Alcohols, Phenols and Ethers

Introduction of alcohol
It belongs to category of groups which when attached to a carbon chain
governs the properties of organic compound or in other words we can say it is
a functional groups. They are indicated by presence of—OH group in a chain
.This -OH is regarded as hydroxyl group.
Functional group – OH
Suffix used: “ol”
Examples: Its homologous series is :
Methanol (CH3OH)
Ethanol (C2H5OH)
Propanol (C3H7OH)
Butanol (C4H9OH)
Pentanol (C5 H11 OH) and so on
Classification of alcohols
We can classify alcohols on the basis of different factors:
• Number of hydroxyl groups attached , hybridization ,number of alkyl
groups attached to alpha carbon (alpha carbon is that which has
functional groups attached to it )
1. On the basis of number of -OH(hydroxyl ) group attached we have :
• Monohydric alcohols: They are those that have only one hydroxyl group
attached.
Example: methanol (CH3OH) ethanol (C2H5OH) and more
• Dihydric alcohols: They have two hydroxyl groups attached.
Example: ethylene-glycol
 • Polyhydric alcohol: That have three or more hydroxyl groups in it.
Example glycerol

(2). Based on the type of hybridization:

• It can be sp3 like ethanol - CH3-CH2-OH
• Another example :
It can be sp2 like Benzyl alcohol-
In this second carbon is alpha carbon and that is sp 3

(Benzyl alcohol)
Allyl alcohol CH2=CH- CH2OH (In it also alpha carbon is sp 3 hybridised ).
Another type of hybridization they possess is sp 2
Example: Phenol C6H5OH, Vinyl alcohol CH3-CH2 =CH-OH etc
(c) Classification is on the basis of primary secondary or tertiary carbon atom
(alpha carbon)

10 20 30

Preparation of alcohols:
It can be prepared by following methods:
 1. From Haloalkane: When any haloalkane reacts with aqueous KOH it
undergoes nucleophilic substitution and leads to the formation of
alcohol and potassium halide .

If we take secondary alcohol than secondary alcohol potassium halide and

traces of alkenes is formed.
Example: If we take tertiary alkyl halide then on reacting with KOH we get
alkene as major product and potassium halide.

( 2-methyl butene)

2. By reduction of aldehyde and ketones: Whenever we reduce aldehyde

or ketones in presence of reducing agent like Ni, Pd ,Pt, LiAlH 4 etc we get
alcohol .

We can’t produce tertiary alcohol by this method.

3. By reduction of carboxylic acid: Whenever we reduce carboxylic acid in
presence of reducing agent it forms respective alcohol as shown
 4. From Grignard reagent i.e RMgX

• Please remember whenever Grignard reagent reacts with formaldehyde

it forms primary alcohol.
• When Grignard reagent reacts with any other alcohol it forms secondary
alcohol.
• When Grignard reagent reacts with ketone it forms tertiary alcohol.
5. By hydrolysis of ester: Whenever ester reacts with caustic soda or water
it forms alcohol and sodium salt of carboxylic acid.

6. From
alkenes: by their acidic hydration

Another method employed for alkenes is: Hydroboration oxidation reaction

In this we add BH3 to unsymmetrical alkenes:
 7. From aliphatic primary amines: Whenever amine reacts with nitrous
acid in presence of NaNO2 and HCl it forms respective alcohol and
nitrogen gas and water.
Example:

Industrial preparation of alcohol is by two methods: Hydration of alkene and

fermentation of sugar (used in breweries)
1. Fermentation - Breakdown of complex substance into simple substance
by action of enzymes released by anaerobic bacteria.
• By this method we can prepare only ethanol.
• In this firstly the sugarcane juice and water are mixed and heated to form
sweet liquid called molasses.
• Then in presence of yeast and enzyme invertase it breaks in to glucose
and fructose and then further glucose and fructose break into further
simpler substances called ethanol and carbon dioxide.
• This method is generally carried out in breweries.
 2. Hydration of alkene: This is a method by which any alcohol can be
prepared and accordingly we take member of alkene. Suppose we need
to prepare ethanol than we need to take ethene. When water is added
to ethene in presence of some weak acid like phosphoric acid then
ethene undergoes addition reaction and leads to formation of ethanol.

Isomerism in alcohols
Isomerism in alcohols: They basically show
• Position isomerism
• Chain isomerism
• Functional isomerism
• Optical isomerism
Position: In this the position of –OH group changes.
Examples:

(2-propanol) (Propanol)
CHAIN ISOMERISM: In this the number of carbon atom in parent chain is
going to be different.
Example

Functional isomerism: they are functional isomer of alcohol & ether

Example: CH3CH2CH2OH and CH3CH2O CH3 are functional isomers
(Propanol) (Methoxy ethane)
Optical Isomerism: they also show optical isomerism but there should be a
chiral centre
Like: in the given molecule of alcohol

(2-butanol)
(In this there is the chiral centre marked as C* as it has different groups
attached to it).
PHYSICAL PROPERTIES OF ALCOHOL
1. State of existence: Lower members are colorless liquids with
characterize smell. Higher members with more than 12 carbons are solid
2. Boiling point: They have high boiling points due to hydrogen bonding.
• If we compare their boiling points with hydrocarbons they will possess
higher boiling point because of existence of hydrogen bonds in them due
to which they occur at associated molecules.

• It is noted that boiling point increase with increase in carbons in chain:

As no. of carbon atoms increases Vander wall force increases hence
boiling point increases.
Example:
• If we look for the molecule of alcohol out of them with higher boiling
point than :
CH3CH2CH2OH AND CH3CH2CH2 CH2CH2OH
The Second compound will definitely have the higher boiling point as it has
more number of carbon atoms.
 • Boiling point decreases with branching: as surface area gets reduced
therefore Vander wall force decrease and boiling point also decreases.
Example: If we look for the molecule of alcohol out of them with higher boiling
point than:

(Primary) (Secondary) (Tertiary)

The one degree will have higher boiling point as it has more surface area.

3. Solubility: They are soluble in water due to formation of hydrogen bonds

in them .However solubility decreases with increase in number of carbon
atoms in chain as non polar part increases therefore solubility decreases.
Example: If we look for the molecule of alcohol out of them with higher
solubility than:
CH3CH2CH2OH and CH3CH2CH2 CH2CH2OH
The second one will have lower solubility because the non polar part is more in
it.

Chemical properties of alcohols

Alcohol is most versatile organic compound. They can behave in different
manner to give different reaction. Three type of reaction we will study
1. Alcohol behaves as nucleophiles
They are electron rich species

2. Alcohols behave as electrophile

Electron deficient
Carbocation is formed
R-OH --> R+ + OH-
alcohol carbocation Hydroxide ion
Mixed reaction
Involving alkyl and OH group

1. Reaction as nucleophiles
It shows their acidic character.
1. Reaction with active metals

Comparison of acidic character of H2O with alcohol.

In alcohols R is electron releasing group which increases electron density on

oxygen and pass of electron from O-H bond to O becomes difficult due to
+inductive effect. Therefore water is more acidic than alcohols.
Order of reactivity as nucleophile /acidic strength
1. If we compare acidic strength of primary, secondary and tertiary alcohols
we found that more the alkyl groups attached, more they release
electrons and more is the difficulty in loosing H +
Primary Alcohols (Less Acidic), Secondary Alcohols(Acidic) and Teritary
Alcohols(Most Acidic)
Here are some reactions showing acidic strength of alcohols:
• Reaction with metal hydrates

• Reaction with carboxylic acid : Esterification

• Order of reacting of alcohols towards esterification :

CH3 OH > 10 > 20> 30 (alcohol)
• Order of reactivity of carboxylic acid towards esterification:
H COOH > CH3COOH > (CH3)2 CH COOH > (CH3)3 COOH
Less number of alkyl groups attached, more is the acidic strength that is release
of hydrogen ion becomes easy.
2.Alcohol behave as electrophiles
In this the bond break in such a way that electrophile is generated
R -OH --> R+ + OH-
• Reaction with HX: This reaction takes place in presence of zinc chloride
and the equation involved is given below.
 The order of reactivity of different halogen acids towards this reaction is :
HI > HBr > HCl > HF
In this HI is most reactive towards this reaction as the bond that exist between
H and I is weak bond whereas HF do not participate in this reaction as the bond
between them is strong enough due to comparable sizes .
• Reaction With PCl5 and PCl3
ROH + PCl5 ---> RCl + POCl3 + H2O
Alcohol PhosphorousPentachloride ChloroAlkane
PhosphorylChoride
ROH + PCl3 ---> RCl + H3PO3
Alcohol Phosphoroustrichloride AlkylHalide Phosphoric Acid
• Reaction With SOCl2
2. Clevage of both alkyl group and hydroxyl group
• Acidic dehydration of alcohols

(Ethanol) (ethene)
Mechanism:
 • Dehydrogenation - It is also called as oxidation reaction.
In this primary alcohols give aldehydes in presence of oxidizing agent acid
• Acidified K2Cr2O7,CrO3, Collins-reagent, CrO3-pyridine,PCC (pyridinium
chlorochromate), PDC (Pyridium dichromate).

Please note: If we want to stop the reaction at stage of aldehyde, we can use
mild oxidizing agent. It is to be noted that primary alcohols give aldehyde and
secondary alcohols give ketones.

We have reactions where you will see that secondary alcohols gives ketones
but under drastic conditions like use of potassium dichromate it gives
carboxylic acid with less number of carbon atom than in alcohol.
Tertiary alcohols – Gives alkenes because they do not have H atom so oxidation
is not possible and they show elimination reaction.

• Dehydrogenation - removal of Hydrogen.

• Please note that C2H5OH is used for drinking purpose are beverage but
CH3 OH is not good to consume. When in C 2H5OH, CH3OH is added it becomes
denatured alcohol if it is consumed by anyone it causes death. It hits the
nervous system and can cause blindness.
Partial Oxidation
CH3OH --> HCHO
Methanol Methanal
Chemical properties of phenols
1. Acidic nature of phenols –

• It is sp2 hybridized that is it has 33% s character and 67% p character that
shows it is more electronegative . As a result electron density on oxygen
decreases and Polarity of O – H bond increase therefore Hydrogen is not
easily removed.
• Although phenol is acidic but it is less acidic than carboxylic acid
therefore It doesn’t react with Na 2CO3 and NaHCO3 but reacts with
sodium metal as shown below.

• As compared with alcohol, phenol is more acidic than alcohol. Because in

alcohol it is sp2 hybridised in phenol and Sp 3 hybridised C atom in
alcohol.
• The phenoxide ion is resonantly stabilized due to resonance as shown :

In this only one negative charge is getting dispersed.

On the other hand:
C2H5OH --> C2H5 O- + H+
ethanol ethoxide ion

No such resonance is possible therefore stability of alkoxide is less than

phenoxide as a result phenol has more tendency to form phenoxide ion due to
which phenol is more acidic than alcohols.
If electron withdrawing group is present at ortho or para position like NO2 , CN
, Cl etc then they disperse this negative charge and will enhance acidic
strength, whereas if electron donating group’s like CH 3, alkyl group,
NH2 (amine) or OR etc are present they decrease the acidic strength.
1. Reacting with zinc dust: Benzene is formed .

(phenol) (Zinc) (benzene)

2. Reaction with NH3: aniline is formed
 3. Reaction with Acid chloride: Phenyl ethanoate is formed .The reaction is
called as acetylation. If we react this phenyl ethanoate with ethyl
anhydride then we get aspirin :

3. Fries rearrangement

Phenyl ethanoate O – (hydroxy acetophenone)

5. Shorten baumem reaction

(Phenol) ( benzoyl chloride) (phenyl benzoate)

In all these reaction cleavage takes place between O and H.

Reactions of benzene ring

In this Electrophile substitution reaction takes place .As we know OH-
group is Ortho and Para directing so according to resonating structures the
negative charge is on the Ortho and Para position. Therefore Electrophile
attacks at O and P position.
Reactions involved:
1. Bromination: Substitution by bromine
If it occurs in presence of CS2 then mixture of ortho and para isomers are
formed:

1. Nitration: Substitution by nitro group by adding nitric acid. If we use

Concentrated HNO3 we get tri-substituted

2. Friedel craft alkylation reaction

3. Sulphonation: Substitution by SO 3H group.

There are certain reactions that phenol undergoes –
• Kolbe’s reaction

By this Aspirin and salol can be formed a shown :

• Aspirin :

• Salol – phenyl salicylate

• Reimer – tieman reaction –

• Reaction with carbon tetra chloride

• Coupling reaction – in this we get dyes of different colours.

 • Hydrogenation reaction –

• With Zn dust

• Oxidation reaction

Test to distinguish between 10 and 20 and 30alcohol

• First test :Lucas test

1. Primary alcohol + HCl( ZnCl2 / warm) ----> Turbidity appears on warm

Less reactive

2. Secondary alcohol + HCl (ZnCl2 / NO warming) -->Turbid on standing

On its own.
3. Tertiary alcohol + HCl (ZnCl2 ) ---> immediate turbid
 • Second test
Victor Mayer’s test

Test to distinguish between alcohol and phenol

1. Litmus test: Phenol turns blue litmus red, whereas alcohols have no
effect.

2. Coupling reaction – azo dye test

Phenol give orange colour, alcohol do not give any reaction.

3. Bromine water test

When Phenol is added to Br 2water they give white ppt. Due to formation of
2,4,5 tri nitro phenol But alcohol do not give any such test.
Introduction
They are functional isomers of alcohols .The functional group in them is
ROR and are represented as ROR where R is alkyl group.
Depending upon the type of alkyl group on both sides we can classify ethers
as:
1. Symmetrical ethers: When it has same R on both sides.
Like: CH3 OCH3 C2 H5OC2 H5
Di methyl ether Diethyl ether

2. Unsymmetrical ethers: They have different R on both sides.

Like: CH3OC2 H5
Ethyl methyl ether
Depending upon the number of alkyl groups present we can classify ethers
as:
1. Primary ,secondary and tertiary ethers

IUPAC:
The common name used for them is alkoxy alkane. In this smaller group is
written as alkoxy group and bigger group is written as Alkane.

Isomerism in ethers
1. Chain isomerism: In this chain is going to be different.
 2. Functional Isomerism: In this the functional group changes.

3. Metamerism: it is shown by only ethers , ester and ketones.

Preparation of ethers

1. By dehydration of alcohol : by this method only primary ethers can be

prepared but not tertiary or unsymmetrical ethers .the reaction involved
is shown below .

1. The Conditions required to form ether from alcohol

• Temperature must be maintained at 413k.

• Large amount of alcohol should be used as we will see in the mechanism
we need more alcohol as shown below in second step of mechanism.
• Alkyl group should be unhindered.

Mechanism: Protonation and deprotonation

(a)From of protonated alcohol

Ethanol hydrogen ion (protonated alcohol)

(b)Another molecule of alcohol also react

(c)De protonation: removal of proton

3. Williamson’s synthesis - By this method tertiary ether ,unsymmetrical

ether can be prepared .The reaction involved is given .

Key points –
• If secondary or tertiary ether have to formed than the RX should be
 • From secondary or tertiary RX we get alkenes instead of ether.

4. From alkyl halides by treating with dry silver oxide

5. By action of diazomethane on alcohol

Physical properties of ethers

1. Existence: Lower members are gases and higher members may be liquids
or solid due to increase in the Vander wall force.
2. Dipole moment: Ethers have higher dipole moments because of electro
negativity difference and structure is bent.
• They have larger bond angles than alcohol. Alcohol have one hydrogen
and ether there are two bulky groups so, repulsion between bulky
groups are more therefore Bond angle will increase.
• More the bulky group’s, lower is the value of dipole moments.
CH3 - O - CH3 C2 H5OC2 H5
1.3D 1.18D
3. Boiling point: Ethers have low boiling point because of less polarity.
CH3 CH2 O CH2 CH3 CH3 CH2CH2CH2 OH
Boiling point – 307.6k boiling point – 390k
“more polarity”
4. Solubility: lower members are more soluble .
Example – C2 H5 OH CH3OCH3 ] same solubility
• But as number of Carbon atoms increase, solubility decrease because
non polar part increase.
Chemical properties of ethers
Ethers are very stable compounds –therefore they are least reactive among all
functional groups .still we have few reactions lets study them.

1. [ Reaction of ethereal oxygen]

ROR (ether )
CH3OCH3 (methoxy methane )
 1. Action of air on ether

1. With Lewis acid

1. Cleavage of C = O bond of ether

(a)Cleavage by halogen acids: The order of reactivity of halogen acids towards
this reaction is:
HI > HBr > HCl > Hl
The HI bond is broken easily but HF bond can’t be broken .The reaction
involved is

The Mechanism involved:

 • In case of unsymmetrical ether :

Another example:

• If we take tertiary than Iodide goes with tertiary group

• More positive is the carbocation more is the tendency of iodine to

attach.

2. Reaction of alkyl groups

Reaction taking place in dark in which chlorine molecule is added
Reaction taking place in light in which chlorine molecule is added

CH3CH2OCH2CH3Cl2 --- > CCl3CCl2OCCl2CCl3

( Light ) Perchloro diethyl ether

3. Ring substitution reaction in ether
If we look at resonance structures of ether ,we see that attack occur at ortho
and para position because on those position electron density is high so attack
of electrophile occur at ortho and para .

• Halogenations: Attack of halogen.

• Chlorination
 (B) Nitration: Reaction with nitric acid

• Friedel craft alkylation and acylation

Uses of ethers

1. Ethers are used as a refrigerant.

2. They are used as industrial solvent for fat and oils.
3. When mixed with alcohol they make alcohol denatured.
4. They are used in Perfumery like:
• In aniseeds – Anethol is present which is a phenyl ether.
• In clove oil – Eugenol is present.
• In vanilla extract vanillin is present.
• In mint – Thymol is present.