Chapter 5

Alcohols
Thiols Ethers

Structure of Water and

Methanol

Oxygen is sp3 hybridized and tetrahedral.

The HOH angle in water is 104.5.
The COH angle in methyl alcohol is 108.9.
Chapter 10

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

Examples of
Classifications
OH

CH3
CH3

CH3

CH CH2OH
*

CH CH2CH3

CH3
CH3

C* OH
CH3

Chapter 10

Examples of
Classifications
OH

CH3
CH3

CH3

CH CH2OH
*

CH CH2CH3

Primary alcohol

CH3
CH3

C* OH
CH3

Chapter 10

Examples of
Classifications
OH

CH3
CH3

CH3

CH CH2OH
*

Primary alcohol

CH CH2CH3

Secondary alcohol

CH3
CH3

C* OH
CH3

Chapter 10

Examples of
Classifications
OH

CH3
CH3

CH3

CH CH2OH
*

Primary alcohol

CH CH2CH3

Secondary alcohol

CH3
CH3

C* OH

Tertiary alcohol

CH3

Chapter 10

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

Examples of
Nomenclature
OH

CH3
CH3

CH3

CH CH2OH

2-methyl-1-propanol
2-methylpropan-1-ol

CH3

CH3
1
C OH
CH3

CH CH2CH3
2

2-butanol
butan-2-ol

2-methyl-2-propanol
2-methylpropan-2-ol

Chapter 10

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
OH
ene before -ol
CH2
5

CHCH2CHCH3
4

2 1

4-penten-2-ol
pent-4-ene-2-ol

Chapter 10

10

Naming Priority
Highest ranking

Lowest ranking

1. Acids
2. Esters
3. Aldehydes
4. Ketones
5. Alcohols
6. Amines
7. Alkenes
8. Alkynes
9. Alkanes
10. Ethers
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

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.
OH

CH3
CH3

CH CH2OH

isobutyl alcohol

CH3

CH CH2CH3

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

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.

ethane-1,2- diol
ethylene glycol

propane-1,2- diol
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
(meta-chlorophenol)

4-methylphenol
(para-cresol)
Chapter 10

16

Solved Problem 1
Givethesystematic(IUPAC)nameforthefollowingalcohol.

Solution
Thelongestchaincontainssixcarbonatoms,butitdoesnotcontainthecarbonbondedtothehydroxyl
group.ThelongestchaincontainingthecarbonbondedtotheOHgroupistheoneoutlinedbythe
greenbox,containingfivecarbonatoms.Thischainisnumberedfromrighttoleftinordertogivethe
hydroxylbearingcarbonatomthelowestpossiblenumber.

Thecorrectnameforthiscompoundis3(iodomethyl)2isopropylpentan1ol.
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
1215% 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: 15.518.0 (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 tertbutanol 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 1
alcohol.
Reduction of ketone yields 2 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
1 alcohols.
Chapter 10

32

Reduction with LiAlH4

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

1, 2, 3 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
CH3CHCH2CH3

Na2Cr2O7 / H2SO4

O
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

CH3CH2CH2CH2

O
CH3CH2CH2CH

Chapter 11

44

3 Alcohols Dont
Oxidize

Cannot lose 2 Hs
Basis for chromic acid test

Chapter 11

45

Alcohol as a Nucleophile
H
C

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
+

C-Nuc bond forms,

C-O bond breaks

Chapter 11

47

Reduction of Alcohols
Dehydrate with conc. H2SO4, then add
H2
OH
CH3CHCH3
alcohol

H2SO4

CH2

CHCH3

alkene

Chapter 11

H2
Pt

CH3CH2CH3
alkane

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.

R O H

H3O

H
R O H

Chapter 11

Br

R Br

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, 140C and below, favors ether
High temp, 180C and above, favors alkene

Chapter 11

53

Ethers
H

O
H

Hydrogen Oxide
Aka Water

H
Alcohol

R
Ether

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

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

Dimethyl ether

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

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

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

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

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

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

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

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
CH3CHCH3

H2SO4

OH
CH3CHCH3

CH3CHCH3

alcohol
H2O

CH3OH

H3O

CH2

CHCH3

CH3

CH3

OH2

O CH3
H

CH3OH

H2O
Chapter 11

CH3OCH3

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

C OH

CH3
+ H O CH2CH2CHCH3

CH3

CH3C OCH2CH2CHCH3
+ HOH

Chapter 11

68

Sulfate Esters
Alcohol + Sulfuric Acid
O
HO

OH

+ H O CH2CH3

OCH2CH3

O
O

CH3CH2O H + HO

HO

OCH2CH3

Chapter 11

CH3CH2O

OCH2CH3

=>

69

Nitrate Esters
O
O

N OH

H O CH2CH3

O
O

Chapter 11

N OCH2CH3

70

Phosphate Esters

=>
Chapter 11

71

Phosphate Esters in
DNA
O CH2

base

H
H

H
O

CH2

P
O

base

H
O

CH2

P
O

base

H
O

CH2

P
O

base

H
O

O
P

O
Chapter 11

=>
72

End of
Chapter 5
Chapter 11

73