Chap 9:ORGANIC CHEMISTRY

ALCOHOLS

1
Saturated Open Chain mono-
alcohol
Definition :
An organic compound containing one
hydroxyl group attached to a saturated
open carbon chain has a
General formula:
CnH2n+2O ; n ≥ 1
CnH2n+1OH
R-OH Alkanols R = CnH2n+1-
2
Nomenclature of Alcohols -
IUPAC
■ IUPAC name - The OH group is a site
of reactivity (a functional group)
■ Functional group is denoted by the
suffix, “ol”
■ Alkane + ol = Alkanol
■ Start counting from side closer to
hydroxyl group. Indicate the position of
the –OH group.
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 Nomenclature of Alcohols -
IUPAC

■ Alkyl groups: CnH2n+1-

Methyl: CH3-
Ethyl: C2H5-
Propyl: C3H7-

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 Nomenclature of Alcohols -
IUPAC
■ System is summarized as:
x - alkyl - y- alkanol

x = number of carbon bearing the substituent

Alkyl = ‘branch’
y = number of carbon bearing the –OH
group
Alkanol = parent chain containing the – OH group

5
 Nomenclature of Alcohols -
IUPAC

• Parent Hydrocarbon is the longest

continuous chain that contains the OH
• Number the chain in direction that gives
functional group the lowest number
• If both a substituent and a functional group
are present, the functional group gets the
lower number
6
 Nomenclature of Alcohols -
IUPAC
• If the functional group gets the same number
when counted from both directions, use
direction which gives the substituent the
lower number
• If there is more than one substituent, cite
substituents in alphabetical order

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Saturated mono-alcohol
Examples:
CH3CH2OH
CH3CH(OH)CH3

8
Nomenclature of Alcohols -
IUPAC
Molecular, Condensed/Semi-structural, and
Structural formulas
Ethanol:
⮚Molecular formula: C2H6O
⮚Condensed or semi structure: CH3CH2OH
⮚Structural :

9
Alcohols are classified as primary (1º), secondary (2º),
or tertiary (3º), depending on the number of carbons
connected to the alcoholic carbon:

10
Alcohols
Classification
Class Definition Example

Primary the carbon bearing the

OH group attached to
ONE alkyl group.(or 2H
at least)
Secondary the carbon bearing the
OH group attached to
TWO alkyl groups. (1H)

Tertiary the carbon bearing the

OH group attached to
THREE alkyl groups.(0H)

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Saturated mono-alcohol
■ Classification
Primary (1°) alcohol: the carbon which carries the -
OH group is only attached to one alkyl group. 2 or 3
H)

CH3OH methanol 1-propanol 2-methyl-1- propanol

ethanol

12
Saturated mono-alcohol
■ Classification
Secondary (2°) alcohol: the carbon with the -OH
group attached is joined directly to two alkyl
groups, which may be the same or different.

2-propanol 2-butanol 3-pentanol

13
Saturated mono-alcohol
■ Classification
Tertiary (3°) alcohol, the carbon atom holding the -
OH group is attached directly to three alkyl groups,
which may be any combination of same or different.
2-methyl-2-propanol 2-methyl-2-butanol

14
 Isomers of Alcohols
■ Alcohols exhibit three types of isomers:
1. Positional isomers: Same hydrocarbon
skeleton but different position of –OH in
the parent chain.
2. Skeletal (or chain): Similar positions of –
OH group but different skeleton branching
3. Functional isomers: ethers.

15
 Isomers of Alcohols
■ Ethers: Same molecular formula as alcohols: CnH2n+2O
Ether is a class of organic compoundsEther is a class of
organic compounds that contain an ether groupEther is a
class of organic compounds that contain an ether group
— an oxygenEther is a class of organic compounds that
contain an ether group — an oxygen atomEther is a
class of organic compounds that contain an ether group
— an oxygen atom connected to two alkyl groups

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 Isomers of Alcohols
■ Ethers:
In the IUPAC nomenclature system,
ethers are named using the general formula
"alkoxyalkane", for example:
CH3-O-CH2CH3 : methoxyethane
CH3-O-CH2CH2CH3 : 1- methoxypropane

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 Nomenclature of Alcohols -
IUPAC
Hydrocarbon # of carbon
■ Prefixes : prefix atoms
           Meth 1
           Eth 2
           Prop 3
           But 4
           Pent 5
           Hex 6
           Hept 7
           Oct 8
           Non 9
           Dec 10 18
Isomerism and Nomenclature
■ CH3OH --- n=1 CnH2n+2O
■ C2H6O --- n=2
■ C3H8O
■ C4H10O
■ C5H12O

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20
1-methoxypropane

ethoxyethane

2-methoxypropane

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 Nomenclature of Alcohols -
IUPAC

Name the following compounds:

Text book , page 225

Exercise 1, 2 and 3 a) b) c) only

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 Physical Properties of Alcohols
Density, Boiling point and
Melting Point, Solubility, State
❖ Saturated mono-alcohols are liquids and
solids, whose densities level off at around
0.8
❖ The liquids are good solvents for organic
and inorganic substances

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 Physical Properties of Alcohols
■ Boiling Points
❖The boiling point of an
alcohol is always much higher
than that of the alkane with
the same number of carbon
atoms.

❖The boiling points of the

alcohols increase as the
number of carbon atoms
increases.
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 Physical Properties of Alcohols
■ Solubility of alcohols in water

❖ The small alcohols (chains with1 to 4

carbons) are completely soluble in water.

❖ Solubility falls as the length of the

hydrocarbon chain in the alcohol increases
i.e beyond 4 carbons.

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 Physical Properties of Alcohols
■ The hydrogen bond
Hydrogen bonding occurs between molecules
where you have a hydrogen atom attached to
one of the electronegative elements: fluorine,
oxygen or nitrogen .i.e. O-H, F-H, N-H.
Hydrogen acts as a bridge between two small
and highly electronegative atoms.

26
 The hydrogen bond

-O-H bond is a highly polar bond due to high difference in

electronegativity between O and H.

-Hydrogen Bonds: strongest intermolecular forces:

Hydrogen acts as a bridge between two small and highly
electronegative atoms

-Compounds with O-H , N-H or F-H only exhibit H-bonds

-Result: alcohols have a relatively high b.p and m.p and

highly soluble in water due to associated hydrogen bonds
and H- bonds with water.
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Hydrogen Bonds

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 Physical Properties of Alcohols

In the case of
alcohols, there are
hydrogen bonds set
up between the
slightly positive
hydrogen atoms
and lone pairs on
oxygens in other
molecules

29
 Physical Properties of Alcohols
■ The hydrogen bond & alcohols solubility in water

30
Nomenclature of Alcohols -
IUPAC

■ IUPAC name - The OH group is a site

of reactivity (a functional group)
■ Functional group is denoted by the
suffix, “ol”

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Substitution Halo alkane
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Chemical Properties of Alcohols-
Common Properties (1o, 2o, 3o)
■ Chemical reactions of alcohols occur by :
A. R-OH cleavage
B. RO-H cleavage
C. R-OH & RO-H cleavage (rare in 3o)

33
 Chemical Properties of Alcohols-
Distinctive Properties

■ Mild oxidation: carbon chain remains

intact, functional group altered
A- Catalytic oxidation in the presence of
oxygen.
B- Catalytic dehydrogenation (no oxygen)
C-Using strong oxidants ( KMnO4, K2Cr2O7
in acidic medium)
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 Simple Distillation
Heating
mantle
■ Other heating devices may be used, such as
electric heaters and heating mantles (figures to
the right)
■ Boiling chips or glass beads are used with the
reaction mixture to avoid bumping resulting Electric
for superheated solution. Boiling chips are a heater
way of introducing seed bubbles, through the
course surfaces and thus the amounts of air
that fill the tiny gaps on the chips surface

35
 Chemical Properties of
Alcohols
■ 1. Esterification
■ 2. Mild Oxidation (3 methods)
A. Catalytic oxidation in the presence of
oxygen.
B. Catalytic dehydrogenation (no oxygen)
C. Using strong oxidants (KMnO4, K2Cr2O7
in acidic medium)

36
 Chemical Properties of Alcohols-
Common Properties
■ RO-H cleavage: Esterification

R’O - H
O R’
Experimental conditions: Catalyst (H2SO4, H3PO4)
and heat under reflux
Athermal, Slow and Reversible
Reversible reaction: how can we increase the yield of
the reaction?

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38
 Esterification
■ Write the equation of the reaction between methanoic acid
HCOOH and 2-propanol.
H+
■ HCOOH + CH3-CH(OH)-CH3 ⇔ HCO-OCH-CH3 + H2O
O O CH3
HC-OH
■ Write the equation between ethanoic acid and 2-methyl-1-
butanol.
CH3COOH + CH3-CH2-CH-CH2OH ⇔ CH3COO-CH2-CH-CH2CH3
CH3 CH3
+ H2O

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Reactivity of Alcohols
📫Highest yield with primary alcohols
📫 ≈ 67%
📫Reactivity: CH3OH > 1o > 2o >3o

- To increase yield of ester add one reactant

in excess or remove one of the products
by distillation.

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Esterification: Heating under reflux

41
 Comments on the Apparatus

■The water bath is not always

necessary
■Boiling chips or glass beads are
introduced to the reaction mixture to
avoid bumping.
■The use of thermometer is not always
necessary
■Other heating devices may be used,
such as Bunsen burners and heating
mantles (figure to the right)

42
 Advantages of Refluxing

A liquid reaction mixture is placed in a

vessel open only at the top. This vessel is
connected to a vertical condenser, such
that any vapours given off are cooled
back to liquid, and fall back into the
reaction vessel. The vessel is then heated
vigorously for the course of the reaction.
43
 Advantages of Refluxing
The purpose is to thermally accelerate
the reaction by conducting it at an
elevated temperature. The advantage of
this technique is that it can be left for a
long period of time without the fear of
losing any of the reaction components
(especially volatile reactants and
products) by evaporation.
44
 Advantages of Refluxing

For slow reactions temperature will speed

the reaction. Any vapour is immediately
condensed in the vertical condenser. In
addition, as a given solvent will always
boil at a certain temperature, one can be
sure that the reaction will proceed at a
constant temperature.
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 Oxidation of alcohols (Reductants)

Excess Alcohol Excess oxidant

Excess Alcohol

• Mild oxidation: no change in the hydrocarbon chain

• Alcohols are reducing agents
46
 Chemical Properties of Alcohols-
Distinctive Properties
■ Mild oxidation: carbon chain remains
intact, functional group is altered.
A. Catalytic oxidation in the presence of
oxygen.
B. Catalytic dehydrogenation (no oxygen)
C. Using strong oxidants ( KMnO4, K2Cr2O7

in acidic medium)
47
 Alcohols Chemical Properties

[O] Represents an
Mild oxidation of alcohol oxidizing agent

48
 Alcohols
During oxidation the following colors are noticed

49
 Chemical Properties of Alcohols-
Distinctive Properties

Catalytic mild oxidation ( exothermic)

Case of primary alcohol (RCH2OH ): Continuous
mild oxidation
RCH2OH + ½ O2(g) → RCHO (Aldehyde ) + H2O
RCHO + ½ O2(g) → RCOOH ( carboxylic acid)
RCH2OH + O2(g) → RCOOH + H2O
Experimental conditions: catalyst ( Pt, Pd, or Cu) and
heat 50
Aldehyde (Alkanal)

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Carboxylic acid (alkanoic acid)

52
 Chemical Properties of Alcohols-
Distinctive Properties

Catalytic mild oxidation ( exothermic)

Case of secondary alcohol [RCH(OH)R’ ]:
RCH(OH)R + ½ O2(g) → RCOR’ (Ketone) + H2O
No further oxidation can take place
Experimental conditions: catalyst ( Pt, Pd, or Cu)
and heat

53
Ketone (alkanone)

54
 Chemical Properties of
alcohols- Distinctive properties

Catalytic mild oxidation Case of tertiary

alcohol (R3COH):
No mild oxidation can take place

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Flameless Lamp

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 Flameless Lamp
Ethanol vapours and oxygen gas (from air)
collide and react at the surface of the strongly
heated catalyst ( copper spring). The heat
liberated from the exothermic oxidation
reaction (towards formation of ethanal and
ethanoic acid) maintains the glowing of the
copper spring.

57
 Chemical Properties of Alcohols-
Distinctive Properties

Catalytic dehydrogenation (endothermic)

Case of primary alcohol (RCH2OH ):
RCH2OH → RCHO (Aldehyde ) + H2(g)

Experimental conditions: Cu/300 0C

58
 Chemical Properties of Alcohols-
Distinctive Properties

Catalytic dehydrogenation (endothermic)

Case of secondary alcohol [RCH(OH)R’] :
RCH(OH)R’ → RCOR’ (Ketone ) + H2(g)

Experimental conditions: Cu/300 0C

59
 Chemical Properties of Alcohols-
Distinctive Properties

Catalytic dehydrogenation
Case of tertiary alcohol [R3C(OH)] :
No dehydrogenation takes place

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Catalytic dehydrogenation

61
 Chemical Properties of Alcohols-
Distinctive Properties

Oxidation by an oxidant ( KMnO4 in acidic

medium)
Case of primary alcohol: towards aldehyde
Couples : MnO4-/ Mn2+ & RCHO/RCH2OH
The spontaneous reaction between the stronger oxidant
and the stronger reductant:
MnO4- +RCH2OH → Mn2+ + RCHO
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 MnO4- +RCH2OH → Mn2+ + RCHO

Reduction half-reaction:
■(MnO4- + 8H+ + 5e- 🡪 Mn2+ + 4H2O)x2
Oxidation half-reaction:
■(RCH2OH + 🡪 RCHO + 2H+ + 2e-)x5
■2MnO4- + 5RCH2OH + 6H+ 🡪 2Mn2+ +
5RCHO + 8H2O

63
 Chemical Properties of Alcohols-
Distinctive Properties

Case of primary alcohol: Towards carboxylic

acid
Couples : MnO4-/ Mn2+ & RCOOH/RCH2OH
The spontaneous reaction between the stronger
oxidant and the stronger reductant:
MnO4- + RCH2OH → Mn2+ + RCOOH
Purple Colorless Colorless Colorless
64
 MnO4- +RCH2OH → Mn2+ + RCOOH

Reduction half-reaction:
■(MnO4- + 8H+ + 5e- 🡪 Mn2+ + 4H2O)x4
Oxidation half-reaction:
■(RCH2OH + H2O 🡪RCOOH + 4H++ 4e-)x5
■4MnO4- + 5RCH2OH + 12H+ 🡪 4Mn2+ +
5RCOOH + 11H2O

65
 Chemical Properties of Alcohols-
Distinctive Properties

Case of secondary alcohol: Towards ketone

Couples : Cr2O72-/ Cr3+ & RCOR’/RCH(OH )R’
The spontaneous reaction between the stronger
oxidant and the stronger reductant:
Cr2O72- + RCH(OH )R’ → Cr3+ + RCOR’
Orange Colorless Green Colorless

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 Cr2O72- + RCH(OH )R’ → Cr3+ + RCOR’
Orange Colorless Green Colorless

Red.
■Cr2O72- + 14H+ + 6e- 🡪 2Cr3+ + 7H2O
Oxid.
■(RCH(OH )R’ 🡪 RCOR’ + 2H+ + 2e-) x3
■Cr2O72- + 8H+ + 3RCH(OH)R’ 🡪 2Cr3+ + 3RCOR’
+ 7H2O

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Important Experimental Hint-
Primary alcohols

■ Simple distillation used to separate aldehyde

once it is formed to prevent continuous
oxidation of primary alcohols
■ Refluxing is used whenever continuous
oxidation is required

68
 Chemical Properties of Alcohols-
Distinctive Properties

Tertiary alcohols do not undergo mild

oxidation

69
 MnO4- +RCH2OH → Mn2+ + RCHO

Reduction half-reaction:
■(MnO4- + 8H+ + 5e- 🡪 Mn2+ + 4H2O)x2
Oxidation half-reaction:
■(RCH2OH + 🡪 RCHO + 2H+ + 2e-)x5
■2MnO4- + 5RCH2OH + 6H+ 🡪 2Mn2+ +
5RCHO + 8H2O

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 MnO4- +RCH2OH → Mn2+ + RCOOH

Reduction half-reaction:
■(MnO4- + 8H+ + 5e- 🡪 Mn2+ + 4H2O)x4
Oxidation half-reaction:
■(RCH2OH + H2O 🡪RCOOH + 4H++ 4e-)x5
■4MnO4- + 5RCH2OH + 12H+ 🡪 4Mn2+ +
5RCOOH + 11H2O

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