厦门大学化学化工学院：《有机化学》课程教学资源（课件讲稿，双语版）第十一章 醇和醚（11.15-11.21）Synthesis of Ethers

ORGANIC CHEMISTRY Chapter ll CH H2SO4 HOCH, CH,CH, Br CH,=CCH3 BrCH2 CH2 CH2O-C-CH3 CH3 CH CH NaC三CH HO HC=C-CHbCHCH0-C-CH H CH3 CH HC=C-CHCHChOH CH2-C-OH 4-Pentyn-I-ol CH Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 HOCH2CH2CH2Br CH2 CCH3 CH3 + H2SO4 BrCH2CH2CH2O C CH3 CH3 CH3 NaC CH CH2CH2CH2O C CH3 CH3 CH3 HC C H2O H+ HC C CH2CH2CH2OH C CH3 CH3 CH3 + OH 4-Pentyn-1-ol

ORGANIC CHEMISTRY Chapter ll 11. 15D Silyl Ether Protecting Groups CH CH imidazole ROH +C1-Si-C(CH3)3 DMI RO-SI-C(CH3)3 F CH CH tert-Butylchlorodimethylsilane (TBDMSCI (RO-TBDMS) mIdazole HN、/N CH BUNF CH RO-SI-C(CH3)3 ROH F-Si-C(CH3)3 THE CH CH3 Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15D Silyl Ether Protecting Groups ROH Si CH3 C(CH3)3 CH3 + Cl imidazole DMF RO Si CH3 C(CH3)3 CH3 tert-Butylchlorodimethylsilane (TBDMSCl) (RO TBDMS) imidazole HN N RO Si CH3 C(CH3)3 CH3 THF ROH Si CH3 C(CH3)3 CH3 + F Bu4N F

ORGANIC CHEMISTRY Chapter ll 11 16 Reactions of ethers Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.16 Reactions of Ethers

ORGANIC CHEMISTRY Chapter ll o The oxygen of ether linkage makes ether basic Ether can react with proton donors to form oxonium salts HBr R-0-R R-0-R H An oxonium salt R R-OR+ BF3 O:BF R R R R O: Mg: O R R R Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 The oxygen of ether linkage makes ether basic. Ether can react with proton donors to form oxonium salts. R O R R O R H HBr An oxonium salt R O R R O R + BF3 R O R Mg R R R O R BF3

ORGANIC CHEMISTRY Chapter ll o Heating dialkyl ethers with very strong acids(hl, hBr and h,sO4) cause tem to undergo reactions in which the carbon-oxygen bond breaks chr CHOCHo CH2+ hBr-chr2 ch Br Chrchooh HBr CHr CH,Br H,O CH3-O-CH3 + HI-CH3oH Ch3I HI CHal (CH3)3C-0-CH3 +HI(CH3)3CI CH3OH 少-0CH+H OH+ CH3I Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 Heating dialkyl ethers with very strong acids (HI, HBr, and H2SO4) cause tem to undergo reactions in which the carbon-oxygen bond breaks. CH CH3CH2Br 3CH2OCH2CH3 + HBr + H2O + CH3CH2OH HBr CH3CH2Br CH3 O CH3 + HI CH3OH + CH3I CH3I (CH3)3C O CH3 + HI (CH3)3CI + CH3OH OCH3 + HI OH + CH3I HI