Lab manual

Semester spring-2021
Submission date (31-03-2021)

Course Title: Organic Chemistry-III (P)

Course Code: CHEM-312

Submitted to
Dr. Ghulam Mustafa

Submitted by
Rukhsana Yasmin
Roll no # 18551507-019
BS chemistry VI (A)

Department 0f Chemistry
University 0f Gujrat

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EXPERIMENT NO# 1
Synthesis of p-chlorobenzoic acid and p- chlorobenzyl alcohol from p-
chlorobenzaldehyde through Cannizzaro’s reaction

Theory
The Cannizzaro reaction, named after its discoverer Stanislao Cannizzaro, is a chemical reaction
that involves the base-induced disproportionation of an aldehyde lacking a hydrogen atom in the
alpha position. It means aldehydes with no alpha-hydrogen give this type of reaction.
Disproportionation reactions are those in which half of the reactant molecule is oxidized and half
are reduced. In this case the half aldehyde is oxidized to carboxylic acid and other half is reduced
to alcohol. The reaction is carried out in the presence of strong base like NaOH or KOH.

General reaction

Aldehyde + Base alcohol + carboxylic

acid

2 C6H5CHO + KOH → C6H5CH2OH + C6H5COOK

Here the oxidation product is a salt of a carboxylic acid and the reduction product is an alcohol.

Reaction mechanism

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The reaction mechanism involves a nucleophilic acyl substitution on an aldehyde, with the
leaving group simultaneously attacking another aldehyde in the second step. First, hydroxide

attacks a carbonyl. The resulting tetrahedral intermediate then collapses, re-forming the carbonyl
and transferring hydride to attack another carbonyl. In the final step of the reaction, the acid and
alkoxide ions formed exchange a proton. In the presence of a very high concentration of base, the
aldehyde first forms a doubly charged anion from which a hydride ion is transferred to the
second molecule of aldehyde to form carboxylate and alkoxide ions. Subsequently, the alkoxide
ion acquires a proton from the solvent.

Principle
Two molecles of p-chlorobenzaldehyde reacts with the base KOH and it undergo redox reaction
in which half reactant molecule is oxidized and half is reduced. The resulting product is p-
chlorobenzoic acid and p-chlorobenzyl alcohol.
Material required

 Round bottom flask 100ml

 Condenser
 Heating plate

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  Magnetic bar
 Separatory funnel

Chemicals required

 p-chlorobenzaldehyde
 Methanol
 Distilled water
 Dichloromethane
 Potassium hydroxide KOH
 Sodium sulfate

Experimental Procedure

1. First of all weigh 2g of p-chlorobenzaldehyde and then dissolve in 2.5ml of

methanol in 100ml of round bottom flask
2. Then take 1.5ml of 50% KOH solution and then add in above flask.
3. After that reflux the solution on heating plate for at least 1.5 hours and check
the progress of reaction with the help of TLC plate ater regular interval of
time.
4. After 1.5 hour cool the reaction mixture and then add 5ml of water into the
flask.
5. After that transfer the contents of flask to the separatory funnel and add
dichloromethane as and organic solvent in it with three separate portion of
5ml of it. The newly formed alcohol go into the organic layer while the
carboxylic acid left behind the aqueous layer. The organic layer is emulsify
by using the 5ml brine solution.

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 6. Now by using anhydrous sodium sulfate the organic layer is dried to remove
any moisture and by using rotary evaporator the dichloromethane in organic
layer is evaporated.
7. In organic layer the crude p-chlorobenzyl alcohol is purified by
recrystallizing it by using 3 mL of 4% acetone in hexane.
8. The aqueous layer is cooled in ice bath after acidified by adding 3 mL of
conc. HCl. White precipitates are collected by vacuum filtration, washed the
filtered cake using 5 mL water and dry the product in air and then
recrystallize in methanol.
9. Check the melting points of products and then calculate the %age yield by
take weights of products.

Observation and calculations

Mass of Potassium hydroxide= 5g

No. of moles of KOH = mass/ molecular mass of KOH

= 5/56.1g = 0.089 moles

Mass of p-chlorobenzaldehyde = 2g

No. of moles of p-chlorobenzaldehyde = 2/140.6g = 0.014 moles

Also 0.014/2=0.0071 moles for each product

(0.007 mol) (157.6 g/mol 4-chlorobenzoic acid) = 1.10g←theoretical yield (acid)

(0.007 mol) (142.6g/mol 4-chlorobenzil alcohol) = 0.99g←theoretical yield (alcohol)

Mass of aqueous layer/acid = 0.8989g

Melting point of aqueous layer/acid = 243°C

Mass of organic layer/alcohol = 0.8214g

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Melting point of organic layer = 71°C

Product Theoretical Actual % Literature Melting

Yield Yield Yield Point
(Grams) (Grams) Range
p-chlorobenzoic 1.10g 0.89g 81% 237-243°C
acid
p-chlorobenzyl 0.99g 0.82g 82% 70-73°C
alcohol

actual yield
% yield of p-chlorobenzoic acid = Theoretical yield x 100

0.89 g
= 1.10 g x 100

= 81%

actual yield
% yield of p- chlorobenzyl alcohol = Theoretical yield x 100

0.82 g
=  0.99 g x 100

                             = 82%

 IR Spectra p-chlorobenzoic acid

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Identification of peaks

In this spectra of p- chlorobenzoic acid the different functional groups have different wavelength
peaks.

i. C=O has 1677 wavelength peak

ii. OH (acid) has 3094, 2649,2548 wavelength peak
iii. C-H (aliphatic) has 2808, 1421,1400, 1320 wavelength peak
iv. =C-H (aromatic) has 3094, 1798 & 1677 wavelength peak
v. C-Cl has 681, 712 & 759 wavelength peak

IR Spectra p- chlorobenzyl alcohol       

Identification of peaks

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In this spectra of p- chlorobenzyl alcohol the different functional groups have different
wavelength peaks

I. OH functional group has wavelength peak of 3336 

II. C-H (aliphatic) has 2854, 1404, 1341 wavelength peak
III. =C-H (aromatic) has 3048, 1904 wavelength peak
IV. C-Cl has 711 wavelength peak

Results
The crystals of p-chlorobenzyl alcohol and p-
chlorobenzoic acid have been formed having % yield 82%
and 81% respectively.

Refrences

 https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental_Modules_(Organi
c_Chemistry)/Reactions/Organic_Reactions/Cannizzaro_Reaction
 http://www.rsc.org/suppdata/books/184973/9781849739634/bk9781849739634-chapter
%2017.pdf
 http://www.studou.com

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