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Atomic Structure 1

Chapter 4
Alkanes

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Cycloalkanes

Cycloalkanes contain carbons joined in one or more

rings.
• Because their general formula is CnH2n, they have two fewer H
atoms than an acyclic alkane with the same number of
carbons.

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Tetrahedral Geometry of Carbon Drawing Propane

All C atoms in an alkane are surrounded by four groups, making The three-carbon alkane CH3CH2CH3, called propane,
them sp3 hybridized and tetrahedral, with all bond angles of 109.5°. has a molecular formula C3H8.
The 3-D representations and ball-and-stick models for these alkanes In the 3-D drawing that each C atom has two bonds in
indicate the tetrahedral geometry around each C atom.
the plane (solid lines), one bond in front (on a wedge)
In contrast, the Lewis structures are not meant to imply any and one bond behind the plane (on a dashed line).
3-D arrangement.

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Drawing Pentane Constitutional Isomers

The five-carbon alkane CH3CH2CH2CH2CH3, called There are two different ways to arrange four carbons,
pentane, has a molecular formula C5H12. giving two compounds with molecular formula C4H10,
Carbon skeleton of pentane can be drawn in a variety named butane and isobutane.
of ways. Butane and isobutane are constitutional isomers—two
Each of the following representations has five carbons different compounds with the same molecular formula.
in a row and represents pentane, not an isomer of Constitutional isomers (also called structural isomers)
pentane. differ in the way the atoms are connected to each
other.

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Summary: Predicting Geometry Based on

Cycloalkanes
Number of Groups
The suffix “-ane” identifies a molecule as an alkane. Cycloalkanes have molecular formula CnH2n and
Table 4.1 Summary: Straight-Chain Alkanes
contain carbon atoms arranged in a ring.
Number of
Number of
Number Molecular Name (n-
constitutional
Number of C Molecular Name (n- constitutio Simple cycloalkanes are named by adding the prefix
of C formula alkane) atoms formula alkane) nal
atoms
isomers
isomers cyclo- to the name of the acyclic alkane having the
1 CH4 methane — 9 C9H20 nonane 35 same number of carbons.
2 C2H6 ethane — 10 C10C22 decane 75

3 C3H8 propane — 11 C11C24 undecane 159

4 C4H10 butane 2 12 C12H26 dodecane 355

5 C5H12 pentane 3 13 C13C28 tridecane 802

6 C6C12 Hexane 5 14 C14H30 tetradecane 1858

7 C7C14 heptane 9 15 C15H32 pentadecane 4347

8 C8H18 octane 18 20 C20H42 icosane 366,319

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Nomenclature Naming Substituents -Alkyl Groups

The name of every organic molecule has 3 parts: Carbon substituents bonded to a long carbon chain are
1. The parent name indicates the number of carbons in the called alkyl groups.
longest continuous chain.
An alkyl group is formed by removing one H atom from
2. The suffix indicates what functional group is present.
an alkane.
3. The prefix tells us the identity, location, and number of
substituents attached to the carbon chain. To name an alkyl group, change the –ane ending of the
parent alkane to –yl.

Thus, methane (CH4) becomes methyl (CH3—) and

ethane (CH3CH3) becomes ethyl (CH3CH2—).

“First Point of Difference Rule”

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Naming Three Carbon Alkyl Groups Naming Four Carbon Alkyl Groups
Naming three- or four-carbon alkyl groups is more complicated There are two different butane isomers which yield four
because the parent hydrocarbons have more than one type of possible alkyl groups containing four carbon atoms.
hydrogen atom.

For example, propane has both 1 degree and 2 ℃ H atoms, and

removal of each of these H atoms forms a different alkyl group
with a different name, propyl or isopropyl.

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HOW TO Name an Alkane Using Naming Structures with Chains of

the IUPAC System Equal Length
Step [1] Find the parent (longest continuous) carbon If there are two chains of equal length, pick the chain
chain and add the suffix. with more substituents.
In the following example, two different chains in the
same alkane have seven C atoms.
We circle the longest continuous chain as shown in
the diagram on the left, since this results in the greater
number of substituents.
It does not matter if the chain is straight or it bends.

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Numbering Alkanes with Substituents Numbering Substituents-1

Step [2] Number the atoms in the carbon chain to give If the first substituent is the same distance from both
the first substituent the lowest number. ends, number the chain to give the second substituent
the lower number.

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Numbering Substituents-2 Naming Substituents

When numbering a carbon chain results in the same Step [3] Name and number the substituents.
numbers from either end of the chain, assign the lower • Name the substituents as alkyl groups.
number alphabetically to the first substituent.
• Every carbon belongs to either the longest chain or a
substituent, not both.
• Each substituent needs its own number.
• If two or more identical substituents are bonded to the longest
chain, use prefixes to indicate how many: di- for two groups,
tri- for three groups, tetra- for four groups, and so forth.

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Completing Structure Names-1 Completing Structure Names-2

Step [4] Combine substituent names and numbers + Step [4] cont. Combine substituent names and
parent + suffix. numbers + parent + suffix.
• Precede the name of the parent by the names of the • Separate numbers by commas and separate numbers from
substituents. letters by hyphens.
• Alphabetize the names of the substituents, ignoring all • The name of an alkane is a single word, with no spaces after
prefixes except iso, as in isopropyl and isobutyl. hyphens and commas.
• Precede the name of each substituent by the number that
indicates its location.

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How to Name a Cycloalkane Using the How to Name a Cycloalkane Using the
IUPAC System-1 IUPAC System-2
Cycloalkanes are named by using similar rules, but the Step [2] Name and number the substituents. No
prefix cyclo- immediately precedes the name of the number is needed to indicate the location of a single
parent. substituent.

For rings with more than one substituent, begin

Step [1] Find the parent cycloalkane.
numbering at one substituent and proceed around the
ring to give the second substituent the lowest number.

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Naming Cycloalkane Substituents

Naming Alkanes vs. Cycloalkanes
Alphabetically
With two different substituents, number the ring to If the number of carbons in the ring is greater than or equal
assign the lower number to the substituents to the number of carbons in the longest chain, the
alphabetically. compound is named as a cycloalkane.
If there are more carbons in the chain, the compound is
named as an alkane.
Figure 4.2

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Examples of Naming Cycloalkanes Properties of Alkanes

Alkanes contain only nonpolar C—C and C—H bonds.

• They only exhibit weak van der Waals forces.
• This affects solubility and boiling point and melting point
characteristics of alkanes.

Solubility of alkanes
• Alkanes are soluble in organic solvents.
• Alkanes are insoluble in water.

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Boiling and Melting Points of Alkanes-1 Boiling and Melting Points of Alkanes-2

Alkanes have low bp’s an mp’s compared to more The bp of isomers decreases with branching due to
polar compounds of comparable size. decreased surface area.
Bp and mp increase as the number of carbons Mp increases with increased symmetry.
increases due to increased surface area.

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Solubility of Alkanes Conformations of Acyclic Alkanes

Alkanes are more soluble in organic solvents. Conformations are different arrangements of atoms
that are interconverted by rotation about single bonds.
Alkanes are insoluble in water.

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Eclipsed and Staggered Conformations Conformations and Dihedral Angle

Names are given to two different conformations. Rotating the atoms on one carbon by 60 ℃ converts an eclipsed
conformation into a staggered conformation, and vice versa.
In the eclipsed conformation, the C—H bonds on one
The angle that separates a bond on one atom from a bond on an
carbon are directly aligned with the C—H bonds on the adjacent atom is called a dihedral angle.
adjacent carbon.
For ethane in the staggered conformation, the dihedral angle for
In the staggered conformation, the C—H bonds on one the C—H bonds is 60 ℃; for eclipsed ethane, it is 0 ℃.
carbon bisect the H—C—H bond angle on the adjacent
carbon.

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Newman Projections Completing a Newman Projection-1

End-on representations for conformations are Step 2. Draw in the bonds.

commonly drawn using a convention called a Newman • Draw the bonds on the front C as three lines meeting at the
projection. center of the circle.

HOW TO Draw a Newman Projection: • Draw the bonds on the back C as three lines coming out of the
edge of the circle.
Step [1] Look directly down the C—C bond (end-on),
and draw a circle with a dot in the center to represent
the carbons of the C—C bond.

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Completing a Newman Projection-2 Newman Projections - Ethane

Step 3. Add the atoms on each bond. Figure 4.6

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Conformations of Ethane Torsional Energy of Ethane

The staggered and eclipsed conformations of ethane interconvert The difference in energy between staggered and eclipsed
at room temperature. conformers is ~3 kcal/mol, with each eclipsed C—H bond
contributing 1 kcal/mol.
The staggered conformations are more stable (lower in energy)
than the eclipsed conformations. The energy difference between staggered and eclipsed
conformers is called torsional energy.
Electron-electron repulsion between bonds in the eclipsed
conformation increases its energy compared with the staggered Torsional strain is an increase in energy caused by eclipsing
conformation, where the bonding electrons are farther apart. interactions.
Figure 4.8

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Newman Projections - Propane Newman Projections - Butane

An energy minimum and maximum occur every 60 ℃ as the
conformation changes from staggered to eclipsed.
Conformations that are neither staggered nor eclipsed are
intermediate in energy.
Butane and higher molecular weight alkanes have several C—C
bonds, all capable of rotation.

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Anti and Gauche Conformations Steric Strain

A staggered conformation with two larger groups 180 ℃ from each The relative energies of the individual staggered
other is called anti. conformations depend on their steric strain.
A staggered conformation with two larger groups 60 ℃ from each
other is called gauche. Steric strain is an increase in energy resulting when
non-bonded atoms are forced too close to one another.
The staggered conformations are lower in energy than the
eclipsed conformations. Gauche conformations are generally higher in energy
than anti conformations because of steric strain.
Steric strain caused by two eclipsed CH3 groups

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Conformation and Energy of Butane Barrier to Rotation

Table 4.3 Summary: Torsional and Steric strain
Energies in Acyclic Alkanes
Energy Increase Energy Increase
Type of interaction KJ/mol Kcal/mol
H,H eclipsing 4.0 1.0

H,CH3 eclipsing 6.0 1.4

CH3,CH3 eclipsing 11 2..6

gauche CH3 groups 3.8 0.9

The energy difference between the lowest and highest

energy conformations is called a barrier to rotation.

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Zigzag Skeletal Structures Angle Strain in Cycloalkanes

Since the lowest energy conformation has all bonds Besides torsional strain and steric strain, the
staggered and all large groups anti, alkanes are often conformations of cycloalkanes are also affected by
drawn in zigzag skeletal structures to indicate this. angle strain.
Angle strain is an increase in energy when bond angles
deviate from the optimum tetrahedral angle of 109.5 ℃.
Cycloalkanes with more than three C atoms in the ring
are not flat molecules. They are puckered to reduce
strain.

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Three to Ten Carbon Cycloalkanes Cyclohexane

Figure 4.11

In reality, cyclohexane adopts a puckered “chair”

Cycloalkanes distort their shapes to alleviate angle and conformation, which is more stable than any other
torsional strain. possible conformation.

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Chair Conformation Axial and Equatorial Positions

The chair conformation is so stable because it eliminates angle Each C in cyclohexane has two different kinds of hydrogens:
strain (all C—C—C angles are 109.5 ℃), and torsional strain (all
hydrogens on adjacent C atoms are staggered). (1) Axial hydrogens are located above and below the ring
(along a perpendicular axis).

(2) Equatorial hydrogens are located in the plane of the ring

(around the equator).

Figure 4.12

In cyclohexane, three C atoms pucker up and three C atoms

pucker down, alternating around the ring.

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HOW TO Draw the Chair Form

of Cyclohexane-1
Step [1] Draw the carbon skeleton
• Draw three parts of the chair, a wedge, a set of
parallel lines, and another wedge.
• Then, join them together.
• The bottom 3 C’s come out of the page, and bonds
to them are sometimes in bold.

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HOW TO Draw the Chair Form HOW TO Draw the Chair Form
of Cyclohexane-2 of Cyclohexane-3
Step [2] Label the up C’s and the down C’s on the ring. Step [3] Draw in the axial H atoms
• There are 3 up and 3 down C’s and they alternate • On an up C the axial H is up.
around the ring.
• On a down C the axial H is down.

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HOW TO Draw the Chair Form

Conformational Change – Ring-Flipping-1
of Cyclohexane-4
Step [4] Draw in the equatorial H atoms. Cyclohexanes undergo a conformational change called
“ring-flipping.”
• The axial H is down on a down C, so the equatorial
H must be up. • As a result of a ring flip, the up carbons become down
carbons, and the down carbons become up carbons.
• The axial H is up on an up C, so the equatorial H
• Axial and equatorial H atoms are also interconverted during a
must be down. ring-flip; axial H atoms become equatorial H atoms, and
equatorial H atoms become axial H atoms.

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Conformational Change – Ring-Flipping-2 Boat Conformation of Cyclohexane

There are two possible chair conformations. Cyclohexane also can exist in a boat conformation.

The equatorial position has more room than the axial The boat forms of cyclohexane are 7 kcal/mol less stable than the
chair forms.
position, so larger substituents are more stable in the
equatorial position. The boat conformation is destabilized by torsional strain because
the hydrogens on the four carbon atoms in the plane are eclipsed.
Figure 4.13
Additionally, there is steric strain because two hydrogens at either
end of the boat, the “flag pole” hydrogens, are forced close to
each other.
Figure 4.14

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HOW TO Draw the Two Conformations for HOW TO Draw the Two Conformations for
a Substituted Cyclohexane-1 a Substituted Cyclohexane-2
Step [1] Draw one chair form and add the substituents Step [2] Ring-flip the cyclohexane ring.
• Arbitrarily pick a ring carbon, classify it as an up or • Convert the up C’s to down C’s and vice versa. The
down carbon, and draw the bonds. Each C has one chosen C now puckers down.
axial and one equatorial bond.
• Add the substituents H and CH3, placing one axial
and one equatorial.
• This forms conformation A.

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HOW TO Draw the Two Conformations for

Chair Conformations and Energy
a Substituted Cyclohexane-3
Step [3] Add the substituents to the second The two chair conformations of cyclohexane are different, so they
conformation. are not equally stable.
Larger axial substituents create destabilizing (and thus
• Draw axial and equatorial bonds. On a down C the unfavorable) 1,3-diaxial interactions.
axial bond is down.
In methylcyclohexane, each unfavorable H,CH3 interaction
• Ring flipping converts axial bonds to equatorial destabilizes the conformation by 0.9 kcal/mol, so Conformation B is
bonds. The equatorial CH3 becomes axial. 1.8 kcal/mol less stable than Conformation A.

• This forms Conformation B.

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Preference of Equatorial Position in Preference of Equatorial Position in

Substituted Cyclohexanes-1 Substituted Cyclohexanes-2
Three dimensional representations for the two chair The larger the substituent on the six-membered ring, the higher
conformations of methylcyclohexane. the percentage of the equatorial conformation at equilibrium.
With a very large substituent like tert-butyl [(CH3)3C-], essentially
none of the conformation containing an axial tert-butyl group is
Figure 4.15 present at room temperature.

Figure 4.16

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Disubstituted Cycloalkanes Cis and Trans Stereoisomers

There are two different 1,2-dimethylcyclopentanes— Stereoisomers are isomers that differ only in the way the atoms are
one having two CH3 groups on the same side of the oriented in space.
ring and one having them on opposite sides of the ring. The prefixes cis and trans are used to distinguish these isomers.
The cis isomer has two groups on the same side of the ring.
The trans isomer has two groups on opposite sides of the ring.

A and B are stereoisomers.

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HOW TO Draw Disubstituted

Disubstituted Cycloalkanes
Cyclohexane-1
A disubstituted cyclohexane, such as 1,4-dimethylcyclo- Step [1] Draw one chair form and add the substituents
hexane, also has cis and trans stereoisomers. • For trans-1,4-dimethylcyclohexane, pick two C’s located 1,4- to
each other, classify them as up or down, and draw in
Each of these stereoisomers has two possible chair substituents.
conformations.
• The trans isomer must have one group above the ring (on an up
bond) and one group below the ring (on a down bond). This is a
diaxial arrangement.
• The result is Conformation A.

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HOW TO Draw Disubstituted

Trans Disubstituted Cycloalkanes
Cyclohexane-2
Step [2] Ring-flip the cyclohexane ring
• The up C flips down, and the down C flips up.

Step [3] Add the substituents to the second conformation.

Conformations 1 and 2 are not equally stable.
• Ring flipping converts axial bonds to equatorial, and vice versa.
Because conformation 2 has both CH3 groups in the
roomier equatorial position, it is lower in energy.
A trans isomer has two substituents on opposite sides,
one up and one down.

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Cis Disubstituted Cycloalkanes Oxidation and Reduction Reactions

A cis isomer has two groups on the same side of the Oxidation results in an increase in the number of C—Z bonds.
ring, either both up or both down. Oxidation results in a decrease in the number of C—H bonds.

In this example, Conformations 1 and 2 have two CH3 Reduction results in a decrease in the number of C—Z bonds.
groups drawn up. Reduction results in an increase in the number of C—H bonds.

Both conformations have one CH3 group axial and one

equatorial, making them equally stable.

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Combustion of Alkanes

Alkanes undergo combustion — that is, they burn in

the presence of oxygen to form carbon dioxide and
water.
This is an example of an oxidation-reduction reaction.
Every C—H and C—C bond in the starting material is
converted to a C—O bond in the product. End

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