Organic Chemistry I

SIC 1003, SCES1220

Prof. Dr. Issam A. Mohammed

Textbook
Organic Chemistry, 8th Edition
Author: Francis A. Carey and
Robert M. Giuliano
Other References
Organic Chemistry,
by
1. Janice Gorzynski Smith
2. Paula Yurkanis Bruice
3. L. G. Wade, Jr.
 Learning outcomes
1. Define and explain electronegativity.
2. Define, differentiate and explain chemical bonding.
3. Draw Lewis and chemical structures.
4. Identify and explain hybridzation in organic
molecules.
5. Draw resonance structures.
6. Identify acid and bases: Bronsted-Lowry, Lewis
7. Identify types of bond breakages.
8. Chemical reactivity.
9. Define and explain electrophilicity, nucleophilicity
and free radical.
10. Identify nucleophilic and electrophilic centers.
11. Explain polar reaction mechanisms.
 Introduction

• Organic chemistry is the chemistry of

carbon compounds.
• Carbon-containing compounds were once
considered “organic compounds”
available only from living organisms.
• Not all compounds containing carbon
atoms are organic (e.g CO2, Na2CO3,
NaHCO3 – these are inorganic
compounds).
• The synthesis of the simple organic
compound urea in 1828 showed that
organic compounds can be prepared in
the laboratory from non-living material.

Today, organic natural products are

routinely synthesized in the laboratory.
Why Carbon?
• Carbon neither gives up nor accepts electrons
because it is in the center of the second
periodic row.
Why Carbon?

• Consequently, carbon forms bonds with

other carbons and other atoms by sharing
electrons.

• The capacity of carbon to form bonds

in this fashion makes it the building block
of all living organisms.
Why Study Organic Chemistry?
• Since carbon is the building block of all living
organisms, a knowledge of Organic
Chemistry is a prerequisite to understanding
Biochemistry, Medicinal Chemistry, and
Pharmacology.

• Indeed, Organic Chemistry is a required

course for studying Pharmacy, Medicine,
Dentistry, Food Technology and etc.

• Admission into these professional programs

is highly dependent on your performance in
Organic Chemistry.
Methotrexate, Anticancer Drug
5-Fluorouracil, Colon
Cancer Drug

AZT, HIV Drug Tamiflu, Influenza Drug

 Structure and Bonding
Atomic Structure

The nucleus contains positively charged protons

and uncharged neutrons.
The electron cloud is composed of negatively
charged electrons.
• Nucleus is extremely small (10-14 to 10-15
m in diameter), but essentially carry all
the mass of the atom.

• Electrons have negligible mass, circulate

around the nucleus at a distance of 10 -10
m.
 Atomic Structure
• The atomic number is the number of protons
in the nucleus and also the number of
electrons surrounding (i.e., protons =
electrons).
• The atomic mass is the number of protons
plus neutrons in the nucleus (e.g., 126C has six
protons and six neutrons).
• Carbon’s atomic number is 6; its atomic mass
is 12.
• In a neutral atom, the number of protons
equals the number of electrons.
Ions
• In addition to neutral atoms, atoms can
exist as ions.
• A cation is positively charged and has
fewer electrons than its neutral form.

• An anion is negatively charged and

has more electrons than the neutral
form.
 Isotopes

Isotopes are two atoms of the same element

having a different number of neutrons.
 Atomic Orbitals

• Quantum mechanics uses the mathematical

equation of wave motions to characterize the
motion of an electron around a nucleus.
• Wave functions or orbitals tell us the energy of the
electron and the volume of space around the nucleus
where an electron is most likely to be found.
 Atomic Orbitals: shapes and types

• An s orbital has a sphere of electron density and is

lower in energy than the other orbitals of the same
shell.
• A p orbital has a dumbbell shape and contains a node
(no electron density) at the nucleus. It is higher in
energy than an s orbital.
S Orbital
 P Orbital
Shapes of the 2p orbitals – each of the three
perpendicular to each other, dumbbell-shaped orbitals has
a node between the two lobes.
Orbitals
• Orbitals are organized into different layers, or
shells, of successively larger size and energy.

• Different shells contain different number and

kinds of orbitals.

• Each orbital can be occupied by maximum of

two electrons.
 Energy levels of electrons in an
atom
3d
3rd shell
(capacity 18 electrons) 3p
3s

2nd shell 2p
(capacity 8 electrons)
2s

1st shell
(capacity 2 electrons) 1s
The Periodic Table
 Periodic Table
 Elements in the same row are similar in size.
 Elements in the same column have similar electronic
and chemical properties.
Periodic Table
• The First Row
• There is only one orbital in the first shell.
• Each shell can hold a maximum of two electrons.
• Therefore, there are two elements in the first row: H
and He.
 Periodic Table
• The Second Row
• Each element in the second row of the periodic table
has four orbitals available to accept additional
electrons: one 2s orbital, and three 2p orbitals.
Periodic Table
• The Second Row
• Each of the four orbitals in the second shell hold two
electrons.

• The second row of the periodic table consists of eight

elements, obtained by adding electrons to the 2s and
three 2p orbitals.
Electronic Configuration
• 1 or 2 electrons per orbital, opposite spins (Pauli’s
principle)
• Singly as far as possible (Hunds Rule)
• Lowest energy gets filled first (Aufbau principle)

Eg.
Carbon atom
No. of electron = 6 E

Electronic configuration: 2px 2py 2pz

1s2 2s2 2px1 2py1 2s

1s
Valence Electrons
• Valence shell (outermost shell).
• Atoms tend to achieve stable electronic configuration of nearest
noble gas.
• ‘octet rule’ – 8 electron in outermost shell i.e. Ne (2 + 8), Kr (2 + 8
+ 18 + 8).
• Lose, gain or share electrons in valence shell (bonding).
• Valency – no. of atoms typically bonded to a given atom.

Element Z Number E. configuration Valence electrons Valency

H 1 1s1 1 1

C 6 1s2 2s2 2p2 4 4

N 7 1s2 2s2 2p3 5 3

O 8 1s2 2s2 2p4 6 2

Valence Electrons
• Second row elements can have no more than eight
electrons around them. For neutral molecules, this has
two consequences:
• Atoms with one, two, three, or four valence
electrons form one, two, three, or four bonds,
respectively, in neutral molecules (e.g., BF3, CH4).

• Atoms with five or more valence electrons form

enough bonds to give an octet (e.g., NH3). This results
in the following equation:
Nonbonded Electrons
• When second-row elements form fewer than four
bonds their octets consist of both bonding (shared)
and nonbonding (unshared) electrons. Unshared
electrons are also called lone pairs.
 Molecular Orbitals, MOs
The AO model gives more information (energy
and bond direction) than does a Lewis structure
(which just shows valence electrons), but it lacks
information about excited states of molecules.

• Molecular orbitals (MOs) belong to the whole

molecule.
• MO theory explains electron excited states.
• MO theory describes AOs combining (mixing) to
form new orbitals.
• s bond: formed by overlapping of two s orbitals.
• Bond strength/bond dissociation: energy required
to break a bond or energy released to form a bond.
In-phase overlap forms a bonding MO; out-of-phase
overlap forms an antibonding MO:
Sigma bond () is formed by end-on overlap of
two p orbitals:
Pi bond () is formed by sideways overlap of two
parallel p orbitals:
Summary

s orbital + s orbital bonding

p orbital + p orbital bonding

s orbital + p orbital bonding

bonding
p orbital + p orbital
(side to side)
Hybridization
• Hybridization is the combination of two or
more atomic orbitals to form the same
number of hybrid orbitals, each having the
same shape and energy.

• Or…. mathematical mixing of atomic orbitals

prior to formation of molecular orbital.
Methane (CH4)- sp3 hybridization
Electronic configuration of C: 1s2, 2s2 2p2
Energy diagram

2px py pz 2px py pz
2sp3
Energy
2s 2s

1s 1s 1s

Ground Higher-energy sp3 hybrid state of

electronic state electronic state of carbon
of carbon carbon

In 1931, Linus Pauling showed how an s orbital and three p

orbitals on an atom can combine, or hybridize, to form four
equivalents atomic orbitals with tetrahedral orientation.
Hybridization of One s and Three p Orbitals
Bonding in Methane
• When the four identical orbitals of an sp3 hybridized
carbon atom overlap with the 1s orbitals of four
hydrogen atoms, four identical C-H bonds are formed
and methane results.

• The bond angle formed by each H-C-H is 109.5o and

bond length of 110 pm, i.e. tetrahedron angle.
Methane (CH4)
The orbitals used in bond formation determine the
bond angles.

• Tetrahedral bond angle: 109.5°

• Electron
pairs spread themselves into space as far from
each other as possible.
Ethane structure
• The simplest molecule containing a C-C bond.

• The two carbon atoms bonded to each other by the

overlap of sp3 hybrid orbitals from each one.

• The remaining three sp3 hybrid orbitals on each carbon

overlap with hydrogen 1s orbitals to form six C-H bonds.

• All the angles are approximately tetrahedron value,

109.5o.
Ethene (CH2=CH2): sp2 hybridisation
Energy diagram

H H
2p 2pz
Energy C C
sp2
2s H H
1s 1s

• To form sp2 bonding orbitals, carbon hybridizes its 2s orbital

with only two of its 2p orbitals.
• One p orbitals remains unhybridized on the carbon atom.
• Each sp2 orbitals has a shape similar to that of an sp3
orbital and contain 1e that can be used for bonding.
• In ethene, (CH2=CH2), two sp2 carbons are joined by a
sigma bond (s) formed overlap of one sp2 orbital from
each carbon atom.
• The other two sp2 orbitals are left for bonding with
hydrogen

Each carbon also has a p orbital containing one electron.

These two orbitals overlap their sides to form pi () bond – a

bonding molecular orbital joining the two carbons and located
above and below the sigma () bond

The  bond is the second bond of the double bond.

 Ethyne (CH≡CH): sp hybridisation
• When a carbon atom joined to only two other atoms, as
in ethyne (acetylene), its hybridization is sp.
• One 2s orbital blends with only one 2p orbital to form
two sp-hybrid orbitals.
• Two unhybridized 2p orbitals remain, each with one
electron.

2p 2p
Energy

Energy diagram sp
2s

1s 1s
Higher-energy sp hybridise
electronic state of carbon electronic state of carbon
• The two sp orbitals are far apart in a straight line with
180o angle between them.
• The p orbitals are perpendicular to each other and to the
line of the sp orbitals

p orbitals perpendicular to
each other

One sp orbital Two sp orbitals

Two p orbitals
• In HC≡CH, the two carbon atoms are joined by
sp-sp sigma bond.
• Each carbon is bonded to a hydrogen atom by
an sp-s sigma bond.
• The two p orbitals of one carbon then overlap
with the two orbitals of the other carbon to
form two pi (p) bonds.
• One pi bond is above and below the line of
sigma bond.
Summary of Covalent Bonds
Bond Length and Bond Strength
• As the number of electrons between two nuclei
increases, bonds become shorter and stronger.
• Triple bonds are shorter and stronger than
double bonds, which are shorter and stronger
than single bonds.
Carbon-Hydrogen Bonds
• The length and strength of C—H bonds vary
depending on the hybridization of the carbon
atom.
Percent s-Character
 Summary
• The shorter the bond, the stronger it is.
• The greater the electron density in the region of
orbital overlap, the stronger is the bond.
• The more s character, the shorter and stronger is the
bond.

• The more s character, the larger is the bond angle.

Electronegativities
• Electronegativities can be used to predict whether a
bond will be polar and the direction of its dipole
moment.
• Since the electronegativities of carbon and hydrogen
are similar, C—H bonds are considered to be nonpolar.
Electronegativity is a measure of an atom’s
attraction for electrons in a bond.
• Patterns in electronegativity (EN):

• EN increases across a period

• The no. of charges on nucleus increases, bonding
electrons are attracted more strongly.

• EN decreases down a group

• The bonding electrons are increasingly distant from the
attraction of the nucleus.

• Shielding by electrons in inner orbitals are also

increasingly greater.
Bonding
• Bonding is the joining of two atoms in a stable
arrangement.
• Through bonding, atoms attain a complete outer shell of
valence electrons (stable noble gas configuration).
• Atoms can form either ionic or covalent bonds to attain a
complete outer shell (octet rule for second row elements).

 Ionic bonds result from the transfer of

electrons from one element to another.

 Covalent bonds result from the sharing of

electrons between two nuclei.
Ionic Bonding
• An ionic bond generally occurs when elements on the
far left side of the periodic table combine with elements
on the far right side, ignoring noble gases.
• A positively charged cation formed from the element on
the left side attracts a negatively charged anion formed
from the element on the right side (e.g., sodium
chloride, NaCl).
Ionic Bonds
• Remember ionic bond occurs with the transfer of electron from
one atom to another atom.

• Na -has electronic configuration 1s2, 2s2, 2p6, 3s1 (11e)

-has to release 1e valence to form ion Na+ (1s2, 2s2, 2p6)

• Cl -has electronic configuration (1s2, 2s2, 2p6, 3s2, 3p5) (17e)

-much easier to accept 1e to form ion Cl (1s2, 2s2, 2p6, 3s2, 3p6)

* Thus, ionic bond can be formed between sodium and chlorine

atoms,. Na+Cl-
Ionic Bonding
• Li loses its one electron to make Li+ which has no
electrons in second shell. However, it has a complete
first shell.
• F gains one electron to make F- which has a filled
valence shell (an octet of electrons), like neon.
Covalent Bonding

• Covalent bonding occurs with elements like carbon

in the middle of the table (e.g., CH4) with elements
that have similar electronegativity.
• Covalent bonds also occur between two of the same
elements from the sides of the table (e.g., H 2, Cl2).

• A covalent bond is a two-electron bond, and a

compound with covalent bonds is called a molecule.
 Hint

Valence electrons that are not

used for bonding are called
nonbonding electrons or lone-pair
electrons.
Polar Covalent Bond
• Equal sharing of electrons: nonpolar covalent bond (e.g.,
H2)
• Sharing of electrons between atoms of different
electronegativities: polar covalent bond (e.g., HF)
Polar Covalent Bond
• A polar covalent bond has a slight positive charge on
one end and a slight negative charge on the other
Polar Covalent Bond
• F, Cl and Br atoms are more electronegative than H

• The shared electron will be more attracted to F, Cl or Br

atoms

• As a result, F, Cl or Br atoms will have more negative

charge (-) and atom H will have more positive charge
(+)

• Hence, the bond form is polar covalent bond

Types of bonding
A Polar Bond Has a Dipole Moment
• A polar bond has a negative end and a positive end
dipole moment (D) = m = e x d
• (e) : magnitude of the charge on the atom
• (d) : distance between the two charges
 H
O

C N
O H H
H H
H H H
H

Some compounds have zero dipole moment although

have polar covalent bonds.
They have symmetrical structures. Individual bond
polarities and lone pair contributions exactly cancel.

H Cl

O C O C C
H Cl
H Cl
H Cl
= 0 = 0 = 0
Electrostatic Potential Maps
Formal Charge
• Formal charge is the charge assigned to individual atoms in
a Lewis structure.
• Formal charge is calculated as follows:

• The number of electrons “owned” by an atom is determined by

its number of bonds and lone pairs.
• An atom “owns” all of its unshared electrons and half of its
shared electrons.
Electron Ownership
• The number of electrons “owned” by different atoms is indicated in
the following examples:
Lewis Structure
Nitrogen has five valence electrons

Carbon has four valence electrons

Hydrogen has one valence electron and halogen has

seven
Structure and Bonding
• How many bonds?
• a) how many valence electrons (VE) b) how many more to
achieve octet
• Atoms with 1, 2, 3 VE’s 1, 2, 3 bonds
• Atoms with 4 or more VE’s as many bonds as it need to fill valence
shell with electrons to achieve octet
• Eg. B (2s22p1) 3 VE’s - forms 3 covalent bonds
• C (2s22p2) 4 VE’s - forms 4 covalent bonds
• N (2s2 2p3) 5 VE’s - forms 3 covalent bonds (carries 1 lone pair)
• O (2s22p4) 2 VE’s - forms 2 covalent bonds (carries 2 lone pair)
• F (3s2 3p5) 7 VE’s - forms 1 covalent bond (carries 3 lone pairs)
Drawing Lewis structures

• How many bonds?

H F Cl Br O

N B C

Drawing Lewis structures:

• help us to understand the bonding within a molecule of the
compound
• either all electrons shown or
• bonding electrons as dash & non-bonding electrons as dots
• a few simple rules
Drawing Lewis Structures
• Step 1
You need to know how the individual atoms are
attached to each other (connectivity). If you do not
know or cannot guess which atoms are attached to
which other atoms, you cannot draw the structure.
Fortunately, it is often easy to guess the connectivity of
the atoms of a compound. If that is not possible, you
will be told how the atoms are connected.
 • Eg. formaldehyde (CH2O) -
• carbon is attached to 2 different hydrogens and an
oxygen
Step 2
Determine the total number of electrons in the valence shells of O
all of the atoms of the molecule. This is done simply by
multiplying the Group A number from the Periodic Table (i.e VE) C
by the number of atoms of that element found in the molecule.
For formaldehyde the results yield 12 total electrons. (for cations H H
and anions, minus or add the number of charges from the total
valence electrons, respectively)
Hydrogen: 2x1=2
Carbon: 1x4=4
Oxygen: 1x6=6
Total Valence Electrons: 12
• Step 3
• We begin the process of bonding by placing pairs of
electrons between all atoms known to be bonded to
one another (Step 1). As we use the electrons we
keep a running total of how many electrons are
remaining of the total we started with in Step 2.

O
• Three pairs of electrons (6) used.
• 12 – 6 = 6 electrons remaining. C

H H
• Step 4
• If any electrons remain after Step 3, they should be placed
in pairs on the most electronegative atoms (closest to F on
the P.T.) first until each atom has a maximum of 8 electrons
or until you run out of electrons. Never place additional
electrons on hydrogen as it can accommodate only 2
electrons maximum. If you run out of electrons before you
have eight on all atoms (except H), you must stop adding
electrons and proceed to Step 5. If you have electrons left
over, add them to the most electronegative atom of the
compound up to a maximum of 12 total electrons.

H H
• Step 5
• If, after placing all electrons on the atoms of the
molecule, any atom other than hydrogen has fewer
than eight electrons; you must move unshared pairs
from adjacent atoms between the two atoms so that
each atom has eight. You may have a maximum of 6
electrons (3 pairs) between any two atoms.
• Only 6 electrons on carbon, so move one of the pair
on oxygen

O O O

or C
C C

H H H H
H H
 CH3F C 1(4) = 4 H N2 2N 2(5) = 10 N N
3H 3(1) = 3
H C F
F 1(7) = 7 CO2 C 1(4) = 4 O C O
Total VE = 14 H
2O 2(6) = 12

Total = 16
H H
C2H4 2C 2(4) = 8
4H 4(1) = 4 C C

Total = 12 H H

• ClO3-
• NH4+
• SO42-
Other than carbon compounds:

lone pair lone pair

lone pair

O P
N lone pair
H H H
H
H H
H H

104.5
107.3
ammonia, NH3 water, H2O phosphine, PH3
Chemical formulas:

C6H13 molecular formula

H C H
CH3
H H H
H
H3C C C C CH2
H C C C C C H2 H H
H
H H H Condensed formulas

Line-Bond or Kekule

CH3

H3C CH2

line or structural formulas

Resonance
• Some molecules may be drawn as 2 or more Lewis
structure, e.g. nitromethane

Double bond to this oxygen?

H O H
..O -
+ +
N N
H
H ..O - H O
H

Or to this oxygen

The two Lewis structures for nitromethane are called

resonance forms.
Guidelines to interpret and draw resonance forms

1. Individual resonance forms are imaginary.

The real structure is composite, or resonance hybrid, of
the different forms.
• 2. Resonance forms differ only in the placement of
their p and nonbonding electrons

a lone pair of electron moves a new resonance structure

to become N=O double bond with double bond here

H .. - H
O O
+ +
H C N H C N

H
O
H
O -

two electrons from N=O a lone pair electrons

move to become a lone pair here
3. Different resonance forms of a substance don’t have to
be equivalent.
E.g. acetone anion. Both resonance forms are not
equivalent, but both contribute to the overall resonance
hybrid.
negative charge negative charge
on carbon on oxygen

.. O .. .. O ..-

..
H -
.. H H H

H H H
H H H

If the resonance form are nonequivalent, the actual molecule

will resemble the most stable form.
4. Resonance forms must be valid Lewis structures and
obey valency rules.

H H
.. - H O
O

..
O
..

..

..
.. 10 electron

..
H C C H C C H C
-C on carbon
.. -
O O O

..
..

..
..

..
..
H H H
NOT a valid
resonance form

5. All resonance forms contribute to the overall resonance

hybrid.

The resonance hybrid is more stable than the

individual resonance form.
6. The larger the number of forms, the more stable the
substance is.
E.g. 2,4-pentadione anion can have 3 resonance
structures

O O
- O O

-
H3C CH3 H3C CH3

H H

.. -
O O

H3C CH3

H
Rules For Writing Resonance Structures

1. Atomic positions cannot change. Only electron

positions can vary.
O
H3C N H3C O N O
O
Nitromethane Methyl nitrite

• Nitromethane and methyl nitrite are isomers not

resonance structures.
2. Second row elements cannot have more than 8
electrons. Hydrogen can never have more than two
(2) electrons.

The octet rule may be exceeded for elements beyond

the second row.

O O O
H3C N Cl S Cl Cl S Cl
O
Is Not a Legal Resonance Structure Is a Legal Resonance Structure
Nitrogen Cannot Have 10 Electrons S (Row 3) Can Have 10 Electrons
3. When two or more resonance structures are possible, the most
stable one is the one with the smallest separation of oppositely
charged ions.

H3C O N O H3C O N O

More Stable

O O
Cl S Cl Cl S Cl

More Stable
4. In a resonance structure that bears a formal charge, the
most stable structure will be the one with the negative
charge on the most electronegative atom and the
positive charge on the most electropositive atom.

N C O N C O

More stable

Formal charge (FC) -indicates electron ownership in a molecule

-applies for atom with abnormal number of bond

VE = valence electrcon
FC = VE – BE/2 – NBE BE = bonding electron
NBE = non-bonding electron
• 5. All contributing resonance structures must
have the same number of electrons and
same net charge.

• 6. All contributing resonance structures must

have the same number of unpaired electrons.
 Resonance Is Not The Same as
Equilibrium
• Ozone does not have a single bonded and a double
bonded oxygen. The central oxygen is identically bonded
to both terminal oxygens.

O O O O O = O
O O O
-1/2
• Lewis structures show electron location as localized -1/2
between atoms. Resonance structures help us to show
that electrons are sometimes delocalized between
several atoms.
The allyl radical as a resonance hybrid

• The allyl radical is a resonance hybrid of two structures.

CH . .H C
H H
H2C C 2 2 C CH2

The allyl radical does not correspond to either structures, but

rather to a structure intermediate between them
Both structures make equal contribution to the hybrid
H2C C
H
CH2 . .H C
2 C
H
CH2 Equivalent to H2C C CH2
H
.
The odd electron is not localized on one carbon, but is delocalized
– being equally distributed over both terminal carbons.
The allyl cation as a resonance hybrid

• Let us turn to heterolytic chemistry, the occurrence of a

double bond in the substrate
• Let us examine the structure of allyl cation

H2C C CH2 + + H C C CH
2 2 Equivalent to H2C C CH2
H H H
+
We can draw two allyl cation structures and the structures
differ only in the arrangement of electrons.
According to resonance theory, neither structures represent
the cation; it is instead a hybrid of both.
The occurrence of resonance give considerable
stabilization.
With regard to stability of carbocation, the following
sequence applies:
3o > allyl 2o > 1o > CH3
The role of unshared electron pairs
• Molecule or cation with unshared electron pairs tend to
share these electrons, thus acquiring positive charge;
example methoxymethyl cation.

H H

H3C O C H H3C O C H
+ +

Stable - every atom

has octet electron

We can draw structures for these cations. The two

structures differ only in the arrangement of electrons,
hence resonance form.
1) Draw three resonance forms for the carbonate ion, CO 32-

- -
O O O

- - - -
O O O O O O

2) Draw the resonance forms of pentadienyl radical.

H H
H . H

H H H
3) Draw the resonance forms of each of the
following species:

a) The nitrate ion, NO3-

b) The allyl cation, H2C=CH-CH2+

c) CH3CO2-
 Summary

• These structures are called resonance structures or

resonance forms. A double-headed arrow is used to
separate the two resonance structures.
 Resonance structures are two Lewis structures having the
same placement of atoms but a different arrangement of
electrons.
• Neither resonance structure is an accurate
representation for (HCONH)¯. The true structure is a
composite of both resonance forms and is called a
resonance hybrid.

• The hybrid shows characteristics of both structures.

• Resonance allows certain electron pairs to be

delocalized over two or more atoms, and this
delocalization adds stability.

• A molecule with two or more resonance forms is said

to be resonance stabilized.
• Resonance structures are not real. An individual
resonance structure does not accurately represent
the structure of a molecule or ion. Only the hybrid
does.

• Resonance structures are not in equilibrium with

each other. There is no movement of electrons from
one form to another.

• Resonance structures are not isomers. Two isomers

differ in the arrangement of both atoms and
electrons, whereas resonance structures differ only
in the arrangement of electrons.
 Acids and bases
• A Bronsted-Lowry acid is a substance that donates
a hydrogen ions (H+, proton)
• A Bronsted-Lowry base is a substance that accepts
H+

• E.g. When gaseous hydrogen chloride dissolves in

water, an acid-base reaction occurs. A polar HCl
molecule donates a proton (H+ ion) , and a water
molecule accepts the proton, yielding hydronium ion
(H3O+) and a chlorine ion (Cl-).
.. .. +
H Cl + H O H O H + Cl-
..

H H
Acid Base Conjugate Conjugate
acid base
Acids and bases
• Chloride ion, the product when acid HCl loses a proton,
is called conjugate base of the acid
• Hydronium ion, the product that results when the base
H2O gain a proton, is called the conjugate acid of the
base.
• Other strong acids that completely transfer a proton when
dissolved in water are:
HI + H2O H3O+ + I-
HBr + H2O H3O+ + Br-
H2SO4 + H2O H3O+ + HSO4-
HSO4- + H2O H3O+ + SO42-
In general, the following applies:
H A + :B A :- + H B+

Acid Base Conjugate Conjugate

base acid
For examples
O O
- :O -
H H + : : H
:O

:
H
: +

: :
O O H

H H H H H
Conjugate Conjugate
Acid Base
base acid

:O - :N - :O
:

: :
+ H

:
H + H N H
H H H
Conjugate Conjugate
Acid Base
base acid
 • Strong acid reacts almost completely with water (dissociates)

• Acid strength in water expressed as:

HA
- + H3O+
+ H2O A

pKa normally used to express acid strength

pKa = -log Ka For dilute aqueous solution, [H2O]
is nearly constant, at 55.6M at
+ -
Keq = [ H3O ][ A ] 25oC
[ HA ][ H2O ]
Ka = acidity constant

Ka = Keq [H2O] = [ H3O+ ][ A- ]

• strong acids – largerKa smaller pKa
[ HA ]
• weak acids – smaller Ka larger pKa
 Predicting acid-base reactions
• 1. H+ will always go from stronger acid to the
stronger base i.e an acid with low pKa reacts with
conjugate base of acid with high pKa

2. products of an acid-base reaction are more stable

than the reactants i.e. product conjugate acid (H2O)
is a weaker acid than the starting acid and product
conjugate base (CH3COO-) is a weaker base than
the starting base
O O
H2O +
CH3COH + HO CH3CO

stronger acid stronger base weaker acid weaker base

Predict which of these acid-base reaction will
occur?
?
HCN + CH3CO2-Na+ Na+ CN- + CH3CO2H

pKa = 9.3 pKa = 4.7

?
CH3CH2OH +
+ Na CN - CH3CH2O-Na+ + HCN

pKa = 9.3
pKa = 16

O O
?
+ Na+ NH2 + NH3
C C
H3C CH3 H3C CH2 Na+

pKa = 19 pKa = 36
Acids and Bases : Organic acid
• Two main types of organic acid
• acids with hydrogen (H) bonded to oxygen (O)
• e.g. alcohol, carboxylic acid

- H+
O O -ve charge on highly electronegative
H3C H H3C atom (O) – thus the anion is stable
methanol
pKa = 15.4

O O O
- H+
C H C
H3C O
C
H3C O H3C O
acetic acid
-ve charge on highly electronegative atom (O), two resonance
pKa = 4.76
forms contributing to the real structure– thus the anion is stable
Acids and Base: Organic acids
• Acids with hydrogen (H) bonded to carbon next to a C=O
group
O O O
H C H - H+ H C H
C C H C
C C C C H
H H H H H H H H H H
acetone
pKa = 19.3
-ve charge on highly electronegative
atom (O), 2 resonance forms contributing to
the real structure– thus the anion is stable

Organic bases: contains a nitrogen (N) atom H

with lone electron pair that can bond with H+ H N

C H
H H
methylamine
The stability of a base is affected by its size and
its electronegativity
When atoms are very different in size, the stronger
acid will have its proton attached to the largest atom
Inductive Effect
Acetic acid is more acidic than ethanol

The delocalized electrons in acetic acid are shared by

more than two atoms, thereby stabilizing the conjugated
base.
Lewis Acids and Lewis Bases
• Lewis bases are species with available
electrons than can be donated to form a
new bond.
• Lewis acids are species that can accept
these electrons to form new bonds.

• Since a Lewis acid accepts a pair of

electrons, it is called an electrophile.
 A Lewis base is an electron pair donor
• Lewis bases are structurally the same as Br Ønsted-
Lowry bases. Both have an available electron pair-a lone
pair or an electron pair in a  bond.
• A BrØnsted-Lowry base always donates this electron pair
to a proton, but a Lewis base donates this electron pair
to anything that is electron deficient.
A Lewis acid is an electron pair acceptor
• Any species that is electron deficient and capable of
accepting an electron pair is also a Lewis acid.
• All BrØnsted-Lowry acids are also Lewis acids, but the
reverse is not necessarily true.
• Common examples of Lewis acids (which are not BrØnsted-
Lowry acids) contain elements in group 3A of the periodic
table that can accept an electron pair because they do not
have filled valence shells of electrons.
Lewis Acid-Base Reactions
• In a Lewis acid-base reaction, a Lewis base donates an electron
pair to a Lewis acid.
• This is illustrated in the reaction of BF3 with H2O. H2O donates
an electron pair to BF3 to form a new bond.
 - + +
: -

:
Cl H + O H H O H + Cl
H H
Hydrogen chloride Water
(a Lewis acid) Lewis base Hydronium ion

Cl CH3 Cl CH3
Cl Al + :N CH3 Cl
-Al N
+ CH
3
Cl CH3 Cl CH3
Aluminium Trimethylamine
trichloride
Lewis base
Lewis acid

Aluminium trichloride accept the electron pair of ammonia and form

covalent bond with nitrogen atom. This happen because aluminium atom
have only sextet of electron.
Thus, when it accept electron pair, in Lewis definition, it is acting as
acids.
Chemical reactivity
• Chemical Reaction: A transformation resulting in a
change of composition, constitution and/or
configuration of a compound ( referred to as the
reactant or substrate ).
• Reactivity refers to the rate at which a
chemical substance tends to undergo a
chemical reaction in time.
• Two factors play role for the reaction, which are
thermodynamic factors and kinetic factors, whether or
not a substance reacts and how fast it reacts. Both
factors are actually distinct, and both commonly depend
on temperature.
Types of Organic reactions
• Addition reaction
• Two reactants add to form one product with no atoms left
over
H Br
H H
+ H Br H C C H
H H
H H
• Elimination reaction
• One reactant splits into two products

H Cl
base
H H
H C C H + H Cl

H H H H
• Substitution reaction
• Two reactants exchange parts to yield two
new products

H H
light
H C H + Cl Cl H C Cl + H Cl

H H

• Rearrangement reaction
• One reactant undergoes reorganization of bonds
and atoms to yield an isomeric product

CH3CH2 H CH3 H
acid catalyst

H H H CH3
How organic reaction occur: Reaction mechanism
• Reaction mechanism describes bond breaking and
bond forming process
• Account for reactants and products
BREAKING OF BONDS
a) Homolysis- symmetrical cleavage of bonds (free radicals)
one bonding electron stays with each products

A B A + B
b) Heterolysis - unsymmetrical cleavage of bonds (polar reactions)
two bonding electron stay with one product

A B A + B
FORMATION OF BOND

• a) Homogenic – symmetrical bond making (free

radical)
one bonding electron is donated by each reactant

A + B A B
• b) Heterogenic - unsymmetrical bond making
(polar reactions) two bonding electrons are donated
by one reactant

A + B A B
VARIOUS REAGENTS IN ORGANIC CHEMISTRY

• In any organic chemistry reactions, the following will occur:

• Reagents + substrates Product of

reactions

• The main reagents are: Nucleophiles

• Electrophiles
• Free radicals
Nucleophiles and Electrophiles
• Nucleophile: Donates electrons to a nucleus
with an empty orbital.
• Electrophile: Accepts a pair of electrons.
• When forming a bond, the nucleophile
attacks the electrophile, so the arrow goes
from negative to positive.
• When breaking a bond, the more
electronegative atom receives the electrons.
Nucleophiles
Nucleus loving. Represented as Nu or :Nu
•Can donate a pair of electrons to substrate
•Anions or neutral molecules containing unshared electrons
•Examples: X (halide ion), OH, NH2, ArO, CH3O, etc.
•Examples of neutral molecules are: H2O, C2H5OH, NH3, CH3NH2
•In a chemical reaction, nucleophile will attack the positively
charge substrate. Example:

+ - - -
C Br + CH3O C OCH3 + Br

136
 Electrophiles
•Capable of accepting a pair of electron from substrate.

•Cations such as H+, NO2+, Br+ and Ar-N2+ (diazonium salt)

•But metal ions such as Na+, Mg2+, Li+ etc are not electrophiles
because they already achieve the noble gas configuration.

•Due to this reason that the negatively charged substrate or

electron rich will attack electrophile (accept e). Example:

H H
+ - + -
C C + H Br C C + Br C C

Br

137
Freeradicals
• This is produced via homolytic cleavage:

R X R + X
radicals

• Reaction easily takes place in polar solvent at high

temperature with the presence of ultraviolet (UV) light.

• Normally reaction takes place between atoms with

same value of electeronegativity or nearly the same.
Example:
Br2 hν 2Br.
• Free radicals are very reactive.
• Capable of accepting H to form new free radical.
• CH4 + Br . CH3 . + HBr

• It can combine with identical free radical to form new

covalent bond.

• CH3. + Br . CH3: Br
• CH .
3 + CH3 . CH : CH 3 3
Relationship Between Nucleophile And
Electrophile With Lewis Acid-base
• Lewis base
• Donate electron/ Nucleophile
• Examples:
• Negatively charge species:
• OH, OR, CN , Cl, Br, I, RS
-, RCO  -, NH 
2 2
• Neutral compounds:
• RNH2, R2NH, R3N, H2O, ROH,
ROR
• (presence of lone pair e)
Lewis acid
Accept electron/ Electrophile
Examples:
• Positively charge species:
H+, H3O+, Br+, Cl+, NO2+, R+,
RCO2+, SO3H+
• Neutral compounds:
Br2, Cl2, I2, AlCl3, BF3
[halides of metals Al, B, Fe, Sn
and Zn e.g. ALX3, BX3, FeX3,
Sn2X3, ZnX2 (X = F, Br, Cl, I)]
Using curved arrows in polar reaction mechanisms

Rule 1
Electrons move from a nucleophile (Nu:) to an electrophilic sink (E)
the nucleophilic source must have an electron pair available (lone
pair or double bond)
E
O E N E CH E C C

• the electrophilic sink must be able to accept an electron pair

(have +ve charge or a positively polarized atom in a functional
group Nu Nu Nu Nu
    
C C X 
H O C O

141
Rule 2
The Nu: can be either negatively charged or neutral
• if negatively charged, the atom that gives away an electron
pair becomes neutral

CH3 O + H Br CH3 O + Br

H
Negatively charged atom neutral

• if neutral, the atom that gives away an electron pair acquires

a positive charge
H
H H H
C C + H Br C C H + Br
H H H
H
neutral positively charged atom
142
Rule 3
E can be either positively charged or neutral
• if positively charged, the atom bearing that charge becomes
neutral after accepting an electron pair
H H
O O
neutral
positively charged atom + C N
C C
H H H C N
H
• if neutral, the atom that accepts the electron pair acquires a
negative charge but the negative charge must be stabilized by
being on an electronegative atom (O, N, Halogen)

H
H H H
C C + H Br C C H + Br
H H H
H
neutral Stable, negatively charged ion
143
Rule 4
The octet rule must be followed. No 2nd row element can be left
with more than 8 electrons (or 2 for hydrogen).
If an electron pair moves to an atom that already has an octet (or
duet for hydrogen) another electron pair must concurrently move
from that atom to maintain the octet.
H H
O O
+ C N
C C
H H H C N
H
The carbon already has 8 electrons when an electron pair from CN- move
to it, an electron pair in the C=O bond must leave. This two electrons
stayed with oxygen neutralizing the positive charge

144
More examples:

O H O

C + H C Br C CH3 + Br
CH3 CH2 CH3 CH2
H

Cl

H N H + Cl Cl H N H + Cl
H H

H
+ H C Br CH3 O CH3 + Br
CH3 O
H

145