Organic Chemistry, 7th Edition L. G. Wade, Jr.

Chapter 14
Ethers, Epoxides, and Sulfides

© 2010, Prentice Hall

Ethers
• Formula is R—O—R′, where R and R′ are alkyl or aryl. • Symmetrical or unsymmetrical
CH3 O CH3

O CH3

Chapter 14

2

Structure and Polarity
• Oxygen is ________ hybridized. • ________ molecular geometry. • C—O—C angles is _________°. • Polar C—O bonds. • Dipole moment of 1.3 D.
Chapter 14 3

Chapter 14 4 Hydrogen Bond Acceptor • Ethers cannot hydrogen-bond with other ether molecules. • Molecules that cannot hydrogen-bond intermolecularly have a _____________ boiling point. Chapter 14 6 . ether cannot serve as hydrogenbond donors. so they do not solvate small anions well.Boiling Points Similar to alkanes of comparable molecular weight. Chapter 14 5 Solvation of Ions with Ether • An ionic substance such as lithium iodide is moderately soluble in ethers because the small lithium cation is strongly solvated by the ether’s lone pairs of electrons. • Unlike alcohols. • Ether molecules can hydrogen-bond with water and alcohol molecules.

CH3 CH3CH2 O CH2CH3 CH3 O C CH3 CH3 Chapter 14 9 . Chapter 14 8 Common Names of Ethers • Name the two alkyl groups attached to the oxygen and add the word ether. • The size of the cation will determine the size of the ring needed. • Name the groups in alphabetical order • Symmetrical: Use dialkyl or just alkyl. • Electrophiles: The ethers nonbonding electrons stabilize the borane (BH3). • Complexation by crown ethers often allows polar inorganic salts to dissolve in nonpolar organic solvents.Ether Complexes • Grignard reagents: Complexation of an ether with a Grignard reagent stabilizes the reagent and helps keep it in solution. Chapter 14 H _ + O B H H BH3 THF 7 Crown Ether Complexes • Crown ethers can complex metal cations inside the ring.

• Epoxides (oxiranes) • Oxetanes • Furans • Pyrans O O H2C CH2 O O (Oxolanes (Oxanes O O ) ) O O •Dioxanes Chapter 14 11 Epoxide Nomenclature • Name the starting alkene and add “oxide”. The small group (with the oxygen) becomes an “alkoxy” group. H O H Chapter 14 12 .IUPAC Names • The more complex alkyl group is the alkane name. peroxybenzoic acid H O H • The oxygen can be treated as a substituent (epoxy) on the compound. CH3 CH3 O C CH3 CH3 O CH3 Chapter 14 10 Cyclic Ethers • Heterocyclic: Oxygen is part of the ring. Use numbers to specify position.

• Many compounds have the C—O stretch. Chapter 14 14 MS Spectrometry of Ethers • Main fragmentation is the _______________ to form the resonance-stabilized oxonium ion. • Either alkyl group can be cleaved this way. H CH3CH 2 O CH 3 H Chapter 14 13 IR Spectroscopy of Ethers • IR: The C—O stretch is in the fingerprint region around 1000–1200 cm-1. the carbons are 2 and 3). Substituents are named in alphabetical order. then the compound is most likely an ether.Epoxide Nomenclature (Continued) • The three-membered oxirane ring is the parent (oxygen is 1. • If the IR spectrum has the C—O stretch but does not have a C═O or an OH stretch. Chapter 14 15 .

1H—C—O signal between δ 3. Chapter 14 18 .Loss of an Alkyl Group • The C—O bond can be cleaved to produce a carbocation. Chapter 14 16 MS Spectra of Diethyl Ether Chapter 14 17 NMR Spectroscopy of Ethers • The typical chemical shift for ethers in NMR are: 13C—O signal between δ 65–δ90.5–δ4.

Williamson Ether Synthesis • This method involves an SN2 attack of the alkoxide on an ________________________ halide or tosylate. • Phenyl halides or tosylates cannot be used in this synthesis method. Chapter 14 19 Examples of the Williamson Synthesis Chapter 14 20 Phenyl Ethers O H + NaOH _ O Na+ + HOH • Phenoxide ions are easily produced for because the alcohol proton is acidic. Chapter 14 21 .

• Reactivity: HI > HBr >> HCl Chapter 14 24 . Chapter 14 22 Industrial Ether Synthesis • Industrial method. The alcohol will react with the intermediate mercurinium ion by attacking the __________ substituted carbon. CH3CH2 O H + H O CH2CH3 H2SO4 CH3CH2 O CH2CH3 140°C Chapter 14 23 Cleavage of Ethers • Ethers are __________________. alkene forms. which makes them ideal solvents for a lot of different reactions. • They can be cleaved by heating with HBr and HI. • If temperature is too high. not good lab synthesis.Alkoxymercuration– Demercuration Reaction • Use mercuric acetate with an alcohol.

halide attacks. • Precautions: Do not distill to dryness. => Phenyl Ether Cleavage • Phenol cannot react further to become halide because an SN2 reaction cannot occur on an sp2 carbon. Store in full bottles with tight caps. ethers slowly _______________ to hydroperoxides and dialkyl peroxides. _ Br CH3 H + O CH3 Br CH3 + H O CH3 • Alcohol is protonated. • Both are highly explosive. and another molecule of alkyl bromide is formed.Mechanism for Cleavage • Ether is ____________________. CH3 O CH3 H Br CH3 H + O CH3 + Br _ _ • Alcohol leaves as halide attacks. O CH2CH3 OH HBr + CH3CH2 Br Chapter 14 26 Autoxidation of Ethers • In the presence of atmospheric oxygen. Chapter 14 27 .

Mechanism of Autoxidation Chapter 14 28 Synthesis of Epoxides • Peroxyacids are used to convert alkenes to epoxides. • The reaction is carried out in an aprotic acid to prevent the opening of the epoxide. making selective epoxidation possible. Chapter 14 29 Selectivity of Epoxidation • The most electron-rich double bond reacts faster. Chapter 14 30 . Most commonly used peroxyacid is metachloroperoxybenzoic acid (MCPBA).

Chapter 14 33 . the alkoxide may displace a halide ion and form a ring. • Anti stereochemistry results from the backside attack of water on the protonated epoxide. • Treatment of a halohydrin with a base leads to an epoxide through this _______________ Chapter 14 31 attack. Epoxides via Halohydrins Chapter 14 32 Acid-Catalyzed Opening of Epoxides • Acid-catalyzed hydrolysis of epoxides gives glycols with _________ stereochemistry.Halohydrin Cyclization • If an alkoxide and a halogen are located in the same molecule.

• This reaction produces an alkoxy alcohol with _________ stereochemistry. Chapter 14 36 . • The diol is obtained after protonation of the alkoxide with water. • Release of the ring strain makes the opening of an epoxide thermodynamically favored. Chapter 14 35 Ring Opening in Base • An epoxide is higher in energy than an acyclic ether by about 25 kcal/mol ring strain. Chapter 14 34 Base-Catalyzed Opening of Epoxides • The hydroxide ion attacks and opens the ring.Acid-Catalyzed Opening of Epoxides in Alcohol Solution • A molecule of alcohol acts as the nucleophile and attacks and opens the epoxide.

Regioselectivity of Epoxidation Chapter 14 37 Reaction of Epoxides with Grignard and Organolithiums OH O H2C CHCH3 + 2) H3O MgBr 1) ether + CH2 CHCH3 • Strong bases. such as Grignards and organolithiums. Chapter 14 38 Epoxy Resins Polymer of bisphenol A and epichlorohydrin CH3 HO C CH3 bisphenol A OH O H2C CHCH2Cl epichlorohydrin . open the epoxide ring by attacking the _________ hindered carbon.

analog of ether. CH3 S CH3 H2O2 CH3COOH O CH3 S CH3 H2O2 CH3COOH O CH3 S CH3 O • Sulfides react with unhindered alkyl halides to give sulfonium salts. using dithiolate as the nucleophile. CH3 S CH3 + CH3 I Chapter 14 CH3 + S CH3 CH3 _ I 42 . Chapter 14 41 Sulfide Reactions • Sulfides are easily oxidized to sulfoxides and sulfones. replacing “sulfide” for “ether” in common name. or “alkylthio” for “alkoxy” in IUPAC system. S CH3 methyl phenyl sulfide or methylthiobenzene Chapter 14 40 Thiols and Thiolates • Thiolates are easily synthesized by the Williamson ether synthesis. • Name sulfides like ethers.Sulfides (Thioethers) • R—S—R′.

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