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ALCOHOLS AND PHENOLS

These are compounds containing C – O single bond. The functional group present in Alcohols and phenols is –
OH (hydroxyl) group and that present in ethers is –O – group (oxy group). In alcohols, the –OH group is bonded to an
alkyl group. So the general formula of alcohols is R-OH. But in phenols, the –OH groupis bonded to an aryl group. So
the general formula of phenols is Ar-OH.
Classification of Alcohols
1. Depending on the number of –OH groups: Based on this alcohols are classified as monohydric (contain only
one –OH group), dihydric (contain two –OH groups), trihydric (contain three –OH groups) and polyhydric (contain
more than two –OH groups). Examples for monohydric alcohols are methanol (CH 3-OH),ethanol (CH3-CH2-OH) etc.
Example for dihydric alcohol is ethylene glycol (HO-CH2-CH2-OH) and for trihydricalcohol is glycerol (HOCH2-CHOH-
CH2OH).
Monohydric alcohols may be further classified according to the hybridisation of the carbon atom to which the hydroxyl
group is attached.
i) Compounds containing sp3 C-OH bond: Here the –OH group is attached to an sp3 hybridised carbon
atom of an alkyl group. They are further classified as follows: Primary, secondary and tertiary
alcohols.
Allylic alcohols: In these alcohols, the —OH group is attached to an sp3 hybridised carbon next tothe
carbon-carbon double bond. E.g. CH2=CH-CH2-OH (Allyl alcohol)
Benzylic alcohols: In these alcohols, the —OH group is attached to an sp3 hybridised carbon atomnext to
an aromatic ring.
Allylic and benzylic alcohols may be primary, secondary or tertiary.
ii) Compounds containing sp2 C −OH bond: These alcohols contain —OH group bonded to a carbon-carbon
double. These may be vinyl alcohols or phenols.
Vinyl alcohols: CH2=CH-OH
Phenols:

Nomenclature of Alcohols
Common Name: By suffixing alcohol to the name of alkyl group (i.e. word root + yl alcohol)
IUPAC Name: By substituting ‘e’ of alkane with the suffix ‘ol’. (i.e. alkanol)
Some examples:
Compound Common Name IUPAC name
CH3-OH Methyl alcohol Methanol
CH3-CH2-OH Ethyl alcohol Ethanol
CH3-CH2-CH2-OH n-Propyl alcohol 1-Propanol
CH3-CHOH-CH3 Isopropyl alcohol 2-Propanol
CH3-CH2-CH2-CH2-OH n-Butyl alcohol 1-Butanol
CH3-CHOH-CH2-CH3 sec-butyl alcohol 2-Butanol
(CH3)2CH-CH2-OH Isobutyl alcohol 2-Methylpropan-1-ol
(CH3)3C-OH tert-butyl alcohol 2-Methylpropan-2-ol
(CH3)3C-CH2-OH Neopentyl alcohol 2,2-Dimethylpropan-1-ol
Nomenclature of Phenols

Preparation of Alcohols
1. From alkenes:
i) By acid catalysed hydration: Alkenes react with water in the presence of acid as catalyst to
formalcohols. In the case of unsymmetrical alkenes, the addition reaction takes place in accordance
withMarkovnikov’s rule.

ii) By hydroboration–oxidation reaction: Alkenes add diborane to give trialkyl boranes as addition
product. This on oxidation by hydrogen peroxide in the presence of aqueous sodium hydroxide to
form alcohols. This reaction is known as hydroboration -oxidation reaction.
The net reaction is the addition of a water molecule to the alkene in a way opposite to the
Markovnikov’s rule.

2. From carbonyl compounds

i) Reduction: Carbonyl compounds (aldehydes and ketones) when reduced using lithium aluminium
hydride (LiAlH4 or sodium borohydride (NaBH4) or on catalytic hydrogenation (using finely divided
metal such as nickel, platinum or palladium), we get alcohols.
Aldehydes give primary alcohols and ketones give secondary alcohols.
 R-CHO + [H] LiAlH4 R-CH2OH
R2CO + [H] LiAlH4 R2CH-OH
Commercially, acids are reduced to alcohols by converting them to the esters followed by their
reduction using hydrogen in the presence of catalyst (catalytic hydrogenation).

ii) From Grignard reagents: Aldehydes and ketones add Grignard reagent followed by hydrolysis, we
get alcohols.

Formaldehyde (methanal) gives primary alcohols, aldehydes other than formaldehyde gives
secondary alcohols and ketones give tertiary alcohols.
H-CHO + RMgX R-CH2-OMgX H2O R-CH2-OH + MgX(OH)
Formaldehyde adduct 10 alcohol
R-CHO + RMgX R2CHOMgX H2O R2CHOH + MgX(OH)
Aldehyde adduct 20 alcohol
R2CO + RMgX R3COMgX H2O R3C-OH + MgX(OH)
Ketone adduct 30 alcohol
Preparation of Phenols
1. From haloarenes: When chlorobenzene is fused with NaOH at 623K temperature and 320
atmospheric pressure, sodium phenoxide is formed which on acidification, we get phenol.

Chlorobenzene Sodium phenoxide Phenol

2. From benzene sulphonic acid: Benzene on sulphonation with oleum, benzene sulphonic acid is
formed which on treating with NaOH followed by acidification, we get phenol.

3. From diazonium salts: When an aromatic primary amine (e.g. aniline) is treated with nitrous
acid (prepared by mixing NaNO2 & HCl) at 273-278K, a diazonium salt is formed, which on
warming with water or treating with dilute acids, we get phenol.

4. From cumene: Cumene is isopropylbenzene (2-phenyl propane). It is oxidised in presence of air,

we get cumene hydroperoxide, which on treating with dilute acid, phenol and acetone are
formed. This method is used for the manufacture of phenol.
 Physical Properties of Alcohols and Phenols
1. Boiling Points: Boiling points of alcohols and phenols are higher than hydrocarbons, ethers,
haloalkanes and haloarenes of comparable molecular masses. This is because the –OH group in
alcohols and phenols is involved in intermolecular hydrogen bonding.
H R H R H R H R H R H

R – O…..H – O…..H – O….. H – O…..H – O….. H – O…..H – O….. H – O…..H – O….. H – O…..H – O…..

H – O…………..H – O……………H – O…………..H – O………… H – O……………H – O…...........H – O……

The boiling points of alcohols and phenols increase with increase in the number of carbon atoms. This is
because as the number of carbon atoms increases, the van der Waals forces of attraction increases and
hence the boiling point. In alcohols, the boiling points decrease with increase of branching in carbon
chain (because of decrease in van der Waals forces with decrease in surface area).
2. Solubility: Alcohols and phenols are soluble in water. But the solubility of alcohols is higher than that
of phenols. Solubility of alcohols and phenols in water is due to their ability to form hydrogen bonds with
water molecules (inter molecular hydrogen bonding). The solubility decreases with increase in size of
alkyl/aryl groups.
Chemical Reactions of Alcohols and Phenols
A) Reactions involving cleavage of O–H bond
1. Acidity of alcohols and phenols:
i) Reaction with metals: Alcohols and phenols react with active metals such as sodium, potassium
and aluminium to yield corresponding alkoxides/phenoxides and hydrogen.
R-OH + Na → R-ONa + ½ H2
(sod. Alkoxide)
C6H5-OH + Na → C6H5-ONa + ½ H2
(sod. Phenoxide)
Phenols also react with aqueous sodium hydroxide to form sodium phenoxides.
C6H5-OH + NaOH → C6H5-ONa + H2O
The above reactions show that alcohols and phenols are acidic in nature.
ii) Acidity of alcohols: The acidic character of alcohols is due to the polar nature of O–H bond. An
electron-releasing group (e.g. alkyl groups like –CH3, –C2H5 etc.) increases the electron density on oxygen and
hence decrease the polarity of O-H bond. This decreases the acid strength. So the acid strength of alcohols
decreases in the order:
Primary alcohols > Secondary alcohols > Tertiary alcohols
But alcohols are weaker acids than water.
 iii) Acidity of phenols: In phenols, the –OH group is directly bonded to an sp2 hybridized carbon atom
of the benzene ring. Due to the greater electronegativity of sp2 hybridized carbon (due to greater s-character),
the benzene ring acts as an electron withdrawing group. So the lone pair electrons present in oxygen atom of
–OH group enters in the benzene ring and the following resonating structures are obtained:

(I) (II) (III) (IV) (V)

In the resonating structures (II), (III) and (IV), there is a positive charge on the electronegative oxygen
atom and hence it attracts the bond pair of electrons in O-H bond. So it is easy to remove the hydrogen atom
as H+ ion and thus phenol is acidic in nature.
Phenol is more acidic than alcohol. This is due to the following reasons:
1. In alcohol, the O-H group is directly bonded to an sp3 hybridized carbon atom, but in phenol, it is
bonded to an sp2 hybridized carbon. Due to the greater s-character and electronegativity of sp2
hybridized carbon, the ease of O-H bond cleavage is greater on phenol and hence it is more
acidic than alcohol.
2. The ionization of alcohol and phenol is as follows:

The alkoxide ion (R-O-) formed by the ionization of alcohol is not resonance stabilized. So the negative
charge is localized on oxygen atom. But the phenoxide ion (C6H5-O-) formed by the ionization of phenol is
resonance stabilized as follows.

Due to resonance, the negative charge is delocalized and hence phenoxide ion is more stable which favours
the ionization of phenol. Also phenoxide ion is more stable than phenol, because in phenol, there is a +ve
charge on electronegative oxygen atom. So it is less stable and readily lose H+ ion.
The presence of electron withdrawing groups (like nitro group) at ortho and para positions
increases the acidic strength of phenol. It is due to the effective delocalisation of negative charge in
phenoxide ion. On the other hand, electron releasing groups (like alkyl groups) at these positions
decreases the acidic strength of phenol. So cresols are less acidic than phenol.
2. Esterification:
Alcohols and phenols react with carboxylic acids, acid chlorides and acid anhydrides to form
esters. The reaction with carboxylic acid and acid anhydride are carried out in the presence of conc. H2SO4.
The reaction with acid chloride is carried out in the presence of a base (pyridine) so as to neutralise HCl
formed during the reaction.
R-OH + R’-COOH R-OCOR’ + H2O
(ester)
C6H5-OH + R’-COOH C6H5-OCOR’ + H2O
R-OH + (R’CO)2O R-OCOR’ + R’COOH
(acid anhydride)
C6H5-OH + (R’CO)2O C6H5-OCOR’ + R’COOH

R-OH + R’-COCl pyridine R-OCOR’ + HCl [Schotten-Baumann reaction]

(acid chloride)
C6H5-OH + R’-COCl pyridine C6H5-OCOR’ + HCl
The introduction of acetyl (CH3CO) group in alcohols or phenols is known as acetylation.
Acetylation of salicylic acid produces aspirin, which is used as an analgesic.

B) Reactions involving cleavage of carbon – oxygen (C–O) bond in alcohols

1. Reaction with hydrogen halides: Alcohols react with hydrogen halides in presence of anhydrous zinc
chloride (ZnCl2) to form alkyl halides.
ROH + HX an. ZnCl2 R–X + H2O
The reactivity of primary, secondary and tertiary alcohols with HCl is different and hence this reaction is used
for the distinction of the three types of alcohols by a test called Lucas Test.
The difference in reactivity of three classes of alcohols with HCl distinguishes them from one another (Lucas
test).
LUCAS TEST:
Lucas reagent is amixture of Conc. HCl and anhydrous ZnCl2. Alcohols are soluble in Lucas reagent
while their halides are immiscible and produce turbidity in solution.
Tertiary alcohols react with Lucas reagent and form immediate turbidity; secondary alcohols
form turbidity within 5 minutes, while primary alcohols do not produce turbidity at room temperature.
They give turbidity only on heating.
2. Reaction with phosphorus trihalides (PX 3): Alcohols react with phosphorus trihalides to give alkyl
halides.
3R-OH + PX3 3 R-X + H3PO3 (X= Cl or Br)
3. Dehydration: Alcohols undergo dehydration (removal of a molecule of water) on treating with a
protic acid like concentrated H2SO4 or H3PO4, or catalysts such as anhydrous zinc chloride or alumina to form
alkenes.

The relative ease of dehydration of alcohols follows the order: Tertiary > Secondary > Primary.
 For example ethanol undergoes dehydration by heating it with concentrated H2SO4 at 443 K, we
get ethene.

Secondary and tertiary alcohols are dehydrated under milder conditions.

4. Oxidation:
Alcohols on oxidation give carbonyl compounds (aldehydes and ketones) or carboxylic acids
depending on the nature of oxidising agent used. Primary alcohols when oxidized using mild oxidising agent
like anhydrous CrO3, we get aldehydes. But with strong oxidising agents like acidified potassium
permanganate or potassium dichromate, carboxylic acids are formed.
R-CH2OH [O] R-CHO [O] R-COOH
RCH2OH CrO3 RCHO
Primary alcohols are oxidised to aldehydes in good yield by pyridinium chlorochromate (PCC) [a
complex of chromium trioxide with pyridine and HCl].
CH3 −CH = CH−CH2OH ⎯⎯PCC⎯→ CH3 – CH = CH−CHO
[crotyl alcohol] [crotanaldehyde]
Secondary alcohols are oxidised to ketones by chromic anhydride (CrO 3).
R2CHOH CrO3 R2CO
With strong oxidising agents, secondary alcohols give carboxylic acids with lesser number of carbon atoms.
R2CHOH [O] R2CO [O] R-COOH
Tertiary alcohols do not readily undergo oxidation reaction. But in presence of strong oxidising agents
(KMnO4) and at high temperature, they first give ketones with lesser number of carbon atoms which on
further oxidation give carboxylic acids with still lesser number of carbon atoms.
R3C-OH [O] R2CO [O] R-COOH
5. Reaction with hot copper catalyst
Primary alcoholic vapours when passed through hot Cu catalyst at 573K, undergo dehydrogenation to
form aldehydes, while secondary alcohols undergo dehydrogenation to give ketones.
R-CH2OH hot Cu/573K R-CHO
R2CHOH hot Cu/573K R2CO
Tertiary alcohols react with hot Cu catalyst at 573 K, undergo dehydration to give alkenes.

REACTIONS OF PHENOLS
1. Electrophilic Substitution reaction:
In phenol, the –OH group attached to the benzene ring donate electron pairs and hence it activates it
towards electrophilic substitution. Also, in the resonating structures of phenol, the electron density is greater
on ortho and para positions. So the electrophile enters at these positions.
The common electrophilic aromatic substitution reactions taking place in phenol are:
a) Nitration: Phenol reacts with conc. Nitric acid to give an yellow precipitate of 2,4,6-
trinitrophenol commonly called picric acid.

Picric acid can also be prepared by treating phenol first with concentrated sulphuric acid followed by
treating with concentrated nitric acid.
For the preparation of ortho and para nitrophenols, phenol is treated with dil. HNO 3 at low
temperature (298K).

The ortho and para isomers can be separated by steam distillation. o-Nitrophenol is steam
volatile due to intramolecular hydrogen bonding while p-nitrophenol is less volatile due to intermolecular
hydrogen bonding which causes the association of molecules.
b) Halogenation: When phenol is brominated using Br 2 in CHCl3 or CS2 at low temperature, we get a
mixture of ortho and para bromophenols. The reaction takes place in the absence of Lewis acid
catalyst (like FeBr3). It is due to the highly activating effect of –OH group attached to the benzene ring.

When phenol is treated with bromine water, we get a white precipitate of 2,4,6-tribromophenol.

2. Kolbe’s Reaction: Phenol when treated with sodium hydroxide, we get sodium phenoxide which
on treating with carbon dioxide followed by acidification, we get orthohydroxybenzoic acid
commonly called Salycilic acid. This reaction is called Kolbe’s reaction.
 3. Reimer-Tiemann reaction: Phenol when treated with chloroform in the presence of sodium
hydroxide, followed by acidification, we get salycylaldehyde (o-hydroxybenzaldehyde). Thiis
reaction is known as Reimer - Tiemann reaction.

4. Reaction with zinc dust: Phenol when heated with Zn dust, we get benzene.

5. Oxidation: When phenol is oxidised with chromic acid we get a conjugated diketone known as
benzoquinone.

In the presence of air, phenols are slowly oxidised to dark coloured mixtures containing quinones.

Some Commercially Important Alcohols

1. Methanol (CH3OH):
Methanol is also known as ‘wood spirit’ since it can be produced by the destructive distillation of wood.
It is manufactured by the catalytic hydrogenation of carbon monoxide at about 573-673 K
temperature and 200-300 atm pressure and in the presence of ZnO – Cr2O3 catalyst.

It is highly poisonous in nature. It is used as a solvent in paints, varnishes and for making formaldehyde.
2. Ethanol (CH3CH2OH):
Ethanol is commonly known as spirit or grain alcohol. It is obtained commercially by the fermentation
of sugar. The sugar in molasses, sugarcane or fruits like grapes is converted to glucose and fructose, in
the presence of an enzyme, invertase. Glucose and fructose undergo fermentation in the presence of
another enzyme, zymase to give ethanol and carbondioxide. Both the enzymes invertase and zymase are
produced by yeast.
C12H22O11 + H2O Invertase C6H12O6 + C6H12O6
Sucrose Glucose Fructose
C6H12O6 Zymase 2C2H5OH + 2 CO2
Ethanol
Fermentation takes place in anaerobic conditions i.e. in absence of air. If air gets into fermentation
mixture, the oxygen of air oxidises ethanol to ethanoic acid (acetic acid), which destroys the taste of alcohol.
 The ethanol solution obtained by fermentation contains only 8-10% ethanol and it is called wash. It can
be concentrated upto 95.6% by fractional distillation. 95.6% alcohol is called Rectified spirit. It is
concentrated to 100% by distilling with small amount of benzene. Ethanol free from water and other
impurities (100% pure ethanol) is known as absolute alcohol.
Ethanol is a colourless liquid. It is used as a solvent in paint industry and in the preparation of a number of
carbon compounds.
The commercial alcohol is made unfit for drinking by mixing in it some copper sulphate (to give it a
colour) and pyridine (a foul smelling liquid). It is known as denaturation of alcohol and the resulting
alcohol is known as denatured spirit. If methanol is used for denaturation, it is called methylated spirit.
Ethanol can also be manufactured by hydration of ethene.
CH2=CH2 + H2O H+ CH3-CH2-OH
ETHERS
Nomenclature
Common names of ethers are derived from the names of alkyl/aryl groups written as separate words
in alphabetical order and adding the word ‘ether’ at the end. If both the alkyl groups are the same, the prefix
‘di’ is added before the alkyl group.
In IUPAC system of nomenclature, ethers are named as ‘Alkoxyalkane’. The larger alkyl (R) group is
chosen as the parent hydrocarbon.
Some examples are:
Compound Common Name IUPAC Name
CH3OCH3 Dimethyl ether Methoxymethane
C2H5OC2H5 Diethyl ether Ethoxyethane
CH3OCH2CH2CH3 Methyl n-propyl ether 1-Methoxypropane
C6H5OCH3 Methylphenyl ether Methoxybenzene
(Anisole) (Anisole)
C6H5OCH2CH3 Ethylphenyl ether Ethoxybenzene
(Phenetole)
C6H5O(CH2)6 – CH3 Heptylphenyl ether 1-Phenoxyheptane

If the two alkyl groups on both sides of the –O- group are identical, it is called symmetric ether and if they are
different, it is called asymmetric ether.

Preparation of ethers
1. By dehydration of alcohols:
Alcohols undergo dehydration in the presence of protic acids like H2SO4 or H3PO4 to give ethers based on
the reaction conditions.
For example, ethanol when dehydrated with conc. H2SO4 at 413 K, we get diethyl ether but at 443 K, we
get ethene.

This method is suitable for the preparation of ethers having primary alkyl groups only. In the case of 2 0 and 30
alcohols, alkenes are formed as the major product.
 2. Williamson’s ether synthesis:
Alkyl halide reacts with sodium alkoxide to form ether. This reaction is called Williamson’s ether
synthesis.
R-X + R’-ONa → R-O-R’ + NaX
For preparing ethers containing secondary and tertiary alkyl groups, the alkyl halide used should
be primary and the alkoxide should be secondary or tertiary.

If the alkoxide used is primary, dehydrohalogenation occurs and the product formed is an
alkene. This is because of the strong basic character of 10 alkoxide.

The reaction follows SN2 mechanism.

For the preparation of aromatic ethers, one of the reactants should be sodium phenoxide.

Physical Properties
Ethers have lower boiling point than alcohols. This is because in alcohols, there is inter molecular
hydrogen bonding, which is absent in ethers. Lower ethers are miscible with water due to the formation of
hydrogen bonding with water.
Chemical reactions
1. Reaction with HX:
Ethers on reaction with Hydrogen halide, the C-O bond cleavage occurs and alkyl halides are formed.
R-O-R + HX → R-OH + R-X
R-OH + HX → R-X + H2O
In the case of ethers containing two different alkyl groups (primary and secondary), the lower alkyl
group forms the alkyl halide (10 alkyl halide).
CH3-O-CH2-CH3 + HI CH3-I + CH3-CH2-OH
The order of reactivity of hydrogen halides is as follows: HI > HBr > HCl.
Mechanism:
Step 1: The ether molecule is protonated to form an oxonium ion.

Step 2: The Iodide ion attacks the least substituted carbon of the oxonium ion and displaces an alcohol
molecule by SN2 mechanism.

When one of the alkyl group is tertiary, the halide formed is a tertiary halide.
This is because in step 2 of the reaction, the departure of leaving group (HO–CH3) creates a more stable
carbocation [(CH3)3C+], and the reaction follows SN1 mechanism.

In the reaction of alkyl aryl ethers with HX, one of the products formed is always phenol. Here
the O-R bond is weaker than the O–C6H5 bond because the carbon of phenyl group is sp2 hybridised and there
is a partial double bond character.

2. Electrophilic substitution Reactions: The alkoxy group (-OR) is ortho, para directing and activates the
benzene ring. So the product formed is a mixture of ortho and para isomers.
a) Halogenation: Anisole on bromination with bromine in ethanoic acid to give a mixture of o-
bromoanisole and p-bromoanisole

b) Nitration: Anisole reacts with a mixture of conc. sulphuric acid and conc. nitric acid to give a mixture
of ortho and para nitroanisole.

c) Friedel-Crafts reactions:
i) Alkylation: Anisole undergoes Friedel-Crafts alkylation reaction in presence of anhydrous
aluminium chloride (a Lewis acid) as catalyst, we get a mixture of ortho and para alkylated
anisole.
ii) Acylation: