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CHAPTER 6:
1.
2.
3.

HYDROXYL COMPOUNDS
(ALCOHOLS AND PHENOL)

4.
5.

6.

* Reactions of phenols:
- Reaction with sodium
- Esterification
- Halogenation of the ring
- Nitration of the ring
7. Tests to distinguish classes of alcohols:
i) Lucas test
ii) Oxidation

Nomenclature of alcohols, phenols.

Classification of alcohols.
Physical properties of alcohols:
- Physical state
- Boiling points
- Solubility of alcohols in water
Acidity of alcohols and phenols
Preparation of alcohol:
-hydration of alkene
-Reduction of COOH
-Hydrolysis of ester
-Grgnard reagent with aldehyde/ketone
Reactions of alcohols:
- Reaction with sodium
- Oxidation
- Esterification
- Halogenation and haloform reactions
- Dehydration
- Formation of ether (Williamson ether synthesis)

Alcohols: Organic compounds containing hydroxyl (-OH)

functional groups.
R

8. Haloform test to identify methyl alcohol group

- Iodoform
- Bromoform

OH

Phenols: Compounds with hydroxyl group bonded directly to

an aromatic (benzene) ring.

OH
9. Uses of alcohols and phenols.

1.

2.

3.

4.

Organic chemistry

Select the longest continuous chain of carbon atoms

containing the hydroxyl group.
Number the carbon atoms in this chain so that the one
bonded to the OH group has the lowest possible number.
Form the parent alcohol name by replacing the final e of
the corresponding alkane name by ol. When isomers are
possible, locate the position of the OH by placing the
number (hyphenated) of the carbon atom to which the
OH is bonded immediately before the parent alcohol name.
Name each alkyl branch chain (or other group) and
designate its position by number.

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This is the longest continuous chain that contains an

hydroxyl group.

4
3

Select this chain as the parent compound.

This end of the chain is closest to the

OH. Begin numbering here.

Using the prefix cycloThe hydroxyl group is assumed to be on C1.

OH

6 1
5
43 2

3-methyl-2-butanol

NOMENCLATURE OF ALCOHOLS
CONTAINING TWO DIFFERENT
FUNCTIONAL GROUPS

Alcohol containing double and triple bonds:

- use the ol suffix after the alkene or alkyne name. Ex Penten-2-ol

The alcohol functional group takes precedence over double and triple
bonds, so the chain is numbered in order to give the lowest possible
number to the carbon atom bonded to the hydroxyl group.

The position of the OH group is given by putting its number before

the ol suffix.

Numbers for the multiple bonds were once given early in the name.

Organic chemistry

Br
IUPAC name:

HO CH2CH3

trans-2-bromocyclohexanol

new IUPAC name: trans-2-bromocyclohexan-1-ol

1-ethylcyclopropanol
1-ethylcyclopropan-1-ol

NOMENCLATURE OF ALCOHOLS CONTAINING

TWO DIFFERENT FUNCTIONAL GROUPS
MAIN GROUPS

decreasing priority

Acids
Esters
Aldehydes
Ketones
Alcohols
Amines
Alkenes
Alkynes
Alkanes
Ethers
Halides

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NOMENCLATURE OF ALCOHOLS CONTAINING TWO

DIFFERENT FUNCTIONAL GROUPS

NOMENCLATURE OF ALCOHOLS CONTAINING TWO

DIFFERENT FUNCTIONAL GROUPS

Some consideration:

CH2 CH

CH2

CH

CH3
- OH functional group is named as a hydroxy substituent
when it appears on a structure with a higher priority
functional group such as acids, esters, aldehydes and ketones.

OH
1) Longest carbon chain that contains OH group
- 5 carbon

- Examples:

2) Position of OH group
- Carbon-2

OH
4

CH3

3) Position of C=C
- Carbon-4

CH

O
2

CH2

OH

3-hydroxybutanoic acid

4 3 2
5 1
6

OH

O
2-hydroxycyclohexanone

COMPLETE NAME = 4-penten-2-ol

Alcohols with two OH groups are called diols or glycols.

Naming of diols is like other alcohols except that the suffix

diol is used and two numbers are needed to tell where the two
hydroxyl groups are located.

The terms ortho (1,2-disubstituted), meta (1,3-disubstituted)

and para (1,4-disubstituted) are often used in the common
names.
OH

O2N

CH3CH2

Br
5

OH
3

CH3

IUPAC name

CH

CH2

OH

propane-1,2-diol

IUPAC name:

OH

common name: ortho-bromophenol

2-bromophenol

3-nitrophenol

4-ethylphenol

OH

OH

OH

3 2

meta-nitrophenol

para-ethylphenol

trans-cyclopentane-1,2-diol

CLASSIFICATION OF ALCOHOL

Phenols may be monohydric, dihydric or trihydric

according to the number of hydroxyl groups present in the
benzene ring.
OH

OH

OH
OH

OH
benzene-1,3-diol

Organic chemistry

OH
benzene-1,4-diol

OH
benzene-1,2,3-triol

According to the type of carbinol carbon atom (C bonded

to the OH group).
C

OH

Classes:
i) Primary alcohol
- -OH group attached to a primary carbon atom
ii) Secondary alcohol
- -OH group attached to a secondary carbon atom
iii) Tertiary alcohol
- -OH group attached to a tertiary carbon atom

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TYPE
Primary (1)

i)

Secondary (2)

ii)

iii)

Tertiary (3)

STRUCTURE
H
R C
H

EXAMPLES
CH3

OH

R'
R C OH
H

CH3CH2-OH

CH3CHCH2 OH

ethanol

2-methyl-1-propanol

OH

OH

H3C CH CH2CH3
2-butanol

R'
R C OH
R''

cyclohexanol

CH3
H3C C OH
CH3
2-methyl-2-propanol

PHYSICAL STATES OF ALCOHOLS

- simple aliphatic alcohols and lower aromatic alcohols (such as
phenylmethanol, C6H5CH2OH) liquids at room
temperature.
- highly branched alcohols and alcohols with twelve or more
carbon atoms solids.

BOILING POINTS

- The boiling points of alcohols are higher than those of alkanes and chloroalkanes of similar
relative molecular mass.
- For example:
C2H5OH
CH3CH2CH3
CH3Cl
Relative molecular mass:
46
44
50.5
Boiling point:
78C
-42C
-24C
- Reason:
intermolecular hydrogen bonds exist between the OH groups in the alcohol molecules.

OH hydrogen bonding

Ar

R
H

Ohydrogen bonding

Ar

- Branched chain alcohols boils at a lower

temperature (more volatile) than the straight chain
alcohols with the same number of carbon atoms.

SOLUBILITY OF ALCOHOLS IN WATER

i) alcohols with short carbon chains (such as methanol, ethanol, and
propanol) dissolve in water.
- when alcohols dissolve in water, hydrogen bonds are formed
between the OH group of the alcohol molecule and the OH group
of the water molecule.
ii) the solubility of alcohols in water decreases sharply with the
increasing length of the carbon chain.
- alcohol contains a polar end (-OH group) called hydrophilic and a
non-polar end (the alkyl group) called hydrophobic.
- the water solubility decreases as the alkyl group becomes larger.

Organic chemistry

iii) alcohols with more than one hydroxyl group (polyhydroxy

alcohols) are more soluble than monohydroxy alcohols with the
same number of carbon atoms. This is because they can form more
hydrogen bonds with water molecule.
iv) branched hydrocarbon increases the solubility of alcohol in water.
- reason: branched hydrocarbon cause the hydrophobic region
becomes compact.
* Phenol is unusually soluble (9.3%) because of its compact shape
and the particularly strong hydrogen bonds formed between
phenolic OH groups and water molecules.

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1. Alcohol is weakly acidic.

In aqueous solution, alcohol will donated its proton to water
molecule to give an alkoxide ion (R-O-).
R-O- + H3O+

R-OH + H2O

Ka = ~ 10-16 to 10-18

2. Phenol is a stronger acid than alcohols and water.

R-O- + H3O+

R-OH + H2O
alcohol

Ka = ~ 10-16 to 10-18

alkoxide ion

alkoxide ion

Example
CH3CH2-OH + H2O

OH

CH3CH2-O- + H3O+

The acid-dissociation constant, Ka, of an alcohol is defined by the

equilibrium
R-OH + H2O

Ka

Ka = [H3O+] [RO-]

R-O- + H3O+
pKa = - log (Ka)

i) The alkoxide ion (RO-)

- the negative charge is confined to the oxygen and is not
spread over the alkyl group.
- this makes the RO- ion less stable and more susceptible to
attack by positive ions such as H+ ions.

HO- + H3O+

Ka = 1.8 x 10-16

ii) The phenoxide ion

- one of the lone pairs of electrons on the oxygen atom is delocalised into the
benzene ring.
- the phenoxide ion is more stable than the alkoxide ion because the negative
charge is not confined to the oxygen atom but delocalised into the benzene
ring.
- the phenoxide ion is resonance stabilised by the benzene ring and this
decreases the tendency for the phenoxide ion to react with H3O+.

The acidity decreases as the substitution on the alkyl group increase.

- Reason: a more highly substituted alkyl group inhibits solvation of the

alkoxide ion and drives the dissociation equilibrium to the left.
- For example: methanol is more acidic than t-butyl alcohol.

Ka = 1.2 x 10-10

The ionisation of an alcohol and phenol takes place as

follows:
Due to stability of phenoxide ion PHENO IS MORE
ACIDIC IN alcohol due to oxygen atom polarity of O-H
bond is decreases, this decrease in acid strength.

H3O

hydroxide ion

* smaller the pKa value,

the alcohol is more
acidic

Phenol is more acidic than alcohols by considering the

resonance effect.

phenoxide ion

H2O + H2O

[ROH]

H2O

phenol

The present of electron-withdrawing atoms enhances the acidity of alcohols.

- Reason: the electron withdrawing atom helps to stabilize the alkoxide ion.
- For example: 2-chloroethanol is more acidic than ethanol because the
electron-withdrawing chlorine atom helps to stabilize the 2-chloroethoxide
ion.
- alcohol with more than one electron withdrawing atoms are more acidic. For
example, 2,2,-dichloroethanol is more acidic than 2-chloroethanol.
- Example of electron-withdrawing atom/groups:
Halogen atoms and NO2.

Organic chemistry

Hydration of ALKENE
Reduction of COOH
Hydrolysis of esters
Grignard reaction with ALDEHYDE and KETONE

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Markovnikov addition
Water is added to yield alcohol
Catalyst : an acidic catalyst (H3PO4) with 300C and pressure 60-70
atm
Formation of most stable carbocation
Shifts/rearrangements possible

H 2O
R' H
R

R''

R'

C OH

LiAlH

LiAlH

RCH 2OH + OH

OH H

H 2O

A strong reducing agent : Lithium Aluminum Hydride

C OR'

RCH 2OH + R'OH

O
R''

OH H

Formation of primary, secondary, and tertiary alcohols

REVERSE of esterification
Broken down by reaction with water

H C H

RMgX

RCH 2OH

Primary ROH

O
H

Ethyl Ethanoate

Water

R' C H

Ethanoic Acid

RMgX

R' C R

Secondary ROH

OH
R"

R' C R"

Ethanol

Reaction with sodium

Oxidation
Esterification
Halogenation and haloform reactions
Dehydration

RMgX

R' C R

Tertiary ROH

OH

Alcohols reacts with Na at room temperature to form salts (sodium

alkoxides) and hydrogen.

2R-O-H + 2Na 2R-O- Na+ + H2

For example:
CH3CH2OH + Na CH3CH2O-Na+ + 1/2H2
alcohol
sodium ethoxide

Organic chemistry

Reactivity of alcohols towards the reactions with sodium:

CH3 > 1 > 2 > 3

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Examples:
1 alcohol

O
PCC

CH3(CH2)4-CH2-OH

CH3(CH2)4-C-H

1-hexanol

hexanal

1 alcohol

OH

Pyridinium chlorochromate (PCC)

CH2Cl2, 25oC

R-C=O

H
1o alcohol

2 alcohol

Cu or Cr3O/pyridine

OH

H
R

R-C=O

O
C

H+

H O

carboxylic acid

ethanol

alcohol

EXAMPLES

CH3CH2-O-H

R'

ethanoic acid

O
CH3-O-H

C OH

methanol

R'

CH3

OCH2CH3

no reaction

or CrO3/H

Esterification also occurs when alcohols

react with derivatives of carboxylic acids
such as acid chlorides

H2O

H+

KMnO4/H or K2Cr2O7/H

3o alcohol

ester

O
CH3

C OH
R'

carboxylic acid

Esterification:
- the reaction between an alcohol and a carboxylic acid to form an
ester and H2O.
R

ketone

R"
R

R-C-OH

O
R-C-R'

or CrO3/H+

1 alcohol

or CrO3/H+

KMnO4/H+ or K2Cr2O7/H+

KMnO4/H or K2Cr2O7/H

2o alcohol

3 alcohol

H
OH

C OH
R'

aldehyde

1 alcohol
Cr3O/pyridine = Collins reagent

hexanoic acid

or CrO3/H

1-hexanol

O
CH3(CH2)4-C-OH

aldehyde

H
R

KMnO4/H or K2Cr2O7/H

CH3(CH2)4-CH2-OH

CH3-O-H

CH3 C Cl

CH3 C OCH3

methanol

ethanoyl chloride

methyl ethanoate

HCl

H2O

ethyl ethanoate
H+

benzoic acid

O
C OCH3

H2O

methyl benzoate

H+ = catalyst

2) Phosphorus trihalides, PX3

3R-OH + PX3
3R-X + H3PO3
(PX3 = PCl3 or PBr3 or PI3)
1) Hydrogen halides (HBr or HCl or HI)
R-OH + H-X R-X + H2O
H+
Example:
C2H5-OH + H-Br

C2H5-Br + H2O

of hydrogen halides decreases in order HI > HBr > HCl

Reactivity of alcohols with hydrogen halides:
3 > 2 > 1

Example:
(CH3)2CHCH2-OH + PBr3 (CH3)2CHCH2-Br
isobutyl alcohol
isobutyl bromide
3) Thionyl chloride (SOCl2)

Reactivity

R-OH + SOCl2 R-Cl + SO2 + HCl

Example:
CH3(CH2)5CH2-OH + SOCl2 CH3(CH2)5CH2-Cl + SO2 + HCl
1-heptanol
1-chloroheptane

Organic chemistry

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Dehydration of alcohols will formed alkenes and the products will

followed Saytzeff rules.

R-CH2-CH2-OH

conc. H2SO4

R-CH=CH2 + H2O

Saytzeff rule:
- A reaction that produces an alkene would favour the formation
of an alkene that has the greatest number of substituents
attached to the C=C group.
H

CH3CH2-CH-CH3
OH
2-butanol

Reactivity of alcohols towards dehydration:

3 > 2 > 1
Reagents for dehydration:
i) Concentrated H2SO4

H+

H 2O

1-butene

CH3CH=CH-CH3 +

CH2=CH2 + H2O

ii) With phosphoric (v) acid

OH
85% H3PO4, 165-170oC

CH3CH2-CH=CH2 +

conc. H2SO4

CH3-CH2-OH

H2O

iii) Vapour phase dehydration of alcohols (Aluminium oxide)

H 2O

Al2O3

CH3CH2OH

2-butene
major product

CH2=CH2 + H2O

heat

EXAMPLES

Involves the SN2 attack of an alkoxide ion on an unhindered

primary alkyl halides.
The alkoxide is made by adding Na, K or NaH to the alcohol.

Na

CH3CH2-OH

CH3CH2-O Na

CH3CH2-O-CH3
R-O- + R-X R-O-R + X(alkoxide)
(R must be primary)

1) Na

CH3CH2-OH

The alkyl halides must be primary, so that a back-side

attack is not hindered.
If the alkyl halides is not primary, elimination usually
occurs to form alkenes.

OH

CH3CH2-O-CH3

2) CH3I

NaI

OCH2CH3

1) Na
2) CH3CH2-OTs

ethoxycyclohexane

CH3

Lucas Test
- The alcohol is shaken with Lucas reagent (a solution of ZnCl 2 in
concentrated HCl).
- Tertiary alcohol - Immediate cloudiness (due to the formation of
alkyl chloride).
- Secondary alcohol - Solution turns cloudy within about 5
minutes.
- Primary alcohol - No cloudiness at room temperature.

NaI

or

cyclohexanol

1)

CH3I

CH3
HCl/ZnCl2

CH3 C CH3
OH

room temperature

Cl

3 alcohol

CH3 CH CH2CH3
OH

(cloudy solution almost immediately)

HCl/ZnCl2
room temperature

CH3 CH CH2CH3
Cl

(cloudy solution within 5 minutes)

2 alcohol

CH3CH2CH2CH2OH

CH3 C CH3

HCl/ZnCl2
room temperature

no reaction

1 alcohol

Organic chemistry

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3RCH2OH
2)

aldehyde

+ 8H

27

3+

3RCHO

+ 2Cr

+ 8H

3RCOOH

(orange)

+ 2Cr

3+

+ 7H2O

(green)

carboxylic acid

R'

+ 7H2O

(green)

aldehyde

R'

3 R CH OH + Cr2O2-7 + 8H+
o

2 alcohol

3+

O + 2Cr

3R C

(orange)

ketone

+ 7H2O

(green)

HALOFORM TEST TO IDENTIFY METHYL

ALCOHOL GROUP

CH3

R + 4I2 + 6NaOH

CHI3 (s) + RCOONa + 5NaI + 5H2O

triiodomethane
(iodoform)
yellow precipitate

OH

1) Iodoform:
Ethanol and secondary alcohols containing the group methyl
alcohol group which react with alkaline solutions of iodine to
form triiodomethane (iodoform, CHI3).
Triiodomethane a pale yellow solid with a characteristic
smell.

where R = hydrogen, alkyl or aryl group

The iodoform test can distinguish ethanol from methanol

H
CH3

H + 4I2 + 6OH

CHI3 (s) + 5I + 5H2O

iodoform

OH

methanoate

H
ethanol

H
C

2-

(orange)

3RCHO + Cr2O

- only primary and secondary alcohols are oxidised by hot acidified

KMnO4 or hot acidified K2Cr2O7 solution.
- the alcohol is heated with KMnO4 or K2Cr2O7 in the presence of dilute
H2SO4.
- 1o or 2o alcohol:
the purple color of KMnO4 solution disappears.
the color of the K 2Cr2O7 solution changes from orange to green.
- 3o alcohol do not react with KMnO4 or K2Cr2O7.

CH3

+ Cr2O

1o alcohol

Oxidation of alcohols

H + 4I2 + 6OH

positive iodoform test

no reaction

OH
methanol

(methyl alcohol group)

OH
negative iodoform test

The iodoform test can distinguish 2-propanol from 1-propanol

CH3
CH3

CHI3 (s) + 5I + 5H2O

2-propanol
H

OH

CH3

O
CH3

positive iodoform test

H + 4I2 + 6OH

ethanoate

iodoform

OH

2) BROMOFORM

O
-

H + 4I2 + 6OH

R + 4Br2 + 6NaOH

CHBr3 (s) + RCOONa + 5NaBr + 5H2O

bromoform

OH
where R = hydrogen, alkyl or aryl group

no reaction

1-propanol

negative iodoform test

reagent

sample

* TERTIARY ALCOHOLS DO NOT GIVE POSITIVE

IODOFORM TEST
iodoform

Organic chemistry

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USES OF ALCOHOLS

As solvents:
- examples: the lower alcohols such as methanol, ethanol and
propanol.
- methanol is used as a solvent for varnish and paints.
As fuels:
- biofuel (fuel derived from a biological source).
- ethanol can be produced from sugars such as sucrose from
sugar cane, through fermentation and distillation. It can be
blended with petrol and used as fuel in motor vehicles.
- methylated spirit is ethanol made undrinkable by the
addition of a little methanol. It is used as a fuel in camping
stoves.

In alcoholic drinks:
- ethanol is used for making wine, beer and etc.

As intermediates:
- methanol can be oxidised to methanal (HCHO), a chemical
feedstock (starting material) for the manufacture of
thermosetting plastics such as bakelite.
- methanol is used to make methyl methacrylate which is used
in the manufacture of another plastic called perspex.

In cosmetics:
- ethanol is used as solvent for fragrances in perfumes and
after-shave lotions.
- polyhydroxyl alcohols (for example, glycerol) are used in
moisturising creams.

USES OF PHENOLS

Making plastics such as bakelite (phenol-methanal plastic).

The synthesis of cyclohexanol and hexanedioic acid to
make nylon 6,6.
Making dyes.
Making antiseptics such as 4-chloro-3,5-dimethylphenol
which is active ingredient in Dettol.

REACTIONS OF PHENOLS
OH

Reaction with sodium

Esterification
Halogenation of the ring
Nitration of the ring

Na

O Na+

1/2 H2(g)

sodium phenoxide

REACTION WITH AQUEOUS SODIUM HYDROXIDE

OH

NaOH

O Na+

H2O

sodium phenoxide

ROH + NaOH

Organic chemistry

no reaction

10

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HALOGENATION

ESTERIFICATION

More reactive towards electrophilic substitution than benzene.

ortho-para director.
OH
OH

EXAMPLES

3X2
O

OH

NaOH
H2O

ONa

X
EXAMPLES

NaCl

OCCH3

NaOH

OH

OH

sodium phenoxide

Br

O
OH

3Br2

O
H+

C OH

3HX

CH3CCl

room
temperature

3HBr
Br

H2O

OC

Br

room
temperature

2,4,6-tribromophenol (white precipitate)

OH

OH

phenyl benzoate

Cl
3Cl2

Cl

room
temperature

3HCl
Cl
2,4,6-trichlorophenol (white precipitate)

monobromophenols are obtained if the bromine is dissolved in a non-polar

solvent such as CCl4

OH
2

OH

OH
Br

2Br2 (CCl4)

2HBr
Br

NITRATION
Monobromophenols are obtained if the bromine
is dissolved in a non-polar solvent such as CCl4.
OH

OH

Dilute nitric (v) acids reacts with phenol at room temperature

to give a mixture of 2- and 4-nitrophenols.

OH
Br

2Br2 (CCl4)

OH

2HBr
2

Br

OH

OH
2HNO3

< 20oC

NO2

2H2O
NO2

2-nitrophenol

By using concentrated nitric (v) acid, the nitration of

phenol yields 2,4,6-trinitrophenol (picric acid).

Picric acid is a bright yellow crystalline solid. It is used

in the dyeing industry and in manufacture of explosives.
OH

4-nitrophenol

OH
3HNO3

O2 N

NO2

3H2O

NO2
2,4,6-trinitrophenol
(picric acid)

Organic chemistry

11