Chapter 8: Ethers and Epoxides
Ether Functional Group
→ Ethers have a general formula: R-O-R′.
→ R and R′ maybe identical or different.
→ R and R′ maybe alkyl or aryl groups.
→ Ethers are usually named by giving the name of each alkyl and aryl group,
in alphabetical order, followed by the word ether
Nomenclature of Ethers
ethyl methyl ether diethyl ether diphenyl ether
2-methoxypentane trans-2-methoxycyclohexanol 1,3,5-trimethoxybenzene
Exercise
Name the following compounds:
Write the structural formula for:
(a) Dicyclopropyl ether (b) 2-methoxyoctane
Physical Properties of Ethers (I)
Boiling points
Compound Formula Boiling point Molecular Weight Water solubility
(g/100ml)
1-butanol CH3CH2CH2CH2OH 118 ◦C 74 7.9
diethylether CH3CH2-O-CH2CH3 35 ◦C 74 7.5
pentane CH3CH2CH2CH2CH3 36 ◦C 72 0.03
→ Ethers have lower boiling point than alcohols with the same molecular weight.
→ This is because ethers have no (O-H bonds), therefore ether molecules cannot form hydrogen bonds
with one another
→ Ethers have the same boiling point with the corresponding hydrocarbon.
Physical Properties of Ethers (II)
Solubility of ethers:
→ Alcohols and ethers are mutually soluble.
→ This is because ethers can form hydrogen bonding with alcohols
→ Low-molecular-weight ethers (e.g. dimethyl ether are quite soluble in water)
→ The solubility of diethyl ether in water is similar to that 1-butanol,
(each of them can form hydrogen bonding with water).
Ethers as Solvents
→ Ethers are relatively inert compounds.
→ Ethers do not usually react with dilute acids, dilute bases, or with common oxidizing and reducing agents.
→ Ethers do not react with metallic sodium (This distinguish them from alcohols)
→ This general inertness in addition to that most organic compounds are ether-soluble,
makes ethers excellent solvents, to carry out organic reactions
Preparation of Ethers (I)
Symmetrical Ethers:
Examples:
Preparation of Ethers (II)
Unsymmetrical Ethers: (Use Williamson Synthesis)
(1)
(2) This step is an SN2 reaction
Remember: In SN2 reaction the following order of reactivity is applied:
CH3X ˃ 1◦ ˃ 2◦ ˃ 3◦
Example:
methyl halide 1◦ alkyl halide
Preparation of Ethers (III)
Another example (for Williamson’s synthesis):
1◦ alkyl halide 2◦ alkyl halide
Cleavage of Ethers (I)
→ Ethers have unshared electron pairs on the oxygen atom.
→ Therefore, ethers are Lewis bases.
→ Ethers react with strong proton acids.
Lewis base Lewis acid
Cleavage of Ethers (II)
Examples:
Cleavage of Ethers (III)
Examples:
Cleavage of Ethers (IV)
Further examples (unsymmetrical ethers):
For unsymmetrical ethers the strong nucleophile such as I- or Br- will attack by an SN2 process
Epoxides (Oxiranes)
→ Epoxides (or oxiranes) are cyclic ethers with a three-membered ring containing one oxygen atom.
ethylene oxide cis-2-butene oxide trans-2-butene oxide
cyclohexene oxide
Preparation of Epoxides
Examples:
peroxy acid or peracid
Common example on peracid:
m-chloroperbenzoic acid
(MCPBA)
Reactions of Epoxides
Cyclic Ethers
→ Cyclic ethers whose rings are larger than the three membered epoxides.
→ The most common are five- or six-membered rings.
Examples:
tetrahydrofuran tetrahydropyran 1,4-dioxane
The Grignard Reagent; An Organometallic Compound
→ Preparation of Grignard reagents is one of the most striking examples of the solvating power of ethers
carbon halogen bond is broken Both alkyl group and halogen become
bonded to the Mg
The Role of Ether as a Solvent of Grignard Reagent
Acting as a Lewis base,
ether stabilizes a Grignard reagent
The two common ethers which are used in Grignard preparations are: To be used in Grignard preparation,
(1) Diethyl ether ether should be dry
(free of water traces or alcohols)
(2) Tetrahydrofuran (THF)
Examples of Grignard Reagent Preparation
Grignard Reagent as A carbanion
→ Grignard reagents usually react as if the alkyl or aryl group is negatively charged (a carbanion)
and the magnesium atom is positively charged
→ Carbanions are strong bases. They are the conjugate bases of hydrocarbons, which they are very weak acid
→ Grignard reagents react vigorously with weak acids (e.g. water), or with any other compound
with an OH, SH, or NH bond.
Example:
Organolithium Compounds
→ Grignard reagents are organometallic compounds; they contain carbon-metal bond.
→ Many other types of organometallic compounds are known.
→ Organolithium compounds, which can be prepared in a manner similar to that for Grignard reagents,
are also useful in syntheis