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Organic Chemistry

BKF1323

References:
Graham S. Robert, A.and Francis Gingrich and Maitland Jones Organic Chemistry
McGraw-Hill.
Graham S. Organic chemistry ., John Wiley & Sons.
Janice G. Smith., Organic Chemistry., McGraw-Hill 1st edition.
John McMurry., Fundamentals of Organic Chemistry, Seventh Edition., Brooks/Cole
Paul M Dewick Essential of Organic Chemistry., John Wiley & Sons.
CHAPTER 1

1. Structure of Organic Molecules

2. Empirical, Rational and Structural Formulas, and

Shapes of Molecules,

3. Classification and Principals Application of Organic

Compounds
Organic Chemistry

Organic chemistry is the study of the compounds of carbon. Perhaps

its most remarkable feature is that most organic compounds consist

of carbon and only a few other elements chiefly, hydrogen, oxygen,

and nitrogen.
Structure and Bonding in Organic

Molecules
Two central premises are fundamental:
1. The atoms in organic compounds can
form a xed number of bonds using
their outermost shell (valence)
electrons.

2. A carbon atom can use one or more of


its valence electrons to form bonds to
other carbon atoms:
Empirical, Rational and Structural Formulas

A formula that shows only the number of atoms of each element in the compound
is an Empirical Formula; if any supposed arrangement is exhibited the formula is
termed rational. When the symbols are displayed so as to indicate probable
relations of the atoms to each other the formula is termed structural (sometimes
graphic}. The following formulas exemplify these terms :

Empirical. Rational. Structural.

C6H14 CH3CH2CH2CH2CH2CH3

Leffmann And Lawall. Text-book of Organic Chemistry. P.


Blakiston's Son & Co.
The Principles of Organic Chemistry

In order to understand the Principles of Organic Chemistry the elementary principles


of bonding concepts useful to predicting the chemical reactivity and the physical
properties of organic molecules.

1. Coulomb Forces: A Simplied View of Bonding

2. Ionic and Covalent Bonds: The Octet Rule

3. Electron-Dot Model of Bonding: Lewis Structures

4. Atomic Orbitals: A Quantum Mechanical Description of Electrons Around the


Nucleus

5. Molecular Orbitals and Covalent Bonding

6. Hybrid Orbitals: Bonding in Complex Molecules


Vollhardt, K. Peter C., Organic chemistry : structure and function 6th ed. W. H.
Freeman., Chapter 1
Coulomb Forces: A Simplied View of Bonding

Bonds are made by simultaneous coulombic attraction and


electron exchange
Each atom consists of a nucleus, containing electrically neutral particles, or neutrons,
and positively charged protons. Surrounding the nucleus are negatively charged electrons,
equal in number to the protons so that the net charge is zero.

Sort of bonding is described by Coulombs* law

Figure 1.1: A schematic view of an atom. Most of the mass


of an atom is concentrated in its small, dense nucleus.
Vollhardt, K. Peter C., Organic chemistry : structure and function 6th ed. W. H.
Formation of Ionic and Covalent Bonds: The Octet Rule

1. A covalent bond is formed by the sharing of electrons (as


shown in Figure 1).

Figure 1

2. An ionic bond is based on the electrostatic attraction of two ions with


opposite
charges (as shown in Figure 2).

Figure 2

Vollhardt, K. Peter C., Organic chemistry : structure and function 6th ed. W. H.
The Periodic Table Underlies The Octet Rule
An atom that gains electrons becomes an anion (a negatively charged ion), and an
atom that loses electrons becomes a cation (a positively charged ion). This ionic
interaction is often referred to as an ionic bond.
bond

An atom may share electrons with one or more other atoms to complete its
valence
shell.
BondsAmay
chemical bond formed
be partially by partially
ionic and sharing electrons
covalentisthese
covalent; calledbonds
a covalent bond.
are called polar
covalent bonds.
bonds

William H. Brown., Organic Chemistry, Sixth Edition., 2012, 2009 Brooks/Cole.,


Formation of Ions

Ions are formed by the transfer of electrons from the valence shell of an atom of
lower electronegativity to the valence shell of an atom of higher electronegativity.
Example,
Example ions are formed from sodium (electronegativity 0.9) and l fluorine
(electronegativity 4.0).

Example
William H. Brown., Organic Chemistry, Sixth Edition., 2012, 2009 Brooks/Cole.,
Ionization Potential & Electron Affinity

Energy to remove an electron from an atom. This energy is the ionization


potential (IP) of the atom.

Conversely, energy may be released when an electron attaches itself to an


atom this energy, called its electron affinity (EA).

Example

Vollhardt, K. Peter C., Organic chemistry : structure and function 6th ed. W. H.
Covalent Bonds

A covalent bond is a chemical bond formed between atoms by the sharing of one
or
more pairs of electrons to give a noble gas configuration at each atom.

In this pairing, a large amount of energy is released, meaning that two hydro-
gen atoms are unstable relative to H2. The same amount of energy, called the Bond
Dissociation Enthalpy (BDE),
(BDE) also known as the bond dissociation energy) would
have to be absorbed to break the bond.

William H. Brown., Organic Chemistry, Sixth Edition., 2012, 2009 Brooks/Cole.,


Functional Groups
Heteroatoms and bonds confer reactivity on a particular
molecule.
Heteroatoms have lone pairs and create electron-deficient
sites on carbon.
Bonds are easily broken in chemical reactions. A bond
makes a molecule a base and a nucleophile.

the CC and CH bonds are important. They form the carbon


backbone or skeleton to which the functional group is
attached.
Functional Groups
Ethane: This molecule has only CC and CH bonds, so it has
no functional group. Ethane has no polar bonds, no lone pairs,
and no bonds, so it has no reactive sites. Consequently, ethane
and molecules like it are very unreactive.
Ethanol: This molecule has an OH group attached to its
backbone. This functional group is called a hydroxy group.
Ethanol has lone pairs and polar bonds that make it reactive with
a variety of reagents.
o The hydroxy group makes the properties of ethanol very
different from the properties of ethane.
1.2 An Overview of Functional Groups
Functional Groups
Hydrocarbons are compounds made up of only the elements
carbon and hydrogen. They may be aliphatic or aromatic.
Functional Groups
Aromatic hydrocarbons are so named because many of the
earliest known aromatic compounds had strong characteristic
odors.
The simplest aromatic hydrocarbon is benzene. The six-
membered ring and three bonds of benzene comprise a single
functional group.
When a benzene ring is bonded to another group, it is called a
phenyl group.
Functional Groups
Functional Groups

Compounds Containing the C=O Group:


This group is called a carbonyl group.
The polar CO bond makes the carbonyl carbon an
electrophile, while the lone pairs on O allow it to react
as a nucleophile and base.
The carbonyl group also contains a bond that is more
easily broken than a CO bond.
Functional Groups
Functional Groups

Molecules Containing the C=O Functional Group


Functional Groups

It should be noted that the importance of a functional


group cannot be overstated.

A functional group determines all of the following


properties of a molecule:
bonding and shape
type and strength of intermolecular forces
physical properties
Nomenclature
chemical reactivity
1.3 Intermolecular forces
Intermolecular Forces
Intermolecular forces are also referred to as
noncovalent interactions or nonbonded interactions.
There are several types of intermolecular interactions.

Ionic compounds contain


oppositely charged particles
held together by extremely
strong electrostatic inter-
actions. These ionic inter-
actions are much stronger
than the intermolecular forces
present between covalent
molecules.
Intermolecular Forces

Covalent compounds are composed of discrete


molecules.
The nature of the forces between molecules depends on
the functional group present.
There are three different types of interactions, shown
below in order of increasing strength:
van der Waals forces
dipole-dipole interactions
hydrogen bonding
Intermolecular Forces-van der Waals forces

van der Waals forces are also known as London forces.


They are weak interactions caused by momentary changes in
electron density in a molecule.
They are the only attractive forces present in nonpolar
compounds.

Even though CH4 has no net


dipole, at any one instant its
electron density may not be
completely symmetrical, resulting
in a temporary dipole. This can
induce a temporary dipole in
another molecule. The weak
interaction of these temporary
dipoles constituents van der
Waals forces.
Intermolecular Forces -van der Waals forces
All compounds exhibit van der Waals forces.
The surface area of a molecule determines the strength of the
van der Waals interactions between molecules. The larger the
surface area, the larger the attractive force between two
molecules, and the stronger the intermolecular forces.
Intermolecular Forces -van der Waals forces
van der Waals forces are also affected by polarizability.
Polarizability is a measure of how the electron cloud around an
atom responds to changes in its electronic environment.

Larger atoms, like iodine,


which have more loosely
held valence electrons,
are more polarizable than
smaller atoms like
fluorine, which have more
tightly held electrons.

Thus, two F2 molecules


have little attractive force
between them since the
electrons are tightly held
and temporary dipoles
are difficult to induce.
Intermolecular Forces dipole-dipole interactions
Dipoledipole interactions are the attractive forces between
the permanent dipoles of two polar molecules.
Consider acetone (below). The dipoles in adjacent molecules
align so that the partial positive and partial negative charges
are in close proximity. These attractive forces caused by
permanent dipoles are much stronger than weak van der Waals
forces.
Intermolecular Forces hydrogen bonding

Hydrogen bonding typically occurs when a hydrogen


atom bonded to O, N, or F, is electrostatically attracted
to a lone pair of electrons on an O, N, or F atom in
another molecule.
Intermolecular Forces hydrogen bonding

Note: as the polarity of an organic molecule increases, so


does the strength of its intermolecular forces.
1.4 Physical Properties
Physical Properties Boiling Point
The boiling point of a compound is the temperature at which
liquid molecules are converted into gas.
In boiling, energy is needed to overcome the attractive forces
in the more ordered liquid state.
The stronger the intermolecular forces, the higher the boiling
point.
For compounds with approximately the same molecular
weight:
Physical Properties Boiling Point
Consider the example below. Note that the relative
strength of the intermolecular forces increases from
pentane to butanal to 1-butanol. The boiling points of
these compounds increase in the same order.

For two compounds with similar functional groups:


The larger the surface area, the higher the boiling point.
The more polarizable the atoms, the higher the boiling
point.
Physical Properties Boiling Point
Consider the examples below which illustrate the effect of
size and polarizability on boiling points.
Physical Properties Boiling Point
Liquids having different boiling points can be separated in the
laboratory using a distillation apparatus, shown in Figure 3.4.
Physical Properties Melting Point

The melting point is the temperature at which a solid is


converted to its liquid phase.
In melting, energy is needed to overcome the attractive
forces in the more ordered crystalline solid.
The stronger the intermolecular forces, the higher the
melting point.
Given the same functional group, the more symmetrical
the compound, the higher the melting point.
Physical Properties Melting Point
Because ionic compounds are held together by
extremely strong interactions, they have very high
melting points.
With covalent molecules, the melting point depends
upon the identity of the functional group. For
compounds of approximately the same molecular
weight:
Physical Properties Melting Point
The trend in melting points of pentane, butanal, and 1-
butanol parallels the trend observed in their boiling
points.
Physical Properties Melting Point

Symmetry also plays a role in determining the melting points of


compounds having the same functional group and similar
molecular weights, but very different shapes.
Physical Properties Solubility

Solubility is the extent to which a compound, called a


solute, dissolves in a liquid, called a solvent.
In dissolving a
compound, the
energy needed to
break up the
interactions
between the
molecules or ions
of the solute comes
from new
interactions
between the solute
and the solvent.
Physical Properties Solubility
Compounds dissolve in solvents having similar kinds of
intermolecular forces.
Polar compounds dissolve in polar solvents. Nonpolar or
weakly polar compounds dissolve in nonpolar or weakly
polar solvents.
Water and organic solvents are two different kinds of
solvents.
Water is very polar since it is capable of hydrogen
bonding with a solute.
Many organic solvents are either nonpolar, like carbon
tetrachloride (CCl4) and hexane [CH3(CH2)4CH3], or weakly
polar, like diethyl ether (CH3CH2OCH2CH3).
Most ionic compounds are soluble in water, but insoluble
in organic solvents.
Physical Properties Solubility
An organic compound is water soluble only if it contains
one polar functional group capable of hydrogen bonding
with the solvent for every five C atoms it contains. For
example, compare the solubility of butane and acetone in
H2O and CCl4.
Physical Properties Solubility
Since butane and acetone are both organic compounds
having a CC and CH backbone, they are soluble in
the organic solvent CCl4. Butane, which is nonpolar, is
insoluble in H2O. Acetone is soluble in H2O because it
contains only three C atoms and its O atom can
hydrogen bond with an H atom of H2O.
Physical Properties Solubility
The size of an organic molecule with a polar functional group
determines its water solubility.
A low molecular weight alcohol like ethanol is water soluble
since it has a small carbon skeleton of 5 C atoms),
compared to the size of its polar OH group.
Cholesterol has 27 carbon atoms and only one OH group. Its
carbon skeleton is too large for the OH group to solubilize by
hydrogen bonding, so cholesterol is insoluble in water.
Physical Properties Solubility
The nonpolar part of a molecule that is not attracted to H2O is
said to be hydrophobic.
The polar part of a molecule that can hydrogen bond to H2O is
said to be hydrophilic.
In cholesterol, for example, the hydroxy group is hydrophilic,
whereas the carbon skeleton is hydrophobic.