McMur Chapter 3

Organic Compounds: Alkanes

and Their Stereochemist
 Functional Groups
• A functional group is a group of atoms within a molecule
that has a characteristic chemical behavior.
• The chemist of eve organic molecule, regardless of size
and complexity, is determined by the functional groups it
contains.
 Functional Groups
•Molecules are classi ed by the functional
group(s) they contain.

Akenes: contain carbon-carbon double bonds

Alkynes: contain carbon-carbon triple bonds
Arenes: contain alternating double and single bonds in a
six- membered ring of carbon atoms
Functional Groups
• These polar
C-X bonds
each
exhibit
unique but
similar
reactivity
• X = Cl, Br, I,
O, N, S
Functional Groups
• All Carbonyl
groups contain
a highly
polarized C=O
double bond
and exhibit
similar reactivity
 Alkanes
•Alkanes , also called aliphatic compounds.
•Alkanes are also referred to as saturated
hydrocarbons.
– Saturated – containing only single bonds; no pi bonds
or rings
– Hydrocarbon – made up of only carbon and hydrogen
 Alkanes
•All saturated hydrocarbons have the molecular
formula
CnH2n+2
• Alkanes with carbons connected in a row are called
straight-chain
_________________________________ alkanes.
• Straight-chain alkanes are named based on the
number of carbon atoms they contain:
n=1 CH4 methane n = 7 C7H16 heptane
n=2 C2H6 ethane n = 8 C8H18 octane
n=3 C3H8 propane n = 9 C9H20 nonane
n=4 C4H10 butane n = 10 C10H22 decane
n=5 C5H12 pentane n = 11 C11H24 undecane
n=6 C6H14 hexane n = 12 C12H26 dodecane
 Alkanes
•an
When there
alkane, it are
is more than
possible to three
have carbons
normal in
and
branched-chain isomers.

•the Isomers
________________________: molecules that have
same molecular formulas but
are connected in a di erent order the atoms
Constitutional Isomers
• There are two di erent
constitutional isomers
of butane and three
di erent constitutional
isomers of pentane.
Draw all possible constitutional isomers of
hexane. How many are there?
Alkyl Groups Alkanes
If you imagine removing a hydrogen atom from an alkane, the
pa ial structure that remains is called an alkyl group.
– Alkyl groups are named by removing the –ane su x from the
parent alkane and replacing it with –yl.
 Alkyl Groups
•There are two di erent propyl groups
because there are two di erent types of
______________ hydrogens that can be removed
from propane.
How many di erent butyl groups can you draw
(each with the formula C4H9)?
 Alkyl Groups
_____________________________________________
•One way to distinguish di erent alkyl groups is
by the number of other carbon atoms attached
to the branching carbon.
 Prima (1), Seconda (2), and
Te ia (3)
• Used to classify
molecules and
distinguish
between
di erent sites
within a
molecule
 Alkyl Groups
•1°, 2°, and 3° are used
to di erentiate
between the four butyl
isomers.
•But there are eight
di erent pentyl groups
and seventeen hexyl
groups.
•We need a more
systematic way of Butyl Groups – Common
naming alkanes and Names
alkyl groups.
 IUPAC Nomenclature
•The International Union of Pure and Applied
Chemist (IUPAC) developed a systematic way
of naming organic molecules.
•Eve IUPAC name uses the parent alkane
backbone as the base name.
IUPAC Nomenclature
We’ll use this molecule as an
example as we walk through the
naming rules…
 IUPAC Nomenclature
Step 1: Find the longest carbon chain. If there are
two di erent chains of equal length, choose the
one with the larger number of branch points as
the parent chain.
Step 2: Number the carbon chain, beginning with
the end closest to the nearest branch point.
– If there is branching an equal distance away
from both ends, begin numbering at the end
nearer the second branch point. The rst
point of di erence breaks a tie.
 IUPAC Nomenclature
Step 3: Identify and number the substituents.
– Use pre xes (di-, tri-, tetra-, etc.) if there is
more than one of the same kind of
substituent on the chain.
Step 4: Write the name as a single word, listing
the substituents alphabetically before the parent
alkane.
– Use commas to separate numbers and
hyphens to separate numbers from words.
– Do not alphabetize multiplier pre xes (di, tri,
tetra, etc.).
 IUPAC Nomenclature
Complex Substituents
•Use IUPAC rules to name branched substituents.
– Begin numbering the longest carbon chain at
the point of attachment.
– Alphabetize complex substituent by the rst
letter of the complete name (including
numerical pre xes).
– Put name of alkyl group in parentheses.
 IUPAC
Common Names
Nomenclature
•Some branched-chain alkyl groups are often
named using their common names.
•You should be familiar with these names and
structures.
-Iso and neo are the
only pre xes that are
not hyphenated and are
used when
alphabetizing.
Provide IUPAC names for the following
compounds.
Provide structures for the following IUPAC names.
•4-t-butylheptane

•3,4,5-trimethyl-4-n-propyloctane
 Prope ies of Alkanes
•Alkanes are fairly ine , but they will undergo
_________________________________________.
Combustion:
CH4 + 2 O2  CO2 + 2 H2O H = -890 kJ/mol

Halogenation:
 Prope ies of Alkanes
•The melting and boiling points of alkanes
increase with increasing size – due to increased
London dispersion forces.
Conformational Analysis of Alkanes
– Conformations: structures related by bond
rotations; usually interconve ible at room
temperature
– Conformer: sho for conformational isomer;
term used to indicate a speci c
conformation
 Conformational Analysis of
Alkanes
•There is free rotation around C-C sigma
bonds.

•Di erent conformations have di erent

energies (di erent levels of stability).
 Conformational Analysis of
Alkanes
_________________________
•Newman projections are conformational
drawings that allow you to look straight down
a bond.
– Ve useful for comparing conformers
 Conformational Analysis of
Ethane

Staggered Skewed Eclipsed

 = 60  0 <  < 60  =0
Erel = 0 kJ/mol 0 < Erel < 12 kJ/mol Erel = ~12 kJ/mol
Erel = 0 kcal/mol 0 < Erel < 3.0 kcal/mol Erel = 3.0 kcal/mol
Draw Newman projections for the eclipsed and
staggered conformers of ethane.
Rotational Energy Diagram for Ethane

(3.0 kcal/mol)

Barrier to Rotation = Ehighest – Elowest

Ethane: Barrier = 3.0 – 0 = 3.0 kcal/mol
 Conformational Analysis of
Ethane
•The eclipsed conformer of ethane is higher in
energy than the staggered conformer
because of torsional strain.
•_______________________________strain caused by
electron repulsion between eclipsed bonds
– As the dihedral angle gets smaller, the bonds are
forced closer together, and the repulsion is
increased.
– The angle between the bonds () is at a maximum
in in the low energy staggered conformer (60)
and at a minimum in the high energy eclipsed
conformer (0).
 Conformational Analysis of Ethane
•The conformational energies of ethane can be
broken down into individual eclipsing
interactions.
– Three pairs of eclipsed
hydrogen bonds lead to
3.0 kcal/mol of torsional
strain.
– One H/H-eclipsing
interaction = 1.0 kcal/mol
•Draw a Newman
projection of propane
from the perspective
indicated.
 Conformational Analysis of Propane

Staggered Eclipsed
 = 60  =0
Erel = 0 kJ/mol Erel = ~14 kJ/mol
Erel = 0 kcal/mol Erel = 3.4 kcal/mol
 Conformational Analysis of Propane
•The conformational energies of propane can be
broken down into individual eclipsing
interactions.
– Two pairs of eclipsed
hydrogen bonds lead to
2.0 kcal/mol of torsional
strain.
– One H/CH3-eclipsing
interaction = 1.4 kcal/mol
Draw a Newman projection of the
C2-C3 bond of butane from the
perspective shown.
 There are two energetically di erent staggered
conformations of butane with respect to the C2-C3
bond. Draw a Newman projection for each and predict
which one is lower in energy.
 There are two energetically di erent eclipsed conformations of
butane with respect to the C2-C3 bond. Draw a Newman projection
for each and predict which one is higher in energy.
 Conformational Analysis of
Butane
•To distinguish between the four di erent
conformers of butane, Me/Me is de ned as the
dihedral angle between the two methyl groups.
Conformational Analysis of Butane

Butane: Barrier = 4.5 – 0 = 4.5 kcal/mol