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 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
Lowest ranking 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 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

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 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
OH are cresols.
OH

H3C
Cl
3-chlorophenol 4-methylphenol
(meta-chlorophenol) (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 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 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 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 Dont
Oxidize
Cannot lose 2 Hs
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, 140C and below, favors ether
High temp, 180C 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
 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 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