Phenols

 Phenol is an aromatic compound. The chemical formula of this organic compound is C 6H6O.
 Phenol is also known as Carbolic acid.
 Term Phenol is derived from an old name of benzene
 Phene
 Phenyl: -C6H5

 Phenol is a crystalline solid white in colour and needs to be handled with care as it can cause
chemical burns. Friedlieb Ferdinand Runge discovered Phenol in the year 1834.
 It was extracted from coal tar.
 It is also known as phenolic acid.
 If a compound is consisting of a six-membered aromatic ring and bonded to a hydroxyl group
directly, then it can be referred to as phenol.
 Classification of Phenol

 Depending on the number of hydroxyl groups attached, phenols can be classified into three types.

 Monohydric phenols: They contain one -OH group.

 Dihydric phenols: They contain two -OH groups. They may be ortho-, meta- or para- derivative.

 Trihydric phenols: They contain three -OH groups.

 Although phenols have similar properties (as both phenol and general alcohol have the hydroxyl
group) phenols are unique due to their aromatic ring.
  PHYSICAL PROPERTIES OF PHENOLS

 Colorless, crystalline, poisonous solid with phenolic odor

 Melting point 41°C and Boiling Point 182°C

 Sparingly soluble in water forming pink solution at room temperature

 Completely soluble above 68.5°C

 Causes blisters on skin

Used as disinfectants

 Acidity of Phenol : Compare to alcohols, phenols are stronger acid as the pKa value for phenol is 10 while for
alcohols it’s close to 16.

 Because of acidic nature, phenols can turn blue litmus red and react with aqueous alkali to form phenate.

 Both reactions are not shown by alcohols.

 Compare to carboxylic acids, phenols are weaker acid.. The acidity of phenol is due to its ability to loose
hydrogen ion to form phenoxide ion.

 Phenol is a weak acid

 The negative charge on the oxygen atom is delocalized around the ring. As result the negative
charge is no longer entirely localized on the oxygen nut is spread out around the whole ion.

 The negative charge of phenolate ion is stabilized by resonance. This makes the phenoxide ion
more stable.

 Acidity of Phenol : Phenoxide ion has greater stability than phenols

as in the case of phenol charge separation takes place during
resonance
 Resonance structure of phenoxide
ion is more stable than phenol due to charge separation

Thus phenol can easily donate proton which indicates the

acidic nature of phenol.
 Acidic characteristics of phenol:
 i) pH of dilute solution of phenol in water ranges between 5-6.

 (ii) Phenol reacts with sodium hydroxide solution to give colourless solution containing sodium
phenoxide.

 (iii) Due to weak acidic nature, phenol partially reacts with sodium carbonate to give sodium
phenoxide and sodium bicarbonate.

 Unlike other carboxylic acids, phenol is not acidic enough to react with sodium bicarbonate to
produce carbon dioxide and water.
 (iv) Like other acids, phenol reacts with metallic sodium/potassium to give hydrogen gas. Phenol
being a weak acid it is a slow reaction.
 Phenols are more acidic than alcohols because the phenoxide anion is resonance-stabilized by the
aromatic ring. Sharing the negative charge over the ring increases the stability of the phenoxide
anion and thus increases the tendency of the corresponding phenol to dissociate

 Effect of Substituents on Acidity of phenol:

 As the acidic nature of phenol is due to the resonance stabilization of phenate compare to phenol.
 Therefore the presence of any substituent on aromatic ring which can stabilized the phenoxide ion
will tend to increases the acidity of phenol. While any substituent which destabilized the phenate
ion by increasing the negative charge will decrease the acidic nature of phenol.
 In other words; the presence of electron withdrawing group on benzene ring in phenol increase the
acidity of phenol NO2, Cl, CN, CHO, COOH , Halogens, Ketones.
 electron releasing (donating) group will decrease the acidity CH3, OCH3, -NH2

 Ex:

 electron withdrawing group on benzene ring in phenol increase the acidity of phenol and electron
releasing group will decrease the acidity if there is a nitro group substituted on phenol, it will
increase the acidic nature of phenol. Hence nitrophenol will be more acidic than phenol.
 The position of nitro group on phenol will affect the acidity of phenol. A nitro group at -ortho and
para-position withdraws electrons from hydroxy group of phenol by stronger –M effect while nitro
group at -meta position withdraws electrons by weaker –I effect only, as meta position cannot
involve in resonance with hydroxy group.
 Hence o- and p-nitrophenols are more acidic than m-nitrophenol. Similarly as the number of nitro
groups increases on phenol, the acidic nature of phenol increases. The decreasing order of acidity
of nitrophenols is as given below.
 2,4,6-trinitrophenol > 2,4-dinitrophenol > 4-Nitrophenol > 2-Nitrophenol > Phenol

 Electron donating groups like amino (-NH2), alkyl (-R), lone pair decreases the acidity of phenol.
 For example, cresol or methylphenols are less acidic compare to phenol due to positive inductive
effect as well as hyperconjugation of methyl group.
 As both of these effects increases the electron density on hydroxy group and results in low acidity
of phenols.
 Some of the substituted phenols with their pKa values are as follow.

 Why is meta-nitrophenol less acidic than para-nitrophenol?

 . In the case of m-nitrophenol and p-nitrophenol, the relative stability can be determined by looking
at the resonance structures. - Whereas p-nitrophenol has an additional resonance structure where
the negative charge is delocalised onto the oxygen’s of the nitro group, which is highly
electronegative and therefore stabilise the charge effectively. This stabilisation is not possible in the
case of m-nitrophenol because there is no opportunity via resonance for delocalisation onto the
nitro group.
 Preparation of Phenols

 phenol was primarily synthesized from coal tar. However, with advancements in technology,
several new methods have been devised for the preparation of phenols. In laboratories, phenol is
primarily synthesized from benzene derivatives.

 Preparation of Phenols from Haloarenes:

Chlorobenzene is an example of a haloarene which is formed by the monosubstitution of the
benzene ring.
When chlorobenzene is fused with sodium hydroxide at 623K and 320 atm, sodium phenoxide is
produced. Finally, sodium phenoxide on acidification gives phenol.

1. Mechanism:
 Preparation of Phenols

2. Preparation of Phenols from Benzene Sulphonic Acid: Benzenesulphonic acid can be obtained from
benzene by reacting it with oleum. This benzene sulphonic acid can be treated with molten sodium
hydroxide at high temperatures to encourage the formation of sodium phenoxide. Finally, sodium
phenoxide on acidification gives phenol.

Mechanism:

3. Preparation of Phenols from Diazonium Salts: When an aromatic primary amine is treated with nitrous
(NaNO2 + HCl) acid at 273 – 278 K, diazonium salts are obtained. These diazonium salts are highly reactive
in nature. Upon warming with water, these diazonium salts finally hydrolyze to phenols. Phenols can also
be obtained from diazonium salts by treating it with dilute acids.

. Mechanism: When an aromatic primary amine is treated with nitrous (NaNO2 + HCl) acid at 273 –
278 K, diazonium salts are obtained. These diazonium salts are highly reactive in nature. Upon warming
with water, these diazonium salts finally hydrolyze to phenols. Phenols can also be obtained from
diazonium salts by treating it with dilute acids.
 4. From Salicylic acid: Sodium salicylate when heated with sodalime undergoes decorboxylation to
give sodium phenoxide which on acidification gives phenol.

 PHYSICAL PROPERTIES OF PHENOLS

 1) Pure phenols occur in the form of solids or colourless liquids, but due to its gradual oxidation by
air it may become coloured.
 Phenols have a characteristic smell due to the formation of phenoquinone.

 Due to the presence of large hydrocarbon molecule, phenols are sparingly soluble in water but
readily soluble in organic solvents (such as benzene, ether, etc.). Phenol itself is fairly soluble in
water because of its capability to form hydrogen bond as shown below:

 Boiling point : Phenols have much higher boiling point than there corresponding hydrocarbons due
to intermolecular hydrogen bonding
 Sparingly soluble in water forming pink solution at room temperature
 Completely soluble above 68.5°C
 CHEMCIAL PROPERTIES OF PHENOL

 (i) Kolbe's reaction: When phenol is treated with sodium hydroxide, sodium phenoxide is produced.
further sodium phenoxide treated with carbon dioxide, followed by acidification, undergoes
electrophilic substitution to give ortho-hydroxybenzoic acid as the main product. This reaction is
known as Kolbe's reaction.

ii_) Halogenation of Phenols: When phenols are treated with bromine in the presence of a solvent of low
polarity like CHCl3 at low temperatures, monobromophenols are formed. When phenol is treated with
bromine water, a white precipitate of 2, 4, 6-tribromophenol is formed.
 iii) Nitration of Phenols: Phenols upon treatment with dilute nitric acid undergo nitration at low
temperature (298 K) to give a mixture of ortho and para nitrophenols.

 When phenol is treated with concentrated nitric acid, the nitration results in the formation of 2, 4,
6-trinitrophenol (commonly called picric acid).

iv) Combustion of phenol: Phenol burns in presence of oxygen to give carbon dioxide and water.
Phenol tends to burn in air with an extremely smoky flame due to the high proportion of carbon in
phenol.

v) Reduction of phenol: Phenol is reduced to benzene when it is distilled with zinc dust or when
phenol vapour is passed over granules of zinc at 400°C.
 C6H5OH + Zn C6H6 + ZnO

vi) Reimer-Tiemann Reaction: When phenol is treated with chloroform in the presence of sodium
hydroxide, an aldehyde group is formed at the ortho position of the benzene ring. This reaction is popularly known
as the Reimer-Tiemann reaction.
 Qualitative Test for Phenolic Group

To identify the presence of a phenolic functional group in a given organic compound.

 Litmus test
 Ferric chloride test
 Libermann’s test
 Bromine water test

 Phthalein dye test

 a) Litmus Test:

 Scientists use litmus paper to test whether the given solution is acidic or basic. Red litmus paper turns blue
while blue litmus paper remains unchanged in the presence of a base.

 Phenol turns blue litmus paper red. This shows that phenol is acidic in nature. Carboxylic acid also gives this
test. Compared to carboxylic acid, phenol is weakly acidic and it does not give an effervescence with
aqueous sodium carbonate.

 Procedure:

 1. Place the drop of given organic solution or a small crystal on moist blue litmus paper. 2. Observe the
change in colour, if it changes to red then phenolic group may be present

(b) Ferric Chloride Test:

Aqueous solution of phenol reacts with freshly prepared ferric chloride solution gives coloured complex.
Most phenols give dark coloured solutions.
The chemical reaction is given below.
6C6H5OH + FeCl3 → [Fe(C6H5O)6]3– (violet colour complex)+ 3HCl + 3H+
Ex:
Phenol, resorcinol, Ortho cresol, Para cresol Violet or blue colouration.
Procedure:
1. Dissolve the given organic compounds in water.
2. Add neutral solution of ferric chloride slowly dropwise.
3. Observe the change in colour.

4. . A red, blue, green or purple colouration indicates the presence of phenol.

c) Libermann’s Test: Phenol reacts with concentrated sulfuric acid and sodium nitrite forms a yellow colour
quinone monoxime complex.

With excess of phenol and sulfuric acid a deep blue indophenol complex is formed. On dilution a red colour
indophenol is formed which turns to deep blue colour sodium salt solution of indophenol on treatment
with sodium hydroxide.
Procedure:

 Place the crystals of sodium nitrite in a clean dry test tube.

 Add 1ml of phenol to the sodium nitrite solution.
 Heat the mixture gently and allow it to cool.
 Add 1ml of concentrated sulfuric acid to it and shake the contents.
 Observe the change in the colour of the solution.

 Dilute the solution with water so that the given compound turns red if a phenolic group is present.
Now add sodium hydroxide solution, the blue colour solution or green colour solution appears.

(d) Bromine Water Test:

Phenol undergoes electrophilic substitution reaction with bromine. When bromine water is added to
aqueous solution of phenol the brown colour of bromine disappears and a white precipitate of
tribromophenol is formed.
The chemical reaction is given below.
Procedure:

 Dissolve the given organic compound in glacial acetic acid.

 Add bromine water solution to this dropwise.
 If the colour of bromine disappears then it indicates the presence of phenol.
e) Phthalein Dye Test: Phenol on heating with phthalic anhydride in the presence of concentrated sulfuric
acid forms a colourless condensation compound called phenolphthalein. On further reaction with dilute
sodium hydroxide solution gives a pink colour fluorescent compound called fluorescein. Characteristic
colours are produced by different phenolic compounds which can be viewed under white background. The
chemical reaction is given below
Procedure:
 Take the organic compound to be tested in a test tube.
 Add 200mg of phthalic anhydride to it.

 Add drops of concentrated sulfuric acid to the mixture.

 Heat the solution for 2-3 minutes.
 Cool the mixture and pour it into a beaker containing dilute sodium hydroxide solution.
 Dilute the whole mixture with equal volume of water.
 Observe the change in the colour in a white background.

 If fluorescence colour exists the view it in a black background.

 Phenol is also known as carbolic acid.

 It is an aromatic compound having molecular formula C6H5OH.
 The molecule consist of a phenyl group (CH) bonded to a hydroxy group (OH).
 It is slightly acidic in nature phenol have stronger hydrogen bond as compare to alcohol so it is
more soluble in water and have high boiling points.
  It occurs as either colorless liquid or white solids at room temperature and may be highly toxic and
caustic

Use

 Phenol is widely used in a lot of industries for varied purposes. A complete list of the uses of phenols is given
below:

I. Phenol is the most commonly used disinfectant since ancient times.

II. It has got amazing antiseptic properties too. It was one of the most common chemicals used to clean
household materials, especially washrooms and floor tiles.

III. Phenol is proven to be an effective anti-bacterial, anti-fungi, and anti-viral agent.

IV. Phenol is an active ingredient of various pharmaceutical lotions, ointments, and ear drops used to prevent
bacterial or fungal infections.

V. Phenol, although in very minor quantity, is also used in the manufacturing of mouthwashes for effective
cleansing of the mouth and removal of mouth bacteria.

VI. Phenol is used as one of the starting materials for the synthesis of many chemicals such as picric acid,
pharmaceutical drugs, explosive materials, and plastic polymers.

VII. Phenols are one of the starting materials for the formation of azo dyes in the coloring industry.

VIII. Phenol is also used as a preservative in the wood industry to keep wood safe from the attack of
microorganisms like bacteria or fungi.

IX. Medically it is used temporarily to treat the pharyngitis.

 CRESOLS (C7H8O)

 Cresols are organic compounds which are also known as hydroxy toluene or methyl phenols.
 Cresols are solid or liquid, depends upon temperature on long exposure to air they are oxidised and
the impurities oftenly gives cresols a yellowish to brown red tint.
 Cresols have characteristic odour like phenols.

 Structure:
 In cresols structure methyl group substituted on to the ring of phenol.
 There are three isomers of cresol i.e. o-cresol, m-cresol and p-cresol.
 The mixture of these isomers of cresol is called tricresol. Cresol is extracted from coal tar or
synthetically produced by methylation of phenol or hydrolysis of chlorotoluenes.

Use:

 They are used as germicides.

 They are used as disinfectants and antiseptics even in low concentrations also used in sheep-dips
(disinfectants containing insecticides and pesticides) in low concentrations.,
 They are important components of creosote (a wood preservative produced as by product of coal
tar distillation).
 They provide antibacterial and insecticidal properties to creosote.
 Being phenol derivatives, they can be used in phenol-formaldehyde resins.

 The m-cresol form is used in making photographic developers and explosives.

 8) The p-cresol form is converted into Butylated Hydroxytoluene (BHT, an antioxidantin foods).
 M-cresol is a precursor for various compounds such as synthetic Vitamin E and preservatives in
some insulin.
 Chloro-3-cresol is used as household disinfectants.
 Resorsinol
 Structure: RESORCINOL (C6H6O2) Benzene-1,3-diol
 It is 1,3-isomer of benzenediol.
 It is colorless, readily soluble in water, alcohol and ether but insoluble in chloroform and CS2,

 It reduces the Fehling's solution.

 It condenses with acid and acid chlorides to give resacetophenone.
 It condense readily with aldehyde to give form- aldehyde.
 It undergoes electrophillic as well as nucleophllic substitution reactions.
 . It has a sweet taste.

 On exposure to Resorsinol irritation on skin and mucous membrane can occur.

 IUPAC Name: Benzene-1,3-diol

Uses:

Resorcinol has the following uses:

 . It is used as an antiseptic and disinfectant.
 It's ointment (5 to 10%) used in the treatment of psoriasis, eczema and hidradenitis (skin disease
characterized by occurence of inflamed and swollen lumps).
 It's 2% solution is used in hay fever and in whooping cough.
 It is also used in anti-dandruff shampoo or in sunscreen cosmetics.
 It has been also employed in treatment of gastric ulcer.

 It has also having analgesic effect so used as an ingredient in some drugs like Resinol, Vagisil and
clearasil.
 It is used in the production of diazodyes and plasticizers and as a UV absorber in resin.
 Resorcinol is used as an analytical reagent for determination of Ketoses sugar.
 Resorcinol is mainly used for the field of rubber adhesives and synthetic resins.
 It can be used for making glue silk and the adhesive agent of tire cord for nylon- purpose, making
wood glue and adhesive for vinyl material.

NAPHTHOLS (C H O)
10 8

 Structure:

 Naphthol is composed of a hydroxyl group bonded to a naphthalene ring.

 It can exist as one of two isomers i.e. 1-naphthol and 2-naphthol.
 These two isomers differ by which car bon in the naphthalene ring, the hydroxyl group is bonded
to.
 Being its aromatic nature it has alternating double and single bonds throughout its rings.
 Due to more electronegativity of oxygen, than both Carbon and hydrogen, naphthol is highly polar
in nature. 1-naphthol (α-naphthol) is a white solid, fluorescent compound and soluble in alcohols,
ethers and chloroform.
 2-naphthol (B-naphthol) is a colorless or yellow crystalline solid, fluorescent having same solubility
as 1-naphthol.

 They are used for manufacturing dyes and dye intermediates.

 They are also used in other areas of chemical industries.

 1-Naphthol is used for making several dyes, and it is converted into large amounts of compounds
incorporated into other dyes.

 2-Naphthol is converted into various dyes, dye intermediates, tanning agents. antioxidants, and antiseptics.

 1-Naphthol is an ingredient of Molisch's reagent which is used for detecting the presence of carbohydrates.

 . 1-Naphthol is a precursor of variety of insecticides like carbanyl.

 . 1-Naphthol is used to detect the presence of arginine in proteins by Sakaguchi test.

 .. 2-Naphthol is precursor for preparation of Sudan dyes (used as dyes for various 5.