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Chapter 16
Ethers, Epoxides, and
Sulfides
Nomenclature of Ethers
Substitutive IUPAC Nomenclature: name as
alkoxy derivatives of alkanes
Functional Class Nomenclature: name the
groups attached to oxygen in alphabetical order
as separate words; ether is last word.
CH3OCH2 CH3
CH3CH2OCH2 CH3
methoxyethane
ethoxyethane
ethyl methyl ether
diethyl
y ether
CH3CH2OCH2CH2CH2Cl
1-chloro-3-ethoxypropane
3-chloropropyl ethyl ether
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Nomenclature of Sulfides
Substitutive IUPAC Nomenclature: name as
alkylthio derivatives of alkanes.
Functional Class Nomenclature: Analogous
g
to
ethers, but replace ether as last word in the name
by sulfide
CH3SCH2 CH3
CH3CH2SCH2 CH3
methylthioethane
ethylthioethane
ethyl methyl sulfide
diethyl sulfide
SCH3
(methylthio)cyclopentane
cyclopentyl methyl sulfide
S
Thiolane
S
Thietane
S
Thiane
O
1,4-Dioxane
O
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Polyethers
C(CH3)3
132
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Most stable
conformation of diethyl
ether resembles that of
pentane (staggered).
OH
117C
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solubility in water
(g/100 mL)
OH
Crown Ethers
Structure
Properties
Applications
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18-Crown-6
O
O
O
K+
O
O
O
O
O
O
O
O
O
K+F
benzene
O
K+
O
O
O
+ F
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Preparation of Ethers
Acid catalyzed condensation of alcohols (15.7)
Addition of alcohols to alkenes
Williamson ether synthesis
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H2SO4, 130C
CH3CH2CH2CH2OCH2CH2CH2CH3
(60%)
*Discussed earlier in Section 15.7
Method works best for the synthesis of symmetrical
ethers
H+
(CH3)3COCH3
tert-Butyl
tert
Butyl methyl ether
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Another Example
Tertiary and secondary (crowded) alkyl halides
readily undergo E2 elimination reactions in the
presence of strong bases such as alkoxides
CH2Cl
CH3CHCH3
ONa
CH2OCHCH3
(84%)
CH3
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Origin of Reactants
CH3CHCH3
CH2OH
OH
HCl
CH2Cl
Na
+
CH3CHCH3
ONa
CH2OCHCH3
(84%)
CH3
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CH3CHCH2CH3 + CH3Br
heat
OCH3
Br
(81%)
ICH2CH2CH2CH2I
(65%)
Mechanism
CH3CHCH2CH3
O
CH3
CH3CHCH2CH3
Br
Br
CH3CHCH2CH3
Br
HBr
O
CH3
+
H
CH3CHCH2CH3
O
H
Br CH
3
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Mechanism
ICH2CH2CH2CH2I
HI
HI
I
O+
H
Preparation of Epoxides
Epoxides are prepared by two major methods.
Both begin with alkenes.
Reaction of alkenes with peroxy acids (Section
6.19)
Conversion of alkenes to vicinal halohydrins,
followed by treatment with base (Section 16.10)
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H
OH
NaOH
H2O
Br
via:
(81%) H
H
H
Br
NaOH
H2O
anti
addition
OH
inversion
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Reactions of Epoxides
MgX
CH2
H2C
O
R
CH2
CH2
OMgX
H3O+
RCH2CH2OH
Reactions of epoxides involve attack by a
nucleophile and proceed with ring-opening.
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NuH + H2C
NuCH2CH2OH
O
CH2
CH2MgCl + H2C
O
1. diethyl ether
2. H3O+
CH2CH2CH2OH
(71%)
In General...
For epoxides where the two carbons of the ring are
differently substituted:
Nucleophiles attack here
when the reaction is
catalyzed by acids:
R
CH2
C
H
Anionic nucleophiles
attack here:
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H2C
O
CH3CH2O CH2CH2OH
(50%)
NaOCH2CH3
CH3CH2OH
CH3CH2
CH2
H2C
CH3CH2
CH3CH2
CH2CH2
CH2CH2
CH2CH3
CH2CH3
Example
CH2 KSCH2CH2CH2CH3
H2C
O
ethanol-water, 0C
CH3CH2CH2CH2S CH2CH2OH
(99%)
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Stereochemistry
H
H
NaOCH2CH3
CH3CH2OH
OCH2CH3
H
H (67%)
OH
Inversion of configuration at carbon being
attacked by nucleophile.
Suggests SN2-like transition state.
CH3
H3C
R
H3C H
NH3
H2O
H2N
OH
CH3
(70%)
Stereochemistry
H3C
H
R
CH3
H3C H
+
H3N
NH3
H2O
H2N
OH
(70%)
CH3
H3C
H
O
H3C
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CH3
C
C
H
NaOCH3
CH3OH
CH3O
CH3
CH3CH
CCH3
(53%)
OH
CH3
MgBr + H2C
CHCH3
1. diethyl ether
2. H3O+
O
CH2CHCH3
(60%)
OH
H2C
O
CH(CH2)7CH3
OH
(90%)
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CH2 CH CH OH
3
2
CH3CH2OCH2CH2OH
O
(87-92%)
(87
92%)
H SO , 25
25C
C
2
H2C
O
HBr
BrCH2CH2OH
10C
(87-92%)
Mechanism
CH2
H2C
H2C
Br
Br
CH2
+
O
H
Br
CH2CH2
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CH2
H2C
Step 2
CH2
+
O
H
H2C
H
H
H2C
+
O
CH2CH2
CH2
+
O
H
H
+
H O
H
O
CH2CH2
+
H O
CH2CH2
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CH3
C
C
H
CH3OH
CH3
H2SO4
OCH3
CH3CH
CCH3
OH CH3
(76%)
Consistent with carbocation character at
transition state
O
Stereochemistry
H
OH
O
HBr
(73%)
H
H
Br
Inversion of configuration at carbon being
attacked by nucleophile
H3C
H
R
H3C H
CH3
CH3OH
H2SO4
CH3O
H
H
CH3
OH
(57%)
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Stereochemistry
H3C
H
CH3
CH3OH
CH3O
H2SO4
H3C H
OH
CH3
+
CH3O
H
H3C
H
+
H3C
+
O H
anti-Hydroxylation of Alkenes
H
CH3COOH
H
H
H2O
H
OH
HClO4
H
(80%)
OH
+ enantiomer
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+ O2 + H+
+ NADH
C
enzyme
+ H2O + NAD+
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CH3CHCH
CH2
R'
NaSCH3
R'
CH3CHCH
CH2
methanol
Cl
SCH3
R'
+
S R'
2+
S R'
O
sulfide
sulfoxide
sulfone
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NaIO4
water
SCH3
+
SCH3
(91%)
Sodium metaperiodate oxidizes sulfides to sulfoxides
and no further.
O
H2O2
2+
SCH CH2
SCH CH2
(2 equiv)
O (74-78%)
1 equiv of H2O2 or a peroxy acid gives a sulfoxide,
2 equiv give a sulfone.
R"
+
S
R'
R'
Product is a sulfonium salt.
CH3(CH2)10CH2SCH3
CH3I
R"
+
CH3(CH2)10CH2SCH3 I
CH3
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Infrared Spectroscopy
CO stretching of ethers: 1070 and 1150 cm-1
(strong)
Epoxides exhibit bands for CO stretching at:
810-950 cm-1 (asymmetric stretch) and 1250 cm-1
(symmetric stretch).
There is also a third band in the range 750-840
cm-1.
CH2(CH2)8CH3
H
C
H
C
O
Infrared Spectroscopy
= 1050 cm-1
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1H
NMR
0.8 ppm
1.4 ppm
0.8 ppm
1H
NMR
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13C
Carbons of COC
appear in the range
57-87 ppm.
26
O
68
NMR
H
47 C
H
C 52
O
UV-VIS
Simple ethers have their absorption maximum at
about 185 nm and are transparent to ultraviolet
radiation above about 220 nm
nm.
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Mass Spectrometry
Molecular ion fragments to give oxygen-stabilized
carbocation.
+
CH3CH2O
CHCH2CH3
m/z 102
CH3
+
CH3CH2O
CH
m/z 73
CH3
+
CH3CH2O
CHCH2CH3
m/z 87
30