Presented by

K.BINDU MEENAKSHI
REGD NO:11AB1R0028

Under the Guidance of
MR.A.VISWANATH M.Pharm
Associate Professor
Department Of Organic Chemistry

VIGNAN PHARMACY COLLEGE
(Approved by AICTE, PCI & affiliated to JNTU-K)
VADLAMUDI, GUNTUR DISTRICT ANDHRA PRADESH, INDIA
PIN NO: 522213

PREPARATION OF
ALKANES,ALKENES,ALKYNES
CONTENTS:
INTODUCTION
NOMENCLATURE
METHOD OF PREPARATION
PHYSICAL PROPERTIES
CHEMICAL PROPERTIES
STRUCTURE OF ALKANES:
Alkanes contains only a single bond.
General formula for alkanes is C
n
H
2n+2
.


All the carbon atoms are sp3 hybridized.
C-C Bond length is 1.54A(or)0.154nm and the C-H Bond
length is 1.10A(or)0.110nm.
The bond angle is109.28.
Sp3-Sp3
SP3-S
SP3-S



1.10A
1.54A

109.28
NOMENCLATURE OF ALKANES:
Suffix:-ane
CH
3
CH CH
3
CH
3
METHYLPROPANE
CH
3
CH CH
2
CH
3
CH
3
CH
2
2-METHYLPENTANE
CH
3
CH CH
2
CH
3
CH
3
CH
3
2,2-DIMETHYLBUTANE
1
2 3
4 5
1 2 3
4
METHODS OF PREPARATIONS OF
ALKANES:
HYDROGENATION OF ALKENES OR ALKYNES:

a) R-CH=CH
2
+ H
2


Ni

R-CH
2
-CH
3
ALKENE
ALKANE
CH
2
=CH
2
+ H
2
CH
3
-CH
3
ETHYLENE ETHANE
Ni
b) R-C=CH + 2H
2
R-CH
2
-CH
3

Ni

ALKYNE ALKANE
CH=CH + 2H
2
CH
3
-CH
3
Ni

ACETYLENE
ETHANE


REDUCTION OF ALKYL HALIDE:
Alkyl halides undergoes reduction with nascent hydrogen to form
alkanes.
R-X + 2[H] R-H + HX
ALKYLHALIDE ALKANE
CH
3
CH
2
-Br + 2[H] CH
3
-CH
3
+ HBr
ETHYL BROMIDE ETHANE
DECARBOXYLATION OF CARBOXYLIC ACID:
When the sodium salts of carboxylic acid is heated strongly with
soda lime(NaOH +CaO) , carbonate and an alkane is formed.
R-COONa + NaOH RH + NaCO
3





CH
3
-COONa + NaOH CH
4
+ Na
2
CO
3
SODIUM ACETATE METHANE
ALKANE
HYDROLYSIS OF GRIGNARD REAGENT:
Alkyl halide on treatment with magnesium in anhydrous ether
gives Grignard reagent.
RX + Mg RMgX
ALKYL MAGNESIUM HALIDE
CH
3
CH
2
Br + Mg CH
3
CH
2
MgBr
ETHYLBROMIDE ETHYL MAGNESIUM BROMIDE
This reagent on treatment with water gives alkanes.
RMgX + HOH RH +MgX(OH)
ALKANE
CH
3
MgI + HOH CH
4
+ MgI(OH)
METHYL MAGNESIUM IODIDE METHANE
ETHER
ETHER
WURTZ SYNTHESIS:
Higher alkanes are produced by heating an alkyl halide with
sodium metal in dry ether solution.

CH
3
-Br + 2Na + Br-CH
3
CH
3
-CH
3
+ 2NaBr
METHYL BROMIDE ETHANE
The reaction between 2 different alkyl halides and sodium gives a
alkane.
CH
3
CH
2
-Cl + 2Na + Cl-CH
3
CH
3
CH
2
-CH
3
+ 2NaCl
ETHYL CHLORIDE METHYL CHLORIDE PROPANE
LIMITATIONS:
Separation of compounds is difficult due to little difference in the
boiling point.
R-X + 2Na + X-R R-R + 2NaX
ETHER
ETHER
SYMETRICAL ALKANE

ETHER
COREY HOUSE ALKANE SYNTHESIS:
Developed by E.J.Corey and Herbert House in 1960s.
Lithium dialkyl copper and an alkyl halide on reaction gives
alkanes.
R
2
-CuLi + RX R-R + RCu + LiX
LITHIUM ALKYL ALKANE
DIALKYL HALIDE
COPPER
Synthesis of propane from ethyl bromide
CH
3
CH
2
BR CH
2
CH
2
Li (CH
3
CH
2
)
2
CuLi
CH
3
Br
CH
3
CH
2
CH
3
PROPANE
LITHIUM DIETHYL COPPER
ETHYL LITHIUM
BROMO ETHANE
Li CuI
KOLBES SYNTHESIS:
When a concentrated solution of sodium salt of a carboxylic
acid is electrolyzed, an alkane is formed.

2RCOONa + 2H
2
O R-R +2CO
2
+2NaOH +H
2


2CH
3
COONa+ 2H
2
O CH
3
-CH
3
+2CO
2
+2NaOH+H
2


SODIUM CARBOXYLATE AT ANODE AT CATHODE
SODIUM ACETATE
AT ANODE
AT CATHODE
ETHANE
Soluble in non-polar solvents .
Insoluble in polar solvents like water.
Densities of alkanes are around 0.7g/ml ,
which is less than water . Hence insoluble in water.
Both the boiling and melting point of alkanes
increases with increase in molecular weight.

PHYSICIAL PROPERTIES OF ALKANES:
gases
liquids
solids
IR Spectrum :
The IR spectra of alkanes show absorption corresponding to the C-H
stretching frequencies at 2850-3000cm1.
CHEMICAL PROPERTIES OF ALKANES:
Halogenation:
Alkanes react with chlorine in the presence of UV light or diffused
sunlight or at a temperature of 300-400c yielding a mixture of
product. This reaction is not stopped at this stage.
CH
4
+ Cl
2
CH
3
Cl + HCl
METHANE METHYL CHLORIDE

This reaction is not stopped at this stage.
CH
3
Cl + Cl
2
CH
2
Cl + HCl
METHYLENE CHLORIDE


h

CH
2
Cl + Cl
2
CHCl
3
+ HCl
CHLOROFORM
CH
3
Cl + Cl
2
CCl
4
+ HCl
CARBON TETRACHLORIDE
MECHANISM:
1)Chain initiation step:
Cl : Cl Cl + Cl
2)Chain propagation step:





Cl + H CH
3
H Cl + CH
3
H
3
C + Cl : Cl H
3
C :Cl + Cl
METHANE
METHYL CHLORIDE
METHYL RADICAL
a)
b)
h

Both a and b steps are repeated .Thus chain reaction is
propagated.
3)Chain termination reaction:
Cl + Cl Cl-Cl
CH
3
+ Cl CH
3
-Cl
CH
3
+ CH
3
CH
3
-CH
3
REACTION WITH SULFURYLCHLORIDE:
Alkanes react with sulfurylchloride in presence of benzoyl peroxide at
60-80c to form alkyl halide.








BENZOYL

PEROXIDE
SOCl
2

PEROXIDE
2,3-DIMETHYL BUTANE
1-CHLORO-2,3-DI
METYL BUTANE
2-CHLORO-2,3-DI
METYL BUTANE
+ CH3 C C CH3
CH3
CH3
Cl H
C C
CH
3
CH
3
CH
3
CH
3
CH
3
C C CH
2
Cl
CH
3
CH
3
H
H
CH
3
CH
3

R-H + Cl-S-Cl R-Cl + SO
2
+HCl
O
O
NITRATION:
Nitration of ethane with HNO
3
at 400 to 500 c and under high
pressure gives a mixture of nitro methane and nitro ethane.
CH
3
-CH
3
+HO-NO
2
CH
3
-CH
2
-NO
2
+CH
3
-NO
2
+H
2
O
ETHANE NITROETHANE NITROMETHANE
MECHANISM:
Chain initiation step:

ETHANE ETHYL FREE RADICAL

CH3CH2:H
CH
3
CH
2
+ H
400-500 C
CH3 : CH3
2CH
3
METHYL FREE RADICAL

ETHANE
Chain propagation step:

CH
3
CH
2
+ HO:NO
2
CH
3
CH
2
-
NO
2
+HO
CH
3
CH
2
H + HO
CH3CH2 + H2O
Chain termination step:

CH
3
+CH
3
CH
3
:CH
3
ETHANE
CH
3
CH
3
+ CH
3
CH
3
CH
3
CH
2
:CH
2
CH
3

BUTANE
NITROETHANE
HYDROXYL
RADICAL
ETHYL FREE RADICAL
ETHANE
ETHYL RADICAL
SULFONATION:
This involves the substitution of hydrogen atom of alkane with
SO
3
H group .

R-H + HO-SO
3
H R-SO
3
H + H
2
O
ALKANE FUMING ALKANE SULFONIC
ACID
R=C
6
H
15
or Larger alkyl group

Lower alkanes like methane and ethane do not give this reaction.




COMBUSTION(OXIDATION):
General equation of the combustion of hydrocarbon is
C
x
H
y
+(x+y/4)O
2
xCO
2
+ y/2 H
2
O
CH
4
+ 2O
2
CO
2
+ 2H
2
O
The heat of combustion of 2 isomers , pentane and
2-methylbutane are 845.2kcal/mol and 843.5kcal/mol.
The mass balance equation for the combustion of these 2 isomers
are the same.
C
5
H
12
(g) + 8O
2
(g) 5CO
2
(g) + 6H
2
O + Heat
ISOMERIZATION:
Normal alkanes are converted to their branched chain isomers in
the presence of aluminum chloride and HCl at 25 c.

CH
3
-CH
2
-CH
2
-CH
3

n-BUTANE
ISOBUTANE
(2-METHYL PROPANE)
AROMATIZATION:
n-Hexane is passed over Cr
2
O
3
supported over alumina at 600 c ,
benzene is produced.
CH
3
CH
2
CH
2
CH
2
CH
2
CH
3
+4H
2

n-HEXANE BENZENE

CH
3
-CH-CH
3
CH3
AlCl
3
O
Cr
2
O
2
-Al
2
O
3
HCl
PYROLYSIS(CRACKING):
Ethane when heated to 500 c in the absence of air , gives a
mixture of methane , ethylene and hydrogen.
CH
3
CH
3
CH
2
=CH
2
+ CH
4
+H
2
ETHANE ETHYLENE METHANE
MECHANISM:
Chain initiation step:
H
3
C:CH
3
2H
3
C

Chain propagation step:

a)





ETHANE
METHANE ETHYL RADICAL
H
3
C + HCH
2
CH
3
CH
4
+ CH
2
CH
3
METHYL FREE RADICAL ETHANE
METHYL
RADICAL

b)





c)



Step (b) and (c) are repeated over and over again.
Chain termination step:
CH
3
CH
2
+ H CH
3
CH
3
ETHYL RADICAL ETHANE
H
2
C CH
2
+H
H
2
C CH
3

H + H : CH
2
CH
3
H-H + CH
2
CH
3
ETHYLENE
ETHYL RADICAL
ETHANE
ETHYL RADICAL
CYCLOALKANES:
Cycloalkanes or cycloparaffins are saturated hydrocarbon in which
the carbon atom are joined by single covalent bond to form a ring.
General formula C
n
H
2n
.

First member of the series is cyclopropane , C
3
H
6
.

=
CYCLOBUTANE
CYCLOPENTANE
CYCLOHEXANE
ALKENES:
Alkenes are the hydrocarbons with Double bond.
General formula is C
n
H
2n
.
Commonly known as Olefins.
First member of alkenes is Ethylene.
Bond angle is 120.
C-C Bond length is 1.34A.
C-H Bond length is 1.09A.

Numbering is done so that the double bond has lowest possible
number.
When 2 or more double bonds are present the ending name is
replaced with adiene or atriene.
NOMENCLATURE:
Suffix: -ylene.
CH
2
= CH CH
2
CH
3


1-butene
3-ethyl-2-pentene
l
CH
2
CH
3

CH
3
CH
2
C=CH CH
3

5 4 3 2 1
1
2 3 4
METHOD OF PREPARATION OF ALKENES:
BY DEHYDRATION OF ALCOHOL:
When alcohol is heated in the presence of sulfuric acid, a molecule
of water is eliminated and alkene is formed.


R CH CH
2
O
OH
R CH CH
2
+H
2
O
H
2
SO
4


ALKENE
CH CH
2
O
OH
CH CH
2
+H
2
O CH
3
CH
3
H
2
SO
4

170C
1-PROPANOL
PROPENE
With unsymmetrical 2 and 3 alcohol elimination can proceed in 2
ways and a mixture of alkenes is formed.






This is in accordance with SATYZEFF RULE.
CH CH
OH
CH
3
CH
3
H
CH
3
CH
CH CH
3
H
2
SO
4


2-BUTANOL
2-BUTENE(80%)
H
2
SO
4


CH
2
CH
OH
CH
3
CH
2
CH
3
CH
2
CH CH
2
H
BY DEHYDROHALOGENATION OF ALKYL
HALIDE:
When an alkyl halide is heated with an alcoholic solution of
sodium or potassium hydroxide , a molecule of hydrogen halide is
eliminated and an alkene is formed.


CH CH
2
+ KOH
H X
CH
CH
2
+ KX + H
2
O R
R
ALCOHOL


ALKYL HALIDE
ALKENE
H
3
C CH CH
2
+ KOH
H Br
CH
2
+ KBr + H
2
O CH
3
CH
ALCOHOL


PROPENE
1-BROMOPROPANE
BY DEHALOGENATION OF VICINAL
DIHALIDE:
Alkenes are formed when vic-dihalide are heated with zinc dust
in ethyl alcohol.

R CH3 CH
2
+ Zn
Br Br
R CH
CH
2
+ ZnBr
2
VIC-DIHALIDE
ALCOHOL


ALKENE
H
3
C
CH
CH
2
+ Zn
Br
Br
CH3
CH
2
+ ZnBr
2
CH
3
ALCOHOL


1,2-DIBROMOPROPANE
PROPENE
BY CONTROLLED HYDRGENATION OF
ALKYNES:
Alkynes react with lindlars catalyst to give alkenes.

ALKYNE
R
C
C
H + H
2
R CH CH
2
ALKENE
Pd-CaCO
3

QUINOLINE
CH
3
C
C H + H
2
CH
3
CH CH
2
Pd-CaCO
3

QUINOLINE
PROPYNE PROPENE
BY CRACKING OF ALKANES:
Alkanes when heated at 500-800c in the absence of air decompose
to yield lower molecular weight alkenes,alkanes,hydrogen.
CH
3
-CH
3
CH
2
=CH
2
+ CH
4
+ H
2
ETHANE ETHYLENE
CH
3
-CH
2
-CH
3
CH
3
-CH=CH
2
+ CH
2
=CH
2
PROPANE PROPENE ETHYLENE
+ CH
4
+ H
2


PHYSICAL PROPERTIES:
All are colorless and odorless except ethene.
Insoluble in water and quiet soluble in non polar solvents.
Less dense than water.
Boiling point increases with carbon number.
Melting point , boiling point, specific
gravity rises with increase of molecular
weight in homologous series.
IR Spectra of alkenes show C-H
stretching absorption at 3000-3100cm .

1
CHEMICAL PROPERTIES:
Alkenes are more reactive than alkanes because of electrons of the
double bond.
ADDITION OF HYDROGEN HALIDES:
Alkenes react with hydrogen halide to form alkyl halide.

CH
3
-CH=CH-CH
3
+ HBr CH
3
-CH
2
-CH-CH
3
2-BUTENE 2-BROMOBUTANE
MARKOVNIKOV RULE:
This rule on the basis of mechanism of HX addition.






Br
|
Br
|
CH
3
-CH=CH
2
+ HBr CH
3
-CH-CH
3
PROPENE
2-BROMOPROPENE
MECHANISM:
STEP 1:






STEP 2:


CH
3
CH CH
2
+ H
Br
CH
3
CH
2
CH
2
+
Br
CH
3
CH3 CH
3
+ Br
PROPENE
1CARBOCATION
2CARBOCATION
CH
3
CH CH
3
+ Br
CH
3
CH CH
3
Br
2CARBOCATION
2-BROMOPROPENE
MECHANISM OF ADDITION OF HYDROGEN
HALIDE:
STEP 1:



STEP 2:


CH
3
C C CH
3
+ H
H H
CH
3
C C CH
3
+ Br
H H
H
Br
2-BUTENE CARBOCATION
CH
3
C C CH
3
+ Br
H H
H
CH
3
C C CH
3
H H
H
Br
NUCLEOPHILE
2-BROMOBUTANE
ADDITION OF HYPOHALOUS ACID:
Alkenes react with hypohalous acid to give halohydrins.



ADDITION OF HYDROGEN:
Alkenes add hydrogen under pressure and in the presence of Ni , Pt
or Pd catalyzed to produce saturated hydrocarbons.
CH
2
= CH
2
+ H
2
CH
3
CH
3
ETHYLENE ETHANE

CH
2
CH
2
+ HO Cl CH
2
CH
2
OH Cl
ETHYLENE ETHYLENE CHLOROHYDRIN
Ni


ADDITION OF WATER:
Alkenes react with water in the presence of a strong acidic catalyst
to form alcohol.
CH
3
-CH=CH
2
+ H
2
O CH
3
-CH-CH
3

MECHANISM:
STEP 1:

STEP 2:





OH
l
PROPENE 2-PROPANOL
CH
3
CH CH
2
+ H
+
CH
3
CH CH
3
CH
3
CH CH
3
+ H
2
O
CH
3
CH CH
3
O H
H
PROPENE 2CARBOCATION
PROTONATED ALCOHOL
H
ADDITION OF H
2
SO
4
:
Alkene react with H
2
SO
4
yields an alkyl hydrogen sulfate.



MECHANISM:
STEP 1:
CH
3
-CH=CH
2
+ H CH
3
-CH-CH
3





CH
3
-CH=CH
2
+ H-OSO
3
H CH
3
-CH-CH
3
OSO
3
H
l
PROPENE
1-METHYL ETHYL
HYDROGEN SULFATE
STEP 2:
PROPENE 2CARBOCATION
CH
3
-CH-CH
3
+ OSO
3
H CH
3
-CH-CH
3

l
OSO
3
H
1-METHYL ETHYL HYDROGEN SULFATE
OXIDATION WITH COLD KMnO
4
SOLUTION:
Alkenes react with cold dil.KMnO
4
solution to form glycols.



CATALYTIC OXIDATION:
Alkenes react with O
2
in the presence of silver catalyst at 250-400c
to form epoxides.



CH
2
=CH
2
CH
2
-CH
2
OH
l
OH
l
KMnO
4

H
2
O
ETHYLENE
ETHYLENE OXIDE
CH
2
CH
2
+ O
2
H
2
C CH
2
O
ETHYLENE
ETHYLENE GLYCOL
ADDITION OF HALOGEN:
Alkenes react rapidly with halogens in carbon tetrachloride solvent to
form dihalide.


MECHANISM:
STEP 1:


STEP 2:


CCl
4
C C
H
H
3
C
H
H
+ Br
2
H C C
H
H
H Br
Br
C C
H
H
3
C
H
H
+ Br Br C C
H Br
H
H CH
3
+ Br
C C
H Br
H
H CH
3
Br
CH
3
C
C
H
Br
H Br
H
PROPENE
1,2-DIBROMOPROPENE
1,2-DIBROMOPROPENE
PROPENE
BROMONIUM ION
OXYMERCURATION-DEMERCURATION OF
ALKENES:
Mercuric acetate and water add to alkenes in a reaction called
oxymercuration.



The product of oxymercuration is reduced with sodium borohydride
in a subsequent reaction called demercuration.


CH
3
CH CH
2
CH
3
CH CH
2
HgO
OH
C
O
CH
3
Hg(O C
O
CH
3
)
2
H
2
O
CH
3
CH CH
2
HgO
OH
C
O
CH
3
CH
3
CH CH
3
OH
NaBH
4
PROPENE
2-PROPANOL
MECHANISM:
STEP 1:


R CH CH
2
R CH CH
2
Hg
OAc
R CH C H
H
HgOAc
O
H H
R C C H
OH H
HgOAc H
Hg OAc
OAc
H
2
O
OAc
R C C H
OH H
HgOAc H
R CH CH
2
OH H
STEP 2:
ALKENE
MERCURIC
ACETATE
MERCURINIUM ION
ORGANOMERCURY
COMPOUND
ALOCHOL
NaBH
4
C
O
CH
3
Ac=
HEAT OF HYDROGENATION:
It is the energy difference between the starting alkene and the
product alkane.
COMUSTION:
Alkenes when burnt in air , oxidizes to CO
2
and water.
CH
2
=CH
2
+ 3O
2
2CO
2
+ 2H
2
O + HEAT
ETHYLENE
OXIDATION WITH HOT KMnO4 SOLUTION:
On treatment with hot KMnO
4
alkenes split double bond to form
ketones and acid.
CH
3
-CH=CH
2
CH
3
-C-OH +CO
2
+ H
2
O

POLYMERISATION:
simple alkenes polymerize to form long chain addition polymer.

nCH
2
=CH
2
CH
2
-CH
2
O
ll
[O]

HOT KMnO
4


ACETIC ACID PROPYLENE
POLYMERISATION
ETHYLENE
POLYETHYLENE
ALKYNES:
Alkynes are unsaturated hydrocarbons containing triple bond.
General formula is C
n
H
2n-2
.
First member of the series is Acetylene.
H-C-C Bond angle is 180.
C-H Bond length is 1.09A.
C-C Bond length is 1.20A.
sp-sp
s-sp
s-sp
NOMENCLTURE:
common names: alkyl acetylene .
Suffix : -yne

Long continuous chain with triple bond parent chain.
Position of triple bond is indicated by prefixing the no. of carbon
preceding it to the name of alkyne.
CH
3
CH
2
CCH HCCCHCH
2
CH
3

1-butyne 3-methyl-1-pentyne
ethyl acetylene sec-butyl acetylene
CH
3
|
1 2 3 4
1 2 3 4 5
METHOD OF PREPARATION OF ALKYNES:
DEHYDROHALOGENATION OF VICINAL
DIHALIDES:
Alkynes are obtained by treating vicinal dihalides with alcoholic
KOH followed by sodium amide(NaNH
2
).

H C C H
H C C H
H Br
Br H
H
Br
H C C H
KOH

ALCOHOL
NaNH
2
1,2-DIBROMO ETHANE
VINYL BROMIDE
ACETYLENE
DEHALOGENATION OF TETREHALIDE:
When 1,1,2,2-tetrahalide are heated with zinc dust in alcohol ,
alkynes are formed.




REACTION OF CALCIUM CARBIDE WITH H
2
O:
Calcium carbide react with water to yield acetylene.
R C C
R + 2Zn R C
C
R + 2ZnX
2
X
X
X
X
TETRAHALIDE
ALKYNE
ALCOHOL


CaC
2
+ H
2
O
H
C
C
H + Ca(OH)
2
CALCIUM CARBIDE ACETYLENE
REACTION OF SODIUM ACETYLIDE WITH 1
ALKYL HALIDE:
Sodium acetylide react with primary alkyl halide to form alkynes.

H C
C:Na + CH
3
CH
2
Br
H C C CH
2
CH
3
+ NaBr
SODIUM ACETYLIDE ETHYL
BROMIDE
1-BUTYNE
PHYSICAL PROPERTIES OF AKLYNES:
Colorless and odorless except acetylene.
Slightly soluble in water.
Readily soluble in organic solvents.
Boiling , melting point and specific gravities show regular increase
with increase in mol. Wt.
IR Spectra of alkynes show C-H stretching absorptions at
~3300cm.

1
CHEMICAL PROPERTIES:
Alkynes give same type of addition reactions as alkenes.
ADDITION OF HYDROGEN:
In presence of Ni,Pt or Pd, alkynes with hydrogen gives alkenes
and alkanes.

R
C
CH + H
2
R
CH
CH
2
R
CH
2
CH
3
ALKYNE
ALKENE
ALKANE
PROPYNE PROPENE
PROPANE
Ni
Ni
H
2

Ni
H
2

Ni
C CH + H
2
CH
3
CH
3
CH
CH
2
CH
3
CH
2
CH
3
METAL-AMMONIA REDUCTION TO TRANS
ALKENES:
Sodium metal in liquid ammonia reduces alkynes with
antistereochemistry into trans alkenes.



MECHANISM:
STEP 1:







CH
3
C C CH
3
C
C
CH
3
H
H
CH
3
2-BUTYNE
TRANS-2-BUTENE
CH
3
C C CH
3
+ Na
C CH + Na
+
CH
3
H
3
C
RADICAL ANION
2-BUTYNE
Na

Liq NH
3
STEP 2:




STEP 3:





STEP 4:

C C + H
CH
3
H
3
C
NH
2
C C
CH
3
H
3
C
H
+ NaNH
2
C C
CH
3
H
3
C
H
+ H
NH
2
C C
CH
3
H
3
C
H
+ NaNH
2
H
C C
CH
3
H
3
C
H
+ Na C C
CH
3
H
3
C
H
+ Na
+
TRANS-2- BUTENE
ADDITION OF HALOGEN:
Halogen added to alkyne to form a dihalide and then tetra halide.

R
C CH +X
2
R
C CH
X X
R
C
C H
X
X
X
X
C
CH +Br
2
CH
3
CH
3
CBr
CHBr
CH
3
CBr
2
CHBr
2
PROPYNE
1,2-DIBROMOPROPENE
1,1,2,2-TETRABROMO PROPANE
ADDITION OF HALOGEN ACIDS :
Two molecules of acid when added to symmetrical alkynes gives
the following products.



MECHANISM:
STEP 1:

H C C H + HBr
H C C
H
H
Br
H C C H
H
H X
Br
ACETYLENE 1-BROMOMETHANE
1,1-DIBROMOMETHANE
H
3
C C C H + H
+
CH
3
C CH
2
+
PROPYNE CARBOCATION
STEP 2:




STEP 3:





STEP 4:








CH
3
C CH
2
+ :Br
-
+
CH
3
C CH
2
Br
2-BROMO PROPENE
CH
3
C CH
2
+ H
+
Br
CH
3
C CH
3
Br
+
2-BROMO PROPENE
CH
3
C CH
3
+ :Br
-
Br
+
CH
3
C CH
3
Br
Br
2,2-DIBROMOPROPANE
CARBOCATION
ADDITION OF HYPOHALOUS ACID:
Addition of 2 molecules of hypohalous acid to alkynes gives
dihaloketone.



ADDITION OF HYDROGEN CYANIDE:
Alkynes react with HCN in the presence of Ba(CN)
2
catalyst gives
vinyl cyanide.

CH
3
C CH + 2HO Br CH
3
C
CHBr
2
OH
OH
CH
3
C
CHBr
2
o
PROPYNE 1,1-DIBROMO ACETONE
-H
2
O
H
C
C H + HCN
CH
2
CH
CN
ACETYLENE
Ba(CN)
2

PRESSURE
VINYL CYANIDE
OXIDATION WITH KMnO
4
:
Oxidation of alkynes with alkaline KMnO4 forms carboxylic acid
and CO2.


POLYMERIZATION:
Alkynes when passed through a red hot tube gives aromatic
hydrocarbons.
CH
3
COOH + CO
2
CH
3
C
C
H + 4
PROPYNE
ACETIC ACID
C
CH
3
CH
HC
C
C
CH
3 CH
3
CH
C
HC
CH
C C
C
CH
3
CH
3 CH
3
HOT TUBE

400C
1,3,5-TRIMETHYL BENZENE PROPYNE
OZONOLYSIS:
Alkynes react with ozone to give ozonide gives following product.


ALKYNE
R C C R + O
3
R C
C
O
O O
R
R C C R + H
2
O
R
C OH + R
C OH
O O
O O
OZONIDE
DIKETONE CARBOXYLIC ACIDS
H
2
O
MERCURIC ION-CATALYSED HYDRATION:
Alkynes undergo acid-catalyzed addition of water , in the
presence of mercuric ion as a catalyst.



MECHANISM:
STEP 1:



CH
3
C C H + H
2
O CH
3
C CH
2
OH
CH
3
C
CH
3
O
PROPYNE
H
2
SO
4

HgSO
4
ENOL
ACETONE
H
CH
3
C C
CH
3
C C
H H
Hg
2+
: Hg
2+
A BRIDGED MERCURIUM
ION INTERMEDIATE
STEP 2:






STEP 3:


CH
3
C C H
Hg
2+
O
H H
C C
H
Hg
+
H
3
C
+
O
H
H
O
H
H
C C
H
Hg
+
H
3
C
+
O
H
H
+
C C
H
Hg
+
H
3
C
O
H
+ H
3
O
+
ORGANOMERCURY
STEP 4:



STEP 5:



STEP 6:


C C
H
3
C
HO
Hg
+
H
CH
3
C CH
2
Hg
+
o
H O H + CH
3
H
C CH
2
Hg
+
O
+
CH
3
C CH
2
Hg
+
+ H
2
O
O
H
+
CH
3
C CH
2
Hg
+
O
H
+
Hg
2+
+ CH
3
C CH
2
O
H
CH
3
C CH
3
O
ENOL FORM
KETO FORM
ENOL FORM
KETO FORM
OXONIUM ION
CONCLUSION:
Alkane , Alkenes , alkynes are the basic fundamental structure in
organic chemistry.
Almost all the compounds contains single or double or triple bonds
in their structure.
Alkanes and Alkenes are used as fuel and in production of
polymers.
Alkynes are pharmaceutically used in the preparation of
contraceptives.


REFERENCES:
Arun Bahl,B.S Bahl , Advanced Organic Chemistry ,
Pg No:184-240,262-356.
Morrison and Boyd , Organic Chemistry ,
6
th
edition , Pg No:112-158,309-327.
Bruice , Organic Chemistry, 3
rd
edition,
Pg No:111-171,240-398,461-476.
Vogel's, Practical Organic Chemistry, 5
th
edition,
Pg No:470-517.
Lloyd N . Ferguson , Textbook of Organic
Chemistry,2
nd
edition , Pg No. 59-138 .
Raj . K . Bansal , Textbook of Organic
Chemistry , 5
th
edition , Pg No. 168-269.


ACKNOWLEDGEMENT
I would like to thank my guide MR.A.VISWANATH sir
for his constant support and guidance.
I also thank our principal Dr . P.SRINIVAS BABU sir and
SEMINAR COMMITTE for giving me this opportunity.