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CHEM331 ‐ Organic Chemistry (3 cr.)
Fall 2020‐2021
Course Instructor: Jean El Achkar, PhD, Assistant Professor
E‐mail: [email protected]
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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