Chapter 18: Ethers

Naming of Ethers
Physical Properties
Preparation of Ethers
General Structure
R
O
R' R
S
R' H
S
R'
Ether
Thiol
Sulfide
R or R' can be alkyl, aryl or vinyl and the R groups may be attached in a ring shape
Simple ethers are named by naming the two substituent groups followed by the word ether.
O
ethyl methyl ether
O
diphenyl ether
O
tert-butyl isopropyl ether
O
cyclohexyl propyl ether
If other functional groups are present then the group is considered to be an alkoxy substituent.
O
3-propoxy-cyclohexene
O
OH
2-Methoxy-ethanol
O
1-Propoxy-but-2-yne
O O
Dimethoxy-methane
H
3
C
O
CH
3
112

Boiling points of ethers are elevated relative to similar alkanes. This

is due to a molecular dipole caused by the R-O-R bond.
Simple, symmetric ethers are prepared industrially by the dehydration of alcohols:
OH
diethyl ether synthesis:
2
H
2
SO
4
O
OH OH
2
This reaction is an easy way to make symmetric ethers, yet is impractical for most laboratory applications.
Cleavage of Ethers
Williamson Ether Synthesis: SN2 reaction with alkoxide as nucleophile on a primary carbon with a good leaving group
R O Na
X R'
R=any alkyl, phenyl or vinyl group
X=any good leaving group (Cl, Br, I or tosylate)
R
O R'
Alkoxides can be genarated with sodium hydroxide in some cases or sodium hydride (NaH).
R OH
NaH
R O Na H
2
Williamson ether synthesis reactions are usually only done with a primary electrophilc substrate since
otherwise E2 elimination reactions would compete.
Alkoxymercuration of Alkenes
Hg(CF
3
COO)
2
OH
O
HgO
2
CF
3
NaBH
4
O
Very simlar to alcohols synthesis using oxymercuration. This varierty uses the trifluoracetoxy ligand for Hg
instead of acetate. An alcohol serves as the nucleophile instead of water.
A mercurinium bridge is formed followed by nucleophilc attack by the alcohol and subsequent reduction.
The alcohol nucleophile will attack the more subsituted carbon due to greater partial positive charge at this
site.
Ethers may be cleaved to yield an alcohol and an alkyl halide. Strong conditions are usually necessary for
ether cleavage. Note: If two or more equivalents of acid are used further dehydration can occur on formed alcohols.
HI or HBr in refluxing water are need for cleavage of ether with primary or secondary substituents. These
ethers are cleaved via an S
N
2 mechansim.
With tertiary, allylic, or benzylic substituetns an S
N
1 mechanism is observed for cleavage which can be
done with strong acids such as H
2
SO
4
or CF
3
COOH.
O
H
2
SO
4
O
H
O
H
H
O
H
O
O
HI
H
I
OH
I
nucleophile attacks less substituted carbon
more stable carbocation formed
Claisen Rearrangement
O
Look for
this group!!!

Thermally catalyzed, 6 electron pericyclic
O
O
H
OH
Cyclic Ethers and Epoxides
Cyclic ethers have essentially the same reactivity of their acyclic counterparts. Epoxides are an
exception, owing their reactivity to a strained three membered ring.
O
O
O
O
tetrahydrofuran
(THF) 1,4-dioxane
ethylene oxide
(an epoxide)
Prepartion of Epoxides
Epoxides can be formed by oxidation of a doble bond with a peroxy acid (peracid). A common example
of such a reagent is meta-chloroperoxybenzoic acid (m-CPBA).
O O
H
O
Cl
m-CPBA
O
m-CPBA
Mechanism:
O
O
H
O
R
O
O
OH
R
Epoxide formation via an intramolecular Williamson ether synthesis of a halohydrin.
OH
Br
NaOH
O
Br
O
groups anti to one another
Br
2
H
2
O
Opening/Cleavage of Epoxides
Crown Ethers
Epoxides can be opened in a few different ways. Epoxides react at conditions milder then those needed to
cleave non-strained ethers. Nucleophilic attack occurs from the backside of the epoxide oxygen. It is often
possible for mixtures of products to result.
O
H Cl
O H
Cl
attack is S
N
2 like: on the less substituted carbon
O
H Cl
Acid Catalyzed: Primary and Secondary carbons
Acid Catalyzed: Tertiary carbons
O
H Cl
O H
O H
Cl
O
H
Cl
attack is SN1 like: more stable carbocation formed followed by attack
major
product
major
product
Base-Catalyzed Epoxide Openigs-occur due to ring strain
O
OH
O
HO
H
2
O
OH
HO
attack is S
N
2 like: on the less substituted carbon
Hydroxide acts as a nuclophile displacing the epoxide oxygen as a leaving group. Other nucleophiles,
such as Grignard reagents, alkoxides, hydrides, can perform this same reaction.
O
O
O
O O
O
18-crown-6
K
Host molecules for cation guests of various sizes.
Named by specifying the number of atoms and the number of oxygens
separated by the word crown.
(total atom #)-crown-(oxygen #)
Thiols and Sulfides
Thiols (Mercaptans)- Sulfur analog of alcohols, named like alcohols except use thiol instead of -ol
Sulfides- Sulfur analog of ethers, named like ethers except use sulfide instead of the word ether
SH Mercapto Group
Br
Preparation of thiols
NaSH
S
N
2
SH Note: prone to many side products
Br
SH
H
2
N NH
2
S
NH
2
NH
2
S
H
2
O
OH
Disulfide formation from thiols
SH
2
oxidation
Br
2
or I
2
S
S
reduction
Zn, H
H
2
N
SH
O
OH
cysteine
S
Sulfides
R X S
R
S
N
2
S
H
3
C I
S
Trialkyl Sulfonium Ion
S
Oxidation of Sulfides to Sulfones
H
2
O
2
S
O
m-CPBA
S
O
O
Preparation
DMSO
(dimethylsulfoxide)