ALCOHOLS,

PHENOLS
AND
ETHERS
Kimia Organik

Bonding for oxygen atoms in

organic compounds
Oxygen is commonly
found in two forms in
organic compounds:

Oxygen is group 6A
Needs to form two bonds
to get an octet.

Structural characteristics of
alcohols
Alcohols have the general formula:
R-OH
where R involves a saturated C-atom
(bound to hydrogens and/or other
carbons).
For example:

Alcohols, Ethers and Epoxides

IntroductionStructure and Bonding

Alcohols contain a hydroxy group (OH) bonded to an sp3 hybridized

carbon.

 When an OH group is bonded to a ring, the ring is numbered

beginning with the OH group.
Because the functional group is at C1, the 1 is usually
omitted from the name. (OH pada posisi -! Dihilangkan)
The ring is then numbered in a clockwise or counterclockwise
fashion to give the next substituent the lowest number.

Figure 9.2
Examples: Naming
cyclic alcohols

 Common names are often used for simple alcohols. To assign a

common name:

Name all the carbon atoms of the molecule as a

single alkyl group.
Add the word alcohol, separating the words with a
space.

Structural characteristics of
alcohols
Condensed structural formulas or line-angle
structures are commonly used for depicting
alcohols
IUPAC name
1-Propanol
1-Butanol

2-Propanol
2-Methyl-1-propanol
(Isobutanol)

Nomenclature for alcohols

Common names for alcohols

Name the C-atoms of a single alkyl group

as for alkanes.
Add the word alcohol following a space
after the alkyl name.

Nomenclature for alcohols

IUPAC
Naming

Find longest, continuous C-chain to which the OH

group (hydroxyl) is bound. Number the chain in a
way that gives the OH group the lowest
numbering.
Name and number other substituents present.
The name for the corresponding alkane chain
(e.g. for a 6-C chain, hexane) loses the e and
picks up ol (hexanol).
For cyclic alcohols, the OH group is understood to
be attached to C-1.

 Compounds having a hydroxy group on a sp2 hybridized carbonenols

and phenolsundergo different reactions than alcohols.

Ethers have two alkyl groups bonded to an oxygen atom.

11

 Epoxides are ethers having the oxygen atom in a three-membered ring.

Epoxides are also called oxiranes.

The COC bond angle for an epoxide must be 60, a considerable

deviation from the tetrahedral bond angle of 109.5. Thus, epoxides
have angle strain, making them more reactive than other ethers.

12

 The oxygen atom in alcohols, ethers and epoxides is sp3 hybridized.

Alcohols and ethers have a bent shape like that in H2O.
The bond angle around the O atom in an alcohol or ether is similar to
the tetrahedral bond angle of 109.5.
Because the O atom is much more electronegative than carbon or
hydrogen, the CO and OH bonds are all polar.

13

Alcohols with more than one

OH group
Polyhydroxyl alcohols possess more
than one OH group.
Alcohols which possess two OH
groups are called diols and those
with three OH groups are called
triols

Alkane name + diol, triol, etc.

 Compounds with two hydroxy groups are called diols or glycols.

Compounds with three hydroxy groups are called triols and so forth.

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Isomerism for alcohols

Commonly encountered
alcohols
Youve probably used a few of the
following alcohols:
Methyl and ethyl alcohol
Isopropyl alcohol
Ethylene glycol (1,2-Ethane diol)
Propylene glycol (1,2-Propane diol)
Glycerol (1,2,3-Propane triol)

Commonly encountered
Methanol (CHalcohols
OH) finds use as a solvent in
3

chemical reactions and in fuel for highperformance combustion engines.

Can cause permanent blindness or death in
high amounts
Vapors are very dangerous as well
Drinking methanol is a no-no. It is
metabolized to formaldehyde and formic acid
by the liver (alcohol dehydrogenase):

Commonly encountered
alcohols
Ethanol (CH3CH2OH) is also metabolized by the body, and
this reaction produces acetaldehyde and acetic acid:

Excessive drinking leads to liver cirrhosis, physiological

addiction, loss of memory. Drinking during pregnancy
poses risks for birth defects.
Ethanol is sometimes rendered undrinkable by the addition
of small quantities of toxic substances (e.g. benzene).
Industrially, ethanol is synthesized by hydration of ethene.

Ethanol
Toxic to humans
Acute poisoning kills several hundred
a year (drinking contests)
Long term poisioning
Most serious drug problem in US
40 times more addicts than heroin

Commonly encountered
alcohols

Isopropyl alcohol is used in rubbing alcohol

(70% isopropyl alcohol in H 2O) and in
cosmetics.
Rapid evaporation
Antiseptic
More toxic than ethanol, but induces
vomitting
Ingested, isopropyl alcohol is metabolized to
acetone:

Commonly encountered
alcohols
Ethylene glycol and propylene glycol are colorless

and odorless and very water-soluble. Used as

anti-freeze and reactants for the synthesis in
polyesters.
When ingested, ethylene glycol is metabolized to
oxalic acid, which causes renal problems:

Propylene glycol is metabolized to pyruvic acid,

which is non-toxic:

Commonly encountered
alcohols
Gycerol 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:

a non-polar (alkane-like) chain
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 monoydroxy
alcohols.
Boiling points
London forces

Ethane: -89 C London + H-bonding

Methanol: 65oC
Ethanol: 78oC London + H-bonding
London + more
1,2-Ethane diol: 197oC
H-bonding
o

Physical properties of
alcohols
The water-solubility of alcohols depends on the
length of the alkyl chain in the alcohol.
Monohydroxy alcohols having chains longer than
three carbons are not very water-soluble.
Polyhydroxy alcohols are more soluble because
they have more opportunities for hydrogenbonding with water.

Physical properties of
alcohols
Alcohols have higher
boiling points than
alkanes of the same chain
length (because they
hydrogen bond to each
other; the intermolecular
forces for alkanes are
only London forces)
Alcohols of a given chain
length are far more watersoluble than alkanes.

Remember: H-bonding is the strongest intermolecular force.

London forces are weak by comparison.

Classification of alcohols
Alcohols may be classified as 1o, 2o, or 3o, by considering the
number of carbons bound to the hydroxy-bearing carbon.

Although alcohols are able to H-bond, their ability to do so

becomes impaired by other carbon atoms near the hydroxy
group. The more carbon groups that are bound to the
hydroxy-bearing carbon, the more they get in the way of Hbonding (steric hindrance).

Nomenclature of Ethers
Simple ethers are usually assigned common names. To do so:

Name both alkyl groups bonded to the oxygen,

arrange these names alphabetically, and add the word
ether.
For symmetrical ethers, name the alkyl group and add
the prefix di-.

29

 More complex ethers are named using the IUPAC system.

One alkyl group is named as a hydrocarbon chain, and the
other is named as part of a substituent bonded to that
chain:
Name the simpler alkyl group as an alkoxy substituent by
changing the yl ending of the alkyl group to oxy.
Name the remaining alkyl group as an alkane, with the
alkoxy group as a substituent bonded to this chain.

Cyclic ethers have an O atom

in the ring. A common
example is tetrahydrofuran
(THF).

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Nomenclature of Epoxides
Epoxides can be named in three different waysAs epoxyalkanes,
oxiranes, or alkene oxides.
To name an epoxide as an epoxyalkane, first name the alkane chain or
ring to which the O atom is attached, and use the prefix epoxy to
name the epoxide as a substituent. Use two numbers to designate the
location of the atoms to which the Os are bonded.

31

 Epoxides bonded to a chain of carbon atoms can also be named as

derivatives of oxirane, the simplest epoxide having two carbons and
one oxygen atom in a ring.
The oxirane ring is numbered to put the O atom at position one, and
the first substituent at position two.
No number is used for a substituent in a monosubstituted oxirane.

32

 Epoxides are also named as alkene oxides, since they are often
prepared by adding an O atom to an alkene. To name an epoxide in this
way:

Mentally replace the epoxide oxygen with a double

bond.
Name the alkene.
Add the word oxide.

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Physical Properties
Alcohols, ethers and epoxides exhibit dipole-dipole
interactions because they have a bent structure with two
polar bonds.
Alcohols are capable of intermolecular hydrogen bonding.
Thus, alcohols are more polar than ethers and epoxides.

Steric factors affect hydrogen bonding.

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35

Preparation of Alcohols, Ethers, and Epoxides

Alcohols and ethers are both common products of nucleophilic
substitution.

The preparation of ethers by the method shown in the last two

equations is called the Williamson ether synthesis.
36

 In theory, unsymmetrical ethers can be synthesized in two different

ways; in practice, one path is usually preferred.

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 An alkoxide salt is needed to make an ether.

Alkoxides can be prepared from alcohols by a Brnsted-Lowry acid
base reaction. For example, sodium ethoxide (NaOCH 2CH3) is prepared
by treating ethanol with NaH.

NaH is an especially good base for forming alkoxide because the byproduct of the reaction, H2, is a gas that just bubbles out of the reaction
mixture.
38

 Organic compounds that contain both a hydroxy group and a halogen

atom on adjacent carbons are called halohydrins.
In halohydrins, an intramolecular version of the Williamson ether
synthesis can occur to form epoxides.

39

Preparation of alcohols
1. Alcohols can be prepared by hydration of alkenes
(as we saw in Chapter-13):

2. They can also be prepared by the hydrogenation

of C-O double bonds:

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

Chemical reactions of
alcohols
1.Combustion makes CO2 and H2O
2.Dehydration (loss of water
intramolecular) make an alkene
3.Dehydration (loss of water
intermolecular) makes an ether
4.Oxidation makes a carboxylic acid

Chemical reactions of
alcohols
Combustion reactions
1. 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:

Chemical reactions of
Elimination reactions
alcohols

2. 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, theres more than one of these)

Chemical reactions of
Elimination reactions
alcohols

Chemical reactions of
Elimination reactions
alcohols
In general, these kinds of reactions
(eliminations) proceed as follows:

Chemical reactions of
Elimination reactions
alcohols

If there is more than one adjacent carbon

atom from which loss of a H-atom can
occur, there will be more than one possible
alkene dehydration product:

Use Zaitsevs Rule to predict which alkene will be produced in the greate

Chemical reactions of
Elimination reactions
alcohols
Zaitsevs 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.

Chemical reactions of
Elimination reactions
alcohols
3. The alcohol dehydration reaction (like all

chemical reactions) is an equilibrium. Since

it occurs through elimination of an H2O
molecule, conditions that favor H2O loss (dry
conditions (concentrated H2SO4), high
temperatures) favor alkene formation.
On the other hand, if this reaction were run
in dilute H2SO4, alcohol formation would be
favored.

Chemical reactions of
Condensation reactions
alcohols
4. When lower temperatures are used than those that
yield alkenes, intermolecular loss of water tends to
occur (involving two alcohol molecules) to produce
ethers:

Dimethyl ether

A condensation reaction is a reaction in which two molecules combine to fo

a larger molecule while liberating a small molecule like water.

Chemical reactions of
alcohols
Example 14.3, pg. 414: identify the alcohol
needed to produce each of the following alcohol
dehydration products:

Chemical reactions of
Oxidation reactions
alcohols
Oxidation/reduction reactions involving organic
compounds result in a change in the number of Hatoms and/or the number of O-atoms bound to
carbons in the molecule:
Oxidations increase the number of C-O bonds
and/or decrease the number of C-H bonds in a
molecule.
Reductions decrease the number of C-O bonds
and/or increase the number of C-H bonds in a
molecule.

Chemical reactions of
Oxidation reactions
alcohols

Primary and secondary alcohols can be oxidized by mild

oxidizing agents to produce compounds with C-O double
bonds (aldehydes, ketones, carboxylic acids).

No H on OH-bearing
carbon to remove here.

Structural characteristics of
phenols
Phenols are aromatic compounds that bear a OH
group.
phenol = phenyl alcohol

This is another special case compound as far as

IUPAC naming goes. Hydroxyl groups have higher
priority than CH3 groups (or others weve seen so
far) for ring-numbering.

Structural characteristics of
phenols
Benzenes that are substituted with both
OH and CH3 groups are called cresols
(IUPAC-accepted common names):

For testing purposes, can also call these methylphenols

Structural characteristics of
phenols
For dihidroxy-benzene structures, the following
IUPAC-accepted common names are used:

Can also call these benzene diols (1,2-,

1,3-, 1,4-).

Physical and chemical properties

of phenols
Alcohols and phenols are flammable.
Alcohols can be dehydrated, but not
phenols
1o and 2o alcohols are oxidized by mild
oxidizing agents. 3o alcohols and phenols
do not undergo oxidation in these
conditions.
Alcohols and phenols can undergo
halogenation where the OH group is
replaced by a halogen.

Physical and chemical

properties of phenols
Phenols are weak acids in water.
They undergo deprotonation, as
discussed in Ch-10:

Occurrence and uses of

phenols

an antiseptic

disinfectants

antioxidants

Ethers
Derivatives of water
Both hydrogen atoms are replaced

Naming
Symmetrical
Name groups attached and add ether

Properties
Quite inert
Although react violently in the air
Low boiling pointsno hydrogen
bonds
Diethyl ether
Forms a peroxide in air
First general anesthetic

Nomenclature for ethers

Ethers are organic compounds in which two
saturated carbon atoms are bound through a
single oxygen atom.

Examples:

common names

Nomenclature for ethers

The IUPAC system for naming ethers:

1. Longest continuous carbon chain is used as parent
name (might have substituents)
2. Other chain is named as an alkoxy-substituent: change
the yl part of the other alkyl chain to oxy (e.g.
methyl to methoxy)
3. Name as alkoxy name then the parent chain. Number
the alkoxy substituent to indicate where it attaches to
the parent alkane.

Alcohol group has higher priority

Isomerism in ethers
Because ethers contain C, H, and O atoms, the
possibilities for isomers is greater than for
hydrocarbons.
For example, an ether having two three carbon
chains will have the following constitutional
isomers:

Isomerism in ethers
and then the following functional group isomers
(ethers have the same general formulas as
alcohols).

Functional group isomers: constitutional isomers that contain different functi

Physical and chemical properties

of ethers
Boiling points and melting points are dictated by
intermolecular forces. Compared with alkanes of
similar molar mass, an ether will have a similar
boiling point. Compared to an alcohol of the
same molar mass, the ether will have a much
lower boiling point.
Intermolecular force
London forces
London forces

London forces
+
H-bonding

Physical and chemical

properties of ethers
Ethers are more water-soluble than alkanes, because
water molecules can H-bond with them.
An ether and an alcohol of the same molar mass have
about the same solubility in water.
Some important chemical properties of ethers:
Ethers are highly flammable. The b.p. of diethyl ether is 35oC
and ether vapor ignites readily.
Ethers react with O2 to form hydroperoxides and peroxides
(unstable compounds which can explode)

Otherwise, ethers react similar to alkanes in combustion and

halogenation reactions.

Cyclic ethers
Cyclic ethers are similar to
cycloalkanes/cycloalkenes, but possess an Oatom as part of the ring.
Cyclic organic compounds in which one or more
carbon atoms of the ring have been replaced by
atoms of other elements are called heterocyclic
organic compounds.

Reaction of Ethers with Strong Acid

In order for ethers to undergo substitution or

elimination reactions, their poor leaving group
must first be converted into a good leaving
group by reaction with strong acids such as
HBr and HI. HBr and HI are strong acids that
are also sources of good nucleophiles (Br and
I respectively).
When ethers react with HBr or HI, both CO
bonds are cleaved and two alkyl halides are
formed as products.

68

Reactions of Epoxides
Recall that epoxides do not contain a good
leaving group.
Epoxides do contain a strained threemembered ring with two polar bonds.
Nucleophilic attack opens the strained threemembered ring, making it a favorable process
even with a poor leaving group.

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Sulfur analogs of alcohols

Thiols have the general formula R-SH. This is like
an alcohol (R-OH), and both O and S are group 6
elements (and thus possess similar chemistry).
The SH group of the thiol is called a sulfhydryl
group.
Nomenclature: named similar to alcohols, but the
ol part of the becomes thiol; also, the alkane
part of the name becomes retained:

Sulfur analogs of alcohols

The common naming system for
thiols involves use of the term
mercaptan

Sulfur analogs of alcohols

In terms of properties and chemical
reactions of thiols:
They generally have lower boiling points
than alcohols of similar structure (no Hbonding)
They stink

Chemical reactions:
Thiols are easily oxidized to form disulfides
(important for protein chemistry)

Sulfur analogs of ethers

Thioethers are organic compounds in which two
saturated carbon atoms are linked through a
single sulfur atom.
The common naming system for thioethers is
similar to that for ethers, with the name ether
being replaced by sulfide
Common
IUPAC

Methylthiomethane

Methoxymethane

Methylthiobenzene

Methylthioethane

Replace alkoxy with alkylthio in IUPAC name

Sulfur analogs of ethers

In general, thioethers and thiols are more
reactive than their ether and alcohol
counterparts.
C-S bonds are weaker than C-O bonds
Functional group isomers are also a
possibility for sulfur compounds