Chapter 4 Alkynes

Introduction
Containing triple bonds

General formula : CnH2n-2

nomenclature:
common names: “alkylacetylene”
IUPAC: parent chain = longest continuous carbon chain
that contains the triple bond.
add -yne

CH3CH2CCCH3 2-pentyne
“terminal” alkynes have the triple bond at the
end of the chain:

CH3
CH3CH2CCH HCCCHCH2CH3
1-butyne 3-methyl-1-pentyne
Physical properties:
 weakly or non-polar, no H-bonding
 relatively low mp/bp but higher than
alkanes and alkenes with same carbon
number
 water insoluble
 Chemical properties
Containing 1 σ bond and 2 π bonds.

Similar chemical properties with alkenes.

Reactions of alkynes:
1. addition of H2 (reduction)
2. addition of X2
3. addition of HX
4. addition of H2O, H+
5. Polymerisation
6. oxidation
1.Addition of H2
(a)Completely hydrogenation

| | Ni, 200˚C Ni, 200˚C

C  C + 2 H2 H2C=CH2 H3C-CH3

requires catalyst (Ni, Pt or Pd), 180-200˚C

(b) Partially hydrogenation
 To prevent hydrogenation of the alkene, a less reactive catalyst
must be employed. 

 Lindlar catalyst, which is a mixture of Pd, CaCO3, and lead salts

[Pd/(PbO 、 CaCO3), is the catalyst of choice in catalytic
hydrogenation of alkynes to give alkenes.
Lindlar catalyst
HC≡CH + H2 CH2=CH2
2. Addition of X2

X X X
| | |
— C C— + X2  — C = C — + X2  — C — C —
| | |
X X X

Br Br Br
CH3CCH + Br2  CH3C=CH + Br2  CH3-C-CH
Br Br Br
3. Addition of hydrogen halides:
H H X
| | |
— C C— + HX  — C = C — + HX  — C — C —
| | |
X H X
a) HX = HI, HBr, HCl
b) Markovnikov rules

Cl
CH3CCH + HCl  CH3C=CH2 + HCl  CH3CCH3
Cl Cl
With HgCl2 catalyst. Ethyne only undergoes 1 step
addition reaction.
HgCl2
HC≡CH+ HCl CH2=CHCl
4. Addition of water. Hydration.(H2SO4/HgSO4)
H2SO4/HgSO4 H2SO4/HgSO4
— C  C — + H2O CH2=CH CH3-CH
Ethyne OH rearranged O
Ethanal
H2SO4/HgSO4
H2SO4/HgSO4
CH3CH2CCH + H2O CH3CH2 C= CH2
rearranged
OH
CH3CH2 C- CH3
O
Butanone
5. Polymerisation
On heating alkynes undergo polymerization in the presence of
catalyst. The nature of products depends upon the
conditions. For example,

Fe, 500 ˚C
3 HC≡CH C6H6 /
6. Oxidation
 Complete combustion to produce CO2 and H2O
 Reactions of alkynes with oxidizing agents such as
potassium permanganate usually result in cleavage of the
triple-bond to give carboxylic acid products.
KMnO4/H+
RC≡CR'     ——>  RCO H   +   R'CO H
2 2

KMnO4 can use to test the presence of triple bond. (purple to

colourless)
 (a) Cold alkaline KMnO4
3 HC≡CH + 10 KMnO4 + 2H2O 6 CO2 + 10 KOH + 10 MnO2
Observation: purple colour solution becomes decolourises, brown
colour of MnO2 precipitate is produced.

(b) Cold acidic KMnO4

3 HC≡CH + 2 KMnO4 + 3H2 SO4 2 CO2 + K2SO4 + 2 MnSO4 + 4H2O

Observation: purple colour solution becomes decolourises, no precipitate produce

5CH3C≡CH + 8KMnO4 + 12 H2SO4 5CO2 + 5CH3COOH + 8MnSO4 + 4K2SO4 + 12H2O

KMnO4/H+
CH3CH2CCCH3 CH3CH2COOH + HOOCCH3

KMnO4/H+
CH3CCH CH3COOH + CO2

KMnO4/H+
CH3CCCH3 2 CH3COOH
7. Substitution Reaction 
These substitution reactions which ethynes undergo to
form compounds with metals are not occur with the
alkenes.

Not all the alkynes also has this types of reaction, only
terminal alkynes (RC≡CH)
These reactions can be used as tests to distinguish
between acetylene(ethyne) and ethene. When acetylene
is passed through an ammoniacal solution of silver
nitrate or cuprous chloride, at room temperature,
precipitates of silver acetylide (white) or cuprous
acetylide (red) are formed.
Industrial source of ethyne
1.
2000-3000˚C
CaO+3C CaC2+CO

Calcium dicarbide reacts with water, releasing ethyne gas.

CaC2 (s) + 2 H2O(l) HC≡CH (g) + Ca(OH)2 (aq)

2. From natural gas

Partial oxidation of methane

1500˚C - 1600 ˚C
2 CH4 HC≡CH + 3H2
 Ag-C≡C-Ag + 2NH4+ + 2NH3

Purple colour of potassium

manganate (VII) is decolourised.
Aromatic hydrocarbon (Arenes)
Refer to hydrocarbons with the benzene ring.

Benzene has the molecular formula C6H6

H H
H C H H C H
C C C C
Two possible ring structures. C C C C
H C H H C H
H H
Bonding and shape of benzene
• All the six carbon atoms and the six hydrogen atoms in the
benzene molecule lie in the same plane forming a planar
hexagonal ring through σ-bonds.

• The carbon atoms in benzene are sp2 hybridized and each

carbon atom has one unhybridised p orbital that overlaps
sideways to form a π-bond.

• The π electrons are delocalized and this stabilizes the

benzene molecule.
The structure of benzene was formulated by Kekulé who first
proposed the delocalization or resonance principle.

The six carbon atoms form a perfectly regular hexagon. All of

the carbon-carbon bonds have exactly the same lengths -
somewhere between single and double bonds.
 There are delocalized electrons above and below the
plane of the ring, which makes benzene particularly
stable.

 Benzene resists addition reactions because those

reactions would involve breaking the delocalization and
losing that stability.
 Aromatic Compounds
Arene: A compound containing one or more benzene rings.
H
H C H
C C

Aromatic compounds are named:

C C
H C H
H
A Kekulé structure A Kekulé structure
showing all atoms as a line-angle formula
Naphthalene Anthracene Phenanthrene Benzo[a]pyrene

• With benzene as the parent chain when number of

carbon of alkyl group ≤ 2
• Name of substituent comes in front of the “benzene”.
CH3 Cl CH2-CH3
CH2 CH3 CH3 CH=CH2 CH2 CH3 CH3 CH=CH2
CH2 CH3 CH3 CH=CH2

Ethylbenzene Toluene Styrene Ethylbenzene Toluene Styrene

Ethylbenzene Toluene Styrene

Methylbenzene/toluene Chlorobenzene Ethylbenzene

 Naming of Aromatic Compounds

Some substituted benzenes have common names.

O O
CH3 OH OCH3 NH2 C-H C-OH
O O
OH OCH3 NH2 C-H C-OH

Phenol Anisole Aniline Benzaldehyde Benzoic acid

Toluene Phenol Anisole Aniline Benzaldehyde Benzoic acid

O O
OH OCH3 NH2 C-H C-OH

Phenol Anisole Aniline Benzaldehyde Benzoic acid

 Naming of Aromatic Compounds
When two groups are attached to benzene, the ring is numbered to give
the lower numbers to the substituents.

Start numbering from a special name (if we have).

If we do not have, number them to get the smallest set of numbers.
- List them by alphabetical order.
COOH CH2 CH3
CH3 4
1
2 Br 1
3
2

3 2
CH3 1
3-methyltoluene Cl
2-Bromobenzoic acid 1,3-Dimethylbenzene 1-Chloro-4-ethylbenzene
(o-Bromobenzoic acid) (m-Xylene) (p-Chloroethylbenzene)

Ortho Meta Para

 Naming of Aromatic Compounds
If we have three or more substituents:

- Start numbering from a special name (if we have).

- If we do not have, number them to get the smallest set of numbers.
- List them by alphabetical order.
o
-COOH > -SO3H > -CHO > -CN > -C- > -OH > -NH2 > -R > -NO2 > -X
CH3 OH NO2
1
2 NO2 Br 6
1
2 Br 4
3

2
3 5 3
4 4
1
Br
Cl Br CH2 CH3
4-Chloro-2- 2,4,6-Tribromophenol 2-Bromo-1-ethyl-4-
nitrotoluene nitrobenzene
 Physical properties of arene
Colourless and flammable liquid with a characteristic
smell
Boiling point= 80.1˚C, melting point= 5.5˚C
Less dense than water but RMM larger than water
Insoluble in water but soluble in organic solvent
Cause smoky yellow and luminous flame when burnt
Toxic
 Chemical reactions of Arenes
Benzene and other arenes are usually stable compared
to alkenes. They are stabilized by the resonance
structure formed by the delocalization of the six π
electrons.
Do not undergo addition reactions or oxidation which
will result in the loss of its stable resonance structure
formed by the delocalized π electrons.
They undergo substitution reaction whereby the H
atom in the benzene ring may be substituted by other
atoms or groups and yet maintain the stability of the
resonance in the ring.
Substitution reactions
Nitration
Halogenation
Sulphonation
Friedel-Crafts Alkylation and Acylation
 Halogenation
Substitution of a hydrogen atom in the ring by a halogen
atom, chlorine in chlorination and bromine in bromination.

Benzene does not react with halogen in the dark. However, in

the presence of catalysts known as halogen carriers, benzene
reacts readily with halogen dissolved in tetrachloromethane at
room temperature to produce halobenzene.

Examples of halogen carriers are Fe, FeCl3, FeBr3, AlCl3 or

AlBr3
 Benzene does not
react with bromine in
the absence of
halogen carrier
White fumes
catalysts. Hence the
Chlorobenzene reaction with
bromine can be used
to differentiate an
alkene and benzene
 Nitration of benzene
Substitution of a hydrogen atom in the ring by the nitro group (-NO2)

Takes place when benzene is refluxed with concentrated nitric acid

and concentrated sulphuric acid.

At a temperature of 60˚C, nitrobenzene is formed as a yellow oil with

an almond smell.
Concentrated
Concentrated H SO
2 4
H + HNO3 NO2 + H2 O
60˚C
Nitrobenzene
If the temperature reached 100˚C-110˚C, further nitration is
possible producing dinitrobenzene or trinitrobenzene.

Concentrated H2SO4 is used as a catalyst in this reaction.

Very little reaction occurs when only concentrated HNO3 is
used alone as the concentration of the NO2+ produced is
too low
2H2SO4 + HNO3 NO2+ + 2HSO4- + H3O+
Sulphonation
SO3H

Concentrated 80˚C
H2SO4
 Friedel-Crafts Alkylation
Substitution of a hydrogen atom in the benzene ring by an alkyl
group, -R:

In the presence of aluminium chloride as a catalyst, benzene and

benzene derivatives react with haloalkanes to form alkylbenzenes.
 Friedel-Crafts Acylation
oSubstitution of a hydrogen atom in the benzene ring
by an acyl group, RCO-. Examples are –COCH3
(ethanoyl) and –COC6H5 (benzoyl)

oIn the presence of aluminium chloride as a catalyst,

benzene and benzene derivatives react with acyl
chlorides to form phenylketones.
Ethanoyl chloride Phenylethanone
 Stability of Benzene towards Oxidation
Benzene is more stable than aliphatic alkenes towards
oxidation.

Benzene does not react with oxidizing agents.

The inability of benzene to decolourise KMnO4 solution can

be used to differentiate an alkene and benzene

However benzene can undergo combustion to produce carbon

dioxide and water.

The flame is sooty due to high carbon to hydrogen ratio

 Addition reactions
Hydrogenation

Ni, 180 ˚C- 250 ˚C

Addition of chlorine
 Physical properties of alkybenzene
(methylbenzene/toluene)
Colourless liquid, used as solvent
Flammable
Melting point is lower than benzene, but
boiling point is higher than benzene
Insoluble in water but soluble in organic
solvent
Obtained from coal tar and petroleum oil
Chemical reactions of methylbenzene (Toluene)
3 sets of reactions:
(a) substitution reactions of benzene ring (as in benzene)
(b) substitution reactions of the –CH3 group (as in alkane)
(c) oxidation of the –CH3 group
Substitution reaction of
the –CH3 group

Substitution reaction of
the benzene ring
The types of reactions that will occur
(benzene ring or alkyl side chain) depends on
(a) the type of reagents used
(b) the conditions of the reactions
 Substituent effect

Ring- activating group Ring-deactivating group

-usually single -usually

atom/saturate -electron unsaturated
-Electron donor d group acceptor group
-increase the -ortho and containing
-decrease the either double
electron density para directing electron
of the benzene bonds or triple
density of the bonds
ring benzene ring
-meta directing
 Ortho and para Meta directors
directors
-R (alkyl), -OH , -
NH2, -X (Halogen)
and –OR (alkoxide)
Explain why ring-activating group, such as –OH, is 2-, 4- and 6-directing.
The lone pair electrons on the oxygen atom can shift to
form a carbon-oxygen double bond, causing the
migration of the electrons in one of the carbon-carbon
double bonds giving rise to the resonance structures
shown below. The delocalization causes
an increase in the
electron density in C-2,
C-4 and C-6. As a result,
they are more susceptible
to attack by electrophiles
than C-3 and C-5.
Explain why ring-deactivating group, such as –COOH are 3-and 5-directing.
The electron-withdrawing effect of the –COOH group
causes the benzene ring to acquire a positive charge that
is delocalized over carbon-2, carbon-4 and carbon-6 as
shown below.
The electron density at C-3
and C-5 is higher than those
on C-2, C-4 and C-6. This
makes C-3 and C-5 more
susceptible to attack by
electrophiles.
Halogen groups such as –Cl in chlorobenzene are
exceptions to the general rule: Halogen substituents are
deactivating (electrons withdrawing group)but are
ortho- and para-directing
Chemical reactions of methylbenzene (Toluene)

Halogenation
When halogen such as chlorine reacts with methylbenzene, 2
types of substitutions can take place depending on the
conditions of reaction.

(a) substitution of the benzene ring will take place if a

halogen carrier catalyst is present.
(b) substitution of the methyl side chain will take place if
u.v. or sunlight is present.
 (a) Substitution of the benzene ring
In the presence of catalyst such as AlCl3, methyl group (-CH3)
activate the ring and methylbenzene reacts faster than benzene

Alkyl group is ortho- and para-directing.

Major products formed are the ortho and para products with a
trace amount of meta product
 Chlorine is passed through methylbenzene in the presence of
catalyst AlCl3, a mixture of ortho-chloromethylbenzene and
para-chloromethylbenzene are produced.

AlCl3
2 + 2Cl2 + + 2HCl

2-chlorotoluene 4-chlorotoluene
(b) Substitution of the methyl side chain
 The hydrogen atoms in the methyl side chain will be
substituted successively by halogen in the presence of
u.v. or sunlight.
 When chlorine is passed through methylbenzene in u.v
light, forming a mixture of products.
CH2Cl

u.v.
+ Cl2 + HCl
Nitration
Substitution of the benzene ring

Concentrated
H2SO4 2-nitromethylbenzene
30˚C

4-nitromethylbenzene
 Conc.
H2SO4 + 3 H2O
+ 3conc.HNO3
100˚C

2,4,6-trinitromethylbenzene /TNT
AlI3
Oxidation of methylbenzene
Do not react with an oxidising agent in the cold.
However, if methylbenzene is refluxed with a strong
oxidising agent such as acidified KMnO4, the alkyl side
chain is oxidised to –COOH group and benzoic acid is
formed. COOH

KMnO4 / H+
∆
Any alkyl group that is attached directly to the
benzene ring is oxidised to the –COOH group, producing
benzoic acid as the final product, regardless of the
length of the alkyl group.
Oxidation by acidified
COOH KMnO4 can used to
CH2CH3
differentiate between
benzene and alkylbenzene
KMnO4 / H+ Alkylbenzene
+ CO2 decolourise the purple
∆ colour of acidified KMnO4
whereas benzene does not
If the carbon atom that is bonded directly to the benzene ring
has no hydrogen attached to it, then it is not oxidisable.
Preparation of methylbenzene
Exercise (pg4-7)
Simple chemical test to differentiate the following pairs:
(a)Ethane and ethene
Reagent used: acidified KMnO4 solution / bromine in CCl4
Observation: ethene decolourise the purple colour of acidified
KMnO4/ ethene decolourise the reddish brown colour of
bromine, but ethane does not shows any changes.
Equation:
(b) Cyclohexane and cyclohexene
Reagent used: acidified KMnO4 solution / Bromine in CCl4
Observation: cyclohexene decolourise the purple colour of
acidified KMnO4/ decolourise the reddish brown colour of
bromine, but cyclohexane does not shows any changes.
Equation :
 pg- 5-8
(a) Methylbenzene and benzene
Reagent used: acidified KMnO4 solution
Observation: methylbenzene decolourise the purple colour of acidified
KMnO4 and oxidised to benzoic acid whereas benzene does not show
any changes.
Equation:
COOH

KMnO4 / H+
 (b) Ethyne and ethene
Reagent used: ammoniacal silver nitrate solution / ammoniacal copper(I)
nitrate solution
Observation: ethyne will gives a white precipitate / red precipitate but
ethene does not shows any changes
Equation:
 
H-C≡C-H + 2Ag(NH3)2+ ——> Ag-C≡C-Ag  + 2NH3 + 2NH4+
white precipitate

H-C≡C-H + 2Cu(NH3)2+  ——> Cu-C≡C-Cu  + 2NH + 2NH 3 4

+

red precipitate
 (c) 1-butyne and 2-butyne
Reagent used: ammoniacal silver nitrate solution / ammoniacal copper(I)
nitrate solution
Observation: 1-butyne will gives a white precipitate / red precipitate but
2-butyne does not shows any changes
Equation:

 
HC≡CCH2CH3 + Ag(NH3)2+ ——> Ag-C≡CCH2CH3 +NH3+ NH4+
 (d) Cyclohexene and benzene pg- 5-8
Reagent used: acidified KMnO4 solution / bromine in CCl4

Observation: Cyclohexene decolourise the purple colour of acidified

KMnO4/ Cyclohexene decolourise the reddish brown colour of
bromine, but benzene does not shows any changes.
 pg- 5-8
ethylbenzene and phenylethene
Reagent used: bromine in CCl4

Observation: phenylethene decolourise the reddish brown colour of

bromine, but ethylbenzene does not shows any changes.
Equation: Br Br
H-C – CH2

+ Br2