CHAPTER 1
Introduction to Organic Chemistry
1.1 Introduction
1.2 Hydrocarbon
1.3 Structural Formula
1.4 Classification Of Organic Compounds
1.5 Isomerism
1.6 Basic Reaction In Organic Compounds
1.1 INTRODUCTION
What is organic chemistry?
Organic chemistry is the study of compounds that
contain the element carbon.
Organic Molecules
Most organic molecules are made up of long rings
or chains of carbon atoms with atoms of other
elements attached.
Common elements besides carbon (C) that are
found in organic compounds include hydrogen (H),
oxygen (O), nitrogen (N), phosphorus (P)& sulfur (S)
EXAMPLES :
UREA
DDT GLUCOSE
METHANE
PENICILLIN
1.2 HYROCARBON
The simplest class of organic compounds is
the hydrocarbon.
Hydrocarbon are compounds which contain only
carbon and hydrogen atoms.
Hydrocarbon can be classified into:
i) Saturated and unsaturated
ii) Aliphatic and aromatic
4
Carbon can form 4 covalent bonds with carbons or other elements:
HYDROCARBONS
Saturated Unsaturated
ALKANES /
ALKENES / ARENE
CYCLOALKANES ALKYNES
CYCLOALKANES Contain
contain only Contain C≡C
contain C=C benzene ring
single bond
Aliphatic Aromatic 6
Saturated & unsaturated hydrocarbon
Saturated hydrocarbons contain only single bonds
such as alkanes and cycloalkanes.
Unsaturated hydrocarbons contain multiple bonds such
as alkenes, cycloalkenes, alkynes and aromatic
hydrocarbons.
7
Aliphatic & aromatic hydrocarbon
Aliphatic compound are composed of straight-chained,
branched, or cyclic compounds and can be saturated (alkanes)
or unsaturated (alkenes, alkynes, and others)
Aromatic compounds have one or more conjugated,
benzene or heterocyclic rings within their structures.
“Conjugated” refers to the presence of delocalized (shared)
electrons within the chemical structure, such as benzene.
8
Example
Classify each of the following hydrocarbon.
Saturated / unsaturated Aliphatic / aromatic
CH3CH2CH3
CH3
CH3CH≡CHCH3
9
Answer
Saturated / unsaturated Aliphatic / aromatic
CH3CH2CH3 Saturated Aliphatic
CH3
Unsaturated Aromatic
CH3CH≡CHCH3 Unsaturated Aliphatic
Saturated Aliphatic
Unsaturated Aromatic
Unsaturated Aliphatic
10
1.3 STRUCTURAL FORMULA
Structural formula is a formula that shows how the
atoms of a molecule are bonded to one another
Expanded
Structure
Types of
Structural
Skeletal Formula Condensed
Structure Structure
11
Structural
Description Example : C4H9Cl
formula
Shows all atoms and H H H H
Expanded bonds; bonds are drawn as
H C C C C Cl
structure lines
H H H H
Bonds are not always
shown; subscripts are used CH3CH2 CH2 CH2 Cl
Condensed
to indicate the number of or
structure
identical groups attached to
a particular atom. CH3(CH2)3Cl
Skeletal Shows the carbon skeleton
structure/ and functional groups Cl
Bond-line
formula
12
Example
Draw the expanded, condensed or skeletal structure for the
followings :
Condensed
Expanded Structure Skeletal Structure
Structure
1)
(CH3)2CHOH
2)
Cl
3) H H H H H
H C C C C C H
H H H H H
13
Exercise 1
Rewrite each of the following structures as skeletal
structural formula.
1. O
CH3 CH2 CH2 C CH3
H
2.
H2C CH CH2 CH2C CH CH3
3. H3C CH2 CH CH2 CH2 C OH
CH3 O
4. (CH3)2CHCH2CH2CH(CH3)CH2CH3
14
Exercise 2
Expand the following bond-line representations to
show all the atoms including carbon and hydrogen
c)
a)
OH
d)
b)
15
Exercise 3
Draw the skeletal structural formula for each of the
followings :
a) CH3CH2CH(OH)CH2CH2CH3
b) CH3CH(CH3)CH2CH3
c) CH3CO(CH2)2C(CH3)3
O
d)
C
H2 C CH2
H2 C CH2
C(CH3)2 16
Answer
Example
Condensed
Expanded Structure Skeletal Structure
Structure
H H
OH
1) H C C O H
(CH3)2CHOH
HH C H
H
2) H Cl H
H C C C H (CH3)3CCl
Cl
H H C HH
H
3) H H H H H
H C C C C C H CH3(CH2)3CH3
H H H H H
17
Exercise 1 (answer)
O
1.
2.
O
3.
OH
4.
18
Exercise 2 (answer)
H H
H C H H C H
H H H
a) H C C C C C H
H H H
H
H C H
H
H
H C H
H H C H H H H
b)
H C C C C C C C C H
H H H H H
19
Exercise 2 (answer)
H
c)
H C H
H H
H C C C H
H H
H
C H H H
H
H C C H
d)
O
H C
H C C H H H H
H C
H H C C CC H
H H
H H H
H C H
H
20
Exercise 3 (answer)
C)
a)
OH
b) d)
21
Classification of carbon & hydrogen atoms in
organic molecules
In organic molecules, carbon atom can be
classified as primary (1o), secondary (2o),
tertiary (3o) or quaternary (4o) carbon.
It’s class is depend on the number of other
carbon atoms that are bonded to it.
* Classification of carbon atoms involve only C―C
single bond, C―C multiple bonds cannot be classified
22
Same as carbon atoms, hydrogen atom can
also be classified as primary (1o),
secondary (2o) or tertiary (3o) hydrogen.
However, it’s class is depend on the class
of carbon at which it is attached to.
23
Primary carbon (1oC) and primary hydrogen (1oH)
Atom Description
Carbon 1o Carbon that bonded to one other carbon atom
Hydrogen 1o Hydrogen that bonded to primary carbon
1oC
1oH H
1oH H C CH3
H 1oH
1oH
24
Secondary carbon (2o C) and Secondary
hydrogen (2o H)
Atom Description
Carbon 2o Carbon that bonded to two other carbon atoms
Hydrogen 2o Hydrogen that bonded to a secondary carbon
2 oH 2o C
H
H3C C CH3
H
2 oH
25
Tertiary carbon (3oC) and Tertiary hydrogen (3oH)
Atom Description
Carbon 3o Carbon that bonded to three other carbon
atoms
Hydrogen 3o Hydrogen that bonded to tertiary carbon
3oH 3o C
H
H3C C CH3
CH3
26
Quaternary Carbon (4o)
Atom Description
Carbon 4o Carbon that bonded to four other
carbon atoms
Hydrogen -
CH3 4o C
H3C C CH3
CH3
27
Exercise
Classify the carbon atoms the following
compounds as 1o, 2o and 3o.
i. CH3 CH3
HO C C CH2CH3
CH3
ii.
28
Exercise (answer)
1o 1o
i. CH3 CH3
HO C C CH2 CH3
3o
4o 2o 1o
CH3
1o
2o 2o
o
3o 1o
3
ii.
2o 1o
2o
29
1.4 Classification Of Organic Compounds
Functional group
Functional group is an atom or a group of atoms in a
molecule which determines its chemical and physical
properties.
It serve as :
- a basic for naming organic compounds
- the site of a chemical reaction to occur
30
Functional General
Class Example
group Formula
CH4
Alkane none CnH2n+2
methane
C=C
CH2= CH2
Alkene (C-C double CnH2n
ethene
bond)
CC CH CH
Alkyne CnH2n-2
(C-C triple bond) ethyne
CH3
Arene CnH2n-6
(aromatic ring)
methylbenzene
Haloalkane/ CH3CH2Cl
–X (halogen) CnH2n+1X
Alkyl Halide chloroethane
31
Functional General
Class Example
group Formula
–OH CH3CH2OH
Alcohol CnH2n+1 OH
(hydroxyl) ethanol
– OR CH3OCH3
Ether CnH2n+2O
(alkoxy) methoxymethane
O CH3C=O
Aldehyde C H CnH2nO
H
(carbonyl) ethanal
O CH3C=O
Ketone CnH2nO
C
CH3
(carbonyl) propanone
32
Functional General
Class Example
group Formula
O CH3C=O
Carboxylic
C OH CnH2nO2
acid OH
(carboxyl) ethanoic acid
O CH3C=O
acyl chloride CnH2n+1COCl
C Cl Cl
(acyl ) ethanoyl chloride
O
CH3CONH2
Amide CnH2n+1 CONH2
C NH2
Ethanamide
(amide)
33
Functional General
Class Example
group Formula
O
Ester C O C CnH2nO2 CH3COOCH3
(ester) ethyl ethanoate
O O O O
CH3C O C CH3
Anhydride (CnH2n+1 CO)O
C O C Ethanoic
anhydride anhydride
CH3NH2
Amine -NH2 (amino) CnH2n+1 NH2
methanamine
C N
CH3CN
Nitrile CnH2n+1 CN
ethane nitrile
(cyano)
34
EXAMPLE
Consider the following compounds. For each compound,
i. circle and name the functional groups
ii. classify them based on their functional groups
a) CH3 O b) CH3 c)
CH3O CH2CH3
CH3CCH2 C
NH2
CH3
d) CH2CH3 e) f) H3C
H3C
CHC N
C OCH2CH3
H3C
O
35
EXAMPLE (answer)
Consider the following compounds. For each compound,
i. circle and name the functional groups
ii. classify them based on their functional groups
CH3 O
a)
CH3CCH2 C i. amide
NH2 ii. amide
CH3
CH3
b) i. Carbon-carbon ouble bond
ii. alkene
i. alkoxy
c) CH3O CH2CH3 ii. ether
36
EXAMPLE (answer)
CH2CH3
d) i. aromatic ring
ii. benzene
e) H3C
i. ester
C O CH2CH3 ii. ester
O
H3C i. cyano
f)
CHC N ii. nitrile
H3C
37
Homologous Series
Homologous series are series of
compounds that have the same functional
group whereby each member differs from
the next by a constant
–CH2 unit
38
Example
a) Homologus Series of Alkane
i) CH4
ii) CH4 + CH2 C2H6
iii) C2H6 + CH2 C3H8 etc..
b) Homologus Series of Alkene; functional group : C-C double
bond
i) C2H4
ii) C2H4 + CH2 C3H6
iii) C3H6 + CH2 C4H8 etc..
c) Homologus Series of Alkohol ; functional group : hydroxyl
i) CH3OH
ii) CH3OH + CH2 C2H5OH
iii) C2H5OH + CH2 C3H7OH etc..
39
Some common features of the members of a
particular homologous series are:
Have the same general formula
Have the same functional group & have the
same chemical properties
The physical properties change gradually
(gas – liquid – solid) as the number of carbon
atoms increase.
Successive members of a series differs by a
– CH2 group
40
Alkane homologous series
Chemical
Structural formula Name
formula
CH4 CH4 Methane
C2H6 CH3 CH3 Ethane
C3H8 CH3 CH2 CH3 Propane
C4H10 CH3 (CH2)2 CH3 Butane
C5H12 CH3(CH2)3 CH3 Pentane
C6H14 CH3 (CH2)4 CH3 Hexane
C7H16 CH3 (CH2)5 CH3 Heptane
C8H18 CH3 (CH2)6 CH3 Octane
C9H20 CH3 (CH2)7 CH3 Nonane
C10H22 CH3 (CH2)8 CH3 Decane 41
Alkanes and cycloalkanes (alkanes with cyclic
structures) belong to the same class of compound
but different homogous series. Why?
Both have same functional group, thus they
belong to the same class of compound.
They have different general formula, thus they
are in different homologous series.
alkane – CnH2n+2
cycloalkane – CnH2n
Cyclo- is a prefix designating a cyclic (ring) compound
42
1.5 ISOMERISM
Isomerism is the existence of compound with
the same molecular formula but different
structural formulas
Isomers
Isomers are compounds that have the same
molecular formula but different structural
formulas
43
Isomerism
1) Structural/
2) Stereoisomerism
Constitutional Isomerism
Functional Group diastreomer enantiomer
Chain Positional
Isomerism Isomerism Isomerism
cis-trans Other diastreomers
isomerism (Molecule with two
or more chiral carbon)
1. Constitutional isomers
Different compounds that have the same molecular
formula but differ in their connectivity, that is, in
the sequence in which their atoms are bonded
together.
1) Structural/
Constitutional Isomerism
Chain Positional Functional Group
Isomerism Isomerism Isomerism
45
a) Chain Isomers
The isomers differ in the carbon skeleton
(different in the longest carbon chain).
They possess the same functional group and
belong to the same homologous series.
They have the same chemical properties but
different physical properties
46
Example 1:
Draw all the chain isomers of C5H12
CH3
CH3 CH2 CH2 CH2 CH3
pentane CH3 CH CH2 CH3
CH3 2-methylbutane
H3C C CH3
CH3
2,2-dimethylpropane
47
b) Positional isomers
These isomers have a substituent group in different
positions in the same carbon skeleton.
Example 2 :
Draw all the positional isomers of C5H11Cl
5 4 3 2 1
CH3 CH2 CH2 CH2 CH2 Cl
1-chloropentane
5 4 3 2 1 5 4 3 2 1
CH3 CH2 CH2 CH CH3 CH3 CH2 CH CH2 CH3
Cl Cl
2-chloropentane 3-chloropentane 48
Example 3 :
Draw all the positional isomers of C4H8 and C8H10
4 3 2 1 4 3 2 1
CH3 CH2 CH CH2 CH3 CH CH CH3
1-butene 2-butene
CH3
CH3
CH3 1
1 6 2
1 CH3 6 2
6 5
2 3
5 3
4
5 3 CH3
4
CH3
4 1,3-dimethylbenzene
1,2-dimethylbenzene 1,4-dimethylbenzene
49
Exercise:
Draw all the chain & positional isomers of C4H9Cl
CH3
CH3 CH2 CH2 CH2 Cl
CH3 CH CH2 Cl
A B
CH3
CH3 CH2 CH CH3 CH3 C CH3
Cl Cl
C D
Chain isomers – A & B , C & D
Positional Isomers – A & C , B & D
50
c) Functional group isomers
These isomers have different functional groups and
belong to different homologous series with the same
general formula.
Different classes of compounds that exhibit functional
group isomerism are :
Classes of compounds General Formula
Alcohol & Ether CnH2n + 2O
Aldehyde & Ketone CnH2nO
Carboxylic acid & Ester CnH2nO2
Alkene & Cycloalkane CnH2n
51
Classes of General Functional Group
compounds Formula Isomers
Alcohol & Ether CnH2n + 2O CH3 CH2 OH
Alcohol (ethanol)
C2H6O H3C O CH3
Ether (methoxymethane)
Aldehyde & CnH2nO CH3 CH2 C H
Ketone
O
C3H6O Aldehyde (propanal)
H3C C CH3
O
A ketone (propanone)
Classes of General Functional Group
compounds Formula Isomers
Carboxylic acid & CnH2nO2
CH3 CH2 C OH
Ester
C3H6O2 O
Carboxylic acid
(propanoic acid)
H3C O C CH3
O
Ester (methyl ethanoate)
53
Classes of General Functional Group
compounds Formula Isomers
Alkene & CnH2n
Cycloalkane H2C CHCH2CH2CH2 CH3
Alkene (1-hexene)
C6H12
Cycloalkane (cyclohexane)
54
1.6 REACTIONS OF ORGANIC COMPOUNDS
Reactions of organic compounds involve the
forming and breaking of covalent bonds.
A covalent bond may break in two fundamentally
different ways:
a) Homolytic cleavage
b) Heterolytic cleavage
55
a) Homolytic Cleavage
Occurs in a non-polar bond of two atoms of similar
electronegativity. unpaired
electron
X X X + X
free radicals
A single bond breaks symmetrically into two equal parts;
leaving each atom with one unpaired electron, known as
a free radical as the product.
Shown by a single headed arrow,
56
Example : Homolytic cleavage in some molecules
uv
i) Cl Cl Cl + Cl
Free radicals
H H H H
ii) H C C H H C + H C
H H H H
H H
iii) H
H C H H C +
H H 57
b) Heterolytic Cleavage
Occurs in a polar bond of two atoms with different
electronegativities.
A single bond breaks unsymmetrically in which both
bonding pair electrons are transferred to the more
electronegative atom thus form a cation and anion.
bonding pair e
δ- δ+
- +
A B A + B
anion cation
Shown by a double headed arrow,
58
A heterolytic cleavage that forms a carbocation
CH3 CH3
δ+ δ- + -
H3 C C Cl H3 C C + Cl
CH3 CH3
carbocation anion
chlorine is more electronegative than carbon thus the
C—Cl bond is polar.
both bonding pair electrons are transferred to Cl atom.
a carbocation (CH3)3C+ and a chloride, Cl- ion is formed.
If the heterolytic cleavage involves carbon atom, either a
carbocation (+ve charge on the carbon atom) or a
carbanion (–ve charged carbon atom) is formed. 59
A heterolytic cleavage that forms a carbanion
CH3 CH3
- +
H3C C Li H3C C Li
+
CH3 CH3 cation
carbanion
carbon is more electronegative than Li thus the C—Li
bond is polar.
both bonding pair electrons are transferred to
carbon atom.
a carbanion (CH3)3C- and a lithium, Li+ ion is formed.
60
The differences between homolytic cleavage and
heterolytic cleavage
homolytic cleavage heterolytic cleavage
Occurs in a non-polar bond of Occurs in a polar bond of two
two atoms of similar atoms with different
electronegativity. electronegativities.
A single bond breaks A single bond breaks
symmetrically into two equal unsymmetrically in which both
parts; leaving each atom with bonding pair electrons are
one unpaired electron, known transferred to the more
as a free radical as the product. electronegative atom thus form
a cation and anion.
FREE RADICAL
Free Radical is atom or molecule that bears an unpaired
electron.
CARBOCATION
A carbocation is a positively charged carbon atoms.
Free radical & carbocation do not satisfy the octet rule,
therefore they are unstable intermediates and highly reactive.
Stability of free radical
The stability of free radical increases as more alkyl
groups (electron releasing group) are attached to
the carbon atom with the unpaired electron.
The alkyl group is an electron-releasing group
which will increase the electron density at C•
inductively, thus help to stabilize the unpaired
electron of carbon atom.
Stability of free radical
H H CH3 CH3
H C < H3C C < H3 C C < H3C C
H H CH3
H
1º 2º 3º
Methyl free free free
free radical radical radical radical
Ascending order of stability of carbon free radical
64
Stability of carbocation
The stability of carbocation increases with
the number of alkyl groups present.
The alkyl group is an electron-releasing
group which will increase the electron density
at C+ inductively, thus help to stabilize the
positive charge on the carbocation.
65
H H CH3 CH3
+ + +
+
H C < H3C C < H3 C C < H3 C C
CH3
H H H
methyl 1º 2º 3º
carbocation carbocation carbocation carbocation
The ascending order of stability of carbocation
66
There are 4 main types of organic reaction
Types of
Organic
Reactions
Addition Substitution Elimination Rearrangement
67
1) Addition Reaction
A reaction in which atoms or group of atoms are
added to adjacent atoms of a multiple bond.
Involves compounds with multiple bonds
(unsaturated) such as alkenes and carbonyl
compounds.
68
Examples :
CCl4
CH3CH=CH2 + Br2 CH3CHBrCH2Br
room
temperature
C=C C-C
O CN
H3C C CH3 + HCN H3C C CH3
OH
C=O C-O
69
2) Substitution Reaction
A reaction in which an atom or group in a molecule is
replaced by another atom or group.
A typical reactions of saturated compounds.
Examples :
uv
CH3CH3 + Cl2 CH3CH2Cl + HCl
One H atom is
substituted by Cl
70
H
Br
FeBr3
+ Br2 + HBr
One H atom is
substituted by Br
H3CH2C Br + OH-(aq) Δ CH3CH2OH + Br-(aq)
One Br atom is
substituted by OH
71
3) Elimination Reaction
An atoms or groups are removed from adjacent
carbon atoms of a molecule to form a multiple
bond (double or triple bond).
Results in the formation of unsaturated molecules.
Example :
H H H H
KOH C C + HBr
H C C H
ethanol, reflux
H Br H H
C-C C=C
72
Exercise
Identify the type of chemical reactions below:
CH3
CH3
i) CH3 CH CH CH3 concentrated H 2SO4
CH3 C CH CH3 + H2O
OH
CH3 CH3
ii) H3C C Br + NaOH(aq) H3C C OH + NaBr(aq)
CH3 CH3
73
H CH3
AlCl3
iii) + CH3Cl + HCl
iv) CH3 CH2 OH + HCl CH3 CH2 Cl + H2O
v) CH3 CH3 + Cl2 uv CH3 CH2 Cl + HCl
74
O OH
H2SO4
vi) CH3 C H + NaCN CH3 C H
CN
vii) CH3 CH CH2 + Br2 CH3CH CH2
Br Br
75
Answer :
i. Elimination reaction
ii. Substitution reaction
iii. Substitution reaction
iv. Substitution reaction
v. Substitution reaction
vi. Addition reaction
vii. Addition reaction
76
