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H
Br C O
Organic Chemistry H H
H
Chapter 11
Reactions of Alcohols
CH3CH2CH2
H
Br C O
H
H H
Types of Alcohol Reactions
Dehydration to alkene
Oxidation to aldehyde, ketone
Substitution to form alkyl halide
Reduction to alkane
Esterification
Tosylation
Williamson synthesis of ether =>
Chapter 11 2
CH3CH2CH2
H
Br C O
H
H H
Summary Table
=>
Chapter 11 3
CH3CH2CH2
H
Br C O
H
H H
Oxidation States
Easy for inorganic salts
CrO42- reduced to Cr2O3
KMnO4 reduced to MnO2
Oxidation: loss of H2, gain of O, O2, or X2
Reduction: gain of H2 or H-, loss of O, O2, or
X2
Neither: gain or loss of H+, H2O, HX
=>
Chapter 11 4
CH3CH2CH2
H
1, 2, 3 Carbons Br C O
H H
H
=>
Chapter 11 5
CH3CH2CH2
H
Br C O
H
H H
Oxidation of 2 Alcohols
2 alcohol becomes a ketone
Reagent is Na2Cr2O7/H2SO4
Active reagent probably H2CrO4
Color change: orange to greenish-blue
OH O
Na2Cr2O7 / H2SO4
CH3CHCH2CH3 CH3CCH2CH3
=>
Chapter 11 6
CH3CH2CH2
H
Br C O
Oxidation of 1 Alcohols H H
H
OH N H CrO3Cl O
CH3CH2CH2CH2 CH3CH2CH2CH
=>
Chapter 11 7
CH3CH2CH2
H
Br C O
3 Alcohols Dont Oxidize H H
H
Cannot lose 2 Hs
Basis for chromic acid test
=>
Chapter 11 8
CH3CH2CH2
H
Br C O
H
H H
Other Oxidation Reagents
Collins reagent: Cr2O3 in pyridine
Jones reagent: chromic acid in acetone
KMnO4 (strong oxidizer)
Nitric acid (strong oxidizer)
CuO, 300C (industrial dehydrogenation)
Swern oxidation: dimethylsulfoxide, with
oxalyl chloride and hindered base,
oxidizes 2 alcohols to ketones and 1
alcohols to aldehydes. =>
Chapter 11 9
CH3CH2CH2
Biological Oxidation Br C O
H
H
H H
Chapter 11 13
CH3CH2CH2
H
Br C O
H
SN2 Reactions of Tosylates H H
Chapter 11 14
CH3CH2CH2
H
Br C O
Summary of Tosylate H H
H
Reactions
=>
Chapter 11 15
CH3CH2CH2
H
Br C O
Reduction of Alcohols H H
H
OH OTs
TsCl LiAlH4
CH3CHCH3 CH3CHCH3 CH3CH2CH3 =>
alcohol tosylate alkane
Chapter 11 16
CH3CH2CH2
H
Br C O
Reaction with HBr H H
H
+ H -
H3O Br
R O H R O H R Br =>
Chapter 11 17
CH3CH2CH2
H
Reaction with HCl Br C O
H H
H
=>
Chapter 11 19
CH3CH2CH2
H
Br C O
Reactions with H H
H
Phosphorus Halides
Good yields with 1 and 2 alcohols
PCl3 for alkyl chloride (but SOCl2 better)
PBr3 for alkyl bromide
P and I2 for alkyl iodide (PI3 not stable)
=>
Chapter 11 20
CH3CH2CH2
Mechanism with PBr3 Br C O
H H
H
H
Chapter 11 23
CH3CH2CH2
H
Br C O
H
H H
Dehydration Mechanisms
H
OH OH
H2SO4
CH3CHCH3 CH3CHCH3
CH3CHCH3
alcohol
H2O
CH2 CHCH3
+
H3O
CH3OH CH3 OH2 CH3 O CH3
H
CH3OH CH3OCH3
H2O
=>
Chapter 11 24
CH3CH2CH2
H
Energy Diagram, E1 Br C O
H H
H
=>
Chapter 11 25
CH3CH2CH2
H
Br C O
H
H H
Unique Reactions of Diols
Pinacol rearrangement
Periodic acid cleavage
=>
Chapter 11 26
CH3CH2CH2
H
Br C O
Pinacol Rearrangement H H
H
Pinacol: 2,3-dimethyl-2,3-butanediol
Dehydration with sulfuric acid
CH3 CH3 CH3 CH3 CH3
+
H CH3
CH3 C C CH3 CH3 C C CH3 CH3 C C
CH3
OH OH OH OH OH
H
CH3 CH3 CH3
CH3
CH3 C C CH3 C C CH3 CH3 C C CH3
CH3
OH OH CH3 OH CH3
CH3
CH3 C C CH3 =>
O CH3
Chapter 11pinacolone 27
CH3CH2CH2
H
Periodic Cleavage Br C O
H H
H
of Glycols
Same products formed as from
ozonolysis of the corresponding alkene.
H CH3 CH3
HIO 4 H
CH3 C C CH3 CH3 C C CH3
+
OH OH O O
OsO 4 O3
H2O2 (CH3)2S
H CH3
C C =>
H3C CH3
Chapter 11 28
CH3CH2CH2
H
Br C O
H
H H
Esterification
Fischer: alcohol + carboxylic acid
Tosylate esters
Sulfate esters
Nitrate esters
Phosphate esters
=>
Chapter 11 29
CH3CH2CH2
H
Br C O
H
H H
Fischer Esterification
Acid + Alcohol yields Ester + Water
Sulfuric acid is a catalyst.
Each step is reversible.
O CH3 + O CH3
H
CH3 C OH + H O CH2CH2CHCH3 CH3C OCH2CH2CHCH3
+ HOH
=>
Chapter 11 30
CH3CH2CH2
H
Br C O
H
H H
Tosylate Esters
Alcohol + p-Toluenesulfonic acid, TsOH
Acid chloride is actually used, TsCl
O
CH3CH2 O H + HO S CH3
O
O
CH3CH2 O S CH3 =>
O
+ HOH
Chapter 11 31
CH3CH2CH2
H
Br C O
H
H H
Sulfate Esters
Alcohol + Sulfuric Acid
O +
O
H
HO S OH + H O CH2CH3 HO S OCH2CH3
O O
O + O
H
CH3CH2O H + HO S OCH2CH3 CH3CH2O S OCH2CH3
O O =>
Chapter 11 32
CH3CH2CH2
H
Br C O
H
H H
Nitrate Esters
O +
H O
N OH + H O CH2CH3 N OCH2CH3
O O
CH2 O H CH2 O NO 2
CH2 O H + 3 HO NO2 CH2 O NO 2
CH2 O H CH2 O NO 2
Chapter 11 33
CH3CH2CH2
H
Br C O
H
H H
Phosphate Esters
O O O
CH3OH CH3OH
HO P OH CH3O P OH CH3O P OCH3
OH OH OH
CH3OH
O
CH3O P OCH3
=>
OCH3
Chapter 11 34
CH3CH2CH2
H
Br C O
Phosphate Esters in DNA H H
H
O CH2 base
O
H
H H
O O CH2 base
O
P
O O H
H H
O O CH2 base
O
P
O O H
H H
O O CH2 base
O
P
O O H
H H
O O
P
O O =>
Chapter 11 35
CH3CH2CH2
H
Br C O
H
H H
Alkoxide Ions
ROH + Na (or NaH) yields sodium alkoxide
RO- + 1 alkyl halide yields ether (Williamson
ether synthesis)
CH3
CH3CH2CHCH3 + CH3CH2 Br CH2CH2CH O CH2CH3
O
=>
Chapter 11 36
CH3CH2CH2
H
Br C O
H
H H
End of Chapter 11
Chapter 11 37