TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

CHAPTER 4.0: INTRODUCTION TO ORGANIC CHEMISTRY

MAPPING COGNITIVE
TOPIC SUBTOPIC LEARNING OUTCOMES DOMAINS
C1 C2 C3 C4
a) Define structural formula. √
b) Show structural formula in the form of expanded,
4.1 Molecular & condensed and skeletal structures based on molecular √
Structural formula.
Formulae c) Classify carbons into primary, secondary, tertiary or
quaternary and hydrogens into primary, secondary or √
tertiary.
a) Define functional group. √
b) State functional groups of the following class of
compounds:
i. Alkene
ii. Alkyne
iii. Aromatic
iv. Haloalkane
v. Alcohol
vi. Ether
vii. Aldehyde √
viii. Ketone
ix. Carboxylic acid
4.2 Functional x. Acyl chloride
Groups and xi. Anhydride
Homologous xii. Ester
Introduction to Series xiii. Amide
organic chemistry xiv. Amine
xv. Nitrile
c) Identify functional groups in a given compound. √ √
d) Define homologous series. √
e) Explain general characteristics of homologous series:
i. Represented by a general formula;
ii. Same functional group and chemical properties;
iii. Gradual change in physical properties with √
increasing number of carbon atoms;
iv. Successive member of a series differs by a –CH - 2

group.
a) Define isomerism, constitutional isomerism and
√
stereoisomerism
b) Construct constitutional isomers:
i. Chain isomers;
√
ii. Positional isomers;
iii. Functional group isomers.
c) Describe cis-trans isomerism due to restricted rotation
about:
√
4.3 Isomerism i. C=C bond;
ii. C-C bond in cyclic compounds.
d) Identify cis-trans isomerism of a given structural formula. √ √
e) Define chirality centre and enantiomers. √
f) Identify chirality centre(s) in a molecule. √ √
g) Determine optical activity of a compound. √
h) Draw a pair of enantiomers using 3-dimensional formula
√
*restricted to molecules with one chirality centre
CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 1
 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

MAPPING COGNITIVE
TOPIC SUBTOPIC LEARNING OUTCOMES DOMAINS
C1 C2 C3 C4
a) Explain covalent bond cleavage:
i. homolytic cleavage, √
ii. heterolytic cleavage
b) Differentiate between homolytic cleavage and heterolytic
√
cleavage
c) State the relative stabilities of primary, secondary and tertiary
√
free radicals, carbocations and carbanions.
4.4 Reactions d) Compare the stabilities of carbocations and carbanions by using
Introduction √
of Organic the inductive effect of alkyl group.
to organic
Compounds e) Define
chemistry
i. electrophile;
ii. nucleophile; √
iii. Lewis acid; and
iv. Lewis base
f) Explain the types of organic reactions:
i. addition (nucleophilic and electrophilic);
ii. substitution (free radical, nucleophilic and electrophilic);
√
iii. elimination; and
iv. rearrangement.
g) Predict the type of organic reaction from a given equation. √

CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 2

 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

MAPPING COGNITIVE
SUBTOPIC LEARNING OUTCOMES DOMAINS
C1 C2 C3 C4
a) Define structural formula √
4.1 Molecular & b) Show structural formula in the form of expanded, condensed and √
Structural skeletal structures based on molecular formula
Formulae c) Classify carbons into primary, secondary, tertiary or quaternary √
and hydrogens into primary, secondary or tertiary

INTRODUCTION TO ORGANIC CHEMISTRY

4.1 MOLECULAR AND 4.3 ISOMERISM 4.4 REACTIONS

STRUCTURAL OF ORGANIC
FORMULA COMPOUND

4.2 FUNCTIONAL GROUPS

AND HOMOLOGOUS SERIES

INTRODUCTION

ORGANIC ➢ Organic chemistry is the chemistry of carbon compounds.

CHEMISTRY ➢ All organic compounds contain C and in the majority of
cases also contain H.
➢ Some organic compounds also contain elements such as
O, N, P, S and halogens (F, Cl, Br)

Properties of ➢ Has 4 valence electrons.

carbon atom: ➢ Can form 4 covalent bonds.

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

SINGLE BOND DOUBLE BOND TRIPLE BOND

Single Bond Double Bond Triple Bond

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

STRUCTURAL Shows how the atoms in a molecule are bonded to

FORMULA each other (arrangement of atoms)

TYPES OF STRUCTURAL STRUCTURE

Expanded Structure Condensed Structure Skeletal Structure

➢ Show all covalent ➢ Does not show single ➢ Shows only the
bonds between bonds between carbon carbon skeleton.
atoms. and hydrogen atoms, but
double and triple bonds ➢ C chains are drawn
➢ Not representation
are shown. zigzag and rings are
of actual shape of
➢ All atoms that are attached drawn as polygons.
molecule.
to a carbon are written ➢ H atoms are not
immediately after that written.
carbon.
➢ Functional groups
➢ Use ( ) in condensed are shown.
structure to show
heteroatoms, functional ➢ Other atoms such as
groups, alkyl groups at the O, Cl, and N etc. are
side chain. shown.
➢ ( ) is used around similar
alkyl groups bonded to
same atom.
➢ ( ) is used to indicate
repeating structures.

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Expanded Structure Condensed Structure Skeletal Structure

1. Alkanes (C4H10)

↑ it ↑ it
H
C C ( ASCH > CHZCH }
~
-

C C -

H
-
-
-

I
I 1 1
H H
H H

2. Cycloalkanes (C6H12)
"

E
①
,
H , ( H2

"
1 41-12
It (Hr
1- [
H
HTH

Exercises

1. Complete the table below:

Molecular Expanded Condensed Skeletal
Formula Structure Structure Structure
it it it ↑
C4H9Cl
~
C C C/ CHZCHZCH ( Hzcl
H C C
- -
- -

(haloalkane)
-
<

' ' ' '

CI
H H H H

C2H5OH it it
(alcohol) C
H C 011 CH }CHz0H
~
-
-

I 1 OH
1-1 It

it Y
C3H6O2
(carboxylic H -
C -
¥
C -
ii.
C
-
.

Y
-
H CH ] CHZÉOH "

#
acid) I / OH

H H

"
C4H8 it
GHz
-
Utz
(cycloalkane) I
1
- C C
-
H CH - CH ,
*
,
H It

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

2. Write the skeletal formula for each of the following expanded formula.
Expanded Structure Skeletal Structure

:
"
a "

-
OH

3. The skeletal formulae of four organic compounds are shown below. Write the
condensed structural formula for each compound.

Skeletal
Structure

Condensed
Structure
cɥHz CHI
CH3%HCHCH3
¥42 CH -
IH -

CH -
CH} At CHCH
-

CHICA}
, ,
di
@

U7g( HCBRICHCCIICH}

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

4. Fill in the blanks with suitable formulae.

Expanded Formula Condensed Formula Skeletal Formula

NHZ
, ,H2
N
, , I
-
C -
C -

C C OH
CH3CH(NH2)CH2CH2OH
- -

I 1 I 1 OH

UPS 2007/2008
Convert the following structural formula to skeletal structure.

OH

UPS 2010/2011
Consider the following molecular structure:
H
i' it {
'

C
H
it
/ \ < '
, ✓ C -
C C H
µ
-
-
H I

_
{ I H

IT C- It
we -
'
1 H
Cl

Redraw the above structure

in the form of expanded and
condensed structure.

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Classification of Carbon

Classes of C Depends on the number of alkyl group

atoms attached to the C.

Primary Secondary Tertiary Quarternary

Carbon (1°) Carbon (2°) Carbon (3°) Carbon (4°)

Class of C atom Formula Comments

Primary Carbon ➢ carbon that bonded

(1°) to only 1 carbon
atom.

Secondary Carbon ➢ carbon that bonded

(2°) to only 2 carbon
atoms.

Tertiary Carbon ➢ carbon that bonded

(3°) to only 3 carbon
atoms.

Quarternary Carbon ➢ carbon that bonded

(4°) to 4 carbon atoms.

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

TAKE NOTE!!!

NO CLASSIFICATION FOR C ATOMS IN METHANE AND IN MULTIPLE BONDS!

Methane Propene

Classification of Hydrogen

Classes of H atoms → Depending on the class of carbon atom bonded to it.

Primary Hydrogen (1°) Secondary Hydrogen (2°) Tertiary Hydrogen (3°)

Class of H atom Formula Comments

Primary Hydrogen ➢ 1o hydrogen atom

(1°) attached to 1o C

Secondary Hydrogen ➢ 2o hydrogen atom

(2°) attached to 2o C

Tertiary Hydrogen ➢ 3o hydrogen atom

(3°) attached to 3o C

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Exercises:
1. Indicate and state separately the class of carbon atoms in the following
molecule.

2. Determine the number of primary, secondary, tertiary and quaternary

carbonatoms in the following molecule:

UPS 2005/2006
Classify the carbons labelled X and Y

UPS 2006/2007
Redraw the following molecular structure, then label and state the number of
primary, secondary and tertiary carbon

CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 11

 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

MAPPING COGNITIVE
LEARNING
SUBTOPIC DOMAINS
OUTCOMES
C1 C2 C3 C4
a) Define functional group √
b) State functional groups of the following class of compounds √
c) Identify functional groups in a given compound √ √
4.2 Functional
Groups and d) Define homologous series √
Homologous e) Explain general characteristics of homologous series:
Series i. Represented by a general formula.
ii. Same functional group and chemical properties √
iii. Gradual change in physical properties with increasing
number of carbon atoms.
iv. Successive member of a series differs by a –CH2- group.

FUNCTIONAL ➢ Is an atom or group of atoms in an organic molecule which

GROUP characterised the molecule and enables it to react in
specific ways which determines its chemical properties.

➢ Importance of functional groups:

• Organic compound is classified based on the

functional groups present in their molecules.
• To name the organic compounds.
• A particular functional group will always undergo similar
types of chemical reactions.

CLASSIFICATION OF ORGANIC COMPOUND

Class of Compound Functional Group

(Homologous) Structure Name Example

Alkane none − CH3CH3

Alkene Carbon-carbon
C C double bond CH3CH=CH2

Alkyne C C Carbon-carbon CH3C≡CH

triple bond

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Class of Compound Functional Group

(Homologous) Structure Name Example
CH3
Arene
Aromatic ring

Haloalkane −X Halogen CH3CH2Cl

(F, Cl, Br or I)

Alcohol −OH Hydroxyl CH3CH2OH

−OH OH
Phenol Hydroxyl

Ether Alkoxy CH3OCH3

C O C

O O
Aldehyde Carbonyl
C H CH3 C H

O O
Ketone Carbonyl
C CH3 C CH3

O Carboxyl O
Carboxylic Acid
C OH CH3C OH

O O
Ester Carboalkoxy
C O C CH3C OCH3

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Class of Compound Functional Group

(Homologous) Structure Name Example

Acyl Chloride Acyl Halides

Acid
Anhydride Anhydride

Amide Carboxamide

Amine −NH2 Amino CH3NH2

Nitrile −C≡N Cyano group CH3C≡N

Exercises:
1. For the following structure, circle, and name all the functional group:

(a)

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

(b)
O

HO NH CH3

(c)
H2C CH2 OH
O

O
CH3

H2N

(d)
O O
O C O C CH3
HO C CH2
CH3 OH
H3C C C C HC C NH2

CH C O CH3 O
NH2
O
CH2

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

HOMOLOGOUS ➢ Is a series of compounds which all contain the

SERIES same functional group and each member differs
from the next member by a constant – CH2 unit.
➢ Members of the same homologous series are
called homologs.

Characteristic ➢ share the same general formula.

➢ same functional group and have similar
chemical properties.
➢ show a gradual change in physical properties
as molar mass increases.
➢ Each member differs from the next member by a
constant –CH2 unit.

Example

General formula CnH2n+2 ➢ Gradual change in physical properties

with increasing number of carbon
Homologous series of alkane atoms
CH4 Methane
CH3CH3 Ethane Example
CH3CH2CH3 Propane
CH3CH2CH2CH3 Butane C1 – C4 → gas phase Boiling
CH3CH2CH2CH2CH3 Pentane C5 – C17 → liquid phase point
C18 → onward solid phase increase

General formula CnH2n+1OH ➢ Gradual change in physical properties

with increasing number of carbon
Homologous series of alkane atoms
CH3OH Methanol
CH3CH2OH Ethanol Example
CH3CH2CH2OH Propanol
CH3CH2CH2CH2OH Butanol ➢ Increasing boiling point
CH3CH2CH2CH2CH3OH Pentanol ➢ Decreasing solubility in water

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

MAPPING COGNITIVE
SUBTOPIC LEARNING OUTCOMES DOMAINS
C1 C2 C3 C4
a) Define isomerism, constitutional isomerism and
4.3 Isomerism √
stereoisomerism.

ISOMERISM ➢ The existence of different compounds with the same

molecular formula. 4-4-12
(Compound that have the same molecular formula but
different arrangements of atoms)

ISOMERISM

Constitutional Isomerism/
Structural Isomerism Stereoisomerism

Isomers with the same molecular Isomers with the same molecular formula
formula but different in order of and same connectivity but different
attachment of atoms. arrangement of atoms in space.

① Skeletal
Chain Isomerism/
Isomerism
③ Functional Group
Isomerism
Diastereomers
(Cis-trans Isomerism
/Geometrical Isomerism)

➢ Different in fg ✗ Sama

carbon chain ➢ Have different ➢ A pair of

functional groups stereoisomers with
➢ Same and belong to different structures that are
chain homologous series not mirror image of
functional
✗ Sama each other
group and
func group belong to
the same
Sama
homologous ② Positional Isomerism Enantiomer
series. (Optical Isomerism)

Chain Have same carbon skeleton and

same belong to the same homologous
series, but differ in the Stereoisomers in that mirror
tune group
position of functional group images are not superimposable
Sama
Sama
position f. g ✗

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

MAPPING COGNITIVE
SUBTOPIC LEARNING OUTCOMES DOMAINS
C1 C2 C3 C4
b) Construct constitutional isomers:
i. Chain isomer √
4.3 Isomerism
ii. Positional isomer
iii. Functional group isomer

CONSTITUTIONAL ISOMERISM / STRUCTURAL ISOMERISM

➢ Isomers with the same molecular formula but different in order

of attachment of atoms.
Type of Isomerism Example
1. Chain/Skeletal Molecular Isomer
Isomerism Formula
H "
➢ Differ in the 1. C5H12 "
1 it I 1 it
carbon skeleton alkane C C C C H
C
-
- -
-

(different carbon H
- -

chain) ¥ it it it ¥
➢ Same functional
group and belong CH CH
CH CHI ,
-
-

to the same }
I
homologous
series Cltz

➢ Different physical
411-3
properties but CH -
C -
CH }
similar chemical }
properties.
{ It 3
➢ Characteristic of 2. C4H9OH
chain isomer for
boiling point:
CHI CHI CHI CHI OH
suvfhllpn• Straight chain
aveh isomers have
↑ OH
INF higher boiling CH } CH
-
-
CHI
points than
BP ↑ branched chain
isomers.
LH }
• Greater the degree
of branching, the
lower boiling
point.

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Type of Isomerism Example

2. Positional Molecular Isomer
Isomerism Formula

➢ Have same carbon 1. C3H7Br

skeleton and
belong to the same Gt3
-

CHI CHE ⑨
homologous
series.

➢ Differ in the CH -3 CH -
CH }
position of
functional group.

➢ Different physical
"B①
properties but
similar chemical
properties.

2. C4H8

alkene
GE CH z
4+5 CHI

CH CH}
Gt3
-

CH =

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Type of Isomerism Example

3. Functional Group Molecular Isomer

Isomerism Formula
1. C5H10
➢ Same molecular
CH 9+2
Gtj CHICA
-

formula but different alkene

-_

functional groups cycloalkahl

and belong to

÷
different
homologous series.

➢ Different physical
properties but
similar chemical
properties. 2. C3H6O
( hltano CH3CH< C -

H aldehyde
➢ Classes of
compound that

cH3ÉCH
exibit functional
group isomerism:
} (ketone )

General Classes of
formula compounds
CnH2n+2O alcohol &
(n > 1) ether 3. C2H6O

@ 10h01)
CnH2nO aldehyde & ↳ H2n
(n ≥ 3) ketone -120 CH }CHz0H
CnH2nO2 carboxylic
(n ≥ 2) acid & ester
O CH } ( ether )
( Hz
-

CnH2n alkene & C- 0 (

-
-

(n ≥ 3) cycloalkane

4. C3H6O2 carboxylic
[ OH
-
C- OH Hzcltz acid
cuvbox

it
% -
O -
C CH - C - O -
CH } ester
}

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Exercises
1. State how many isomers with the following molecular formula and identify the
type of isomerism and draw the structural formula of the isomers.
C5H10O2 carboxylic / ester

① cltscltzctlz.CI/-z&- OH
① chain =
142
2
} }
,

,
/
{ 3,174
374,546
,

@ positional -

-547,528
② É OH
CH3CHzCH ③
-

145,245
-
=
functional
{ 1+3

③ CH } CH -
( HzÉ -
OH

It }
(¥3 if
④ CH -
C- C- OH
,
7

Utz

⑤ CHgCHzCH2É -
O -

CH }

⑥ CH
} CH
- É - O -
CH }

⑦ CH } CH ,
É -
O -
CHIH >

⑧ CH >
-
O -
CH -
CH }
I
CH ]

⑨ CtzÉ -
o -
CHZCH > CH }

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

MAPPING COGNITIVE
SUBTOPIC LEARNING OUTCOMES DOMAINS
C1 C2 C3 C4
c) Describe cis-trans isomerism due to restricted rotation about:
i. C=C bond. √
4.3 Isomerism ii. C-C bond in cyclic compound.
d) Identify cis-trans isomerism of a given structural formula. √ √

STEREOISOMERISM

➢ Isomers with the same molecular formula and same connectivity but
different arrangement of atoms in space.
➢ Draw in 3D-formula also known as “line – wedge – dashed wedge” formula.

CIS-TRANS ISOMER @ OPTICAL ISOMER

GEOMETRICAL ISOMERS (ENANTIOMER)
(DIASTEREOMER)
image
mirror I

%
""'
/ "

i
1
I

Stereoisomers have the Compounds that have their atoms

same molecular formula and connected in same order but differ in
structural formula! arrangement in space.

CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 22

 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

CIS-TRANS ISOMERISM / GEOMETRICAL ISOMERISM (DIASTEREOMER)

Requirements for a molecule to exhibit cis-trans isomerism:

1. Restricted rotation about C=C (double bond) in alkenes or C-C (single bond) in
cyclic compounds.
2. Each carbon atom at the site of restricted rotation has two different groups
attached to it.

➢ Restricted rotation about:

i. C=C (double bond) in alkenes or
ii. C‒C (single bond) in cyclic compounds.

Restricted rotation of double bond:

CIS-ISOMER TRANS-ISOMER

Same atoms or groups of atoms on the Same atoms or groups of atoms on the
same side opposite side

cis-2-butene trans-2-butene

Restricted rotation of cyclic compound:

CIS-ISOMER TRANS-ISOMER

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

➢ Each carbon atom at the site of restricted rotation has two different atoms
or groups attached to it.

Example:

H3C H
CH3

H3C
C C
CH3
¥ H
← '

a ✗
Not cis-trans isomer because it has 2 identical groups
attached at the same carbon

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Exercises
1. Which of the following compounds can exist as a pair of cis−trans isomers?
Draw each cis−trans pair.

a) CH3CH=CH2
✗ 0000
b) CH3CH2CH=CHCH3

" *
i = c- cis -
trans
'

CH { H2
/ 4+3
* CH }
\
[ = c-
'
/
H
CH 311+2

c) 0000
ClCH=CHBr ✓
Ca
d) (CH3)2C=CHCH3
✗
"
"
i = c- trans
'
if Br

% = c-
H

'
/ Bv
C,

C- 003
e) CH3CH2C(CH3)=CHCH Ca
f) CH3CH=C(Cl)
- -
2

CH31142
"

I
-

= c-
\
CH } CH g

CH
-3
, = c
/ c* ,
( H
} CH 2

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Exercises
2. Which cycloalkane shows cis-trans isomers? Draw each cis−trans pair.

a) " b)
-
CH3 I
✗ HO CH3

It at }

it ◦
☒
H H
OH CH }

c) d) H

CH2 CH3 I
OH
'
×
-
H

OH

OH

1 OH / H

OH OH

CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 26

 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Exercises
3. For which alkenes are cis and trans isomers possible. Draw the cis-trans pair.

a) '"

*,
:* !"%④ ✗
④
a
b) H2C=CHCH2CH2CH3
✗

c) ¥ = c-
"
§ -
H
C
-0 C
CH CH =

A
. .

I
W
It ①

UPS 2010/2011
Which of the following cycloalkanes exhibits cis-trans isomerism? Draw the cis-
trans isomers.
"
¥ CH2 CH3 CH2CH3
" H3C CH3
H
-

, \
CH3

CH3 ✗
✓
I II III
" "
✗ "

EE H CH
H H }

cis trans
CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 27
 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

MAPPING COGNITIVE
SUBTOPIC LEARNING OUTCOMES DOMAINS
C1 C2 C3 C4
e) Define chirality centre and enantiomers √
f) Identify chirality centre(s) in a molecule √ √
4.3 Isomerism
g) Determine optical activity of a compound √
g) Draw a pair of enantiomers using 3-dimensional formula √
*Restricted to molecules with one chirality centre

OPTICAL ISOMERISM
Definition:
➢ Optical activity is the ability of certain crystals or solutions of certain
substances to rotate the plane of plane-polarised light.
➢ Substances that can rotate the plane of plane-polarised light is said to be
optically active.
➢ Optically active substances which possess the same structural formula but
differ in their effect on plane-polarised light are called optical isomers.
Rotate plane of polarisation to right → (+) isomer (dextrorotatory)
Rotate plane of polarisation to left → (−) isomer (levorotatory)

Rotating plane-polarized light

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

The requirements for optical isomerism:-

1. Molecule contains a chiral carbon or chirality centre.
2. Molecule and its mirror image are not superimposable with each other.

1. Molecule contains a chiral carbon or chirality centre.

Chiral carbon → carbon atom with 4 different groups attached to it

Chirality centre → an sp3 hybridised carbon atom with four different

atoms or groups attached to it.

Example:
Determine the chirality centre for this molecule.

CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 29

 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Chirality in cyclic compound:

To determine whether a ring carbon is chiral, look for any difference in the path
around the ring in each direction.
Identical groups

H H
-
-
- •
-
-
-
-

CH3 CH3
✗
Chiral carbon or not?

☆ ☆
- - - - - -
→ - - - - - -o ☆

* ÷ :*

Example:
Label (  ) at the chiral carbon(s) (chirality centre) of the following molecules:

:
•
☆ ☆
•
☆
•

CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 30

 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

2. Molecule and its mirror image are not superimposable with each other.
Example: mirror

H H

Cl C CH3 H3C C Cl
Br Br

A pair of enantiomers

Additional info: ➢ Also known as ...“line – wedge – dashed wedge formula”

➢ Describes how the atoms of a molecule are arranged in space.
*3-D ➢ Only for chiral carbon.
Structural
Formula
Indication : : bonds that lie in the plane of the page.

: bonds that lie behind the plane.

: bonds that project out of the plane.

Example
2‒ bromomethane (CH3CH2CH(Br)CH3)
☆

t,④C④
Brc
it
↑
{ " '"
'"
3 at

CH }CHz Bv \
,µ
, ,µ
f
,
Bv

,
of enantiomers
a pair

CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 31

 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

ENANTIOMERS

Enantiomers are a pair of mirror image molecules that are not superimposable.
 Have one or more chiral carbons.
 A chiral carbon has four different atoms or group atoms attached to it.

A pair of
enantiomers
DRAW in 3D

Example: 2−butanol

c.

It It
1

C ""
at
i
;%µH3CH2
}
/ Bs at
(A) CHZ OH

CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 32

 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Exercises
1. Identify chiral centre using asterisk (*) and draw the enantiomer for the following
compounds.
a) CH3CH(OH)CH2OH It t
↑
it
'
% (
*

( *_ CHUK
(

Hw¥µ\cH3
CH -
/ ""
} 41-204 I
I 4+3 % /
[

OH /
b) CH3CH(OH)NH2
H "
-

f
I H
CH } - I ?
Nitz [
* /
c
'

g+""NHc
_
O'H at
}

% Nti !§ʰµH ,

c) CH3CH(Cl)CH2CH3
H
i
'

it
'
CH ☆
-1*24+3

fan
}
-

( "" ☆
, / 4+24+3
;¥q
☒ _
, CH } CH
]
(1
,

d) CH2(OH)CH(NH2)COOH
NH
Nite -c
I
4/+2

f
1

H -
C -
COOH C "" e
/ "° " '

it.cat ) " ☆
C -112104 )
coo ☒
4+204
H

e) CH3CH2CH(COOH)CH3
it ↑ it
citrate
/
C LH }
"%
- -

% "cHs
"
"
cA3CHz
-

I /
ay ,µ , µ;
[
COOH COOH
,
Coon,

CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 33

 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Exercises
2. Lactic acid is produced by the fermentation of lactose by certain bacteria and is
found in sour milk. The acid has the structural formula CH3CH(OH)COOH
a) What is meant by chiral centre?
b) Draw the 3-dimensional formula of the lactic acid and its enantiomers.

it

|
it it
-
000A C
CH
}
-
C "ii. C
- -
, [µ
, *
coat
go ,¥q c ,+
,
OH OH OH

enantiomer

3. A type of ά-amino acid, serine (2−amino−3−hydroxypropanoic acid) has

molecular structure as follow:
CH2(OH)CH(NH2)COOH cis-trans
1- enantiomer
Mark the chirality centre and draw its stereoisomers.

|
H H

it *
I 1
<

,o¥☒q
[ HUH -
( -
look
""
' " "
cook "
CH20H
at COOH
ÑHz NHC NH

enantiomer

4. For the following structure, mark the chiral carbon with asterisk(*) and drawn a
pair of stereoisomers using 3D formula It

/
H
i'
+3 it I

d
☆

HzC=c -
C [ It , ,
C. "
"" 44-3
"+3
-

OH OH }e=k
*
*
OH
at
;"⑨ -1=9+3

Name the type of stereoisomerism.

enantiomer
enantiomer

CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 34

 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Exercises
5. By using 3-dimensional formula, draw a pair of enantiomers for the following
structure:
OH

CHCH 3
OH OH

{
1 I

✓↳
""
CH } at >
*" Fg J
it It

6. The structure of A is given below:

O CH3

H3 C C CH C CH3

CH3 CH3

a) Name the functional group present in A. carbonyl A have chirality centre

b) Is A optically active? Explain. Yes bcs Compound ,

c) Draw a pair of enantiomers of A. and ability to rotate plane polarised light

It H
CH
I }
it
jµ§ %
'
c at
} C
/ "
"i C-CH } - C -
CH }
µ ,←c ☒
["
CH
3- I
} , CH }
CH >

CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 35

 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

MAPPING COGNITIVE
SUBTOPIC LEARNING OUTCOMES DOMAINS
C1 C2 C3 C4
a) Explain covalent bond cleavage:
4.4 Reaction of
i. homolytic cleavage; and √
Organic ii. heterolytic cleavage
Compound b) Differentiate between homolytic cleavage and heterolytic cleavage √

Reaction in ➢ All chemical reactions involved bond breaking and bond

Organic forming.
Compound
➢ The breaking of chemical bond is called cleavage or fission.

Types of covalent bond cleavage

HOMOLYTIC CLEAVAGE HETEROLYTIC CLEAVAGE

• Occurs in non-polar bond involving • Occur in polar bond involving
two atoms of similar unequal sharing of electron pair
electronegativity. between two atoms of different
electronegativity. iii iii. a
-

'

e e
É
'
'
'

• A single bond breaks • A single bond breaks

.
.

symmetrically into two equal unsymmetrically and both the

parts, leaving each atom with one bonding electrons are transferred
unpaired electron. to the more electronegative atom.

• Forms free radicals. • Forms cation and anion.

Example: Example:

' free radical

uv
A A A• + A•
%

CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 36

 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Example: Example:

Ii ?Br
Br
uv
Br • + Br • HI
it'
'
Br H+ + Br :−
1 I

: represents the transfer of one electron.

: represents the transfer of two electrons or a pair of electrons.

CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 37

 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

MAPPING COGNITIVE
LEARNING OUTCOMES DOMAINS
C1 C2 C3 C4
4.4 Reaction of c) State the relative stabilities of primary, secondary and tertiary free
radicals, carbocations and carbanions. √
Organic
d) Compare the stabilities of carbocations and carbanions by using
Compound the inductive effect of alkyl group √
intermediate
f)
reactant → product
Reaction Intermediate Unstable and highly reactive

CARBOCATION CARBANION FREE RADICAL

• very reactive species • very reactive species • very reactive species

with a positive with a negative charge with an unpaired
charge on a carbon on a carbon atom. electron.
atom.

• formed in heterolytic • formed in heterolytic • formed in homolytic

cleavage. cleavage. cleavage.

Example: Example: Example:

→ ←
i f
!
-1

9
-

St s s
-

i , ~
uv
Cl ; Cl Cl• + Cl•

free radical

carbocation anion carbanion cation

CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 38

 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Classification of Carbocations, Carbanions and Free Radicals

Primary (1°) Secondary (2°) Tertiary (3°)

(1°)
RELATIVE STABILITIES OF CLASSIFICATION OF CARBOCATIONS,
CARBANIONS AND FREE RADICALS

Inductive Effects

EDG EWG
(Electron Donating Group) (Electron Withdrawing Group)
.CH 3

CH CH }
Example:
-

z
Example:
−R (alkyl group) −COOH (carboxyl group)
-

Type of Explanation
Intermediate
Carbocation ➢ The stability of carbocation increases with the number
Stability of alkyl groups present.
➢ The greater the number of alkyl group on the carbon
atom, the greater its stability.
➢ The alkyl groups (electron donating group, EDG)
stabilise the positive charge on the carbocation.

'
9¥

Methyl (1°) (2°) (3°)

carbocation

Stability increases

↑ ↑ stable
alkyl group
CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 39
 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Type of Intermediate Explanation

Free Radical ➢ The stability of free radical increases with the number
Stability of alkyl groups present.

➢ The greater the number of alkyl group on the carbon

atom, the greater its stability.

➢ The alkyl groups (electron donating group, EDG)

stabilise the unpaired electron on the carbon.

Methyl
(1°) (2°) (3°)
carbanion

Stability increases

Carbanion Stability ➢ The stability of carbanion decreases with the number

of alkyl groups present.

➢ The alkyl groups (electron donating group, EDG)

destabilise carbanions.

Methyl
(1°) (2°) (3°)
carbanion

Stability decreases

↑ R .
↓ stable
CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 40
 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Exercises
1. Arrange the following species in order of increasing stability. Explain.
a)
CH3 CH3
+
CH3 C C CH3
3°
10
+ C H3
CH3 CH2 CH2CH2 +
A C
B

C < A < B

b)
H H CH 3
H
C+ C+ C+
H C+ H3C

H H CH3 CH
3
A B C D

ACB < CCD

2. Which would you expect to be the most stable free radical and carbanion?

10 M
‒ 2°
‒ ‒
my
20 (
°

•CH2CH3 (CH3)2CH• •CH3 CH2CH3 (CH3)2CH• •CH3

✓

CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 41

 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

MAPPING COGNITIVE
SUBTOPIC LEARNING OUTCOMES DOMAINS
C1 C2 C3 C4
4.4 Reaction of e) Define
Organic i. electrophile; √
Compound ii. nucleophile;
iii. Lewis acid; and
iv. Lewis base

REAGENTS AND SITES OF ORGANIC REACTION

Reagents in organic reactions can be classified into …

Miskin Electrophile Kaya Nucleophile

➢ Is an electron-deficient species ➢ Is an electron-rich species which

which attacked by high electron attacks low electron density species.
density species.
➢ Accept an electron pair to form ➢ Donate an electron pair to form
covalent bond. covalent bond.
➢ Can be either neutral or positively ➢ Can be either neutral or negatively
charged. charged.

Example: Example:

Cations : H+, H3O+, NO2+ Anions : NO2−, OH−,Cl−, CN−

Carbocation : C+ Carbanion : C−
Lewis acid (species that accept an Lewis bases (species that donate an
electron pair): AlCl3, FeCl3, BF3 electron pair): NH3, H2O, H2S
Oxidizing agent: Cl2, Br2, I2 Reducing agent: Cl−, Br−, I−
Lone pairs: O−H

Electrophilic Sites: Nucleophilic Sites:

Molecules with low electron density Molecules with high electron density
around a polar bond
it around the carbon-carbon multiple bond
C "
-
electrophilic CH3CH=CH ≥
site
CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 42
 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Example
↳aclemtja
Identify species that can act as nucleophile and electrophile
R P
,
+ 1
8- 8
:
I
electro phllu
,
site

(
I 1

nucleophile

electrophile

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

MAPPING COGNITIVE
SUBTOPIC LEARNING OUTCOMES DOMAINS
C1 C2 C3 C4
f) Explain the types of organic reactions:
i. addition (electrophilic and nucleophilic); √
4.4 Reaction of
ii. substitution (free radical, electrophilic and nucleophilic);
Organic iii. elimination; and
Compound iv. rearrangement.
g) Predict the type of organic reaction from a given reaction equation. √

TYPES OF ORGANIC REACTIONS

Types of Organic Reaction

Addition Substitution Elimination

A reaction in which A reaction in which an A reaction in which

atoms or groups add atom or group in a atoms or groups of
to adjacent atoms of molecule is replaced by atoms are removed
a multiple bond. another atom or group. from adjacent
carbon atoms of a
molecule to form a
Electrophilic Addition Free radical multiple bond =/ I
Substitution
Nucleophilic Addition Electrophilic Rearrangement
Substitution
A reaction in which
Nucleophilic atoms and bonds in a
Substitution molecule change
position & occurs
when a single bond
reactant reorganizes
the bonds and atoms.

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Types of reaction Explanation & Example

Addition Addition reaction occur with organic compound containing:

➢ A reaction in
which atoms or
groups added to
adjacent atoms
of a multiple bond
➢ Only one product
is produced
➢ Involve breaking
of one σ bond to
form two σ bonds
C=C (double bond),
C≡C (triple bond) or
C=O in aldehyde and ketones
Electrophilic Addition
➢ Initiated by an electrophile accepting è from a
nucleophile.
➢ Typical reaction of unsaturated compounds such as
alkenes and alkynes.

H CH3 00
Br Br
CH2Cl2
C C + Br2 H C C CH3
H H H H
electro
hucleo

Nucleophilic Addition

➢ Initiated by a nucleophile, which attacks an electrophilic

site of a molecule.
➢ Typical reaction of carbonyl compounds.

OH
O f-
-

CN H SO
2 4
+ NaCN CH3C H
CH3C H
J -1 nacho
@
CN
even ✓

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Types of reaction Explanation & Example

Substitution Free Radical Substitution

➢ A reaction in which ➢ Substitution reaction which involves free radical as
an atom or group intermediate species.
in a molecule is
replaced by ➢ Typical reaction of alkanes
another atom or
group. CH3CH3 + Cl2 uv CH3CH2 Cl + HCl
☆

Electrophilic Substitution electrophilic

aromatic subs
➢ Typical reaction of aromatic compounds. 1712am
➢ The benzene ring has high electron density, thus it is
nucleophilic and is prone to electrophilic attack.

H Br
AlBr 3
+ Br2 + HBr
eec

nuc
✓

Nucleophilic Substitution

➢ Typical reaction of saturated organic compounds

bearing polar bond as functional group, such as
reaction of haloalkanes and alcohol.

CH3 CH3
Not
_

OH
H3C C Br + NaOH(aq) H3C C OH + NaBr(aq)
ft f-
CH3 hue CH3
elec

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Types of reaction Explanation & Example

Elimination ➢ A reaction in which atoms or groups of atoms are

removed from adjacent carbon atoms of a molecule
to form a multiple bond.

Rearrangement ➢ A reaction in which atoms and bonds in a molecule

change position.
➢ Occurs when a single reactant reorganizes the bonds
and atoms.

CH3 CH C CH3 CH3 CH2 C CH3

OH O

O O
C Cl C Cl
catalyst

CH2 CH2 OH CH CH3
OH

CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 47

 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

Exercises
UPS 2005/2006
1. Determine the type of each of the following reactions.
KOH elimination
i. CH3CHBrCH2CH3 CH3CH=CH3
ethanol

uv radical subs
ii. CH3CH3 + Cl2 CH3CH2Cl + HCl free

room electrophilic addition

iii. CH3CH=CH2 + Br2 CH3CHBrCH2Br
temperature
hue
eiec
←

UPS 2006/2007
2. State the type of chemical reaction below:
uv f. r . Subs
i. CH3CH3 + Cl2 CH3CH2Cl + HCl
CI
! CI

ii. What type of cleavage occurs in this reaction?

hemolytic cleavage

UPS 2007/2008
3. Name the type of reactions below:

i. nuc
electrophilic
elec
CH3 aromatic
substitution
AlCl3
+ H3C Cl + HCl

ii.
O f- OH nucleophilic
addition
H3 C C CH3 + HCN H3 C C CH3
f-1
nul
Cleo CN
←

CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY Page 48

 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

UPS 2007/2008
4. Name the type of reaction for steps A, B, C and D in the following scheme:
nucleophilic
aromatic
substitution elimination

o
COOH o
COCl COCl

S OCl2 K OH/alcohol
A B
f
CHCH3 CHCH3 CH=CH2

Br Br electrophilic
C H2O/H+ addition

COCl COCl
rearrangement

catalys t
CH2CH3 CH2CH2OH
D

HO

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 TOPIC 4: INTRODUCTION TO ORGANIC CHEMISTRY

CHAPTER 4 − INTRODUCTION TO ORGANIC CHEMISTRY