SCH 1202

Organic Chemistry I

SCH 1211
Introduction to Organic Chemistry

Lecturer: Dr. Paul Tanui.

 Course Orientation

Course Objectives
To introduce the students to Organic and Applied Chemistry

Expected outcomes
Demonstrate good knowledge on the significance of saturated and unsaturated
hydrocarbons
Demonstrate good understanding on organic nitrogen compounds and organic
halogens
Demonstrate good understanding on organic functional groups
Demonstrate good understanding of applied chemistry
 Course Evaluation

Assignments 5%
Tests 15%
Practicals10%
Final Exam 70%
 Alkanes and Cycloalkanes:
Introduction to Hydrocarbons
 Bonding Properties of Carbon
• Carbon forms covalent bonds in all its elemental forms
and compounds.
– The ground state electron configuration of C is [He]2s22p2; the
formation of carbon ions is therefore energetically unfavorable.
– C has an electronegativity of 2.5, which is midway between that of
most metals and nonmetals. C prefers to share electrons.
• Carbon exhibits catenation, the ability to bond to itself
and form stable chain, ring, and branched compounds.
– The small size of the C atom allows it to form short, strong bonds.
– The tetrahedral shape of the C atom allows catenation.
Position of Carbon in the Periodic Table
 Comparison of Carbon and Silicon
• As atomic size increases down the group, bonds between
identical atoms become longer and weaker.
– A C–C bond is much stronger than a Si–Si bond.
• The bond energies of a C–C bond, a C–O bond, and a C–
Cl bond are very similar.
– C compounds can undergo a variety of reactions and remain
stable, while Si compounds cannot.
• Si has low energy d orbitals available for reaction,
allowing Si compounds to be more reactive than C
compounds.
Diversity & Reactivity of Organic Molecules
• Many organic compounds contain heteroatoms, atoms
other than C and H.
– The most common of these are O, N, and the halogens.
• Most reactions involve the interaction of electron rich area
in one molecule with an electron poor site in another.
– C–C bonds and C–H bonds tend to be unreactive.
– Bonds between C and a heteroatom are usually polar, creating an
imbalance in electron density and providing a site for reactions to
occur.
 Carbon Skeleton
Each C atom can form a maximum of 4 bonds.
Groups joined by a single bond can rotate, so there are
often several different arrangements of a given carbon
skeleton that are equivalent:
Some Five-Carbon Skeleton
 Drawing Carbon Skeletons

Each C atom can form a maximum of four bonds.

These may be four single bonds, OR one double and two single bonds,
OR one triple and one single bond.

The arrangement of C atoms determines the skeleton, so a

straight chain and a bent chain represent the same
skeleton.

Groups joined by a single bond can rotate freely, so a

branch pointing down is the same as one point up.
 Classes of Hydrocarbons
• Hydrocarbons only contain carbon and hydrogen atoms.
• Hydrocarbons are either classed as aliphatic or aromatic.
• Aliphatic hydrocarbons contain three main groups:
alkanes which only have carbon-carbon single bonds,
alkenes which have a carbon-carbon double bond, or
alkynes which have a carbon-carbon triple bond.
 Classes of Hydrocarbons
•Aromatic hydrocarbons are more complex but the
simplest aromatic hydrocarbon is benzene. Aromatic
hydrocarbons are called arenes.
 Models for Chemical Bonding

• Valence Bond Theory

constructive interference between electron
waves of two half-filled atomic orbitals is basis
of shared-electron bond

• Molecular Orbital Theory

derive wave functions of molecules
by combining wave functions of atoms
 The Sigma () Bond
A bond in which the orbitals overlap along a line
connecting the atoms is called a sigma (s) bond.
Two perpendicular views are shown below.
 Small Alkanes
General formula for alkanes is CnH2n+2.

Smallest alkane is methane CH4 - also the most abundant.

Ethane (C2H6) and propane (C3H8) are the next alkanes.

Natural gas is 75% methane 10% ethane and 5% propane.

These alkanes have the lowest boiling points.
 Structures of
Alkanes
All carbons in methane, ethane and propane have four
bonds.

Bond angles (which are close to 109.5o) and bond lengths

are:
 Properties of sp3 Hybrid Orbitals
All four sp3 orbitals are of equal energy.

The axes of the sp3 orbitals point toward the corners of a

tetrahedron.

σ Bonds involving sp3 hybrid orbitals of carbon are

stronger than those involving unhybridized
2s or 2p orbitals.
 Bonding with sp3 Hybrid Orbitals
Bonding in methane involves orbital overlap between each
partially filled carbon sp3 orbital and a partially filled s
orbital of the hydrogen atom.
 Structure of Ethane

•Ethane also has tetrahedral geometry about the carbon

atoms.
•Hybridization can be used to rationalize the bonding.
•The C-H bonds are formed as described for methane.
•The C-C bond is formed by overlap of sp3 orbitals on
each of the carbon atoms.
 C-C Bond Formation in Ethane

Two half-filled sp3 Electrons with

orbitals on each C opposite spin

Overlap of orbitals

to form a bonding
orbital.
 Structure of Ethylene

•Ethylene is planar with bond angles close to 120o.

•sp3 Hybridization cannot be used to explain this bonding.
•Three atoms are bonded to each carbon so three hybrid
orbitals are formed. Called sp2 orbitals.
•One p orbital is not hybridized.
 Pi () Bonding in Ethylene

Form second C-C

bond by overlap
of p orbitals on
each carbon

This called a pi () bond and the electrons in the

bond are called  electrons.
 Structure of Acetyene

•Acetylene is linear with bond angles of 180o.

•sp3 and sp2 Hybridization cannot explain this bonding.
•sp Hybridization explains this. There are two half filled
p orbitals no hybridized.
 Sigma () Bonding in Acetylene

Form C-H bonds

by overlap of sp
and s orbitals

Form C-C bond

by overlap of sp
orbitals on each
carbon
These are all sigma () bonds. Two unfilled p
orbitals remain on each carbon atom.
 Hybridization of Carbon

•Carbons bonded to four atoms are sp3 hybridized with

bond angles of approximately 109.5o.

•Carbons bonded to three atoms are sp2 hybridized with

bond angles of approximately 1200 and one C-C -bond.

•Carbons bonded to two atoms are sp hybridized with

bond angles of approximately 1800 and two C-C -bonds.
 Isomers of Butane
•There is only one isomer for each of the molecular
formulas CH4, C2H6 and C3H8.
•For C4H10 there are two distinct connectivities of the
carbon atoms. They are constitutional isomers.
H

H C H
H H H H H H
C
H C C C C H C C
H H
H
H H H H H H

Bondline
formulas
 Isomers of Butane

•The isomers have different physical properties.

•All carbon atoms are sp3 hybridized.
 Higher n-Alkanes

•n-Alkanes are straight-chain alkanes with general formula

CH3(CH2)nCH3. n-Pentane is CH3CH2CH2CH2CH3 and
n-hexane is CH3CH2CH2CH2CH2CH3. These formulas can be
abbreviated as CH3(CH2)3CH3 or CH3(CH2)4CH3.
 Isomers of C5H12

•There are three isomers C5H12.

It is important to realize that these are all representations

of isopentane.
 Isomers of higher n-alkanes

•For higher n-alkanes there are many isomers and it is not

possible to easily predict how many isomers can be formed.
 IUPAC Naming
•Alkane names are the basis of the IUPAC system of
nomenclature. The –ane suffix is specific to alkanes.
The IUPAC Rules for Branched Alkanes

•Rules for naming branched alkanes:

1.Find the longest continuous carbon chain and its
IUPAC name. This is the parent alkane.
2.Identify the substituents on this chain.

substituent

longest chain
(5 carbons)
The IUPAC Rules for Branched Alkanes
•Rules for naming branched alkanes:
•3. Number the longest continuous chain in the direction
that gives the lowest number to the first substituent.
•4. Write the name of the compound. The parent alkane
is the last part of the name and is preceded by the
names of the substituents and their numerical
locations (locants). Hyphens separate the locants
from the words.

2-methylpentane
The IUPAC Rules for Branched Alkanes
•Rules for naming branched alkanes:
5.When the same substituent appears more than once,
•use the multiplying prefixes di-, tri-, tetra-, and so on.
A separate locant for each substituent.
Locants are separated from each other by commas
and from the words by hyphens.

2,2-dimethylbutane 2,3-dimethylbutane
 Alkyl Groups

Alkyl groups are substituents derived from alkanes.

They lack one hydrogen at the point of attachment.

The alkyl group is named from the alkane by replacing the

-ane suffix with –yl.

For example a CH3CH2CH2CH2- substituent is a butyl group.

 Classification of Carbon Atoms
Carbon atoms are defined as primary, secondary, tertiary
or quaternary.

A primary carbon is directly attached to one other carbon.

A secondary carbon is directly attached to two other

carbons. A tertiary carbon to 3 and a quaternary carbon
to 4.
 Complex Alkyl Groups (Substituents)
Secondary and tertiary groups may have common names

and IUPAC names.

The base name of these groups is the longest chain

including the attachment carbon form and the
substituents are located on this chain.
 Naming Highly Branched Alkanes
When two or more different substituents are present
number from the end closest to the first point of difference.

When two or more different substituents are present, they

are listed in alphabetical order in the name. Prefixes such
as di-, tri-, and tetra- are used but ignored when alphabetizing.
tert-Butyl precedes isobutyl. sec-Butyl precedes tert-butyl.

4-ethyl-3-methyloctane
 Naming Highly Branched Alkanes
When two or more different substituents are present
number from the end closest to the first point of difference.

If the first substituent is located an equal distance from each

end then the second substituent becomes the first potential
point of difference and so on.
 Naming Cycloalkanes
Cycloalkanes contain a ring of carbons and have general
formula CnH2n.

Add the prefix cyclo- to the name of the corresponding

alkane.
 Naming Cycloalkanes
Identify and name substituents as before.

For one substituent no numbers are used.

 Naming Cycloalkanes
For multiple substituents the locations must be specified.

Number the carbon atoms of the ring in the direction that

gives the lowest number to the substituents at the first
point of difference.

First substituent is on C1 by default.

 Practice Question
What is the correct IUPAC name for the
compound on the right?

A) 1-ethyl-2-methylcyclohexane
B) 2-ethyl-1-methylcyclohexane
C) 1-methyl-2-ethylcyclohexane
D) 2-methyl-1-ethylcyclohexane
 Naming Cycloalkanes
If the ring has fewer carbons than the alkyl group attached
to it then the ring is the substituent.
 Boiling Point
Boiling points of n-alkanes increase with increasing
molecular weight (number of carbons).
Branched alkanes generally have lower boiling points than
unbranched alkanes with the same number of carbons.
 Intermolecular Forces and Boiling Point
Attractive forces between molecules in the liquid phase
affect the boiling point of the liquid.

These Intermolecular forces are van der Waals forces and

may be divided into three types:
Dipole-dipole (including hydrogen bonding);
Induced dipole-dipole; or
Induced dipole-induced dipole.
Alkanes have no dipole so the van der Waals forces are the
temporary induced dipole-induced dipole..
 Intermolecular Forces and Alkanes
Branched alkanes have lower surface area than isomeric n-
alkanes and therefore have lower boiling points.
 Practice Question
• Which alkane has the highest boiling point?
• A) hexane
• B) 2,2-dimethylbutane
• C) 2-methylpentane
• D) 2,3-dimethylbutane
 Solubility of Alkanes in
Water

Alkanes (and all hydrocarbons) are virtually insoluble in

water and are said to be hydrophobic.

The densities of most alkanes are in the range 0.6-0.8

g/mL therefore alkanes float on the surface of water.
 Acidity of Hydrocarbons

Hydrocarbons are very weak acids. Alkynes have the

lowest pKa.
 Combustion of Hydrocarbons

Combustion of hydrocarbons is exothermic generating

CO2 and water.
 Combustion of Relative Stability
All isomers of C8H18 generate 8 molecules of CO2 and 9
of H2O yet different amounts of energy. This energy
difference must be directly related to the relative energies
of the isomers.

Least stable
isomer
Most stable
isomer

Least energy
released
Oxidation and Reduction in Organic Chemistry
Assuming the oxidation state of H is +1 and O is -2 it is
possible to calculate the oxidation state of C in
compounds containing C, H and O.
Oxidation and Reduction in Organic Chemistry
Oxidation of carbon corresponds to an increase in the
number of bonds between carbon and oxygen or to a
decrease in the number of carbon–hydrogen bonds.

Reduction corresponds to an increase in the number of

carbon–hydrogen bonds or to a decrease in the number
of carbon–oxygen bonds.
Oxidation and Reduction in Organic Chemistry
Any element more electronegative than C has the same
effect as O on the oxidation state of C.

Oxidation state of C is +2 in CH3Cl and CH3OH.

Any element less electronegative than C has the same

effect as H on the oxidation state of C.

Oxidation state of C is -4 in CH4 and CH3Li.