Compounds With Oxygen & Sulfur

Alcohols, Phenols, and Ethers

An alcohol has an –OH bonded to an alkyl group; a phenol
has an –OH bonded directly to an aromatic ring; and an
ether has an O bonded to two organic groups.

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 Physical properties
• Ethyl alcohol, dimethyl ether, and propane have similar molecular weights,
yet ethyl alcohol boils more than 100° higher than the other two.
• The high boiling points of ethyl alcohol and water are due to hydrogen
bonding.
• Alkanes and ethers do not have hydroxyl groups and cannot form
hydrogen bonds among themselves. As a result, they have lower boiling
points. Ethers, in fact, resemble alkanes in many of their properties.

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 Naming Alcohols
• Common names of many alcohols identify the alkyl group and
then add the word “alcohol.” In the IUPAC system:
• STEP 1: Name the parent compound. Find the longest chain
that has the hydroxyl substituent attached, and name the
chain by replacing the -e ending of the corresponding alkane
with -ol:

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• STEP 2: Number the carbon atoms in the main chain. Begin
at the end nearer the hydroxyl group, ignoring the location of
other substituents:
• If the compound is a cyclic alcohol, add the -ol ending to the
name of the parent cycloalkane. In a cyclic alcohol, begin with
the carbon that bears the –OH group and proceed in a
direction that gives the other substituents the lowest possible
numbers.

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 STEP 3: Write the name, placing the number that locates the
hydroxyl group immediately before the parent compound name.
Number the positions of all other substituents, and list them
alphabetically. Note that in a cyclic alcohol, it is not necessary to
use the number “1” to specify the location of the –OH group.

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 SUMMARY
IUPAC Rules for Naming Alcohols
• 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
• Number the chain from the end nearer the hydroxyl group
• Number substituents according to position on chain, listing the
substituents in alphabetical order

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• Dialcohols, or diols, are often called glycols.
• Ethylene glycol is the simplest glycol; propylene glycol is often
used as a solvent for medicines that need to be inhaled or
rubbed onto the skin.
• Numbering starts from the end closer to an –OH group, and
the -diol name ending is used.

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• Alcohols are classified as primary, secondary, or tertiary
according to the number of carbon substituents bonded to
the hydroxyl-bearing carbon.
• Alcohols with one substituent are said to be primary, those
with two substituents are secondary, and those with three
substituents are tertiary.

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 Properties of Alcohols
• Alcohols are much more polar than hydrocarbons. Hydrogen
bonding occurs and has a strong influence on alcohol properties.
• Straight-chain alcohols with up to 12 C’s are liquids, and each
boils at a considerably higher temperature than the related
alkane.
• Alcohols with a small organic part resemble water. Methanol and
ethanol are miscible with water and they can dissolve small
amounts of many salts.
• Alcohols with a large organic part are more like alkanes. 1-
Heptanol is nearly insoluble in water and can’t dissolve salts but
does dissolve alkanes.

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Alcohols with 2 or more –OH groups can form more than one
hydrogen bond. They have higher boiling points and are more
water soluble than similar alcohols with one –OH group.

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 Reactions of Alcohols

• Alcohols undergo loss of water (dehydration) on treatment

with a strong acid catalyst.
• The –OH group is lost from a C, and an –H is lost from an
adjacent C to yield an alkene product:

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• When more than one alkene can result from dehydration of
an alcohol, a mixture of products is usually formed.

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 Alcohols undergo dehydration (loss of water molecule) in acidic medium to give olefins. A
double bond is formed due to loss of water molecule. It is an elimination reaction. According
to Saytzeff's rule, during dehydration, more substituted alkene (olefin) is formed as a major
product, since the greater the substitution of double bond the greater is the stability of
alkene.

Sulfuric acid is a strong acid and ionizes to give a proton:

Thus formed H+ ion attacks the -OH group. The OH2+ group formed is good leaving group
due to accumulation of positive charge on oxygen atom. Now the loss of H2O creates positive
charge on the carbon atom and thus by forming a tertiary carbocation.
Finally, one of the hydrogens adjacent to the positively charged carbon is
removed as proton, H+ to make a double bond. However, there are three
adjacent hydrogen atoms (indicated by descriptors I, II & III). Hence three
different alkenes are possible. According to Saytzeff's rule, highly substituted
alkene, as shown below by the loss of H+(I), is formed as a major product.
 Saytzeff’s Rule

The major product is the one that results when the

hydrogen is removed from the carbon atom with
the smallest number of hydrogen atoms. “The poor
get poorer”

2H 3H
H
H+
Heat 2-Butene (major product)
+H2O
OH
2-Butanol 1-Butene (minor product)

THE MOST SUBSTITUTED C=C IS THE MAJOR PRODUCT

 ANOTHER KIND OF DEHYDRATION
Formation of Ethers
Ethers form when the dehydration of alcohols occurs at lower
temperatures in the presence of an acid catalyst.

H+
R—OH + HO—R’ R—O—R’ + H2O
Low Heat

The components of water are removed from two molecules: an H–

from one alcohol and the –OH from another.
 Oxidation of Alcohols
The reactions of alcohols have a central role in organic chemistry because
alcohols can be converted to many of the other functional groups.

Oxidation is Reduction is
• a loss of electrons • a gain of electrons
• a more positive oxidation number • a less positive oxidation number
• a loss of hydrogen atoms • a gain of hydrogen atoms
• the addition of oxygen atoms. • the loss of oxygen atoms
• more bonds to oxygen • the loss of bonds to oxygen.

1 Bond to O 2 Bonds to O 3 Bonds to O

Alkane Alcohol (1°) Aldehyde Carboxylic acid

[O] OH [O] O [O] O
[O] CO2 + H 2O
CH3 CH3 CH3 CH2 CH3 C H CH3 C OH
 OXIDATION REACTIONS
Oxidation of Primary Alcohols

Primary and secondary alcohols

are converted into carbonyl-
containing compounds on
treatment with an oxidizing agent.
A carbonyl group is a functional
group that has a C=O. The symbol
[O] will indicate a generalized
oxidizing agent

[O] [O]
Primary alcohol aldehyde carboxylic acid
Example: oxidation of methanol

CH3OH  CH2O  HCO2H

 Oxidation of Secondary Alcohol

[O]
Secondary alcohol Ketone

Double bonds forms

Two hydrogen atoms removed

OH O
[O]
R1 CH R2 R1 C R2 H2O
2° Alcohol
Ketone

R1, R2: alkyl groups

 Oxidation of Tertiary Alcohol
[O]
Tertiary alcohol No reaction

Only one hydrogen atom, not the two required to be removed

OH
[O]
R1-C-R2 NR
R3
3° Alcohol

R1, R2, R3: alkyl groups

 Conversion of Alcohols into Esters

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Esterification
 Some Common Alcohols
► Simple alcohols are very common organic chemicals. They are
useful as solvents, antifreeze agents, and disinfectants, and they
are involved in the metabolic processes of all living organisms.
► Methyl alcohol - colorless, miscible with water, and toxic to
humans and animals.

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 Methyl alcohol

Mechanism of Toxicity
By itself, methanol is relatively non-toxic; however, it is
metabolized to highly toxic compounds that are responsible for
the acidosis and blindness characteristic of methanol poisoning.

ALCOHOL ALDEHYDE
DEHYDROGENASE DEHYDROGENASE

FORMIC
METHANOL FORMALDEHYDE ACID

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 Ethyl alcohol
• Ethyl alcohol produced by fermentation is the alcohol
in alcoholic beverages.

Krebs Cycle Acetyl-CoA

ALCOHOL ALDEHYDE
DEHYDROGENASE DEHYDROGENASE
ACETIC
ETHANOL ACETALDEHYDE ACID
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• Ethylene glycol, a diol, is a toxic, colorless liquid, miscible with
water and insoluble in nonpolar solvents. Its two major houshold
use is as antifreeze.

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Toxicity of Ethylene glycol
• The triol, glycerol (glycerin) is a nontoxic, colorless
liquid that is miscible with water. It is used as a
sweetener and a moisturizer, and esterified with fatty
acids (triacylglycerol) is the main component of fat.

Propane-1,2,3-triol

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 14.6 Phenols
• Phenol is the name both of a specific compound,
hydroxybenzene, and of a family of compounds.
• Phenols are usually named with the ending -phenol rather
than -benzene even though their structures include a benzene
ring.
• Phenols have hydroxyl groups bonded directly to a benzene
ring

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– Nomenclature of Phenols
• Phenol is the parent name for the family of
hydroxybenzenes
– Methylphenols are called cresols

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 Acidity of Alcohols and Phenols
Alcohols and phenols are weakly acidic. They dissociate
slightly in water and establish equilibria between neutral and
anionic forms:

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Alcohols and Phenols are Weak Brønsted
Acids
• Can transfer a proton to water to a very small extent
• Produces H3O+ and an alkoxide ion, RO−, or a phenoxide
ion, ArO−

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 Acidity Measurements
We use the ionization of acids in water to measure acid strength (Ka):
HBase + H2O H3O+ + Base-

• The acidity constant, Ka, measures the extent to which a

Brønsted acid transfers a proton to water
[A−] [H3O+]
Ka = ————— and pKa = −log Ka
[HA]

• ROH Ka ~ 10-16 - 10-18

• ArOH Ka ~ 10-10

• Relative acidities are more conveniently presented on a

logarithmic scale, pKa
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 pKa Values for Typical OH Compounds

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 Relative Acidities of Alcohols
• Simple alcohols are about as acidic as water
• Alkyl groups make an alcohol a weaker acid
• The more easily the alkoxide ion is solvated by water the
more its formation is energetically favored
• Steric effects are important

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 Inductive Effects
• Electron-withdrawing groups make an alcohol a stronger
acid by stabilizing the conjugate base (alkoxide)

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 Phenol Acidity
• Phenols (pKa ~10) are much more acidic than alcohols (pKa
~ 16) due to resonance stabilization of the phenoxide ion
• Phenols react with NaOH solutions (but alcohols do not),
forming salts that are soluble in dilute aqueous solution

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• Phenol is much more acidic than cyclohexanol

• oxygen of a phenol is more positive and this makes the

attached hydrogen more acidic
– The oxygen of phenol is more positive because it is attached to an
electronegative sp2 carbon of the benzene ring
– Resonance contributors to the phenol molecule also make the
oxygen more positive

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Resonance effects involving aromatic structures can have a dramatic influence
on acidity and basicity. Notice, for example, the difference in acidity between
phenol and ethanol.

In the conjugate base of phenol the negative charge can be delocalized by

resonance to three different carbons on the aromatic ring. The benzene ring
is acting as an electron-withdrawing group.
The base-stabilizing effect of an aromatic ring can also be accentuated by the
presence of an additional electron-withdrawing substituent, such as a
carbonyl. The aromatic aldehyde is more acidic than phenol.
 Reactions of Phenols
• The hydroxyl group is a strongly activating, making
phenols substrates for electrophilic halogenation,
nitration, sulfonation etc.
• Reaction of a phenol with strong oxidizing agents yields a
quinone

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 Reduction and oxidation of quinones

Loss of a proton and an

electron generates a
phenoxyl radical

Loss of a second proton and

a second electron completes
the oxidation

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 Quinones

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 Quinones in Nature
• Ubiquinones mediate electron-transfer processes involved
in energy production through their redox reactions

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 Quinones in Nature
O O−
CH3O CH3 CH3O CH3
e−
CH3 CH3
CH3O (CH2 CH C CH2)nH CH3O (CH2 CH C CH2)nH
O
coenzyme Q O
coenzyme Q •−
e− + 2 H+
OH
CH3O CH3

CH3
CH3O (CH2 CH C CH2)nH
OH coenzyme QH2
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Other Reactions of the -OH Group of Phenols
Ester formation (similar to alcohols)
 Reactions of the Benzene Ring of Phenols
Electrophilic Aromatic Substitution
The –OH group is a powerful activating group in EAS and an ortho/para
director.
a) Nitration
b) Halogenation
c) Sulfonation

OH OH
H2SO4, 15-20oC SO3H

OH

H2SO4, 100oC

SO3H

At low temperature the lower Eact ortho-product is formed.

At high temperature more stable para-product is formed.
 14.8 Ethers
Ethers, compounds with two organic groups bonded to
the same O atom, are named by identifying the two
organic groups and adding the word ether.

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 Compounds that contain the oxygen atom in a ring
are classified as cyclic ethers and are often given
common names.

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 • An –OR group is referred to as an alkoxy group;
-OCH3 is a methoxy group, -OCH2CH3 is an ethoxy
group, and so on.

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 Naming Cyclic Ethers
O O

Oxacyclopropane Oxacyclobutane O
(oxirane, ethylene oxide) (oxetane)

O
O
Oxacyclohexane
(tetrahydropyran)
O
Oxacyclopentane 1,4-Dioxacyclohexane
(tetrahydrofuran) (1,4-dioxane)

• Can Use Replacement Nomenclature (oxa  O replaces CH2)

• Also Many Common Names (Acceptable to Use)

Not all compounds of the formula R-O-R are
ethers!
Ethers are not to be confused with the
following classes of compounds with the
same general structure R-O-R:
• Aromatic compounds like furan where the
oxygen is part of the aromatic system.
• Compounds where one of the carbon
atoms next to the oxygen is connected
to oxygen, nitrogen, or sulfur:
– Esters R-C(=O)-O-R
– Acetals R-CH(-O-R)-O-R
– Aminals R-CH(-NH-R)-O-R
– Anhydrides R-C(=O)-O-C(=O)-R

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Reactivity of Ethers
Autoxidation
 14.9 Thiols and Disulfides
Thiols or mercaptans, are sulfur analogs of alcohols.
The systematic name of a thiol is formed by adding -
thiol to the parent name.

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 Nomenclature of Thiols

1) Analogous to alcohols, but suffix is -thiol rather than

-ol
2) Final -e of alkane name is retained, not dropped as
with alcohols

CH3CHCH2CH2SH

CH3

3-Methyl-1-butanethiol
 Properties of Thiols

• Bonding is much weaker in thiols (dipol-dipol) than in alcohols (hydrogen bonding)

• Thiols are more easily oxidized than alcohols; oxidation takes place at sulfur

• Thiols are stronger acids than alcohols

R-SH R-S- + H+ pKa ~ 10

 Oxidation of thiols takes place at sulfur

•• •• ••
RS H RS SR
•• •• ••
thiol disulfide
• thiol-disulfide redox pair is important in biochemistry
• other oxidative processes place 1,2, or 3 oxygen atoms on sulfur

RS H

O– O-

RS OH RS + OH RS2+ OH

O-
sulfenic acid sulfinic acid sulfonic acid
 Biologically Important Thiols
As functional group of the
amino acid cysteine, the thiol
group plays an important role
in biological systems. When
the thiol groups of two
cysteine residues are brought
near each other in the course
of protein folding, an
oxidation reaction can create
a cystine unit with a disulfide
bond (-S-S-).

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 Biologically Important Thiols

Glutathione is a
tripeptide commonly
abbreviated as GSH. It is
a major cellular
antioxidant.

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Recommended reading
Fundamentals of general, Organic, and Biological
Chemistry
by McMurry, Castellion, Ballantine, Hoeger,
Peterson (Pearson)

General, Organic, & Biological Chemistry by

Janice Gorzynski Smith, McGrasw Hill Education

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