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5) Cyclic Ethers
a) O group is called and “oxa-” substituent: oxacycloalkanes
b) Common names are prevalent
O O
1
1 O 1
O 1 4
O
Oxacyclopropane Oxacyclopentane Oxacyclohexane 1,4-Dioxacyclohexane
Epoxide Tetrahydrofuran (THF) Tetrahydropyran 1,4-Dioxane
B. Physical Properties
1) Same molecular formula as Alcohol: CnH2n+2O
2) No Hydrogen Bonding is possible in R—O—R
3) Boiling Points are much lower than alcohols, more like haloalkanes
4) Water solubility much less than alcohols
a) MeOMe and EtOEt have some water solubility
b) Larger ethers are insoluble, very much like alkanes
5) Fairly unreactive, nonpolar solvents for organic reactions
O O
C. Metal Complexation by Crown Ethers
O O
1) Crown Ether is a cyclic polyether: --(CH2CH2O)— 6-crown-2
2) Named as: (# of total atoms in ring)-Crown-(# of oxygens) O O
3) Oxygen lone pair can be donated to M+ to form complexes
12-crown-4
4) Allows dissolution of metal salts in organic solvents
5) Size of cavity dictates which metal fits: 18-crown-6 K+ > Rb+ >Na+ etc…
O O
O O O O
+ KMnO4 K+ + MnO4
-
O O O O
O O
18-crown-6
II. Williamson Ether Synthesis
A. Alkoxides are good nucleophiles and strong bases
1) Reaction with primary, unhindered electrophile gives SN2
2) Reaction with non-primary or hindered electrophiles gives E2
RCH2I Ether
O-Na+ OCH2R
Williamson Ether
Synthesis
Alkene
Br
slower HO
OH
3) Ring size effects rate: k3 > k5 > k6 > k4 > k7 > k8
O-
a) Ring strain says k3 slow, Entropy makes k3 fast O
b) k4 is slow because ring strain > entropy Br
4) Intramolecular Williamson Ether Synthesis is Stereospecific
a) Like E2 elimination, the leaving group must be anti to nucleophile
b) Gauche leaving group won’t give product
- -
O D O O H
H Br
H D H
H Br R H H D
S gauche
anti
HBr H Br-
ROH R O RBr + H2O
H
H
H2SO4 H ROH -H+
ROH R O R O R O R
R
H -H2O
3) Only makes symmetric ethers
4) Follows SN2 for primary alcohols, SN1 for 2o and 3o alcohols
5) Useful for making mixed 3o/1o ethers
H+ CH3OH
OH OH2+ OCH3
MeOH MeOH
Br OMe OMe
H
IV. Reactions of Ethers
A. Peroxide formation
1) Ethers open to oxygen can form expolosive peroxide compounds
2) Never use old ethers as solvents or reactants; store ethers properly
2 R O CH + O2 2 R O C O O C O R
peroxide (explosive)
B. Cleavage by Strong Acid
1) Reverse of Ether Synthesis by Strong Acid
2) Tertiary Ethers are most reactive to cleavage
H
+ OH + E1
H O
O
V. Reactions of Oxacyclopropanes
A. Nucleophilic Ring Opening
1) Ether Oxygen behaves as an intramolecular leaving group
2) Anionic Nucleophiles can open the oxacyclopropane ring by SN2 attack
O O- H2O HO
- OH
O SN 2 O H2O
-
CH3S CH3 CH3
CH3S CH3S
CH3
2) Alkylmetal reagents also react with epoxides only among the ethers
O
SN2 CH3 D OH
CH3CH2MgBr + CH3 CH3 inverts CH3
D CH3 CH3CH2 CH3
C. Acid Catalyzed Oxacyclopropane Ring Opening
1) Mechanism
H H
O O O CH3
+ HO
H CH3
H CH3 H CH3 = H CH3 H
Nu Nu
H CH3 H CH3 H CH3 H
1. Li, NH3
2. H+, H2O