CHAPTER 6

ALCOHOLS AND ETHER

BWK10303 ORGANIC CHEMISTRY 1

SEMESTER I SESSION 2023/2024
CHM. DR. SALIZA BINTI ASMAN
OUTLINE
1. Alcohols
2. Structure, nomenclature and physical properties
3. Preparation
4. Reactions
5. Ether
6. Structure, nomenclature and physical properties
7. Preparation and reactions
8. Simple chemical test of alcohols and ether
 INTRODUCTION

Glycol ether - solvent Tetrahydrofuran (THF) - solvent

Diethyl ether - anesthetic Anisole (methyl phenyl ether) Methyl tert-butyl ether
- perfume (MTBE) – addictive in
gasoline
 INTRODUCTION
❖ General formula: R-O-R’ , where R/R’ = alkyl or aryl
❖ Symmetry if R = R’
❖ Unsymmetry if R ≠ R’

OCH3
H3C O CH3
O

H3C O CH2CH2CH3
STRUCTURE AND POLARITY
O O
❖ Bent molecular geometry
H H R R
❖ Tetrahedral angle
❖ Still strongly polar compounds 105° 110°

Dimethyl ether
STRUCTURE AND POLARITY
HYDROGEN BOND ACCEPTOR

❖ Ethers cannot form 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.
 NOMENCLATURE OF ETHER
Common Names of Ethers
❖ Applied for simple ethers
❖ Alphabetical order
❖ Organic group, R or Ar group name in R or Ar + ether
❖ Symmetrical ether, only one group is named eg. Dimethyl ether
❖ Symmetrical ethers: use dialkyl + ether CH3
CH3 O C CH3

H3C O CH3 CH3CH2 − O − CH2CH3 CH3

tert-butyl methyl
Dimethyl ether Diethyl ether ether
 NOMENCLATURE OF ETHER OCH3

IUPAC NAMES
❖ Named as alkoxy alkane or alkene; more complex + ether
❖ Numbering depends on the position of alkoxy group on the main Methoxycyclohexane
chain
OCH3
❖ Smallest alkoxy group name first (RO− = alkoxy group)
C
H3
O
H
3COCC
H3
C
H3 Methoxybenzene
2-methyl-2-methoxypropane cyclohexoxycyclohexane
Cl OCH2CH3
CH2=CHOCH3 H2CCl O CH3
methoxyethene chloromethoxymethane 1-chloro-4-ethoxybenzene
 NOMENCLATURE OF ETHER
CYCLIC ETHERS OR EPOXIDE
❖ Heterocyclic: oxygen is in ring
O
❖ Epoxides (oxiranes) H2C CH2

❖ Furans (Oxolanes)
O O

❖ Pyrans (Oxanes)
O O

O O
❖ Dioxanes (Dioxin)

O 1,4-dioxane O 1,4-dioxine
 NOMENCLATURE OF ETHER
1. Epoxides (Oxiranes)
❖ Three-membered cyclic ethers
❖ Common name – use alkene base & end with –oxide
❖ I U PAC name – epoxy group, C with epoxy group with the lowest number
O
O O 4-methoxyhexene oxide
1 4 5 6 1 2
H C C H H3C 2 3 CHCH2CH3 (2,3-epoxy-4-methoxyhexane)
Ethylene oxide
H 1 2 H Oxirane
OCH3

O 3
H C CH3
C
H 1 2 CH3
2-methylpropene oxide
(1,2-epoxy-2-methylpropane)
NOMENCLATURE OF ETHER
2. Oxetanes
❖ Least common cyclic ethers
❖ Four-membered cyclic ethers
❖ Oxygen atoms are numbered as 1

1
4
O O
H3C CH2CH3 3 2

CH3 oxetane
NOMENCLATURE OF ETHER
3. Furans
❖ Five-membered cyclic ethers
❖ Named after aromatic member, furan (unsaturated)
❖ Saturated have 4 more H (tetrahydro + furan)
NOMENCLATURE OF ETHER
4. Pyrans(Oxanes)
❖ Six-membered cyclic ethers
❖ name as derivatives of pyran (unsaturated ether)
❖ saturated ether have 4 more H (tetrahydro +
pyran)
NOMENCLATURE OF ETHER
5. Dioxanes
❖ Heterocyclic ether with 2 oxygen atoms in a six-membered ring
❖ most common form 1,4-relationship
NOMENCLATURE OF ETHER
6. Crown Ether
❖ Polymer cyclic ethylene glycol
❖ Name according x–crown–y
❖ (x = total of C & O atoms in the ring, y = number of O)
 NOMENCLATURE OF ETHER
❖ 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

H O CH3
trans-2-ethyl-3-methyloxirane
CH3CH2 H
QUESTIONS
i) Give a common name (when possible) and a systematic name for each compound.

ii) Name the following heterocyclic ethers.

PHYSICAL PROPERTIES
Boiling Points

*Similar to alkanes of comparable molecular weight

PHYSICAL PROPERTIES
 PHYSICAL PROPERTIES
Solvent properties
❖ Nonpolar solutes dissolve better in ether than in alcohol.
❖ Ether has a large dipole moment, so polar solutes also dissolve.
❖ Ethers solvate cations.
PREPARATION OF ETHER
1. Williamson synthesis
❖ to produce symmetry and unsymmetry ethers
❖ SN2 reaction: 1º alkyl halide (or tosylate) react with sodium alkoxide/sodium
phenoxide (Na, K, NaH)

R'X + NaOR R'OR + NaX

R'X + NaOAr R'OAr + NaX

 PREPARATION OF ETHER
EXAMPLE:
 PREPARATION OF ETHER
E2 REACTION if:
 PREPARATION OF ETHER
E2 REACTION if:
PREPARATION OF ETHER
 PREPARATION OF ETHER
2. Alkoxymercuration-Demercuration
❖ Use mercuric acetate with an alcohol to add RO-H to a double bond and form the Markovnikov product.
 PREPARATION OF ETHER
3. Bimolecular dehydration of alcohols
❖ Industrial method, not good lab synthesis
❖ dehydration of 2 molecules of 1 ROH at 140 C in the presence of concentrated
H2SO4 or H3PO4
❖ If temperature is too high (~ 180 C) => alkene
❖ If 2 or 3 ROH used => alkene
PREPARATION OF ETHER
DEHYDRATION OF ROH (SN2)
PREPARATION OF EPOXIDES
A) PEROXYACID EPOXIDATION
❖ reagent : meta-chloroperoxybenzoic acid (mCPBA) in CH2Cl2
❖ product: same stereochemistry (cis-alkene ➝ cis-epoxy)
PREPARATION OF EPOXIDES
 PREPARATION OF EPOXIDES
B) CYCLIZATION OF HALOHYDRIN
❖ alkenes react with aqueous halogen to form halohydrin
❖ halohydrin reacts with base (aqueous NaOH) to form epoxide

_ _
H OH O H O
H2O, Cl2 HO

H H Cl Cl H H
H H
PREPARATION OF EPOXIDES
 QUESTION
Predict the product of this Williamson ether reaction:
 QUESTION
Predict the product of this Williamson ether reaction:
REACTION OF ETHER
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
 REACTION OF ETHER
Mechanism for cleavage
 REACTION OF ETHER
Phenyl ether cleavage
❖ Phenol cannot react further to become halide.
❖ Example:
 REACTION OF ETHER
Autoxidation of ethers
❖ When ethers are stored in the presence of atmospheric oxygen, they slowly oxidize to
produce
hydroperoxides and dialkyl peroxides, both of which are explosive.
❖ Such a spontaneous oxidation by atmospheric oxygen is called autoxidation.
 REACTION OF ETHER
Autoxidation of ethers
❖ In the presence of atmospheric oxygen, ethers slowly oxidize to hydroperoxides and
dialkyl peroxides.
❖ Both are highly explosive.
REACTION OF EPOXIDE
Ring opening in acid
a) Trans diol formed in water solvent (H2O)
REACTION OF EPOXIDE
b) Alkoxy alcohol formed in alcohol solvent (ROH)

c) 1,2-Dihalide formed with HI or HBr

 REACTION OF EPOXIDE
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.
 REACTION OF EPOXIDE
❖ Strong bases and nucleophiles do not attack and cleave most ethers (epoxides are more reactive)
❖ Strong bases can attack and open epoxides, even though the leaving group is an alkoxide.
REACTION OF EPOXIDE
Ring Opening for Unsymmetrical Epoxide
 REACTION OF EPOXIDE
ORIENTATION OF EPOXIDE OPENING
a) Attacks the least hindered carbon

b) In acid, the nucleophile attacks the protonated epoxide at the most substituted
carbon
 REACTION OF EPOXIDE
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+
QUESTION
Predict the product

a)

b)