Alcohols, Phenols and Ethers Part - 1

Func�onal Group- OH Structure

Suffix to be used - ol
Homologous series-
142 pm
:O: 96 pm
Methanol (CH3OH) H
Ethanol (C2H5OH) Alcohol C 108.90 H
Propanol (C3H7OH) H
Butanol (C4H9OH) H
Pentanol (C5H11OH) and so on Methanol
Classifica�on Nomenclature
C2H5OH Compound Common name IUPAC name
Monohydric alcohols CH3-OH Methyl alcohol Methanol

CH3-CH2-CH2-OH n-Propyl alcohol Propan-1-ol

Compounds Compounds
containing containing CH3-CH-CH3 Isopropyl alcohol Propan-2-ol
OH
C -OH bond C -OH bond
sp3 sp2 CH3-CH2-CH2-CH2-OH n-Butyl alcohol Butan-1-ol

CH3-CH2-CH2-CH2-OH sec-Butyl alcohol Butan-2-ol

* Primary, secondary * Vinylic alcohol CH3-CH-CH2-OH Isobutyl alcohol 2-Methylpropan-1-ol

CH3
and ter�ary alcohols CH3
* Allylic alcohols CH3-C-OH tert-Butyl alcohol 2-Methylpropan-2-ol
CH3
* Benzylic alcohols HO-H2C-CH2-OH Ethylene glycol Ethane-1,2-diol

CH2-CH-CH2 Glycerol Propane -1,2,3-triol

CH2OH CH2OH OH OH OH

CH2OH CHOH OH
OH CH3
CH2OH
Dihydric alcohols Trihydric alcohols Cyclohexanol 2-Methylcyclopentanol

Preparatory Methods Physical Proper�es

R-CH=CH2 H2O/H⁺
1. Boiling Point-
Markownikoff addi�on H2O 2 * Higher than other organic compounds having
equal molecular masses
R-CH=CH2 B2H6 * The boiling point decreases with an increase
in branching in alipha�c carbon chains
An� markownikoff addi�on H2O2/H2O
2. Solubility-
* The hydroxyl group in alcohol is involved in the
R-C-Cl N2/H2
forma�on of intermolecular hydrogen bonding
O Na + C2H5OH * The solubility of alcohol in water decreases
R-OH with the increase in the size of the alkyl group
H2/Pd
RCHO
LiAlH4
R-COOH i) LiAlH4
R-COO-R’ ii) H2O H O
H
CH3 - CH2 - CH2 - O: H O
:

For the prepara�on of -

10 alcohol – HCHO
H H
i) RMgX
20 alcohol – RCHO O
30 alcohol – R-C-R ii) H2O/H⁺ H H
O

Reac�ons involving cleavage of O-H bond Reac�ons involving cleavage of C–O bond
Reac�on with Metals
2R-O-H + 2Na 2R-O-Na+H2 ROH + HX → R-X + H2O
Sodium Reac�on with
alkoxide hydrogen halides
CH3 CH3
6 CH3-C-OH + 2Al ( )
2 CH3-C-O Al+3H2 Acidity of Alcohols
RCH2OH
Cu
CH3 3
RCHO
CH3 573K
tert-Butyl alcohol Aluminium
tert-butoxide Cu
R-CH-R’ R-C-R’
R R Dehydrogena�on OH
573K
O
R CH2OH > CHOH >> R C- OH
R R CH3 CH3
CH3-C=CH2
Primary Secondary Ter�ary Cu
R-C-OH
Chemical CH3
573K
Proper�es
Alcohols: Weaker acids than water
Acidity H OH
RCH2OH
Oxida�on
R-O: + H-O:-H R-O-H + :OH
: :

: :

: :

of Alcohols R-C=O R-C=O

Base Acid Conjugate Conjugate Aldehyde Carboxylic
CrO3
acid
RCH2OH
acid base
RCHO
Oxida�on
PCC
Esterifica�on CH3-CH=CH-CH2OH CH3-CH=CH-CHO
CrO3
O H⁺ O R-CH-R’ R-C-R’
R-C-OH + H-O-R R-C-O-R’ + H-O-H OH O
⥮

Esterifica�on Sec- alcohol Ketone

Acid Alcohol Ester

Reac�on with phosphorus trihalides

Some Commercially Important Alcohols

3CH3-CH2-CH2-OH + PCl3 → 3CH3-CH2-CH2-Cl + H3PO3

Dehydra�on
Methanol
H2SO4
Prepara�on C2H5OH CH2=CH2+H2O
443K
ZnO-Cr2O3
CO + 2H2 CH3OH OH
200-300 atm 85%H3PO4
573-673 K CH3CHCH3 CH3-CH=CH2+H2O
440K
Proper�es
CH3 CH2
20%H3PO4
* Methanol is a colourless liquid and boils CH3-C-OH CH3-C-CH3+H2O
at 337 K 358K
CH3
* It is highly poisonous in nature
The rela�ve ease of dehydra�on of alcohols follows the
Ethanol following order:
Ter�ary > Secondary > Primary
Prepara�on
Invertase
C12H22O11 + H2O C6H12O6 + C6H12O6
Glucose Fructose

Zymase
C6H12O6 2C2H5OH + 2CO2
Proper�es

* Ethanol is a colourless liquid with boiling point 351 K

* It is used as a solvent in paint industry and in the prepara�on of a number of carbon compounds
Alcohols, Phenols and Ethers Part - 2

Structure
It is a white crystalline compound that has a
dis�nc�ve odour 1090
H
OH Phenol

:
O

:
136 pm

Classifica�on Nomenclature
OH OH
CH3
OH CH3 CH3 CH3
OH
Monohydric Phenol
OH
OH
OH
Phenol o-Cresol m-Cresol p-Cresol
OH Phenol 2-Methylphenol 3-Methylphenol 4-Methylphenol

Dihydric Phenol OH
OH OH
OH OH

OH
OH
OH
OH Catechol
Benzene-1,2-diol
Hydroquinone or quinol
Benzene-1,4-diol
Trihydric Phenol

Physical Proper�es Prepara�on

- +
1. Boiling Point- OH O Na OH From
* Phenols have higher boiling points in +NaOH
623 K HCl Haloarenes
300 atm
comparison to other organic compounds
having equal molecular masses
From
R R
-
O Na
+
OH Benzenesul-
H O
R-O-H-O-H-O-H-O- R O R Oleum (i) NaOH
phonic acid
H R H (ii) H⁺
H H
H-O-H-O-H-O- O O
From
Phenols + -
NH2 N2Cl OH Diazonium
NaNO2 H 2O salts
+N2+HCl
+HCl Warm
Aniline Benzene diazonium
2. Solubility- chloride
* The hydroxyl groups are responsible for the
solubility of phenol in water CH3 CH3 From
* The solubility of phenol decreases with the CH3-CH CH3-C-O-O-H OH Cumene
O2 H⁺
increase in the size of the aryl group +CH3COCH3
H2 O
Cumene Cumene
hydroperoxide

Chemical Proper�es

Electrophilic aroma�c subs�tu�on Reimer-Tiemann Reac�on

OH O Na⁺ O Na⁺ OH
1) Nitra�on CHCl2 NaOH CHO H⁺ CHO
CHCl3 + aq NaOH

OH OH OH
Dilute HNO3 NO2 Intermediate Salicylaldehyde
+

NO2 Reac�on of Phenol with zinc dust

o-Nitrophenol p-Nitrophenol
OH
2) Halogena�on
+ Zn + ZnO
OH OH OH
Br2 in CS2 Br
+
273 K
Br Oxida�on
Minor Major
OH O
Kolbe’s reac�on
Na2Cr2O7
OH ONa OH H2SO4
NaOH (i) CO2 COOH
O
(iI) H⁺
benzoquinne
2-Hydroxybenzoic acid
(salicylic acid)
Alcohols, Phenols and Ethers Part - 3
sp3 hybridised
Structure
141 pm
:O:
H H
Ether C 111.7 0
C
H H
H H
Methoxymethane
Classifica�on Nomenclature
Compound Common name IUPAC name
CH3OCH3 Dimethyl ether Methoxymethane
CH3 CH2 - O - CH2 CH3 O
diethyl ether tetrahydrofuran C2H5OC2H5 Diethyl ether Ethoxyethane

CH3OCH2CH2CH3 Methyl n-propyl ether 1-Methoxypropane

Symmetrical Ethers
C6H5OCH3 Methyl phenyl ether Methoxybenzene
(Anisole) (Anisole)

C6H5OCH2CH3 Ethyl phenyl ether Ehoxybenzene

(Phenetole)

C6H5O(CH2)6-CH3 Heptyl phenyl ether 1-Phenoxyheptane

O CH3
CH3O-CH-CH3 Methyl isopropyl ether 2-Methoxypropane
CH3

C6H5-O-CH2-CH2-CH-CH3 Phenyl isopentyl ether 3-Methylbutoxybenzene

CH3

methyl phenyl ether CH3-O-CH2-CH2-OCH3 1,2-Dimethoxyethane

Unsymmetrical Ethers H3C CH3

OC2H5 2-Ethoxy-
-1,1-dimethylcyclohexane

Prepara�on Physical Proper�es

1. Miscibility
1. By dehydra�on of alcohol
Miscibility with water resembles those of
H2SO4 alcohols of the same molecular mass
CH2=CH2
443 K
CH3CH2OH
H2SO4
C2H5OC2H5 R
413 K :O: H H
O
: :

2. Williamson synthesis R

R-X+R’-ONa⁺ R-O-R’+Na X
: :

: :

2. Boiling Points
* Lower than alcohols
- + * This is due to the presence of hydrogen
:OH :O Na :O-R
:

bonding in alcohols which is absent in

ethers
R-X
+ NaOH

+
:OR +OR +OR OR OR
:

- -
↔ ↔ ↔ ↔
-

R-O-R + HX → RX + R-OH Electrophilic subs�tu�on

R-OH+HX → R-X + H2O Cleavage of C–O bond in ethers

OCH3 OCH3 OCH3
Br2 in Br
+
O-R OH Ethanoic acid
Chemical Br

+H-X +R-X Proper�es p - Bromoanisole o - Bromoanisole

(major) (minor)

Halogena�on

Friedel-Cra�s reac�on

Nitra�on
OCH3 OCH3 OCH3
CH3
Anhyd. AlCl3
+CH3Cl +
CS2
OCH3 OCH3 OCH3
H2SO4 NO2 CH3
HNO3
+ Methyl 2- methoxy- 4- methoxy-
chloride toluene toluene
NO2 (Minor) (Major)
2- Nitroanisole 4- Nitroanisole
(Minor) (Major) OCH3 OCH3 OCH3
COCH3
Anhyd. AlCl3
+CH3COCl +

COCH3
Ethanoyl 2- methoxy- 4- methoxy-
chloride acetophenone acetophenone
(Minor) (Major)