Organic Ph. Ch.

Practice
Dr.Sawsan
Lab:5
Date:1/4/2023

Practical Organic
Pharmaceutical Chemistry
II
Synthesis of Phenol

 Phenol is a compound in which one of the hydrogen atoms of the

benzene ring is substituted by hydroxyl group (OH). Phenol, itself,
occurs as a colorless to light – pink like crystals with a
characteristic odor, freely soluble in organic solvents such as:
alcohol, ether, chloroform and glycerol but only slightly soluble in
water (one in 12 parts).
 Phenol is one of the oldest antiseptic. It has bactericidal and
bacteriostatic properties besides its caustic and slight anesthetic
activities. It is used in 0.1-1% in lotions and ointments.

‫سوسن حسن حمودي‬.‫م‬.‫م‬

 Methods of Preparation:
Phenol can be prepared in the laboratory by one of the following methods:
Preparation of phenol from haloarenes
Chlorobenzene is an example of haloarenes which is formed by mono
substitution of benzene ring. When chlorobenzene is fused with sodium
hydroxide at 350°C under high pressure, sodium phenoxide is produced.
Finally, sodium phenoxide on acidification gives phenols.

‫سوسن حسن حمودي‬.‫م‬.‫م‬

Preparation of phenol from benzene sulphonic acid

Benzene sulfonic acid is reacted with aqueous sodium hydroxide.

The resulting salt is mixed with solid sodium hydroxide and fused at
a high temperature (350 °C). The product of this reaction is sodium
phenoxide, which is acidified with aqueous acid to yield phenol.

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Preparation of phenol from aniline
When an aromatic primary amine is treated with sodium nitrite (NaNO2)
in acidic media at temperature 0-5°C, diazonium salts are obtained.
These diazonium salts are highly reactive in nature. Upon warming with
water, these diazonium salts finally hydrolyse to phenols. Phenols can
also be obtained from diazonium salts by treating it with dilute acids.
This procedure is the simplest method than other methods.

‫سوسن حسن حمودي‬.‫م‬.‫م‬

Procedure:
 To a 150ml of water contained in a 400ml beaker add carefully and with stirring
27.5ml of concentrated H2SO4. To this warm solution add 24 ml of aniline while
stirring vigorously, cool the solution and replace the beaker in an ice-bath. Stir
the solution from time to time. The appearance of solid precipitate which is
aniline sulfate occur at this point.
 Prepare a solution of sodium nitrite (20g NaNO2 in 50ml of water) and place the
solution in a dropping funnel. At 0 °C temperature, add the nitrite from the
dropping funnel slowly with vigorous stirring to the aniline sulfate solution.
Never allowing the temperature up after the addition of all the nitrite, then test for
the presence of free nitrous acid which indicates complete formation of benzene
diazonium sulfate. The test for HNO2 is made by taking a drop from the solution,
diluting it in 1ml of distilled water then taking a drop of this diluted solution and
test it with starch iodide paper, if blue color appear it indicates the presence of
‫سوسن حسن حمودي‬.‫م‬.‫م‬
free HNO2.
 Now place the solution in a round-bottom flask, attach an air condenser and
heat on a water bath until all the nitrogen (formed from decomposition of the
diazzo salt) has evolved.
 After the decomposition of the diazzo salt, collect the phenol through steam
distillation, until it no longer gives a test for phenol. Test for phenol; by
taking 1-2 ml of the distillate and add it to 1-2 ml of bromine water. A white
ppt. (2,4,6-tribromophenol) indicates the presence of phenol.

 Now saturate the distillate with NaCl (to reduce the miscibility of phenol and
water, water molecule will associate with ions so decrease the tendency of
water to solvate phenol) and place in a separatory funnel. Extract with three
‫سوسن حسن حمودي‬.‫م‬.‫م‬
separate 30 ml portions of ether. Combine the ethereal extracts, dry over
calcium chloride and distill of the ether. Transfer the remainder to the
smallest available distilling flask attach an air condenser and distill the
phenol, collecting the fraction at 180-183 °C.