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Chapter 15
Alcohols, Diols, and Thiols
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15.1
Sources of Alcohols
Methanol
Methanol is an industrial chemical.
End uses: solvent, antifreeze, fuel.
Principal use: preparation of formaldehyde.
Prepared by hydrogenation of carbon
monoxide.
CO + 2H2  CH3OH
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 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 of Alcohols
Reactions discussed in earlier chapters (Table 15.1)
Hydration of alkenes
Hydroboration-oxidation of alkenes
Hydrolysis of alkyl halides
Syntheses using
Grignard reagents
Organolithium reagents
Sources of Alcohols
New methods in Chapter 15
Reduction of aldehydes and ketones
Reduction of carboxylic acids
Reaction of Grignard reagents with epoxides
Diols by hydroxylation of alkenes
15.2
Preparation of Alcohols
by
Reduction of Aldehydes and Ketones
Reduction of Aldehydes Gives Primary Alcohols
R
R
C
H
O
H
C
H
OH
Example: Catalytic Hydrogenation
O
CH3O
CH
+
H2
Pt, ethanol
CH3O
CH2OH
(92%)
Reduction of Ketones Gives Secondary Alcohols
R
R
C
R'
O
H
C
R'
OH
Example: Catalytic Hydrogenation
H
O
+
H2
OH
Pt
ethanol
(93-95%)
Retrosynthetic Analysis
R
H
C
R
OH
H:–
R
C
R'
O
C
O
H
H
H
C
R
OH
H:–
R'
Metal Hydride Reducing Agents
H
H
+
Na H
–
B
H
Li
+
Al
H
H
H
Sodium
borohydride
H
–
Lithium
aluminum hydride
act as hydride donors
Examples: Sodium Borohydride
Aldehyde
O2N
O2N
O
NaBH4
CH2OH
CH
methanol
(82%)
Ketone
O
NaBH4
ethanol
H OH
(84%)
Lithium Aluminum Hydride
More reactive than sodium borohydride.
Cannot use water, ethanol, methanol etc.
as solvents.
Diethyl ether is most commonly used solvent.
Examples: Lithium Aluminum Hydride
Aldehyde
O
CH3(CH2)5CH
1. LiAlH4
diethyl ether
2. H2O
CH3(CH2)5CH2OH
(86%)
Ketone
O
(C6H5)2CHCCH3
1. LiAlH4
diethyl ether
2. H2O
OH
(C6H5)2CHCHCH3
(84%)
Selectivity
Neither NaBH4 or LiAlH4
reduces carbon-carbon
double bonds.
O
1. LiAlH4
diethyl ether
2. H2O
(90%)
H
OH
15.3
Preparation of Alcohols By Reduction
of Carboxylic Acids
Reduction of Carboxylic Acids
Gives Primary Alcohols
R
R
C
HO
O
H
C
H
lithium aluminum hydride is only
effective reducing agent
OH
Example: Reduction of a Carboxylic Acid
O
COH
1. LiAlH4
diethyl ether
2. H2O
CH2OH
(78%)
15.4
Preparation of Alcohols From Epoxides
Reaction of Grignard Reagents
with Epoxides
R
MgX
CH2
H2C
O
R
CH2
CH2
OMgX
H3O+
RCH2CH2OH
Example
CH2
CH3(CH2)4CH2MgBr + H2C
O
1. diethyl ether
2. H3O+
CH3(CH2)4CH2CH2CH2OH
(71%)
15.5
Preparation of Diols
Diols are Prepared by...
Reactions used to prepare alcohols
Hydroxylation of alkenes
Example: Reduction of a Dialdehyde
O
O
HCCH2CHCH2CH
CH3
H2 (100 atm)
Ni, 125°C
HOCH2CH2CHCH2CH2OH
CH3
3-Methyl-1,5-pentanediol
(81-83%)
Hydroxylation of Alkenes
Gives Vicinal Diols
Vicinal diols have hydroxyl groups on adjacent
carbons.
Ethylene glycol (HOCH2CH2OH) is most familiar
example.
Osmium Tetraoxide is Key Reagent
C
C
C
C
HO
C
OsO4
C
O
O
Os
O
O
Cyclic osmate ester
OH
Example
CH3(CH2)7CH
CH2
(CH3)3COOH
OsO4 (cat)
tert-Butyl alcohol
HO–
CH3(CH2)7CHCH2OH
OH
(73%)
Example
Stereospecific
syn addition of —OH groups to each carbon
of double bond
H
(CH3)3COOH
OsO4 (cat)
H
tert-Butyl alcohol
HO–
H
H
HO
OH
(62%)