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General

Organic Chemistry
Two credits
Second Semester 2009

King Saud bin Abdulaziz University for Health Science

Reference Book: Organic Chemistry: A Brief Course,


by Robert C. Atkins and Francis A. Carey
Third Edition

Instructor: Rabih O. Al-Kaysi, PhD.


Lecture 16

Chapter 10

Alcohols, Ethers and Phenols


Sources of Alcohols
Methanol
Methanol

Methanol is an industrial chemical


end uses: solvent, antifreeze, fuel
principal use: preparation of
formaldehyde
Methanol
Methanol

Methanol is an industrial chemical


end uses: solvent, antifreeze, fuel
principal use: preparation of
formaldehyde
prepared by hydrogenation of carbon
monoxide
CO 2H22→
CO ++ 2H → CH
CH3OH
3OH
Ethanol
Ethanol

Ethanol is an industrial chemical


Most ethanol comes from fermentation
Synthetic ethanol is produced by hydration
of ethylene
Synthetic ethanol is denatured (made
unfit for drinking) by adding methanol, benzene,
pyridine, castor oil, gasoline, etc.
Other
Otheralcohols
alcohols

Isopropyl alcohol is prepared by hydration of


propene.
All alcohols with four carbons or fewer are
readily available.
Most alcohols with five or six carbons are
readily available.
Sources
Sourcesof
ofalcohols
alcohols

Reactions discussed in earlier chapters

Hydration of alkenes
Hydroboration-oxidation of alkenes
Hydrolysis of alkyl halides
Syntheses using
Grignard reagents
organolithium reagents
Sources
Sourcesof
ofalcohols
alcohols

New methods in Chapter

Reduction of aldehydes and ketones


Reduction of carboxylic acids
Reduction of esters
Reaction of Grignard reagents with
epoxides
Diols by hydroxylation of alkenes
Preparation of Alcohols
by
Reduction of Aldehydes and Ketones
Reduction
Reductionof
ofAldehydes
AldehydesGives
GivesPrimary
PrimaryAlcohols
Alcohols

R R

C O H C OH
H H
Example:
Example: Catalytic
CatalyticHydrogenation
Hydrogenation

O
CH3O CH + H2

Pt, ethanol

CH3O CH2OH

(92%)
Reduction
Reductionof
ofKetones
KetonesGives
GivesSecondary
SecondaryAlcohols
Alcohols

R R

C O H C OH
R' R'
Example:
Example: Catalytic
CatalyticHydrogenation
Hydrogenation

O H OH

Pt
+ H2
ethanol
(93-95%)
Metal
MetalHydride
HydrideReducing
ReducingAgents
Agents

H H
+ – + –
Na H B H Li H Al H

H H

Sodium Lithium
borohydride aluminum hydride

act as hydride donors


Examples:
Examples: Sodium
SodiumBorohydride
Borohydride

Aldehyde
O2N O2N
O NaBH4
CH CH2OH
methanol
(82%)
Ketone

O NaBH4 H OH

ethanol
(84%)
Lithium
Lithiumaluminum
aluminumhydride
hydride

more reactive than sodium borohydride


cannot use water, ethanol, methanol etc.
as solvents
diethyl ether is most commonly used solvent
Examples:
Examples: Lithium
LithiumAluminum
AluminumHydride
Hydride

Aldehyde

O 1. LiAlH4
diethyl ether
CH3(CH2)5CH CH3(CH2)5CH2OH
2. H2O
(86%)
Ketone
O 1. LiAlH4 OH
diethyl ether
(C6H5)2CHCCH3 (C6H5)2CHCHCH3
2. H2O
(84%)
Preparation of Diols
Diols
Diolsare
areprepared
preparedby...
by...

reactions used to prepare alcohols


hydroxylation of alkenes
Example:
Example: reduction
reductionof
ofaadialdehyde
dialdehyde

O O
H2 (100 atm)
HCCH2CHCH2CH
Ni, 125°C
CH3

HOCH2CH2CHCH2CH2OH

CH3
3-Methyl-1,5-pentanediol
(81-83%)
Hydroxylation
Hydroxylationof
ofAlkenes
Alkenes
Gives
GivesVicinal
VicinalDiols
Diols

vicinal diols have hydroxyl groups on adjacent


carbons
ethylene glycol (HOCH2CH2OH) is most familiar
example

Just for general knowledge, will not be tested on


Osmium
OsmiumTetraoxide
TetraoxideisisKey
KeyReagent
Reagent

syn addition of —OH groups to each carbon


of double bond

C C
C C
HO OH
C C
O O
Os
O O
Just for general knowledge, will not be tested on
Just for general knowledge, will not be tested on
Example
Example

CH3(CH2)7CH CH2

(CH3)3COOH
OsO4 (cat)
tert-Butyl alcohol
HO–

CH3(CH2)7CHCH2OH

OH
(73%)
Reactions of Alcohols
Review
Reviewof
ofReactions
Reactionsof
ofAlcohols
Alcohols

reaction with hydrogen halides


acid-catalyzed dehydration
New
NewReactions
Reactionsof
ofAlcohols
AlcoholsininThis
This
Chapter
Chapter
conversion to ethers
esterification
esters of inorganic acids
oxidation
cleavage of vicinal diols
Conversion of Alcohols to Ethers
Conversion
Conversionof
ofAlcohols
Alcoholsto
toEthers
Ethers

RCH2O CH2R

H OH

H+

RCH2O CH2R + H OH

acid-catalyzed
referred to as a "condensation"
equilibrium; most favorable for primary alcohols
Example
Example

2CH3CH2CH2CH2OH

H2SO4, 130°C

CH3CH2CH2CH2OCH2CH2CH2CH3

(60%)
Mechanism
Mechanismof
ofFormation
Formationof
ofDiethyl
DiethylEther
Ether

Step 1:
•• •
CH3CH2O • H OSO2OH
H

H
+ –
CH3CH2O •• + OSO2OH
H knowledge, will not be tested on
Just for general
Mechanism
Mechanismof
ofFormation
Formationof
ofDiethyl
DiethylEther
Ether

Step 2:

H H
CH3CH2
CH3CH2 ••
+O
+ + •• O ••
+•
H CH3CH2O •
H
•• •
CH3CH2O • H

Just for general knowledge, will not be tested on


Mechanism
Mechanismof
ofFormation
Formationof
ofDiethyl
DiethylEther
Ether

Step 3:

CH3CH2 CH3CH2
+•
CH3CH2O • CH3CH2O •• +
••
H
••
•• OSO ••
2OH H OSO2OH
– •• ••

Just for general knowledge, will not be tested on


Ethers
Nomenclature of Ethers, Epoxides
Functional
FunctionalClass
ClassIUPAC
IUPACNames
Namesof
ofEthers
Ethers

name the groups attached to oxygen in


alphabetical order as separate words; "ether" is
last word

CH3OCH2 CH3

ethyl methyl ether CH3CH2OCH2CH2CH2Cl

3-chloropropyl ethyl ether


CH3CH2OCH2 CH3

diethyl ether
Functional
FunctionalClass
ClassIUPAC
IUPACNames
Namesof
ofSulfides
Sulfides

analogous to ethers, but replace “ether” as last


word in the name by “sulfide.”

CH3SCH2 CH3
SCH3
ethyl methyl sulfide

cyclopentyl methyl sulfide


CH3CH2SCH2 CH3

diethyl sulfide
Names
Namesof
ofCyclic
CyclicEthers
Ethers

O O O
Oxirane Oxetane Oxolane
(Ethylene oxide) (tetrahydrofuran)

O O
Oxane 1,4-Dioxane
(tetrahydropyran)
Just for general knowledge, will not be tested on
Names
Namesof
ofCyclic
CyclicSulfides
Sulfides

S S S
Thiirane Thietane Thiolane

S
Thiane
Just for general knowledge, will not be tested on
Structure and Bonding
in
Ethers and Epoxides

bent geometry at oxygen


analogous
to water and alcohols,
i.e. sp3 hybidization
Bond
Bondangles
anglesat
atoxygen
oxygenarearesensitive
sensitive
to
tosteric
stericeffects
effects

O O
H H CH3 H
105° 108.5°

O O
CH3 CH3 (CH3)3C C(CH3)3

112° 132°
An
Anoxygen
oxygenatom
atomaffects
affectsgeometry
geometryin
inmuch
muchthe
the
same
sameway
wayasasaaCH
CH22group
group

most stable conformation of diethyl ether


resembles pentane
Physical Properties of Ethers
Ethers
Ethersresemble
resemblealkanes
alkanesmore
morethan
thanalcohols
alcohols
with
withrespect
respectto
toboiling
boilingpoint
point

boiling point

36°C Intermolecular hydrogen


bonding possible in
alcohols; not possible
O 35°C in alkanes or ethers.

OH 117°C
Ethers
Ethersresemble
resemblealcohols
alcoholsmore
morethan
thanalkanes
alkanes
with
withrespect
respectto
tosolubility
solubilityin
inwater
water

solubility in water (g/100 mL)

very small
Hydrogen bonding to
7.5 water possible for ethers
O
and alcohols; not
possible for alkanes.

OH 9