Alcohols Phenols and Ethers

Alcohols Phenols and

Ethers
Monohydric Alcohols
Dihydric & Trihydric Alcohols
(few more examples)
Primary, Secondary & Tertiary
Methods of Preparation
Hydration of alkenes
Direct hydration
Indirect hydration
H2SO4 – H2O Addition
Hydroboration-oxidation
Direct Hydration

Here the acid used is a dilute acid (eg: Dil. HCl or Dil. H2SO4)
Indirect Hydration

Here the acid used is a conc. H2SO4

Indirect Hydration: hydroboration
oxidation (anti-morkownikoff’s)
A simple consolidated equation is

good enough. The steps are for
understanding.
Other preparation methods
From Grignard reagent
Hydrolysis of alkyl halides
Reduction of carbonyl compounds
From Primary amines
From Grignard reagent
 1º, 2º, 3º alcohols can be prepared (based on
suitable aldehyde or ketone)
Primary alcohols (from Grignard
Reagent)
Secondary alcohols (from Grignard
Reagent)
Tertiary alcohols (from Grignard
Reagent)
Reduction of carbonyl compounds
Aldehydes give primary alcohols
Ketones give secondary alcohols

Carboxylic acid give primary alcohols (only LiAlH4)

Esters also give primary alcohols (LiAlH4 or with Na/C2H5OH)

Hydrolysis of alkyl halides
From primary amines
By fermentation of alcohols
Fermentation is the oldest chemical process for the preparation of
ethanol from carbohydrates.
Even today, fermentation of carbohydrates is one of the most
widely used methods for the industrial preparation of ethyl alcohol
 The carbohydrates generally used for this purpose are sugars
(present in molasses, grapes, beets, etc.) or starch (present in
barley, potatoes, rice, etc.).
By fermentation of molasses

Molasses from sugar industry is used for fermentation
H2SO4 is used to stop the growth of unwanted bacteria.


Yeast is added (contains invertase and zymase).

Fermented liquid contains 8-10 % ethanol

After fractional distillation, 95 % ethanol is obtained (called as rectified spirit)

By azeotropic distillation 100 % alcohol
By fermentation of starch
Potatoes, rice, maize, barley, etc is rich in starch.
They are steamed at 140-150 C under pressure.
Yeast is added (contains maltase and zymase)
Fermented liquid on distillation gives ethanol as earlier

Manufacture of Methanol: Bosch
Process
Methanol: Methanol is better known as wood spirit or wood alcohol.
On commercial scale, it is manufactured from water gas which on
mixing with half of its volume with hydrogen is compressed to 200-300
atm pressure and passed over copper-zinc oxide-chromium oxide
catalyst at 573-673K. Methanol vapours formed are then condensed
which is 99% pure.
Physical Properties of Alcohols
Physical state: The lower alcohols are colorless liquids having
characteristic alcoholic odour and burning taste.
The higher members with more than twelve carbon atoms are
colourless and odorless waxy solids.
Alcohols exist as associated liquids due to the presence of inter
molecular hydrogen bond
Chemical Properties
Acidic nature of alcohols
Alcohols are weaker acids than water
Ka of water is 10-14

Ka of Ethanol is approximately 10-18
Due to the inductive effect of CH3 Groups
Reaction with sodium
Alcohols are acidic enough to react with Na & even Al
Esterification with mechanism
Reaction
Mechanism
Reaction with hydrogen halides
Order of Reactivity
3º > 2º > 1º
For HCI (less reactive), ZnCl2 (catalyst & dehydrating agent) is used for 1º & 2º alcohol
For 3º alcohol, reaction happens at RT without a catalyst.
Reaction with PCl3, PCl5 and SOCl2
Advantage of thionyl chloride over other methods is very important.

Reaction with acid chlorides and acid anhydrides
Oxidation
Stops at aldehyde when Collin’s reagent is used (cromic oxide-pyridine complex)
Ketones are further oxidised to carboxylic acids with less number of carbon atoms
Oxidised not by alkaline or neutral KMnO4, but only by acidified KMnO 4 or K2Cr2O7 to
give a mixture of ketone and carboxylic acid
Dehydration of alcohols
(sulphuric acid)
Conc. H2SO4 (440 K) / H3PO4)

If there is possibility of more than one product then Saytzeff product is
more favorable (more substituted alkene)
Dehydration of alcohols: Mechanism
Step: 1
Step: 2
Ease of dehydration
3º > 2º > 1º
Step: 3
Dehydration of alcohols
(sulphuric acid)
With excess of ethanol

Dehydration of alcohols (Alumina)
Products vary with temperature
Alumina is a substance which can absorb molecules of water,

At high temperatures it is used as a dehydrant
Other dehydration reactions
Dehydrogenation
Dehydrogenation
Dehydration
Conversion of one alcohol into another
Lower to higher
higher to lower
Primary to Secondary
Primary to Tertiary
Secondary to Tertiary
Lucas’ Test: To Distinguish 1° , 2° and 3° alcohol
3° alcohol forms turbidity immediately.

2° alcohol forms turbidity within five minutes.
1° alcohol shows no turbidity at room temperature.
Uses of alcohols
Alcohol is used as high-efficiency fuel. It gives carbon dioxide and water when it burns.
It is also used to make vinegar.
It is used as an antiseptic, dressing for wounds, and antidote for snake bites. It is also used as a mild
sedative.
Alcohol is a common cough remedy ingredient that can be found in most cough syrups.
Since alcohol has antifungal and antibacterial properties, it is used in disinfectants.
To eliminate microbial contamination, alcohol is used as a cleaning agent in hospitals, medical
facilities, and laboratories.
Ethanol, Methanol, and Isopropanol are solvents used in analytical chemistry processes, such as
chromatography analysis.
Some of the commonly used alcohols are methanol, ethanol, propanol and butanol.
Phenols
Names
Preparation from diazonium salt
from Chlorobenzene (Dow’s process)
from Benzene sulphonic acid
Manufacture from Cumene
Physical properties: state and solubility.
It is a colourless, crystalline, deliquescent solid
having melting point 42°C. It turns pink on exposure
to air and light.
Unlike alcohols, phenols are sparingly soluble in
water.
Chemical Properties
Acidic character of phenol
It does not react with Na2CO3 and NaHCO3, because it is a weaker acid than carbonic acid. Phenols are
more acidic than alcohols due to resonance stabilization of phenoxide ion.
Electron withdrawing groups like -NO2, -CN, -X etc., which stabilize the phenoxide ion increase the
acidity
Electron donating groups like -NH2, -OR, -R, -OH etc., which destabilize the phenoxide ion by
increasing the negative charge tend to decrease the acidic strength of phenols.
These resonance
structures are for
understanding.
p-Nitrophenol > o-Nitrophenol > m-Nitrophenol > Phenol

Reaction with sodium hydroxide
Reaction with sodium
Reaction with zinc
Reaction with acetyl chloride and acetic anhydride
Bromination
Electrophilic substitution reactions: nitration and sulphonation
A mixture of conc. nitric

acid + conc. sulfuric acid is
called as nitrating mixture
Electrophilic substitution reactions: nitration and sulphonation
Kolbe’s reaction (formation of salicylic acid)
Lengthy textbook version
simpler version of
the same reaction
Reimer – Tiemann reaction
Test for phenol – FeCl3 test, azo dye test
FeCl3 Test:
Azo-dye test.
Uses of Phenol
It is used as antiseptic in soaps, lotions and ointments.
Ethers
Ethers: structure of ethereal group
Common IUPAC Common IUPAC
Name Name
Ethers: structure of ethereal group
Preparation from alcohol (Williamson’s
synthesis)
 Williamson's synthesis involves SN2 attack of an alkoxide ion on primary alkyl halide.
 Better results are obtained when the alkyl halide is primary.
 If the alkyl halide is secondary or tertiary, elimination competes over substitution as explained below.
Physical properties: state, miscibility
Dimethyl ether and ethyl methyl ether are gases at ordinary temperatures, while other aliphatic
ethers are colourless liquids with pleasant characteristic ethereal odour.
The aryl ethers are also liquids at ordinary temperatures and possess characteristic odour.
Ethers are sparingly soluble in water but dissolve readily in organic solvents such as benzene,
chloroform, etc. The solubility of ethers in water decreases with increase in the molecular mass.
The comparatively higher solubility of lower ethers in water is due to the formation of hydrogen
bonds between ether and water molecules as shown below.
Chemical Properties
Reaction with chlorine
Reaction with HI
Substitution happens in Under severe/drastic

carbon which is less crowded conditions the reaction goes
(stearic effect) one step further
The reactivity of halogen acids in this reaction follows the order HI > HBr > HCl.
Because Nucleophilicity order is I > Br> Cl, better put the leaving group as Y
and explain
Reaction with PCl5
PCl5 can act as a lewis acid in the mechanism

Oxidation (peroxide formation)
When ethers are allowed to stand in contact with air they slowly react
with atmospheric oxygen to form peroxides or hydroperoxides. The
reaction is catalysed by UV rays.
Aryl ethers
Physical properties – state and solubility
Aryl ethers are liquids at ordinary temperature with
characteristic odour
Aryl ethers (or anisole) are almost insoluble in water due
to their high molecular mass and presence of hydrophobic
aromatic ring but they are fairly soluble in organic solvents.
Preparation of Anisole (Williamson’s
synthesis)
The reaction would not work the other way around, with
bromobenene and sodium methoxide. Find out why?
Electrophilic Substitution(halogenation,
nitration and Friedel-Crafts reaction)
Electrophilic Substitution (Halogenation)
Already, highly reactive, in In non-polar solvent (carbon

the presence of a catalyst give disulphide) give mono bromo
tribromo product products
Electrophilic Substitution(Friedel-Crafts
reaction)
Highly reactive Slightly less reactive

Uses of ether
Ethers are widely used as laboratory and Protonated
alcohol, industrial solvents for fats, oils, gums, resins.
Diethyl ether is a general anaestheicia (now replaced with
better ones)
Used as a solvent for extraction
Also used as refrigerants

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Alcohols Phenols and Ethers

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Alcohols Phenols and

Here the acid used is a conc. H2SO4

A simple consolidated equation is

Aldehydes give primary alcohols

Ketones give secondary alcohols

Carboxylic acid give primary alcohols (only LiAlH4)

Esters also give primary alcohols (LiAlH4 or with Na/C2H5OH)

Yeast is added (contains maltase and zymase)

Fermented liquid on distillation gives ethanol as earlier

Ka of water is 10-14

Advantage of thionyl chloride over other methods is very important.

Stops at aldehyde when Collin’s reagent is used (cromic oxide-pyridine complex)

Conc. H2SO4 (440 K) / H3PO4)

With excess of ethanol

Products vary with temperature

Alumina is a substance which can absorb molecules of water,

3° alcohol forms turbidity immediately.

p-Nitrophenol > o-Nitrophenol > m-Nitrophenol > Phenol

A mixture of conc. nitric

Lengthy textbook version

Substitution happens in Under severe/drastic

PCl5 can act as a lewis acid in the mechanism

Already, highly reactive, in In non-polar solvent (carbon

Highly reactive Slightly less reactive

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