SSCK1603

Alcohol & Phenol

Week 9

Ether & Epoxide

Assoc. Prof. Dr Shajarahtunnur Jamil

Department of Chemistry
Faculty of Science
UTM
Semester I 20202021

23/12/2020 1
 Introduction
 General formula: R-O-R’ , where R/R’ = alkyl or aryl
 Symmetry if R = R’
 Unsymmetry if R ≠ R’

O OCH3
H3C O CH3

O
H3C O CH2CH2CH3
 Structure and Polarity
 Bent molecular geometry
 Oxygen is sp3 hybridized
 Tetrahedral angle
 Boiling Points
Similar to alkanes of comparable molecular weight.
 Hydrogen Bond Acceptor

 Ethers cannot formed

hydrogen-bond to each
other.
 In the presence of
-OH or -NH (donor), the
lone pair of electrons from
ether forms a hydrogen
bond with the -OH or -NH.
 Solvent Properties
 Nonpolar solutes dissolve better in ether than in
alcohol.
 Ether has large dipole moment, so polar solutes
also dissolve.
 Ethers solvate cations.
 Ethers do not react with strong bases.
 Common Names of Ethers

 Alkyl alkyl ether

 Current rule: alphabetical order
 Old rule: order of increasing complexity
 Symmetrical ethers: use dialkyl

CH3
CH3CH2 O CH2CH3 CH3 O C CH3
diethyl ether
CH3
t-butyl methyl ether
 IUPAC Names
 Alkoxy alkane

CH3 OCH3
CH3 O C CH3
CH3
Methoxycyclohexane
2-methyl-2-methoxypropane

OCH3

Methoxybenzene
 O ClH2C O CH3
cyclohexoxycyclohexane chloromethoxymethane

Cl OCH2CH3
CH2=CHOCH3
methoxyethene 1-chloro-4-ethoxybenzene
 Cyclic Ethers

 Heterocyclic: oxygen is in ring

O
 Epoxides (oxiranes) H2C CH2
O
 Oxetanes

 Furans (Oxolanes)
O O

 Pyrans (Oxanes)
O O
O
Dioxanes
O
 Naming Epoxides

 Alkene oxide, from usual synthesis method

H
peroxybenzoic acid
O cyclohexene oxide
H

 Epoxy attachment to parent compound,

1,2-epoxycyclohexane

 Oxirane as parent, oxygen number 1

O
H CH3
trans-2-ethyl-3-methyloxirane
CH3CH2 H
SYNTHESIS OF
ETHERS
 Williamson Synthesis (1)

 to produce symmetry and unsymmetry ethers

 SN2 reaction: 1° alkyl halide (or tosylate) react with
sodium alkoxide/sodium phenoxide

R'X + NaOR R'OR + NaX

R'X + NaOAr R'OAr + NaX

 Example:

CH3 CH3
- +
H3C C OH + Na H3C C O Na
CH3 CH3

CH3 CH3
- + -
H3C C O Na + H3C I H3C C OCH3 + I
CH3 CH3
E2 reaction if:

CH3OH + Na CH3O-Na+

CH3 CH3
CH3O-Na+ + H3C C Cl H3C C OCH3
CH3 CH3

CH2=CCH3 + CH3OH + Cl-

CH3
 - +
OH O Na
+ NaOH

O-Na+ OCH3
+ CH3 I

No reaction if used aryl or vinyl X

halides; halogen atom bonded CH2=CHX
to sp2-carbon (strong bond)
 Alkoxymercuration-Demercuration (2)
 Use mercuric acetate with an alcohol to add RO-H to a double
bond and form the Markovnikov product.
 Bimolecular Dehydration of Alcohols (3)

 Industrial method, not good lab synthesis

 dehydration of 2 molecules of 1° ROH at 140°C in the
presence of conc. H2SO4 or H3PO4
 If temperature is too high (~ 180 °C) => alkene
 If 2° or 3° ROH used => alkene

H2SO4
CH3CH2 O H + H O CH2CH3 CH3CH2 O CH2CH3
140°C
 Dehydration of ROH (SN2)
Step 1: Protonation of alcohol

+
H3C OH + H

Step 2: Nucleophile attacks the protonated alcohol

H3C OH + H3C OH H3C O CH3 + H2O

H H

Step 3: Deprotonation of protonated ether

H3C O CH3 H3C O CH3 + H3O+

H
H2O
REACTIONS OF ETHERS
 Cleavage of Ethers

 Ethers are unreactive toward base, but protonated

ethers can undergo substitution reactions with strong
acids.
 Alcohol leaving group is replaced by a halide.
 Reactivity: HI > HBr >> HCl
Mechanism for Cleavage
 Phenyl Ether Cleavage

 Phenol cannot react further to become halide.

 Example:

O CH2CH3 OH
HBr
+ CH3CH2 Br
 Autoxidation of Ethers
 In the presence of atmospheric oxygen, ethers slowly
oxidize to hydroperoxides and dialkyl peroxides.
 Both are highly explosive.
SYNTHESIS OF EPOXIDES
a)Peroxyacid epoxidation
reagent : MCPBA in CH2Cl2
product: same stereochemistry (cis-alkene -> cis-epoxy)
 b) Cyclization of Halohydrin
 alkenes react with aqueus halogen to form halohydrin
 halohydrin reacts with base (aqueus NaOH) to form epoxide

_ _ O
HO H OH O H
H2O, Cl2
H H Cl Cl H H
H H
REACTION OF EPOXIDES
a) Ring Opening in Acid

 Trans diol formed in water solvent (H2O)

 Alkoxy alcohol formed in alcohol solvent (ROH)
 1,2-Dihalide formed with HI or HBr
b) Ring Opening in Base
 Epoxide’s high ring strain makes it susceptible to
nucleophilic attack.
 with H2O or alcohol as solvents, epoxide ring will
cleave to form same product as in acid
 Different products are formed in acid and base if
epoxide is unsymmetrical.
Ring Opening for Unsymmetrical Epoxide
 Orientation of Epoxide Opening
 Base attacks the least hindered carbon.
_
O O OH
CH3CH2OH
HC CH2 HC CH2 HC CH2
CH3 OCH2CH3 CH3 OCH2CH3 CH3 OCH2CH3

 In acid, the nucleophile attacks the protonated

epoxide at the most substituted carbon.

H H3C OH H3C OH
O+ HC CH2 HC CH2
HC CH2 OCH2CH3
H OCH
+
2CH3
CH3
CH3CH2OH
 Reaction with Grignard and R-Li
 Grignard and R-Li are strong Nu
 Strong base opens the epoxide ring by attacking the less
hindered carbon.

OH
O MgBr CH2 CHCH3
1) ether
H2C CHCH3 +
+
2) H3O