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CHEM331 ‐ Organic Chemistry (3 cr.)
Fall 2020‐2021

Course Instructor: Jean El Achkar, PhD, Assistant Professor
E‐mail: j.achkar@bau.edu.lb

Chapter 6: Alcohols

ALCOHOLS
 Alcohols: Organic compounds containing
hydroxyl (‐OH) functional groups.
R OH

 Phenols: Compounds with hydroxyl group bonded

directly to an aromatic (benzene) ring.

OH

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Classification

carbinol 
carbon 
H CH3
atom 
i) Primary (1 ) R C OH CH3CH2-OH CH3CHCH2 OH
H ethanol 2-methyl-1-propanol

ii) Secondary (2 ) R' OH

OH
R C OH H3C CH CH2CH3
H
2-butanol cyclohexanol

R' CH3
iii) Tertiary (3 )
R C OH H3C C OH
R '' CH3

2-methyl-2-propanol

Polyhydroxy Alcohols

 Alcohols that contain more than one OH group ‐

polyhydroxy alcohols.
 Monohydroxy: one OH group.
 Dihydroxy: two OH groups.
 Trihydroxy: three OH groups.

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Commonly encountered alcohols

 Methanol (CH3OH) finds use as a solvent in chemical reactions

and in fuel for high‐performance combustion engines.

 Methanol is metabolized to formaldehyde and formic acid by the

liver (alcohol dehydrogenase):

Formaldehyde Formic acid

alcohol
dehydrogenase
(oxidation) (oxidation)

Commonly encountered alcohols

 Ethanol (CH3CH2OH) is also metabolized by the body, and this reaction

produces acetaldehyde and acetic acid:
Acetaldehyde Acetic acid
alcohol
dehydrogenase
(oxidation) (oxidation)

 Excessive drinking leads to liver cirrhosis, physiological addiction, loss of

memory. Drinking during pregnancy poses risks for birth defects.
 Industrially, ethanol is synthesized by hydration of ethene.

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Commonly encountered alcohols

 Glycerol is a thick liquid that is normally present in the

body (it is a product of fat metabolism).
 Because of its affinity for water, it is often added to
pharmaceutical preparations such as skin lotions and soap,
and for shaving cream and glycerol suppositories.

Physical properties of alcohols

 Alcohols consist of: C H3 C H2 C H2 O H

 a non‐polar (alkane‐like) chain

alkane-like (non-polar) polar O-H bond
 a polar hydroxyl group
 Thus, alcohols might be water‐soluble, or not (depending on the length
of the carbon chain).
 We already saw that the boiling points of alkanes increase with increasing
chain length. The same is true for alcohols.
 Alcohols with more than one hydroxyl group (polyhydroxy alcohols) have
higher boiling points than monohydroxy alcohols.

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Preparation of alcohols

 Alcohols can be prepared by hydration of alkenes:

H2SO4

 They can also be prepared by the hydrogenation of C‐O double bonds:

H2

(Hydrogenation of this double bond is equivalent to a reduction in organic chemistry)

Chemical reactions of alcohols

Combustion reactions

 Any organic molecule can undergo a combustion reaction. In

combustion reactions involving alcohols, CO2 and H2O are
produced:
– CH3OH + O2  CO2 + 2H2O
– CH3CH2OH + O2  2CO2 + 3H2O

Or, for 2‐Propanol:

2 9 O2 6CO2 8H2O

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Chemical reactions of alcohols

Elimination reactions

• In an intramolecular alcohol dehydration, a water molecule is

lost (eliminated) from a single alcohol molecule.
• The elimination involved loss of the OH group and a H‐atom
from an adjacent C‐atom (sometimes, there’s more than one of
these)

H2SO4
H-OH
180oC

H2SO4
H-OH
180oC

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Chemical reactions of alcohols

Elimination reactions

 In general, these kinds of reactions (eliminations)

proceed as follows:

A-B

Two atoms (or groups of atoms) on neighboring carbons are removed,

leaving a multiple bond between these carbon atoms

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Chemical reactions of alcohols

Elimination reactions

 Zaitsev’s Rule (for alcohol dehydrations): for cases where more

than one alkene product might be formed from an elimination
reaction, the hydrogen atom tends to be removed from the
carbon that already possesses the fewest hydrogens.

C H3 C H2 C H C H2
this carbon has this carbon has 1-butene
two H-atoms three H-atoms

H2SO4
C H3 C H2 C H CH3 + + H2O
180oC
OH

CH3 C H CH C H3

2-butene
major product
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Chemical reactions of alcohols

Condensation reactions

 A condensation reaction is a reaction in which two molecules

(like two alcohol molecules) combine to form a larger molecule
while liberating a small molecule like water.

H2SO4
H2O
140oC

H2O
Dimethyl ether

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Chemical reactions of alcohols

Oxidation reactions

Oxidation/reduction reactions involving organic compounds result in a

change in the number of H‐atoms and/or the number of O‐atoms bound
to carbons in the molecule:

Methanol Formaldehyde Formic acid

oxidation oxidation

reduction reduction

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Chemical reactions of alcohols

Oxidation reactions
Primary and secondary alcohols can be oxidized by mild oxidizing
agents to produce compounds with C‐O double bonds
(aldehydes, ketones, carboxylic acids).
[O] [O]

an aldehyde a carboxylic acid

a primary alcohol

[O]
mild oxidizing
agent = [O]
a ketone

a secondary alcohol

[O]
no reaction

a tertiary alcohol 16

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Nomenclature of alcohols

This is the longest continuous chain that contains a

hydroxyl group.

Select this chain as the parent compound.

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Nomenclature of alcohols

4
3

2 1

This end of the chain is closest to the

OH. Begin numbering here.

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Nomenclature of alcohols

4
3

2 1

IUPAC name: 3-methyl-2-butanol

New IUPAC name: 3-methylbutan-2-ol
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Nomenclature of alcohols

This is the longest continuous chain that contains a

hydroxyl group.

Select this chain as the parent compound.

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Nomenclature of alcohols

5 4 3

2 1

This end of the chain is closest to the OH. Begin

numbering here.

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Nomenclature of alcohols

5 4 3

2 1

IUPAC name: 3‐methyl‐2‐pentanol
New IUPAC name: 3‐methylpentan‐2‐ol

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Nomenclature of cyclic alcohols

 Using the prefix cyclo‐

 The hydroxyl group is assumed to be on C1.

trans-2-bromocyclohexan-1-ol

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Nomenclature of alcohols containing two different functional

groups

1) Longest carbon chain that contains –OH group

‐ 5 carbon

2) Position of –OH group

‐ Carbon‐2

3) Position of C=C
‐ Carbon‐4
Complete name = 4‐penten‐2‐ol
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Nomenclature of alcohols containing two different functional groups

Some consideration:
‐ OH functional group is named as a hydroxy
substituent when it appears on a structure with a
higher priority functional group such as acids, esters,
aldehydes and ketones.

‐ Examples:
OH O OH
4 3 2
4 3 2 1 5 1
CH3 CH CH2 C OH 6
O
3‐hydroxybutanoic acid 2‐hydroxycyclohexanone
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Nomenclature of alcohols containing two different functional groups

MAIN GROUPS

Acids 
Esters 
Aldehydes 
Ketones 
Alcohols 
decreasing priority Amines 
Alkenes 
Alkynes 
Alkanes 
Ethers 
Halides

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Nomenclature of diols

 Alcohols with two –OH groups diols

 Naming of diols is like other alcohols except that the suffix

diol is used, and two numbers are needed to tell where the
two hydroxyl groups are located.

5
OH OH
4 1
3 2 1
CH CH CH 2 OH OH
3 3 2
IUPAC name propane-1,2-diol trans-cyclopentane-1,2-diol

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Nomenclature of phenols

 The terms ortho (1,2‐disubstituted), meta (1,3‐

disubstituted) and para (1,4‐disubstituted) are often used
in the common names.

OH
OH O2N OH
CH3CH2
Br
IUPAC name: 2-bromophenol 3-nitrophenol 4-ethylphenol

common name: ortho-bromophenol meta-nitrophenol para-ethylphenol

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Nomenclature of phenols

 Phenols may be monohydric, dihydric or trihydric ‐

(number of hydroxyl groups) in the benzene ring.

OH
OH OH
OH

OH OH
OH
benzene-1,3-diol benzene-1,4-diol benzene-1,2,3-triol

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Thank you for attention

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