LAB REPORT

MODULE 3: ABOUT SYNTHESIS

SUBJECT: ORGANIC CHEMISTRY (LAB)

SUBMITTED TO: DR NOSHEEN

GROUP MEMBERS

ZUNAIRA KAUSAR (2023-B, CHEM-78)

LAIBA SAEED (2023-B, CHEM-82)

IQRA QUDDOS (2023-B, CHEM-32)

MAIMOONA KHATOON (2023-B, CHEM-40)

NIMRA NOOR (2023, B-CHEM-52)

MUNIBA TARIQ (2023-B, CHEM-23)

DPARTMENT OF CHEMISTRY

SECTION B

SEMESTER II [BS]

ACADEMIC YEAR 2023-2027 [FJWU]

 EXPERIMENT 1: TRIBROMOPHENOL SYNTHESIS

AIM:
Preparation of 2,4,6- tri-bromophenol and determine its practical yield, theoretical yield and
percentage of yield.

Abstract:
2,4,6-tribromophenol is a brominated derivative of phenol. It is used as a fungicide, as a wood
preservative, and an intermediate in the preparation of flame retardants.

When phenol is allow to react with bromine water it gives 2,4,6-tribromophenol. Hydrogen
atoms at 2,4,6 position of phenol are substituted by 3 bromine atoms, hence called bromination
of phenol.

Introduction:
A method of producing 2,4,6-tribromophenol by phenol bromination using a metal bromide
salt, characterized in that the process is carried out under the action of hydrogen peroxide on a
metal bromide salt in a sulphuric acid solution, where bromine is generated and regenerated from
the resulting hydrobromic acid.

Molar mass: 330.801 g/mol−1

Formula: C6H3Br3O

Melting point: 95.5 °C

Appearance: White needles or prisms

Boiling point: 244 °C

Solubility in water: Slightly soluble; 59-61 mg/L

 Method:
 Chemical Required:
 Phenol = 5g
 Bromine Water = 8 ml
 Ethanol = 20 ml
 Apparatus Required:
 Round Bottom flask (Conical flask)
 Test tube
 Test tube holder
 Stirring rod
 Watch glass
 Beaker

 Procedure:
i. Take 5g phenol in a chemical flask and dissolve it in 100 ml of distilled water.
ii. Keep the flask in an ice bath for 10 minutes.
iii. Take 8 ml of bromine water( liquid) in a test tube and plug the mouth of test tube with cotton
immediately.
iv. Keep this test tube in an ice bath for 5 minutes.
v. Add drop-wise this cooled bromine water slowly with continous shaking to cold solution of
phenol.
vi. Filter the content.
vii. Residue obtained on the filter paper is ‘Crude’ white crystal (or ppt) of 2,4,6- tri-
bromophenol.
viii. Transfer it in a clean and dry watch glass.
ix. Dry the compound in air over a night or in a oven.
x. Weight them and note down the yield.

 Chemical Reaction:
  Calculation:

1) Practical Yield: 14.76 g

2) Theoretical Yield:
94.11g Phenol = 330.80 g of 2,4,6 tribromophenol

5 g Phenol = 5/ 330.80/ 94.11g

Theoretical Yield= 17.58g

3) Percentage Yield:
Yield % = Experimental Yield/ 100 / Theoretical yield

= 14.76 / 17.50 (100)

Yield % = 83.96

 Results:

Structure of Practical Yield Theoretical Percentage

the product (gm) Yield (gm) Yield (%)
Tribromophenol 14.76 g 17.58 g 83.96 %

The yield of synthesized of 2,4,6-tribromophenol was found to be 83.96%.

Fig: 2,4,6-tribromophenol (Powdered form)

 Conclusion:
Reaction of phenol with bromine water is so fast because the -OH group activates the benzene
ring by increasing the electron density, especially at carbons 2, 4, and 6. This makes it more
reactive (attractive) to electrophiles so that three hydrogen atoms are substituted by bromines,
not just the one replaced.

EXPERIMENT 2: BENZOIC ACID SYNTHESIS

Benzoic acid, the simplest benzene-based Carboxylic acid, has been known since the 16th
century. One of its discoverers was the legendary clairvoyant Nostradamus. Its most common
natural source is gum benzoin; a resin found in the bark of trees of the genus styrax.Most
Benzoic acid produced today is synthetic.

Its first industrial Synthesis was the hydrolysis of benzotrichloride to Calcium benzoate,
followed by acidification. This method has been completely displaced by the air oxidation of
toluene which avoids the problem of product contamination with chlorinated byproducts.Many
processed foods contain benzoic acid or one of its salt as a preservative. The acid inhibits the
growth of bacteria, molds, and yeasts. It works best when the food has an acidic pH value.
Benzoic acid also is often found in topical antifungal preparations.
 Background:

A fungistatic that is widely used as a food preservative, it is conjugated to GLYCINE in the liver
and excreted as hippuric acid. As the sodium salt form, sodium benzoate is used as a treatment
for urea cycle disorders due to its ability to bind amino acids. This lead to excretion of these
amino acid and a decrease in ammonia level. Recent research shows that sodium benzoate may
be beneficial as an aid on therapy in schizophrenia. Total positive and Negative syndrome scale
scores dropped by 21 percent compared to placebo.

Structure:

The structure of a C6H5COOH molecule is illustrated below. This molecule consists of a

benzene ring to which the Carboxyl functional group is linked. The molecule consists of 7
carbon atoms,6 hydrogen atoms, and 2 oxygen atoms.

.Production:

Benzoic acid is produced by the following method:

1. Industrial Preparations
Benzoic acid is produced commercially by Partial oxidation of toluene with oxygen. The
process is catalysed by Cobalt or manganese naphthenates. The process uses cheap raw
materials, proceeds in high yield and is considered environmentally green.

2. Laboratory Synthesis by following methods

Benzoic acid is cheap and readily available so the Laboratory Synthesis of benzoic acid is mainly
practiced for its pedogical value. It is a common undergraduate preparation and an unusual
feature of the compound is that its melting point equals to its molecular weight. For all syntheses,
benzoic acid can be purified by recrystallization from water owing to its high solubility in hot
and poor solubility in cold water. The avoidance of organic solvents for recrystallization makes
this experience particularly safe.

 Hydrolysis
Like any other nitrile or amide, benzonitrile and benzamide can be hydrolyzed to benzoic
acid or its Conjugate base in acid or basic conditions.

The other methods are mentioned below

 From Benzaldehyde:
The base-induced disproportionation of Benzaldehyde Cannizaros reaction affords equal
amounts of benzoate and benzyl alcohol the latter can be removed by distillation

 From Bromobenzene:
Bromobenzene in diethyl ether is stirred with magnesium turnings to produce phenyl magnesium
bromide C6H5MGBr.This Grignard reagent is slowly added to dry ice (solid carbon dioxide) to
give benzoate. Dilute acid is added to form benzoic acid.

 From Benzyl chloride:

Benzoic acid can be prepared by oxidation of benzyl chloride in the presence of alkaline KMO4.

3. Historical preparation
The first industrial process involved the reaction of benzotrichloride with calcium hydroxide in
water using iron or iron salts as catalyst. The resulting calcium benzoate is converted to benzoic
acid with hydrochloric acid. The product contains significant amounts of chlorinated benzoic
acid derivatives. For this reason, benzoic acid for human consumption was obtained by dry
distillation of gum benzoin. Food grade benzoic acid is now produced synthetically

Preparation of Benzoic acid experiment :

 Aim Of the Experiment:

This experiment was carried out to prepare the benzoic acid by using Sodium hydroxide and
Benzaldehyde, KMnO4, sodium Carbonate and distilled water. The experiment is followed by
adding hydrochloric acid to get benzoic acid with a good yield.

 List of Apparatus and Chemicals:

 5 cm3 of methyl benzoate
 250 cm3 of round bottom flask.
 Graduated pipette
 Measuring Cylinder
 50 cm3 of Benzaldehyde.
 2.5cm3 of sodium carbonate
 KMnO4 solution
 Dropper
 Fume cupboard
 Vertical Condenser
 20 ml of Concentrated HCL
 Filter Paper
 Spatula.

 Procedure:

i. Obtain a sample of benzoic acid

ii. Add approximately 0.5g of the contaminated benzoic acid and 5mL of water to a 25 mL
of Erlenmeyer flask.
iii. Warm the flask and its content on a hot plate and slowly add near boiling water to
dissolve the solids.
iv. Continue warm the flask and add near boiling water until all of the solid have dissolved.
v. Remove the flask from the hot plate and allow it to cool slowly on the bench top,
covering the flask with a beaker can help slow rate at which the solution cools.
vi. . After approximately twenty minutes, crystals will have formed. Cool the suspension
further using an ice bath.
vii. If crystals have not formed after 20 minutes, there are few techniques that can be used to
coax the crystals out of solution. Often scratching the glass container with a glass rod will
induce crystallisation. Alternatively a seed crystal can be obtained by evaporating a drop
of solution on the tip of stirring rod or Spatula. Returning this seed crystal to the super
saturated solution will cause crystals to form.If none of these techniques work it could be
that too much water has been added.

viii. Transfer the crystals to a Hirsch funnel and filter the benzoic acid water suspension by
vacuum filtration.
ix. While continuing to use the vacuum filtration Apparatus wash the benzoic acid crystals
with ice cooled water by pouring ice cold water over the crystals.
x. Dry the crystals on the Hirsch funnel that is allowing the vacuum filtration system to
draw air through the crystals until the mass of crystals remain relatively constant. Place
the benzoic acid in your drawer and allow it to dry completely.

xi. After allowing the benzoic acid crystals to dry for a week determine the mass and the
melting point of the benzoic acid.

EXPERIMENT 3: NITROBENZENE PREPRATION

Nitrobenzene was one of the first organic compounds studied by classical polarog-raphy in the
1920's, and it is not surprising that nitro (and nitroso) compounds have been among the most
extensively investigated by both organic and analytical electrochemists.

Nitrobenzene is the simplest aromatic nitro compound, having the molecular formula C6H5NO2.
It is used in the manufacture of aniline, benzidine, and other organic chemicals.

Nitrobenzene is a colourless to pale yellow, oily, highly toxic liquid with the odour of bitter
almonds. It is moderately soluble in water (1.9 g/l at 20 °C) and is soluble in alcohol, acetone, ether,
and benzene (IARC, 1996). It has an explosive limit of 1.8% by volume in air, representing a fire
hazard.

. Nitrobenzene induces liver cancer in rats and is an IARC group 2B (possible) human
carcinogen. Similar to TNT, nitrobenzene is associated with hematologic affects such as
methemoglobinemia, and liver injury has been described in human case reports supported by
animal studies. Liver injury ranges from bile stasis with isolated hyperbilirubinemia to steatosis
and severe centrilobular necrosis. Importantly, as in other forms of occupational liver disease,
routine liver enzymes are not a good biomarker for nitrobenzene-related liver disease. The
proposed mode of action of nitrobenzene involves free radicals, inflammation, and epigenetic
changes.

PREPRATION

Nitrobenzene was first prepared in 1834 by the German chemist Eilhardt Mitscherlich, who
treated benzene with fuming nitric acid. Nitrobenzene is produced commercially by the
exothermic nitration of benzene with fuming nitric acid in the presence of a sulfuric acid catalyst
at 50 to 65℃. The crude nitrobenzene is passed through washer-separators to remove residual
acid and is then distilled to remove benzene and water.

 Nitrobenzene undergoes nitration, halogenations, and sulfonation much more slowly

than benzene does. It may be reduced to a variety of compounds, depending on the
reaction conditions.
Most nitrobenzene produced is reduced to aniline; smaller amounts are converted to
azobenzene, hydrazobenzene (the intermediate for benzidine), and phenyl
hydroxylamine. Reduction of both the nitro group and the benzene ring affords
 cyclohexylamine. Nitrobenzene is used as a mild oxidizing agent in the syntheses of
quinoline and fuchsin.

Importance of Nitrobenzene?

Nitrobenzene is a crucial chemical with various important applications:

1. Aniline production: Nitrobenzene is the primary precursor to aniline, a vital chemical in the
production of dyes, pigments, and pharmaceuticals.

2. Pharmaceutical industry: Nitrobenzene is used in the synthesis of paracetamol

(acetaminophen), a widely used pain reliever and fever reducer.

3. Agriculture: Nitrobenzene is used as a plant growth regulator and flowering stimulant,

promoting fruit set and yield in various crops.

4. Electrochemistry: Nitrobenzene is used in Kerr cells, which are electro-optic devices used in
optical modulators and shutters.

5. Fuel additive: Nitrobenzene has been explored as a fuel additive to improve engine
performance and reduce emissions.

6. Chemical synthesis: Nitrobenzene is a versatile intermediate in organic synthesis, used to

produce various chemicals, such as explosives, plastics, and pharmaceuticals.

7. Research: Nitrobenzene is used as a solvent and a reagent in various scientific research

applications, including materials science and nanotechnology.

Overall, nitrobenzene plays a significant role in various industries, including pharmaceuticals,

agriculture, and chemical synthesis, making it a valuable chemical in modern industries.

PURIFICATION METHOD
Common impurities include nitrotoluene, dinitrothiophene, dinitrobenzene and aniline. Most
impurities can be removed by steam distillation in the presence of dilute H2SO4, followed by
drying with CaCl2, and shaking with, then distilling at low pressure from BaO, P2O5, AlCl3 or
activated alumina. It can also be purified by fractional crystallization from absolute EtOH (by
refrigeration).

Another purification process includes extraction with aqueous 2M NaOH, then water, dilute
HCl, and water, followed by drying (CaCl2, MgSO4 or CaSO4) and fractional distillation under
reduced pressure. The pure material is stored in a brown bottle, in contact with silica gel or
CaH2.

It is very hygroscopic [Hygroscopic refers to a material's ability to attract and absorb water
molecules from the air. Hygroscopic materials have a strong affinity for water and can absorb it
readily, often resulting in changes to their physical properties].

Q: Precautions that should be taken while handling Nitrobenzene?

Handling nitrobenzene requires caution and adherence to safety guidelines to minimize exposure
and potential health risks. Here are some precautions to take when handling nitrobenzene:

i. Personal Protective Equipment (PPE):

- Wear lab coats, gloves, safety glasses or goggles, and closed-toe shoes.

- Ensure gloves are resistant to nitrobenzene, such as butyl or nitrile.

ii. Handling and Storage:

- Handle nitrobenzene in a fume hood or well-ventilated area.

- Keep away from heat sources, sparks, and open flames.

- Store in a cool, dry place, away from incompatible substances.

- Use approved containers and label them properly.

iii. Exposure Prevention:

- Avoid skin contact and inhalation of vapors.

- Use tongs or other tools to handle nitrobenzene, minimizing direct contact.

- Monitor air concentrations and use respiratory protection if necessary.

 iv. Spill and Accident Procedures:

- Have a spill response plan in place.

- Wear appropriate PPE when cleaning up spills.

- Neutralize spills with sodium bicarbonate or sand, and dispose of properly.

v. Disposal:

- Dispose of nitrobenzene and contaminated materials according to local regulations and

guidelines.

vi. Training and Emergency Preparedness:

- Ensure personnel handling nitrobenzene are properly trained.

- Have a first aid kit and emergency contact information readily available.

Remember to consult safety data sheets (SDS) and follow established protocols for handling
nitrobenzene in your specific workplace or laboratory.

EXPERIMENT OF NITROBENZENE PREPRATION IN LAB

NOTE: Never heat organic solvents (petrol) directly. Always heat them through water bath
or oil bath.

 Chemicals required :
 HNO3--- Nitric acid [14 ml]
 H2SO4---Sulphuric acid [16 ml]
 C6H6----Benzene [8 ml]
 CaCl2
 NaOH [5M or 100 ml]

 Procedure :
a) Take 100 ml beaker and place it in ice bath.
b) Add HNO3 and H2SO4 to the beaker.
First add HNO3 and then add H2SO4.
Note: frequently mix the solution while adding H2SO4
c) A nitrating mixture will be formed and we will use it to nitrate the benzene
d) Take 100 ml Erlenmeyer flask and add 8 ml benzene to it.
e) Erlenmeyer flask should be placed in the ice bath after this.
f) Place a separating funnel on top of the Erlenmeyer flask.
Make sure the valve is closed before adding our reactant.
g) Add the nitrating mixture into the separating funnel.
h) We will see fumes arising from the nitrating mixture.
i) Open the valve of separating funnel.
j) Add the nitrating mixture into the benzene that is in the Erlenmeyer flask.
k) We will be provided with separate layers in the Erlenmeyer flask.
l) Two layers (yellow solution)
Top= organic layer
Bottom= acid mixture
m) Prepare a hot water bath [temperature=60 degree Celsius]
n) Place the Erlenmeyer flask in the hot water bath for about 30-45 mints.
o) Benzene will react with nitrating mixture to form nitrobenzene.
p) Vigorously shake the flask and place it back in the hot water bath.
q) Give it a shake during this span.

AROMATIC ELECTROPHILIC SUBSTITUTION TAKES PLACE

r) Now after 45 mints, we take out the Erlenmeyer flask and leave it to rest/cool.
s) We will pour it in to ice cooled distilled water (150 ml)
t) After this the organic layer will go towards the bottom because the density of acid
decreases.
u) Now we will pour this mixture into a separatory funnel and separate the
nitrobenzene.
v) Now, to the separated nitrobenzene, we will add NaOH (100 ml) to it in order to
remove all the precipitate in it.
w) The solution will acquire yellow colour.
x) We will use a separatory funnel again and place the solution in it.
y) We will collect the nitrobenzene in a measuring cylinder.
z) The nitrobenzene will contain a bit of water in it, to remove this water, we will
add anhydrous CaCl2 to it that will perform its role of drying agent. The
water will be absorbed by the calcium chloride and
We will get a clean Nitrobenzene solution (yellow solution)
 OBSERVATIONS AND CALCULATIONS

 CALCULATING MOLAR MASS:

Molar Mass of HNO3= 1+16×14

=63 g/mol

Molar Mass of C6H6= 12×6+6×1

= 78g/mol

Molar Mass of C6H6-N02= 12×6+5×1+14+16×2

=72+5+14+32

=123g/mol

 CALCULATING MOLES:

Stoichiometric calculation

Moles of HNO3= 14 Moles of C6H6= 8

63 78
= 0.223 moles =0.102 moles

Stoichiometric calculations
HNO3 ⁚ C6H5-NO2 C6H5 ⁚ C6H5-N02
 1 1 1 1
0.223 X 0.102 X
X= 0.223 X=0.102

 C6H6 give fewer product, hence it is the limiting reactant

So,
Theoretical yield = Moles × Molar mass
(mass of C6H5-NO2) = 0.102 × 123

= 12.56g

Percentage Yield= 12 × 100

12.56

= 95.54%

RESULT
Nitrobenzene is formed that appear yellow in colour and is in liquid form

Boiling point= 210 degree Celsius

EXPERIMENT 4: SYNTHESIS OF ACETANILIDE

Aim:
The aim of this experiment is to synthesis acetanilide by the reaction aniline and acetic
anhydride. And to determine the melting point.

Introduction:
Acetanilide is like a leaflets structure or white crystal power which are odourless. In 1886 it was
used in tablets as a fever reducing drug but later on its effectiveness on relieving pain was
discovered whereby it was used a aspirin for treating headache and rheumatism. In this
experiment, aniline acts a nucleophile, donating a lone pair of electrons to the electrophile which
is the acyl group CH3CO to, and after losing hydrogen, is acetanilide or N, as shown in the
reaction mechanism. It forms the best resonance structure called phenyl acetamide. Under;
 Methodology:
7.5g of aniline, 6.75cm3 of concentrated HCl followed by 200cm3 of water was placed on the
conical flask whereby the mixture was stirred until the aniline dissolved completely. And into
this solution 10.25g of acetic anhydride was added than it was stirred to dissolve after that 13g of
sodium acetate in 37.5cm3 of water was added to it.

The mixture was stirred rapidly and then it was placed in ice-water bath. The solid acetanilide
was separated by suction filtration; the product was recrystallized in 175cm3 of boiling water
containing 3.75cm3 of ethanol than it was washed with ice water to remove the impurities. Then
the product was dried in the oven for 15 minutes. After that the melting point and yield of
product was determined.

The melting point of acetanilide is 166°c

Aniline 1st reacts with HCl to form Anilinium chloride

After this sodium acetate is added which performs equilibrium reaction with Anilinium chloride
Then the free aniline produced will react with Acetic anhydride to form acetanilide which is
insoluble in water and hence precipitates out.

Calculation:
HCl: Density = 1.22 g/cm3

D=m/v n=m/mr

1.22=m/6.75 =8.235/36.5

m= 8.235g n= 0.225

Aniline(C6H5NH2) :Density = 1.02g/cm3

D=m/v n=m/mr

1.02=m/7.5 = 7.65/93

=7.65g n =0.0823

Acetic anhydride (O[oCH3]2) : Density = 1.08g/cm3

D=m/v n=m/mr

1.08=m/9.5 =10.26/102

m=10.26g n=0.1005

HCl : C6H5NH2 : O[OCH3]2

1 :1 : 1
 0.225 : 0.0823 : 0.1005

Aniline has the smallest mole ratio therefore Aniline is the limiting reagent

Calculating theoretical mass of Acetanilide

Mass = n x mr

= 0.0823 x 135

= 11.1105 g

% yield

Theoretical mass = 11.1105 g

Actual mass is 3.381g %

yield = 3.381 / 11.1105 x 100

% yield = 30.43%

Post lab answers:

1. Aniline is non-polar whereby it is insoluble in water however when it reacts with HCl it
forms complex salt compound, it has a net polar dipole moment when it dissolves in
water. NH3+ and Cl- dissolves in polar water as shown above.
2. Sodium acetic acid derivation performs balance response with anilinium chloride forming
free aniline which can respond with acidic anhydride to create acetanilide
3. Acetanilide breaks up in ethanol at room temperature subsequently ethanol is not a great
dissolvable for recrystallization.

Conclusion:
At the end of this experiment the product yield came up to 30.43% which is very low; there
would be experimental errors such as measuring the weight of the product incorrectly.
Percentage yields can be higher in the future when correct amounts of reagents are used also the
weight is measured correctly. The melting point was 166°c and the literature value is 114.3°c,
therefore it can be concluded that the sample contained impurities.

Reference:
Sidrah, M. & Rosen, N. 2019, "History of NSAID Use in the Treatment of Headaches Pre and
Postindustrial Revolution in the United States: The Rise and Fall of Antipyrine, Salicylic Acid,
and Acetanilide", Current pain and headache reports, vol. 23, no. 1.

Lewis, RA 2016, Hawley's Condensed Chemical Dictionary, John Wiley & Sons, Incorporated,
Hoboken. Available from: ProQuest E-book Central.

EXPERIMENT 5: ASPIRIN SYNTHESIS (ACETYLSALICYCLIC ACID)

Abstract
The purpose of this experiment was to synthesize aspirin (acetylsalicylic acid) from salicylic acid
and acetic anhydride using sulfuric acid as a catalyst. The reaction's progress was monitored by
testing for the presence of salicylic acid. The final product was purified through recrystallization
and characterized by melting point determination. The yield and purity of the synthesized aspirin
were evaluated.

Introduction
Aspirin, or acetylsalicylic acid, is a widely used analgesic, antipyretic, and anti-inflammatory
medication. It is synthesized through an esterification reaction between salicylic acid and acetic
anhydride, catalyzed by sulfuric acid. The synthesis of aspirin is a classic experiment in organic
chemistry that demonstrates key concepts such as esterification, recrystallization, and purity
analysis.

SIMPLE EXPERIMENT IN LAB

 Materials:
 Salicylic acid
  Acetic anhydride
 Sulfuric acid (H₂SO₄)
 Distilled water
 Ice
 Ethanol
 Equipment:
 Erlenmeyer flasks
 Beakers
 Stirring rod
 Water bath
 Suction filtration apparatus
 Melting point apparatus

 Procedure:

1. Synthesis Reaction:

 In a 250 mL Erlenmeyer flask, 2.0 g of salicylic acid was combined with 5.0
mL of acetic anhydride.
 To this mixture, 5 drops of concentrated sulfuric acid were added to catalyze
the reaction.
 The flask was gently swirled and then heated in a water bath at 50-60°C for
15 minutes.

2. Isolation of Crude Aspirin:

 After heating, the mixture was allowed to cool to room temperature.
 30 mL of cold distilled water was added to the reaction mixture to precipitate the aspirin.
 The precipitate was collected by suction filtration and washed with cold distilled water.
3. Recrystallization:

 The crude aspirin was dissolved in a minimum amount of warm ethanol.

 The solution was allowed to cool slowly to room temperature, then placed in an ice bath
to complete crystallization.
 The purified aspirin crystals were collected by suction filtration and dried.

4. Characterization:

 The melting point of the purified aspirin was determined using a melting point
apparatus to assess purity.

Results
 Crude Product:
 Mass of salicylic acid: 2.0 g
 Mass of crude aspirin: 2.5 g
 Appearance: white crystalline solid

Recrystallized Product:
 Mass of recrystallized aspirin: 1.8 g
 Melting point: 134-136°C (literature melting point of pure aspirin: 135-136°C)

 Yield Calculation:
 Theoretical yield: 2.63 g
 Percent yield: (1.8 g / 2.63 g) * 100% = 68.4%

Discussion
The synthesis of aspirin was successful, as indicated by the appearance of white crystalline
aspirin and a melting point close to the literature value. The percent yield of 68.4% suggests that
some product was lost during recrystallization or filtration. The presence of impurities could
have affected the yield and melting point range. Further purification steps could improve the
yield and purity.

The experiment demonstrated the esterification process effectively. The use of sulfuric acid as a
catalyst was essential in driving the reaction to completion. Recrystallization was an effective
method for purifying the product, although some product loss is typical in this step.

Conclusion
The synthesis of aspirin was achieved with a reasonable yield and high purity, as evidenced by
the melting point determination. This experiment reinforced the principles of esterification and
recrystallization in organic synthesis. The procedure could be optimized further to improve yield
and purity.

Calculations:

 Moles of salicylic acid: (2.0 g / 138.12 g/mol) = 0.0145 mol

 Theoretical yield: 0.0145 mol × 180.16 g/mol = 2.63 g

EXPERIMENT 6: ETHYL BENZOATE SYNTHESIS

Ethyl benzoate is a fragrant chemical compound with a sweet, floral scent, used in perfumery,
flavorings, pharmaceuticals, and agriculture. It is a colorless liquid ester formed by the reaction
of benzoic acid and ethanol, with a fruity, floral, and slightly spicy odor.

History:

Ethyl benzoate has been known since the late 19th century. It is a component of some fragrances
and artificial fruit flavors. It is also a primary flavor compound in cranberries. Ethyl benzoate is a
colorless liquid that is almost insoluble in water, but miscible with most organic solvents.
 Reaction:

Benzoic acid (C6H5COOH) + Ethanol (C2H5OH) → Ethyl benzoate (C9H10O2) + Water

(H2O)

Mechanism:

1. Benzoic acid is protonated by the sulfuric acid catalyst, forming a carbocation intermediate.

2. The ethanol molecule attacks the carbocation, forming a tetrahedral intermediate.

3. The intermediate rearranges, releasing water and forming the ester bond.

4. The resulting ethyl benzoate is separated and purified.

Conditions:

1. Catalyst: Sulfuric acid (H2SO4)

2. Solvent: None or minimal amount of water
3. Temperature: 100-110°C
4. Time: 2-3 hours
5. Pressure: Atmospheric or slightly elevated

 Yield and Purity:

1. Yield: 70-90%
2. Purity: 95-99% (depending on the specific conditions and workup)
 Simple Experiment in Lab

 Apparatus

1. Round-bottom flask (RB flask)

2. Condenser

3. Heating mantle

4. Oil bath

5. Dean-Stark apparatus

6. Separator funnel

7. Drying tube (or CaCl2 tube)

8. Distillation apparatus

9. Thermometer

10. Stirring rod (or magnetic stirrer)

11. Glass funnel

12. Filter paper

13. Buchner funnel

14. Erlenmeyer flask

15. Vacuum adapter (if performing vacuum distillation)

 Chemicals

1. Benzoic acid (C6H5COOH)

2. Ethanol (C2H5OH)

3. Sulfuric acid (H2SO4) (catalyst)

4. Water (H2O) (solvent)

5. Sodium bicarbonate (NaHCO3) (for washing and neutralizing the acid)

6. Anhydrous sodium sulfate (Na2SO4) (drying agent)

7. Calcium chloride (CaCl2) (drying agent)

8. Activated charcoal (optional, for color removal

 Procedure

1. Mix the reactants: Combine benzoic acid (C6H5COOH) and ethanol (C2H5OH) in a round-
bottom flask.

2. Add the catalyst: Add a few drops of sulfuric acid (H2SO4) to the mixture.

3. Reflux the mixture: Heat the mixture to 100-110°C using a heating mantle or oil bath, and
reflux for 2-3 hours.
4. Cool and separate: Allow the mixture to cool, then separate the layers using a separatory
funnel.

5. Wash and dry: Wash the organic layer with sodium bicarbonate solution, then dry it with
anhydrous sodium sulfate.

6. Distill: Distill the ethyl benzoate under vacuum or at atmospheric pressure.

7. Collect and analyze: Collect the distilled ethyl benzoate and analyze it using techniques like
GC-MS or NMR to confirm its purity and identity.

Reference

 Author: Jerry March and Michael Smith, [Title] Advanced Organic Chemistry, Chapter
No.: 10 (Esterification), Published by Wiley, 2013- Hoboken, New Jersey, USA

Exp 1: Tribromophenol  P.W.G. Smith and A.R.Tatchell[Title] Organic chemistry

for general degree students volume 2 Aromatic
Chemistry, published by pergamon in 1969

Exp 2: Benzoic acid synthesis  Axel Wibbertmann, [Title] Benzoic acid and sodium
benzoate, published by World health organization in 2000.

 Frank Abraham Strauss,[Title] Benzoic Acid from

Benzene: A Study of a Possible Commercial

Synthesis, published by Columbia university in

2009 and originally published in 1921,

Exp 3: Nitrobenzene prepration  Chester T. Duda, Peter T. Kissinger, in Techniques in the

Behavioral and Neural Sciences, 1993
 Thomas D. Boyer, Michael P. Manns and Arun J. Sanyal,
[Title] Zakim and Boyer's Hepatology: a text book of liver
 disease (Sixth Edition), 2012
 Chemical Book, CAS database list, Nitrobenzene
https://www.chemicalbook.com/
ChemicalProductProperty_EN_CB7854756.htm
- :~:text=Nitrobenzene%20(chemical%20formula%3A
%20C6H4NO2),is%20an%20important%20industrial%20precursor

Exp 4: Acetanilide synthesis  Sidrah, M. & Rosen, N. 2019, "History of NSAID Use in
the Treatment of Headaches Pre and Postindustrial
Revolution in the United States: The Rise and Fall of
Antipyrine, Salicylic Acid, and Acetanilide", Current pain
and headache reports, vol. 23, no. 1.
 Lewis, RA 2016, Hawley's Condensed Chemical
Dictionary, John Wiley & Sons, Incorporated, Hoboken.
Available from: ProQuest E-book Central.

Exp 5: Aspirin synthesis  Frederick George Mann, [Title] Practical:Organic

Chemistry, Publish by Longman in 1960, in United States
of America

Exp 6: Ethyl Benzoate  Jerry March and Michael Smith, [Title] Advanced
synthesis Organic Chemistry, Chapter No.: 10, Published by Wiley
in 2013, in Hoboken, New Jersey, USA