CH3CH2CH2

Organic Chemistry, 5th Edition L. G. Wade, Jr.

Br

C O H H H

H

Chapter 11 Reactions of Alcohols

Jo Blackburn Richland College, Dallas, TX Dallas County Community College District ¥2003, Prentice Hall

CH3CH2CH2 Br

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

C O H H H

H

=>
2

CH3CH2CH2 Br

Summary Table

C O H H H

H

Chapter 11

3

=>

CH3CH2CH2 Br

Oxidation States
‡ Easy for inorganic salts 
CrO42- reduced to Cr2O3 KMnO4 reduced to MnO2

C O H H H

H

‡ 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

1º, 2º, 3º Carbons

Br

C O H H H

H

=>
Chapter 11 5

CH3CH2CH2 Br

Oxidation of 2° Alcohols
‡ ‡ ‡ ‡

C O H H H

H

2° alcohol becomes a ketone Reagent is Na2Cr2O7/H2SO4 Active reagent probably H2CrO4 Color change: orange to greenish-blue
OH CH3CHCH2CH3 Na2Cr2O7 / H2SO 4 O CH3CCH2CH3
=>
Chapter 11 6

CH3CH2CH2

Oxidation of 1° Alcohols

Br

C O H 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 CH3CH2CH2CH2
Chapter 11

H CrO 3Cl

O CH3CH2CH2CH

=>
7

CH3CH2CH2

3° Alcohols Don¶t Oxidize
‡ Cannot lose 2 H¶s ‡ Basis for chromic acid test

Br

C O H H H

H

Chapter 11

=>

8

CH3CH2CH2 Br

Other Oxidation Reagents
‡ ‡ ‡ ‡ ‡ ‡

C O H H H

H

Collins reagent: Cr2O3 in pyridine Jones reagent: chromic acid in acetone KMnO4 (strong oxidizer) Nitric acid (strong oxidizer) CuO, 300°C (industrial dehydrogenation) Swern oxidation: dimethylsulfoxide, with oxalyl chloride and hindered base, oxidizes 2r alcohols to ketones and 1r alcohols to aldehydes. =>
Chapter 11 9

Biological Oxidation

CH3CH2CH2 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 Br

Alcohol as a Nucleophile H
C O

C O H H H

H

R X

‡ ROH is weak nucleophile ‡ RO- is strong nucleophile ‡ New O-C bond forms, O-H bond breaks.
=>
Chapter 11 11

CH3CH2CH2

Alcohol as an Electrophile
‡ OH- is not a good leaving group unless it is protonated, but most nucleophiles are strong bases which would remove H+. ‡ Convert to tosylate (good leaving group) to react with strong nucleophile (base)
=>
Chapter 11

Br

C O H H H

H

H
x+

C

O

C-Nuc bond forms, C-O bond breaks

12

CH3CH2CH2 Br

Formation of Tosylate Ester
H O C O O
N O O

C O H H H

H

Cl

C H O

C O O O

CH3

CH3

CH3

p-toluenesulfonyl chloride TsCl, ³tosyl chloride´

ROTs, a tosylate ester =>
13

Chapter 11

CH3CH2CH2 Br

SN2 Reactions of Tosylates
‡ ‡ ‡ ‡ ‡ ‡ 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

C O H H H

H

=>
Chapter 11 14

CH3CH2CH2

Summary of Tosylate Reactions

Br

C O H H H

H

=>

Chapter 11

15

CH3CH2CH2

Reduction of Alcohols

Br

C O H H H

H

‡ Dehydrate with conc. H2SO4, then add H2 ‡ Tosylate, then reduce with LiAlH4
OH CH3CHCH3 alcohol
OH CH3CHCH3 alcohol

H2 O 4

CH2

CHCH3

H2 Pt

alkene
OTs CH3CHCH3 tosylate

CH3CH2CH3 alkane

TsCl

LiAlH4

CH3CH2CH3 alkane

=>

Chapter 11

16

CH3CH2CH2

Reaction with HBr
‡ ‡ ‡ ‡

Br

C O H 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
H3O
+

H R O H

Br

-

R O H

R

Br

=>

Chapter 11

17

CH3CH2CH2

Reaction with HCl

Br

C O H 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. 2r alcohols react in 1-5 minutes. 3r alcohols react in less than 1 minute. =>
Chapter 11 18

CH3CH2CH2 Br

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.

C O H H H

H

=>
Chapter 11 19

CH3CH2CH2

Reactions with Phosphorus Halides
‡ ‡ ‡ ‡

Br

C O H H H

H

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

Reaction with Thionyl Chloride

CH3CH2CH2 Br

C O H H H

H

‡ ‡ ‡ ‡

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 Br

Dehydration Reactions
‡ ‡ ‡ ‡ ‡ ‡

C O H H H

H

Conc. H2SO4 produces alkene Carbocation intermediate Saytzeff product Bimolecular dehydration produces ether Low temp, 140°C and below, favors ether High temp, 180°C and above, favors alkene =>
Chapter 11 23

CH3CH2CH2 Br

Dehydration Mechanisms
H OH CH3CHCH3 alcohol
H2O CH3OH H3O
+

C O H H H

H

H2SO 4

OH CH3CHCH3
CH3CHCH3

CH2

CHCH3

CH3

OH2

CH3

O CH3 H

CH3OH

H2O
Chapter 11

CH3OCH3

=>
24

CH3CH2CH2 Br

Esterification
‡ ‡ ‡ ‡ ‡ Fischer: alcohol + carboxylic acid Tosylate esters Sulfate esters Nitrate esters Phosphate esters

C O H H H

H

=>

Chapter 11

25

CH3CH2CH2 Br

Fischer Esterification
‡ Acid + Alcohol yields Ester + Water ‡ Sulfuric acid is a catalyst. ‡ Each step is reversible.
O CH3 C OH CH3 + H O CH2CH2CHCH3
H
+

C O H H H

H

O

CH3

CH3C OCH2CH2CHCH3 + HOH

=>
Chapter 11 26

CH3CH2CH2 Br

Tosylate Esters

C O H H H

H

‡ Alcohol + p-Toluenesulfonic acid, TsOH ‡ Acid chloride is actually used, TsCl
O CH3CH2 O H + HO S O
O CH3CH2 O S O
Chapter 11

CH3

CH3 => + HOH
27

CH3CH2CH2 Br

Sulfate Esters
Alcohol + Sulfuric Acid
O HO O OH + H O CH2CH3

C O H H H

H

H

+

O HO O OCH2CH3

O CH3CH2O H + HO O
Chapter 11

OCH2CH3

H

+

O CH3CH2O O OCH2CH3

=>
28

CH3CH2CH2 Br

Nitrate Esters
O O N OH + H O CH2CH3 H
+

C O H H H

H

O O

N OCH2CH3

CH2 CH2 CH2

O H O H O H + 3 HO NO 2

CH2 CH2 CH2

O NO 2 O NO 2 O NO 2

glycerine

nitroglycerine =>

Chapter 11

29

CH3CH2CH2 Br

Phosphate Esters
O HO P OH OH CH3OH CH3O O P OH OH
CH3OH O CH3O P OH
CH3OH O CH3O P OCH3 OCH3

C O H H H

H

OCH3

=>

Chapter 11

30

CH3CH2CH2 Br

C O H H H

H

End of Chapter 11

Chapter 11

31

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