Alcohols, Phenols,
Ethers, Thiols
Introduction
Alcohol – organic compound that
contains a hydroxyl (-OH) group
attached to an alkyl group
Phenol – organic compound that
contains a hydroxyl (-OH) group
attached to an aryl group
Ether – organic compound that has two
alkyl or aryl groups attached to the
oxygen atom; can be thought of as a
substituted alcohol.
Examples
Alcohols R-O-H CH3-OH
CH3CH2-OH
OH
Phenols Ap-O-H
Ethers R-O-R CH3-O-CH3
Practice Problem 1
Classify each as an alcohol (1), phenol (2), or
an ether (3):
A. _____ CH3CH2-O-CH3 C. _____ CH3CH2OH
OH
B. _____
CH3
Alcohols
Structure and Properties
R-O-H portion of alcohol is similar to the structure
of water.
The oxygen and two atoms bonded to it lie in
the same plane.
The bond angle is 104°
Hydroxyl groups are very polar because of
significantly different electronegativities.
Hydrogen bonding can form between
alcohol molecules.
Hydrogen Bonding
+
O
+ H
−
H
H O
−
R O
R
+ H
− O
H
H
Results of Hydrogen Bonding
Alcohols boil at much higher temperatures than
hydrocarbons of similar molecular weight.
Alcohols with fewer than five carbons are very
soluble in water.
Alcohols with five to eight carbons are
moderately soluble in water.
As the nonpolar (R) portion of the alcohol gets
larger, the water solubility decreases.
Solubility of Alcohols
Very large alcohols are not soluble in water.
Hydrophobic – “water fearing”; used to describe
nonpolar region of molecule
Hydrophilic – “water loving”; used to describe
polar region of molecule
CH3CH2CH2CH2CH2CH2CH2CH2CH2OH
Hydrophobic Hydrophilic
Solubility of Alcohols
An increase in the number of hydroxyl groups will
increase the influence of the polar hydroxyl
group.
Diols and triols are more
water soluble than alcohols
with only a single hydroxyl
group.
Practice Problem 2
Circle the more soluble alcohol in each pair.
H2 H2
OH C C
A. H3C C OR
H2 H3C C OH
H2
OH
OH OR OH
B.
OH
C. OR
Nomenclature of Alcohols
A carbon compound that contain -OH (hydroxyl) group
In IUPAC name, the -e in alkane name is replaced with -ol.
CH4 methane
CH3OH methanol (methyl alcohol)
CH3CH3 ethane
CH3CH2OH ethanol (ethyl alcohol)
More Names of Alcohols
IUPAC names for longer chains number the
chain from the end nearest the -OH group.
Alcohols that contain more
than one hydroxyl group
Alcohols containing two hydroxyl groups are
named –diols.
Alcohols containing three hydroxyl groups are
named –triols.
A number giving the position of each of the
hydroxyl groups is needed in these cases.
Classification of Alcohols
Alcohols can be classified as primary (1°), secondary (2°), or
tertiary (3°) depending on the number of alkyl groups
attached to the carbon bearing the –OH group.
H H CH3 CH3
H C H H3C C OH H3C C H H3C C CH3
OH H OH OH
Methanol 1° alcohol 2° alcohol 3° alcohol
ethanol 2-propanol 2-methyl-2-propanol
Practice Problem 4
Classify each of the following alcohols as
primary, secondary, tertiary, or aromatic.
1. 1-butanol
2. 3-pentanol
3. 1-methylcyclopentanol
4. 2-methyl-2-pentanol
Preparation of Alcohols
REVIEW: Hydration – an addition reaction in
which a water molecule is added to an
alkene; requires acid as catalyst
R
R R H H+
+ R H
O H
R OH
R R
R
Alkene Water Alcohol
◼ Markovnikov’s rule applies!!
Preparation of Alcohols
Hydrogenation of aldehydes and ketones
OH
O H Catalyst
+ R1 R2
H
R1 R2 H
In an aldehyde, R1 and R2 may be either alkyl groups or H.
In a ketone, R1 and R2 are both alkyl groups.
Preparation of Alcohols
YOU TRY THESE!
+
Dehydration of Alcohols
Alcohols undergo dehydration (lose water) when
heating with concentrated sulfuric or phosphoric
acid.
Dehydration is an example of an elimination
reaction.
Elimination reaction – a reaction in which a
molecule loses atoms or ions from its structure.
Dehydration is opposite of hydration!
Dehydration of Alcohols
General Reaction
H+
RCH2CH2OH RCH=CH2 + H 2O
Heat
Ethanol
H+
CH3CH2OH
Heat
2-butanol
H H OH H
H+
H C C C C H
Heat
H H H H
Dehydration of Alcohols
Zaitsev’s rule – in an elimination reaction, the
alkene with the greatest number of alkyl groups
on the double bonded carbon (more highly
substituted alkene) is the major product of the
reaction
Another example:
Oxidation of Alcohols
Alcohols can be oxidized into a variety of carbonyl compounds
depending on the nature of the alcohol and the oxidizing agent
used.
YOU TRY THESE!
H H OH H
[O]
H C C C C H
H H H H
[O]
OH
[O]
HO
[O]
CH3CH2OH
Phenols
Phenols
Phenols – compounds in which the hydroxyl
group is attached to a benzene ring
They are polar compounds because of the polar
hydroxyl group.
Smaller phenols are somewhat soluble in water.
They are found in fragrances and flavorings and
are also used as preservatives and germicides.
Common Phenols and their
Uses
Thymol (mint)
(CH3)2HC CH3
OH
(CH3)2HC CH3
Carvacrol (savory)
OH
Common Phenols and their
Uses
C(CH3)3
H3C OH
Butylated hydroxytoluene,
(CH3)3C BHT(Food preservative)
Phenol
(Carbolic acid when dissolved in water)
Antiseptic and disinfectant used by
OH Joseph Lister to bathe wounds and sterilize
instruments
Ethers
Structure of Ethers
Similar structure to alcohols
Alcohols: R-OH
–OH is “hydroxy” group
Ethers: R-OR
–OR is “alkoxy” group
Alkoxy group
“R” groups can “R” groups can
be the same: be different:
CH3-O-CH3 CH3CH2CH2-O-CH3
Both “R” groups One “R” group
has three
have one carbon
carbons while the
other has one
Alkoxy group
The root names are used with –oxy to name that portion of the
ether:
meth- + -oxy = methoxy
eth- + -oxy = ethoxy
prop- + -oxy = propoxy
Naming ethers – IUPAC Way
1. Find the root name of the smaller “R” group
Ex: meth-, eth-, prop-
2. Add –oxy
Ex: methoxy, ethoxy, propoxy
3. Add the full name of the larger “R” group
EXAMPLE:
O
methoxypropane
Name that ether
O O
O
Draw the structure of:
1. methoxypropane
2. methoxyoctane
3. propoxypropane
4. ethoxypentane
Naming Ethers – Common Name
Name by placing the names of the two
alkyl groups attached to the ether oxygen
as words in front of the word “ether.”
Typically this is done in alphabetical order.
O O
Diethyl Ether Ethyl methyl ether
O Butyl propyl ether
Properties of ethers
The C-O bond in ethers is polar, making the molecule polar
Ethers have very low boiling points
Ethers are relatively inert, but flammable in air
Let’s compare…
Ether Alcohol
CH3 –O-CH2CH3 CH3CH2CH2-OH
Molecular Formula: Molecular Formula:
C3H8O C3H8O
Molecular Weight: Molecular Weight:
60.09g/mol 60.09g/mol
Boiling Point: Boiling Point:
7.9°C 97.2°C
Preparing ethers
Ethers are formed from alcohols
R-OH + R’-OH →
H
R-O-R’ +H2O+
R and R’ can be the same or
different
Called a dehydration reaction
Predict the products
CH3OH + CH3CH2OH H+
CH3CH2CH2OH + CH3CHCH3 H+
OH
Common uses
Ethers as anesthetics:
Penthrane
Enthrane
Ethers as additives in gasoline
MTBE – methyl tert-butyl ether
Thiols
Compounds that contain the sulfhydryl group (-
SH)
Similar to alcohols in structure, but the sulfur atom
replaces the oxygen atom
Have nauseating aromas – defense spray of North
American striped skunk
H CH3
H 2C H
SH
Trans-2-butene-1-thiol
Thiols
Naming Thiols
Use the same rules as for alcohols except
that the full name of the alkane is retained.
Add the suffix –thiol.
CH3CH2SH ethanethiol
CH3
CH3CHCH2CH2 3-methyl-1-butanethiol
SH
HSCH2CH2SH 1,2-ethanedithiol
Uses of Thiols
Thiols are involved in protein structure
and conformation.
Cysteine is an amino acid that contains
a sulfhydryl group.
BAL (British Anti-Lewisite) is used as an
antidote for mercury poisoning.
Coenzyme A serves as a carrier of acetyl
groups in biochemical reactions.
End of the Presentation…
