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(UNIT 2C)
2.9 Alkynes
2.10 Drawing structural formula
2.11 IUPAC naming system for alkynes
2.12 Physical and chemical properties of alkynes
2.13 Reactions of alkynes
2.14 Usage of alkynes
General formula
CnH2n–2
Synthesis Reactions
of Alkynes of alkynes
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SYNTHESIS OF ALKYNES
From dihaloalkanes-
Alkynes may be prepared by dehydrohalogenation (elimination) of
dihaloalkanes preferably bromo derivatives. There are two methods of
preparation for the two types of dihaloalkanes such as vic. Dihalides, gem.
Dihalides.
From alkane halides (vic.-dihalides)
An alkylene dihalide has two halogen atoms, one each on the two adjacent
carbon atoms. When boiled with alcoholic potash, the molecule loses 2
molecules of hydrogen halide and the corresponding alkyne is obtained.
The aldehyde or ketone is called the keto form, and the keto ≡ enol
equilibration is referred to as keto–enol isomerism or keto–enol tautomerism.
Tautomers are constitutional isomers that equilibrate by migration of an atom
or group, and their equilibration is called tautomerism.
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ADDITION OF HALOGENS TO ALKYNES
Alkynes react with chlorine and bromine to yield tetrahaloalkanes. Two
molecules of the halogen add to the triple bond.
H C C H H C C H CH 2 CH C CH
Cu 2Cl 2
CH 2 CH C CH NH
4Cl
CH 2 CH C CH CH 2
4 2
H
H H H 3
H H
Dewar formula K e k u le ' f o rm u la
Hybrid resonance
structure
4 2
NO2
O2N
3
p h e n y le th e n e m e th y lb e n z e n e CH3
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2,4,6-trinitrom ethylbenzene
DR. M. DANISH, UNIKL MICET, ALOR GAJAH, MELAKA 32
( c o m m o n n a m e : s ty r e n e ) (c o m m o n n a m e : to lu e n e ) (common name: TNT)
Naming monosubstituted benzene
F Cl NO2
Aniline Phenol
Benzoic acid Benzaldehyde
(aminobenzene) (hydroxylbenzene)
(phenylmethanal)
Cl
Br 1
6 2
1
6 Br
1,2-dibromobenzene 3
2 5
or 4
5
3 o-dibromobenzene
4 Cl
1,4-dichlorobenzene
CH3 or
1 1,3-dimethylbenzene p-dichlorobenzene
6 2 or
5 3 m-dimethylbenzene
4 CH3
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PRIORITY OF
FUNCTIONAL GROUPS IN
A COMPOUNDS
NO2
CH3 COOH
H3C
Br
CH3 OH
1 1
6 NO2 6 Br
2 2
5 3 5 3
4 4
NO2 NO2
2,4-dinitromethylbenzene 2-bromo-4-nitrophenol
or
2,4-dinitrotoulene
COOH
1
6
3,5-dihydroxybenzoic acid
2
5 3
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HO 4 OH DR. M. DANISH, UNIKL MICET, ALOR GAJAH, MELAKA 38
When benzene ring is attached to a carbon chain containing other functional
group, the benzene ring is named as a substituent.
1 2 3 4
CH2CH=CHCH3 C6H5 -, phenyl
1-phenylbut-2-ene
benzyl chloride
If a compound is composed of a benzene ring and one saturated chain, the compound is
named as a derivative of the larger structural unit.
If the chain is unsaturated, it is usually named as derivatives of the unsaturated compound
even if it has fewer carbon atoms
Substitution reactions
(leaving group)
Bromobutane Butanol Bromide ion
Ethene Bromoethane
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ELIMINATION REACTION
Removal of atoms or groups of atoms from a saturated molecule to form an
unsaturated molecule.
Dehydration of alcohol
H2SO4
CH3CH2CH2CH2–OH CH3CH2CH=CH2 + H2O
Butanol Butene
Tautomerism of keto-enol
OH O
Propenol Propanone
Nitration reactions
Sulfonations reactions
Friedel-Crafts Alkylation
Friedel-Crafts Acylation
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HALOGENATION REACTIONS
the reaction occurs in the presence of Lewis acid catalyst such as Fe X3, AlX3 (x=
Cl or Br).
the catalyst polarized the halogen molecule and acts as an electrophile.
X
+ X2 Fe or FeX3
+ Br2 FeBr3
NO2
H2SO4 (conc.) + H2O
+ HNO3
heat
EXAMPLE:
CH2CH3
+ CH3CH2Cl AlCl3
+ HCl
Benzene Chloroethane
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Ethylbenzene DR. M. DANISH, UNIKL MICET, ALOR GAJAH, MELAKA 57
FRIEDEL-CRAFTS ACYLATION
O
Two common acyl groups are the acetyl group and the
benzoyl group. O O
CH 3C C
acetyl group
(ethanoyl group) Benzoyl group
In the presence of anhydrous aluminium chloride, benzene react with acyl
group to form ketone.
O O
AlCl 3
+ CH 3C Cl 80C C CH 3 + HCl
acetyl chloride
ketone
1. Activating group
G
is the electron donating group that
cause the ring to be more reactive
than benzene.
2. Deactivating group
G
is the electron withdrawing group
that cause the ring to be less
reactive than benzene.
Groups that effect the orientation
1. Ortho-para director
2. Meta director
CH3 CH3
CH3 NHO3 / H2SO4 NO2
heat and
methylbenzene
Ortho-para director NO2
NO2
NO2 NHO3 / H2SO4
heat NO2
nitrobenzene
meta director
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3/9/2018 DR. M. DANISH, UNIKL MICET, ALOR GAJAH, MELAKA 66
ADDITIONAL PROBLEMS
1. Write structural formulas for each of the following;
CH3 Br OH
Br
O 2N NO 2
Br o-dibromobenzene 3,5-dinitrophenol
p-bromotoluene
Benzyl bromide
tert-butylbenzene
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