Teacher Orientation :

Class – XII Topic - Alcohol, Phenol and Ethers.

The following topics will be covered in this chapter.

Classification: Alcohol, Phenol and Ethers.

Nomenclature: Alcohol, Phenol and Ethers.

Structure of Functional Groups

Alcohols and Phenols: Prepapration, Physical and Chemical Properties.

Ethers: Prepapration, Physical and Chemical Properties.

Student Orientation:

Topic - Alcohol, Phenol and Ethers.

Concept Detail:

Alcohol, Phenols and Ethers.

Here are the general formula and examples of each.

alcohol phenol ether

general
structure
R OH OH R O R

H H H H H
example OH
structure
H C C OH H C C O C H
H H Br H H H

ethanol o-bromo phenol ethylmethyl ether

example
or or or
name
ethyl alcohol 2-bromo phenol methoxy ethane

Nomenclature of Alcohols:

1. Select the longest chain containing the alcohol, -OH.

2. Number the chain with the –OH group getting the lowest possible number.
3. Replace the –e at the end of the suffix with –ol.
4. If there are more than one –OH group do not remove the –e from the suffix, but add a di- or
tri- prefix to the –ol suffix.
5. Add a prefix number to indicate which carbon the –OH group is bonded to. This is not
always necessary.
Examples:

2-propanol
or
ethanol 2,4-pentanediol cyclopentanol
isopropyl alcohol
(rubbing alcohol)
H H H OH H
H C C OH H C C C H OH
OH OH
H H H H H
 For the first example there is no prefix number to indicate the location of the –OH group.
The reason is that no matter which carbon the –OH group is attached to that carbon is
carbon number one. The name 1-ethanol would be redundant.
 For the last example there is no prefix number to indicate the location of the –OH group.
The reason is that no matter which carbon the –OH group is attached to that carbon is
carbon number one. The name 1-cyclopentanol would be redundant.
Alcohols are often classified based on the classification of the carbon they are attached to.
Remember the following diagrams.
 primary carbon is bonded to one other carbon:
o both of these carbons
H H
H C C H
H H

 secondary carbon is bonded to two other carbons:

o the center red carbon only
H H H
H C C C H
H H H

 tertiary carbon is bonded to three other carbons:

o the center red carbon only
H
H C H
H H
H C C C H
H H H

Following the format of the above diagrams, if we replace one hydrogen with a –OH group we
get the following classifications of alcohols:

 1, primary alcohol has –OH group bonded to a carbon which is bonded to one other
carbon:
 H H
H C C OH
H H

 2, secondary alcohol has –OH group bonded to a carbon which is bonded to two other
carbon:
H OH H
H C C C H
H H H

 3, tertiary alcohol has –OH group bonded to a carbon which is bonded to three other
carbon:
H
H C H
H H
H C C C H
H OH H

The classification dictates what types of reactions the alcohol will undergo. A simple test can be
performed to determine which classification of alcohol is present.

Redox reactions (oxidation/reduction reactions) are very important to alcohols. The oxidation
state of the carbon bonding to the functional group is important in determining what types of
compounds could be formed.

The oxidation state of carbon in various common compounds is as follows:

alkanes  alcohols  aldehydes  carboxylic acids  carbon dioxide

-4 -2 0 +2 +4
+ +
-2 -2
H H
+ + + -2
+
O O -2 -2
+ -2 + O C O
H C H H C -2 OH + +
-4 H C H H C OH +4
+H
H+ 0 +2

In each step along carbon’s path, from the alkanes to carbon dioxide, the carbon is oxidized and
will lose 2 electrons.

For reactions involving alcohols an oxidizing agent such as potassium dichromate, K2Cr2O7, is
often used in acidic solutions and potassium permanganate, KMnO4, is often used in basic
solutions. These by no means are the only chemicals used to oxidize alcohols. There are
many useful oxidizing agents available for experimentation and testing. The symbol [O] is often
used as the short hand meaning for an oxidizing agent. This would be used when the reader is
not concerned with which oxidizing agent is being used, but to simply to show that an oxidation
took place.

The following are generalized reactions for the three classes of alcohols, 1, 2 and 3.

H H H O H O
[O] [O]
H C C OH H C C H H C C OH
H H H H

primary alcohol aldehyde carboxylic acid

H OH H H O H
[O] [O]
H C C C H H C C C H NR
H H H H H

secondary alcohol ketone

H
H C H
H H [O]
NR
H C C C H
H OH H
tertiary alcohol

The oxidation of the primary alcohol ethanol, also known as grain alcohol which is the alcohol
you find in wine, beer and spirits, is the least toxic of the alcohol classes. But a few fluid ounces
of a secondary or tertiary alcohol can destroy a person’s liver.

If you look at the products of this first reaction you will find an aldehyde is the first chemical
produced by the oxidation of the ethanol. This is accomplished by enzymes found in most
humans. Humans of certain ethnic backgrounds are able to produce more of these enzymes
ethnicities. A person of German decent will normally have many more of these enzymes than a
person of American Indian decent. This intermediate aldehyde is toxic to the liver organ, but as
quickly as it is produced the body oxidizes this compound to a carboxylic acid. Carboxylic acids
can easily be metabolized for energy use and will not harm your liver.
Alcohol overdose can be accomplished by a few mechanisms, one is overloading of ethanol to
the point that your liver can not produce enough enzyme to oxidize the ethanol to aldehyde and
the aldehyde to a carboxylic acid. The aldehyde and ethanol persist in the liver and cause it to
fail.

Another alcohol overdose can be accomplished by much smaller amounts if a secondary

alcohol is consumed. As you can see, if you consumed a secondary alcohol a ketone will be
produced. Then no reaction will occur. A ketone can not be oxidized inside most organisms.
This can easily be accomplished by combustion, but if you liver is combusting the ketone in your
system you have worries bigger than liver failure, like finding a fire extinguisher.

Back to our alcohol overdose scenario, since the ketone is not converted into another
compound it sits in your liver. You liver will fail with only a small ingestion of this secondary
alcohol. By the way, this alcohol is isopropyl alcohol (2-propanol) other wise known as rubbing
alcohol.

Another alcohol overdose can be accomplished by even smaller amounts if a tertiary alcohol is
consumed. Again, if you consumed a tertiary alcohol no reaction will occur. The tertiary alcohol
will persist in your liver until it fails, then you will die.

Knowing the toxicity of the different classifications of alcohols to the human body, which class,
1, 2 or 3, do you think, causes the most deaths each year?

The 1, as ethanol or drinking alcohol, has caused many thousands more deaths than the 2
and the 3 combined.

Here are two more reactions discussed previously that should still be included in this section:

1. Dehydration:

loss of a water

production of an unsaturated hydrocarbon

 H H
H H
H C C H H+ + H2O
C C
H OH H H

2. Hydration:

gain of a water

addition of the water across a double or triple bond

H
H H H
H C H H H H H+
C C + O H C C C H
H H H OH H

Real World Example:

CH3CH2OH + Cr2O7
-2
 
H 2 SO4 CH3COOH + Cr
+3

ethanol dichromate acetic acid chromium (III) ion

clear reddish orange clear Green

This reaction is utilized by the inexpensive blood alcohol tests. You simply blow your breath into
a small tube and the tube changes color from reddish orange to green.

Ethanol Production in Alcoholic Beverages:

C6H12O6  2 CH CH OH
yeast
3 2 + 2 CO2

Yeast converts the reactant glucose into ethanol and carbon dioxide. This is why beer and
champagne are carbonated beverages. To keep some beverages from being carbonated, wine
and spirits, a weak strain of yeast is used. This yeast dies in low concentrations of ethanol.

An interesting note, when you make ethanol in a lab by hydrating an alkene, an additive must be
included in the solution to make it undrinkable. If not the government will tax this production.

Solubility and MP/BP of Alcohols:

The solubility and melting/boiling points of alcohols depend on two factors, the length of the
carbon chain and the number of alcohols on the molecule. The longer the carbon chain, the
less soluble the alcohol will be. The BP and MP will also increase with carbon chain length.
Longer carbon chained alcohols are less likely to mix with water. The longer the alcohols
carbon chain, the better the chance that the alcohol will be a solid at room temperature.

More alcohols on the chain will increase the chains solubility. The more alcohols on the carbon
chain, the better the chance that the alcohol will be a solid at room temperature.

Longer means less soluble, less alcohols means less soluble.

Shorter means more soluble, more alcohols means more soluble.

Phenols:
A phenol is a simply an –OH bonded to a benzene ring.

OH

This compound is a solid, but is normally used in a liquefied form by dissolving in any number of
solvents. Phenol is very corrosive to human skin. It can chew through your skin in a few
seconds. Having said this, many phenol derivatives can be found in different foods, see below.

OH OH OH
OCH3 OCH3 3 (CH3 )C C(CH3)3

H C O CH2CH CH2 CH3

BHT
butyrate hydroxytoluene
vanilla cloves
or
2,6-di-t-butyl-4-methyl phenol

The disubstituted nomenclature for aromatics applies to the phenol.

Remember the following relationships for substitutions of benzene rings.

 ortho meta para

Examples:

OH

Structure

NH2
OH
name meta-amino phenol para-methyl phenol
name m-amino phenol p-methyl phenol
name 3-amino phenol 4-methyl phenol

Reactions of Phenols:
OH OH
NO2
+

NO2

OH
O2N NO2
O3
HN
O2N
O3
HN OH OH
nc. Br
Co
OH +

CS 2
Br 2 i n Br
OH
Br Br
Br2 water

Br
Zn D
ust
Na
2 Cr
O
HS 2 7
2 O
4
O

O
Ethers:
An ether is a hydrocarbon with an oxygen sandwiched between the carbons. They are very
useful in organic chemistry. They tend to by very good solvents, much like water, and have
relatively low reactivity. They are very resistant to oxidizing agents like potassium dichromate
and potassium permanganate, as well as most acids and bases if the temperature is near room
temperature.

Ether Nomenclature:

There are two predominate methods of naming ethers. The first is the common method and is
most useful with simple ethers.

For the first method, if the carbon chains on either side of the oxygen are considered alkyl
groups you simply name the groups then write ether.

Examples:

O O O

ethylmethylether butylethylether phenylpropylether

The other method follows the official IUPAC rules:

1. Determine the longest alkyl chain for the root name.

2. Treat the oxygen and the remaining carbons as a side chain.
3. The prefix includes the alkyl chain with a suffix of oxy for the oxygen.

Examples:

O O O

methoxyethane 1-ethoxybutane 1-phenoxypropane

Preparation of Ethers:

1. Dehydration of two alcohols:

CH3CH2OH
CH3CH2OCH2CH3 H2O
CH3CH2OH

2. Alkyl halide and alkoxide:

CH3F + CH3CH2OK  CH3CH2OCH2CH3 + KF

3. Williamson synthesis: This reaction is used for the synthesis of symmetrical and
unsymmetrical ethers.

Important Named Reactions of Alcohols, Phenols And Ethers

1. Dow’s Process: This process is used for the formation of phenols from chlorobenzene.

a.
2. Reimer Tiemann Reaction: In this reaction, salicyaldehyde(2-Hydroxy benzaldehyde) is
prepared on reaction of phenols with chloroform while salicylic acid(2-Hydroxy benzoic
acid) is formed when phenols are treated with carbon tetrachloride.

a.
3. Kolbe’s Reaction: In this reaction , salicylic acid is prepared by the reaction of sodium
phenoxide with carbon dioxide followed by acidification.
 a.
4. Williamson synthesis: This reaction is used for the synthesis of symmetrical and
unsymmetrical ethers.

5. ESTERIFICATION

Con H2SO4
CH3COOH + C2H5OH CH3COOC2H5 + H2O

Important Mechanisms

1. REIMER TIEMANN

2. KOLBE SCHMIDT REACTION

3. HYDRATION OF ETHENE TO YIELD ETHANOL.

Step (i) : — Protonation of alkene to form carbocation by electrophilic attack :
 H H
—C=C + H — O+ — H ——— — C — C+ + H2O

Step (ii) : — Nucleophilic attack of water on carbocation :

H H
— C — C+ + H2O ——— — C — C — O+ — H
H

Step (iii) : — Deprotonation to form an alcohol :

H H OH
—C—C—O —H +
+ H2 O ——— — C — C — + H3O+
H

4. ESTERIFICATION

Con H2SO4
CH3COOH + C2H5OH CH3COOC2H5 + H2O

Mechanism:
O O+ - H OH
|| ||
i) CH3 – C – O – H + H+ CH3 – C – OH CH3 – C+

OH
OH H OH H
|
ii) CH3-C+ + :O - C2H5 CH3 – C – O – C2H5
+
OH OH

OH H OH2
| |
iii) CH3 – C – O - C2H5 CH3 – C – O – C2H5
| +
OH OH

OH2 +
iv) CH3 – C – O – C2H5 CH3-C+-OC2H5 + H2O
| |
OH OH

-H+
v) CH3 – C – O- C2H5 CH3 – C – OC2H5
| ||
O–H O
Identification Test :
1. Lucas Test: To differentiate between primary, secondary and Tertiery alcohol.
3O alcohol + Lucas Reagent ---------------- immediate turbidity
2O alcohol + Lucas Reagent ---------------- turbidity after heating
1O alcohol + Lucas Reagent ---------------- No turbidity
2. FeCl3 Test : To differentiate between alcohol and phenol.
Alcohol + FeCl3 ----------------No Change
Phenol + FeCl3 ---------------- Change in colouration of FeCl3
Activity
3. To differentiate between primary, secondary and Tertiery alcohol.
4. To differentiate between alcohol and phenols.
Instant Diagnosis Question
1. What do you mean by 10, 20, 30 alcohols?
2. Alcohols have higher boilng points than corresponding ethers, why?
3. What is Lucas reagent?

Formative Assignment

1.What is the main product obtained when vapors of t-butyl alcohol are passed over
copper at 300°C ?
2.Phenol has smaller dipole moment than methanol. Why ?
3. Explain the following
(a) Cyclohexanol is more soluble in water than 1-Hexanol.
(b) Propane 1,3-diol is more soluble in the water than propan-1-ol.
4. Riemer-Tieman Reaction.
5. Kolbe.s Reaction.
6. Esterification.
7. Why is preparation of ethers by acid catalysed dehydration of 2° and 3° alcohols not a
suitable method ?
Level Wise Assignment:
Level 1
1. Arrange the following compounds in the increasing order of acid strength.
Propan-1-ol, 2,4,6-trinitrophenol, 3-nitrophenol, 3,5-dinitrophenol
2. Di-tert butyl ether cannot be made by Williamson’s synthesis. Why ?
3. Arrange the following alcohols in the order of increasing reactivity towards Lucas
Reagent: 2-butanol, 1-butanol, 2-methyl-2-propanol
Level 2:
1. How will you account for the following :
Ethers possess a net dipole moment even if they are symmetrical in structure ?
2. The treatment of alkyl chlorides with aq KOH leads to the formation of alcohols
but in presence of alcoholic KOH, alkenes are the major products. Explain.
3. How is tert-butyl alcohol obtained from acetone ?
Level 3:
1. An organic compound A with molecular formula C6H6Ogives a characteristic colour with
aq. FeCl3 Solution. When A is treated with CO2 and NaOH at 410 K, under pressure, it
gives compound Bwhich on acidification gives compound C. compound C react with
acetyl chloride to give d which is a popular pain killer. Deduce the structures of A, B, C
and D and explain all the reactions involved.
2. Explain why dehydration of alcohols to form alkenes is always carried out with conc.
H2SO4 and not with conc. HCl or HNO3?
3. An ether A (C5H12O) when heated with excess of hot concentrated HI produced two alkyl
halides which on hydrolysis from compounds B and C. Oxidation of B gives an acid D
whereas oxidation of C gave a ketone E. Deduce the structures of A, B, C, D and E.

Project:

To make Roadmap of whole chapter.