You are on page 1of 59

General

Organic Chemistry
Two credits
Second Semester 2009

King Saud bin Abdulaziz University for Health Science

Reference Book: Organic Chemistry: A Brief Course,


by Robert C. Atkins and Francis A. Carey
Third Edition

Instructor: Rabih O. Al-Kaysi, PhD.


Lecture 3

Chapter 2

Alkanes and
Cycloalkanes
IUPAC Nomenclature of
Unbranched Alkanes
IUPAC Names of Unbranched Alkanes

Retained:
methane CH4

ethane CH3CH3

propane CH3CH2CH3

butane CH3CH2CH2CH3
IUPAC Names of Unbranched Alkanes

Note:
n-prefix is not part of IUPAC name of
any alkane.
For example: n-butane is "common name"
for CH3CH2CH2CH3; butane is "IUPAC name."

Others:

Latin or Greek prefix for number of


carbons + ane suffix
IUPAC Names of Unbranched Alkanes

Number of carbons Name Structure


5 pentane CH3(CH2)3CH3
6 hexane CH3(CH2)4CH3
7 heptane CH3(CH2)5CH3
8 octane CH3(CH2)6CH3
9 nonane CH3(CH2)7CH3
10 decane CH3(CH2)8CH3
IUPAC Names of Unbranched Alkanes

Number of carbons Name Structure


11 undecane CH3(CH2)9CH3
12 dodecane CH3(CH2)10CH3
13 tridecane CH3(CH2)11CH3
14 tetradecane CH3(CH2)12CH3
15 pentadecane CH3(CH2)7CH3
16 hexadecane CH3(CH2)8CH3
Applying the IUPAC Rules:
The Names of the C6H14 Isomers
The C6H14 Isomers

CH3CH2CH2CH2CH2CH3

(CH3)2CHCH2CH2CH3

(CH3CH2)2CHCH3

(CH3)2CHCH(CH3)2

(CH3)3CCH2CH3
The C6H14 Isomers

CH3CH2CH2CH2CH2CH3

Hexane

The IUPAC name of the unbranched alkane


with a chain of 6 carbons is hexane.
IUPAC Nomenclature of Branched
Alkanes

Step 1) Find the longest continuous carbon


chain and use the IUPAC name of the
unbranched alkane as the basis.
Step 2) Add name of substituent as a prefix.
Step 3) Number the chain from the end nearest
the substituent, and identify the carbon to
which the substituent is attached by number.
The C6H14 Isomers

(CH3)2CHCH2CH2CH3

2-Methylpentane

(CH3CH2)2CHCH3

3-Methylpentane
The C6H14 Isomers

(CH3)2CHCH(CH3)2

2,3-Dimethylbutane

(CH3)3CCH2CH3

2,2-Dimethylbutane

Use replicating prefixes (di-, tri-, tetra-, etc.)


according to the number of identical substituents
attached to the main chain.
Alkyl Groups
Methyl and Ethyl Groups

Methyl H C or CH3

H H

Ethyl H C C or CH3CH2

H H
Unbranched Alkyl Groups

R H R
If potential point of attachment is at the end
of the chain, take the IUPAC name of the
corresponding unbranched alkane and replace
the -ane ending by -yl.
Unbranched Alkyl Groups

R H R
If potential point of attachment is at the end
of the chain, take the IUPAC name of the
corresponding unbranched alkane and replace
the -ane ending by -yl.
H H H H

H C C C C or CH3CH2CH2CH2

H H H H
Butyl
Unbranched Alkyl Groups

CH3(CH2)4CH2 Hexyl

CH3(CH2)5CH2 Heptyl

CH3(CH2)16 CH2 Octadecyl


The C3H7 Alkyl Groups

H H H

H C C C or CH3CH2CH2

H H H
and

H H H

H C C C H or CH3CHCH3

H H
The C3H7 Alkyl Groups

H H H

H C C C or CH3CH2CH2

H H H

IUPAC name: Propyl


Common name: n-Propyl
Naming Alkyl Groups

Step 1: Identify longest continuous chain starting at


point of attachment.
Step 2: Drop -ane ending from name of unbranched
alkane having same number of carbons as
longest continuous chain and replace by -yl.
Step 3: Identify substituents on longest continuous
chain.
Step 4: Chain is always numbered starting at
point of attachment.
The C3H7 Alkyl Groups

H H H

H C C C H or CH3CHCH3

H H

IUPAC name: 1-Methylethyl


Common name: Isopropyl
The C3H7 Alkyl Groups

H H H

H C C C or CH3CH2CH2

H H H

Classification: Primary alkyl group


Alkyl groups are classified according to the
degree of substitution at the carbon that bears the
point of attachment. A carbon that is directly
attached to one other carbon is a primary carbon.
The C3H7 Alkyl Groups

H H H

H C C C H or CH3CHCH3

H H

Classification: Secondary alkyl group


Alkyl groups are classified according to the
degree of substitution at the carbon that bears the
point of attachment. A carbon that is directly
attached to two other carbons is a secondary carbon.
The C4H9 Alkyl Groups

CH3
3 2 1
CH3 C CH2

IUPAC name: 2-Methylpropyl


Common name: Isobutyl
Classification: Primary alkyl group
The C4H9 Alkyl Groups

CH3
1 2
CH3 C CH3

IUPAC name: 1,1-Dimethylethyl


Common name: tert-Butyl
Classification: Tertiary alkyl group
IUPAC Names of Highly
Branched Alkanes
Branched alkanes

Octane
Branched alkanes

4-Ethyloctane
Branched alkanes

4-Ethyl-3-methyloctane

List substituents in alphabetical order.


Branched alkanes

4-Ethyl-3,5-dimethyloctane

List substituents in alphabetical order.


But don't alphabetize di-, tri-, tetra-, etc.
First Point of Difference Rule

2 4 6 8 7 5 3 1
3 5 7 6 4 2
1 8

What is correct name?


2,3,3,7,7-Pentamethyloctane?
2,2,6,6,7-Pentamethyloctane?

The chain is numbered in the direction that


gives the lower locant to the substituent at the
first point of difference in the names.
Don't add locants!
Just for general knowledge, will not be tested on
Just for general knowledge, will not be tested on
First Point of Difference Rule

7 5 3 1
6 4 2
8

What is correct name?

2,2,6,6,7-Pentamethyloctane?

The chain is numbered in the direction that


gives the lower locant to the substituent at the
first point of difference in the names.
Don't add locants!
Cn H2 n

Cycloalkane Nomenclature
Cycloalkanes
Cycloalkanes are alkanes that contain a ring of
three or more carbons.
Count the number of carbons in the ring, and add
the prefix cyclo to the IUPAC name of the
unbranched alkane that has that number of
carbons.

Cyclopentane Cyclohexane
Cycloalkanes
Name any alkyl groups on the ring in the usual
way.

CH2CH3

Ethylcyclopentane
Cycloalkanes
Name any alkyl groups on the ring in the usual
way.
List substituents in alphabetical order and count
in the direction that gives the lowest numerical
locant at the first point of difference.
H3C CH3

CH2CH3
3-Ethyl-1,1-dimethylcyclohexane
Sources of Alkanes and Cycloalkanes

Just for general knowledge, will not be tested on


Crude oil

Just for general knowledge, will not be tested on


Naphtha
Naphtha Kerosene
Kerosene
(bp
(bp95-150
95-150°C)
°C) (bp:
(bp: 150-230
150-230°C)
°C)
C5-C12 C12 -C15

Light
Lightgasoline
gasoline
(bp:
(bp:25-95
25-95°C)
°C)
Crude oil C15 -C25

Gas
Gasoil
oil
Refinery
Refinerygas
gas (bp:
(bp: 230-340
230-340°C)
°C)
C1-C4 Residue
Residue
Just for general knowledge, will not be tested on
Petroleum Refining

Cracking
converts high molecular weight hydrocarbons
to more useful, low molecular weight ones

Reforming
increases branching of hydrocarbon chains
branched hydrocarbons have better burning
characteristics for automobile engines
Physical Properties of Alkanes
and Cycloalkanes
Boiling Points of Alkanes

governed by strength of intermolecular


attractive forces
alkanes are nonpolar, so dipole-dipole and
dipole-induced dipole forces are absent
only forces of intermolecular attraction are
induced dipole-induced dipole forces
Induced dipole-Induced dipole attractive forces

+ +–
––

two nonpolar molecules


center of positive charge and center of negative
charge coincide in each

Just for general knowledge, will not be tested on


Induced dipole-Induced dipole attractive forces

+ +–
––

movement of electrons creates an


instantaneous dipole in one molecule (left)

Just for general knowledge, will not be tested on


Induced dipole-Induced dipole attractive forces

+ – +–

temporary dipole in one molecule (left) induces


a complementary dipole in other molecule
(right)

Just for general knowledge, will not be tested on


Induced dipole-Induced dipole attractive forces

+ – + –

temporary dipole in one molecule (left) induces


a complementary dipole in other molecule
(right)

Just for general knowledge, will not be tested on


Induced dipole-Induced dipole attractive forces

+ – + –

the result is a small attractive force between


the two molecules

Just for general knowledge, will not be tested on


Induced dipole-Induced dipole attractive forces

– + – +

the result is a small attractive force between


the two molecules

Just for general knowledge, will not be tested on


Boiling Points

increase with increasing number of carbons


more atoms, more electrons, more
opportunities for induced dipole-induced
dipole forces
decrease with chain branching
branched molecules are more compact with
smaller surface area—fewer points of contact
with other molecules
Boiling Points

increase with increasing number of carbons


more atoms, more electrons, more
opportunities for induced dipole-induced
dipole forces

Heptane Octane Nonane


bp 98°C bp 125°C bp 150°C
Boiling Points

decrease with chain branching


branched molecules are more compact with
smaller surface area—fewer points of contact
with other molecules

Octane: bp 125°C

2-Methylheptane: bp 118°C

2,2,3,3-Tetramethylbutane: bp 107°C
Chemical Properties:
Combustion of Alkanes

All alkanes burn in air to give


carbon dioxide and water.
Heats of Combustion

increase with increasing number of carbons


more moles of O2 consumed, more moles
of CO2 and H2O formed
Heats of Combustion

Heptane 4817 kJ/mol


654 kJ/mol

Octane 5471 kJ/mol


654 kJ/mol
Nonane 6125 kJ/mol

Just for general knowledge, will not be tested on


Heats of Combustion

increase with increasing number of carbons


more moles of O2 consumed, more moles
of CO2 and H2O formed

decrease with chain branching


branched molecules are more stable
(have less potential energy) than their
unbranched isomers
Heats of Combustion

5471 kJ/mol
5 kJ/mol
5466 kJ/mol
8 kJ/mol
5458 kJ/mol
6 kJ/mol
5452 kJ/mol

Just for general knowledge, will not be tested on


Important Point

Isomers can differ in respect to their stability.


Equivalent statement:
Isomers differ in respect to their potential energy.
Differences in potential energy can be measured by
comparing heats of combustion.
Just for general knowledge, will not be tested on

5471 kJ/mol

25 5466 kJ/mol
+ O2
2 5458 kJ/mol
5452 kJ/mol
25
+ O2 25
2 + O2 25
2 + O2
2

8CO2 + 9H2O