Unit 2: Alcohols, Phenols and Ethers

UNIT LEARNING OUTCOMES

 Distinguish and differentiate alcohols, phenols and ethers.
 Demonstrate proficiency in naming and structure writing of alcohols, phenols
and ethers
 Analyze and understand physical and chemical properties of alcohols,
phenols and ethers including their preparations addition reactions, isomerism
 Identify common and important sources, practical uses and their
applications in industrial setting

ENGAGE

Source: https://www.gurneys.com/category/grape-vines
The phenol resveratrol, found in the skin of red grapes, continues to be studied for its
potential anti-cancer, antiarthritis, and hypoglycemic properties

Reflection 2.2: Identify one alcohol/phenol/ether found at home and take a selfie.
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Reflection 2.2 FAMILY NAME, GIVEN NAME

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 EXPLORE

Alcohols
 General Formula: R-OH where R refers to any alkyl group
 Functional Group: -OH or hydroxyl group
 A composite of an alkane and water: (R-H) + (H2O) → R-OH
 Alkanol group

Classification of Alcohol
Alcohols are classified as primary (1°), secondary (2°), or tertiary (3°)
depending on the number of carbon atoms bonded to the carbon atom that bears
the hydroxyl group. A primary alcohol is an alcohol in which the hydroxyl-bearing
carbon atom is bonded to only one other carbon atom. A secondary alcohol is an
alcohol in which the hydroxyl bearing carbon atom is bonded to two other carbon
atoms. A tertiary alcohol is an alcohol in which the hydroxyl-bearing carbon atom is
bonded to three other carbon atoms. Chemical reactions of alcohols often depend
on alcohol class.

Naming of Alcohols
A. Common Naming: Alkyl alcohol
B. IUPAC Naming:
1. Select the longest carbon chain containing the hydroxyl group, and derive the
parent name by replacing the -e ending of the corresponding alkane with -ol. The
ending -e is deleted to prevent the occurrence of two adjacent vowels: propanol
rather than propaneol, for example.
2. Number the alkane chain beginning at the end nearer the hydroxyl group.
3. Number the substituents according to their position on the chain, and write the
name, listing the substituents in alphabetical order and identifying the position to
which the -OH is bonded. Note that in naming cis-1,4-cyclohexanediol, the final -e of
cyclohexane is not deleted because the next letter, d, is not a vowel; that is,
cyclohexanediol rather than cyclohexandiol. Also, as with alkenes newer IUPAC
naming recommendations place the locant immediately before the suffix rather
than before the parent.

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 Some simple and widely occurring alcohols have common names that are
accepted by IUPAC. For example:

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 Properties of Alcohols
 Alcohols consist of a non-polar (alkane-like) chain and a polar hydroxyl group.
Thus, alcohols might be water-soluble, or not (depending on the length of the
carbon chain).

alkane-like (non-polar) polar O-H bond

 Because of the presence of the –OH group, alcohols are polar compounds.
Alcohols with 1 to 4 carbon atoms are highly soluble in water. Solubility in water
decreases as the number of carbon atoms and branches increases. Alcohols
have much higher solubility in water than alkanes of similar molecular mass.
 The boiling point for 1-alcohols, unbranched-chain alcohols with an —OH
group on an end carbon, increases as the length of the carbon chain
increases. Alcohols with more than one hydroxyl group present have
significantly higher boiling points than their monohydroxy counterparts.
Alcohols have higher boiling points than alkanes of similar molecular mass.
Alcohols have the highest boiling points as compared to ethers and
hydrocarbons of the same molecular weights.
 Low MW alcohols are colorless liquids of specific odour (unpleasant from C4),
narcotic effect, toxic.
 Polyhydroxy alcohols have sweet taste.
 Higher alcohols (from C12) are solid compounds

Reactions of Alcohol
A. Common Preparation of Alcohols
1. Fermentation of Carbohydrates

2. Hydration of Alkenes

3. Oxidation of Alkene

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 B. Other Methods of Synthesizing Alcohol

C. Oxidation of Alcohol

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 D. Dehydration of Alcohol

E. Acid-base properties of alcohols. Alcohols can act as weak acids or weak bases
(undergo protonation and deprotonation) due to the nature of the –OH group as
shown here.

(1) Alcohols form oxonium ions in the presence of a strong acid. Here methanol
reacts with sulfuric acid and behaves like a base.

(2) Alcohols form alkoxide ions (RO-) in the presence of strong bases or an alkali
metal. Here ethanol reacts with sodium and behaves like an acid. The order of
reactivity of alcohols with alkali metals is 1° > 2° > 3°.

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 Important Alcohols
A. Methyl Alcohol (Methanol)
 Methyl alcohol, with one carbon atom and one —OH group, is the simplest
alcohol. Colorless liquid and is a good fuel for internal combustion engines.
 has excellent solvent properties, and it is the solvent of choice for paints,
shellacs, and varnishes.
 Sometimes called wood alcohol
 Drinking methyl alcohol is very dangerous
B. Ethyl Alcohol (Ethanol)
 Ethyl alcohol, the two-carbon monohydroxy alcohol, is the alcohol present in
alcoholic beverages and is commonly referred to simply as alcohol or drinking
alcohol. Also known as grain alcohol.
 Fermentation is the process by which ethyl alcohol for alcoholic beverages is
produced.
C. Isopropyl Alcohol (2-Propanol)
 Isopropyl alcohol is one of two three-carbon monohydroxy alcohols; the other
is propyl alcohol.
 A 70% isopropyl alcohol–30% water solution is marketed as rubbing alcohol.
 Isopropyl alcohol’s rapid evaporation rate creates a dramatic cooling effect
when it is applied to the skin
 Use in cosmetics formulations such as after-shave lotion and hand lotions.
 Isopropyl alcohol has a bitter taste.
 Its toxicity is twice that of ethyl alcohol
D. Ethylene Glycol (Ethane-1,2-diol) and Propylene Glycol (Propane-1,2-diol)
 Ethylene glycol and propylene glycol are the two simplest alcohols possessing
two —OH groups. Besides being diols, they are also classified as glycols. A
glycol is a diol in which the two —OH groups are on adjacent carbon atoms.
 Both of these glycols are colorless, odorless, high-boiling liquids that are
completely miscible with water. Their major uses are as the main ingredient in
automobile “year-round” antifreeze and airplane “de-icers” and as a starting
material for the manufacture of polyester fibers.
E. Glycerol (Propane-1,2,3-triol)
 Glycerol often called glycerin, is a clear, thick liquid that has the consistency
of honey. Its molecular structure involves three —OH groups
 Glycerol is normally present in the human body. It is present, in combined form,
in all animal fats and vegetable oils.
 In some Arctic species, glycerol functions as a “biological antifreeze”
 Because glycerol has a great affinity for water vapor (moisture), it is often
added to pharmaceutical preparations such as skin lotions and soap.
 Its lubricative properties also make it useful in shaving creams and in
applications such as glycerol suppositories for rectal administration of
medicines.
 It is used in candies and icings as a retardant for preventing sugar
crystallization.

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 EXPLAIN

Phenols
 Class of chemical compounds consisting of
a hydrohyl group (-OH) bonded directly to
an aromatic hydrocarbon group.
 Phenols with a single hydroxyl group,
meaning mono hydroxyl phenols
 Phenols with more than one hydroxyl
groups in the molecule, meaning poly
hydroxyl phenols
 Found in coal tar and petroleum.
 Used to be called CARBOLIC ACID.

Nomenclature of Phenol
Phenol is the IUPAC name for benzene with a hydroxyl group. The IUPAC rules for
naming phenols are simply extensions of the rules used to name benzene erivatives
with hydrocarbon or halogen substituents.

Methyl and hydroxy derivatives of phenol have IUPAC-accepted common names.

Methylphenols are called cresols. The name cresol applies to all three isomeric
methylphenols.

For hydroxyphenols, each of the three isomers has a different common name.

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 Physical Properties of Phenol
 Polar, can form hydrogen bond
 Water insoluble
 Stronger acids than water and will dissolve in 5% NaOH but weaker acids
than carbonic acid
 Many are used as antiseptics and disinfectants.

Chemical Reactions of Phenol

1. Phenols are weak acids in solution Phenols will react with a strong base like NaOH
but not with weaker bases like NaHCO3.

2. Oxidation of phenols to quinones.

Uses and Occurrence of Phenol

 Phenol is obtained from coal tar but it is also produced synthetically by the
process shown below.

 The toxicity of phenols to microorganisms make them excellent antiseptics. For

example 4-hexylresorcinol is used as an antiseptic in many pharmaceutical
preparations. The phenol derivatives o-phenylphenol and 2-benzyl-4-
chlorophenol are the active ingredients in Lysol, a disinfectant for walls, floors,
and furniture in homes and hospitals.

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  Phenols possess antioxidant activity. An antioxidant is a substance that
protects other substances from being oxidized by being oxidized itself in
preference to the other substances. Two commercial phenolic antioxidant
food additives are BHA (butylated hydroxy anisole) and BHT (butylated
hydroxy toluene)

 A naturally occurring phenolic antioxidant that is important in the functioning

of the human body is vitamin E

 A number of phenols found in plants are used as flavoring agents and/or

antibacterials. Included among these phenols are Thymol, obtained from the
herb thyme, used as an ingredient in several mouthwash formulations. Eugenol
is responsible for the flavor of cloves, used clove oil as an antiseptic.
Isoeugenol, is responsible for the odor associated with nutmeg. Vanillin, which
gives vanilla its flavor, is extracted from the dried seed pods of the vanilla
orchid.

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 ELABORATE

Ether
 An ether is an organic compound in which an oxygen atom is bonded to two
carbon atoms by single bonds. In an ether, the carbon atoms that are
attached to the oxygen atom can be part of alkyl, cycloalkyl, or aryl groups.
 All ethers contain a C—O—C unit, which is the ether functional group.
 Generalized formulas for ethers, R—O—R (where R is either alkyl or aryl group)

Nomenclature of Ether
A. Common Naming
Formed from the names of the groups attached to the oxygen atom, followed by
the word ether as shown.

B. IUPAC Naming
In this system, ethers are named as substituted hydrocarbons. The smaller
hydrocarbon attachment and the oxygen atom are called an alkoxy group, and this
group is considered a substituent on the larger hydrocarbon group. An alkoxy group
is an —OR group, an alkyl (or aryl) group attached to an oxygen atom. Simple alkoxy
groups include the following:

General IUPAC naming rules still applies.

The simplest aromatic ether involves a methoxy group attached to a benzene ring
goes by the common name anisole.

Uses, Structures and Properties of Ether

 Ethers have a bent shape similar to water and alcohols.
 Ethers are polar enough to dissolve some polar substances like water but also
nonpolar enough to dissolve many nonpolar organic compounds.
 The slight solubility of ether in water and sulfuric can be explained by hydrogen
bonding as shown here.

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  Because no –OH group is present, hydrogen bonding does not occur between
ether molecules. This lack of hydrogen bonding can be seen by comparing
the boiling points of a hydrocarbon, an ether, and an alcohol of similar molar
mass. The boiling point of the ether is somewhat above that of the
hydrocarbon but much lower than that of the more polar alcohol.
 Ethers are common solvents found in laboratories because they are good
solvents for polar and nonpolar compounds and have low chemical reactivity.
 However, their use can be dangerous, since low-molar-mass ethers are volatile
and highly flammable.
 Another hazard of ethers is that, despite their generally low chemical
reactivity, oxygen in the air slowly reacts with them to form unstable peroxides
that are subject to explosive decomposition.

Reaction of Ether
1. Ethers are formed from the dehydration of 2 alcohols takes place in the presence
of acid catalyst and under controlled temperature. Applicable for symmetrical
ether.

2. Ethers are also formed by Williamson Synthesis this is used in preparation of

unsymmetrical ether.
R-ONa + R-X → R-O-R + NaX
(phenoxide) (alkyl halide) (ether) (salt)
Where R-ONa may be methyl, 1 , 2 , 3 or aryl group
O O O

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 3. Cleavage of ethers by hot concentrated acid. The acid most often used in this
reaction are HI, HBr and HCl.

Cyclic Ethers
Cyclic ethers contain ether functional groups as part of a ring system. Some
examples of such cyclic ethers, along with their common names, follow:

Ethylene oxide has few direct uses. Its importance is as a starting material for the
production of ethylene glycol, a major component of automobile antifreeze. THF is
a particularly useful solvent in that it dissolves many organic compounds and yet is
miscible with water. In carbohydrate chemistry, five-membered (furan) and six-
membered (pyran) cyclic ether systems are carbohydrate derivatives are called
furanoses and pyranoses, respectively

Graded Assignment 2.2: Concept Application: Show all necessary computations

and or illustrations.
(1) Write the condensed structural formula of the following alcohols and their
classification.
a. 2-heptanol b. 2-methyl-2-heptanol
c. 3-phenyl-1-butanol d. 2,2-dimethyl-1-hexanol
e. 3-ethyl-2-pentanol f. 3,5-dimethylcylohexanol

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 2. Draw the structural formula for each of the following:
Phenol Ether
a. 3-bromophenol a. butyl methyl ether
b. hydroquinone b. anisole
c. catechol c. phenyl propyl ether
d. m-ethylphenol d. 3-propoxyheptane
e. o-cresol e. 1,3-dimethoxybenzene
f. 2,6-dichlorophenol f. ethoxycyclobutane
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EVALUATE

Graded Test 4: Concept Analysis/Application

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