Alkanes, Alkenes, Alkyne and Aromatic Compounds

1.
2 ALKANES AND
CYCLOALKANES
PREPARED BY
SYED ABDUL ILLAH ALYAHYA
UNIVERSITI TEKNOLOGI MARA
PUNCAK ALAM CAMPUS
1.2 ALKANES AND CYCLOALKANES
Introduction to Hydrocarbons
Alkanes and Cycloalkanes
Nomenclature of Alkanes and Cycloalkanes
Reactions of Alkanes and Cycloalkanes
Alkenes and Cycloalkenes
Nomenclature of Alkenes and Cycloalkanes
Reactions of Alkenes and Cycloalkenes
Alkynes
Nomenclature of Alkynes
Reactions of Alkynes
Aromatic hydrocarbons and Nomenclature
2
Hydrocarbons contain only C and H
aliphatic or aromatic
Insoluble in water
no polar bonds to attract water molecules
Aliphatic hydrocarbons
saturated or unsaturated aliphatics
saturated = alkanes, unsaturated =
alkenes or alkynes
may be chains (no rings or acyclic) or
rings (cyclic e.g :cycloalkanes is alcyclic).
chains may be straight or branched
Aromatic hydrocarbons
3
1.2 Alkanes and Cycloalkanes

Alkanes
Alkanes are saturated hydrocarbons
Single bonds with C-C and C-H
Formula :CnH2n+2 n= integer 1,2,3,4.
Carbon can form sp3 hybridized
Aliphatic (Greek aleiphas = fat) thus, like fat

Alkanes
Methane, CH4
H
H C H
1
Ethane, CH3CH3
H H
H C1 C2 H
H H
2
1
6

Alkanes
Propane, CH3CH2CH3
H H H
H C 1 C2 C 3 H
H H H
Butane, CH3CH2CH2CH3
H H H H
H C1 C 2 C 3 C 4 H
H H H H
4
3
7

Alkanes
Straight chain alkanes
Butane, CH3CH2CH2CH3
Pentane, CH3CH2CH2CH2CH3
Hexane, CH3CH2CH2CH2CH2CH3
Heptane, CH3CH2CH2CH2CH2CH2CH3
Octane, CH3CH2CH2CH2CH2CH2CH2CH3
Nonane,CH3CH2CH2CH2CH2CH2CH2CH2CH3
Decane, CH3CH2CH2CH2CH2CH2CH2CH2CH2CH3
Alkanes
Branch chain alkanes

CH3
CH3CHCHCH3
CH3
CH3 CH3
CH3CH2CHCH2CHCH2CH3

Alkyl Groups
Alkyl group remove one H from an alkane (a
part of a structure)
General abbreviation R (for Radical, an
incomplete species or the rest of the
molecule)
Name: replace -ane ending of alkane with -yl
ending
CH3 is methyl (from methane)
CH2CH3 is ethyl from ethane
See page 84 - 85
10

Alkyl groups
Carbon Substituent
Structural Formula
Methyl
Me
-CH3
Ethyl
Et
-CH2CH3
Propyl
Pr
-CH2CH2CH3
Butyl
Bu
-CH2CH2CH2CH3
Pentyl
-CH2CH2CH2CH2CH3
Hexyl
-CH2(CH2)4CH3
Heptyl
-CH2(CH2)5CH3
Octyl
-CH2(CH2)6CH3
Nonyl
-CH2(CH2)7CH3
10
Decyl
-CH2(CH2)8CH3
See page 84 - 85
11
1.2 Alkanes And Cycloalkanes

Alkyl Groups
See page 84 - 85
12

Alkane Nomenclature
How many carbons?
Prefix Parent - Suffix

Where and what are
substituents?
See page 81 - 86
What is the primary

functional group?
13

Alkane Nomenclature Highly Branched
Step 1: Find the parent hydrocarbon chain
a) Find the longest continuous chain of carbon atoms as
the parent compound. Doesnt matter whether the
carbon skeleton is drawn in an extended straight-chain
form or in one with many bends and turns
CH2CH3
CH3CH2CH2CH
CH3
Named as a substituted hexane
CH2CH3
H3C
CHCH
CH2CH3 Named as a substituted heptane
CH2CH2CH3
14

b) If two different chains or equal length are present,
choose the one with the larger number of branch points
as the parent
CH3
CH3
CH3CHCHCH2CH2CH3
CH3CHCHCH2CH2CH3
CH2CH3
CH2CH3
Named as a hexane
with two substituents
YES
Named as a hexane
with one substituent
NOT
15

Step 2: Number the atoms in the main chain
a) Beginning at the end nearer the first branch point,
number each carbon atom in the parent chain.
2 1
CH2CH3
H3C
4
CHCH
3
CH2CH3
CH2CH2CH3
5 6 7
YES
H3C
6
7
CH2CH3
4
CHCH CH2CH3
5
CH2CH2CH3
3 2 1
NOT
The first branch occurs at C3 in the proper system of

numbering, not at C4
16

Step 2: Number the atoms in the main chain

b) If there is branching an equal distance away from both
ends of parent chain, begin numbering at the end nearer
the second branch point
8 9
CH2CH3
H3C
2 1
CH2CH3
CH3 CH2CH3
CHCH2CH2CH
7 6 5 4
YES
CHCH2CH3
3 2 1
H3C
CH3 CH2CH3
CHCH2CH2CH
3 4 5 6
CHCH2CH3
7 8 9
NOT
17

Step 3: Identify and number the substituents
a) Assign a number, called a locant, to each substituent
to locate its point of attachment to the parent chain.
8 9
CH2CH3
H3C
CH3 CH2CH3
CHCH2CH2CH
7 6 5 4
CHCH2CH3
3 2 1
Substituents :
on C3 , CH2CH3
on C4 , CH3
on C7 , CH3
Named as a nonane
(3-ethyl)
(4-methyl)
(7-methyl)
18

Step 3: Identify and number the substituents
b) If there are two substituents on the same carbon, give
both the same number. There must be as many numbers
in the name as there are substituents
CH3 CH3
4
CH3CH2CCH2CHCH3
3 2 1
5
6
CH2CH3
Substituents :
Named as a hexane
on C2 , CH3
on C4 , CH3
on C4 , CH2CH3
(3-methyl)
(4-methyl)
(4-ethyl)
19

Step 4: Write the name as a single word
Use hyphens (-) to separate the different prefixes, and
use comma to separate numbers
If two or more substituents are present, cite them in
alphabetical order
If two or more identical substituents are present, use
prefixes di-, tri-, tetra, and so forth
20

Step 4: Write the name as a single word
8 9
CH2CH3
CH3
3
CH3CHCHCH2CH2CH3
1 2
4 5 6
CH2CH3
3-Ethyl-2-methylhexane
H3C
CHCH2CH2CH
7 6 5 4
CH2CH3
4-Ethyl-2,4-dimethylhexane
CHCH2CH3
3 2 1
3-Ethyl-4,7-dimethylnonane
2 1
CH2CH3
CH3 CH3
4
CH3CH2CCH2CHCH3
3 2 1
5
6
CH3 CH2CH3
H3C
4
CHCH CH2CH3
3
CH2CH2CH3
5 6 7
4-Ethyl-3-methylheptane
21

Step 5: Name a complex substituent as though it
were itself compound
CH3
6
3
CH3CHCHCH2CH2CH
4 5
1 2
CH3
CH3
CH3
CH2CHCH3
1' 2' 3'
CH2CH2CH2CH3
7 8 9 10
2,3-Dimethyl-6-(2-methylpropyl)decane
or
2,3-Dimethyl-6-isobutyldecane
H3C
H
C
1'
CH3
2'
CH3CH2CH2CHCH2CH2CH3
1 2 3 4 5 6
7
-CH2CHCH3
2-methylpropyl group
or
Isobutyl
4-(1-Methylethyl)heptane
or
4-Isopropylheptane
22

For historical reasons, some of the simpler branchedchain alkyl groups also have nonsystematic, common
names
Three-carbon alkyl group
23

Four-carbon
alkyl
groups
24

When writing an alkane name, the nonhyphenated
prefix iso is considered part of the alkyl group name for
alphabetizing purpose, but the hyphenated and
italicized prefixes, sec and tert are not
2'
CH3
8 9
CH2CH3 H3C
H3C
C
1'
CH3
CHCH2CH2CH2 CHCH2CH3
7 6 5 4
3 2 1
3-(1,1-Dimethylethyl)-7-methylnonane
or
3-tert-Butyl-7-methylnonane
H3C
2 1
CH2CH3
4 5 6 7 8
CHCHCH2CH2CH2CH3
3
2CH3
1' CHCH
2' 3'
CH3
4-(1-Methylpropyl)-3-methyloctane
or
4-sec-Butyl-3-methyloctane25

Exercise 7 :Give IUPAC names for the following
compounds
(a)
CH2CH(CH3)2
CH3CHCH2CH2CHCH2CH2CH3
CH3
CH3
(CH3)2CHCH2CHCH3
CH3
CH3CHCH2CHCHCH2CHCH2
CH3
(c)
CH2CH3
(b)
(d)
CH2CH3
CH3
C(CH3)3
CH3CH2CHCHCH2CH2CH2CH2CH2CH3
CH2CH3
26

Exercise 8 : Draw structures corresponding to the
following IUPAC names
(a) 3,4-Dimethylnonane
(b) 3-Ethyl-4,4-dimethylheptane
(c) 2,2-Dimethyl-4-propyloctane
(d) 2,2,4-Trimethylpentane
(e) 4-Ethyl-5-isopropyl-3,6-dimethyloctane
27

Cycloalkanes
Saturated cyclic hydrocarbons are called cycloalkanes, or

alicyclic compounds (aliphatic cyclic)
Because ring is consist of -CH2- units, they have general
formula (CH2)n or CnH2n
cyclopropane
cyclobutane
cyclopentane
cyclohexane
28

Nomenclature of Cycloalkanes
Count the number of carbon atoms in the ring and the
number in the largest substituent chain
If the number of carbon atoms in the ring is equal to or
greater than the number in the substituent, the
compound is named as an alkyl-substituted cycloalkane.
If the number of carbon atoms is the largest substituent
is greater than the number in the ring, the compound is
named as a cycloalkyl-substituted alkane.
29

CH2CH2CH2CH3
CH2CH2CH3
5-carbons
3-carbons
Propylcyclopentane
1-Cyclobutylpentane
3-carbons
4-carbons
1-Cyclopropylbutane
Hexylcyclohexane
30

Step 2 : Number the substituents, and write the name
For an alkyl- or halo-substituted cycloalkane, choose a
point of attachment as carbon 1 and number the
substituent on the ring so that the second substituent has
as low a number as possible.
CH3
CH3
CH3
CH3
1,3-Dimethylcyclohexane
1,5-Dimethylcyclohexane
YES
NOT
Lower
Higher
31

If ambiguity still exists, number so that the third or fourth
substituent has a low a number as possible, until a point
of difference is found.
CH2CH3
CH2CH3
H3C
6
H3C
1
2
CH3
1-Ethyl-2,6-dimethylcycloheptane
Higher
3
4
CH3
Higher
WRONG!!!!!
32

CH2CH3
H3 C
2
4
CH3
Lower
Lower
CORRECT
33

(a) When two or more different alkyl groups that could
potentially receive the same numbers are present,
number them by alphabetical priority.
CH3
CH3
3
4
5
1
CH2CH3
YES
5
1-Ethyl-2-methylcyclopentane
CH2CH3
3
NOT
2-Ethyl-1-methylcyclopentane
34

(b) If halogens are present, treat them just like alkyl
groups
CH3
CH3
2
2
Br
YES
1-Bromo-2-methylcyclobutane
Br
NOT
2-Bromo-1-methylcyclobutane
35

Step 2 : Number the substituents, and write the
name
(c) Some additional examples follow:
Cl
Br
CH3
H3CH2C
CH3
1-Bromo-3-ethyl-5-methylcyclohexane
CH2CH3
1-Chloro-3-ethyl-2-methylcyclopentane
36

Exercise 9 : Give IUPAC names for the following
cycloalkanes
Br
CH3
CHCH2CH3
H3C
C(CH3)3
Br
CH3
CH2CH3
37

Exercise 10 : Draw structures to the following IUPAC
names
(a) 1,1-Dimethylcyclooctane
(b) 3-Cyclobutylhexane
(c) 1,2-Dichlorocyclopentane
(d) 1,3-Dibromo-5-methylcyclohexane
38

Properties of Alkanes
Alkanes is saturated hydrocarbon therefore they do
not react as most chemicals
Burning in flame produce carbon dioxide and water
React with chlorine Cl2 in a presence of light to
replace Hs with Cls
Boiling point increases as the number of carbon
increases
Dispersion forces increases as the molecular size
increases, resulting melting point and boiling point
increases
39

Properties of Alkanes and Cycloalkanes
40

Properties of Alkanes and Cycloalkanes
41

..
..
Cl
..
..
..
Cl
..
H
H C Cl
H
H
H C Cl
..
..
.. . + . ..
Cl
Cl
..
..
H
..
..
H C . + . Cl
..
H
H
H C
Chlorine radical
Methyl radical
..
.
.
+ . Cl
.. .
Carbocation
-.
H C H
H C. +
H+
Carbanion
42

Free Radical Substitution Reaction
replace H with a halogen atom
initiated by addition of energy in the form of heat or
ultraviolet light
to start breaking bonds
generally get multiple products with multiple

substitutions through chain reactions
H
H C H + Cl
H
Cl
Heat OR
UV light
H
H C Cl
HCl
H
43

Chlorination of Methane
Methane reacts with chlorine in the presence of heat
or light to produce a mixture of products through a
sequence of substitution reactions in which the H
atoms are successively replaced by Cl atoms.
CH4 + Cl2
heat or light
CH3Cl + HCl
Cl2
CH3Cl , chloromethane
CH2Cl2 , dichloromethane
CHCl3 , trichloromethane
CCl4 , tetracloromethane
CH2Cl2 + HCl
Cl2
CHCl3 + HCl
Cl2
CCl4 + HCl
44

Free Radical Substitution
The breaking of a covalent bond so that each atom
retains one of the shared electrons will produce two
free radicals.
Free radicals are very reactive. They are
intermediates in reaction mechanism.
The substitution reactions of alkanes follow the free
radical mechanism, which involved three major steps:
1. Initiation: Initial production of free radicals
2. Propagation: Free radicals attack molecules to
produce another free radical
3. Termination: Two free radicals combine to form a
molecule
45
Mechanism of Free Radical substitution

a) Initiation
Dissociation of a chlorine molecule into two chlorine atoms
Cl
2 Cl
Cl
b) Chain propagation
The Cl free radical attacks the CH4 molecule to give a methyl free radical
Step 1: Hydrogen atom is removed from methane by a chlorine atom
H
H
H
Cl
Cl
Step 2: Reaction of methyl radical with molecular chlorine

H
H
Cl
Cl
C
H
Cl
Cl
H
46
Mechanism of Free Radical substitution

c) Termination
Free radicals combine to produce molecules and reaction stops
H
H
H
+
H
Cl
C
H
H
H
Cl
47

Exercise 11 : Write the free radical substitution
mechanism for the monochlorination of the following
molecules.
(a)Ethane
(b)Cyclopropane
48
1.3 Alkenes And Alkynes

Also known as olefins
Aliphatic, unsaturated
C=C double bonds
Formula for one double bond = CnH2n
subtract 2 H from alkane for each double bond
Trigonal shape around C
flat
Polyunsaturated = many double bonds
49

H
H
H
C C
H
H
C
H
H
C
propene = propylene
used to make polypropylene
ethene = ethylene
produced by ripening fruit
used to make polyethylene
50

Straight chain alkenes
Alkenes
Ethene
Propene
1-Butene
2-Butene
1-Pentene
2-Pentene
1-Hexene
2-Hexene
3-Hexene
Structural Formula
CH2=CH2
CH2=CHCH3
CH2=CHCH2CH3
CH3CH=CHCH3
CH2=CHCH2CH2CH3
CH3CH=CHCH2CH3
CH2=CHCH2CH2CH2CH3
CH3CH=CHCH3CH2CH3
CH3CH3CH=CH2CH2CH3
51

Cyclopropene
Cyclopentene
Cyclobutene
Cyclohexene
52

Alkene Nomenclature
Find the longest, continuous C chain that contains
the double bond and name the compound
accordingly, using the suffix -ene
H
CH2CH3
C
H
C
YES
CH2CH2CH3
Named as pentene
CH2CH3
NOT
CH2CH2CH3
as hexene, since the double bond is

not contained in the six-carbon chain
53

Alkene Nomenclature
Step 2: Number the carbon atoms in the chain
Begin at the end nearer the double bond, or if the double
bond is equidistant from the two ends, begin at the end
nearer the first branch point.
CH3
CH3CHCH
1 2 3
CH3
YES
CHCH2CH3
4 5 6
CH2CH3
CH3CHCH2CH CHCHCH2CH3
1 2 3 4 5 6 7 8
CH3
CH3CHCH
6 5 4
CH3
NOT
CHCH2CH3
3 2 1
CH2CH3
8
7 6 5
4 3 2 1
54

Alkene Nomenclature
Step 3: Write the full name
Indicate the position of the double bond by giving the
number of the first alkene carbon and placing that
number directly before the parent name.
Number the substituents according to their positions in
the chain
CH3
CH3CHCH
1 2 3
CHCH2CH3
4 5 6
At C3 : double bond, 3-hexene

At C2 : substituent, CH3 (2-methyl)
2-Methyl-3-hexene
55

Alkene Nomenclature
Write the name in the following order
If more than one substituent attached to main chain
number of first alphabetical substituent: use prefixes to indicate multiple identical substituents
repeat for other substituents
CH3
CH2CH3
CH3
CH3
1
2 3 4
5 6 7 8
CH3CH2CHCH
7 6 5 4
At C4 : double bond, 8-octene

At C2 : substituent, CH3 (2-methyl)
At C6 : substituent, CH2CH3 (6-ethyl)
At C3 : double bond, 3-heptene

At C2 and C5 substituent, CH3 (2-methyl)
6-Ethyl-2-methyl-4-octene
CHCHCH3
3 2 1
2,5-Dimethyl-3-heptene
56

Alkene Nomenclature
Newer naming system for alkenes : but this change has
not been widely accepted by the chemical community.
However well stay with older name. But you may
occasionally encounter the newer system.
CH3
CH2CH3
1 2 3 4 5 6 7 8
CH3
CH3CH2CHCH
7 6 5 4
CH3
CHCHCH3
3 2 1
Older naming system : 6-Ethyl-2-methyl-4-octene
2,5-Dimethyl-3-heptene
Newer naming system : 6-Ethyl-2-methyloct-4-ene
2,5-Dimethylhept-3-ene
57

Exercise 12 : Give IUPAC names for the following
compounds
CHCH
3 3
H2C
CH2CH2CH3
CHCHCCH3
CH3CH2C
CH2CH3
CCH2CH2CH3
CH3
CH3
(a)
HC
CCH2CH2CHCH3
CH3
CH3
(b)
(c)
CH3
CH3
CH3
CH3
CH3
CH3
(d)
CH
(e)
(f)
58

Exercise 13 : Draw structures to the following IUPAC
names
a) 3-Ethyl-2,2-dimethyl-3-heptene
b) 3,4-Diisopropyl-2,5-dimethyl-3-hexene
c) 3-Ethyl-4,4-dimethylcyclopentene
d) 6-Chloro-3,4-dimethylcyclohexene
59

Cycloalkenes Nomenclature
Cycloalkenes are named similarly to open-chain alkenes,
but because there is no chain end to begin from, so we
number the cycloalkenes so that the double bond
between C1 and C2 and the first substituent has as low a
number as possible
CH3
6
5
4
CH3
1
5
4
1
3
1-Methylcyclohexene
CH3
1,5-Dimethylcyclopentene
60

Geometric Isomerism
Because the rotation around a double bond is highly
restricted, you will have different molecules if groups
have different spatial orientation about the double
bond
This is often called cistrans isomerism
When groups on the doubly bonded carbons are cis,
they are on the same side of the double bond
When groups on the doubly bonded carbons are trans,
they are on opposite sides
61

cis/trans Isomers
R
C C
C C
H
All substituents are

on one side
of bond
All substituents are

on different sides
of bond
62

Geometric Isomerism
The cis and trans isomers are
different molecules with
different properties.
See page 110 - 111
63

Relative Stabilities of Alkenes
The stability of alkenes depends upon number of
substituents bonded to sp2 carbon
R
<
C C
H
<
C C
R
<
C C
H
R
H
<
C C
H
<
C C
R
R
C C
The more substituents, the more stable
See page 114 - 116
64
Relative Stabilities of Alkenes

Steric repulsion is responsible for energy differences
among the disubstituted alkenes
H3C
>
C C
H3C
H3C
>
C C
H3C
CH3
1-butene
H
C C
CH3
trans 2-butene
C
C
C
C
mono-substituted
See page 114 - 116
disubstituted
65

Cycloalkene Nomenclature with Cis and Trans
H3CH2CH2C
CH3
H3CH2CH2C
C C
H
H
C C
Cis-2-hexene
CH3
CH3
Trans-2-hexene
CH3
CH2CH3
Trans-1-ethyl-2-methylcyclopent-1-ene
CH2CH3
Cis-1-ethyl-2-methylcyclopent-1-ene
66

How to give a name to the alkenes with more than two
substituents
H3CH2CH2C
CH3
H3CH2CH2C
C C
H3C
H
C C
Cis-3-methyl-2-hexene
This compound is cis

but the two methyl
groups are trans to each other.
H3C
CH3
Trans-3-methyl-2-hexene
This compound is trans

but the two methyl
groups are cis to each other.
67

HMW
HMW
H3CH2CH2C
HMW
CH3
LMW
H3CH2CH2C
C C
LMW
H3C
H
C C
LMW
Cis-3-methyl-2-hexene
LMW
H3C
CH3
HMW
Trans-3-methyl-2-hexene
HMW is high molecular weight

LMW is lower molecular weight
This compound named as cis
because the propyl group and
methyl group are higher molecular
weight and at the same side
This compound named as trans

because the propyl group and
methyl group at opposite side
68

Exercise 14 : Tell whether each of the following pairs is
isomer or not isomer
a
H3C
H
=
C C
H
c
H3C
C C
CH3
CH3
H3CH2C
=
CH3
C C
CH2CH3
H3C
H
C C
CH3
C C
CH2CH3
H3CH2C
H3C
H
C C
H3C
CH3
H3C
H
C C
H3C
b
H3C
CH3
C C
H
69

Exercise 15 : Which pair is more stable
H3CH2C
a
C C
H
H3CH2C
C C
or
H
CH3
CH3
CH3
H
CH3
or
70

Exercise 16 : Arrange of isomeric alkenes in order of
stability
a
71

Physical Properties of Alkenes and Cycloalkenes
72

Reactions of Alkenes
Alkenes are relatively more reactive than
alkanes.
The electron-rich double bond is the active site
or the functional group of the molecule .
Electrophilic Addition Reactions

An addition reaction is a reaction in which an
unsaturated molecule becomes saturated by the
addition of a molecule across a multiple bond.
73

74

Electrophilic Addition Reactions
1. Catalytic Hydrogenation
2. Halogenation
3. Halohydrin
4. Hydration
5. Hydrohalogenation
C C
X-Y
C C
X Y
75

1. Catalytic Hydrogenation of Alkenes
Alkenes and hydrogen react in the presence of a
catalyst to form alkanes.
H
H
C C
H
Ethene
H2
Ni
H H
H C C H
H H
Ethane
Addition of H-H across C=C

Reduction in general is addition of H2 or its equivalent
Requires Pt /Pd/Ni/Rh as powders on carbon and H2
Hydrogen is first adsorbed on catalyst
Reaction is heterogeneous (process is not in solution)
76
Mechanism of Catalytic Hydrogenation of Alkenes

Heterogeneous reaction between phases
Addition of H-H is syn
77

Exercise 17 : The reaction below undergoes catalytic
hydrogenation. Draw the product that formed from
hydrogenation.
H2
Pt
H2
Ni
H2
Pd
78

2. Halogenation of Alkenes
Addition of Halogen in inert solvent
Halogens dissolved in an inert solvent such as
carbon tetrachloride, react readily with alkenes at
room temperature and even in the dark.
H
H
C C
H H
Br2
inert solvent
Br
C C Br
H H
Bromine and chlorine add rapidly to alkenes to give

1,2-dihalides, a process called halogenation
F2 is too reactive and I2 does not add
Cl2 reacts as Cl+ Cl- same goes to Br2
79

2. Halogenation of Alkenes
Addition of Br2 to Cyclopentene
Addition is exclusively trans
..
Br
..
Br
Br
Br
..
..
..
Br
..
Br
H
trans-1,2-Dibromocyclopentane
sole product
H
H
cis-1,2-Dibromocyclopentane
NOT formed
80

Halogenation of Alkenes
Exercise 18 : Write the mechanism for the below
reaction by showing the formation of bromonium ion
H Br Br
H3C C C CH2 + Br2

CH3H
+ Br2
CHCl3
0o
CHCl3
0o
H3C C C CH2
CH3H
Br
Br
81

3. Halohydrin of Alkenes
Addition of Halogen in water
This is formally the addition of HO-X to an alkene to
give a 1,2-halo alcohol, called a halohydrin
The actual reagent is the dihalogen (Br2 or Cl2 in water
in an organic solvent)
H
H
C C
H
Ethene
H H
Br2
H2 O
HO C C Br
H H
2-bromoethanol
(Bromohydrin)
82

Chlorine or bromine dissolved water reacts with
alkene to produce halohydrin as the major product.
Br2(aq) + H2O(l) HBr(aq) + HOBr(aq)
Note: The red-brown colour of the bromine solution will disappeared.
For asymmetric alkene such as propene, the addition of

bromide ion to the carbon less substituent and addition
of hydroxide ion to the highly substituted carbon
CH3
C C
Br2
H2O
H CH3
Br
C C OH
H H
83

Halogen addition in presence of water is
regioselective : Markonikovs rule
The electrophile (Cl or Br) adds to the less substituted
end of double bond, and nucleophile (H2O) adds to the
more substituted end
Carbon with more substituted, OH attached
(H3C)2HC
H
C C
3-methylbutene
OH Br
Br2
H2O
(H3C)2HC C C H
H H
1-bromo-3-methyl-2-butanol
Carbon with less substituted, Br attached
84

Exercise 19 : Give the structure of the major product
formed when each of the following alkenes react with
bromine in water.
(a)
Br2
H2O
(b)
Br2
H2O
(c)
Br2
H2O
85

4. Hydration of Alkenes
Addition with acidified water (H3O+) :
Addition of H and OH groups from a water molecule to a

double bond will produce an alcohol. The reaction is
facilitated by using an acid as a catalyst.
H
C C
H
Ethene
H3O
H H
H C C OH
H H
Ethanol
Note: Hydration of alkenes using concentrated H2SO4

followed by hydrolysis, would give the same results.
86

4. Hydration of Alkenes
For asymmetric alkene such as propene, the addition of
hydrogen atom to the carbon less substituent and
addition of hydroxide ion to the highly substituted carbon
H3CH2C
H
C C
H
1-butene
H3O
OH H
H3CH2C C C H
H H
2-butanol
87

Mechanism of Hydration of Alkenes
The E+ adds to the
sp2 carbon that
H3CH2C
H
bonded to greater
C C
numbers of
H
H
hydrogens
H O+ H
H
The Nu- adds to

H3CH2C
H
carbocation,
H O H
C+ C H
forming a
protonated
H
H
alcohol.
Protonated alcohol is
very strong acid, so it
loses a proton, so form
final product is alcohol.
H3CH2C
C+ C H + H2O
H
H
H H
H O H
+
H3CH2C O H
C C H
H
H
HO
H
H3CH2C C C H
H
H
H3O+
88

Exercise 20 : What is the product formed from each
reaction
H3O+
H2O
H+
H2SO4
Diluted
89

Addition of Hydrogen Halides
Addition reaction of alkenes with hydrogen halides (HX)
form haloalkanes (alkyl halides)
Relative reactivity of HX towards alkenes increases in

the order of HF < HCl < HBr < HI
H
C C
H
Ethene
See page 138 - 141
HBr
H H
Br
C C H
H H
Bromoethane
90

Addition of Hydrogen halides
H
H
C C
H H
H Br
CCl4
H C C Br
H H
H Br
aqueous
Br
H
H3CH2C
H
C C
See page 138 - 141
H3C
H Br
H Br H
H3C C C C H
CCl4
H CH3H
91

Mechanism of Hydrohalogenation
General reaction
H3C
H
H Br
mechanism:
C C
electrophilic addition H3C
H
Attack of electrophile
2-methylpropene
(such as HBr) on
bond of alkene
Produces carbocation
H3C
H
Brand bromide ion
C+ C H
Carbocation is an
H3C
H
electrophile, reacting
Carbocation
with nucleophilic
bromide ion
H3C
C+ C H
H3C
H
Carbocation
Br H
H3C C C H
CH3H
2-bromo-2-methylpropane
92

Mechanism of Hydrohalogenation
H
C C
H Br
CCl4
H Br
aqueous
See page 138 - 141
..
.. Br-..
..
H H
H C C+
H H
H H
H C C Br
H H
..
.. Br-..
..
+
Br
H
H
93

If HX prepared in aqueous, the same product also
formed,
CH3
Br
H Br
H2O
CH3
H
1-methylcyclohexene
1-bromo-1-methylcyclohexane
H Br
Br
H2O
ethylidenecyclopentane
1-bromo-1-ethylcyclopentane
94

The reaction is successful with HCl as well as HI
HI is generated from KI and phosphoric acid
Cl
Br H
H3CH2C
H
HCl
H3CH2C C C H
C C
H3C
H Ether
CH3H
2-methyl-1-butene
H3CH2CH2C
H
C C
H
1-pentene
2-bromo-2-methylbutane
KI
H3CH2CH2C C C H
H3PO4
H H
2-iodopentane
95
Orientation of Electrophilic Addition:

Markovnikovs Rule
In an unsymmetrical alkene, HX reagents can add in
two different ways, but one way may be preferred over
the other
If one orientation predominates, the reaction is
regiospecific
Markovnikov that in the addition of HX to alkene, the H
attaches to the carbon with the most Hs and X
attaches to the other end (to the one with the most
alkyl substituents)
This is Markovnikovs rule
Br
H
HBr
CH3CH2CH2CH C
H
1-pentene
CH3CH2CH2CH C
H
H
+ CH3CH2CH2CH C
Br
Ether
H
2-bromopentane
Sole product
H
1-bromopentane
NOT FORMED
96

Addition of HBr to 1-pentene
Regiospecific one product forms where
two are possible
H
H
1-pentene
Primary carbocation
1-bromopentane
Br
NOT FORMED
HBr
CH3CH2CH2CH C
CH3CH2CH2CH C
CH3CH2CH2CH2 C+
Ether
H
CH3CH2CH2C+HCH
Br
CH3CH2CH2CH C
H
Secondary carbocation
H
2-bromopentane
Sole product
97
Markovnikovs Rule
Addition HBr to 2-methylpropene
More highly substituted carbocation forms as
intermediate rather than less highly substituted one
Tertiary cations and associated transition states are
more stable than primary cations
H
H3C
CH3
H3C
H
C
H3C
H3C
C+
Primary carbocation
Br
CH3 H
1-bromo-2-methylpropene
NOT FORMED
HBr
Ether
H3C
Br
H
H3C
2-methylpropene
CH3 H
Tertiary carbocation
CH3 H
2-bromo-2-methylpropane
Sole product
98
Markovnikovs Rule
Addition HBr to 2-methyl-2-butene
If both ends have similar substitution, then not
regiospecific two products formed
This carbon contains
two alkyl groups
This carbon contains

one alkyl group
H3C
CH3
CH3
H3C
CH3
C
H3C
H3C
C+
CH3
Br
CH3 H
HBr
C
H
Ether
H3C
C+
CH3
H3C
Br
CH3
2-methyl-2-butene
CH3 H
CH3 H
99
Carbocation Structure and Stability

Carbocations are planar and the tricoordinate carbon
is surrounded by only 6 electrons in sp2 orbitals
The fourth orbital on carbon is a vacant p-orbital
The stability of the carbocation (measured by energy
needed to form it from R-X) is increased by the
presence of alkyl substituents
100
Inductive Stabilization of Cation Species

In tertiary carbocation,
all alkyl groups stabilize
carbocations by
releasing electron
density to the positively
charged carbon, thereby
dispersing the positive
charge. However, in
secondary carbocation,
only two alkyl groups will
releases electron but in
the presence of one
proton will withdraws
electron from positively
charged carbon.
H3C
CH3
CH3
CH3 releases electrons, stabilizes carbocation
H3C
C+
CH3
H
H withdraws electron, destabilizes carbocation
101
Carbocation Structure and Stability
102
Mechanism of Electrophilic Addition:

Rearrangements of Carbocations
Carbocations undergo structural rearrangements
following set patterns - hydride shifts occur
Goes to give more stable carbocation
Can go through less stable ions as intermediates
CH3
H3C
CH
C
H
CH3
H
HBr
C
H
H3C
CH3 H
C+
C+
CH3 Br
CH3 H
Br
H3C
Ether
3-methyl-1-butene
H3C
50%
H3C
50%
103
Predicting Major and Minor Addition Products

When an HX molecule is added to an unsymmetrical
alkene, two possible products can be formed:
If we do not run the experiment, but still we can predict

the major and minor from two possible products based
on
-Markovnikovs rule
-Rearrangement of carbocations (Hydride shifts)
H3C
HCl
C
CHCH3
H3C
2-methyl-2-butene
H3C
Cl
CHCH3
H3C
Cl
CHCH3
Ether
CH3
2-chloro-3-methylbutane
Minor product
CH3
Major product
104
Predicting Major and Minor Addition Products

H
C
H3C
CH3
C
+
CH3
2-methyl-2-butene
Cl
CH3
..
.. Cl-..
..
C+
CH3
CH3
CH3
2o carbocation
CH3
CH3
CH3
Cl
Major product
See page 138 - 141
C+ C
H3C
3o carbocation
CH3CH2C
CH3
CH3CH C
CH3
Cl H
Minor product
105

Exercise 21 : What would the major and minor product
obtained from the addition of HBr to each the following
alkenes?
(a)
(c)
(b)
(d)
106
Unsaturation Tests for Alkenes

Alkenes or unsaturated organic compounds may be
identified using simple lab tests
1. Br2 in inert solvent or dilute bromine water are yellow
brown in colour. The solution is decolorised when added to
an alkene (See: Addition reactions with halogens)
2. Reaction with cold, dilute, alkaline KMnO4 (Baeyers test)
Alkenes are oxidised readily by the Baeyers reagent. The
purple colour of the KMnO4 solution disappears, and a
brown precipitate of Mn(IV) oxide appears. The organic
product is a diol.
OH OH
H3C
KMnO4/OHC
CHCH3
H3C
2-methyl-2-butene
H3C
CHCH3
CH3
2-methylbutane-2,3-diol
107

3. Reaction of Alkenes with hot, acidified KMnO4
Vigorous oxidation of alkenes results in the cleavage of
the double bonds producing ketones, carboxylic acids
or CO2
Potassium permanganate (KMnO4) works if Hs are
present on C=C
In this reaction, the KMnO4 solution is decolourised.
By identifying the products, the position of the double
bond in the alkene can be determined.
108

Example Reaction of Alkenes with hot, acidified KMnO4
H3C
CH2CH3
C
H3C
CH2CH3
C
KMnO4/H+
H3C
KMnO4/H+
CH2CH3
C
H3C
CH2CH3
O
C
OH
C
OH
109

4. Ozonolysis
- Alkene is oxidised by ozone in tetrachloromethane to form
unstable ozonide.
- The ozonide is further hydrolysed to produce aldehydes
and/or ketones.
- Ozonolysis is used to identify the location of the C=C.
H3C
CH2CH3
C C
H3C
O3
H3C
o
cold
CH2Cl2, -78
C
H3C
O O
C
C
O
ozonide
CH2CH3
H
Zn/H2O
CH2CH3
H3C
C O
H3C
2-propanone
O C
+ byproduct
H
propanal
110

Exercise 22: What product(s) formed when each of
compound treated with the following reagents
i) Cold, dilute alkaline KMnO4
ii) Hot acidified KMnO4
iii) O3/CH2Cl2 (cold) and Zn/H2O
111

Alkynes
Aliphatic, unsaturated
CC triple bond
Formula for one triple bond = CnH2n2
subtract 4 H from alkane for each triple
bond
Linear shape
Internal alkynes have both triple bond carbons
attached to C
Terminal alkynes have one carbon attached to
H
112

Alkynes
H C C H
Ethyne
H3C C C H
Propyne
both used in welding torches
113

Straight chain alkynes
Alkenes
Structural Formula
Ethyne
Propyne
1-Butyne
2-Butyne
1-Pentyne
2-Pentyne
1-Hexyne
2-Hexyne
3-Hexyne
CHCH
CHCCH3
CHCCH2CH3
CH3CCCH3
CHCCH2CH2CH3
CH3CCCH2CH3
CHCHCH2CH2CH2CH3
CH3CCCH3CH2CH3
CH3CH2CCCH2CH3
114

1. Find the longest, continuous C chain that contains the

triple bond and use it to determine the base name
H3CH2C
H3CH2CHCH2CHCH2C C C H
8
H3C C CH3
H
Longest carbon chain is 8 so parent name given

as 1-octyne
2. Number the chain and substituents
determine the end closest to the triple bond
if triple bond equidistant from both ends,
number from end closest to the substituents
115

3.
Identify the substituent branches
then assign numbers to each substituent based

on the number of the main chain C it is attached
to.
H3CH2C
8
H3C C CH3
H
there are 2 substituents
one is on the C-4 is called ethyl
the other substituent on the C-6 is called isopropyl
116

4.
write the name in the following order

a) substituent number of first alphabetical substituent
substituent name of first alphabetical substituent
use prefixes to indicate multiple identical
substituents
b) repeat for other substituents
c) number of first C in triple bond name of main
chain
H3CH2C
6
8
H3C C CH3
H
4-ethyl-6-isopropyloctyne
117

4
CH2CH3
H3CH2CHCHC C C H
3
H3CHC 5
CH2CH3
6
7
3,4-diethyl-5-methylheptyne
CH3
CH3
H3CH2CC C C CH2CHCH3
8
7 6
CH3
2,6,6-trimethyl-4-octyne
118

Alkynes undergo many reactions similar to alkenes:
1. Hydrogenation = adding H2
a) alkene or alkyne + H2 alkane
b) generally requires a catalyst
2. Halogenation = adding X2
3. Hydrohalogenation = adding HX
a) HX is polar
b) when adding a polar reagent to a double or triple
bond, the positive part attaches to the carbon
with the most Hs
119

1. Hydrogenation of Alkynes
Addition of H2 over a metal catalyst (such as palladium
on carbon, Pd/C) converts alkynes to alkanes
(complete reduction)
The addition of the first equivalent of H2 produces an
alkene, which is more reactive than the alkyne so the
alkene is not observed
H
H3CH2C C C CH2CH3
3-hexyne
H2
H3CH2C C C CH2CH3
Pd
H
3-hexene
H H
H3CH2C C C CH2CH3
H
3-hexene
H2
Pd
H3CH2C C C CH2CH3
H H
hexane
120

2. Halogenation of Alkynes: Addition of X2
Addition reactions of alkynes are similar to those of
alkenes
Intermediate alkene reacts further with excess
reagent
Regiospecificity according to Markovnikov
Initial addition gives trans intermediate
Product with excess reagent is tetrahalide
121

Halogenation of Alkynes : Addition of
Bromine and Chlorine
H3CH2C C C CH2CH3
3-hexyne
Br2
CH2Cl2
Br
H3CH2C C C CH2CH3
Br
3,4-dibromohex-3-ene
Br
H3CH2C C C CH2CH3
Br
3,4-dibromohex-3-ene
Br2
CH2Cl2
Br Br
H3CH2C C C CH2CH3
Br Br
3,3,4,4-tetrabromohexane
122
3. Hydrohalogenation of Alkynes : Involves

Vinylic Carbocations
Addition of H-X to alkyne
should produce a vinylic
carbocation intermediate
Secondary vinyl
carbocations form less
readily than primary alkyl
carbocations
Primary vinyl
carbocations probably do
not form at all
Nonethelss, H-Br can add to
an alkyne to give a vinyl
bromide if the Br is not on a
primary carbon
123

Mechanism of Hydrohalogenation of Alkynes
Alkynes are electron-rich molecules, thus also
electrophilic addition takes place.
d+ d-
HBr
H C
3
CH
H C
3
3
H C
3
2-butyne
vinyl-carbocation
124

H
H C
3
H
+
H C
3
CH
Br
H C
3
Br
After the addition of the nucleophile we obtain an alkene

that still can be attacked by an electrophile.
125

H
H C
3
CH
Br
d+ d-
HBr
CH
H C
3
Br
Formation of a second carbocation
126

H
H
H3C
CH3
Br
H
H
H3C
CH3
Br
Br
H3C
CH3
Br
Br
Both nucleophiles end up on the same carbon.
127

Hydrohalogenation of Alkynes
Exercise 23 : Proposed the mechanism for the reaction,
when 3-methyl-1-pentyne mixed with 2 mol HBr
+
2 HBr
128
1.4 Aromatic Compound

Aromatic hydrocarbons contain a ring structure that
seems to have C=C, but doesnt behave that way
The most prevalent example is benzene (also called
arenes)
C6H6
Other compounds have the benzene ring with other
groups substituted for some of the hydrogens
H
H
H
H
129

Naming Monosubstituted Benzene Derivatives
O
HO
Benzene
Methylbenzene
Benzaldehyde
HO
Phenol
O
H2N
O
Benzoic acid
Aniline
-
Acetophenone
Anisole
Propylbenzene
Styrene
130
O
N+
Br
O
Bromobenzene
Nitrobenzene

Naming Benzene as a Substituent
When the benzene ring is not the base name, it is
called a phenyl group
Attach to alkyl
group
O
OH
2-phenyl-4-octene
6-phenylheptanoic acid
131

Naming Disubstituted Benzene Derivatives
ortho-xylene
para-xylene
meta-xylene
O
O
HO
m-tert-butylanisole
3-tert-butylanisole
1-tert-butyl-3-methoxybenzene
p-Iodophenol
OCH3
4-methoxybenzaldehyde
132

Naming Disubstituted Benzene Derivatives
Number the ring starting at attachment for first
substituent, then move toward second
order substituents alphabetically
use di if both substituents are the same
CH3
Br
Br
Cl
Cl
1-chloro-3-methylbenzene
1-bromo-2-chlorobenzene
CHO
Br
1,2-dibromobenzene
2-iodobenzaldehyde
133
1.4 Aromatic
Exercise 24 : Name these compound
CHO
NO2
Br
H3C
CH3
134

The Concept of Aromaticity
To be a aromatic, a compound must follows Huckels
criteria.
1. cyclic and conjugate
2. all carbon atoms are sp2 hybridized
3. planar or nearly planar
4. the no of pi electrons in the system is (4n + 2) with
n = 0,1,2,3.
- (4n + 2) = 2,6,10,14,18 .. (aromatic)
- 4n = 4, 8, 12, 16(non-aromatic)
See page 192 - 193
135

The Concept of Aromaticity
Cyclobutadiene
NOT AROMATIC
AROMATIC
See page 192 - 193
Cyclooctatetraene
NOT AROMATIC
NON AROMATIC
Naphthalene
AROMATIC
NON AROMATIC
136

Exercise 25 : Predict whether each of the following
compound below is aromatic or non-aromatic? Explain
Indene
Azulene
137

Alkanes, Alkenes, Alkyne and Aromatic Compounds

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1.

1.2 ALKANES AND CYCLOALKANES

1.2 Alkanes and Cycloalkanes

1.2 Alkanes and Cycloalkanes

1.2 Alkanes and Cycloalkanes

1.2 Alkanes and Cycloalkanes

1.2 Alkanes and Cycloalkanes

Branch chain alkanes

1.2 Alkanes and Cycloalkanes

1.2 Alkanes and Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

Prefix Parent - Suffix

What is the primary

1.2 Alkanes And Cycloalkanes

Named as a substituted hexane

CH2CH3 Named as a substituted heptane

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

The first branch occurs at C3 in the proper system of

1.2 Alkanes And Cycloalkanes

Step 2: Number the atoms in the main chain

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

Saturated cyclic hydrocarbons are called cycloalkanes, or

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

generally get multiple products with multiple

1.2 Alkanes And Cycloalkanes

1.2 Alkanes And Cycloalkanes

Mechanism of Free Radical substitution

Step 2: Reaction of methyl radical with molecular chlorine

Mechanism of Free Radical substitution

1.2 Alkanes And Cycloalkanes

1.3 Alkenes And Alkynes

1.3 Alkenes And Alkynes

1.3 Alkenes And Alkynes

1.3 Alkenes And Alkynes

1.3 Alkenes And Alkynes

as hexene, since the double bond is

1.3 Alkenes And Alkynes

1.3 Alkenes And Alkynes