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Chapter 14
Ethers, Epoxides, and Sulfides
Ethers
Formula is ROR, where R and R are alkyl or aryl. Symmetrical or unsymmetrical
CH3 O CH3
O CH3
Chapter 14
Boiling Points
Similar to alkanes of comparable molecular weight.
Chapter 14
Ethers cannot hydrogen-bond with other ether molecules. Molecules that cannot hydrogen-bond intermolecularly have a _____________ boiling point. Ether molecules can hydrogen-bond with water and alcohol molecules.
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An ionic substance such as lithium iodide is moderately soluble in ethers because the small lithium cation is strongly solvated by the ethers lone pairs of electrons. Unlike alcohols, ether cannot serve as hydrogenbond donors, so they do not solvate small anions well.
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Ether Complexes
Grignard reagents: Complexation of an ether with a Grignard reagent stabilizes the reagent and helps keep it in solution.
H _ + O B H H BH3 THF
7
Crown ethers can complex metal cations inside the ring. The size of the cation will determine the size of the ring needed. Complexation by crown ethers often allows polar inorganic salts to dissolve in nonpolar organic solvents.
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CH3CH2
O CH2CH3
CH3
O C CH3 CH3
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IUPAC Names
The more complex alkyl group is the alkane name. The small group (with the oxygen) becomes an alkoxy group.
CH3 CH3 O C CH3 CH3
O CH3
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Cyclic Ethers
Heterocyclic: Oxygen is part of the ring. Epoxides (oxiranes) Oxetanes Furans Pyrans
O
O H2C CH2
(Oxolanes (Oxanes
O
) )
O O
Dioxanes
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Epoxide Nomenclature
Name the starting alkene and add oxide.
peroxybenzoic acid H O H
The oxygen can be treated as a substituent (epoxy) on the compound. Use numbers to specify position.
H O H
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IR Spectroscopy of Ethers
IR: The CO stretch is in the fingerprint region around 10001200 cm-1. Many compounds have the CO stretch. If the IR spectrum has the CO stretch but does not have a CO or an OH stretch, then the compound is most likely an ether.
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MS Spectrometry of Ethers
Main fragmentation is the _______________ to form the resonance-stabilized oxonium ion. Either alkyl group can be cleaved this way.
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This method involves an SN2 attack of the alkoxide on an ________________________ halide or tosylate.
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Phenyl Ethers
O H + NaOH _ O Na+ + HOH
Phenoxide ions are easily produced for because the alcohol proton is acidic. Phenyl halides or tosylates cannot be used in this synthesis method.
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Use mercuric acetate with an alcohol. The alcohol will react with the intermediate mercurinium ion by attacking the __________ substituted carbon.
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140C
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Cleavage of Ethers
Ethers are __________________, which makes them ideal solvents for a lot of different reactions. They can be cleaved by heating with HBr and HI. Reactivity: HI > HBr >> HCl
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Br
CH3
H + O CH3
Br CH3 + H O CH3
Alcohol is protonated, halide attacks, and another molecule of alkyl bromide is formed. =>
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Autoxidation of Ethers
In the presence of atmospheric oxygen, ethers slowly _______________ to hydroperoxides and dialkyl peroxides. Both are highly explosive. Precautions:
Do not distill to dryness. Store in full bottles with tight caps.
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Mechanism of Autoxidation
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Synthesis of Epoxides
Peroxyacids are used to convert alkenes to epoxides. Most commonly used peroxyacid is metachloroperoxybenzoic acid (MCPBA). The reaction is carried out in an aprotic acid to prevent the opening of the epoxide.
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Selectivity of Epoxidation
The most electron-rich double bond reacts faster, making selective epoxidation possible.
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Halohydrin Cyclization
If an alkoxide and a halogen are located in the same molecule, the alkoxide may displace a halide ion and form a ring. Treatment of a halohydrin with a base leads to an epoxide through this _______________ Chapter 14 31 attack.
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Acid-catalyzed hydrolysis of epoxides gives glycols with _________ stereochemistry. Anti stereochemistry results from the backside attack of water on the protonated epoxide. Chapter 14
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A molecule of alcohol acts as the nucleophile and attacks and opens the epoxide. This reaction produces an alkoxy alcohol with _________ stereochemistry.
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The hydroxide ion attacks and opens the ring. The diol is obtained after protonation of the alkoxide with water.
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An epoxide is higher in energy than an acyclic ether by about 25 kcal/mol ring strain. Release of the ring strain makes the opening of an epoxide thermodynamically favored.
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Regioselectivity of Epoxidation
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CH2
CHCH3
Strong bases, such as Grignards and organolithiums, open the epoxide ring by attacking the _________ hindered carbon.
Chapter 14 38
Epoxy Resins
Polymer of bisphenol A and epichlorohydrin
CH3 HO C CH3 bisphenol A OH
Sulfides (Thioethers)
RSR, analog of ether. Name sulfides like ethers, replacing sulfide for ether in common name, or alkylthio for alkoxy in IUPAC system.
S CH3 methyl phenyl sulfide or methylthiobenzene
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Thiolates are easily synthesized by the Williamson ether synthesis, using dithiolate as the nucleophile.
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Sulfide Reactions
Sulfides are easily oxidized to sulfoxides and sulfones.
CH3 S CH3 H2O2 CH3COOH O CH3 S CH3 H2O2 CH3COOH O CH3 S CH3 O
CH3
+ S CH3 CH3
_ I
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