benzaldehyde will be observedcalled Cannizzaro reaction.
II. Keywords:
oxidation-reduction reaction, Cannizzaro reaction, base-catalyzed reaction
III. Introduction
One of the notable organic reactionsin chemistry is the Cannizzaro reaction,named after its discoverer,
StanislaoCannizzaro. It is limited to aldehydes lackingalpha hydrogen centers. It produces analcohol
and carboxylic acid at minimalamounts, accounting only 50% to the yieldeven under ideal conditions.
It is a base-catalyzed reaction, which begins with thenucleophilic attack of OH
-
 on the carbonylcenter. The resulting anion attacks anothermolecule of aldehyde, transferring a
hydrideion. In the final step, the acid and alkoxideions formed exchange a proton. All in all,
thediscovery of Cannizzaro has proven to be oneof the most important reactions in syntheticorganic
chemistry.
IV. Methodology
Major Step 1: Cannizzaro Reaction Setup
First, dissolve 1.0g of KOH in 1 mLdistilled H
2
O in a test tube. Then, weigh 200mg of 4-chlorobenzaldehyde and transfer it toa 25 mL distilling flask,
add 0.5 mL ofmethanol and stir to dissolve the 4-chlorobenzaldehyde. Then, using a Pasteurpipette,
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,assemble the apparatus for heating underreflux.
Major Step 2: Reaction Process
First, place the base of the 25 mLflask in a heating bath, preheated to ~75degree celsius, and heat the
reaction mixturewith stirring for 1.5 hour. Then, remove theflask from the bath and cool the mixture
toroom temperature. Then, add 2.5 mL of waterand transfer the mixture in a small separatoryfunnel.
Extract the aqueous mixture with 3separate 1.0 mL portions of dichloromethaneand collect the
organic layer. Combine all theorganic extracts in a centrifuge tube. Saveboth prgamoc and aqueous
layers.
Major Step 3: Isolation and Purification ofProducts
Wash the combined dichloromethaneextracts with two separate 0.5 mL portions ofsaturated aqueous
sodium chloride. Then,transfer the dichloromethane layer to a drycentrifuge tube and add several tips
full ofanhydrous sodium sulfate. Swirl the tubeoccasionally for ~10-15 minutes. Using asmall filter
pipette, transfer the dried solutionin a clean 5 mL test tube and rinse the sodiumsulfate with ~0.2 mL
dichloromethane andtransfer the rinse to the test tube. Remove thedichloromethane by steam bath.
The crude for4-chlorobenzylalcohol may be recrystallized
 
Chem 35.1
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 TEG
Expt. 7: Base-Catalyzed Oxidation
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 Reduction of Aldehydes by the Cannizzaro Reaction Page 2
from 4% acetone in hexane in a Craug tubeand air dry the product. Then cool theaqueous phase
saved from the initialdichloromethane extraction in an ice-waterbath, acidify the solution by slowly
adding0.5mL of concentrated HCl. Finally, collect theprecipitate via vacuum filtration and wash thefilter
cake with ~1-2 mL water and collect theair dry product, the crude 4-chlorobenzoic acidmay be
recrystallized from methanol in aCraig tube.
V. Results and Discussion
The general equation of the reaction is:
Figure 1. Cannizzaro Reaction of benzaldehyde
 
In this chemical reaction, two moles ofbenzaldehyde are treated hydroxide, areaction in which one
mole of benzaldehyde isoxidized to form benzoic acid while the otherone is reduced to form benzyl
alcohol.The mechanism is believed to be as follows:
Figure 2. Cannizzaro Reaction Mechanism
 A hydroxide ion serves as anucleophile and attacks the carbonyl group ofbenzaldehyde,
generating a tetrahedralintermediate. This tetrahedral intermediatethen functions as a hydride
reducing agent bygiving off a hydride ion to another molecule ofbenzaldehyde. In this manner, one
moleculeof benzaldehyde is oxidized (by the hydroxideion) and forms a benzoic acid molecule;
andanother is reduced (by the hydride ion) andforms benzyl alcohol molecule.The products are then
separated byliquid-liquid extraction through their distinctiveproperties. Benzoic acid is polar,
which makeit soluble to polar solvents such as water bygenerating ions.However, benzyl
alcohol isnonpolar, making it soluble to nonpolarsolvents such as dichloromethane.
VI. Guide Questions
1. Write the mechanism for the reaction.2. After separating the organic and aqueouslayers, the
dichloromethane layer is firstwashed with two portions of saturatedaqueous sodium chloride prior to
the dryingwith anhydrous sodium sulfate. What is the purpose of these washes?
The saturated aqueous sodiumchloride will wash away traces of water andKOH in the
dichloromethane, it will also
decrease the benzyl alcohol’s solubility in
water so the washings will not wash away theproduct. The sodium sulfate also removestraces 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 slowlyin dilute than in concentrated KOH solution.Explain.
 
Chem 35.1
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Expt. 7: Base-Catalyzed Oxidation
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 Reduction of Aldehydes by the Cannizzaro Reaction Page 3
The overall Cannizzaro reaction isthird order kinetics, that is, rate =k[RCHO]
2
[OH
-
]. It is second order on thealdehyde and first order on the hydroxide.Dilute solutions provide less
concentrations ofOH- ions to the reaction, and therefore, thereaction proceeds much slower than
inconcentrated solutions.
4. A carbon-based hydride reducing agent inbiological systems is nicotine amine adeninedinucleotide,
NADH, which reduces carbonylcompounds by a mechanism similar to theCannizzaro reaction. Using
curved arrows tosymbolize the flow of electrons, write themechanism for the hydride transfer
fromNADH to a carbonyl compound. Yourmechanism should show how NADH becomesNAD
+
. What is the driving force for thisreaction?5. Discuss the differences observed in the IRand NMR
spectra of benzaldehyde, benzylalcohol, and benzoic acid that are consistentwith the formation of the
two products frombenzaldehyde by the Cannizzaro reaction.
They all have overtones at 1650 to2000 cm
-
, indicating the presence of anaromatic ring, as well as peaks at 1600-1700cm-. On the H-NMR
spectra, they all havepeaks at 7 to 7.5 ppm, indicating the presenceof a hydrogen in aromatic ring.In
the IR spectra of benzaldehyde,there is a strong peak at 1750 cm
-
, indicatinga carbonyl moiety and peaks at 2750 cm-,indicating the presence of aldehyde moiety. InH-
NMR, a strong stretch is observed at 10.5ppm, indicating an aldehydic moiety.However, in IR
spectra of benzoicacid, a broad peak at 3400cm- is observed,which confirms a hydroxyl group; and
acarbonyl peak at 1750 cm-. On its H-NMRpeak, it also has a chemical stretch at 10 ppm,indicating
a carboxylic acid moiety.On the other hand, the IR spectra ofbenzyl alcohol, there is also a broad
band at3300 cm- to 3600 cm-, confirming thepresence of an alcohol. Also, there is a peakat 1450 cm-,
which is due to an aliphaticcarbon bond. On H-NMR, there is a peak at 4ppm, indicating a C-O bond
and at 2.5 ppm,which depicts the presence of an allylichydrogen.
VII. Conclusion
In the experiment conducted toobserve Cannizzaro reaction, it was observedthat the reaction is done
under basicconditions. The base acts as the nucleophilethat will attack the carbonyl group,
resultinginto benzoic acid (carboxylic acid) and benzylalcohol (alcohol). The order of kinetics
alsoaffect the speed of the reaction, that is, athigher base concentrations, it proceeds fasterthan in
dilute concentrations of base.
VIII. References
Carey, F. (2006). Organic Chemistry,6
th
 EditionKlein, D. (2012).Organic Chemistry.Cannizzaro reaction. Retrieved
from:http://www.britannica.com/EBchecked/topic/92753/Cannizzaro-reaction