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Alcohols ,Phenols and Ethers

Alcohols: Phenols:
Consider Aliphatic hydrocarbon: Consider Aromatic hydrocarbon:
Simplest ex: Methane Simplest ex: Benzene

From methane replace any one From benzene replace any one
hydrogen atom by ─OH group hydrogen atom by ─OH group
(hydroxyl group ) to get Alcohol. (hydroxyl group ) to get Phenol.

An alcohol contains one or more Phenol contains (─OH ) groups

hydroxyl groups (─OH ) directly directly attached to carbon atom of
attached to carbon atom of aliphatic aromatic system.
system
Ethers:
Consider hydrocarbon --- replace any one hydrogen atom by alkoxy
group( -O-R) or aryloxy group (-O-Ar ) to get ether.

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Or consider Alcohol or phenol and replace hydrogen atom by alkyl or
aryl group to get ether.

Classifications of alcohols and phenols:

I. Based on the number of hydroxyl group:
Alcohols and phenols are classified as mono- , di- ,tri- or polyhydric
compounds depending on whether they contain 1, 2, 3 or many hydroxyl
groups in their structure.

II. Classification of monohydric alcohols based on the hybridisation:

A) Compound containing sp3 ─ OH bond :

Here ─OH group is attached to sp3 hybridised carbon atom of an alkyl group

And further classified as primary ,secondary and tertiary alcohols.

Ex :

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i) Allylic Alcohols: The ─OH group is attached to a sp hybridised carbon 3

next to the carbon– carbon double bond.

ii) Benzylic Alcohols: The ─OH group is attached to a sp3 hybridised carbon
next to an aromatic ring.

B) Compound containing sp2 ─ OH bond :

Here ─OH group is attached to sp2 hybridised carbon atom.

i) Aryl Alcohol (phenol): The ─OH group is attached to a sp2 hybridised

carbon atom of an aromatic ring.

ii) Vinylic Alcohol: The ─OH group is attached to a sp2 hybridised carbon
atom of a carbon– carbon double bond.

Classifications of ethers:
I type:

1. Simple or symmetrical ethers: [R─O─R ] :

If the alkyl or aryl groups attached to the oxygen atom are same then it is called
simple or symmetrical ether.

Ex:

2. Mixed or unsymmetrical ethers: [R─O─R’ ] :

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If the alkyl groups attached to the oxygen atom are different then it is called mixed
or unsymmetrical ether.

Ex:

II type:

1. Aliphatic ether: In which both R and R’ are alkyl groups.

Ex :

2. Aromatic ether: In which either one or both R and R’ are aryl groups.

Ex:

III type: Classification of aromatic ether:

1. Phenolic ethers or alkyl aryl ethers: Ethers in which one of the group is aryl
while the other is alkyl.

Ex:

2. Diaryl ether : Ethers in which both the groups are aryl.

Ex:

Nomenclature of Alcohols:
Common Name : Alkyl alcohol IUPAC Name : Alkanol

a.) In case of monohydric alcohols, drop “ e” of alkane by “ol”

1. The position of substituents and hydroxyl group are indicated by numbers of

carbon atoms to which these are attached.

2. Parent chain is numbered starting at the end nearest to the hydroxyl group.

b) In case of di or polyhydric alcohol : “e” of alkane is retained and ending

“ol” is added.

1. The number of ─OH groups are indicated by prefix di, tri etc before ‘ol’

c) In case of Cyclic alcohol :

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1. Use prefix cyclo-

2. Give number 1 to that carbon to which ─OH group is attached.

Ex: Monohydric alcohol

In 6th molecule write CH3 in place of OH and write OH in place of CH3.

Ex: Polyhydric alcohols and cyclic alcohols:

Write the IUPAC name of the following:

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Nomenclature of Phenols:
1. Simplest hydroxy derivative of benzene is Phenol. Its Common and IUPAC
name both are same .i.e. Phenol.

2. Substituted Phenol : Common Name: Mention ….–o , -m and -p

IUPAC Name: Mention 1,2- /1,3- /1,4- disubstituted phenol

3. Di hydroxy derivatives of benzene:

IUPAC Name: 1,2- / 1,3-/1,4- benzenediol

Nomenclature of ethers:
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Common Name:

1. Name the two alkyl or aryl groups linked to the oxygen atom as separate words
in alphabetical order and then add the word ether .

i.e. Name of R name of R’ (in alphabetical order ) + ether.

2. In case of symmetric ether use the prefix di.

i.e. Dialkyl ether or Diaryl ether.

IUPAC Name: Alkoxyalkane

Note:

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Write the IUPAC name for the following:

Structures of functional groups:

In Alcohols: In Phenols : In ethers:

Here both carbon and oxygen are sp3
hybridised.
Out of 4 sp3 hybridised orbitals of
oxygen , 1 sp3 hybridised orbital of
oxygen overlaps with 1s orbital of H to
form O − H σ bond.
Second sp3 hybridised orbital of
oxygen overlaps with sp3 hybridised
orbital of carbon to form C− O σ
bond.
Other 2 sp3hybridised orbital of
oxygen contains lone pair of electrons.
Here carbon is sp2 and oxygen is sp3
hybridised.
Out of 4 sp3 hybridised orbitals of
oxygen , 1 sp3 hybridised orbital of
oxygen overlaps with 1s orbital of H
to form O − H bond.
Second sp3 hybridised orbital of
oxygen overlaps with sp2 hybridised groups ,to form sp –sp ,σ bond.
orbital of carbon to form C− O bond.
Other 2 sp3 hybridised orbital of
oxygen contains lone pair of
electrons.
Ether shows tetrahedral
geometry
Oxygen is sp3 hybridised .
Out of 4 sp3 hybridised orbital 2
sp3 hybridised orbital overlap
with sp3 –orbital of two alkyl
3 3
Remaining two sp3 hybridised
orbitals of oxygen contain s lone
pair of electrons.

❖ C−O−H bond angle is 108.9 o ❖ C−O−H bond angle is ❖ The bond angle in ether
which is slightly less than the 109 o which is slightly less is slightly greater than
tetrahedral bond angle 109o - than the tetrahedral bond the tetrahedral bond
28’ this is due to the lone pair angle 109o - 28’this is due angel:
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–lone pair repulsions. to the lone pair –lone pair Due to :
repulsions. Repulsive interaction
between the two bulky (─ R)
❖ C−O bond length in phenol groups.
is slightly less than that in
methanol : due to C─O bond length (141pm) is
• Partial double bond almost the same as in alcohols.
character of carbon –
oxygen bond on account of
the conjugation of lone pair
electrons of oxygen with
the benzene ring.
• sp2 hybridised state of
carbon to which oxygen is
attached

In alcohol : Oxygen is more electronegative than the carbon and hydrogen.

• Electron density near oxygen is higher than that near carbon and hydrogen
atoms.

• Therefore an alcohol molecule is dipolar in nature with the oxygen

carrying partial negative charge and carbon and hydrogen each carrying a
partial positive charge.

• This is supported by the fact that methanol has dipole moment (1.71 D)

• Dipole moment of phenol is (1.54 D) less than that of methanol:

Due to: C─O bond in phenol is less polar due to the electron -withdrawing
effect of the benzene ring while in methanol C─O bond is more polar due to
electron- donating effect of the CH3 group.

• Due to dipolar nature , alcohols and phenols form intermolecular H- bond.

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Preparation of Alcohols:
I. From Alkenes

II. From Carbonyl compounds

III. From Grignard reagent

I. From Alkenes:

i. By acid catalysed hydration :

→ Hydration means addition of water molecule.

→ Alkenes react with water in the presence of acid as catalyst to form

alcohol.

Ex:

• In case of unsymmetrical alkenes , the addition reaction takes place in

accordance with Markovnikov’s rule.

Ex:

Mechanism:

(How do you convert ethene to ethyl alcohol , write its mechanism ) (3M)

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Write hydrogen atoms in ethene and ethyl alcohol and reversible sign.

I . From Alkene:
ii By- Hydroboration –oxidation :

Diborane B2H6 or (BH3)2 reacts with alkenes to give trialkyl boranes as addition
product. This is oxidised to alcohol by hydrogen peroxide in the presence of
aqueous sodium hydroxide.

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• Diborane is electron deficient and it acts as an electrophile.

• The addition of borane to the double bond takes place in such a manner that
the boron atom gets attached to the sp2 carbon carrying more number of
hydrogen atoms.

• The alcohol so formed looks as if it has been formed by addition of water to

the alkene in a way opposite to the Markovnikov’s rule.

• Diborane adds to the carbon- carbon double bond as BH3. Since BH3 is an
electrophile ,it can add to either of the two carbon –carbon doubled bond.

• In actual practice , addition occurs at the less substituted carbon.

• That is at the terminal carbon atom of propene because it generates a slight

positive charge on second C atom which is stabilized by the + I effect of the
CH3 group.

• As a result complex ( I ) is formed. The positive charge on C2 of this

complex then attracts one of the hydrogen atoms of the BH3. group towards
it leading to the formation of a four centered cyclic transition state ( II )
Which ultimately decomposes to form the additional product( III )

• Further stepwise addition of two more molecules of CH3CH=CH2 to

(III )finally gives addition product..i.e, trialkylborane.

• Tetrahydrofuran (THF) solvent is used for hydroboration

• Hydrogen peroxide replaces the B─C bonds with HO─C bonds and the
boron reagent is converted to boric acid.

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Totally :

II .From Carbonyl compound:

i) By reduction of aldehyde and ketone:

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Aldehydes and ketones are reduced to corresponding alcohols bya)Addition of
H2 in the presence of catalysts like finely divided metals i.e. Pt , Pd or Ni (Process
is catalytic hydrogenation ) Aldehydes give primary alcohols (Write CH2OH
in place of CHO)

b) By complex metal hydrides such as lithium aluminium hydride (LiAlH 4) or

sodium borohydride ( NaBH4). Ketones give secondary alcohols. (Write
CHOH in place of C=O)

ii) By reduction of carboxylic acids and esters:

Carboxylic acids are reduced to primary alcohols by lithium aluminium

hydride, a strong reducing agents. (Write CH2OH in place of COOH)

Commercially, acids are reduced to alcohols by converting them to esters followed

by their reduction using hydrogen in the presence of catalyst (catalyst
hydrogenation ) ( Lithium aluminium hydride is expensive)

III. From Grignard reagent:

Alcohols are produced by the reaction of Grignard reagents with aldehydes and
ketones.

Mechanism:

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I Step: Nucleophilic addition of Grignard reagent to the carbonyl group to form
an adduct.

II Step: Hydrolysis of the adduct gives alcohol.

Formaldehyde or methanal (HCHO) when it reacts with Grignard reagent primary

alcohol is obtained. When aldehydes except formaldehyde (RCHO) reacts with
Grignard reagent secondary alcohol is formed.When ketones (RCOR) reacts with
Grignard reagent tertiary alcohol is formed.

Preparation of Phenol (carbolic acid): Phenols are prepared by

benzene derivatives as follows:

I Industrial preparations:
1. From haloarene: ( Dow’s process):
Phenol is obtained when chlorobenzene is heated with NaOH solution at 623K
under 300 to 320 atmosphere pressure.

2. From Cumene (isopropylbenzene): (i.e from hydrocarbon): (3M)

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Cumene is oxidised in the presence of air to cumene hydroperoxide. This can be
converted into phenol when it reacts with dilute acid.(Acetone is the by product
of this reaction and is obtained in large quantity.)

II Laboratory preparations:
1. From benzenesulphonic acid : (3M)

Benzene is sulphonated with oleum ( H2SO4 +SO3 ) benzene sulphonic acid is

formed.

When benzenesulphonic acid is treated with NaOH, sodium phenoxide is

obtained.

Acidification of this salt (sodium phenoxide) gives phenol.

2. From diazonium salt : (3M)

A diazonium salt is formed by treating aromatic primary amine with nitrous acid
(HNO2 ) , at 273K – 278K.

Diazonium salts are hydrolysed to phenols by warming with water or by treating

with dilute acids.

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Physical properties:

• Alcohols and Phenols consists of two parts

1.Alkyl or aryl group

2. Hydroxyl group

Physical properties of alcohols and phenols are mainly due to the presence of ─OH
group.

Boiling point :

1. Boiling point of alcohols and phenols increases with increase in the number
of carbon atoms: Reason : Increase in Vander Waals forces.

Ex : Methanol < Ethanol < Propanol etc

2. The boiling points of alcohols are much higher than the corresponding
aliphatic hydrocarbons and haloalkanes. Reason : Alcohols contain a hydrogen
atom attached to the strongly electronegative oxygen atom. Therefore alcohol
forms intermolecular hydrogen bonds. As a result , alcohols exist as associated
molecules rather than discrete molecule.

Larger energy is required to break the hydrogen bond hence the boiling point of
alcohol is more than that of the hydrocarbon.

Ex: Methane < Chloromethane < Bromomethane < Methanol

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3.In case of isomeric alcohols, the boiling points decrease with increase of
branching in carbon chain. Reason : decrease of Vander Waals force and
decrease in surface area.

Ex: tertiary alcohol < secondary alcohol < primary alcohol

4.Molecular mass increases then boiling point also increases.

5.Boiling points of phenol is much more than that of the aromatic

hydrocarbon.

Ex: Benzene < chlorobenzene < bromobenzene < phenol

6.Boiling point of ether is in between the boiling point of alcohol and

hydrocarbon. Reason : Because of lacking of intermediate hydrogen bond in
ethers and even in hydrocarbons.

Ex : Hydrocarbon < ether< alcohol.

Solubility :

➢ Alcohols and phenols are soluble in water due to the formation of hydrogen
bond with water. (OH part is hydrophilic in nature )

➢ Solubility decreases with increase in size of alkyl/ aryl (hydrophobic

part ) groups.

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Chemical properties:
• Chemical reactions of alcohols and phenols are due to the their functional
group (─ OH group)

• Based on the structure of hydrocarbon part surrounding the hydroxyl group ,

the chemical reactions of alcohols and phenols can be divided into 2
categories:

1.Reactions involving the cleavage of the oxygen –hydrogen bond or removal

of hydrogen as a proton.

• When the O ─ H Bond is broken ,the alcohol and phenols act as

nucleophiles.

2. Reactions involving the cleavage of the carbon – oxygen bond or removal of

the OH group

• When Bond between C─O is broken ,alcohols act as electrophiles.

( Protonated alcohols reacts in this manner.)
Phenols do not undergo reactions involving C─ O cleavage but instead it
undergo a number of electrophilic substitution reactions of the benzene ring.

Alcohol act both as nucleophiles and electrophiles but phenol usually act as
nucleophiles only .

A . Reactions involving cleavage of O ─ H bond :

Both alcohols and phenols readily undergo cleavage of O ─ H bond . The ease of
cleavage of O ─ H bond : Phenols > primary alcohols> secondary alcohols >
tertiary alcohols.

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• Both alcohols and phenols are acidic in nature and react with active metals
such as sodium ,potassium and aluminium to give corresponding alkoxides and
phenoxides respectively with the liberation of hydrogen.

Ex:

• Phenols reacts with aqueous solution of sodium hydroxide to form

sodium phenoxides .

Above reactions show that alcohols and phenols are acidic in nature . Because H+
is liberated or removed. ( Any substance, which donate proton is an acid ) So
alcohols and phenols are Bronsted Acid. (They donate proton to the stronger base )

2.Esterification: ( reaction with carboxylic acid ):

Alcohols and phenols reacts with carboxylic acid , acid chlorides and acid
anhydrides to form ester.

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Specifically:

Alcohols and phenols reacts with carboxylic acids and acid anhydrides in presence
of Conc. H2SO4 or dry HCl gas as catalyst to form ester. { Reaction is reversible}.

Ester general formula R-CO-OR’ .From OH group replace H by (RCO-)

group to form ester.

Alcohols and phenols reacts with acid chlorides in presence of pyridine

to form ester. { Reaction in not a reversible }

Base pyridine neutralize HCl formed in this reaction and it shifts the
equilibrium to the right hand side.

Preparation of Aspirin :
Acetylation of salicylic acid in presence of acetic anhydride gives
aspirin. [ Acetylation is introducing acetyl (CH3CO-)group to phenol]

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Acidity of alcohols: {O-H bond cleavage }
Acidic character of alcohol is due to … The polar nature of O ─ H
bond. Oxygen is electronegative atom which withdraws the electrons of
the O ─ H bond towards itself. As a result , the O ─ H bond becomes
weak and hence a proton can be easily abstracted by a strong base.

Acidity of an alcohol is related to the ease of removal of H+ ion:

1. Water is more acidic than alcohol

Water H─O─H Alcohol R─O─H

Strong acid Weak acid

Absence of electron donating group. Presence of electron donating group (R)

Electron density around oxygen does not Electron density around oxygen increases
increase ( No + I effect). due to +I effect.

More polar O─H bond Less polar O─H bond

O─H bond is weak O─H bond is strong

Easy to release H+ ion Difficult remove H+ ion

Therefore alcohols are weaker acids than water. Water (S.A) > alcohol(W.A)

58

Alkoxide ion is stronger base than hydroxides.

Ex: Sodium ethoxide is a stronger base than sodium hydroxide.

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Alkoxide ion is better proton acceptor than hydroxide. Alkoxide easily
accept proton from water to form alcohol.(its conjugate acid)
Water easily donate its proton to base (alkoxide ) and forms hydroxide
ion (its conjugate base)
We know that water is strong acid so its conjugate ion (hydroxide ion )
is weak.
Similarly alcohol is weak acid so its conjugate base (alkoxide ion) is
strong.
Alcohol act as Bronsted base , it is due to the presence of unshared
electron pairs on oxygen , which makes them proton acceptor

Acidity order in primary , secondary and tertiary alcohols:

Primary Alcohol Secondary Alcohol Tertiary Alcohol

Contains 1 alkyl group Contains 2 alkyl group Contains 3 alkyl group

Less + I effect Intermediate + I effect More +I effect

Electron density around is in between Electron density around

oxygen is less w..r.t. Tertiary oxygen increases
alcohol
O─H is less polar
O─H is more polar
Strong OH bond.
Weak OH bond
Difficult tot remove proton
Easy to remove proton
Acidic character is more in primary > seconadry > tertiary
alcohol 60

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Acidity in Phenols :

Phenols shows acidic character because of the removal of hydrogen ( in

the form of proton) from OH group which in turn directly attached to the
sp2 hybridised carbon of benzene ring (which act as electron
withdrawing group)
Resonance structure of phenol --- oxygen carries positive charge.

After the removal of hydrogen from OH group of phenol phenoxide ion

is formed .
Resonance structure of phenoxide ion is :

Phenoxide ion is better resonance stabilized than the phenol.

Resonance structure of phenoxide contains only negative charge but
resonance structure of phenol involve separation of positive and
negative charge . Hence phenol has a strong tendency to form more
stable phenoxide ion by releasing a proton.
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Phenol is stronger acid than the alcohols and water.

Ans : Ionization of an alcohol and phenol takes place as follows:

Due to the electronegativity of sp2 hybridised carbon of phenol to which

-OH group is attached , electron density decreases on oxygen. This
increases the polarity of O─H bond and ionization takes place to form
phenoxide ion which is resonance stabilized (or charge is delocalized),
but in case of alcohol, ionization gives alkoxide ion which is not
resonance stabilized. Therefore phenol is stronger acids than the
alcohols.
Reaction of phenol with aqueous sodium hydroxide indicates that
phenols are stronger acids than alcohols.

Acidity in substituted phenols :

1. In presence of electron withdrawing group: Acidity of phenol
increases.
Ex: Electron withdrawing groups such as nitro (-NO2) , enhances the
acidic strength of phenol when it is present at ortho and para positions.
Due to the effective delocalization of negative charge in phenoxide
ion. Nitrophenol > phenol
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2. In presence of electron releasing group: Acidity of phenol
decreases.
Ex: Electron donating groups such as alkyl groups, decreases the
acidic strength of phenol . Because generally electron donating groups
does not favour the formation of phenoxide ion. Cresol <phenol
(Methyl group increases the electron density on oxygen of the
phenoxide ion and stability of phenoxide ion decreases.)

Nitrophenol (S.A) > Phenol ( W.A)

1. Because of resonance stabilization – In resonance structure of nitrophenols–

Electrons of nitro group are in conjugation with electrons of benzene ring .

2. More stabilization = Strong acid

3. Here Resonance effect stronger effect than inductive effect (-R>-I)

m- Electrons of nitro are not in conjugation with electrons of benzene

nitrophenol ring . So least acidic. (More acidic than phenol)
o- forms intra molecular hydrogen bond. Loss of proton becomes
nitrophenol difficult .So less acidic than p –nitro phenol ( more acidic than
m-nitrophenol)
p- More no. of resonance structures and intermolecular hydrogen
nitrophenol bond .
More acidic.
Acidic character : Nitrophenol > phenol
p-nitrophenol>o-nitrophenol>m-nitrophenol>phenol 66

(S.A.= strong acid W.A= weak acid)

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Cresols ( W. A) < Phenols ( S.A)

1. Hyper conjugation effect > + I effect.

m-cresol Hyperconjugation effect is ruled out. So methyl group

at meta does not release electron , it does not increase
electron density around oxygen . So Proton can easily
remove . So more acidic ( but less than phenol)
o-cresol Hyperconjugation and +I effect operates here. Since
methyl group donate electron , electron density around
oxygen increases , so difficult cleave O- H bond . So
least acidic
p-cresol Hyperconjugation > +I effect. So more acidic than
ortho-cresol

Acidic character : Phenol ( S.A) > cresol (W.A)

Phenol>m-cresol > p-cresol > o-cresol.
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Nitrophenol: p >o> m Cresol: m> p>o

cfal-IITJEE-21-CHM-PH CHEMISTRY-II YEAR Page 27

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