Alkynes

 Alkynes are hydrocarbons that contain

carbon-carbon triple bonds.

 The general formula of alkyne is CnH2n-2

Structure of Alkynes
Common Names

Named as substituted acetylene.

CH 3 C CH
methylacetylene
(terminal alkyne)
CH3 CH3
CH3 CH CH2 C C CH CH3

isobutylisopropylacetylene
(internal alkyne)
IUPAC Names
Alkynes are named in the same way that alkenes were
name
1.Change the -ene of alkene to suffix –yne
H C C H H C C CH3 H C C CH2 CH3
e thyne p ro p yne b ut-1-yne
(a c e tyle ne )

2. Choose the longest carbon chain that

contain both atoms of the triple bond
CH3 Br
H3 C C C CH3 H3 C C C C CH2 CHCH3
b ut-2-yne H
6-b ro m o -2-m e thylhe p t-3-yne
3. When additional functional groups are present. The
IUPAC rules give alkenes and alcohols higher priority than
alkynes, so the numbering begins at the end closer to these
higher-priority groups.

CH3 OH
H2 C C C C CH3 H C C CHCH3
2-m e thylp e nt-1-e n-3-yne
b ut-3-yn-2-o l

OCH3
H3 C C C CHCH2 CH3
4-m e tho xyhe x-2-yne
Main groups in order of decreasing priority

RCOOH
ESTERS
AMIDES
NITRILES
ALDEHYDES
KETONES
ALCOHOLS
AMINES
ALKENES
ALKYNES
ALKANES
ETHERS
HALIDES
Types of alkyne
Terminal alkyne
the triple bond at the end of carbon chain
R C C H a c e tyle nic hyd ro g e n

Internal alkyne
has the carbon atom bonded to each carbon
atom of the triple bond
R C C R no a c e tyle nic hyd ro g e n
Physical Properties of Alkynes

Similar to those of the corresponding alkanes and

alkenes

1. Alkynes are insoluble in water but soluble in

organic solvents (ether, chloroform etc)

2. Alkynes of : C2-C4 are gases

C5-C18 are liquids
>C18 wax-like solids
Preparation of Alkynes
1. Dehydrohalogenation of alkyl dihalides using a
strong base
Examples:
Molten KOH or alcoholic KOH forms internal alkynes

Br
KOH, 200 °C (fuse d )
CH3 CH2 CH2 CCH3 H3 CH2 C C C CH3
p e nt-2-yne
Br

NaNH2 forms terminal alkynes

Br
CH3 CH2 CH2 CCH3 (1) Na NH2 , 150 °C H3 CH2 CH2 C C C H
(2) H2 O p e nt-1-yne
Br
2. Reaction of sodium acetylide
with primary alkyl halide

 H+ can be removed from a terminal alkyne by

sodium amide, NaNH2.
Reaction of sodium acetylide with 1 alkyl halides

 Acetylide ions are good nucleophiles

 SN2 reaction with 1 alkyl halides lengthens the alkyne
chain.

Example:
(1) Na NH2
H3 CH2 CH2 C C C H H3 CH2 CH2 C C C CH2 CH3
(2) CH3 CH2 Br
Reaction of alkynes

1. Addition of hydrogen

H2
C C
Pd / Ba SO 4 / H H
q uino line c is H H
H2
C C C C
Pd o r Ni
a lkyne
H H H
Na / NH3
C C a lka ne
H
tra ns
CH3 CH2 CH2 CH2 CH2 CH3
he xa ne

H2
Pd o r Ni
H3 CH2 C CH2 CH3
H2
H3 CH2 C C C CH2 CH3 C C
he x-3-yne Pd / Ba SO 4 / q uino line H H
(Lind la r's c a ta lyst)
Na / NH3 c is-he x-3-e ne

H3 CH2 C H
C C
H CH2 CH3

tra ns-he x-3-e ne

2. Addition of halogens (X2=Cl2, Br2)
X X
X2 X2
R C C R' R C C R' R C C R'
X X X X

Example:
Br2
H3 C C C CH2 CH3 H3 C C C CH2 CH3
Br Br

Br2

Br Br
H3 C C C CH2 CH3
Br Br
3. Addition of hydrogen halides
( HX = HCl, HBr or HI )

H X
HX HX
R C C R' R C C R' R C C R'
H X H X
(Ma rko vniko v o rie nta tio n)

Exampl
e:
Cl
HCl HCl
H C C CH2 CH3 H C C CH2 CH3 H3 C C CH2 CH3
H Cl Cl
This addition follows Markovnikov’s rule
4. Addition of water
a. Catalysed by HgSO4/H2SO4
H
re a rra ng e
Hg SO 4 / H2 SO 4
R C C R' + H2 O R C C R' R C C R'
OH H O H
e no l sta b le
(unsta b le )
Exampl
e:
Hg SO 4 / H2 SO 4
H C C CH2 CH3 + H2 O H C C CH2 CH3
H OH
unsta b le

H3 C C CH2 CH3
O
sta b le
Markovnikov orientation
b. Hydroboration-oxidation
H
(1) BH3 .THF
R C C H R C C H R C C H
(2) H2 O 2 , Na OH
H OH H O
unsta b le sta b le
(a nti-Ma rko vniko v o rie nta tio n)

Example:
(1) BH3 .THF
H C C CH2 CH3 + H2 O H C C CH2 CH3
(2) H2 O 2 , Na OH
OH H
unsta b le

H C CH2 CH2 CH3

O
sta b le
Anti-Markovnikov orientation
Oxidation of Alkynes
 Similar to oxidation of alkenes.
 Dilute, neutral solution of KMnO4 oxidizes
alkynes to a diketone.
 Warm, basic KMnO4 cleaves the triple bond.
 Ozonolysis, followed by hydrolysis, cleaves
the triple bond.

19
Permanganate Oxidation of Alkynes to
Diketones

 Under neutral conditions, a dilute potassium

permanganate solution can oxidize a triple bond
into an diketone.
 The reaction uses aqueous KMnO4 to form a
tetrahydroxy intermediate, which loses two water
molecules to produce the diketone.

20
Permanganate Oxidation of Alkynes to
Carboxylic Acids

 If potassium permanganate is used under basic

conditions or if the solution is heated too much, an
oxidative cleavage will take place and two
molecules of carboxylic acids will be produced.

21
Terminal alkynes??

1. KMnO4, KOH, H2O COOH

+ CO2
+
2. H3O
Ozonolysis
 Ozonolysis of alkynes produces carboxylic acids
(alkenes gave aldehydes and ketones).

O O
(1) O3
CH 3 C C CH 2 CH 3 CH3 C OH + HO C CH 2 CH 3
(2) H 2O

 Used to find location of triple bond in an

unknown compound.

23
Terminal alkynes??
1. O3 COOH O
2. H2O + HO C H
Visual Test for Alkynes
1. Bromine in carbon tetrachloride (CCl4)
Br Br
C C 2Br2 CCl4
+ C C
da rk re d
Br Br
c o lo urle ss
2. Baeyer test
OH OH
c o ld ,d ilute
C C + KMnO 4 C C + MnO 2
p urp le a lka line
OH OH b ro wn
p re c ip ita te
-2 H2 O

C C
O O
To differentiate between terminal alkyne and
internal alkyne

R C C H + Ag NO 3 R C C: Ag
te rm ina l a lkyne inso lub le
p re c ip ita te

R C C R' + Ag NO 3 No Re a c tio n
inte rna l a lkyne
(Cle a r so lutio n)