Chapter 14 Ethers, Epoxides, and Sulfides 有机化学英文版教学课件（美国达拉斯社区学院） 《Organic Chemistry 5th Edition (L.G. Wade JR.)》.pptVIP

Chapter 14 Chapter 14 Ethers, Epoxides, and Sulfides Jo Blackburn Richland College, Dallas, TX Dallas County Community College District ? 2003, Prentice Hall Structure and Polarity Bent molecular geometry Oxygen is sp3 hybridized Tetrahedral angle Hydrogen Bond Acceptor Ethers cannot H-bond to each other. In the presence of -OH or -NH (donor), the lone pair of electrons from ether forms a hydrogen bond with the -OH or -NH.  Common Names of Ethers Alkyl alkyl ether Current rule: alphabetical order Old rule: order of increasing complexity Symmetrical: use dialkyl, or just alkyl. Examples: IUPAC Names Alkoxy alkane Examples: Cyclic Ethers Heterocyclic: oxygen is in ring. Naming Epoxides Spectroscopy of Ethers IR: Compound contains oxygen, but O-H and C=O stretches are absent. MS: ?-cleavage to form oxonium ion, or loss of either alkyl group. NMR: 13C-O signal between ?65 - ?90, 1H-C-O signal between ?3.5 - ?4.  = Williamson Synthesis Alkoxide ion + 1? alkyl bromide (or tosylate) Example: Phenyl Ethers Phenoxide ions are easily produced for use in the Williamson synthesis. Phenyl halides or tosylates cannot be used in this synthesis method. Alkoxymercuration-Demercuration Use mercuric acetate with an alcohol to add RO-H to a double bond and form the Markovnikov product. Bimolecular Dehydration of Alcohols Industrial method, not good lab synthesis. If temperature is too high, alkene forms. Cleavage of Ethers Ethers are unreactive toward base, but protonated ethers can undergo substitution reactions with strong acids. Alcohol leaving group is replaced by a halide. Reactivity: HI HBr HCl = Mechanism for Cleavage Phenyl Ether Cleavage Phenol cannot react further to become halide. Example: Autoxidation of Ethers In the presence of atmospheric oxygen, ethers slowly oxidize to hydroperoxides and dialkyl peroxides. Both are highly explosiv