You are on page 1of 37

CH3CH2CH2

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

1 alcohol to aldehyde to carboxylic acid


Difficult to stop at aldehyde
Use pyridinium chlorochromate (PCC) to
limit the oxidation.
PCC can also be used to oxidize 2
alcohols to ketones.

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

Catalyzed by ADH, alcohol dehydrogenase.


Oxidizing agent is NAD+, nicotinamide
adenine dinucleotide.
Ethanol oxidizes to acetaldehyde, then acetic
acid, a normal metabolite.
Methanol oxidizes to formaldehyde, then
formic acid, more toxic than methanol.
Ethylene glycol oxidizes to oxalic acid, toxic.
Treatment for poisoning is excess ethanol.
=>
Chapter 11 10
CH3CH2CH2
H
Br C O
H
H H
Alcohol as a Nucleophile
H
O
C R X

ROH is weak nucleophile


RO- is strong nucleophile
New O-C bond forms, O-H bond breaks.
=>
Chapter 11 11
CH3CH2CH2
H
Br C O
Alcohol as an Electrophile H H
H

OH- is not a good leaving


group unless it is H
protonated, but most
nucleophiles are strong O
bases which would + C
remove H+.
Convert to tosylate (good
leaving group) to react
with strong nucleophile C-Nuc bond forms,
C-O bond breaks
(base)
=>
Chapter 11 12
CH3CH2CH2
H
Br C O
H
H H
Formation of Tosylate Ester
H
C C
O Cl
C H O O
O S O N
O S O O S O

CH3 CH3 CH3

p-toluenesulfonyl chloride ROTs,


TsCl, tosyl chloride a tosylate ester
=>

Chapter 11 13
CH3CH2CH2
H
Br C O
H
SN2 Reactions of Tosylates H H

With hydroxide produces alcohol


With cyanide produces nitrile
With halide ion produces alkyl halide
With alkoxide ion produces ether
With ammonia produces amine salt
With LiAlH4 produces alkane
=>

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

Dehydrate with conc. H2SO4, then add H2


Tosylate, then reduce with LiAlH4
OH
H2SO4 H2
CH3CHCH3 CH2 CHCH3 CH3CH2CH3
Pt
alcohol alkene alkane

OH OTs
TsCl LiAlH4
CH3CHCH3 CH3CHCH3 CH3CH2CH3 =>
alcohol tosylate alkane

Chapter 11 16
CH3CH2CH2
H
Br C O
Reaction with HBr H H
H

-OH of alcohol is protonated


-OH2+ is good leaving group
3 and 2 alcohols react with Br- via SN1
1 alcohols react via SN2

+ 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

Chloride is a weaker nucleophile than


bromide.
Add ZnCl2, which bonds strongly with
-OH, to promote the reaction.
The chloride product is insoluble.
Lucas test: ZnCl2 in conc. HCl
1 alcohols react slowly or not at all.
2 alcohols react in 1-5 minutes.
3 alcohols react in less than 1 minute.
=>
Chapter 11 18
CH3CH2CH2
H
Br C O
H
H H
Limitations of HX Reactions
HI does not react
Poor yields of 1 and 2 chlorides
May get alkene instead of alkyl halide
Carbocation intermediate may rearrange.

=>

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

P bonds to -OH as Br- leaves


Br- attacks backside (SN2)
HOPBr2 leaves =>
Chapter 11 21
CH3CH2CH2
Reaction with Br C O
H
H
H H
Thionyl Chloride

Produces alkyl chloride, SO2, HCl


S bonds to -OH, Cl- leaves
Cl- abstracts H+ from OH
C-O bond breaks as Cl- transferred to C
Chapter 11 22
=>
CH3CH2CH2
H
Br C O
H
H H
Dehydration Reactions
Conc. H2SO4 produces alkene
Carbocation intermediate
Saytzeff product
Bimolecular dehydration produces ether
Low temp, 140C and below, favors ether
High temp, 180C and above, favors
alkene =>

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

glycerine nitroglycerine =>

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

You might also like