AnnouncementsSlide Number 2Career Direction and Organic ChemistryCareer Direction and Organic ChemistryCareer Direction and Organic ChemistryCareer Direction and Organic ChemistrySlide Number 7Slide Number 8Structure and NomenclatureNomenclature of EthersPhysical Properties of Alcohols and EthersSynthesis of Alcohols from AlkenesOxymercuration–DemercurationHydroboration–OxidationSlide Number 16Slide Number 17Alcohols as AcidsConversion of Alcohols to Alkyl HalidesSlide Number 20Conversion of Alcohols to Alkyl HalidesExamplesSlide Number 23Mechanisms of the Reactions of Alcohols with HXSlide Number 25Slide Number 26Slide Number 27Mechanism(2) Alkyl Halides from the Reaction of Alcohols with SOCl2 MechanismMechanismSlide Number 32Preparation of Mesylates (OMs) and Tosylates (Ots)Slide Number 34SN2 Displacement of Mesylate or TosylateExamplesExamplesAnnouncementsSlide Number 39Slide Number 40MechanismUnsymmetrical EthersUnsymmetrical Ethers: the Williamson Ether SynthesisSlide Number 44ExampleSynthesis of Ethers by alkoxy-mercuration-Demercurationtert-Butyl Ethers by Akylation of alcohols: Protecting groupsSilyl Ether Protecting GroupDeprotection of the Silyl Ether GroupExampleDirect reaction will not work!Slide Number 52Slide Number 53Reactions of EthersMechanismEpoxidesMechanismStereochemistry of EpoxidationReaction of EpoxidesBase-catalyzed ring opening of epoxideSlide Number 61Slide Number 62Epoxide ring-opening: a pathway to anti-DiolCrown EthersPhase Transfer CatalystsPhase Transfer Catalyst 15-crown-5Phase Transfer CatalysisCrown Ethers (Pederson) Kryptands (Lehn and Cram) Slide Number 69Slide Number 70Slide Number 71Slide Number 72Slide Number 73Slide Number 74Announcements • CIOS Survey will open Nov 24th to Dec. 15th – 90% of participation = 10 points on Final – Exempted Students must also contribute! • Final Exam: Dec 11 from 2:50pm to 5:40pm • Survey on T-square about career choices – Only two choices—~5 seconds to respond 12Career Direction and Organic Chemistry 1) Your current plan is to pursue further educational or career options that will require you to use the knowledge of organic chemistry you've acquired as an undergraduate. 2) Your current plan is to pursue further educational or career options that will require you to appreciate the principles of organic chemistry you've acquired as an undergraduate.Career Direction and Organic Chemistry 1) Your current plan is to pursue further educational or career options that will require you to use the knowledge of organic chemistry you've acquired as an undergraduate.  (i) graduate school in Chemistry or Biochemistry,  (ii) graduate school in areas of Chemical and Biomolecular Engineering, Biomedical Engineering, or Materials Science and Engineering with a focus on the molecular properties of matter,  (iii) employment following graduation in Chemistry or Biochemistry (example, environmental monitoring, product design),  (iv) employment following graduation in areas of Chemical and Biomolecular Engineering, Biomedical Engineering, or Materials Science and Engineering with a focus on the molecular properties of matter (example: catalyst development, tissue engineering, smart materials)Career Direction and Organic Chemistry 2) Your current plan is to pursue further educational or career options that will require you to appreciate the principles of organic chemistry you've acquired as an undergraduate.  (i) professional education in health fields such as medicine or dentistry or pharmacy  (ii) teaching science at a secondary school level  (iii) employment following graduation in commercial area of Chemistry or Biochemistry (example technical service, sales)  (iv) employment following graduation in areas of Chemical and Biomolecular Engineering, Biomedical Engineering, or Materials Science and Engineering with a focus on the bulk properties of matter (example: metallurgy, petroleum refining, medical equipment design).Career Direction and Organic Chemistry 1) Your current plan is to pursue further educational or career options that will require you to use the knowledge of organic chemistry you've acquired as an undergraduate. 2) Your current plan is to pursue further educational or career options that will require you to appreciate the principles of organic chemistry you've acquired as an undergraduate.Chapter 11 Alcohols and Ethers 7In this chapter: 1. The structures, properties, and nomenclature of common alcohols and ethers 2. Key molecules that contain such groups 3. The reactivity of alcohols, ethers, and a special group of ethers known as epoxides 8Structure and Nomenclature • Alcohols : Previously covered (see Sec. 4.3F) • Ethers: The oxygen atom and an ether is bonded to two carbon atoms • IUPAC Names- Ethers are named as having an alkoxyl substituent on the main chain. Diethyl ethertert-Butyl methyl etherDivinyl etherOOCH3OOEthyl phenyl ether9Nomenclature of Ethers • Rules of naming ethers – Similar to those with alkyl halides • CH3O– Methoxy • CH3CH2O– Ethoxy • Cyclic ethers OEthoxyethane(diethyl ether)Oxacyclopropaneor oxirane(ethylene oxide)OOOOOOxacyclobutaneor oxetaneOxacyclopentane(tetrahydrofuran or THF)1,4-Dioxacyclohexane(1,4-dioxane)10Physical Properties of Alcohols and Ethers • Ethers have boiling points that are roughly comparable with those of hydrocarbons of the same molecular weight (MW) • Alcohols have much higher boiling points than comparable ethers or hydrocarbons • Both alcohols and ethers can hydrogen bond to water and have similar solubilities in water. Diethyl ether and 1-butanol have solubilites of about 8 g per 100 mL in water. 11Synthesis of Alcohols from Alkenes • Acid-catalyzed Hydration of Alkenes • Regioselectivity: Markovnikov • Carbocation Intermediate • Possible rearrangements • Mechanism—discussed section 8.4 13 HH2O++H-OHH2O-Oxymercuration–Demercuration • Markovnikov regioselectivity • Anti stereoselectivity • Generally takes place without the complication of rearrangements • Mechanism -- discussed in Section 8.5 14 C CH2O, THFC CHgOAcOHHg(OAc)2C CHOHNaOHNaBH4Hydroboration–Oxidation • Anti-Markovnikov regioselectivity • Syn-stereoselectivity • Mechanism -- Discussed in Section 8.7 15 1. BH3 THF2. H2O2, HOOHH+ enantiomerRROHHRHOHH+, H2O or 1. Hg(OAc)2, H2O, THF 2. NaBH4, NaOH 1. BH3 • THF 2. H2O2, NaOH Markovnikov