Organic Chemistry

• In early nineteenth century, scientists classified all known

compounds into two categories:
• Organic compounds - derived from living organisms (plants and animals)
• Inorganic compounds - derived from nonliving sources (minerals and
gases).

• Most organic compounds are derived from a group of

compounds known as hydrocarbons because they are made up of
only hydrogen and carbon.

• Hydrocarbons are divided into two main classes—saturated and

unsaturated.
 Hydrocarbons

Hydrocarbons

Unsaturated Saturated
Hydrocarbons Hydrocarbons

Alkenes Alkynes Arenes Alkanes

Contain one or more Contain one or more Contain one or more

Only C-C single bonds
C-C double bonds C-C triple bonds benzene rings
Hydrocarbons
• On the basis of structure, hydrocarbons are divided into two main
classes—aliphatic and aromatic.
• Aliphatic hydrocarbons DO NOT contain the benzene group,
whereas aromatic hydrocarbons contain one or more benzene
rings.

Aliphatic Aromatic
Alkanes

• Alkanes are saturated hydrocarbons; that is, they

contain only carbon-carbon single bonds.
• In this context, saturated means that each carbon
has the maximum number of hydrogens bonded to
it.
Structure of Alkanes
• Methane (CH4) and ethane (C2H6) are the first two members of the
alkane family.
• The shape of methane is tetrahedral, and all H-C-H bond angles are
109.5°.
• Each carbon atom in ethane is also tetrahedral, and all bond
angles are approximately 109.5°.
Structure of Alkanes
Alkanes have the general formula CnH2n+2 , where n = 1, 2, . . . .
Example: C3H8 and C6H14

EXERCISE
Q. What is the formula of an alkane containing 20H?
Q.What is the formula of an alkane containing 15C?
Structure of Alkanes
• Hydrocarbons can be drawn as structural formulas that show all
carbons and hydrogens.

• They can also be drawn as the condensed structural formulas.

• They are also drawn in an even more abbreviated form called a line-
angle formula (bond-line structures).
Structure of Alkanes
• In a line-angle formula, each vertex and line ending represents a
carbon atom.
• NOTE: Although we do not show hydrogen atoms in line angle
formulas, we assume they are there in sufficient numbers to give
each carbon four bonds.
IUPAC Nomenclature

• In the early nineteenth century, organic compounds were often

named at the whim of their discoverers.
IUPAC Nomenclature
• In 1892, a group of 34 European chemists met in Switzerland and
developed a system of organic nomenclature called the Geneva
rules.

• The group ultimately became known as the International Union of

Pure and Applied Chemistry, or IUPAC (pronounced “I–YOU–
PACK”).

• Names produced by IUPAC rules are called systematic names.

Parent Names for Alkanes
The names of alkanes usually end with the suffix “-ane”.
No. of Parent Name of Alkane No. of Parent Name of Alkane
carbons carbon
s
1 meth methane 11 undec undecane
2 eth ethane 12 dodec dodecane
3 prop propane 13 tridec tridecane
4 but butane 14 tetradec tetradecane
5 pent pentane 15 pentadec pentadecane
6 hex hexane 20 eicos eicosane
7 hept heptane 30 triacont triacontane
8 oct octane 40 tetracont tetracontane
9 non nonane 50 pentacont pentacontane
10 dec decane 100 hect hectane
Alkane Nomenclature – Branched alkanes
• The first step in naming an alkane is to identify the longest chain,
called the parent chain:

• List all the substituents:

Alkane Nomenclature – Branched Alkanes
• Substituents are named with the same terminology used for
naming parents, only we add the letters “yl.”
• For example, a substituent with one carbon atom (a CH3 group) is
called a methyl group. A substituent with two carbon atoms
(CH3CH2 group)is called an ethyl group.
• These groups are generically called alkyl groups.
Parent Name Formula Alkyl group Formula
methane CH4 methyl CH3-
ethane CH3CH3 ethyl CH3CH2-
propane CH3CH2CH3 propyl CH3CH2CH2-
butane CH3CH2CH2CH3 butyl CH3CH2CH2CH2-

Assignment: Determine the structures of t-butyl, isopropyl, isopentyl, t-pentyl, sec-pentyl,

Alkane Nomenclature – Branched Alkanes
• Indicate the substituent position:
NOTE: If one substituent is present, it should be assigned the
lower possible number.

• Assemble the name:

3-methylhexane
Alkane Nomenclature – Branched Alkanes
Exercise:
Q. Write the IUPAC names of the following compounds.
 Alkane Nomenclature- Branched Alkanes
• When multiple substituents are present, assign numbers so that
the first substituent receives the lower number.

CH3CH(CH3)CH2CH2C(CH3)2CH2CH3

2,5,5-trimethylheptane

• If there is a tie, then the second locant should be as low as

possible:

2,3,6-trimethylheptane
Alkane Nomenclature – Branched Alkanes
• When more than one type of substituents are present:
• Arrange the substituents alphabetically
• Place locants in front of each substituent
• For identical substituents, use di, tri, or tetra, which are ignored in
alphabetizing

4-ethyl-3-methylnonane 3-ethyl-4,4-dimethyl-6-propyldecane
Exercise
Q. Give IUPAC name for the following compound.

Q. Write the structural formula of 3-ethyl-2,2-dimethylpentane.

Cycloalkanes
• The term “cyclo” is used to indicate the presence of a ring in the
structure of an alkane.
• Cycloalkanes have the general formula, CnH2n, where n = 3,4,5….
Cycloalkanes Nomenclature
• When naming substituted cycloalkanes:
• Identify the parent ring
• Identify the substituent
• If multiple substituents are present, allocate a locant on each substituent
ensuring all the substituents have the lowest values possible
• Assemble the name following the rules discussed in previous slides.
Example

methylcyclopentane 1,2,4-trimethylcyclohexane 3-ethyl-1,1-dimethylcyclohexane

Cyclopropane as an Inhalation Anesthetic
1840s Chloroform
Diethyl ether

• Heart arrythmias
• Highly flammable • Dangerous drops in blood
• Irritating to respiratory tract pressure
• Causes Nausea and vomiting • Liver damage with prolonged
(lung damage) exposure
Cyclopropane as an Inhalation Anesthetic
1930s
• Did not induce vomiting
• Did not cause liver damage
• Rapid recovery from anesthesia
DRAWBACKS • Maintained normal blood
• Instability due to ring strain pressure
• Slight static spark could cause an
explosion
• Was replaced in the 1960s
Assignment
• Determine the structures of t-butyl, isopropyl, isopentyl, t-pentyl, sec-
pentyl

• Write the structural formula of 3-ethyl-2,2-dimethylpentane

 Branched alkyl groups
• Removing a hydrogen from an alkane results in an alkyl substituent.

CH3 CH3
CH3CH2CH2 CH3CH2CH2CH2
CH3 CHCH2
CH3 CH
propyl butyl
isopropyl isobutyl

tert-butyl sec-butyl
 Branched alkyl groups
• The prefixes sec- (for secondary) and tert- (for tertiary) refer to the
number of other carbon atoms attached to the branching carbon
atom.
• There are four possibilities: primary (1), secondary (2), tertiary (3),
and quaternary (4).
R H R R R R R R
C C C C

H H H H R H R R
Primary carbon (1°) Secondary carbon (2°) Tertiary carbon (3°) Quaternary carbon (4°)
is bonded to one is bonded to two is bonded to three is bonded to four
other carbon. other carbons. other carbons. other carbons.
Branched alkyl groups
• The prefix iso- is considered for alphabetizing purposes.
• The hyphenated and italicized prefixes sec- and tert- are not.
• The symbol R is used in organic chemistry to represent a generalized
organic group.
• The R group can be methyl, ethyl, propyl, isopropyl, e.t.c.
Exercise
Identify the carbon atoms in the following molecules as primary, secondary,
tertiary, or quaternary:
(a) CH3 (b) CH3 CH3

CH3 CHCH2CH2CH3 CH3 CHCH2 CCH3

CH3
Structural Isomerism (Constitutional Isomers)

• Constitutional Isomers are compounds with the same molecular weight

and formula, but different connectivity.

• For an alkane, the number of possible constitutional isomers increases

with increasing molecular size.
Constitutional Isomers
Number of Constitutional Isomers for Various Alkanes
Molecular Formula Number of Constitutional Isomers
C 3 H8 1
C4H10 2
C5H12 3
C6H14 5
C7H16 9
C8H18 18
C9H20 35
C10H22 75
C15H32 4,347
C20H42 366,319
C30H62 4,111,846,763
C40H82 62,481,801,147,341
Constitutional Isomers
Consider C6H14
Constitutional Isomers
Consider C6H14, for which there are five constitutional isomers.

2
1

4
3

5
Constitutional Isomers
• For the molecular formula C4H10, two connectivity's are possible.

Butane 2-methylpropane
b.p = -0.5oC b.p = -11.6oC
• Butane and 2-methylpropane are constitutional isomers; they are
different compounds and have different physical and chemical
properties.
• Their boiling points, for example, differ by approximately 11°C.

Q. Explain the observed b.p of butane and 2-methylpropane

Physical Properties of Alkanes
• Interactions between alkane molecules consist only of very weak
dispersion forces (van der Waals).
• Van der Waals forces are the weakest of all the intermolecular
attractions.
• The boiling points of alkanes are lower than those of almost any
other type of compound of the same molecular weight.
• As the number of atoms and the molecular weight of alkanes
increase, the dispersion forces between their molecules and
boiling and melting points increase.

van der Waals

forces
Physical Properties of Alkanes
• The magnitude of the van der Waals forces that hold alkane
molecules together depends on the area of contact between the
molecules.
• The greater the area of contact, the stronger the van der Waals
forces and the greater the amount of energy needed to overcome
them.

van der Waals

forces
 Physical Properties of Alkanes
• Because the strength of the van der Waals forces depends on the area of
contact between the molecules, branching in a compound lowers the
compounds boiling point by reducing the area of contact.
• If two alkanes have the same molecular weight, the more highly branched
alkane will have a lower boiling point.

CH3CH2CH2CH2CH3 CH3 CH CH2CH3 CH3

CH3 CH3 C CH3
Pentane
2-methylbutane CH3
2,2-dimethylpropane
Bp: 36.1 °C 27.9 °C 9.5 °C
 Uses of Alkanes
• Petroleum and coal are the major sources of hydrocarbons.
• They are complex mixtures of thousands of compounds formed by
the decay and degradation of marine plants and animals.
• Some of these compounds include methane (natural gas), propane
and butane (bottled fuel gas used in rural communities and
camping equipment).
• Hydrocarbons in petroleum are burned as fuel.
• A small portion is converted into petrochemicals such as plastics,
fibres, dyes, detergents, medicines, pesticides and other products.
 Uses of hydrocarbons
• Ethane is a minor component of natural gas;
• ethylene is a precursor of the plastic polyethylene;
• acetylene is the fuel of oxyacetylene torches and is used in
welding; and
• benzene is a petrol component.
Reactions of Alkanes
• Combustion
• General equation: Fuel + O2  CO2 + H2O + Heat

• CH4(g) + 2O2(g)  CO2(g) + H2O(g)

• 2C2H6(g) + 7O2(g)  4CO2(g) + 6H2O(g)

• C3H4(g) + 5O2(g)  3CO2(g) + 4 H2O(g)

 Reactions of Alkanes
• Chlorination.
• Initiation
• Splitting or hemolysis of chlorine in the presence of UV light or sunlight
to form chlorine radical;
h

• Propagation
 Reactions of Alkanes
• Chlorination.
• Chain Termination : Recombination of two radicals;

• Overall reaction: