Chap IV - Etherepox - Thiolsulfides

Chap IV.
Ethers-Epoxides
Thiols-Sulfides
Prof. Dr. Esra ÖNEN BAYRAM

Ethers and Epoxides
• An ether has two organic groups (alkyl, aryl, or vinyl)
bonded to the same oxygen atom, R–O–R.
• Ethers can be either linear or cyclic.
• Examples:
– Diethyl ether is an industrially used solvent
– Tetrahydrofuran (THF) is an organic solvent that is
a cyclic ether
Ethers and Epoxides
Ethers: Nomenclature
• Simple ethers are named by identifying the two
organic substituents and adding the word ether.
Ethers: Nomenclature
• If other functional groups are present, the ether part
is considered an alkoxy substituent.
Ethers: Structure
• R–O–R : bent structure with a bond angle of around
112° in dimethyl ether
• Oxygen is sp3-hybridized
• Oxygen atom gives ethers a slight dipole moment

Ethers: How to obtain?
• Williamson synthesis: a nucleophilic
substitution
– Nucleophile: metal alkoxide
– Leaving group: halide or tosylate
• Silver-oxidized catalyzed ether formation
– One-step ether synthesis from halides in presence
of Ag2O
– Classical glucose –OH protection reaction
• Alkoxymercuration of alkenes:
– alkene+alcohol+mercuric acetate or
trifluoroacetate.
– 2. step: demercuration with NaBH4
– Formation of the Markovnikov product

• Alkoxymercuration of alkenes
Ethers: Reactivity
Acidic cleavage
• Ethers are generally inert.
• Strong acids cleave ethers at high temperatures.
• HI, HBr:
– The less hindered alkyl halide is obtained
– No cleavage with HCl
Ethers: Reactivity
Acidic cleavage
Epoxides: 3-membered cyclic ethers
• Epoxides: cyclic ethers with 3 atoms in the cycle.
• Properties different from other cyclic ethers that

behave like ethers.
• Epoxides also called oxiranes:

– “ox” for oxygen
– “ir” for tri-
– “ane” for saturated carbons
Epoxides: 3-membered cyclic ethers
• Example: Ethylene epoxide
– An important industrial intermediate
– Prepared from the reaction of ethylene with
oxygen at 300C in presence of silver oxide
catalyst.
Epoxides: How to obtain?
• Form an alkene using a peroxacid:
• Form an alkene using a peroxacid:
• From halohydrins:
– HO-X+ alkene: formation of a halohydrin
– Treatment of a halohydrin with a base: epoxide
Intramolecular Williamson ether synthesis.
• From halohydrins:
– HO-X+ alkene: formation of a halohydrin
– Treatment of a halohydrin with a base: epoxide
Intramolecular Williamson ether synthesis.
Epoxides: Reactivity
Acid catalyzed ring opening
• Nucleophile is water:
– Hydrolysis reaction
– Generation of 1,2 diols or vicinal glycols.
• Nucleophile is a hydrogen halide:

– HF, HCl, HBr or HI
– Generation of a halohydrin
• Hydrolysis:
– Ethylene glycol or 1,2-ethanediol synthesized
from the acid catalyzed hydration of ethylene
epoxide.
– Widely used as an automotive antifreeze (lowers

freezing point of water solutions) and polymer
precursor.
• Halohydrin generation:
– Reaction of an epoxide with anhydrous HF, HBr,
HCl, or HI.
– Attack of the halide from the less hindered .
• SN1 or SN2? Difficult to answer…..
– If in the structure only primary and secondary carbons
 attack of the less hindered carbon.
– If presence of a tertiary carbon, attack on it.

Base catalyzed ring opening
• Strain of the three-membered ring is relieved on ring-
opening with bases unlike other ethers.
• Hydroxide cleaves epoxides at elevated temperatures

to give trans 1,2-diols.
with Grignard reagents
• Do not react if acyclic or larger ethers.

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
oxygens atoms
• Central cavity is electronegative and attracts cations

Crown Ethers
Crown Ethers
Crown Ethers: Applications
• Complexes between crown ethers and ionic salts are
soluble in non-polar organic solvents.
• Creates reagents that are free of water that have

useful properties.
• Inorganic salts dissolve in organic solvents leaving the

anion unassociated, enhancing reactivity.
Thiols and Sulfides: Definition
• Thiols (RSH): sulfur analogs of alcohols
– Named with the suffix -thiol
– SH group is called “mercapto group” (“capturer of

mercury”)
Thiols and Sulfides: Definition
• Sulfides (RSR), are sulfur analogs of ethers:
– Named by rules used for ethers, with sulfide instead
of ether for simple compounds and alkylthio instead
of alkoxy.
Thiols and Sulfides: Formation
• From alkyl halides by displacement with a sulfur
nucleophile such as SH.
• Control of reaction is important:

The alkylthiol product can undergo further
reaction with the alkyl halide to give a
symmetrical sulfide.
• Reaction of an alkyl thiol (RSH) with bromine or
iodine gives a disulfide (RSSR).
• The thiol is oxidized in the process and the halogen is

reduced.
• Thiolates (RS) are formed by the reaction of a
thiol with a base.
• Thiolates react with primary or secondary alkyl
halide to give sulfides (RSR’).
• Thiolates are excellent nucleophiles and react
with many electrophiles.
Sulfides: Reactivity
• Sulfides are easily oxidized with H2O2 to the sulfoxide
(R2SO).
• Oxidation of a sulfoxide with a peroxyacid yields a

sulfone (R2SO2)
Summary
• Ethers and epoxides
– Definitions:
• Ether: R-O-R’
• Epoxide: 3-membered heterocyclic ring, called oxirane.
– Reactivity:
• Ethers: acidic cleavege at high temperature (not with HCl)
ÞFormation of the less hindered alkyl halide
• Epoxides:
– Acidic cleavage: H2O gives vicinal glycols, HX halohydrins.
– Base catalyzed cleavage: trans-1,2-diols
Summary
• Thiols and Sulfides:
– Definitions:
• Thiols: R-SH (mercapto group)
• Sulfides: R-S-R’
– Reactivity:
• Thiols:
– With alkyl halides: sulfides
– With halides: symmetrical disulfides
• Sulfides:
– Oxidation: sulfoxide
– Further oxidation of sulfoxide: sulfone

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Chap IV.

Prof. Dr. Esra ÖNEN BAYRAM

• Ethers can be either linear or cyclic.

• Oxygen atom gives ethers a slight dipole moment

– 2. step: demercuration with NaBH4

– Formation of the Markovnikov product

• Strong acids cleave ethers at high temperatures.

• Properties different from other cyclic ethers that

• Epoxides also called oxiranes:

• Nucleophile is a hydrogen halide:

– Widely used as an automotive antifreeze (lowers

– If presence of a tertiary carbon, attack on it.

• Hydroxide cleaves epoxides at elevated temperatures

• Do not react if acyclic or larger ethers.

• Central cavity is electronegative and attracts cations

• Creates reagents that are free of water that have

• Inorganic salts dissolve in organic solvents leaving the

– SH group is called “mercapto group” (“capturer of

• Control of reaction is important:

• The thiol is oxidized in the process and the halogen is

• Oxidation of a sulfoxide with a peroxyacid yields a

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