ethers

Nomenclatures, methods of
preparations, properties,
reactions and uses
• Simple ethers are named by identifying the two organic
substituents and adding the word ether
• If other functional groups are present, the ether part is
considered an alkoxy substituent
• R–O–R ~ tetrahedral bond angle (112° in dimethyl ether)
• Oxygen is sp3-hybridized
• Oxygen atom gives ethers a slight dipole moment
Ether Synthesis:
• Diethyl ether prepared industrially by
sulfuric acid–catalyzed dehydration of
ethanol – also with other primary alcohols
Industrial synthesis for diethyl ether:

2 CH3CH2-OH + H2SO4, 140oC → CH3CH2-O-CH2CH3 + H2O

Not generally useful for syntheses of ethers in the lab:

a) Only symmetric ethers can be made this way.
b) Conditions are very compound specific
( at 180o ethanol would yield ethene instead of the ether)
The Williamson Ether Synthesis
• Reaction of metal alkoxides and primary alkyl halides
• Best method for the preparation of ethers
• Alkoxides prepared by reaction of an alcohol with a strong
base such as sodium hydride, NaH
Synthesis of ethers

1. Williamson Synthesis.

R-O-Na+ + R´-X → R-O-R´ + NaX

R´-X should be CH3 or 1o

SN2 mechanism
Mechanism for the Williamson Synthesis = SN2

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

R´-X should be CH3 or 1o

R-OH + Na → R-O-Na+
→ R-O-R´
R´-OH + HX → R´-X

(CH3)2CH-OH + Na → (CH3)2CH-O-Na+
+ → CH3CH2CH2-O-CH(CH3)2
CH3CH2CH2-OH + HBr → CH3CH2CH2-Br isopropyl n-propyl ether

note: the alkyl halide is primary! ☺

CH3CH2CH2-OH + Na → CH3CH2CH2-ONa
+ → CH3CH2CH2-O-CH(CH3)2
(CH3)2CH-OH + HBr → (CH3)2CH-Br

2o → alkene

The product of this attempted Williamson Synthesis using a

secondary alkyl halide results not in the desired ether but in an
alkene!

The alkyl halide in a Williamson Synthesis must beCH3 or 1o!
 Synthesis of di-tert-butyl ether?
• Can this compound be made via
The Williamson Synthesis?
CH3 CH3
H3C O CH3 • Cannot be made via the
C C Williamson Synthesis.

CH3 CH3
• The alkyl halide would be 3o.
Silver Oxide-Catalyzed Ether
Formation
• Reaction of alcohols with Ag2O directly with alkyl halide
forms ether in one step
• Glucose reacts with excess iodomethane in the presence
of Ag2O to generate a pentaether in 85% yield
 CHEMICAL
PROPERTIES
 R-H R-X R-OH R-O-R

Acids NR NR  
Bases NR   some NR
Metals NR   NR
Oxid. NR NR 
EXPLOSIVE
Reduc.
NR  NR NR
Halogens
NR NR NR NR
Reactions of Ethers: Acidic
Cleavage
• Ethers are generally unreactive
• Strong acid will cleave an ether at elevated temperature
• HI, HBr produce an alkyl halide from less hindered
component by SN2 (tertiary ethers undergo SN1)
Cyclic Ethers: Epoxides

• Cyclic ethers behave like acyclic ethers, except if ring is 3-

membered
• Dioxane and tetrahydrofuran are used as solvents
Epoxides (Oxiranes)
• Three membered ring ether is called an oxirane (root “ir”
from “tri” for 3-membered; prefix “ox” for oxygen; “ane”
for saturated)
• Also called epoxides
• Ethylene oxide (oxirane; 1,2-epoxyethane) is industrially
important as an intermediate
• Prepared by partial oxidation reaction of ethylene with
oxygen at 300 °C and silver oxide catalyst
 Preparation of Epoxides
Using a Peroxyacid

• Treat an alkene with a peroxyacid/ Peracids

 Epoxides from
Halohydrins
• Addition of HO-X to an alkene gives a halohydrin
• Treatment of a halohydrin with base gives an epoxide
• Intramolecular Williamson ether synthesis
 Reactions of Epoxides:
Ring-Opening
• Water adds to epoxides with dilute acid at room
temperature
• Product is a 1,2-diol (on adjacent C’s: vicinal)
• Mechanism: acid protonates oxygen and water adds to
opposite side (trans addition)
 Halohydrins from
Epoxides
• Anhydrous HF, HBr, HCl, or HI combines with an epoxide
• Gives trans product
 Addition of Grignards
to Ethylene Oxide
• Adds –CH2CH2OH to the Grignard reagent’s hydrocarbon
chain
• Acyclic and other larger ring ethers do not react
 Crown Ethers
• Large rings consisting repeating (-OCH2CH2-) or similar units
• Named as x-crown-y
– x is the total number of atoms in the ring
– y is the number of oxygen atoms
– 18-crown-6 ether: 18-membered ring containing 6 oxygen atoms
• Central cavity is electronegative and attracts cations
 Alcohols, Ethers and Epoxides
Interesting Ethers

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