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Systematic nomenclature devised by the International
Union of Pure and Applied Chemistry (IUPAC)
Name has four parts
1. Prefix which specifies the location of functional groups and
other substituents in the molecule
2. Parent selects the main part of the molecule and tells the
number of carbon atoms
3. Locant gives location of primary functional group
4. Suffix identifies functional group family it belongs to
3.4 Naming Alkanes
Alkanes can be named by following four steps
1. Find the parent hydrocarbon
a) Find the longest continuing chain of carbon atoms in the
molecule
b) If two different chains of equal length are present, choose the
one with the larger number of branch points as the parent
Naming Alkanes
2. Number the atoms in the parent chain
a) Number each carbon atom in the parent chain beginning at
end nearer the first branch point
b) If there is a branching point at an equal distance from both
ends of the parent chain, begin numbering at the end nearer
the second branch point
Naming Alkanes
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3. Identify and number the substituents
a) Assign a number (called the locant) to each substituent to locate
its point of attachment to the parent chain
b) If there are two substituents on the same carbon, give them both
the same number. There must be as many numbers in the name
as there are substituents
Naming Alkanes
4. Write the name as a single word
If two or more different substituents are present write them in
alphabetical order
If two or more identical substituents are present, use the
multiplier prefixes di-, tri-, tetra-, and so forth
Do not use these prefixes when alphabetizing
Naming Alkanes
5. Name a branched substituent as though it were
itself a compound
Begin numbering the
branched substituent at
its point of attachment to
the main chain
Substituent alphabetized
according to the first
letter of its complete
name, including any
numerical prefixes, and
is set off in parentheses
when naming the entire
molecule
Naming Alkanes
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More examples
Naming Alkanes
Some alkanes have nonsystematic, common names
1. Three-carbon alkyl group
2. Four-carbon alkyl groups
3. Five-carbon alkyl groups
Naming Alkanes
Some compounds can be named with IUPAC rules or
with common names
Naming Alkanes
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Alphabetization in the naming of alkanes
Nonhyphenated prefix iso- is considered part
of the alkyl-group name when alphabetizing
Isopropyl and isobutyl are listed alphabetically
under i
The hyphenated and italicized prefixes sec-
and tert- are not considered part of the alkyl-
group name when alphabetizing
Sec-butyl and tert-butyl are listed alphabetically
under b
Naming Alkanes
What is the IUPAC name of the following alkane?
Worked Example 3.2
Practice in Naming Alkanes
Draw the structure of 3-isopropyl-2-methylhexane.
Worked Example 3.3
Converting a Chemical Name into a Structure
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Alkanes referred to as paraffins
Latin Parum affinis meaning little affinity
Show little affinity for other substances
Chemically inert to most laboratory reagents
React with oxygen, halogens, and a few other
substances under the appropriate conditions
Reactions of alkanes with oxygen
Occur during combustion in an engine or furnace
when the alkane is used as a fuel
Methane reacts with oxygen
CH
4
+ 2 O
2
CO
2
+ 2 H
2
O + 890 kJ/mol (213
kcal/mol)
3.5 Properties of Alkanes
Reactions of alkanes with the halogen Cl
2
Occurs when a mixture of alkanes and Cl
2
is irradiated with
ultraviolet light
Denoted hn
A sequential substitution of the alkane and hydrogen atoms
by chlorine occurs
Results in a mixture of chlorinated products
Methane reacts with Cl
2
Properties of Alkanes
Alkanes show regular increases in both boiling point and
melting point as molecular weight increases
Due to the presence of weak dispersion forces between
molecules
Dispersion forces increase as molecular size increases
Melting and boiling occur when sufficient thermal energy is applied
to overcome dispersion forces
Properties of Alkanes
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3.6 Conformations of Ethane
Stereochemistry
Branch of chemistry concerned with the three dimensional
aspects of molecules
Three dimensional structures determine properties and
biological behavior of molecules
s-bonds are cylindrically symmetrical
Cylindrical symmetry permits rotation around carbon-
carbon bonds in open-chain molecules
Rotation occurs around the carbon-carbon single bond in
ethane
Conformations
The three-dimensional shape of a molecule at any given instant,
assuming that rotation around single bonds is frozen can be
represented in two ways:
1. Sawhorse representation
Views carbon-carbon bond from an oblique angle and indicates
spatial orientation by showing all C-H bonds
Conformations of Ethane
Conformations
2. Newman projection
Views carbon-carbon bond directly end-on and represents the
two carbon atoms by a circle
Bonds attached to the front carbon are represented by lines to
the center of the circle
Bonds attached to the rear carbon are represented by lines to
the edge of the circle
Conformations of Ethane
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Conformations of Ethane
Stability of conformations
Perfectly free rotation is not observed in ethane
Some conformations are more stable than others
Newman projections
Staggered
Lowest energy, most stable conformation
All six C-H bonds are as far away from one another as possible
Eclipsed
Highest energy, least stable conformation
The six C-H bonds are as close to one another
as possible
Torsional strain
The strain in a molecule caused by interaction between
C-H bonding orbitals on one carbon with antibonding
orbitals on the adjacent carbon
Also known as eclipsing strain
Accounts for the extra 12 kJ/mol of energy present in
the eclipsed conformation of ethane
Conformations of Ethane
Conformations of Ethane
Energy minima occur at staggered conformations
Energy maxima occur at eclipsed conformations
Conformations of Ethane
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Propane
Torsional barrier is 14 kJ/mol (3.4 kcal/mol)
Eclipsed conformation has three interactions
Two ethane-type hydrogen-hydrogen interactions
One additional hydrogen-methyl interaction
3.7 Conformations of Other Alkanes
Butane
The lowest-energy conformation is the anti conformation
The geometric arrangement around a carbon-carbon single bond
in which the two largest substituents are 180 apart as viewed in a
Newman projection
Conformation in which the two methyl groups of butane are as far
apart as possible
Rotation around C2-C3 bond results in the eclipsed conformation
where there are two CH
3
H interactions and one H H
interaction
Conformations of Other Alkanes
Continued bond rotation leads to an energy minimum known
as a Gauche conformation
The conformation of butane in which the two methyl
groups are staggered 60 apart as viewed in a Newman
projection
Higher energy than the anti conformation even though it
has no eclipsing interactions
This conformation has 3.8 kJ/mol steric strain
Conformations of Other Alkanes
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Steric strain
The repulsive interaction in a molecule when two groups are
closer together than their atomic radii allow
Conformations of Other Alkanes
Rotation around C2-C3 bond results in the eclipsed
conformation where there are two H H interactions and
one CH
3
CH
3
interaction
This eclipsed conformation has the highest energy
Both torsional strain and steric strain are present
A total of 19 kJ/mol
Conformations of Other Alkanes
After 0, the rotation becomes a mirror image of the gauche
and eclipsed conformations already seen
Plot of
potential
energy
versus
rotation for
the C2-C3
bond in
butane
Conformations of Other Alkanes
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Conformations of Other Alkanes
The most stable alkane conformation
One in which all substituents are staggered
The carbon-carbon bonds are arranged anti to one another
At room temperature rotation around s-bonds occur so rapidly that all
conformations are in equilibrium. At any given time, a larger
proportion of molecules will be present in a more stable conformation
than in a less stable one
Decane
Conformations of Other Alkanes
Sighting along the C1-C2 bond of 1-chloropropane,
draw Newman projections of the most stable and
least stable conformations.
Worked Example 3.4
Drawing Newman Projections