ETHERS AND

EPOXIDES
B Y S H I N TA N O V I TA S A R I
Ethers and Epoxides

By Shinta Novita Sari

2
 Ethers
Ether is a class of organic compounds that contain an
ether group R–O–R.

For the simplest ether, Dimethyl ether

Classification of Ethers
(I) Aliphatic Ethers (II) Aromatic Ethers

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BOND ANGLES AT OXYGEN ARE SENSITIVE
TO STERIC EFFECTS

O O
H H CH3 H
105° 108.5°

O O
CH3 CH3 (CH3)3C C(CH3)3

112° 132°
Types of Ethers

1- Simple Ethers or Symmetrical Ethers

2- Mixed Ethers or Unsymmetrical Ethers

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NAMING ETHERS
• Common names are used frequently:
1. Name each –R group.
2. Arrange them alphabetically.
3. End with the word “ether.”
 Nomenclature
Common Names
The two-alkyl groups bonded to the functional group (- O -) are
written alphabetically followed by the word ether.

Examples:

7
NAMING ETHERS
• IUPAC systematic names are often used as well:
1. Make the larger of the –R groups the parent chain.
2. Name the smaller of the –R groups as an alkoxy substituent.
IUPAC System
The shorter alkyl group and the oxygen are named as
an alkoxy group attached to the longer alkane.
They are named as alkoxyalkanes.

Examples:

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 5-Chloro-3-ethoxy-hex-1-ene

Methoxybenzene
P-Methoxytoluene

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 Physical Properties
Boiling Points of Ethers:

hydrogen bonds cannot form between ether molecules

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ETHERS RESEMBLE ALKANES MORE THAN ALCOHOLS
WITH RESPECT TO BOILING POINT

boiling point

36°C Intermolecular hydrogen

bonding possible in
alcohols; not possible
35°C in alkanes or ethers.
O

117°C
OH
 Solubility of Ethers:

Ethers are soluble in water, due to their hydrogen bond

formation with water molecules.

The solubility decreases with increase in the number of carbon atoms.

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ETHERS RESEMBLE ALCOHOLS MORE THAN ALKANES
WITH RESPECT TO SOLUBILITY IN WATER

solubility in water (g/100 mL)

very small

O 7.5 Hydrogen bonding to

water possible for ethers
and alcohols; not
9 possible for alkanes.
OH
 Preparation of Ethers
1- Dehydration of Alcohols

140 ⁰C

Example:

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 The dehydration of 2° and 3° alcohol is unsuccessful
to get ethers as alkenes are formed easily.

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 2- Williamson Synthesis
 The reaction of a sodium alkoxide RONa or a sodium
phenoxidex ArONa with an alkyl halide to form an ether.
 The reaction involves nucleophilic substitution of an alkoxide ion
for a halide ion.

Examples:

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MECHANISM
Mechanism for the Williamson Synthesis = SN2

RDS
R O + R' X R O R' + X

R´-X should be CH3 or 1o

P R EPA RATION OF ET H ER S

• Williamson ether synthesis

•Metal alkoxides react with primary alkyl halides by an

SN2 pathway to yield ethers.
•Secondary and tertiary substrates react following an
E2 mechanism

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M ECH A NISM 2 : W I L L IAM SON ET H ER SY NT H ESI S

OH NaH O – Na+ O
THF
+ CH3CH2----I + NaI
THF
+ H2

O THF O– Na+
H
+ Na+ H-
CH3CH2----I

+ H2

NaI +

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 If a secondary ( 2°) or tertiary alkyl halide ( 3°) is used,
an alkene is the only reaction product and no ether is
formed.

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WHAT IF THE ALKYL HALIDE IS NOT PRIMARY?
S N 2 VS E2

CH2ONa + CH3CHCH3

Br

CH2OH + H2C CHCH3

Elimination produces
the major product.
 Reactions of Ethers
Cleavage of Ethers by Acids
Substitution Reactions with strong acids HX,
X could be; I or Br.
Ethers are cleaved by HX to an alcohol and a haloalkane

Examples:

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M ECH A NISM 1 : A CI D CATA LY ZED SY NT H ESI S O F ET H ER S

HCl
OH O +
2 H3 O+ + Cl-
130 C

O
H H
H H O
OH H---Cl O+
H H
O+
+ Cl -

H3O+ + O

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 Point of cleavage:
 If both the alkyl groups are primary or secondary, the smaller
alkyl group gets converted to the alkyl halide predominantly.

 If one of the alkyl group is tertiary, the point of cleavage

is such that the tertiary alkyl halide is formed as the major
product

 If two or more equivalents of acid are used further dehydration

can occur on formed alcohols which may react further to form a second
mole of alkyl halide.

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Mechanism
H
1) CH3CH2 O CH2CH3 + HX CH3CH2 O CH2CH3 + X

H S N2
2) X + CH3CH2 O CH2CH3 CH3CH2 X + HO CH2CH3

3) CH3CH2 OH + HX CH3CH2 OH2 + X

S N2
4) CH3CH2 OH2 + X CH3CH2 X + H2O
 Epoxides (Cyclic Ethers)
Epoxide: a cyclic ether in which oxygen is one atom of
.a three-membered ring

Nomenclature
Although cyclic ethers have IUPAC names, their common
names are more widely used.
IUPAC: prefix ox- shows oxygen in the ring
the suffixes -irane, -etane, -olane, and -ane show three,
four, five, and six atoms in a saturated ring.

2 3 O

1O O O O O
Oxirane Oxetane Oxolane Oxane 1,4-Dioxane
(Ethylene oxide) (Tetrahydrofuran) (Tetrahydropyran) 29
 Preparation of Epoxides
The simplest and the most important epoxide is ethylene oxide.

1. Air Oxidation of Ethylene

By air oxidation of ethylene and silver oxide catalyst.

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2. Dehydration of dialcohols

Examples:

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3-Conversion of Vicinal Halohydrins to Epoxides

Examples:

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 4. Epoxidation method
Epoxides are often prepared from reacting with organic peroxy acids
(peracids) ex; CH3C(O)OOH in a process called epoxidation.

Example:

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 Reactions of Epoxids

Epoxides are highly strained and easily undergo

ring-opening reactions under both acidic and basic conditions.

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REAKSI PEMBUKAAN CINCIN EPOKSIDA
• The three-membered ring of epoxides is highly strained and undergoes
ring-opening reactions with a variety of nucleophiles, as shown below.
Reactions of Epoxids

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REAKSI BERKATALISIS ASAM
M ECH A NISM 2 : W I L L IAM SON ET H ER SY NT H ESI S

OH NaH O – Na+ O
THF
+ CH3CH2----I + NaI
THF
+ H2

O THF O– Na+
H
+ Na+ H-
CH3CH2----I

+ H2

NaI +

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AN OXYGEN ATOM AFFECTS GEOMETRY IN MUCH THE
SAME WAY AS A CH 2 GROUP

most stable conformation of diethyl ether

resembles pentane
AN OXYGEN ATOM AFFECTS GEOMETRY IN MUCH THE
SAME WAY AS A CH 2 GROUP

most stable conformation of tetrahydropyran

resembles cyclohexane
STEREOCHEMISTRY / OPTICAL ACTIVITY
EPOXIDATION STEREOCHEMISTRY

• Epoxidation forms a racemic mixture because reaction

occurs with equal probability on either face of the
double bond.
 ENANTIOSELECTIVE EPOXIDATION
• In order to have an optically active product, one of the
reactants, or reagents, or catalyst in a reaction must be
chiral.
• An example is a Sharpless catalyst, which forms such a
chiral complex that favors the formation of one
enantiomeric epoxide versus the other.
• Catalyst:
 ENANTIOSELECTIVE EPOXIDATION
• The desired epoxide can be formed in excess by choosing
the appropriate catalyst. Note the position of the –OH
group.

• SEE: CONCEPTUAL CHECKPOINT

14.16.