Chapter 5

Alcohols Thiols
Ethers
 Structure of Water and Methanol

• Oxygen is sp3 hybridized and tetrahedral.

• The H—O—H angle in water is 104.5°.
• The C—O—H angle in methyl alcohol is 108.9°.

Chapter 10 2
 Classification of Alcohols

• Primary: carbon with —OH is bonded to one

other carbon.
• Secondary: carbon with —OH is bonded to
two other carbons.
• Tertiary: carbon with —OH is bonded to
three other carbons.
• Aromatic (phenol): —OH is bonded to a
benzene ring.
Chapter 10 3
 Examples of Classifications

CH3 OH
CH3 CH CH2OH CH3 CH CH2CH3
* *

CH3
CH3 C* OH
CH3

Chapter 10 4
 Examples of Classifications

CH3 OH
CH3 CH CH2OH CH3 CH CH2CH3
* *
Primary alcohol

CH3
CH3 C* OH
CH3

Chapter 10 5
 Examples of Classifications

CH3 OH
CH3 CH CH2OH CH3 CH CH2CH3
* *
Primary alcohol Secondary alcohol

CH3
CH3 C* OH
CH3

Chapter 10 6
 Examples of Classifications

CH3 OH
CH3 CH CH2OH CH3 CH CH2CH3
* *
Primary alcohol Secondary alcohol

CH3
CH3 C* OH Tertiary alcohol
CH3

Chapter 10 7
 IUPAC Nomenclature
• Find the longest carbon chain containing the carbon
with the —OH group.
• Drop the -e from the alkane name, add -ol.
• Number the chain giving the —OH group the lowest
number possible.
• Number and name all substituents and write them in
alphabetical order.

Chapter 10 8
Examples of Nomenclature
CH3 OH
CH3 CH CH2OH CH3 CH CH2CH3
3 2 1 1 2 3 4
2-methyl-1-propanol 2-butanol
2-methylpropan-1-ol butan-2-ol

CH3
2 1 2-methyl-2-propanol
CH3 C OH
2-methylpropan-2-ol
CH3

Chapter 10 9
 Alkenols (Enols)
• Hydroxyl group takes precedence. Assign the carbon
with the —OH the lowest number.
• End the name in –ol, but also specify that there is a
double bond by using the ending –ene before -ol

OH
CH2 CHCH2CHCH3
5 4 3 2 1
4-penten-2-ol
pent-4-ene-2-ol

Chapter 10 10
 Naming Priority
Highest ranking 1. Acids
2. Esters
3. Aldehydes
4. Ketones
5. Alcohols
6. Amines
7. Alkenes
8. Alkynes
9. Alkanes
10. Ethers
Lowest ranking
11. Halides
Chapter 10 11
 Hydroxy Substituent
• When —OH is part of a higher priority class of
compound, it is named as hydroxy.

carboxylic acid
OH
CH2CH2CH2COOH
4 3 2 1

4-hydroxybutanoic acid
also known as -hydroxybutyric acid (GHB)
Chapter 10 12
 Common Names
• Alcohol can be named as alkyl alcohol.
• Useful only for small alkyl groups.

CH3 OH
CH3 CH CH2OH CH3 CH CH2CH3

isobutyl alcohol sec-butyl alcohol

Chapter 10 13
 Naming Diols
• Two numbers are needed to locate the two
—OH groups.
• Use -diol as suffix instead of -ol.

1 2 3 4 5 6
OH
OH

hexane-1,6- diol

Chapter 10 14
 Glycols
• 1, 2-diols (vicinal diols) are called glycols.
• Common names for glycols use the name of the alkene
from which they were made.

OH OH
OH OH

ethane-1,2- diol propane-1,2- diol

ethylene glycol propylene glycol

Chapter 10 15
 Phenol Nomenclature
• —OH group is assumed to be on carbon 1.
• For common names of disubstituted phenols, use
ortho- for 1,2; meta- for 1,3; and para- for 1,4.
• Methyl phenols are cresols.

OH
OH

H3C
Cl
3-chlorophenol 4-methylphenol
(meta-chlorophenol) (para-cresol)
Chapter 10 16
 Solved Problem 1
Give the systematic (IUPAC) name for the following alcohol.

Solution
The longest chain contains six carbon atoms, but it does not contain the carbon bonded to the hydroxyl
group. The longest chain containing the carbon bonded to the —OH group is the one outlined by the
green box, containing five carbon atoms. This chain is numbered from right to left in order to give the
hydroxyl-bearing carbon atom the lowest possible number.

The correct name for this compound is 3-(iodomethyl)-2-isopropylpentan-1-ol.

Chapter 10 17
 Physical Properties
• Alcohols have high boiling points due to
hydrogen bonding between molecules.
• Small alcohols are miscible in water, but
solubility decreases as the size of the alkyl
group increases.

Chapter 10 18
 Boiling Points of alcohols

• Alcohols have higher boiling points than ethers and

alkanes because alcohols can form hydrogen bonds.
• The stronger interaction between alcohol molecules will
require more energy to break them resulting in a higher
boiling point.
Chapter 10 19
Solubility in Water

Small alcohols are miscible in

water, but solubility decreases as
the size of the alkyl group
increases.
Chapter 10 20
 Methanol
• “Wood alcohol”
• Industrial production from synthesis gas
• Common industrial solvent
• Toxic Dose: 100 mL methanol
• Used as fuel at Indianapolis 500
– Fire can be extinguished with water
– High octane rating
– Low emissions
– Lower energy content
– Invisible flame
Chapter 10 21
 Ethanol
• Fermentation of sugar and starches in grains
• 12–15% alcohol, then yeast cells die
• Distillation produces “hard” liquors
• Azeotrope: 95% ethanol, constant boiling
• Denatured alcohol used as solvent
• Gasahol: 10% ethanol in gasoline
• Toxic dose: 200 mL

Chapter 10 22
 Acidity of Alcohols
• pKa range: 15.5–18.0 (water: 15.7)
• Acidity decreases as the number of carbons
increase.
• Halogens and other electron withdrawing
groups increase the acidity.
• Phenol is 100 million times more acidic than
cyclohexanol!

Chapter 10 23
Table of Ka Values

Chapter 10 24
 Formation of Alkoxide Ions

• Ethanol reacts with sodium metal to form sodium ethoxide

(NaOCH2CH3), a strong base commonly used for elimination
reactions.
• More hindered alcohols like 2-propanol or tert-butanol react
faster with potassium than with sodium.

Chapter 10 25
 Formation of Phenoxide Ion

The aromatic alcohol phenol is more acidic than aliphatic

alcohols due to the ability of aromatic rings to delocalize
the negative charge of the oxygen within the carbons of
the ring.
Chapter 10 26
Charge Delocalization on the Phenoxide Ion

• The negative charge of the oxygen can be delocalized over four atoms
of the phenoxide ion.
• There are three other resonance structures that can localize the
charge in three different carbons of the ring.
• The true structure is a hybrid between the four resonance forms.
Chapter 10 27
 Synthesis of Alcohols (Review)
• Alcohols can be synthesized by nucleophilic
substitution of alkyl halide.
• Hydration of alkenes also produce alcohols:

Chapter 10 28
 Synthesis of Vicinal Diols
Vicinal diols can be synthesized by two
different methods:
• Syn hydroxylation of alkenes
– Cold, dilute, basic potassium permanganate

Chapter 10 29
 Reduction of Carbonyl
• Reduction of aldehyde yields 1º alcohol.
• Reduction of ketone yields 2º alcohol.
• Reagents:
– Sodium borohydride, NaBH4
– Lithium aluminum hydride, LiAlH4
– Raney nickel

Chapter 10 30
 Sodium Borohydride
• NaBH4 is a source of hydrides (H-)
• Hydride attacks the carbonyl carbon,
forming an alkoxide ion.
• Then the alkoxide ion is protonated by
dilute acid.
• Only reacts with carbonyl of aldehyde or
ketone, not with carbonyls of esters or
carboxylic acids.
Chapter 10 31
 Lithium Aluminum Hydride
• LiAlH4 is source of hydrides (H-)
• Stronger reducing agent than sodium
borohydride, but dangerous to work with.
• Reduces ketones and aldehydes into the
corresponding alcohol.
• Converts esters and carboxylic acids to 1º
alcohols.
Chapter 10 32
 Reduction with LiAlH4

O H H

OCH3 1. LAH OH
2. H3O+

• The LiAlH4 (or LAH) will add two hydrides to the ester
to form the primary alkyl halide.
• The mechanism is similar to the attack of Grignards
on esters.

Chapter 10 33
 Reducing Agents
• NaBH4 can reduce
aldehydes and ketones
but not esters and
carboxylic acids.
• LiAlH4 is a stronger
reducing agent and will
reduce all carbonyls.

Chapter 10 34
 Catalytic Hydrogenation

• Raney nickel is a hydrogen rich nickel powder that is more

reactive than Pd or Pt catalysts.
• This reaction is not commonly used because it will also
reduce double and triple bonds that may be present in the
molecule.
• Hydride reagents are more selective so they are used
more frequently for carbonyl reductions.
Chapter 10 35
 Thiols (Mercaptans)

• Sulfur analogues of alcohols are called thiols.

• The —SH group is called a mercapto group.
• Named by adding the suffix -thiol to the alkane
name.
• They are commonly made by a substitution.
• Primary alkyl halides work better.

Chapter 10 36
 Synthesis of Thiols

• The thiolate will attack the carbon displacing the halide.

• This is a substitution reaction
• methyl halides will react faster than primary alkyl
halides.
• To prevent dialylation use a large excess of sodium
hydrosulfide with the alkyl halide.

Chapter 10 37
 Alcohol Reactions
• Dehydration to alkene
• Oxidation to aldehyde, ketone
• Substitution to form alkyl halide
• Reduction to alkane
• Esterification
• Williamson synthesis of ether

Chapter 11 38
Summary Table

Chapter 11 39
 Oxidation States
• Easy for inorganic salts (reduced, organic oxidized)
– 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 40
 Oxidation States
• Easy for inorganic salts (reduced, organic oxidized)
– 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 41
1º, 2º, 3º Carbons

Chapter 11 42
 Oxidation of 2° Alcohols
• 2° alcohol becomes a ketone
• Reagent is Na2Cr2O7/H2SO4 = H2CrO4
• Active reagent probably H2CrO4
• Color change: orange to greenish-blue
OH O
Na2Cr2O7 / H2SO4
CH3CHCH2CH3 CH3CCH2CH3
=>

Chapter 11 43
 Oxidation of 1° Alcohols
• 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 44
 3° Alcohols Don’t Oxidize
• Cannot lose 2 H’s
• Basis for chromic acid test

Chapter 11 45
 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 46
 Alcohol as an Electrophile
• OH- is not a good leaving group unless it is
protonated to make water.
H
O
+ C

C-Nuc bond forms,

C-O bond breaks

Chapter 11 47
 Reduction of Alcohols
• Dehydrate with conc. H2SO4, then add H2

OH
H2SO4 H2
CH3CHCH3 CH2 CHCH3 CH3CH2CH3
Pt
alcohol alkene alkane

Chapter 11 48
 Reaction with HBr
• -OH of alcohol is protonated
• -OH2+ is good leaving group (water)
• 3° and 2° alcohols react with Br- from HBr
• 1° alcohols react with HBr producing water and an
alkyl halide.

+ H -
H3O Br
R O H R O H R Br

Chapter 11 49
 Reaction with HCl
• Chloride is a weaker nucleophile than
bromide.
• Add ZnCl2 (catalyst), which bonds strongly
with -OH, to promote the reaction.
• The chloride product is insoluble.
• Lucas test: ZnCl2 in conccentrated 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 50
 Limitations of HX Reactions

• Poor yields of 1° and 2° chlorides

• May get alkene instead of alkyl halide

Chapter 11 51
Reactions with Phosphorus Halides
• Good yields with 1° and 2° alcohols
• PCl3 for alkyl chloride (but SOCl2 better)
• PBr3 for alkyl bromide

Chapter 11 52
 Dehydration Reactions
• Conc. H2SO4 (or H3PO4) produces alkene
• Carbocation intermediate
• Zaitsev product (most vinyl hydrogens)
• Bimolecular dehydration produces ether
• Low temp, 140°C and below, favors ether
• High temp, 180°C and above, favors alkene

Chapter 11 53
 Ethers
O O O

H H R R R
H
Hydrogen Oxide Alcohol Ether
Aka Water

• Ethers contain an sp3 hybridized oxygen atom

• Ethers do not hydrogen bond between each
other, but will hydrogen bond with water and
alcohols.
• Ethers are polar and water soluble
 Ether Nomenclature
Common System
Give alkyl names to the carbon groups (alkyl groups)
bonded to the oxygen, followed by ether.
Examples
O O O O

H3C CH3 H3C CH2CH3

 Ether Nomenclature
Common System
Give alkyl names to the carbon groups (alkyl groups)
bonded to the oxygen, followed by ether.
Examples
O O O O

H3C CH3 H3C CH2CH3

Dimethyl ether
 Ether Nomenclature
Common System
Give alkyl names to the carbon groups (alkyl groups)
bonded to the oxygen, followed by ether.
Examples
O O O O

H3C CH3 H3C CH2CH3

Dimethyl ether Ethylmethyl ether
 Ether Nomenclature
Common System
Give alkyl names to the carbon groups (alkyl groups)
bonded to the oxygen, followed by ether.
Examples
O O O O

H3C CH3 H3C CH2CH3

Dimethyl ether Ethylmethyl ether
Isopropylmethyl ether
 Ether Nomenclature
Common System
Give alkyl names to the carbon groups (alkyl groups)
bonded to the oxygen, followed by ether.
Examples
O O O O

H3C CH3 H3C CH2CH3

Dimethyl ether Ethylmethyl ether
Isopropylmethyl ether Sec-butylcyclopropyl
ether
 Ether Nomenclature
IUPAC System

Name the longest chain of carbons in the normal

fashion. The oxygen containing group is named by
giving the carbon portion the Latin root followed by
oxy.
Examples
O O O O

H3C CH3 H3C CH2CH3

Methoxymethane
 Ether Nomenclature
IUPAC System

Name the longest chain of carbons in the normal

fashion. The oxygen containing group is named by
giving the carbon portion the Latin root followed by
oxy.
Examples
O O O O

H3C CH3 H3C CH2CH3

Methoxymethane Methoxyethane
 Ether Nomenclature
IUPAC System

Name the longest chain of carbons in the normal

fashion. The oxygen containing group is named by
giving the carbon portion the Latin root followed by
oxy.
Examples
O O O O

H3C CH3 H3C CH2CH3

Methoxymethane Methoxyethane
2-Methoxypropane
 Ether Nomenclature
IUPAC System

Name the longest chain of carbons in the normal

fashion. The oxygen containing group is named by
giving the carbon portion the Latin root followed by
oxy.
Examples
O O O O

H3C CH3 H3C CH2CH3

Methoxymethane Methoxyethane
2-Methoxypropane 2-Cyclopropoxybutane
 Ether Formation
• Primary alcohols can dehydrate to ethers
• This reaction occurs at lower temperature than the competing dehydration to an alkene
•This method generally does not work with secondary or tertiary alcohols because elimination
competes strongly
The mechanism is an SN2 reaction:
 Williamson Ether Synthesis
• Good for unsymmetrical ethers
 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 66
 Esterification
• Fischer: alcohol + carboxylic acid
• Nitrate esters
• Phosphate esters

Chapter 11 67
 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 68
 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 69
 Nitrate Esters
O +
H O
N OH + H O CH2CH3 N OCH2CH3
O O

Chapter 11 70
Phosphate Esters

=>

Chapter 11 71
Phosphate Esters in DNA
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 72
End of Chapter 5

Chapter 11 73