phenols.

doc

PHENOLS
Compounds that have the hydroxyl group attached to an aromatic ring are called phenols. Thus,
phenol is the specific name for hydroxybenzene, itself; -- and it is the general name for the family of
compounds derived from hydroxybenzene. Pure phenol is a white crystalline solid, mp 42 o. The solid, or
concentrated solutions of phenol can cause painful burns if allow to come into contact with the skin. In
the following tests, a 5% phenol solution will have been prepared by your instructor.
The Acidity of Phenols

The Ferric Chloride Enol Test

As a class, phenols are considered to be

Many

phenols

and

related

enolic

weak acids, and therefore, react with and dissolve

compounds form colored coordination compounds

in strong bases; like sodium hydroxide.

with ferric ions. It is believed by some that six

However, they do not dissolve in the weak base,

molecules of a monohydric phenol are associated

sodiuim bicarbonate, NaHCO3.

with one ferric ion in the complex.

Ar OH
+
NaHCO3
a weak acid a weak base
Ar OH
+
NaOH
a weak acid a strong base

N.R.

OH +

FeCl3

Fe(Ar O)63- 3 Cl

+ 6H

Ar O Na + H2O

Sometimes, the color is fleeting, lasting

only a few second. For others, the color lasts for

Procedure:
A number of phenolic compounds are
provided for you:

6 Ar

5% phenol, -naphthol,

hours; -- and some phenols DO NOT give a color

reaction at all. There is no way to predict which

resorcinol, salicylic acid, and p-nitrophenol. Test

will, or will not, give a color with ferric chloride.

the solubility of each of these by adding about 0.1

Procedure:

g (if a solid) to a few mLs of: (1) water, (2) dil

To a few mLs of ethanol in a test tube,

NaOH, and (3) dil NaHCO 3. If bubbles of CO 2 are

dissolve a few drops, (or a crystal) of a phenolic

evolved, make note of that as well. Most phenols

compound. Then, add a few drops of a 3 percent

have limited solubilities in aqueous solutions, so

aqueous solution of ferric chloride. Shake well,

BE PATIENT; -- GIVE IT A CHANCE!!

and observe.

Record

your observations in the Laboratory Report

provided by placing a (

) in the space where

positive results are obtained, otherwise, leave it

Carry out the test on the phenols provided,

and record your observations in the table provided
in the Laboratory Report Form.

blank.
Oxidation of Phenols

In a small test tube place 1 or 2 mLs of a

on Buchner funnel with suction and wash with

0.5 percent aqueous potassium permanganate

water. Dry a bit of the product by scrubbing it

solution.

back and forth on the clay plate, and determine

Add an equal volume of a 5 percent

aqueous solution of phenol. If necessary, warm

the m.p. (range) of the of the crude product.

the solution in a hot water bath, and shake it

vigorously.

What evidence is there that an

oxidation has taken place?

In a 50 mL Erlenmeyer flask, place 0.01

Carry out a similar test by adding 2-3

drops

of

anisole

(methoxybenzene)

Preparation of Aspirin

to

mole (1.4 g) of pure salicylic acid. Add 0.03 mole

(3.1 g, 3.3 mL) of acetic anhydride, then 5 drops

permanganate solution.

of 85 percent phosphoric acid (syrupy phosphoric

Bromination of Phenol

acid). Heat the mixture for 10 minutes in a hot

CAUTION!

water bath, with occasional stirring. Then, while

BROMINE CAN CAUSE SEVERE

BURNS!!

still hot, add in one portion, 2 mLs of water to

In a medium size test tube, place 1 mL of

5% aqueous phenol solution. From a dropping
bottle, carefully add drops of an aqueous

decompose the unreacted acetic anhydride.

O
C OH

bromine solution until an equal volume has been

added (about 20 drops).

O
C OH
O
O C CH3

Ac2O

OH

Note any change(s) that would suggest

that a reaction had taken place.

salicylic acid

acetyl salicylic acid

Conduct the same test using several

Cool the contents, and, if necessary,

drops of anisole in place of the 5% phenol.

Benzoylation by the Shotten-Baumann Method
In a 125 mL Erlenmeyer flask, place 10 mLs of
5% aqueous phenol solution, and 10 mLs of 10%
NaOH. CAREFULLY, add 0.5 mL (10 drops) of
benzoyl chloride (caution,--irritating vapor!). Swirl
to mix the contents, and warm on a water bath to
about 60oC until the disagreeable odor of benzoyl
chloride can no longer be detected.

(When

testing, s-n-i-f-f,--DO NOT W-H-I-F-F)

Chill the reaction mixture in an ice bath to

promote crystallization. Collect the crude product

scratched the walls of the flask with a stirring rod

to hasten crystallization.

Chill thoroughly, and

collect on Buchner funnel with suction, washing

with very small portions of ice cold water.
Perform the ferric chloride test on a few
milligrams (MILLI grams, that is) of the product.
How did the test on your aspirin compare
with the ferric chloride test on salicylic acid?

phenols-lr.doc

PHENOLS
NAME:________________________________Section________Date:________________
Write the structures of the following:
Phenol

-naphthol

resorcinol

salicylic acid

p-nitrophenol

picric acid

Indicate with a + where a positive test was observed. Leave it blank for a negative test..
H2O

NaOH

NaHCO3

FeCl3

Comments

phenol
-naphthol
resorcinol
salicylic acid
p-nitrophenol
Oxidation of Phenol
Describe any changes in the appearance of the reaction mixture. What evidence did you observe
that suggested that an oxidation had taken place? The dark, solid residue is the reduced product of
the oxidizing agent. What is it?

What was the appearance of the mixture when anisole was the substrate? What evidence is
there that an oxidation had taken place?

Bromination of Phenol
Describe any changes in the appearance of the reaction mixture. What evidence did you observe
that suggested that a reaction had taken place? Write a "skeleton equation" for the reaction; and
give the identity of any solid formed.

Did the anisole undergo bromination?__________

Shotten-Baumann Benzoylation of Phenol
Write a skeleton equation for the reaction; and give the identity of any solid formed.
Record the melting range of the Shotten-Baumann product:___________________

Preparation of Aspirin
Write an equation for the synthesis of aspirin, including the structures of the reactants and
products. How does testing the final product with ferric chloride solution give information regarding
the purity of the product?

THIS REPORT IS DUE ON THE DAY YOU PERFORM THE EXPERIMENT. BE PREPARED.