LABORATORY MANUAL OF ORGANIC

CHEMISTRY PRACTICALS

CHEM 373

MULTI-STAGE PREPARATIONS

1|Page
 EXPERIMENT ONE

PREPARATION OF BENZOPHENONE OXIME

THEORY

Benzophenone condenses with hydroxylamine hydrochloride

in the presence of excess aqueous sodium hydroxide to yield

Benzophenone Oxime.

REAGENTS

1. Benzophenone (5 g)

2. Hydroxy larnine hydrocliride (3g)

3. Sodium hydroxide (5.6g)

4. Ethanol

5. Cone HCL

6. Water.

2|Page
Experiment Instruction

Place in 500 cm 3 round bottomed flask 2.5g benzophenone,

1.53 hydrozylamine hydrochloride. 5cm 3 ethanol and 1cm3 of

water. Add 5.6g of sodium hydroxide pellets in portions with

shaking.

Cool the flask with a running tap as the reaction becomes

vigorous. When all the sodium hydroxide had been added

attach a reflux condenser to the flask and heat the flask to

boiling then reflux for five minutes.

Cool the flask and pour the contents into a solution of 7.5

cm3 of cone. HCL in 50cm of water Contained in a one liter

beaker. Filter off the precipitate (at the pump) and wash

thoroughly with cold water.

Recrystallize the product from methanol (4cm3 per gram).

Dry the benzophenone oxime in a desicator. Weigh and

determine its melting point. Calculate our percentage yield.

2. Notes

1. This crude material dried overnight at about 40° is

practically pure and if used at once is satisfactory for

3|Page
 the preparation of diphenylmethane imine

hydrochloride.

2. In the presence of oxygen and traces of moisture,

benzophenone oxime is gradually converted into a

mixture of benzophenone and nitric acid. A good

method of preserving this oxime is to dry it in a

vacuum desiccator, fill the desiccator with pure carbon

dioxide, re-evacuate, and fill again with carbon dioxide.

The preparation may then be transferred to a bottle,

also filled with carbon dioxide, and sealed against

access of air.

Discussion

Benzophenone oxime has been prepared in quantity by

treating an aqueous alcoholic mixture of benzophenone and

hydroxylamine hydrochloride with hydrochloric acid, with

sodium carbonate, with

alcoholic potassium hydroxide, or with aqueous sodium

hydroxide. It has also been obtained by treating

bisnitrosylbenzohydryl with alcoholic potassium hydroxide,6

magnesium persulfate solution.

5|Page
 EXPERIMENT TWO

PREPARATION OF BENZPHENONE OXIME TO

THEORY

Benzophcnone oxime is converted into bentanilide by

treatment with pnospnorous pentachioride or thionyl

chloride in ether solution. The change of any oxime, into the

substituted amide under this condition is known as the

Beckmann rearrangement

Equation of Reaction

Reagents

Benzophcnone oxinie (2.0g)

6|Page
Anhydrous diehyl ether (2cm)

Pure thionyi chloride (3cm)

Experimental instruction

Dissolve 2.0g of ben/ophenone oxime in a small conical

flask. Add 3cm of pure thionyl chloride. Distill off the solvent

on a water bath and add 25cm 3 of water. Boil for several

minutes and break up any lumo that may form. Decant off

the supernatant liquid and recrystallize the product from

ethanol. Dry the benanilide in a desicator, record the weight,

determine the melting point and percentage yield.

Applications

Benzanilide is used to make dyes, active pharmaceutical

ingredients and perfumes. It is also used to study the

influence of beta-cyclodextrin on photorearrangement of

acetanilide, benzanilide and ethyl phenyl carbonate. Further,

it is used as an amide model compound to study the

reaction between the amide and epoxy. In addition to this, it

7|Page
reacts with aryltriflates in the presence of palladium-based

catalyst system to get N-(2, 6-diarylbenzoyl) anilines.

Procedure

Dissolve 2 g of benzophenone oxime in 20 mL of anhydrous

ether in a 100 ml round-bottomed flask and add 3 ml of

pure thionyl chloride or 3gm of powdered phosphorus penta

chloride (this step should be carried out in a fume

cupboard). Distill of the solvent or other volatile products on

a water bath. Add 25 ml of water boil for several minutes

and break up any lumps which may be formed. Decant the

supernatant liquid (filter at the pump if necessary), and

recrystallise the product from methanol (toxic!). Record

weight of the product, calculate the yield and its physical

constant(melting point).

Discussion

Benzanilide can be prepared by the treatment of aniline with

benzoyl chloride, benzoic anhydride, or benzoic acid.

Benzanilide has also been prepared from benzamide, aniline,

and boron fluoride. The method described in the procedure

is essentially that of Nägeli

8|Page
 EXPERIMENT THREE

PREPARATION OF BENZOIC ACID FROM BENZANILIDE

Principle

The principle involved in the preparation of benzoic acid

from benzanilide is acid catalysed hydrolytic reaction.

Benzanilide undergoes hydrolysis in acidic medium to

yield benzoic acid as colourless crystals. Aniline hydrogen

sulphate being water soluble remains in solution and solid

benzoic acid separates out.

+ H2SO4 + H 2 0 +

Benzanilide Benzoic Acid

PROCEDURE
A mixture of 1gm of benzanilide and 10 ml of 70%H 2SO4

were placed in a round bottom flask fitted with a reflux

9|Page
condenser. The mixture was boiled gently for 30

minutes.10ml of hot water was poured on the inner walls of

the condenser to dissolve benzoic acid which gets solidified

in the condenser. The flask was cooled on ice bath. The

benzoic acid separates. The solid benzoic acid was filtered

off, washed with cold water and dried. Record weight of the

product; calculate the percentage yield and its physical

constant.

Applications

Although it’s not the most-dangerous chemical you might

find in the workplace, proper handling of benzoic acid is a

must to avoid injuries and health risks while on the job.

Benzoic acid is a white, crystalline powder with a faint, non-

offensive odor. It is a compound naturally found in many

plants and is an important precursor for the synthesis of

many other organic substances.

10 | P a g e
Benzoic acid is most commonly found in industrial settings

to manufacture a wide variety of products such as perfumes,

dyes, topical medications and insect repellents.

Benzoic acid’s salt (sodium benzoate) is commonly used as

a pH adjustor and preservative in food, preventing the

growth of microbes to keep food safe. It works by changing

the internal pH of microorganisms to an acidic state that is

incompatible with their growth and survival.

11 | P a g e
 EXPERIMENT FOUR

PREPARATION OF BENZOIC ACID FROM BENZAMIDE

Chemicals: Benzamide (3 g),

0.5 M NaOH (70 cm3),

2 M HCl (~10 cm3),

litmus paper (red and blue),ice,

forcept.

Apparatus: 100 cm3 conical flask fitted with a cork carrying

a glass tubing, 250 cm3 beaker, apparatus for suction

filtration, melting point apparatus, hand len, filter paper (3),

sample tube, dropper.

Principle: Benzamide C6H5CONH2 may be hydrolysed by

12 | P a g e
Structure

Procedure

Weigh out 3.00 g of benzamide. Place it in a 100 cm 3 conical

flask and add to it 70 cm3 of 0.5 M sodium hydroxide

solution. Fit the flask with a cork carrying a glass tubing and

boil the mixture for about 20 minutes. Test the gas evolved

at the head of the glass tubing when the mixture begins to

boil. (What gas would you expect to get? What should be

and then transfer it to a 250 cm3 beaker. Add an excess of 1

M hydrochloric acid with a dropper, swirling continuously

until a copious precipitate is obtained. (How can you tell

when an excess amount of HCl has been added?). Filter the

resulting solution under suction, wash the crystals

thoroughly with minimum amount of ice cold water. (What is

the purpose of washing?). Recrystallize the crude solid from

boiling water, filter to obtain pure but damp crystals of the

product. Dry these crystals thoroughly between filter paper

until no further sign of dampness is seen on the paper.

Inspect the shape of crystals using a hand lens. Measure the

mass of this product, and record it in the table below. Put

this product into a sample tube and hand in after

determination of its melting point. Using the melting point

apparatus, determine the melting point of your product.

Base on the mass of the crystals you obtained, calculate the

percentage yield.

14 | P a g e
 EXPERIMENT FIVE

PREPARATION OF BENZENE-AZO-NAPHTHOL

THEORY

Benzene diazonium salts undergo coupling reaction with 2-

naphthol on alkaline condition to give Benzene- azo – 2-

naphthol. The diazonium salt is readily obtained by

treatment of aniline with sodium nitrite in the presence of

HCL at 5oC (process known as diazotization).

Equation of reaction

15 | P a g e
Reagents

1. Aniline (4.5cm3)

2. Cone HCL

3. 2-Naphthol

4. 10% sodium hydroxide

16 | P a g e
Experimental Instruction
Dissolve 4.5cm aniline in a mixture of 10cm cone. HCL and

20cm3 water. Cool the 20cm3 water. Cool the solution 1 to

5oC and diazotise by adding 4.0cm3 of pure sodium nitrite

dissolved in 20cm 01 water. Maintain the temperate at

about the 5° to avoid decomposition of the diaionium salt.

Dissolve 7g of 2 - naphthol in 60cm of 1 0° sodium

hydroxide solution contained in 200cm3 healer. Cool to 5C

by external cooling, aided by direct addition of 20 - 30 gm of

crushed ice.

Add very slowly to the naphthol solution the diazotized

solution. Continuously stir the mixture as addition

progresses ote the changes in colour. When crystals form

allow the mixture to stand in ihe.ice - stilt mixture for 30

minutes stirrinc the mixture occasion. Filter the mixture

through a Buehner funnel under gentle suckion, wash the

Benzene -azo - 2 - naphthol well water. Drain thoroughly

pressing the crystals well down on the filter with a spatula.

17 | P a g e
Divide your product into three. Recrystallize one part from

glacial acetic acid and reserve the rest for the next

experiment.

Filter of Crystallized crystals at the Pump and wash with a

few cm3 of ethanol to eliminate all ethanoic acid, dry the

product weigh and find the melting point.

EXPERIMENT SIX

PREPARATION OF 1 —AMINO—2—NAPHTHOL FROM

THEORY

benzene—azo- naphthol is readily reduced by stannous

chloride in the precence of HCL to amino-2-napthol.

Equation reaction

18 | P a g e
 C6H5N=N-

Regents

1. Reserved portion of unrecrystalized benzene-azo-2-

naphthol

2. Methylated spirit

3. Pure stannous chloride

4. Conc. HCL

5. Dilute HCl

Experimental instructions

Add the reserved portion of unrecrystallized benzene

naphthol to 100cm3 comical flask. Boil under gentle reflux

till greater part of the azo — compound goes into solution.

Add 60cm3 of cone HCL containing 22gm of pure stannous

chloride.-Continue the boiling under gentle reflux, for the

next 30 minutes. The azo compound will dissolve rapidly.

Decant the solution into a beaker cooled in ice water. Filter

off the line grayish white crystals that separate out. Wash
19 | P a g e
thoroughly with dilute HCI and recrystallize from hot water

contain few drops of dill. HCl. Record the weight, determine

the melting point and calculate the percentage yield.

20 | P a g e