CHAPTER 1

INTRODUCTION TO
ORGANIC CHEMISTRY
 LESSON OUTCOMES
In the end of this chapter, student should be able to :

• Explain the Lewis theory, electronegativity, VSPER theory and formal

charge.

• Write the chemical formula using full structural formula, condensed

structural formula and skeletal formula.

• Define organic chemistry terms such as electrophiles, nucleophiles, Lewis

base or acid.

• Differentiate the isomerism type such as structural isomerism, geometrical

isomerism and optical isomerism.

• Identify the functional group in organic chemistry families such as alkanes,

alkenes, alkynes, cyclic hydrocarbons, aromatic hydrocarbons.

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 CONTENT
Feature of organic
compounds

Common terms in
Isomerism
organic chemistry

Homologous
series

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Wahida, UITM Perlis, 2012 4
 COMPOSITION
• Organic Chemistry- the study of compounds of carbon
• Over 10 million organic compounds have been identified
– about 1000 new ones are discovered or synthesized
and identified each day!
• C is a small atom
– it forms single, double, and triple bonds
– it is intermediate in electronegativity (2.5)
– it forms strong bonds with C, H, O, N, and some
metals

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ORGANIC COMPOUND

Organic
compounds are
everywhere
around us

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 ELECTRONIC STRUCTURE OF ATOM
• a small dense nucleus,
diameter 10-14 - 10-15 m,
which contains positively
charged protons, neutrons 10-10 m
and most of the mass of N ucleus (proton s
and neutron s)
the atom
• extranuclear space,
diameter 10-10 m, which Sp ace occup ied
by electron s
contains negatively
charged electrons
Proton

N eutron
10-15 m
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 …(continue)
• Electrons are confined to regions of space called principle energy levels (shells)

1st Shell = 2 electrons

_
Orbital S

2nd Shell = 8 electrons

_ S
Orbital
_ _ _
Orbital S

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 …(continue)
Electron configuration of atom
- describe of how electron occupy in orbital

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 BONDING
Lewis Model
• Lewis structure (Gilbert N. Lewis)
– the symbol of the atom represents the nucleus and all inner shell electrons
– dots represent valence electrons: electrons in the outermost electron shell of
an atom; these electrons are used in forming chemical bonds

1A 2A 3A 4A 5A 6A 7A 8A
H He

Li Be B C N O F Ne

Na Mg Al Si P S Cl Ar

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 …(continue)
• In neutral molecules containing C, H, N, O, and halogen

Atom Bond Lone pairs of electron

C 4 0
N 3 1
O 2 2
F 1 3
 …(continue)
H O H H Cl
H 2O (8) HCl (8)
Water Hydrogen chloride

H
H C H H N H

H H
CH 4 (8) N H 3 (8)
Methane Ammonia

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 FORMAL CHARGE
• Sometimes Lewis structure contain atoms that bear a positive and
negative charge, called a formal charge
• Formal Charge : the charge on an atom in a molecule or polyatomic ion
 If the atom has one more electron in the molecule, it is shown with a “-” charge
 If the atom has one less electron, it is shown with a “+” charge
 If the molecules neutral, sum of a “+” and a “-” are equal ~ dipolar

• Example; the formal charges on nitrogen in NH3 and NH4+ are thus,
NonBonding
H N H electron H
H Bonding electron H N H
H
Formal charge on nitrogen = 5 - 6- 2 = 0
2 Formal charge = 5 - 8 - 0 = +1
2
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 …(continue)

• Example: draw a Lewis structure and show all formal charges

for these ions

NH4+ OH- CH3- CO32-

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 RESONANCE
• Sometimes more than one Lewis Structure can be written for a
molecule
Double headed arrow
• Example: O3
+ - +
O O O O Curved arrow
-
O O

– individual Lewis structures are called resonance form

– individual resonance form connected by double-headed (resonance) arrow
– Curved arrow: a symbol used to show the movement of valence electrons
from tail to the head of the arrow within atom/bond

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 …(continue)
• All acceptable resonance form must:
have the same number of valence electrons
obey the rules of covalent bonding
differ only in distribution of valence electrons
 have the same number of paired and unpaired
electrons
• Examples of ions and a molecule best represented as resonance
forms Nitrite ion NO2 -
Carbonate ion CO32-
Acetate ion CH3COO-
Acetone CH3COCH3

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• Draw the resonance form for
– Nitrite ion, NO2 -

– Carbonate ion , CO32-

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 ELECTRONEGATIVITY
D i fference in
Electronegativity
Betw een Bonded Atoms Ty pe o f Bo nd
Type of Bonding
less than 0.5 no npo lar co val ent
0.5 to 1.9 po lar coval ent
greater than 1.9 ioni c

Electronegativity:
Tendency of an
atom to attract
electrons in a
covalent bond
toward itself.
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 …(continue)

• Example: difference in electronegativity for H-Cl = 0.9

 H-Cl is polar covalent bond
 Cl is more electronegative atom, attract electron more strongly
than H and has a partial negative charge (d- ) or head arrow ()
or electron rich red region
 H less electronegative atom has a partial positive charge, (d+ ) or
tail arrow (+) or electron poor blue region

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 POLARITY

nonpolar
nonpolar
polar

polar
polar
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 …(continue)
Insert elpot of
carbon d ioxid e
(page 19) d- Insert elpot
O of w ater
d- d+ d- H d+ H
O C O (page 19)
Carbon d ioxid e Water
(n on polar) (polar)

In sert elpot of In sert elpot of In sert elpot of

ammon ia formaldeh yd e acetylene
(page 19) (page 20) (page 20)
d-
d- O
N C
H C C H
H
H d+
H H d+ H
A mmon ia Formald ehyde Acetylene
(p olar) (p olar) (nonpolar)
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 VSEPR (Valence Shell Electron Pair Repulsion)
This model is based on two concepts
– atoms are surrounded by regions of electron density
– regions of electron density repel each other

bonded pair  bonded pair  nonbonded pair  bonded pair  nonbonded pair  nonbonded pair
least repulsive H most repulsive
H
N
H O 105 ºC
109.5 ºC C H 107 ºC H
H H
H H

–The electron pair in a covalent bond feels the attractive force of two nuclei
and is held more tightly compared to a lone pair. The largest repulsive
involved the two lone pairs of oxygen. As the distance of two lone pairs
increases, the H-O-H angle decreases.

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 CHEMICAL FORMULA
H H H H

H C C C C H

H H H H

Expanded structural formula

Ball and stick model
H

H C H
H
C H

Skeletal structural formula H

H
C
H
C
H

H
Fischer model
CH3CH2CH2CH3
Condensed structural formula

Space filling model

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 ACID AND BASE
• In 1884, Svante Arrhenius proposed these definitions
– Arrhenius acid: a substance that produces H3O+ / H+ ions in aqueous solution

+
:

:
: :

: :
H O: + H Cl : H O H + :Cl:-
H H
– Arrhenius base: a substance that produces OH- ions in aqueous solution

H H
-
H N+ H + :O H
:

: :
H N: + HO H
:

H H

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– Bronsted-Lowry Acid: a proton donor
– Lewis acid: any species that accepts an electron pair to form a covalent bond

+
:

:
: :

: :
H O: + H Cl : H O H + :Cl:-
H H
– Bronsted-Lowry Base: a proton acceptor
– Lewis base: any species that donates an electron pair to form a new covalent
bond

- +
A + :B A B new covalent bond
Lewis Lewis formed in this Lewis
acid base acid-base reaction

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 …(continue)
– when HCl dissolves in water,
the HCl acts as Lewis acid (accept electrons)
while, the H2O acts as Lewis base (donor
electrons)
The curved arrows indicated direction of flow
electron from Lewis base (rich electron) to acid
lewis ( poor electron)

H O + H Cl H O H + Cl
H H
Hyd roniu m ion

Lewis base Lewis acid

(rich electron) (poor electron)
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 …(continue)

– when AlCl3 react with NH3,

the AlCl3 acts as Lewis acid (accept electrons) while,
the NH3 acts as Lewis base (donor electrons)
Cl H Cl H

Cl Al + N H Cl Al N H

Cl H Cl H

Lewis acid Lewis base

(poor electron) (rich electron)
Another lewis acids is compound that have atoms with vacant orbital such as
ZnCl2, FeBr3, BF3 etc.

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 …(continue)
– When carbocation reacts with Br - ion;
the C+ acts as Lewis acid (accept electrons) while,
the Br- acts as Lewis base (donor electrons)

bromin e uses a lon e

pair of electrons to form
a new b on d to carbon

+ Br
CH3 -CH-CH3 + Br CH3 -CH-CH3
A n organic cation Bromide ion 2-Bromobutan e
(a Lew is acid) (a Lew is bas e)

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 ELECTROPHILES AND NUCLEOPHILES
• Electrophiles is a substance that is electron-loving or electron seeking
 An electrophile has an electron poor atom and can form a bond by accepting
a pair of electrons from nucleophile
 Electrophile can be either neutral or positively charged.
 Example; Acids (H+), alkyl halide and carbonyl compounds
 Electrophile usually Lewis Acids

• Nucleophiles is a substance that is Nucleus-loving or nucleus seeking

 A nucleophile has an electron rich atom and can form a bond by donating a
pair of electrons to an electron poor atom.
 Nucleophile maybe either neutral or negatively charged.
 Example; NH3, H2O, OH- and Br-
 Nucleophiles usually Lewis base

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Nucleophiles Electrophiles
(Donors pair electron)
` (accept pair electron)

-:OH, RO:- H+ (H3O+), NO2+

Cl-, Br-, I- Cl2, Br2

CN- Cl+, Br+, I+

C- C+

R-OH RN2-, R3C-

CH2=CH2 BF3

:NH3, RNH2 AlCl3

H2O: FeBr3, ZnCl2

Reducing agent Oxidising agent

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Nucleophiles Electrophiles

NH3

C+

BF3

CN-

Cl2

Cl-

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 ISOMERISM
Isomer are compound that have the same
molecular formula but different structure

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 CONSTITUTIONAL ISOMER
• Compounds that have a different order of
attachment in their atoms
CH3
Different carbon CH3CH2CH2CH3
skeletons CH3CHCH3
butane
2-methylpropane

Different functional
CH3CH2OH CH3OCH3
groups
Ethyl alcohol Dimethyl ether
NH2
Different position CH3CH2CH2NH2
of functional group
CH3CHCH3 Propylamine
isopropylamine

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 STEREOISOMER
• Compound with the same order of attachment of atom, but different
orientation of their atom in space
• Stereoisomerism classified by 2 categories;
a. Diastereomers – nonsuperimposable, non-mirror image stereoisomer (cis-
trans)
H H H CH3
C C C C
H3 C CH3 H3 C H
cis-2-Buten e t ra ns-2-Buten e
m p -139°C, bp 4°C m p -106°C, bp 1°C

b. Enantiomers - nonsuperimposable, mirror image stereoisomer (optical)

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 GEOMETRICAL ISOMER
H H H CH3
C C C C
H3 C CH3 H3 C H
cis-2-Buten e t rans-2-Buten e
mp -139°C, bp 4°C mp -106°C, bp 1°C

 there are two geometrical isomers with molecular formula C4H8

 Free rotation about a C-C double bond is not possible, so groups
on adjacent carbons are either cis or trans to each other
 cis - two group of CH3 on the same side of the double bond
 trans - two group of CH3 on the opposite side of the double bond
 These two compounds are different.
 cis alkenes are less stable than trans alkenes because of
nonbonded interaction strain between alkyl substituents on the
same side of the double bond.

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– Other example of geometrical isomer is the ring which is
commonly viewed through an edge or from above
H H
H H H H
H H H H H H3 C
H H H H
CH 3 CH3 CH3 H

H3 C CH3 H3 C CH 3
cis-1,2-D im ethy l- t ra ns-1,2-D imeth yl-
cy clo pentan e cy clo pentane

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OPTICAL ISOMERS

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• Carbon with 4 different groups (example; Cl, Br, OH, CN) is called a chiral
carbon.
Cl
Chiral carbon

C
Br
NC OH
• This type of carbon can exist in two arrangement because of the carbon’s
tetrahedral geometry, which mirror image to each other but it is non
superimposable .
Cl Cl

C C
Br Br
CN
NC OH HO
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mirror
Both A and B have A B
chiral carbon
Cl Cl
A and B are mirror
Br Br
image to each other.
NC C C CN

if you rotate molecule OH HO

B. They still different- no way Cl
to rotate to look exactly the mirror Br
same. They are described as HO C
being non-superimposable CN
These are isomers of each
Cl
other. OH

NC C

Mirror image Br

molecules that are not Cl

CN
superimposable are Br C
called “enantiomers” OH
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 A B

• What happens if carbon Cl Cl

atom in A and B are Br Br
achiral? NC C C CN
• Achiral: identical with its
Br Br
mirror images
• Rotating molecule B this mirror Cl
time shows that it is CN
exactly the same as
molecule A. They are Br C
described as being Br
superimposable. These
are not isomers of each Cl
other Br

Br C
IMPORTANT!! CN
You can get optical
Cl
isomer only if structure Br
have chiral carbon.
NC C

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• Which of the following is chiral carbon?
H3C CH2

CH CH3

Cl

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 H3C CH2

CH CH3

Cl

H
H

C C H H
H
H H C C
H

Cl H

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 H
H

C C H H
H

*
H H C C
H

Cl H

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 • Which of the following compounds have chiral
carbon?
H3C CH2

CH CH3

H3C CH3
A
CH2 CH2 CH3
H3C C CH2
OH
Cl
H3C CH2
C

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• Example: draw the enantiomers of 2-butanol.

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 HOMOLOGOUS SERIES
Organic compounds are sometimes classified by the structure of
their carbon skeletons
Class Characteristic example
Aliphatic • Straight or branched chain Alkanes, alkenes, alkynes
(open chain)

Alicyclic •Closed rings of carbon Cyclohexane (C6H12)

atom Cyclohexene (C6H10)
• The rings may contain
single or multiple bonds

Aromatic (arenes) / • Containing at least one Benzene (C6H6)

homocyclic benzene ring Naphtalene (C10H8)

Heterocyclic •The closed ring consists of Pyridine (C5H5N)

carbon atoms of one or
more atoms or other
N
element (N, O, S) 47
• Functional group: an atom or group of atoms within a molecule that shows a
characteristic set of physical and chemical properties
• Functional groups are important for three reasons, they are
 the units by which we divide organic compounds into classes
 the sites of characteristic chemical reactions
 the basis for naming organic compounds

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• At the end of the topic, students should be able to:

 explain the characteristic features of organic compound

- Composition:
- Electronic Structure of atoms
- Bonding: Lewis model, chemical bond, Hybrid resonance, formal charge, resonance
- Chemical Formula
 Define terms
- Type of reaction, curve arrow, reaction intermediates, electrophiles & nucleopiles, acid & bases
 Differentiate type of isomerism - Constitutional isomer, stereoisomers
 Identify the functional group & Classification of Carbon

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