ORGANIC CHEMISTRY

CHM 207

Chapter 6
Hydroxyl Compounds
(Alcohol and Phenol)
 Content
Nomenclature

Classification,
physical
Uses properties and
Hydroxyl acidity
componds

Reaction of Reaction of
alcohol phenol

- Reaction with sodium - Reactions of phenols:

- Oxidation - Reaction with sodium
- Esterification - Esterification
- Halogenation and haloform reactions - Halogenation of the ring
- Dehydration (to form alkenes) - Nitration of the ring
- Formation of ether
(Williamson ether synthesis)
 HYDROXYL COMPOUNDS

 Hydroxyl compounds contain the hydroxyl

group, (-OH) as the functional groups.

 2 types of hydroxyl compounds:

- Aliphatic alcohol

- Aromatic alcohol (phenol)

R OH OH

-OH attached to alkyl -OH attached to aromatic

group, R. (benzene) ring.
 CLASSIFICATION OF ALCOHOLS
 1o, 2o and 3o

 Primary alcohol (1o)

- 1 alkyl group attached to carbon containing OH (eg:
ethanol)
 Secondary alcohol (2o)
- 2 alkyl group attached to carbon containing OH (eg: 2-
butanol)
 Tertiary alcohol (3o)
- 3 alkyl group attached to carbon containing OH (eg: 2-
methyl-2-propanol)
 TYPE STRUCTURE EXAMPLES

H CH3
i) Primary (1°)
R C OH CH3CH2-OH CH3CHCH2 OH
H ethanol 2-methyl-1-propanol

ii) Secondary (2°)

R' OH
OH
R C OH H3C CH CH2CH3
H
2-butanol cyclohexanol
iii) Tertiary (3°)
CH3
R'
R C OH H3C C OH
R'' CH3
2-methyl-2-propanol
 NOMENCLATURE OF ALCOHOL
(a) Aliphatic alcohol
IUPAC system is widely used through the following rule.

1. Select the longest carbon chain with OH group

attached to it.
2. Number the carbon atoms in this chain so that the one
bonded to the –OH group has the lowest possible
number.
3. Give the parent alcohol name by replacing the final –e
of the corresponding alkane name by –ol.
4. Name each alkyl branch chain (or other group) and
designate its position by number.
Examples:
OH CH3 OH OH

CH3CHCH2CH3 CH3CCH2CHCH3 CH3CH2CHCH2CH3

CH3 3-pentanol
2-methylbutanol
4,4-dimethylpentanol

OH

cyclopentanol
 When there are two or more –OH groups present,
the name ends with diol, triol and so on.

OH OH OH

CH3CHCH2CHCH3 CH3CCH2OH

2,4-pentanediol OH

1,2,2-propanetriol
5 OH
OH
4 1
3 2 1
CH3 CH CH2 OH 3 2 OH
IUPAC name propane-1,2-diol trans-cyclopentane-1,2-diol
 NOMENCLATURE OF ALCOHOL
(b) Aromatic alcohol (phenol)
In most cases, the name phenol is used as the parent’s
name.

OH HO

NO2

H3C 4-methylphenol 3-nitrophenol

 NOMENCLATURE OF PHENOL

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

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

OH
OH O 2N OH
CH3CH2
Br
IUPAC name: 2-bromophenol 3-nitrophenol 4-ethylphenol

common name: ortho-bromophenol meta-nitrophenol para-ethylphenol

 Phenols may be monohydric, dihydric or
trihydric according to the number of hydroxyl
groups present in the benzene ring.

OH
OH OH
OH

OH OH
OH
benzene-1,3-diol benzene-1,4-diol benzene-1,2,3-triol
 NOMENCLATURE OF CYCLIC
ALCOHOLS

Using the prefix cyclo-

The hydroxyl group is assumed to be on C1.

H
OH
5
6 1 HO CH2CH3
43 2 1
3 2
H
Br
IUPAC name: trans-2-bromocyclohexanol 1-ethylcyclopropanol

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

 NOMENCLATURE OF ALCOHOLS
CONTAINING TWO DIFFERENT
FUNCTIONAL GROUPS
 Alcohol containing double and triple bonds:
- use the –ol suffix after the alkene or alkyne name.
 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.
 EXAMPLE
5 4 3 2 1
CH2 CH CH2 CH CH3

OH

1) Longest carbon chain that contains –OH group

- 5 carbon

2) Position of –OH group

- Carbon-2

3) Position of C=C
- Carbon-4

COMPLETE NAME = 4-penten-2-ol

Some consideration:

- 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.

- Examples:

OH O OH
4 3 2
4 3 2 1 5 1
CH3 CH CH2 C OH 6
O
3-hydroxybutanoic acid 2-hydroxycyclohexanone
 MAIN GROUPS

Acids
Esters
Aldehydes
Ketones
decreasing Alcohols
priority Amines
Alkenes
Alkynes
Alkanes
Ethers
Halides
 PHYSICAL PROPERTIES
PHYSICAL STATES OF ALCOHOLS

Number of carbons Physical form

Simple alcohol, C < 12 Liquid, coluorless
C > 12 Solids
Phenol Colourless liquid or low melting point solid
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: 78°C -42°C -24°C

- Reason:
intermolecular hydrogen bonds exist between the –OH
groups in the alcohol molecules.
R Ar δ- δ+
δ- δ+ R O H Ar
O H
O O
H δ-
hydrogen bonding H hydrogen bonding
δ-

- 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. Higher alcohols are
insoluble in water.
- 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.
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.
ACIDITY OF ALCOHOLS AND PHENOLS
a) Acidity of alcohol
 Alcohol is weakly acidic.
 In aqueous solution, alcohol will donated its proton to
water molecule to give an alkoxide ion (R-O-).
R-OH + H2O R-O- + H3O+ Ka = ~ 10-16 to 10-18
Alkoxide ion
Example
CH3CH2-OH + H2O CH3CH2-O- + H3O+

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

equilibrium
Ka
R-OH + H2O R-O- + H3O+ * More smaller the pKa
value, the alcohol is
Ka = [H3O+] [RO-] pKa = - log (Ka) more acidic
[ROH]
b) Acidity of phenol

Phenol is a stronger acid than alcohols and water.

R-OH + H2O R-O- + H3O+ Ka = ~ 10-16 to 10-18

alcohol alkoxide ion

OH H2O O
-
H3O+ Ka = 1.2 x 10-10
phenol phenoxide ion

H2 O + H2 O HO- + H3O+ Ka = 1.8 x 10-16

hydroxide ion
 Phenol is more acidic than alcohols by considering
the resonance effect.

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.
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+.

O O O O
 EFFECTS OF ACIDITY
 The acidity decreases as the substitution on the alkyl group increase.

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

the alkoxide ion.
- For example: methanol is more acidic than t-butyl alcohol.

 The present of electron-withdrawing atoms enhances the acidity of

alcohols.
- Reason: the electron withdrawing atom helps to stabilize the
alkoxide ion.
- Eg: 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.
 REACTIONS OF ALCOHOLS

i. Reaction with sodium

ii. Oxidation
iii. Esterification
iv. Halogenation and haloform reactions
v. Dehydration
vi. Formation of ether (Williamson ether
synthesis)
 i) Reaction with sodium
Alcohols reacts with Na at room temperature to
form salts (sodium alkoxides) and hydrogen.

2R-OH + 2Na → 2R-O- Na+ + H2

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

Reactivity of alcohols towards the reactions with

sodium:
CH3 > 1° > 2° > 3°
 ii) Oxidation
H
1° alcohol Pyridinium chlorochromate (PCC) H
R C OH
CH2Cl2, 25oC R-C=O
H
1o alcohol aldehyde

H
Cu or Cr3O/pyridine H
R C OH
R-C=O
H
1o alcohol aldehyde
Cr3O/pyridine = Collins reagent

H
KMnO4/H+ or K2Cr2O7/H+ O
R C OH
or CrO3/H+ R-C-OH
H
1o alcohol carboxylic acid
Examples:

1° alcohol
O
PCC
CH3(CH2)4-CH2-OH CH3(CH2)4-C-H
1-hexanol hexanal

O
KMnO4/H+ or K2Cr2O7/H+
CH3(CH2)4-CH2-OH CH3(CH2)4-C-OH
or CrO3/H+
1-hexanol hexanoic acid
 H
+ +
KMnO4/H or K2Cr2O7/H O
2° alcohol R C OH
or CrO3/H+ R-C-R'
R'
ketone
2o alcohol

R"
3° alcohol + +
KMnO4/H or K2Cr2O7/H
R C OH no reaction
+
or CrO3/H
R'
3o alcohol

Example:
OH O
+ +
KMnO4/H or K2Cr2O7/H
CH3 CH CH2CH3 CH3 C CH2CH3
+
or CrO3/H
2-butanol 2-butanone
 iii) Esterification
Esterification:
- the reaction between an alcohol and a carboxylic acid to
form an ester and H2O.
O O
H+
R C O H H O R' R C O R' H2O
carboxylic acid alcohol ester

EXAMPLES
O H+ O
CH3CH2-O-H CH3 C O H CH3 C OCH2CH3 H2O
ethanol ethanoic acid ethyl ethanoate
O O
H+
CH3-O-H C OH C OCH3 H2O
methanol benzoic acid methyl benzoate
H+ = catalyst
 Esterification also occurs when alcohols
react with derivatives of carboxylic acids
such as acid chlorides

O O
CH3-O-H CH3 C Cl CH3 C OCH3 HCl
methanol ethanoyl chloride methyl ethanoate
 iv) Halogenation and haloform reactions

1) Hydrogen halides (HBr or HCl or HI)

R-OH + H-X → R-X + H2O

Example:
C2H5-OH + H-Br H+C H -Br + H O
2 5 2

 Reactivity of hydrogen halides decreases in order HI >

HBr > HCl
 Reactivity of alcohols with hydrogen halides:
3° > 2° > 1°
2) Phosphorus trihalides, PX3

3R-OH + PX3 3R-X + H3PO3

(PX3 = PCl3 or PBr3 or PI3)

Example:
(CH3)2CHCH2-OH + PBr3 → (CH3)2CHCH2-Br
isobutyl alcohol isobutyl bromide

3) Phosphorus pentahalides (PX5)

RT

R-OH + PX5 → R-Cl + POCl3 + HCl

phosphorus trichloride oxide
(phosphorus oxychloride)
Example:

CH3CH2-OH + PCl5 → CH3CH2-Cl + POCl3 + HCl

ethanol chloroethane (white fumes of HCl)
4) Thionyl chloride (SOCl2)

R-OH + SOCl2 → R-Cl + SO2 + HCl

Example:

CH3(CH2)5CH2-OH + SOCl2 → CH3(CH2)5CH2-Cl + SO2 + HCl

1-heptanol 1-chloroheptane
 v) Dehydration
Dehydration of alcohols will formed alkenes and the
products will followed Saytzeff rules.
conc. H2SO4
R-CH2-CH2-OH 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=CH2 + H 2O
CH3CH2-CH-CH3 1-butene
OH H+
CH3CH=CH-CH3 + H 2O
2-butanol
2-butene
major product
Reactivity of alcohols towards dehydration:
3° > 2° > 1°
Reagents for dehydration:
i) Concentrated H2SO4
conc. H2SO4
CH3-CH2-OH CH2=CH2 + H2O

ii) With phosphoric (v) acid

OH
85% H3PO4, 165-170oC H2O

iii) Vapour phase dehydration of alcohols

Al2O3
CH3CH2OH CH2=CH2 + H2O
heat
 vi) Formation of ether (Williamson ether
synthesis)
 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.

R-O- + R’-X → R-O-R’ + X-

alkoxide
(R’ must be primary)

 The alkyl halides (or tosylate) 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.
EXAMPLES
+
CH3CH2-OH Na CH3CH2-O Na CH3I

CH3CH2-O-CH3 NaI
or

1) Na
CH3CH2-OH CH3CH2-O-CH3 NaI
2) CH3I

OH OCH2CH3
1) Na
2) CH3CH2-OTs
cyclohexanol ethoxycyclohexane
REACTIONS OF PHENOLS

i. Reaction with sodium

ii. Esterification
iii. Halogenation of the ring
iv. Nitration of the ring
 i) Reaction with sodium

-
OH Na O Na+ 1/2 H2(g)
sodium phenoxide

REACTION WITH AQUEOUS SODIUM HYDROXIDE

-
OH NaOH O Na+ H2O
sodium phenoxide

ROH + NaOH no reaction

 ii) Esterification

EXAMPLES
O
O
NaOH CH3CCl
OH ONa OCCH3 NaCl
H2O NaOH
sodium phenoxide

O O
OH C OH H+ OC H2O

phenyl benzoate
 iii) Halogenation
ortho-para director.

1) Halogenation of phenol:
 If liquid bromine or bromine water is added to an aqueous solution of phenol
at room temperature, decolorisation occurs and a white precipitate of 2,4,6-
tribromophenol is formed (bromination).
 No catalyst (halogen carrier) is needed.
 This reaction is used to test the presence of phenol and determine the mass
of phenol in an aqueous solution.

OH OH
X X
room
3X2 (aq) 3HX
temperature
X
EXAMPLE

OH OH
Br Br
3Br2(aq) room
3HBr
temperature
Br
2,4,6-tribromophenol (white precipitate)
 Phenol reacts similarly with chlorine or chlorine water to form
white precipitate of 2,4,6-trichlorophenol.
 This reaction is called chlorination of phenol.

OH OH
Cl Cl
room
3Cl2 3HCl
temperature
Cl
2,4,6-trichlorophenol (white precipitate)

 Monobromophenols are obtained if the bromine is dissolved in

a non-polar solvent such as CCl4.
OH OH OH
Br
2 2Br2 (CCl4) 2HBr

Br
 iv) Nitration

Dilute nitric (v) acids reacts with phenol at room

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

OH
OH OH
2 < 20oC NO2
2HNO3 2H2O

NO2
2-nitrophenol 4-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 OH
O 2N NO2
3HNO3 3H2O

NO2
2,4,6-trinitrophenol
(picric acid)
 CHEMICAL TESTS FOR PHENOLS
Aqueous FeCl3 and aq. Br are used to test phenols.

i) Complex formation with iron (III) chloride

- when two or three drops of iron (III) chloride solution is
added to a very dilute solution of phenol, a violet-blue
coloration is produced.
- methylphenol (toluene) produce a blue colour.

OH O
6 FeCl3 (neutral) H3[Fe3+ ( )6] 3HCl
phenoxide ligand violet complex
 Phenol Colour of Phenol Colour of
compound complex with compound complex with
FeCl3 (aq) FeCl3 (aq)

OH Violet OH Green
OH

OH Violet OH O Red
CH3 R

OH Blue OH O Violet
OCH3

CH3
Violet
OH
COOH
ii) Bromine water
- when bromine water is added gradually to a concentrated
solution of phenol, the bromine water is decolorised.
- when excess bromine water is added, a white precipitate
of 2,4,6-tribromophenol is obtained.
 TESTS TO DISTINGUISH CLASSES OF
ALCOHOLS

1) Lucas Test
- The alcohol is shaken with Lucas reagent (a solution
of ZnCl2 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.
 CH3 CH3
CH3 C CH3 HCl/ZnCl2
CH3 C CH3
room temperature
OH Cl
o
3 alcohol (cloudy solution almost immediately)

CH3 CH CH2CH3 HCl/ZnCl2

CH3 CH CH2CH3
room temperature
OH Cl
o
2 alcohol (cloudy solution within 5 minutes)

CH3CH2CH2CH2OH HCl/ZnCl2
no reaction
room temperature
1o alcohol
2) Oxidation of alcohols

- 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 colour of KMnO4 solution disappears.
→ the colour of the K2Cr2O7 solution changes from
orange to green.
- 3o alcohol do not react with KMnO4 or K2Cr2O7.
3RCH2OH + Cr2O2-7 + 8H+ 3RCHO + 2Cr
3+
+ 7H2O
1o alcohol (orange) aldehyde (green)

3RCHO + Cr2O2-7 + 8H+ 3RCOOH + 2Cr3+ + 7H2O

aldehyde (orange) carboxylic acid (green)

R' R'
3+
3 R CH OH + Cr2O2-7 + 8H+ 3R C O + 2Cr + 7H2O
o
2 alcohol (orange) ketone (green)
 HALOFORM TEST TO IDENTIFY METHYL
ALCOHOL GROUP

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.

H
CH3 C (methyl alcohol group)

OH
 H
CH3 C R + 4I2 + 6NaOH CHI3 (s) + RCOONa + 5NaI + 5H2O
triiodomethane
OH (iodoform)
yellow precipitate

where R = hydrogen, alkyl or aryl group

• The iodoform test can distinguish ethanol from methanol

H O
-
CH3 C H + 4I2 + 6OH CHI3 (s) + 5I + 5H2O H C O
OH iodoform methanoate

ethanol positive iodoform test

H C H + 4I2 + 6OH no reaction

OH
methanol negative iodoform test
• The iodoform test can distinguish 2-propanol from 1-propanol

CH3 O
-
CH3 C H + 4I2 + 6OH CHI3 (s) + 5I + 5H2O CH3 C O
iodoform ethanoate
OH
2-propanol
positive iodoform test

H H H

H C C C H + 4I2 + 6OH no reaction

H H OH negative iodoform test

1-propanol

* TERTIARY ALCOHOLS DO NOT GIVE POSITIVE IODOFORM

TEST
 2) Bromoform:
H

CH3 C R + 4Br2 + 6NaOH CHBr3 (s) + RCOONa + 5NaBr + 5H2O

bromoform
OH

where R = hydrogen, alkyl or aryl group

sample reagent

bromoform
 USES OF ALCOHOLS
As solvents:
- eg: 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’.