CHAPTER 7

ALCOHOLS AND
ETHERS
• Alcohol is an organic compound in which
the hydroxyl functional group (-OH) is
bound to a carbon atom.

H3CH2C OH

alkyl group hydroxy group

• General formula of alcohol is CnH2n+1 OH.
 Classification of Alcohols
• Alcohols are classified as primary, secondary
and tertiary alcohols depend on the number
of carbon atoms bonded to the carbon with
the –OH group.

• For primary alcohol, the -OH is bonded to

carbon atom with one alkyl group or -OH
group is attached to a carbon atom that
contains two or three hydrogen atoms.
 H R
H C OH H C OH
H H
primary primary

R R
R' C OH R' C OH
H R''
secondary tertiary
 Naming Alcohols
• Find the longest continuous carbon chain
containing the carbon atom attached to
the –OH group and give number to the
carbon atoms. The carbon atom attached
to the –OH group is given the lowest
position number.

• Name all substituents in alphabetical

order.
Example:

4 3 2 1
CH3CH2CH2CH2 OH
• Four carbon = butane, replace the “e”
with the suffix ‘ol”. The parent structure is
butanol

The name of the compound is

1-butanol or butanol
• The compounds with two hydroxyl groups
are called diols or glycols.

HO CH2CH2 OH
1,2-ethanediol
 Naming of Cyclic Alcohols

• Assign the –OH group as C1.

• Proceed to the second substituent either

clockwise or counterclockwise to give the
lowest position number.
Example:
Start from the –OH
carbon

1 Parent name
3
CH3 2
OH Suffix “ane” to “ol”
Subtituent & location

The name of the compound is:

3-methylcyclohexanol
• Name the following compounds.

HO H
CH3
a) b) CHCHCH3
OH
HO H

OH
OH OH
c) d) CH3CHCH2CHCHCH3
CH3
CH3
 Preparation of Alcohols from Hydration
of Alkenes
• Hydration of alkenes with aqueous acid is a
poor reaction in the laboratory, therefore,
1) hydroboration or oxidation will be used to
prepare alkenes which produce non-
Markovnikov’s hydration product; and
2) oxymercuration or reduction produce
Markovnikov’s hydration product.
 hydroboration
(anti Markonikov's) CH3 CH3
H H
BH3/THF H2O2
-
BH2 OH OH
H H

CH3
Hg(OAc)2 OH CH3
mercury(II) acetate
NaBH4 OH
H2O H
oximercuration HgOAc
(obey Markovnikov's)
 Preparation of 1,2-diols

• 1,2-diols can be prepared by

1) direct hydroxylation of alkene with osmium
tetroxide, OsO4 followed by reduction with
sodium bisulfite, NaHSO3 to give a cis- diol;
or by
2) acid-catalysed hydrolysis of an epoxide to
give trans- diol.
 CH3 CH3
O O NaHSO OH
3
OsO4 Os
O O H2O
pyridine OH
H H
an osmate a cis- 1,2-diol

CH3 OH
RCO3H
CH3
CH2Cl2 +
O H3O
OH
H H
1-methyl-1,2-epoxy a trans- 1,2-diol
cyclohexane
 Preparation of Alcohols from Hydrolysis
of Haloalkanes
• Alkyl halide reacts with strong base (NaOH) to
produce alcohols and sodium halide, NaX.

R-X + NaOH ROH + NaX

CH3CH2Br + NaOH CH3CH2OH + NaBr

Cl OH
+ NaOH + NaCl

tert-butyl chloride tert-butyl alcohol

Alcohols as Acids: Formation of Alkoxides
• As a weak acids, alcohols dissociate slightly in
dilute aqueous solution by donating a proton to
water, producing hydronium ion and an alkoxide
ion RO- or a phenoxide ion.

H
R O O +
+ H H R O + H3O
an alcohol an alkoxide ion
 Dehydration of Alcohols to Alkenes

• In dehydration of alcohols, the C-O bond

and their neighbouring C-H bond are
broken and an alkene π bond is formed.

H OH
C C C C + H2O
• The reaction of 1-methylcyclohexanol with
warm aqueous sulfuric acid in a solvent like
tetrahydrofuran results in loss of water and
formation of 1-methylcyclohexene.

H3C OH CH3

H2SO4/H2O/THF + H2O

Obey the Zaitsev’s rule

 Zaitsev’s Rule
• Acid-catalysed dehydrations usually follow
Zaitsev’s rule and yield the more stable
alkene as the major product.
CH3
CH3 H3C C CHCH3
+
H3C C CH2CH3 3 /THF
H O
2-methyl-2-butene + H2O
major
OH
2-methyl-2-butanol CH3
H2C C CH2CH3
2-methyl-1-butene
minor
• The dehydration of alcohols with aqueous acid is
an E1 process and occurs through the three-step
mechanism. Only tertiary alcohols are readily
dehydrated with acid. Secondary alcohols can be
made to react but the conditions are severe.
Primary alcohols are even less reactive and very
harsh conditions are necessary to cause
dehydration.
H H R H R R
C C C
R R OH R OH
OH
primary alcohol secondary alcohol tertiary alcohol

increasing reactivity
• The dehydration of secondary or tertiary alcohols
are effective under mild basic conditions. The
example of reagent used is phosphorus oxychloride
(POCl3) in the basic amine solvent, pyridine, and
the process take place by an E2 mechanism.

H3C CH3
OH
POCl3
pyridine
Mechanism: Acid-Catalyzed Dehydration of an Alcohol
2. C-O bond breaks and two electrons from the bond
stay with O, leaving a carbocation intermediate.
H
O H CH3
H3C H H H 3C O
O H
H H
H + H2O

protonated carbocation
alcohol

1. O atom bond to H+ to produce a

protonated alcohol intermediate. CH3
3. Two electrons from a H
neighbouring C-H bond form
C=C and H+ is eliminated. + H3O+
 Conversion of 3° Alcohols into Alkyl Halides
• Tertiary alcohols react with HCl or HBr by SN1 mechanism.

2. water is expelled to
generate a carbocation.
R R R
R C OH HCl R C OH SN1 R C + H2O
2
R R R
1. acid protonates the a carbocation
hydroxyl oxygen atom.
Cl-
R
R C Cl
3. cation reacts with
R nucleophilic halide ion
to give the alkyl halide.
 Conversion of 1° and 2° Alcohols
into Alkyl Halides
• The reactions of primary and secondary
alcohols with SOCl2 and PBr3 take place by
SN2 mechanism. –OH ion is a poor leaving
group, but the reaction of alcohol with SOCl2
or PBr3 converts the –OH into a much better
leaving group, either a chlorosulfite (-OSOCl)
or a dibromophosphite (-OPBr2), that is
readily expelled by backside nucleophilic
substitution.
 Cl- O
SN2 Cl C + SO2 + Cl-
SOCl2 C O S Cl
ether H H
a chlorosulfite

C OH
H Br-
PBr3
SN2 Br C + Br2PO-
ether C O PBr2
H H
a dibromophosphite
 Conversion of Alcohols into Esters
• In laboratory, the reaction can be carried out if a
strong acid is used as catalyst. However, the reaction
take place by converting the carboxylic acid to acyl
chloride and followed by reaction with the alcohol.

O
O
C
C CH3OH OCH3 + H2O/HCl
OH

O
C
SOCl2 Cl
 Oxidation of Primary Alcohol
• Primary alcohols can be oxidized to aldehyde or
a carboxylic acid depending on the reagent.

• 1° alcohols are oxidized to aldehydes when

react with PCC in CH2Cl2, while it can be further
oxidized to carboxylic acids when treated with
common oxidizing agents example; potassium
permanganate, KMnO4 , or potassium
dichromate, K2Cr2O7 or any strong acids.
General reaction:
O O
[O] R C H [O] R C OH
R' OH
alcohol aldehyde carboxylic acid

OH O
CrO3, H3O+
CH3 C H CH3 C OH
acetone ethanoic acid
H
ethanol
(primary)

Chromic trioxide, CrO3 and an acid in water = Jones oxidation

 Oxidation of Primary Alcohol
O
R' OH PCC R C H
alcohol CH2Cl2 aldehyde

OH O
PCC
CH3 C H CH3 C H
CH2Cl2
ethanal
H
ethanol
(primary)

PCC = Pyridinium chlorochromate

 Oxidation of Secondary Alcohol
• Secondary alcohols are oxidized to ketones.
OH O
KMnO4/H+
R' C R R' C R + H2
heat
H ketone

secondary alcohol

OH O
K2Cr2O7/H+
CH3 C CH3 CH3 C CH3 + H2
heat
H propanone
2-propanol
 Oxidation of Tertiary Alcohol
• 3° alcohols do not have a hydrogen on the -OH
carbon, hence it cannot react with oxidizing
agents.

OH
CH3 C K2Cr 2O 7/H+
CH3 NO reaction
heat
CH3
2-methyl-2-propanol
 Ethers
• Ethers (R-O-R) are organic derivatives of water
but have two organic groups bonded to the
same oxygen atom.
OCH3
H3CH2C O CH2CH3
diethyl ether anisole
used as an anesthetic and solvent a pleasant-smelling aromatic ether
used in perfumery
O

tetrahydrofuran (THF)
used as a solvent
 Naming Ethers
• Simple ethers with no other functional
groups are name by identifying the two
organic substituents and adding the word
ether.

O O
isopropyl methyl ether ethyl phenyl ether
 • If other functional groups are present, the
ether part is considered an alkoxy
substituents.

O O
1,4-dimethoxybenzene 4-tert-butoxy-1-cyclohexene
 Alkoxymercuration of Alkenes to
Produce Ether
• Alkene reacts with an alcohol in the presence of
mercuric trifluoroacetate, (CF3CO2)2Hg
(alkoxymercuration) followed by reaction with
NaBH4 (demercuration) to produce an ether. This
reaction obeys the Markovnikov’s rule.
H H OCH3
H HgO2CCF3 OCH3
C C H C C H H
H C C
H H
(CF3CO2)2Hg NaBH4 H
styrene CH3OH
1-methoxy-1-phenylethane
 The Williamson Ether Synthesis
• Ether can be prepared by the Williamson ether
synthesis. The process take place by SN2 reaction.
The alkoxide ion is prepared from the reaction of
an alcohol with a strong base such as sodium
hydride, NaH and then reacts with a primary alkyl
halide.
H
OH O- Na+ + H C I O
CH3
NaH H
THF
• The free alcohol reacts directly with alkyl
halide to produce ether if silver oxide, Ag2O
is used as a mild base rather than sodium
hydride, NaH.

H3COH2C
HOH2C CH3Cl O
O Ag2O H3CO
HO OCH3
OH H3CO
HO
OH OCH3
Methyl tetra-O-methyl-
ß-D-glucose
ß-D-glucose + HCl
 Reactions of Ethers: Acidic Cleavage
• Ethers are cleaved by strong acids, HBr and HI.
They are unreactive to HCl.

O O
CH3 HBr/H2O H
reflux + CH3Br
anisole phenol
 Classification of Ether
• The terms "primary ether", "secondary ether",
and "tertiary ether" are occasionally used and
refer to the carbon atom next to the ether
oxygen. In a primary ether this carbon is
connected to only one other carbon as in
diethyl ether CH3-CH2-O-CH2-CH3. 

O
diethyl ether O O
diisopropyl ether ditert-butyl ether
• Ethers with only primary and secondary alkyl
groups reacts by SN2 mechanism. I- or Br- attacks at
the protonated ether at the less hindered site. This
results in a cleavage into a single alcohol and a
single alkyl halide.

less hindered
H I CH3 H
CH3 CH3
CH3CH O CH2CH3 SN2
CH3CH O CH2CH3 CH3CH OH
2-ethoxypropane
I
more hindered + I CH2CH3
 Carbocation Stability and the Transition
State

• Tertiary alcohols react the fastest because

they have the most stable tertiary
carbocation-like transition state in the second
step
• Ether with tertiary group cleave by SN1 or E1
mechanism because they can produce stable
intermediate carbocations.

O CH3 OH H3C
C CF3COOH C CH2
+
H3C CH3 H3C
tert-butoxycyclohexane cyclohexanol 2-methylprop-1-ene

CF3COOH = Trifluroacetic acid

 Cyclic Ethers: Epoxides
• Epoxides are prepared by treatment of an alkene
with a peroxyacid (RCO3H), normally used is
m-chloroperoxybenzoic acid (mCPBA).
H
O H
O
Cl C O
O CH2Cl2
+ solvent H
1,2-epoxy cyclohexane

3-chloroperoxybenzoic acid O
mCPBA
Cl C H
O

3-chlorobenzoic acid
• Synthesis of epoxides through the use of
halohydrins is prepared by electrophilic addition
of HO-X to alkenes. When halohydrins are treated
with base, HX is eliminated and an epoxide is
produced by intramolecular Williamson ether
synthesis.
H H
H OH O
Cl2/H2O NaOH

H H H2O
H
Cl Cl
trans-2-chloro
cyclohexanol
H
O
H
1,2-epoxy cyclohexane
 Acid-Catalyzed Epoxide Opening
• Epoxides cleavage take place by SN2 by treatment
with dilute aqueous acid at room temperature to
produce 1,2-diols, also called vicinal glycols.
H H
H
OH
O H3O +
O H
H2O
H H
1,2-epoxy
H H O O
2
cyclohexane H H

H
OH
H3O+ +
H
OH
trans-cyclohexane-
1,2-diol
• Epoxides can also be opened by reaction with
anhydrous HX. The trans- halohydrin is the
product of the conversion.

H
H OH
HX
O
H
H X
 Naming Phenols

O2N NO2
OH

benzyl alcohol OH
(phenylmethanol) 2,4-dinitrophenol
 Oxidation of Phenols
• Phenol can be synthesized from cumene
(isopropylbenzene) when reacts with air at high
temperature. This reaction occurs by benzylic
oxidation through a radical mechanism to form
cumene hydroperoxide which is converted into
phenol and acetone by treatment with acid.
OH
H3C CH3 H3C CH3
C C H3O+ +
O2 OOH
H
O
cumene cumene C
(isopropyl benzene) hydroperoxide
H3C CH3
Electrophilic Aromatic Substitution of Phenols
• Phenols are highly reactive substrates for
electrophilic halogenation, nitration, sulfonation
and Friedel-Crafts reactions.

ortho-para director
OH
OH OH
E
E+ +

E
Applications
of alcohol