Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

Chapter-3

Alcohols and Phenols

University Syllabus: Preparation: Preparation of 1о, 2о and 3о alcohols: using Grignard

reagent, Ester hydrolysis, Reduction of aldehydes, ketones, carboxylic acid and esters.
Reactions: With sodium, HX (Lucas test), esterification, oxidation (with PCC, alc. KMnO4,
acidic dichromate, conc. HNO3). Oppeneauer oxidation Diols: (Upto 6 Carbons) oxidation of
diols, Pinacol-Pinacolone rearrangement. (pp - 493).

Reference Book:
1. Organic Chemistry, Morrison, R.T. & Boyd, R.N. Prentice Hall of India, Sixth Edition,
2007, 213-244 and 889-912.
2. Organic Chemistry, John McMurry, 8th Ed. Brooks/Cole, Cengage Learning.

Part-I: Alcohols
3.1. Introduction
Alcohols are compounds of the general formula ROH, where R is any alkyl or
substituted alkyl group. The –OH group may be bonded to primary, secondary, or tertiary –R
group. –R group may be open-chain or cyclic; it may contain a double bond, a halogen atom,
or an aromatic ring. For example:
OH CH2OH
CH3
CH3CH2OH CH3 C OH

Ethanol CH3
T-butyl alcohol Cyclohxanol benzoyl alcohol

CH2 CH2 CH2 CH CH2

Cl OH OH OH OH
Ethylene Chlorohydrin Glycerol
.
All alcohols contain the hydroxyl (- OH) group and it is the functional group. It
determines the properties or characteristic of alcohols. Variations in structure of the R group
have certain effect on rate of reaction of alcohol and the kind of reaction.
Compounds in which the hydroxyl group is attached directly to an aromatic ring
are not alcohols; they are phenols, and differ so markedly from the alcohols

3.2 Classification of alcohols:

Alcohols can be classified on the basis of number of -OH in molecule.

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Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

Alcohol

Monohydric Dihydric Tri-hydric Polyhydric

Alcohols Alcohols Alcohols Alcohols

Monohydric Alcohol- Molecule of an alcohol contain only one -OH group.

Ex.- CH3OH (methanol), C2H5OH (ethanol)
Dihydric Alcohol: Molecule of an alcohol contain only two -OH group.
Ex.- HO-CH2-CH2-OH (Ethylenediol)
Tri-hydric Alcohol: Molecule of an alcohol contain only three -OH group.
Ex.- HO-CH2-CHOH-CH2- OH (Glycerol)
Polyhydric Alcohol: Molecule of an alcohol contain only more than four -OH group.
Ex.- HO-CH2-(CHOH)4-CH2OH (Sorbitol)
Monohydric classified according to the kind of carbon that bears the -OH group:

Primary Alcohol Secondary Alcohol Tertiary Alcohol

-OH group bonded to -OH group bonded to -OH group bonded to tertiary
primary carbon atom primary carbon atom carbon atom

Primary C atom consists of Secondary C atom consists of Tertiary C atom consists of

one –R group and 2H atoms Two –R group and 1H atoms three –R group bonded to it.
bonded to it. bonded to it. H
H H CH3 C
Tertiary C Atom
CH3 C CH3 C CH3
Primary C Atom Secondary C Atom
H CH3

e.g. Ethanol e.g. Isopropyl alcohol e.g. t-butyl alcohol

H H CH3
CH3 C OH CH3 C OH CH3 C OH
H CH3 CH3

One class of alcohol may differ from other class in –

i) Rate of reaction ii) Mechanism of reaction
Example – i. Oxidation of primary, secondary, and tertiary alcohol take place differently.
ii. Benzyl alcohol appears to be primary alcohol, but it shows properties like tertiary alcohol.
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Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

3.3 Nomenclature
Alcohols arc named by three different systems.
i) Common names are most often used. These consists simply name of the alkyl group
followed by the word alcohol. For example: Methyl alcohol, Ethyl alcohol, Isopropyl
alcohol, t-butyl alcohol, etc.
ii. It is sometimes convenient to name alcohols by the carbinol system. According to this
system, alcohols are considered to be derived from methyl alcohol, CH3OH. An alcohol
can be derived by the replacement of one or more hydrogen atoms from –CH3 group of
methanol by other groups.

CH3 C 2H 5 H H
CH3 C OH C OH C2H5 C OH CH3CH2CH C OH
CH3 C 2H 5 H
Sec. butyl
Tri-methyl Carbinol Triphenyl carbiniol Triethyl carbinol Carbinol

iii. The most versatile system is the IUPAC. The rules are:
a. Select as the parent structure. It should contain longest continuous carbon chain that
contains the OH group
b. The parent structure is named after number of carbon atoms.
c. Depending upon the number of carbon atoms in parent structure name of the alkane is
derived. Name of alcohol is then derived from name of parent alkane by replacing the
terminal -e of the corresponding alkane name by -ol.
d. Position of –OH group in alkane chain is indicated by a number of C atom to which –OH
group is attached.
e. Numbering of C atom in parent alkane is done so that C bearing -OH group have lowest
possible number.
f. Indicate the positions of sub groups attached to the parent chain by name of group and
number of C atom.

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Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

1. Parent structure is selected containing –OH group.

2. C are labelled from right to left so that C bearing –
OH has lowest number.
3. Longest chain of C atom has six C. Therefore,
CH3 2 1
Parent alkane in Hexane.
CH
6 3
CH2CHCH
4 3 2CHCH3
4. Replace suffix ‘e’ in hexane by ‘ol’. Thus, we get
5
OH
basic name as Hexanol.
Parent structure
5. At carbon 2 –OH group is bonded. Thus 2-hexanol.
6. Alkyl branch: -CH3 group bonded to carbon 4,
hence – 4 - methyl.
Thus, in all IUPAC name is 4-methyl 2-hexanol
1. Parent structure is selected containing –OH group.
(C atoms numbered from 1 to 4)
2. C are labelled from the side so that C bearing –OH
has lowest number.
1
CH3 3. Longest chain of C atom has 4 C. Therefore, Parent
2
CH3 C OH alkane in Butane.
4. Replace suffix ‘e’ in hexane by ‘ol’. Thus, we get
CH3 CH2
4 3 basic name as Butanol.
5. At carbon 2 –OH group is bonded. Thus 2-butanol.
6. Alkyl branch: -CH3 group bonded to carbon 2,
hence – 2methyl.
Thus, in all IUPAC name is 2-methyl 2-butanol

3. 4. Physical properties
i) Alcohols are polar in nature. This is due to presence of polar –OH in their structure.

 H
R O
Partial charges of O and H atom of OH group

ii) They show intermolecular hydrogen bonding. This is ue to artial charges on the H and O
atoms of –OH group. ‘O’ bears partial –ve charge (-δ) as it is more electronegative than C
and H atom. ‘H’ bears partial +ve charge (+δ) as it is more electropositive than O atom.
 Hydrogen Bond
 H
R O R
H O
 

iii) Due to hydrogen bonding, they show relatively high MP and BP than corresponding to
alkanes. Since hydrogen bonding increases intermolecular forces of attraction. Thus,
alcohols are either liquids or solids at room temperature.

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Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

iv) MP and BP go on increasing in homologues series. This is due to increase in molecular wt

and surface area of molecules.
v) Lower alcohols are soluble polar solvents. Solubility in polar solvent goes on decreasing
with increase in molecular wt. As molecular wt. increases size of alkyl group i.e. non-
polar part increases in molecule. e.g. Ethanol is water soluble but n-butanol is water
insoluble. Structure of alkyl group affects the solubility. With increasing size of alkyl
group, solubility increases in non-polar solvent.
3.5. Preparation of Alcohols:
3.5.1. Alcohols from Aldehydes and Ketones using reaction with Grignard’s Reagent:
Grignard reagent react with aldehydes and ketones to form alcohol.
Carbony Compound
H2O
C  R C OMgBr R C OH

  Alcohol
R Mg Br
Grignard's Reagent
i. Grignard’s reagent is alkyl magnesium halide such as alkyl magnesium bromide. [R-Mg-
Br].
Grignard Reagent is synthesized in situ.
R-X + Mg Metal → R-Mg-X (reaction is performed in dry ether)
ii. In Grignard’s reagent –R group is –vely charged as it is bonded to electropositive Mg
atom. Mg bear partial +ve charge and Halide partial -Ve charge.
- +2 -
H3C-Mg-Br
iii. ‘C’ in carbonyl group (>C=O) group is positively charged while ‘O’ is –vely charged.
iv. Thus, -vely charged –R group attack on carbonyl carbon to form intermediate.
v. Intermediate on hydrolysis form the alcohol as a product.
Using Grignard’s reagent Primary, secondary and tertiary alcohols can be synthesized
strategically.
a) Formaldehyde gives primary alcohol with Grignard’s reagent.
b) Except formaldehyde all other aldehydes gives secondary alcohols with Grignard’s
reagent.
c) All ketones gives tertiary alcohol with Grignard’s reagent.
Formladehyde convted to ethanol - primary alcohol

H H H
1 C O i. Alcohol ii. H2O CH3
CH3MgBr CH3 C OMgBr C OH
H
methyl magnesium H H
Formaldehyde bromide Ethanol

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Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

Acetaldehyde convted to 2- propanol -secondary alcohol

H3C H H
2 C O i. Alcohol ii. H2O CH3
CH3MgBr CH3 C OMgBr C OH
H
methyl magnesium CH3 CH3
Acetaldehyde bromide 2- propanol
Acetone convted to t-butyl alcohol - tertary alcohol

H3 C CH3 CH3
3 C O i. Alcohol ii. H2O CH3
CH3MgBr CH3 C OMgBr C OH
H3C
methyl magnesium CH3 CH3
Acetone
bromide t-butyl alcohol

Planned synthesis using Grignard’s reagent:

Alcohol of the interest ca be synthesized by roper selection of starting material and
Grignard’s reagent. This is the most important aspect of this method.
For example – We have to synthesize 2-methyl 2-butanol.
C2H5
CH3 C OH
CH3
2-methyl 2-butaol
.
i. It is tertiary alcohol. Thus, we must start with ketone.
ii. The C bearing –OH group consists of 2 – CH3 and one –C2H5 group.
iii. Thus, from 2 – CH3 and one –C2H5 group, one group is transferred from Grignard’s
reagent. Remaining two are from ketone.
iv. Thus, we have to select proper ketone and Grignard’s reagent.
Two alternatives are possible -
a. If we select acetone then we have to select C2H5MgBr as Grignard’s reagent.
b. If we select ethyl methyl ketone then we have to select CH3MgBr as Grignard’s reagent.
Acetone convted to 2-methyl 2-butaol - tertary alcohol
H3C CH3 CH3
C O i. Alcohol ii. H2O C2H5 C OH
C2H5MgBr C2H5 C OMgBr
a H3C
Ethyl magnesium CH3 CH3
Acetone bromide 2-methyl 2-butaol

Ethyl methl keone convted to 2-methyl 2-butaol - tertary alcohol

H5C2 C2H5 C2H5

b C O i. Alcohol ii. H2O CH3
CH3MgBr CH3 C OMgBr C OH
H3C
Ethyl methyl Methyl magnesium CH3 CH3
ketone bromide 2-methyl 2-butaol

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Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

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Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

.
3.5.2. Alcohols from Aldehydes and Ketones by using Reducing Agents:
Reduction of aldehydes and ketones form alcohols.
Reduction can be performed by using one of the following reducing reagents:
i. Raney Ni (finely powdered Ni metal), Pt metal or Pd metal
ii. Na-Hg amalgam in water
iii) NaBH4 or LiAlH4 (Lithium Aluminium Hydride)
3.5.2.1. Reduction with Raney Ni or Pt metal or Pd metal: H2 get added across
>C=O of aldehyde or ketone in presence of catalyst Raney Ni or Pt metal or Pd metal to
alcohol as a product.

H3C H3C
Raney Ni
C O + H2 CH OH
or Pt or Pd
H H
Catalyst Ethanol
Acet aldehyde

H3C H3C
Raney Ni
C O + H2 CH OH
or Pt or Pd
H3C
Catalyst H3C 2-propanol
Acetone .

H2 molecule is less reactive towards the reaction with C=O group. Thus, catalyst is necessary
for the activation of H2 molecule. Catalyst adsorb H2 gas on its surface hence H – H bond get
weaken i.e. H2 molecule get activated and then it reacts with C=O group to form alcohol.

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Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

C O CH OH
H-H +
+ H H
Catalyst Catalyst Catalyst

H-H is adsorbed on product is released and

catalyst surface catalyst is set free
which react with
carbonyl group

3.5.2.2. Reduction with Na-Hg amalgam: Na-Hg amalgam react with water and
release nascent H i.e. H•. H• is highley reactive. It undergoes addition reaction across C=O of
carbonyl compound to form alcohol.

H3C H3C
Na-Hg
C O + 2H CH OH
in H2O
H H
Ethanol
Acet aldehyde

H3C H3C
Na-Hg
C O + 2H CH OH
in H2O
H3C H3C
Acetone 2-propanol
.

3.5.2.3. Reduction of carbonyl compounds with NaBH4 or LiAlH4:

Compounds containing >C=O group are called as carbonyl compounds.
Example – Aldehydes, ketones, carboxylic acids, etc.

10 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

.
NaBH4 and LiAlH4 are very good reducing agent and reduction take place under mild
conditions than catalytic hydrognation. The reaction can be carried out in alcohol or in water
as solvent. LiAlH4 is more reactive than NaBH4 but it is more expensive. LiAlH4 react
violently in alcohol or in water hence solvet like dry ether must be used for the reaction.
LiAlH4 as well NaBH4 transfer H- (hydride ion) to C=O group in first step to form
complex. In second when water is added the complex undergo hydrolysis to form alcohol.
H  H 

H Al
 H H B
 H
Li Na

H H
. .
In LiAlH4, H atoms are bonded to electropositive Al hence Al bear +ve charge while
H bear -ve charge. Thus, H can be transferred as H- ion. Likely in NaBH4, H atoms are
bonded to electropositive B hence B bear +ve charge while H bear -ve charge. Thus, H can be
transferred as H- ion.
Example: a) Reaction of acetaldehyde with LiAlH4 and NaBH4
H  H3C
H3C H3C
+ C O  H H2O 4 CH OH + Al(OH)3
4 + H Al Li CH O Al
- hydrolysis
H
H H Ethanol
H 4
Acetaldehyde Complex Intermediate
tetra aluminium alkoxide

H  H3C
H3C H3C
+ C O  H H2O 4 CH OH + B(OH)3
4 + H Nal Na CH O B
- hydrolysis
H
H H Ethanol
H 4
Acetaldehyde Complex Intermediate
Tetra boron alkoxide .

11 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

H3C
H3C
4 H2O
C O + NaBH4 4 CH OH
H3C
H3C
Acetone 2-propanol
.
NaBH4 is very selective reagent towards reduction of C=O. If other reducible group is
present in substrate, such as C=C then it remains unaffected in reduction reaction.

OH
O
H2O
+ NaBH4 4 H3C C HC CH
4 H3C C HC C + H
H H
H
But-2 ene-1- al H But-2 ene-1- ol
.

b) Reduction of Carboxylic Acids:

Carboxylic acids react with LiAlH4 to form alcohols.

O
H+
+ LiALH4 RCH2OH
R C H2O Alcohol
OH
Acid

O
H+
+ LiALH4 CH3CH2OH
H3C C H2O Ethanol
OH
Acetic Acid

O
H+
+ LiALH4 CH3CH2 CH2OH
H3CH2C C H2O
OH
Propanol
Propanoic Acid

c) Reduction of Esters:
Ester undergoes reduction reaction with LiAlH4 to form two alcohol molecules.

12 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

O
H+
+ LiALH4 RCH2OH + R/OH
R C H2O Alcohol-1 Alcohol-2
OR/
Ester

O
H+
LiALH4 CH3CH2OH + CH3OH
+
H3C C H2O Ethanol Methanol
Methyl acetateOCH3
O
H+
+ LiALH4 CH3CH2CH2OH + CH3OH
H3CH2C C H2O Propanol Methanol
OCH3
Ethyl Acetate

Synthesis of primary, Secondary alcohols from aldehydes and ketones.

13 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

3.6 Reactions of Alcohols

3.6.1 Reaction with Reactive Metal- Reactive metals like Na, K and AL can react with dry
alcohol to form corresponding alkoxide with evolution of H2 gas.
2 R-OH + 2Na (metal)
Alcohol 2 RONa + H2
Sodium Alkoxide
Examples:

CH3OH + 2Na metal 2 CH3ONa + H2

Metanol Sodium Methoxide

C2H5OH + 2K metal 2 C2H5ONa + H2

Potassium Ethoxide
Etanol
The Hydrogen bonded to the O atom in alcohol bear partial positive charge, hence it
can accept electron from the reactive metal (they loss electron very easily) to form H2 gas and
alkoxide. This reaction is an example of acidic nature of an alcohol. Alkoxides are very
strong bases and used as reagents in organic transformations.
Mechanism of reaction

- e
R O R ONa 1/2 H2
Na
H
+ .

3.6.2 Reaction with Carboxylic Acid: Alcohols react with carboxylic acid in presence of
Conc. H2SO4 as catalyst to form ester.
H2SO4
R-OH + R/COOH R/COOR + H2O
Alcohol Carboxylic Ester
Acid
H2SO4
CH3-OH + CH3COOH CH3COOCH3 + H2O
Methanol Methyl Acetate
Acetic Acid

H2SO4
C2H5-OH + CH3COOH CH3COOC2H5 + H2O
Ethanol Acetic Acid Ethyl Acetate
Likely, Alcohols react with carboxylic acid derivatives i.e. anhydrides and acid chlorides to
form ester.

14 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

Reaction with Anhydride

O

H3C C
H2SO4 CH3COOC2H5 + CH3COOH
C2H5-OH + O Ethyl Acetate
Ethanol H3C C

O
Acetic Anhydride
.

Reaction with Acid Chlorides

C2H5-OH + CH3COCl Pyridine CH3COOC2H5 + HCl

Ethanol Acetyl Chloride Ethyl Acetate

3.6.3 Reaction with HX (HCl, HBr): Alcohols react with HCl in presence of anhydrous
ZnCl2 as catalyst to form alkyl halide as a product. Anhydrous ZnCl2-HCl is called Lucas
Reagent.
1. Reaction of primary alcohol with Lukas reagent - The reaction is
slow than secondary alcohol
Anhydrous
C2H5-OH + HCl C2H5Cl + H2O
ZnCl2 Ethyl Chlorid
Ethanol
.

2. Reaction of Secondary alcohol with Lukas reagent - The reaction is

Fast than Primary alcohol
CH3 CH3

H3C OH + HCl Anhydrous

C H3C C Cl + H2O
ZnCl2
H Room temp H
2-propanol 2-Chloropropane
.

3. Reaction of Tertiary alcohol with Lukas reagent - The reaction is

very Fast than Primary and secondary alcohol
CH3 CH3

H3C OH + HCl Anhydrous

C H3C C Cl + H2O
ZnCl2
CH3 Room temp
CH3
t-butyl alcohol t-butyl chloride
.

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Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

Alcohols directly react with HBr to form alkyl bromide. As HBr is more reactive than HCl
catalyst is not required.

1. Reaction of HBr with primary alcohol

C2H5-OH + HBr C2H5Br + H2O

Ethanol Ethyl Bromide

2. Reaction of HBr with Secondary alcohol

CH3
CH3

H3C C Br + H2O
H3C C OH + HBr
H
H
2-Bromopropane
2-propanol

3. Reaction of HBr with Tertiary alcohol

CH3 CH3

H3C C OH + HBr H3C C Br + H2O

CH3 CH3
t-Butyl Bromide
t-butyl alcohol .
Mechanism
H H
H H
+
OH + H Br H3C C O H3C C Br + H2O
H3C C
H
H - H
H Br
Some Secondary and tertiary alcohols undergo rearrangement reaction to form the product.
The alkyl group in the halide does not always have the same structure as the alkyl group in
the parent alcohol. For example:

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Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

The order of reactivity of alcohols toward HX is Tertiary > secondary > primary < CH3OH.
Alcohols directly react with HI to form alkyl Iodide. As HI is more reactive than
HCl, hence catalyst is not required. But with HI many alcohols the yield of product is
very low.

3.6.3 Oxidation of Alcohols:

a) Oxidation with acidic K2Cr2O7: Acidic K2Cr2O7 is strong oxidizing agent. It oxidizes
alcohols to aldehydes and ketones. But reaction can take place further where aldehyde can be
oxidized to carboxylic acid. Thus, before oxidation of aldehyde to carboxylic acid, it must be
removed by special technique.

1. Reaction of dichromate with Primary alcohol

O
O
H
K2Cr2O7 C
K2Cr2O7 C
H3C C OH H2SO4 H3C OH
H2SO4 H3C H

H Acetaldehyde Acetic Acid

Ethanol

2. Reaction of dichromate with Secondary alcohol

O
H
K2Cr2O7 C
H3C C OH
H3C
H2SO4 CH3

CH3 Acetone
2-propanol

3. Reaction of dichromate with Tertiary alcohol

O
CH3
K2Cr2O7 C
H3C C OH
H3C
H2SO4 CH3

CH3 Acetone
T-butyl Alcohol

Reaction of tertiary alcohol take place via formation dehydration i.e. alkene is formed in
between which is then oxidized to ketone.
O
CH3 CH2
+ CO2 + H2O
Dehydration 4[O] C
H3C C OH H3C C Oxidation H3C
CH3

CH3 Acetone
CH3
t-butyl alcohol

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Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

b. Oxidation by KMnO4: Primary alcohols can be oxidized to carboxylic acids, RCOOH,

usually by heating with aqueous KMnO4. When reaction is complete, the aqueous solution
of the soluble potassium salt of the carboxylic acid is filtered from MnO2, and the acid is
liberated by the addition of a stronger mineral acid.
H2 H2O
H3C C OH + KMnO4 CH3COOK + MnO2
Ethanol H+

CH3COOH Acetic Acid

c. Oxidation using PCC reagent: Pyridinium chlorochromate (PCC) is obtained by
reaction of CrO3 with HCl and Pyridine in acetone.

+ CrO3 + HCl

N N CrO3 Cl
Pyridine H PCC reagent

PCC is mild oxidizing agent and reaction stop at aldehyde or ketone stage only.
H O
PCC
H3C C OH H3C C
H
H
t-butyl alcohol Acetaldehyde
.
d. Oppeneauer oxidation: Oppenauer oxidation, named after Rupert Viktor
Oppenauer is a gentle method for selectively oxidizing secondary alcohols to ketones.

The oxidation is highly selective for secondary alcohols and does not oxidize other
sensitive functional groups such as amines and sulfides. The Oppenauer oxidation is
commonly used in various industrial processes such as the synthesis
of steroids, hormones, alkaloids, terpenes, etc.

18 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

3.7. Diols: Pinacol-Pinacolone Rearrangement:

19 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

Part-II: Phenols
Syllabus: Preparation: Cumene hydroperoxide method, from diazonium salts. Reactions:
Electrophilic substitution: Nitration, halogenation and sulphonation. Reimer- Tiemann Reaction,

Houben–Hoesch Condensation.

3.8. Introduction: Organic compounds in which -OH group is directly attached to benzene
ring are called as phenols (phene – benzene, ol – alcohol). Phenols are
acidic in nature, and solids at room temperature.
OH

They can be represented as Ar-OH

Or
Ph-Oh

Phenol .
3.9 Classification: Depending on number of -OH groups phenols are classified as
monohydric, dihydric, tri-hydric phenols. -OH is functional group.
Monohydric Phenols Dihydric Phenols Tri-hydric phenols
OH OH
OH
Phenol Phloro-
OH
Catecol glucinol

HO OH

OH OH OH

OH Pyrogallol
Alfa- Resorcinol or
napthol Benzene 1,2,4
triol
OH
OH

OH OH

OH Benzoquinone OH
or quinol Benzene 1,2,4
triol

OH OH
Beta-napthol
3.10. IUPAC Nomenclature of Phenols:
i. The structure of phenol is considered as basic structure.
ii. The carbon atom to which -OH group is bonded is labelled as carbon-1, then either from
left side or right-side carbons are labelled subsequently as 2 to 6.
iii. Alternatively carbon atoms are labelled as- ortho, meta and para. Caron adjutant to -OH
group on both sides are labelled as ortho i.e. carbon no-2. Caron next to ortho position are
labelled as meta i.e. carbon no-3. Carbon opposite to -OH position is labelled as para.

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Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

OH OH OH

1 1 Ortho position Ortho position

6 2 6
2
or
Meta position Meta position
5 3 5
3
4 4 Para position
.
iv. In assigning the name to phenol then name of group and position of group is indicated
before the word ‘phenol’. Examples are given below
OH OH OH OH

NO2 1 CH3 Br COOH

2-nitro phenol 2-methyl phenol 2-Bromo phenol

2-hydroxy benzoic acid
or or or or
O-Nitro Phenol O-methyl phenol O-bromo Phenol O-hydroxy benzoic acid
(O-cresol) (Salicylic acid)
OH OH OH OH

NO2 CH3 Cl CHO

3-nitro phenol 3-methyl phenol 3-chloro phenol 3-hydroxy benzaldehyde

or or or or
M-Nitro Phenol M-methyl phenol M-chloro Phenol m-hydroxy benzaldehyde
(M-cresol)
OH OH OH OH

1 1 1 1
2 2 2 2

3 3
3 3
4 4
4 4
NO2 CH3
I OC2H5
4-nitro phenol 4-methyl phenol 4-Iodo phenol 4-hydroxy ethyl benzoate
or or or or
p-Nitro Phenol p-methyl phenol p-Iodo Phenol m- hydroxy ethyl benzoate
(P-cresol)
OH OH

O2N
1 NO2 1 CH2
6 2 2

4 3 Cl
NO2 2-benzoyl,3-chloro-phenol
2,4,6 trinitro-phenol
3.11 Characteristics of Structure of Phenol
21 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44
Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

Benzene ring is planar due to sp2 hybrid C atoms. O of -OH group lie
109 28" in plane of benzene ring but -H is out of this plane. This is due to sp3
H
hybridization of O atom. In phenol -OH group is bonded to benzene
O ring. ‘O’ of -OH group is sp3 hybrid hence bond angel at O atom is
109˚28”. C – O bond length is 136 pm which is slightly less than C – O
136 pm
bond length in methanol. This is due to partial double bond character
Phenol in this bond in phenol. The lone pair O can be delocalised between C
and O due to resonance effect.
3.12 Preparation of Phenols
3.12.1 Dow Process: In this method chlorobenzene is used as starting material.
Chlorobenzene is heated with excess aqueous solution of NaOH at 340 ˚C and 300 atm.
pressure. In first step sodium phenoxide is obtained as product which is water soluble.
When this aqueous solution is acidified water insoluble phenol is obtained as a product.
Cl O Na OH

Aq. NaOH HCl

+ 340 C, 300 atm.

Or Pass CO2 gas

.
Chlorobenzene Sodium phenoxide Phenol

2.12.2 From Cumene: Most of the phenol is obtained by this method. In first step,
Cumene (Isopropyl benzene) is oxidized to cumene hydropeoxide. Oxidation is achieved by
using O2 and cobalt naphthenate as a catalyst. In second step, cumene hydropeoxide is heated
in presence of H2SO4 which yield phenol.
CH3 CH3

OH
H3C C H H3C C O OH
O

H2SO4
O2 + C
+ Heat H3C CH3
Co-Naphtheanate
150 C
Chlorobenzene Phenol Acetone
.
Cumene hydroperoxide

3.12.3 From Benzene diazonium salt: Aniline undergoes diazotization reaction with
nitrous acid. The hydrolysis of nitrous acid in acidic medium produce phenol as a product.
NH2 N N Cl OH

H2O
NaNO2 + HCl
H2SO4

Aniline Benzene diazonium Chloride Phenol

.
3.13. Reactions of Phenol:
3.13.1. Acidic nature of phenol and formation of Phenoxide ion: Alcohol is
acidic in nature. It acts as a weak acid. This due to incomplete dissociation of -OH group to
produce phenoxide ion and H+. The dissociation of O-H bond is facilitated by delocalization
of lone pair of electron O by resonance effect.

22 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

H
O O

Dissociation of phenol to form phenoxide ion

+ H+

O O O
O O

Resonance Stabilization of phenoxide ion

.
3.13.2 Electrophilic substitution:
a) Halognation: i) When Phenol is treated with Br2 in CS2 mixture of O-bromo phenol
(minor product) and P-bromo phenol (major product) is obtained as
product.
OH
OH OH

Br
CS2 + 2HBr
+ Br2 +

O-bromo phenol P-bromo phenol

Phenol Br
.
ii) When Phenol is treated with Br2 in water then 2, 4, 6-tribromo phenol is obtained as
product.
OH OH

Br Br

Water +
+ Br2 3HBr

2,4,6 tri-bromo phenol

Phenol
Br
b) Nitration: i) When Phenol is treated with dilute HNO3 mixture of O-nitro phenol
(major product) and P-nitro phenol (minor product) is obtained as product.
OH OH OH

NO2

+ dil. HNO3 +

Phenol O-nitro phenol P-nitro phenol

NO2
.
By steam distillation mixture of o- and p-nitrophenol is separated. O-nitrophenol is pass
along with steam as it has less boiling point. This is due to intramolecular hydrogen bonding in
o-nitrophenol. P-nitrophenol is high boiling as it shows intermolecular hydrogen bonding.

23 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

i) When Phenol is treated with conc. HNO3 mixture of 2,4,6-tri-nitro phenol is obtained as
product.
OH OH

O2N NO2

+ Conc. HNO3

Phenol 2,4,6 tri-nitro phenol

.
NO2

b) Sulfoation: i) When Phenol is treated with conc. H2SO4 at room temperature then
O- phenol sulfonic acid is obtained as product.
OH OH

SO3H

+ Conc. H2SO4 + H2O

written as
HO-SO3H
Phenol O- phenol sulfonic acid .

ii) When Phenol is treated with conc. H2SO4 at 100 ˚C, then P- phenol sulfonic acid is
obtained as product.
OH OH

+ Conc. H2SO4 + H2O

written as
HO-SO3H 100 oC
P- phenol sulfonic acid
Phenol
SO3H
.
Mechanism of electrophilic substitution reaction:
Electrophile is a electron deficient chemical species and it bears +ve charge.
Br2, HNO3 and H2SO4 generate electrophiles as follows:
+ - - +
Can be
Br Br Br Br NHO3 written HO NO2 HO NO2
as
Electrophile Electrophile
- +
Can be HO SO3H
H2SO4 written HO SO3H
as
Electrophile
.
Mechanism of reaction:
OH OH OH
H Br
H Br
+ -
Br + HBr
Br Br

.
Like, this reaction, HNO3 and H2SO4 also react with phenol to form the respective
products.
24 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44
Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

3.13.3. Reimer- Tiemann Reaction: Phenols react with chloroform in presence of

NaOH to form phenolic aldehyde. Reaction take place at ortho position.
OH ONa OH
ONa
H CHCl2 CHO
CHO
NaOH NaOH H+
+ CHCl3

Phenol Salicylaldehyde .

3.13.4. Houben–Hoesch Condensation,

The Hoesch reaction or Houben–Hoesch reaction is an organic reaction in which
a nitrile reacts with an arene compound to form an aryl ketone. The reaction is a type
of Friedel-Crafts acylation with hydrogen chloride and a Lewis acid catalyst.
The synthesis of 2,4,6-Trihydroxyacetophenone (THAP) from phloroglucinol is
representative: If two-equivalents are added, 2,4-Diacetylphloroglucinol is the product.

Part-III: Ethers
3.14. Definition: Ethers are the compounds in which two alkyl or aryl or one alkyl and
one aryl group is bonded to the O atom. They can be considered as alkoxy or arloxy
derivatives of alkanes. Ethers are low boiling liquids at room temperature.
General formula: R – O – R or Ar – O – Ar, or R – O – Ar
Examples:
H3C O CH3 C2 H 5 O CH3 C2H5 O CH2CH2CH3
Dimethy ether Methy Ethy ether Methy n-propyl ether
IUPAC - Methoxymethane IUPAC - Methoxyethane IUPAC - 1-Methoxpropane

O CH3 O C2H5 Br O C2H5

Methy phenyl ether Ethhyl phenyl ether Ethyl4-bromo- phenyl ether

IUPAC - Methoxbenzene IUPAC - Ethoxbenzene IUPAC - 1-Ethox 4-bromobenzene .

25 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

Physical Properties: Ethers are low boiling liquids at room

temperature. They neutral compounds and mainly used as solvents in 141 pm
O
organic synthesis, for purification of organic compounds, solvent
extraction of natural products and organic compounds, etc. At ‘O’ atom H3C 111.7o CH3
structure is angular. This is due to sp3 hybridization of O atom. The C-O- Dimethyl ether
C bond angle is usually larger than tetrahedral bond angle (111.7˚ in
dimethyl ether) which is due to repulsion between alkyl groups.
Metamerism: Ether having same molecular formula but H3C-O-CH2CH2CH3
different alkyl groups bonded to O atoms are called as metamers. and
Metamers are either chain isomers or position isomers H3C-H2C- O-CH2CH3

Chain isomerism: In chain isomerism Alkyl group have H3C-O-CH2CH2CH3

different structure and
CH3
H3C O CH
CH3

3.14. Synthesis:
3.14.1 From Alcohols: Alcohols undergo dehydration on heating in presence of conc.
H2SO4 to form ether.
Conc. H2SO4
2 C2H5 OH C2H5 O C2H5
Ethanol 100 oC Diethy ether .
3.14.2 From Alkyl Halides (Williamson Synthesis): Alkyl halide react with sodium
ethoxide to form the ethers. Simple as well as mixed ethers can be prepared in laboratory by
Williamson Synthesis.
Alcohol
C2H5 ONa + Br C2H5 C2H5 O C2H5
sodium Ethoxide Heat Diethy ether .
ONa O CH3
OH
CH3Br
+ alcoholic NaOH

Phenol Sodium Phenoxide Methyl phenyl ether .

2
This reaction follows SN mechanism. Ether is formed as a result of backside attack by
alkoxide/ phenoxide ion (a nucleophile) on alkyl halide.
H3C H
H
Alcohol H C O C
C Br 3
H3 C O H
H CH3
Methy ethyl ether
Ethyl Bromide
The alkyl halide used in this reaction must be primary. For example: t-butyl methyl
ether can be synthesised by reaction of methyl bromide with sodium t-butoxide.

26 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

H3C H H3C
Alcohol
C O C Br C O CH3
H3C H
H3C
H3C H H3C
t-butoxide Mehyl Bromide Methy t-butyl ether
.
Aryl halide do not form ether with alkoxide. Since aryl halide undergo electrophilic
substitution reaction at benzene ring other than halide position.
3.15: Reactions of ethers: Cleavage of ethers with HI- Depending on reaction
condition, ether give alkyl halide and alcohol or alkyl halide only with HI.
In cold condition ether yield one molecule alkyl halide and one molecule of alcohol.
In hot condition ethers yield two molecules of alkyl halide.
Cold C H I + C H OH
2 5 2 5
ethyl iodide ethyl alcohol
C2H5 O C2H5 + HI
Diethy ether Hot 2 C2H5I + H2O
ethyl iodide .
Phenyl alkyl ether always give phenol and alkyl halide as Ar-O bond is stronger.
O CH3 OH

+ CH3I
+ HI
Methyl iodide
Methyl phenyl ether Phenol
.

Historically, the outbreak World War I provided a stimulus for the industrial
preparation of large amounts of synthetic phenol, which was needed as a raw material to
manufacture the explosive, picric acid (2,4,6- rinitrophenol). Today, approximately 8 million
metric tons of phenol is manufactured worldwide each year for use in such products as
Bakelite resin and adhesives for binding plywood. Most of the phenol is prepared by
oxidation of cumene.

27 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

Mechanism of Cumene Oxidation to form phenol

28 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44