Chapter 8 - Alcohols, Ethers and Epoxides LMS v2

PHYSICAL AND ORGANIC CHEMISTRY
Alcohols, Ethers and Epoxides
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Last Updated:
Wednesday, November 11, 2020
Introduction
• Alcohols are compounds of the general formula R-OH , where R
is an substituted alkyl group.
• The group may be primary,secondary,or tertiary, It may be open
chain or cyclic, it may contain a double,a halogen atom, an
aromatic ring, or additional hydroxyl groups.
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Introduction
• Alcohols can be thought of as org.

derivatives or water in which one or both
of the water hydrogens are replaced by an
org. substituent (H-O-H becomes R-OH).
• Alcohols occur widely in nature and have
many industrial and pharmaceutical
applications.

Classification of Alcohols
• We classify a C atom as 1 º, 2 º or 3 º according to the

number of other C atoms attached to it.An alcohol is
classified according to the kind of C that bears the –OH
group.

Classification of Alcohols

Nomenclature of Alcohols
• Alcohols are named by 2 principal systems,common

names and the IUPAC names.
• Common names sometimes called trivial names.
• In IUPAC, as discussed in the previous chapters

(alkanes, alkenes, alkynes, alkyl halides), the longest
continuous C chain that contain then –OH group is
selected to be the parent structure. The name is derived
by replacing the terminal.

• -ane of alkanes is replaced by –ol.

• The position of the –OH group in the parent chain, generally
using the lowest possible number.
• The other groups attached to the parent chain is indicated by
number according to the –OH group.

• An alcohol containing a double bond is named as an alkenol, with
numbers to indicate the positions of the double bond and the hydroxyl (-
OH ) group.
• Note that –ol takes priority over –ene;-ol appears last in the name,
and,where possible, is given the lower number.

Differences Between Common Names and
IUPAC Names.
Common names IUPAC names
Ethyl alcohol Ethanol
Methyl alcohol Methanol
N-propyl alcohol 1-propanol
Isopropyl alcohol 2-propanol
Sec-butyl alcohol 2-butanol
Tert-butyl alcohol 2-methyl-2-propanol
Isobutyl alcohol 2-methyl-1propanol
Benzene alcohol Phenyl methanol
Allyl alcohol 2-propen-1-01
Alpha –phenyl ethyl alcohol Phenyl ethanol
P-nitrobenzyl alcohol 4-Nitro phenylmethanol
Tert-phenyl alcohol 2-methyl-2-butanol

Physical Properties of Alcohols
• Alcohol, R-OH,contains lipophilic group (alkane-like
group, R-) and hydrophilic group (water-like hydroxyl
group, -OH).
• Of these two groups, it is the –OH group that gives the
alcohol its characteristic physical properties and the alkyl
group that, depending upon its size and shape, modifies
the properties.
• It is a polarized covalent compounds.

hydrophilic
Lipophilic
R-OH
Organic solvent Water soluble
soluble
+ -
R OH } To show the polarity of

hydroxyl (-OH) group

• Alcohols show increase in b.p with increasing C number,
and decrease in b.p with branching. The b.p of alcohols
is usually higher than many other hydrocarbon of the
same corresponding carbon.
• Most of alcohols also behave as solutes that reflects
their ability to form H bond.
• The lower alcohols are miscible with water
• As the lipophilic alkyl group becomes longer, water
solubility of alcohol decreases.

• Due to the ease of hydrogen bonding formation of

alcohols, it also widely use as a solvent.
• Through their lipophilic alkyl group, they can also
dissolve non –ionic compounds: organic substrates. And
though their -OH groups, they can dissolve ionic
compounds:inorganic reagents

Industrial Source of Alcohols
• Alcohols are the important starting materials in

aliphatic chemistry.
• These are 3 principal ways to get simple alcohols
that are backbone of aliphatic org. synthesis.
• These methods are:
 By hydration of alkenes obtained from the cracking of
petroleum
 by fermentation of carbohydrates.

Preparation of Alcohols
@ Alcohols Synthesis
Preparation of Alcohols:Overview
• Alcohols are derived from many types of compounds

• The alcohol hydroxyl can be converted to many other
functional groups
• This makes alcohols useful in synthesis

1) Synthesis of Alcohols From Alkenes
Hydration of Alkenes
General
Equation:
• Water adds to the more reactive alkenes in the presence of acids to

yield alcohol.
• This addition follows MR.
• Example:

General Equation: OH
H2SO4 H2O
R-CH=CH2 R-CH-CH3 R-CH-CH3
H2O +
H
OSO3H

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2) Synthesis of Alcohols From Alkyl Halides
Hydrolysis of Alkyl Halides
General equation:

3) Synthesis of alcohols by reduction of
carbonyl compounds
Intro: Synthesis of alcohols by reduction of
carbonyl compounds
General equation of reduction of carbonyl compounds

to alcohols can be presented as below.

Alcohols from Reduction of Carbonyl
Compounds
• Reduction of a carbonyl compound in general gives an
alcohol
• Aldehydes gives primary alcohols

• Ketones gives secondary alcohols
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Reduction of carbonyl compounds
Aldehydes can be reduced to primary alcohols and ketones to secondary

alcohols, lithium aluminum anhydride, LiAlH4 and sodiumborohydride, NaBH4.
Reduction of an aldehyde gives primary alcohol

O
NaBH4
C H CH2OH
benzaldehyde benzyl alcohol

Reduction of a ketone gives a secondary alcohol
H
O
NaBH4
OH
cyclohexanone cyclohexanol
Reduction of Aldehydes/ Ketones

Mechanism of Reduction
• The reagent adds the equivalent of hydride to the carbon

of C=O and polarizes the group as well
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Reduction of Carboxylic Acids and Esters
• Carboxylic acids and esters are reduced to give primary

alcohols
• LiAlH4 is used because NaBH4 is not effective

4) Preparation of Alcohols by Using
Grignard Reagent/Grignard Synthesis
Reaction of GR With Formaldehyde

Reaction of GR With Higher Aldehydes
Reaction of GR With Ketones
Alcohols from Reaction of Carbonyl
Compounds with Grignard Reagents
• Alkyl and aryl halides react with magnesium in ether or
tetrahydrofuran to generate Grignard reagents, RMgX
• Grignard reagents react with carbonyl compounds to
yield alcohols
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Preparation of Alcohols by Using Grignard Reagent/Grignard Synthesis

Grignard Synthesis of Alcohols
• One of the most important uses of the GR lies in its reaction with
aldehydes and ketones.
• The C-Mg bond of the GR is a highly polar bond, R-MgX.
• GR acts as a nucleophilic reagent to carbonyl compounds.

Grignard Synthesis of Alcohols
• Grignard synthesis is so important due to its ability to

take two organic molecules and convert them into a
bigger one.

Product of the Grignard synthesis
• The class of alcohol that is obtained from a Grignard

synthesis depends upon the type of carbonyl compound
used: formaldehyde, HCHO, yields primary alcohol;
other aldehydes, RCHO yield secondary alcohols; and
ketones, R2CO, yield tertiary alcohols.



Reaction of GR with formaldehyde

Reaction of GR With Higher Aldehydes

Reaction of GR with ketones

5) Preparation of Alcohols by
Hydrogenation of Aldehydes And Ketones
General equation:
O OH
Aldehyde: R-C-H + H2
Pt/Ni/Pd
R-C-H ROH 1°
H
Ketone:
O OH
Pt/Ni/Pd ROH 2°
R-C-R + H2 R-C-R

Example:
Ni
CH3CH=CHCHO + 2H2 CH3CH2CH2CH2OH
2-butenal butanol
H OH
O
H2 / Ni
cyclopentanone cyclopentanol

Reaction of Alcohols
1) Reaction of Alcohols:
Cleavage of the O------H Bond
Cleavage of the C---------oh Bond
Intro: Reaction of Alcohols
• Alcohols reaction take into account of a bond cleavage;

C-OH or O-H cleavages.
• Alkoxides formation (from alcohols) and esterification of
alcohols are belong to the O-H cleavage reaction. While,
the reaction of alcohols with alkyl halides, dehydration
and oxidation are belong to the C-OH cleavage reaction.

Cleavage of the O------H Bond
a) Reaction With Active Metals in the

Formation of Alkoxides
B) Esterification Reaction
Reaction of alcohols: cleavage of the O------H
bond

a) Reaction With Active Metals in the Formation of Alkoxides
Alcohols acts as an acid in this particular reaction.

The acidity of alcohols is shown by their reaction with active metals (Na, K,
Mg, Al, etc) to liberate hydrogen gas and alkoxides.

a) Reaction With Active Metals in the Formation of
Alkoxides
The alkoxides formed are strong base and used in the preparation of ether
(ROR).
Example:
Na
1. CH3CH2OH CH3CH2O-Na+ + 1/2H2
Ethyl alcohol Sodium ethoxide
CH3 H3C
Al
2. CH3 C OH CH3 C O-Al+
H H
Isopropyl alcohol aluminium isopropoxide
H3C
3. CH3
K
CH3 C OH CH3 C O-K+
CH3 CH3
Tert-butyl alcohol Potassium tert-butoxide
Esterification Reaction
• A carboxylic acid, RCOOH, is converted directly into

an ester when heated with an alcohol in the presence
of a little mineral acid, usually H2SO4 or HCl.
• This reaction is reversible and generally reaches
equilibrium when there are appreciable quantities of
both reactants and products present.

Esterification reaction
• For modest and mild reaction condition, especially in

pharmaceutical and cosmetic industries, enzyme is used
in replacement of minerals acids; native lipases and
immobilized lipases (Novozyme 435, Lipozyme, etc.)

Esterification reaction

2) Reaction of alcohols:
Cleavage of the C---------OH bond
a) Reaction With Hydrogen Halides

b) Dehydration of Alcohols
c) Oxidation of Alcohols
2) Reaction of alcohols:
Cleavage of the C---------OH bond

General equation

• This reaction requires the presence of acid into the

actual substrate.
• The protonated alcohol readily loses the weakly basic
water molecule.

General equation
Simple mechanism:


Can be accomplished by inorganic reagents, such as

KMnO4, CrO3, and Na2Cr2O7 or by more selective,
expensive reagents
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• Oxidation of primary alcohol to aldehyde: pyridinium

chlorochromate (PCC, C5H6NCrO3Cl) in dichloromethane
• Other reagents produce carboxylic acids for primary
alcohol
Examples:

Ethers and Epoxides
Ethers
Introduction of Ethers
• Ethers are compounds of the general formula R-O-R, Ar-

O-R, or Ar-O-Ar.
• Two organic compounds (alkyl, allyl and/or benzyl) are
bonded to the same oxygen atom.
• They are a structural isomers of alcohol.

Introduction of Ethers

Structure and Nomenclature of Ethers
• To name simple ethers, we usually name the two groups

that are attached to oxygen, and follow these name by
the word ether.


• To name more complex ethers that more than one

ether linkage is present in the molecule or if other
functional groups are present, the ether group is
considered as an alkoxy substituent on the parent
compound.


Special Name of Ether

Preparation of Ethers
Williamson Synthesis
Preparation of Ethers: Williamson Synthesis
• It can be used to make unsymmetrical ethers as well

as symmetrical ethers.

H H
-
(CH3)2C OH + NaH (CH3)2C O Na+ + H2
Alkoxide ion

H H
-
(CH3)2C O Na+ + CH3CH2CH2 Br (CH3)2C OCH2CH2CH3
+ Na+ Br-
The alkoxide ion reacts with the substrate in an SN 2 reaction, with

the resulting formation of an ether. The substrate must bear a good
leaving group. Typical substrates are alkyl halides, alkyl sulfonates,
and dialkyl sulfates
-L = -Br, -I , OSO2R”, or OSO2OR”


The use of 3º RX will finally produce alkene but not ether.


Reaction of Ethers
Cleavage of Ethers by Strong Acid (or

Acidic Cleavage)
Cleavage of Ethers by Strong Acid
CH3CH2-O-CH2CH3 + HBr CH3CH2Br + CH3CH2OH
HBr
CH3CH2Br
Simple equation:
CH3CH2-O-CH2CH3 + 2HBr 2CH3CH2Br

Epoxides
Epoxides: the Cyclic Ethers
Generally, epoxides are compounds containing the 3-

membered ring.
The one group of cyclic ethers that behave differently from
open-chain ethers is the group of 3-membered ring
compounds called epoxides or oxiranes.

Nomenclature of Epoxides
• The suffix –oxirane is used.

• Oxygen is numbered with the lowest number.

Molecule Common Name IUPAC Name
Ethylene Oxide Oxirane

H2C CH2
O
Propylene Oxide 2-Methyloxirane

H2C CHCH3
O

2,3-Epoxybutane 2,3-
CH3 CH3 Dimethyloxirane
Styrene Oxide 2-Phenyloxirane
H2C
O
1,2- 2,3-
Epoxycyclohexane Cycloheyloxirane
O

Preparation of Epoxides
1. Industrial Synthesis of Epoxides

2. Peroxidation of Carbon-carbon
Double Bonds
Industrial Synthesis of Epoxides
• By far, the most important epoxides is the simplest one,

ethylene oxide. It is prepared in industrial scale by
catalytic oxidation of ethylene by air.

Peroxidation of Carbon-Carbon Double Bonds

A mechanism for the reaction
C O R
+ O C
C
H O
Alkene Peroxide acid
The peroxy acid transfers an oxygen atom to the alkene in a cyclic,

single-step mechanism. The result is the syn addition of the oxygen
to the alkene, with the formation of an epoxide and a carboxylic acid

O R
C
C
O +
C O
H
Epoxide Carboxylic acid

Reactions of Epoxides
•Reaction of Epoxides With HX

Catalyzed by Acid (H+)
•Reaction of Epoxides With Dilute Acid
and H2O
•Reaction of Epoxides With Base
•Reaction of Epoxides With Grignard
Reagents
Reaction of Epoxides With HX Catalyzed by
Acid (H+)
X
C C + HX C C
O OH

Reaction of Epoxides With Dilute Acid and H2O
OH
H 2o
C C + H
+
C C
O OH

Reaction of Epoxides With Base
OH
H 2o
C C + NaOH C C
O OH
CH3 OH
CH3 CH3
H 2o CH3C CH3
C C + NaOH C
CH3 CH3 H
O OH H

Reaction of Epoxides With Grignard Reagents

References
• IUPAC. Compendium of Chemical

Terminology, 2nd ed. (the "Gold
Book"). Compiled by A. D. McNaught
and A. Wilkinson. Blackwell Scientific
Publications, Oxford (1997).
• Solomons, T. W. Graham and Fryhle,
Craig B. (2004). Organic Chemistry. 8th
Edition. John Wiley & Sons, Inc.
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PHYSICAL AND ORGANIC CHEMISTRY

Alcohols, Ethers and Epoxides

Last Updated: © I-Station Solutions Sdn Bhd 2

• Alcohols can be thought of as org.

Last Updated: © I-Station Solutions Sdn Bhd 3

• We classify a C atom as 1 º, 2 º or 3 º according to the

Last Updated: © I-Station Solutions Sdn Bhd 4

Last Updated: © I-Station Solutions Sdn Bhd 5

• Alcohols are named by 2 principal systems,common

• Common names sometimes called trivial names.

• In IUPAC, as discussed in the previous chapters

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• -ane of alkanes is replaced by –ol.

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Methyl alcohol Methanol

N-propyl alcohol 1-propanol

Isopropyl alcohol 2-propanol

Sec-butyl alcohol 2-butanol

Tert-butyl alcohol 2-methyl-2-propanol

Isobutyl alcohol 2-methyl-1propanol

Benzene alcohol Phenyl methanol

Allyl alcohol 2-propen-1-01

Alpha –phenyl ethyl alcohol Phenyl ethanol

P-nitrobenzyl alcohol 4-Nitro phenylmethanol

Tert-phenyl alcohol 2-methyl-2-butanol

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R OH } To show the polarity of

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• Due to the ease of hydrogen bonding formation of

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• Alcohols are the important starting materials in

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• Alcohols are derived from many types of compounds

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• Water adds to the more reactive alkenes in the presence of acids to

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General equation of reduction of carbonyl compounds

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• Aldehydes gives primary alcohols

Aldehydes can be reduced to primary alcohols and ketones to secondary

Reduction of an aldehyde gives primary alcohol

benzaldehyde benzyl alcohol

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• The reagent adds the equivalent of hydride to the carbon

• Carboxylic acids and esters are reduced to give primary

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Reaction of GR With Formaldehyde

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• Grignard synthesis is so important due to its ability to

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• The class of alcohol that is obtained from a Grignard

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