11.15 synthesis of ethers - xiamen universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf ·...
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![Page 1: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/1.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
11.15 Synthesis of Ethers
![Page 2: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/2.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
11.15A Ethers by Intermolecular Dehydration of Alcohols
+R O H ROHH+
R O R + H2O
CH3CH2OH
H2SO4
140°C
H2SO4180°C
CH2 CH2
CH3CH2OCH2CH3
![Page 3: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/3.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
Mechanism Mechanism OH2
SN2 H2OCH3CH2OHH+
CH3CH2HOCH2CH3
CH3CH2OCH2CH3H+
CH3CH2OCH2CH3
H
ROH + R'OHH2SO4
ROR'ROR
R'OR'H2O+
![Page 4: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/4.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
11.15B The Williamson Synthesis of Ethers
ROR'ArOR'+RONa
ArONa LR' + NaL
L = Br, I, OSO2R'' , OSO2OR''
OK
+ CH3CH2Br
OCH2CH3
(CH3)3CONa + CH3I (CH3)3COCH3
![Page 5: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/5.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
11.15C tert-Butyl Ethers by Alkylation of Alcohols. Protecting Groups
RCH2OH CH2 CCH3CH3
+H2SO4 RCH2O C
CH3
CH3
CH3 tert-Butylprotectinggroup
HOCH2CH2CH2Br CHNaC+ NaOCH2CH2CH2Br
CHHC+
CHCHOCH2CH2CH2no
![Page 6: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/6.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
HOCH2CH2CH2Br CH2 CCH3CH3
+H2SO4 BrCH2CH2CH2O C
CH3
CH3
CH3
CHNaCCH2CH2CH2O C
CH3
CH3
CH3CHC
H2OH+
CH2CH2CH2OHCHC CCH3
CH3CH3
OH+
4-Pentyn-1-ol
![Page 7: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/7.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
11.15D Silyl Ether Protecting Groups
ROH SiCH3
C(CH3)3
CH3Cl+
imidazoleDMF
RO SiCH3
C(CH3)3
CH3
tert-Butylchlorodimethylsilane(TBDMSCl) (RO TBDMS)
HN Nimidazole
RO SiCH3
C(CH3)3
CH3
THFROH Si
CH3
C(CH3)3
CH3F+
Bu4N F
![Page 8: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/8.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
11.16 Reactions of Ethers
![Page 9: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/9.jpg)
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 RH
HBr
An oxonium salt
R O RR
OR
BF3+
RO
RMgR
R
RO
R
BF3
![Page 10: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/10.jpg)
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.
CH3CH2BrCH3CH2OCH2CH3 + HBr
+ H2O
CH3CH2OH+
HBr
CH3CH2Br
CH3 O CH3 + HI CH3OH + CH3I
CH3I
(CH3)3C O CH3 + HI (CH3)3CI + CH3OH
OCH3 OH+ HI + CH3I
HI
![Page 11: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/11.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
Mechanism Mechanism
CH3CH2OH
CH3CH2OCH2CH3
H+
CH2CH3
Br
CH3CH3OH + CH3CH2Br
CH3CH3OHH+
CH3CH2 OH2 BrCH3CH2Br
+ H2O
![Page 12: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/12.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
11.17 Epoxides
环氧化合物
![Page 13: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/13.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
Epoxides are cyclic ethers with three-membered rings.
C CO
An epoxide
H2C CH2
O
IUPAC name: oxirane
H2C CH2 + O2Ag
H2C CH2
OPreparation Preparation
RCH CHR + C O OHO
R' RCH CHRO
C OHO
R'+
C CO
CH3
H HCH3
C CO
CH3
H CH3H
C CO
HCH3 H
CH3
CH2 CO
CH3H
C CH2
O
HCH3
![Page 14: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/14.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
11.18 Reactions Epoxides
![Page 15: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/15.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
O
HOCH2CH2OHH2O/ H+
ROH/H+ROCH2CH2OH
HX XCH2CH2OHHCN NCCH2CH2OHBH3 (CH3CH2O)3BNH3 H2NCH2CH2OHRMgX
RCH2CH2OHLiAlH4 HCH2CH2OH
![Page 16: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/16.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
Acid-Catalyzed Ring Opening of an Epoxide
CH3 CH CH2
OCH3 CH CH2
O
CH3 CH CH2
OH
Nu
H+H
Nu
CH3 CH CH2
OH
CH3 CH CH2
Oδ+ δ+
More stable Nu Nu
H
Less stable
![Page 17: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/17.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
Base-Catalyzed Ring Opening of an Epoxide
CH3 CH CH2
OCH3 CH CH2OCH3
OHCH3O
CH3 CH CH2
OCH3 CH CH2OCH3
OCH3O
CH3OHCH3 CH CH2OCH3
OH
CH3 CH CH2
O
CH3 CH CH2
O
OCH3 OCH3
1° Carbon is less hindered.
![Page 18: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/18.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
11.18A Polyether Formation
CH2 CH2
OCH3O + CH2 CH2 OCH3O
CH2 CH2
O
CH2 CH2 OCH3O CH2 CH2 O
etc.CH3OH
CH2 CH2 OCH3O CH2 CH2 OH
Poly(ethylene glycol)
![Page 19: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/19.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
11.19 Anti Hydroxylation of Alkenes Via Epoxides
![Page 20: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/20.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
O
H
H
H2OOH
OH
H
H
H
H
OH
OH
+
C CO
CH3
H HCH3
H2O
CH3OHHHHO
CH3
CH3HHOOHH
CH3
C CO
CH3
H CH3H
C CO
HCH3 H
CH3
H2O H2O
CH3OHHOHH
CH3
![Page 21: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/21.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
11.20 Crown Ethers: Nucleophilic Substitution Reactions in Relatively
Nonpolar Aprotic Solvents by Phase-Transfer Catalysis
![Page 22: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/22.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
11.20A Crown Ethers (冠醚)
OO
O
OOO
18-Crown-618-冠-6
![Page 23: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/23.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
OO
O
OOO
K+O
OO
OOO
K+
Host-guest relationship
![Page 24: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/24.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
OO
O
OOO
+ KMnO4 +
OO
O
OOO
K+
MnO4紫色苯
"Purper benzene"
CH3
KMnO4
CO2H
100%Dicyclohexano-18-crown-6
Benzene
![Page 25: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/25.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
Phase-Transfer Catalysis
CH3(CH2)4CH2Br + KCN(s)
CH2Cl + KCN CH3CN25� , 72 h
CH2CN
20%
CH2Cl + KCN CH3CN25� , 0.4 h
CH2CN
100%
18-C-6
CH3CN18-C-6
CH3(CH2)4CH2CN
90%
Br(CH2)4Br + 2 KCN(s)CH3CN18-C-6
NC(CH2)4CN100%
![Page 26: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/26.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
Phase-Transfer Catalysis
OO
O
OOO
K+
CN
RX +O
OO
OOO
K+
CN
RCN +O
OO
OOO
K+
Cl
OO
O
OOO
K+
Cl+K CNKX +
Aqueous phase
Interphase
Organic phase
![Page 27: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/27.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
11.20B Transport Antibiotics and Crown Ethers
O O OCH3
O CH3
HOO
OOOCH3
OCH3
HH H H
H H H
CH3
CH3
O
O
H3C
H3C
Nonactin
![Page 28: 11.15 Synthesis of Ethers - Xiamen Universitychem.xmu.edu.cn/teach/yjhx/chem/02en/chpt11_3.pdf · ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 11 11.15B The](https://reader031.vdocuments.mx/reader031/viewer/2022011801/5aea110f7f8b9a36698c89d8/html5/thumbnails/28.jpg)
ORGANIC CHEMISTRY
Department of Chemistry, Xiamen University
Chapter 11
11.21 Summary of Reactions of Alkenes, Alcohols, and Ethers