STEM Alcohols,Phenols & Ethers

Alcohols, Phenols and Ethers are the basic compounds for the formation of
Detergents, Antiseptics and Fragrances

ALCOHOLS
1. An alcohol contains one or more hydroxyl groups (–OH) directly attached to aliphatic carbon atom(s).
Ex: Methanol, Ethanol, Ethylene glycol & Glycerol etc.,
2. Ethanol, a simple alcohol is widely used as
a) An antiseptic in the form of rectified spirit.
b) Component of all alcoholic beverages.
c) A solvent for lacquers and varnishes.
3. Some alcohols occur in nature and are used in the manufacture of perfumes and flavours due to their
pleasant smell.
Ex: The fragrance of rose flower is due to unsaturated alcohol , Citronellol
 CH 3 2 C = CHCH 2CH 2CH(CH 3 )CH 2OH
The fragrance of geranium flower is due to unsaturated alcohol, Geraniol
 CH 3 2 C = CHCH 2CH 2C  CH 3  = CHCH 2OH
4. Alcohols are also used as starting materials for the synthesis of other classes of organic compounds such
as Alkanes, Haloalkanes, Ethers, Aldehydes, Ketones, Acids etc.,
Classification
1. Based on number of -OH groups : Alcohols are classified as Mono, Di, Tri and Polyhydric
alcohols if they have one, two, three or more –OH groups in
their molecule.
Ethyl Ethylene Glycerol Sorbitol
alcohol Glycol
CH2 -OH CH2 -OH
CH2 -OH
C2 H 5OH CH - OH CH - OH 4
CH2 -OH
CH2 -OH CH2 -OH
Monohydric Dihydric Trihydric Polyhydric
alcohol alcohol alcohol alcohol

2. Based on type of sp3-C-OH bond :

a) Alkanols : Alcohols are also classified as primary, secondary or tertiary alcohols.
C C
0
0 2 Carbon 30 Carbon
1 Carbon
 OH C C

OH C C

OH
C C

C
Primary alcohol Secondary alcohol Tertiary alcohol

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b) Allylic alcohols : In these alcohols, the sp3-C-OH is attached to the C=C double bond.
May be primary, secondary or tertiary.
R R
3 3
sp sp sp3
H2C CH CH2 OH H2C CH CH OH H2C CH C OH
0 0
1 3
20
Allyl R
Benzylic alcohols : In these alcohols, the sp3-C-OH is attached to an aromatic ring.
May be primary, secondary or tertiary.
R R
3
sp
CH2 OH CH2 OH CH OH C OH
0 0 30
1 2
Benzyl R
2
3. Compounds containing sp -C-OH bond
a) Vinylic alcohols : -OH group bonded to a C=C double bond
H2C CH OH
Vinyl
b) Phenols : -OH group bonded to a benzene ring. But phenol is better treated as aryl
alcohol
OH
Vinyl gp As only double cannot be considered,
whole ring structure should be considered
hence better treated as aryl alcohol
Nomenclature : Alcohols are named by replacing the suffix ‘e’ in the name of alkanes by ‘ol’.
The positions of carbon atoms carring –OH groups are indicated by locants written
after the primary suffix.
Structure of functional group:
W ater Alcohol Phenol Ether
142 pm 96 pm 136 pm 141 pm
O O O O
H 104.5 0 H R 108.9 0 H Ph 109 0 H R 111.7 0 R
R=Alkyl Ph=Phenyl R=Alkyl / Phenyl
Repulsion Repulsion Repulsion
between 2 lp's between 2 lp's between 2 bulky
Bond angle Bond angle gp's Bond angle
decreases decreases increases
1. In alcohols, the oxygen atom of the –OH group is attached to sp3 hybridized carbon atom by a sigma
bond. The bond angle of C  O  H in alcohols is slightly less than the tetrahedral angle. It is due to
repulsion between unshared pair of electrons of oxygen.
2. In phenols, the –OH group is attached to sp2 hybridised carbon of an aromatic ring. The carbon–
oxygen bond length (136 pm) in phenol is slightly less than that in alchohol. This is due to
a) Partial double bond character on account of the conjugation of unshared electron pair of oxygen with
the aromatic ring.
b) sp2 hybridised state of carbon to which oxygen is attached.
3. In ethers, the bond angle is slightly greater than the tetrahedral angle due to the repulsive interaction
between the two bulky (–R) groups. The C–O bond length (141 pm) is almost the same as in alcohols.

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PREPARATIONS.
FROM ALKENES
1. Acid catalysed hydration of alkenes:
Alkenes add water in the presence of an acid catalyst to yield alcohol. The addition takes palce according
to Markovnikov rule.
The reaction is reversibleand the mechanism for the acid-catalysed hydration of an alkene is simply the
reverse of that for the dehydration of an alcohol.

+ 
HA + 
A  
 H 2O
H O
2
 + A  + HA
H H O H O
Alkene H H Alcohol H

Acid catalysed hydration of alkene has limited synthetic utility because carbocation is the intermediate
and rearrangement may take place. Thus a mixture of isomeric alcohols may result.
Mechanism : Involves 3 steps
Step 1: Protonation of alkene to form carbocation by electrophilic attack of H3O+.
H 2 O  H   H 3O 

Step 2: Nucleophilic attack of water on carbocation.

Step 3: Deprotonation to form an alcohol.

2. Hydroboration-oxidation:
a) An alkene reacts with BH3 / THF or diborane to produce an alkylborane.
b) Oxidation and hydrolysis of the alkylborane with hydrogen peroxide and base yields an alcohol.
c) Mechanism :
i) The boron atom of Borane gets attached to the sp2 carbon carrying greater number of H-atoms.
ii) The alcohol so formed is antimarkonikovs addtion.
iii) Yield of alcohol obtained is excellent.
Hydroboration

H2O
3H2O2 / -OH
Propan-1-ol
Oxidation

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3. Oxymercuration Demercuration:
a) Alkenes react with mercuric acetate in a mixture of water and tetrahydrofuran (THF) to produce
(hydroxyalkyl) mercury compounds.(Oxymercuration)
b) These can be reduced to alcohols with sodium borohydride and water. (Demecuration)
c) The net addition of H and OH takes place according to markovnikov rule.
a) Oxymercuration.
O
THF
+ H2O + Hg O C CH3 + CH3COOH
2 O
OH
Hg O C CH 3

b) Demercuration

O + OH + NaBH4 + Hg
OH Hg O C CH 3 OH H

4. Hydroxylation of alkenes
a) Bayers reagent(Alkaline KMnO4), OsO4, Percarboxylic acid (RCO3H) covert alkenes to alkane
diols.
b) Syn addition : Addition of OH group to the double bonded carbons on same side
Ex: Bayers reagent, OsO4.
If optically active compound is formed on addtion the product will be meso compound.
c) Anti addition : Addition of OH group to the double bonded carbons in opposite manner.
Ex: Percarboxylic acid.
If optically active compound is formed on addtion the product will be Racemic mixture.
R1 H H
R1 H H
K M nO 4 or O sO 4 R1 OH
R C O 3H R1 OH
Syn addition
A nti a dd ition
H R2 OH R2
R2 H HO
R2
H
H
M eso com pound R a cem ic m ix tu re

BY REDUCTION OF CARBONYL AND CARBOXYLIC ACID COMPOUNDS

5. Reduction of carboxylic acid and esters:
a) Direct reduction of carboxylic acid is possible with a strong reducing agent like LiAlH4.
O
R C LiAlH4  R — CH2OH .
OH
The product initially formed is an alkoxide which is hydrolysed to give a primary alcohol.
b) Esters can be conveniently reduced by reagents like sodium and ethanol or lithium aluminium hydride
to give mixture of alcohols.
O
R CH2 C LiAlH4
 R — CH2OH  ROH
OR'

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6. Reduction of aldehydes and ketones:
On reduction An Aldehyde gives a Primary alcohol
A Ketone gives a Secondary alcohol.
CHO CH2OH LiAlH
LiAlH4
 O 
4
OH

NaBH4 reduces only the carbonyl compounds and fails to reduce a C = C double bond.

N aB H 4
CH CH CHO     CH CH CH 2 OH

FROM GRIGNARD REAGENT

7. Alcohols are produced by the reaction of Grignard reagents with aldehydes and ketones.
Step I : The first step of the reaction is the nucleophilic addition of Grignard reagent to the
carbonyl group to form an adduct.
Step II : Hydrolysis of the adduct yields an alcohol.
a) Formaldehyde produces primary alcohol.
b) Any other aldehde produces secondary alcohol.
c) Ketone produce tertiary alcohol.
d) Esters initially give ketones and finally tertiary alcohols.
H H OMgX H OH
R'MgX H2O
C O C C 10 Alcohol
H H R' H R'
Formaldehyde

H H OMgX H OH
R'MgX H2O
C O C C 20 Alcohol
R R R' R R'
Aldehyde

R R OMgX R OH
R'MgX C H2O C 30 Alcohol
C O
R R' R R'
R
Ketone

R R OMgX R R OMgX R OH
R'MgX C OR - R'MgX H2O
C O C O C C
RO R'
RO R' R' R' R'
R'
Ester

METHANOL PREPARATION ( INDUSTRIAL)

ZnO-Cr2O 3
CO + 2H 2 
200-300atm,573-673K
 CH 3OH

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ETHANOL PREPARATION(INDUSTRIAL)
1. Ethanol, C2H5OH, is obtained commercially by fermentation
2. The sugar in molasses, sugarcane or fruits such as grapes is converted to glucose and fructose in the
presence of an enzyme invertase.
Invertase
C12 H 22O11 + H 2O  yeast
 C6 H12O 6 + C6 H 12O 6
Sugar Glucose Fructose

3. Glucose and fructose undergo fermentation in the presence of another enzyme zymase found in
yeast to give ethylalcohol. The action of zymase is inhibited once the percentage of alcohol
formed exceeds 14%.
Zymase
C6 H12O 6   2C2 H 5OH  2CO 2
Yeast
4. If air gets into fermentation mixture, the oxygen of air oxidises ethanol to ethanoic acid which in turn
destroys the taste of alcoholic drinks.
PROPERTIES
Physical Properties
1. The alcohols are neutral substancse, the lower members are liquids and have a distinctive smell and a
burning test, the higher members are solids and are almost odourless.
2. In a group of isomeric alcohols
a) primary alcohols have the highest boiling points
b) Tertiary the lowest
c) Secondary having an intermediate value.
3. The lower members are less volatile than higher members due to H-Bonding in the members.
R R R R

—  O —H O —H O —HO —H

4. Solubility :
a) The lower alcohols are very soluble in water.
b) Solubility diminishes as the molecular weight increases.
Reason : a) In the lower alcohols the hydroxyl group constitutes large part of the molecule.
b) As the molecular weight of the alcohol increases the hydrocarbon character of the
molecule increases and hence the solubility in water decreases.
b) The structure of carbon chain plays a part in solubility
Ex: n-butanol is fairly soluble in water
t-butanol is miscible with water in all proportions.
Chemical Properties
REACTIONS INVOLVING CLEAVAGE OF (O-H) BOND
1. Acidic character:
a) Alcohols are very weak acids (Ka = 10–16 – 10–18) even feeble than water (Kw = 10–14)
b) They do not turn blue litmus red.
c) They behave as acids because of the presence of polar O—H group.
Due to greater electro negativity of oxygen atom the shared pair between ‘O’ and H is drawn
towards the oxygen atom helping in release of H+ ion.



R  O  H 
 RO  H
Alcohol alkoxide ion

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d) However the release of H+ ion in alcohol does not takes place with ease and hence the alcohols acts
as very weak acids.
Reason : Explained on the basis of electron releasing nature of alkyl group present in alcohol.
a) The electron releasing tendency of alkyl group increases electron density around the
oxygen atom due to which polarity of O—H bond decreases thus release of H+
becomes difficult.
b) The alkoxide ion formed is also destabilized due to concentration of negative charge
on oxygen atom by electron releasing inductive effect of alkyl group making the
release of H+ ion is difficult.
c) Hence the alcohols have weak acidic character.
e) The order of acidic strength among various types of alcohols is
Primary -OH > Secondary-OH > Tertiary-OH
The order can be explained in terms of electron releasing inductive effect of alkyl groups. Greater is
the number of alkyl group attached to carbon carrying —OH group lesser shall be polarity of —OH
group and hence lesser will be acidic character.

H R R
 
R  C  OH  R  C  OH  R  C  OH

H H R
1° Alcohol 2° Alcohol 3° Alcohol

f) Reaction with Active metals, liberating Hydrogen signifies alcohols are acidic in nature.
1
 RO Na  
ROH  Na  H 
2 2
Alcohols do not react with NaOH (due to low acidic character)
g) Alcohols hydrolyse Grignard reagent
ROH  R MgX 
 R H  Mg(OR)X
Strong acid Weaker acid

2. Esterification :
a) The reaction with carboxylic acid and acid anhydride is carried out in the presence of a small
amount of concentrated sulphuric acid.
b) The reaction is reversible, and therefore, water is removed as soon as it is formed.

c) The reaction with acid chloride is carried out in the presence of a base (pyridine) so as to
neutralise HCl which is formed during the reaction.

REACTIONS INVOLVING CLEAVAGE OF (C-OH) BOND

3. Reaction with hydrogen halide
R—OH + HX  R—X + H2O.

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a) The reactivity of the hydrogen halide is HI > HBr > HCl (HF is generally unreactive)
b) The order of reactivity of alcohols is 3° > 2° > 1° > CH3.
c) i) The least reactive hydrogen halide i.e. HCl generally requires the presence of ZnCl2 for reaction
with 1° and 2° alcohols, however the highly reactive 3° alcohol do not require ZnCl2.
ii) The difference in reactivity of three classes of alcohols with HCl distinguishes them from one
another (Lucas test).
iii) Alcohols are soluble in Lucas reagent (Conc. HCl and ZnCl2) while their halides are immiscible
and produce turbidity in solution.
30 alcohols produce turbidity immediately as they form the halides easily.
20 alcohols prouduce turbidity after some time.
10 alcohols do not produce turbidity at room temperature.

4. Action with Phosphorous halide

3C2 H 5OH + PX3  3C2 H5 X + H 3PO3
C2 H 5OH + PX5  C2 H 5 X + POX3 + HX (X = Cl, Br)
5. Action with thionyl chloride
Pyridine(C5 H 5 N)
C 2 H 5OH + SOCl 2   C 2 H 5Cl + SO 2  +HCl 
6. Dehydration : Heating of most of alcohols with a strong acid causes a loss of water molecule to
form alkenes.


H
—C — C —   CC  H2O


H OH
The relative ease of dehydration of alcohols follows the following order
Tertiary -OH > Secondary-OH > Primary-OH
a) With conc H2SO4 : At different tempertures different products are formed but in all the cases
there is loss of H2O
0
Conc.H 2SO 4 / 100-110 C
i) 2C 2 H 5OH  -H 2O
 C 2 H 5 HSO 4
Ethylhydrogensulphate

0
Conc.H 2SO 4 / 140 C
ii) 2C 2 H 5OH   C2 H 5OC2 H 5 + H 2O
Diethylether

2 H SO
4 (excess) / 170°C
iii) C2 H 5 OH  C 2 H 4 + H 2O
Ethylene

In the formation of ethylene, ethyl hydrogensulphate and diethyl ether are intermediate compounds.
b) Action with alumina
0
Al 2O 3 / 260 C
i) 2C2 H 2OH 
under pressure
 C2 H 5OC2 H 5 + H 2O

0
Al 2O3 / 350 C
ii) C2 H 5OH   CH 2 = CH 2 + H 2O
c) With Phosporic acid: Secondary and tertiary alcohols are dehydrated under milder conditions.

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OH
85% H 3 PO 4
i) CH 3CHCH 3    CH 3CH  CH 2  H 2 O
440 K
Isopropylalchohol (20) Propene
20%H 3PO4
ii) (CH 30) 3 C  OH  2(CH
358K 3 )2 C  CH 2  H 2O
 methylpropene(Isobutene)
3 Bu tanol
d) Mechanism :
Step 1 : Formation of protonated alcohol.

Step 2 : Formation of carbocation: It is the slowest step and hence, the rate determining step of
the reaction.

-H2O
Slow step

Step 3 : Formation of ethene by elimination of a proton.

The acid used in step 1 is released in step 3.

To drive the equilibrium to the right, ethene is removed as it is formed.
e) Since carbocations are formed as intermediates rearrangement is a common feature.
f) Whenever dehydrations produces two different alkenes major product is formed according to
Saytzaff’s rule.
CH3 CH3 CH3
H3PO4
  


OH
Major Minor

Such reactions which can produce two or more structural isomers but one of them is in greater
amount than the other, are called regioselective. If only one product is formed, a reaction is termed as
regiospecific.
g) The dehydration of 10 alcohol goes by E2 mechanism, 20 and 30 alcohols go by E1 mechanism.
OXIDATION
7. a) Oxidation of alcohols involves the formation of a carbon oxygen double bond with cleavage of an
O-H and C-H bonds. Such a cleavage and formation of bonds occur in oxidation reactions.
b) These are also known as dehydrogenation reactions as these involve loss of dihydrogen from
an alcohol molecule.

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c) Depending on the oxidising agent used,

i) Primary alcohol is oxidised to an aldehyde which in turn is oxidised to a carboxylic acid.
Ex: KMnO4 a strong oxidising agent in acidified condition give Carboxylic acids directly.

CrO3 in anhydrous medium is used as the oxidising agent for the isolation of aldehydes.

PCC (pyridinium chlorochromate-a complex of chromium trioxide with pyridine and

HCl) is a better reagent for oxidation of primary alcohols to aldehydes in good yield.

ii) Secondary alcohols are oxidised to ketones by chromic anhyride.

iii) Tertiary alcohols do not undergo oxidation reaction. Under strong reaction conditions such as
strong oxidising agents (KMnO4) and elevated temperatures, cleavage of various C-C bonds
takes place and a mixture of carboxylic acids containing lesser number of carbon atoms is
formed.
d) Dehydrogenation with Cu
a) When the vapours of a primary or a secondary alcohol are passed over heated copper at
573 K, dehydrogenation takes place and an aldehyde or a ketone is formed.

b) Tertiary alcohols undergo dehydration.

8. Formation of addtion compounds

Ethyl alcohol reacts with anhydrous metal salts to form addition compounds.
This is referred as alcohol of crystallisation
a) CaCl 2 .3C2 H 5 OH
b) MgCl 2 .6C2 H5OH
c) CuSO4 .3C2 H5OH

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9. Tests for Alcohols
a) Oxidation by chromic anhydride, CrO3, in aqueous sulfuric acid :
Within two seconds, the clear orange solution turns Blue-green and becomes opaque.
Tertiary alcohols do not give this test.
b) Test Distinguishing 1°, 2° and 3° Alcohols
i) Lucas Test : Lucas reagent is a mixture of conc. HCl and Zinc chloride.
Reagent reacts with alcohol to form corresponding alkyl chlorides which are insoluble.
30 alcohol - Turbidity immdediately
20 alcohol - Turbidity after some time
10 alcohol - No turbidity.
c) Victor Meyer Test:
i) This test is based upon the fact that the three types (1°, 2°, 3°) of nitroalkane (formed by alcohols)
reacts differently with nitrous acid followed by sodium hydroxide.
ii) The three types of alcohol are first converted into corresponding nitro compounds.
iii) Nitro alkane thus obtained is treated with first nitrous acid and then with sodium hydroxide to get
different colours at the end.

d) With Cu at 3000C 10 Alcohol

: - Aldehyde
20 Alcohol - Ketone
30 Alcohol - Alkenes
e) With acidified KMnO4 : 10 Alcohol - Aldehyde to Carboxylic acid with same no of C’s.
20 Alcohol - Ketone then to Carboxylic acid with less no of C’s.
30 Alcohol - (Ketone + acid) with less no of C’s. Then Ketone
acid. Thus mixture of acids are obtained.
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PHENOLS
1. Aromatic hydroxy compounds in which -OH group is bonded to benzene ring directly are called phenols.
Monohydroxy benzene is called phenol. Phenol is also known as carbolic acid.
2. Simple phenol  C6 H 5OH  is an antiseptic. Hexachlorophene is a constituent of several mouth washes,
deodorant soaps and medicinal skin cleansers is a compound of phenol.
Phenols (phenol and cresols) are used in the manufacture of dyes and resins (bakelite).
3. Classification : Phenols are classified as mono, di, trihydric as per one, two or three –OH groups
present in a molecule.
OH OH OH
OH

OH
Monohydric Dihydric OH Trihydric
4. Nomenclature: The simplest hydroxyl derivative of benzene is phenol which is also its accepted
IUPAC name.
OH OH OH OH
CH3

CH3
CH3
P hen ol o -C resol m -C resol p -C resol OH
2-M eth ylp h en ol 3-M eth ylp hen ol 4-M eth ylp hen ol
HO OH
OH OH OH
OH
OH
P yrogallol
OH Ben ze ne-1,2,3-triol
OH HO OH
OH
C atechol R esorcin ol Q uin ol or H yd roq uin on e P hloroglucinol
B en zene -1,2-d iol B en zen e-1,3-dio l B enzen e-1,4-d iol B enzen e-1,3,5-triol
2
5. Structure : In phenols, the –OH group is attached to sp hybridised carbon of an aromatic ring.
The carbon– oxygen bond length (136 pm) in phenol is slightly less than that in
Phenol
136 pm
alcohol. This is due to
O a) Partial double bond character on account of the conjugation of unshared
Ph 1090 H electron pair of oxygen with the aromatic ring
2
Ph=Phenyl b) sp hybridised state of carbon to which oxygen is attached.
The bond angle of C–O–H in phenol is 1090
PREPARATION
1. From haloarenes :

2. From benzene sulphonic acid

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3. From diazonium salt

4. From cumene : (Isopropyl benzene) - Acetone is the bye-product.

PROPERTIES
Physical Properties
1. Phenol has higher boiling point than the arenes or haloarenes or ethers of same molecular weight. It is
due to the formation of intermolecular hydrogen bond.

2. Phenols are relative to pure aromatic hydrocarbons are more soluble in water due to their ability to form
hydrogen bonding with water.

3. As the hydrocarbon part increases in size and mass, the solubility decreases.
Chemical Properties
REACTIONS INVOLVING CLEAVAGE OF (O-H) BOND
1. Acidity of Phenols :
a) The reactions of phenol with metals like sodium, aluminium and sodium hydroxide indicate its acidic
nature.

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b) The hydroxyl group, in phenol is directly attached to the sp2 hybridised carbon of benzene ring which
acts as an electron withdrawing group. This causes the oxygen of –OH group to be positive.

Due to the higher electronegativity of sp2 hybridised carbon of phenol to which –OH is attached,
electron density decreases on oxygen. This increases the polarity of O–H bond and results in an
increase in ionisation of phenols than that of alcohols.
c) The reaction of phenol with aqueous sodium hydroxide indicates that phenols are stronger acids than
alcohols and water.

d) The ionisation of phenol takes as follows :

e) The stability of phenoxide ion.

In phenoxide ion, the charge is delocalised. The delocalisation of negative charge (structures I-V)
makes phenoxide ion more stable and favours the ionisation of phenol.
f) Stability of Phenol v/s Phenoxide :
Although there is charge delocalisation in phenol, its resonance structures have charge separation
due to which the phenol molecule is less stable than phenoxide ion.

Resonce with
charge
dispersal is
more stable
than charge
seperation
Charge seperation Charge dispersal
g) Acidity in Substituted Phenols :
i) The presence of EWG such as nitro group, enhances the acidic strength of phenol.
ii) This effect is more pronounced when such a group is present at ortho and para positions.
It is due to the effective delocalisation of negative charge in phenoxide ion.
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iii) The presence of EDG such as alkyl groups do not favour the formation of phenoxide ion resulting
in decrease in acid strength.
Ex: Cresols are less acidic than phenol
h) Phenol is relatively more acidic than aliphatic alcohol and water.
i) The order of the strength of phenols is as follows
OH OH OH OH OH OH OH OH OH
O 2N NO 2 NO 2 CH 3

>O 2N
>
NO 2
> > >
NO 2
> >
CH 3
>
NO 2 NO 2 CH 3

j) The greater the pKa value, the weaker the acid.

2. Alcohols and phenols react with active metals like Na, K, Al etc to liberate hydrogen gas.
2 C6 H 5 OH + 2Na  2C6 H 5ONa + H 2
3. Phenols also react with aqueous NaOH solution to produce the salt sodium phenoxide and water.
C6 H 5OH + NaOH  C6 H 5ONa + H 2O
4. Even though the electron releasing groups like  CH 3 , C 2 H 5 etc decrease the acidic strength of phenol,
Phenol does not liberate CO2 with Na 2CO 3 or NaHCO 3 because phenol is weakly acidic than
carbonic acid and carboxylic acids.
Relative acid strength
Carboxylic acid > Carbonic acid > Phenol > Methyl alcohol > Water > Other alcohols
5. Esterification of phenol (Schotten-Baumann reaction) :
Phenols react with carboxylic acids and their derivatives like acid chlorides and anhydrides to form
esters. This reaction is benzoylation.
C6 H 5 O  H  RCOOH  C6 H 5O  COR  H 2O
pyridine
C6 H 5OH + RCOCl   C6H 5O - COR + HCl
Salicylic acid on acetylation gives acetyl salicylic acid known as Aspirin.

Electrophilic aromatic substitution reactions : In phenol, -OH group is ring activating and ortho and
para directing as these positions get more electron
density through resonance structures.
6. Nitration
OH OH OH
NO 2
Dil.HNO
 3
 +

NO 2
o-Nitrophenol
p-Nitrophenol

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a) The ortho and para isomers can be separated by steam distillation.

b) o-nitrophenol is steam volatile due to intramolecular hydrogen bond.
c) P-nitrophenol is less volatile due to intermolecular hydrogen bond.
H
O O O O
H
N H O N
O N
O O O
Intramolecular Interamolecular H-bonding
H-bonding

d) Phenol when treated with conc. HNO3 gives 2,4,6-trinitrophenol known as picric acid. Poor yield.

OH OH
O 2N NO2
Conc.HNO 3


NO2

For good yields treating phenol with conc. H 2SO 4 and then with conc. HNO3 .

OH OH OH
SO3H O 2N NO 2
Conc.H 2SO 4
   Conc.HNO 3

SO3H NO2

7. Halogenation
a) When the reaction is carried out in solvents of low polarity such as CHCl3 or CS2 and at low
temperature, Monobromophenols are formed.
b) Here no Lewis acids like FeBr3 are required because highly activating effect of -OH group polarises
bromine quickly.

OH OH OH
0
Br
Br2 /CS 2 , 0 C
  +
Br

c) Phenol reacts with Bromine water and gives 2,4,6-tribromo phenol (white precipitate)
Reason : In water phenol forms phenoxide ion which activates the benzene ring.

OH
OH
Br Br
Br2 / H 2O, 0  50 C


Br

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8. Kolbe’s reaction
Phenoxide ion generated by treating phenol with sodium hydroxide is even more reactive than phenol
towards electrophilic aromatic substitution. Hence, it undergoes electrophilic substitution with
Carbon dioxide, a weak electrophile. Ortho hydroxybenzoic acid (Salicylic acid) is formed as the
main reaction product.

If KOH is used parahydroxy benzoic acid will be formed as major product.

9. Reimer-Tiemann reaction
Phenol when treated with chloroform in the presence of NaOH gives Salicylaldehyde.
The electrophile in this reaction is dichlorocarbene.
The intermediate substituted benzal chloride is hydrolysed in the presence of alkali to produce
salicylaldehyde.

10.Action of Zinc dust

Phenol on heating with zinc dust produces benzene.
OH

ZnDust
  + ZnO

11.Oxidation
Phenol on oxidation with chromic acid ( Na 2Cr2O 7  H 2SO 4 ) produces benzoquinone, which is a
conjugate diketone. In the presence of air, phenols are slowly oxidised to dark coloured mixtures
containing quinones.

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12.Fries rearrangement
OH
OCOCH3 OH OH
COCH3
(CH 3 CO )2 O AlCl 3
   
Rearrangement +

COCH3
13.Alkylation:
a) When phenol is treated with allyl halide in the presence of NaOH formation of aryl allyl ether takes
place.
CH2
OH O

CH 2  CH  CH 2  Br
 NaOH


b) Claisen rearrangement : Allyl phenyl ethers rearrange to o– allyl phenol when heated at 200°C.

 CH2
O OH
  
CH2
200C
  

2-allylphenol
i) If ortho position is free, only ortho rearrangement occurs. However, if both ortho positions are
substituted then rearrangement takes place at para position.
CH2

CH3 OH
O H3C CH3

 
CH3

CH2
4-allyl-2,6-dimethylphenol
ii) An interesting feature of the rearrangement is that when migration takes place to the ortho position,
the -carbon of allyl group attaches itself to the benzene ring. i.e., there is an inversion of allylic
chain.
However, no such inversion of allylic chain takes place with p-migration.

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ETHERS
1. Ethers are the carbon compounds containing oxygen atom linked to two alkyl groups.
2. The general formula of ethers is R  O  R or  Cn H 2n1 2 O or Cn H 2n  2O
3. Ethers are considered to be dialkyl derivatives of water.
4. They are named in two ways namely
a) Common system b) IUPAC system
a) In common system, ethers are named after alkyl groups attached to oxygen atom.
For simple ethers , the common name is di alkyl ether.
For mixed ethers, the common name is alkyl, alkyl ether.
Ethers are named first in the alphabetical order followed by the word ether in common system.
b) In IUPAC system, ethers are named as alkoxy alkanes.
The smaller alkyl group along with oxygen atom is taken as alkoxy part
while the larger alkyl group as alkane part.
Formula Common name IUPAC name
CH 3OCH 3 Dimethyl ether Methoxy methane
CH 3OC2 H 5 Ethylmethylether Methoxy ethane

C2 H 5OC2 H 5 Diethyl ether Ethoxy ethane

CH 3OC3 H 7 Methylpropylether Methoxy propane

C2 H 5OCH  CH 3 2 Ethyl isopropyl ether 2-ethoxy propane
C6 H 5OCH 3 Anisole Anisole
6. Structure of Functional Group
In ethers, the four electron pairs, i.e, the two bond pairs and two lone pairs of electrons on oxygen are
arranged approximately in a tetrahedral arrangment. The bond angle is slightly greater than the tetrahedral
angle due to the repulsive interaction between the two bulky (-R) groups. The C-O bond length (141
pm) is almost the same as in alcohols.

1110
R R

PREPARATION
1. Dehydration of alcohols
a) Ethyl alcohol gives diethyl ether by acid -catalysed condensation reaction
conc.H 2 SO4
C2 H 5OH + HOC2 H 5 
1400 C
C2 H 5OC 2 H 5 + H 2O
b) The catalytic dehydration of ethanol with Al2O3 at 250-2600C
Al 2O3
2C2 H5OH 
2600 C
 C2H 5OC2 H5 + H 2O

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2. The formation of ether is a nucleophilic bimolecular (SN2) involving the attack of alcohol molecule on a
protonated alcohol, as indicated below:

2. Williamson Synthesis
a) Ethyl halide reacts with sodium or potassium ethoxide to form diethyl ether the reaction involves SN2
attack of an alkoxide ion on primary alkyl halide.
C2H5ONa +IC2H5  C2H5OC2H5 +NaI
b) Alkyl halide has to be primary because with other alkyl halides alkenes are formed preferebly .

c) Alkoxides are nucleophiles and also strong bases.

OH ONa OR

NaOH R X
    + NaX

Phenols are also converted to ethers by this method.

3. From ethyl bromide
Ethyl bromide reacts with dry silver oxide to from diethyl ether
C2 H 5 Br + Ag - O - Ag + Br - C2 H 5  C2 H 5OC2 H 5 + 2AgBr
PROPERTIES
Physical Properties :

1. Ether is a colourless, highly volatile liquid(b.p=307.5 K). It is highly inflammable.

2. It has characterstic pleasant odour and produce temporary unconsciousness when its vapours are inhaled.
3. It is slightly soluble in water and readily soluble in organic solvents. It is lighter than water.
4. Due to lack of H-bonding, its bp is less than its functional isomer butyl alcohol(C4H9OH)

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Chemical properties
1. Ethers are less reactive than alcohols due to non-availablity of active hydrogen.
2. Ethers donot react with alkali, acids, metals, phosporous halides.
3. Ethers do not oxidise and reduce easily like alcohols under normal conditions
4. Ethers react with acids, phosporous halides, oxidising agents and reducing agents at high temperatures
but cannot react with metals like sodium.
5. Reactions of ether are classified into three types on the basis of cleavage of bonds.
a) Ethyl groups which undergo substitution reactions
b) Ethereal oxygen which co-ordinates with electron deficient molecules like Lewis acids.
c) Carbon- oxygen bond which shows some cleavage reaction.
Reactions of alkyl group
1. Halogenation
Diethyl ether reacts with chlorine or bromine to from halogen substituted ethers.Hydrogens at  carbon
atoms are easily substituted in the dark condition.

Cl  '
CH3CH2OCH2CH3 2
Dark
 CH 3CH (Cl) - O - CH(Cl)CH 3
( dicholoro diethyl ether)
2 Cl
CH3CH2OCH2CH3 
Sunlight  C2Cl5 – O – C2Cl5
(perchloro diethyl ether)
Reactions of ethereal oxygen
2. C2 H 5 - O - C 2 H 5 + (O)  C2 H 5 - O- C2 H 5

O
Peroxide

3. Formation of oxonium Salts

 + 
C2 H 5 -O-C2 H 5 + HBr   C2 H 5 - O- C2 H 5  Br -

 H 
Diethyloxoniumbromide

 + 
C2 H 5 - O - C2 H 5 + H 2SO 4  C2 H 5 - O- C2 H 5  HSO 4-

 H 
Diethyloxoniumhydrogensulphate

Reactions involving clevage of C–O bond

4. Action of sulphuric acid
C2 H 5 -O-C2 H 5 + H 2 SO4 (conc.)  C2 H 5OH + C2 H 5 HSO 4
5. Action of hydrobromic acid or hydroiodic acid
C2 H 5 -O-C2 H 5 + HI(Cold)  C2 H 5 I + C2 H 5OH

C 2 H 5 -O-C 2 H 5 + 2HI(excess)   2C 2 H 5 I + H 2O
a) Here the cleavage is at alkyl oxygen due to low reactivity of aryl oxygen bond.
b) In the cleavage of mixed ethers lower alkyl group forms alkyl iodide.

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c) If 30 alkyl group is present it forms tertiary halide as major product.

(CH 3 )3 -C-OCH 3 +HI  CH 3OH+(CH 3 )3CI
CH 3 -OC2 H 5 +HI  CH 3 I+C2 H 5OH
OR
OH

+ HX + RX

Alkyl aryl ethers are cleaved at the Alkyl-Oxygen bond due to the
more stable Aryl-Oxygen bond.
6. Hydrolysis
C2 H 5 -O-C2 H 5 +H 2 O(steam)  2C2 H 5OH
7. Action of PCl5
C2 H 5 -O-C 2 H 5 +PCl 5  2C2 H 5Cl+POCl 3
8. Action of acetyl chloride and acetic anhydride
AlCl 3
C2H 5 - O - C2H 5 + CH 3COCl   C2H 5Cl + CH 3COOC2H5
ZnCl 2
C2 H 5 - O - C2 H 5 + (CH 3CO)2 O   2CH 3COOC2 H 5
9. Action of carbon monoxide
0
BF3 /150 C
C2 H 5 - O - C 2 H 5 + CO 
500atms
 C2 H 5COOC2 H 5
Ethylpropionate

10.Oxidation
K 2Cr2O7 K 2 Cr2O 7
C2 H 5O C 2H 5 + (O)   2CH 3CHO   2CH 3COOH
11.Dehydration
0
Al 2O 3 ,360 C
C2 H 5O C 2 H 5   2CH 2 =CH 2 +H 2O
Electrophilic substitution of aryl ethers
1. Halogenation
Phenylalkyl ethers undergo usual halogenation in the benzene ring. It is due to the activation of benzene
ring by the methoxy group. Para isomer obtained in 90% yield.
OCH3 OCH3 OCH3

Br
Br2 /AcOH
+

Anisole p-Bromoanisole o-Bromoanisole

Br (Major) (Minor)
2. Nitration
OCH3 OCH3 OCH3

NO2
Conc.HNO3
Conc.H2SO4
+

p-Nitroanisole o-Nitroanisole
Anisole (Minor)
NO2 (Major)

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Friedel-Crafts reaction

OCH 3 OCH 3 OCH 3

CH3
Anhyd/AlCl3
+ CH3 Cl +
CS 2

Anisole
CH 3
4-Methylaanisole 2-Methylanisole
(Major) (Minor)

OCH3 OCH3 OCH3

COCH3
Anhyd/AlCl3
+ CH3COCl +
CS2

Anisole
COCH3
4-Methoxyacetophenone 2-Methoxyacetophenone
(Major) (Minor)

USES of Ether:
1. As a solvent for oils, fats, waxes, plastics etc.
2. In the extraction of organic compounds from aqueous solutions.
3. As an inert medium for various reactions (ex.Wurtz reaction) and preparation of RMgX
4. As an anaesthetic in surgery without causing any damage to heart or lungs.
(Recently, HALOTHANE is widely used for this purpose since it is harmless and quick in action. )
Halothane CF3CHC Br - 2-Bromo-2- chloro-1,1,1-trifluroethane
5. NATALITE(mixture of alcohol and ether), a substitute for petrol
6. Refrigerant along with dry ice (solid CO2 ) which produces a temperature around 110 C

7. Enthrane (CHFCl  CF2  O  CHF2 ) and Isoflurane( CF3CHCl  O  CHF2 ) are used as
anesthetics in place of diethyl ether as the latter one has slow effect.
8. Substituted anisoles are used as flavouring agents and in perfumes due to their pleasant odour.
OH
OH OH
O CH3
CH (C H 3 ) 2
O CH 3 O CH 3

CH 3
HC CHC H 3 H 2C CH CH 2 CH O Thymol
Anithole E ugenol Vanillin Present in Thym e and Mint
Constituent of Anise seed Found in Cloves Found in Oil of Vanilla Bean U sed in flavours and Perfum es

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