Alkanes and Cycloalkanes

Bonding in H2 : The Valence Bond Model

The characteristic feature of valence bond theory is that it pictures a covalent bond
between two atoms in terms of an in-phase overlap of a half-filled orbital of one atom
with a half-filled orbital of the other, illustrated for the case of H2.

Electrostatic potential maps to show this build-up of

electron density in the region between two hydrogen
atoms as they approach each other closely enough
for their orbitals to overlap.

A bond in which the orbitals overlap along a line

connecting the atoms (the internuclearaxis ) is
called a sigma ( σ) bond. The electron
distribution in a bond is cylindrically
symmetrical; were we to slice through a σ bond
perpendicular to the internuclear axis, its cross
section would appear as a circle.
 In molecules, the problem of understanding the
interactions of electrons with the nuclei is more
Molecular Orbital Theory complicated because there are more nuclei and more
electrons that interact.

Imagine, however, the situation that occurs when two nuclei approach one another. If
the two atoms come close enough together, an AO of one atom which contains a single
electron will occupy to some extent the same region of space as an AO of the second
atom which contains a single electron.

When those AOs overlap, an electron from

one atom shares a region of space with the
electron from the other atom. When such an
event occurs, each electron is no longer
influenced by just one nucleus but by two.

This new fact define a new region of space where there is a high probability of finding
both electrons. Furthermore, only two electrons can occupy any particular region of
space. This new region of space is called a molecular orbital (MO), the electrons in the
MO are of lower energy than when they were in their separate AOs, and the lowered
energy gives rise to a chemical bond between the atoms.

Chemical bonds result from the overlap of singly occupied Aos to

give a doubly occupied MO (called a bonding MO) in which each
electron of the pair interacts with both nuclei.
In order to simplify things, we’ll consider the interaction of the orbitals containing
valence electrons to create molecular orbitals. The wave functions of hydrogen atom
A and hydrogen atom B can interact either constructively or destructively.

Constructively:
Ψ(σ) or Ψ+ = (1/√2 ) [φ(1sa) + φ(1sb) ]
Destructively:
Ψ(σ*) or Ψ- = (1/√2 ) [φ(1sa) - φ(1sb) ]

The bonding orbital results in The antibonding orbital results in a

increased electron density between node between the two nuclei, and is of
the two nuclei, and is of lower energy greater energy than the two separate
than the two separate atomic orbitals. atomic orbitals.
 The result is an energy level
diagram with the bonding orbital
occupied by a pair of electrons. The
filling of the lower molecular orbital
indicates that the molecule is stable
compared to the two individual
atoms.

The bonding orbital is sometimes

given the notation σg, where the g
stands for gerade, or symmetric with
respect to a center of inversion.

The anti-bonding orbital is sometimes

given the notation σu, where the u
stands for ungerade, or asymmetric
with respect to a center of inversion.

The signs on the molecular orbitals indicate the sign of the wave function, not ionic
charge!!!
 Introduction to Alkanes: Methane, Ethane, and
Propane

Methane is the lowest boiling alkane, followed by ethane, then propane.

It is generally true that as the number of carbon atoms

increases, so does the boiling point. All the alkanes with four
carbons or fewer are gases at room temperature and
atmospheric pressure.

All of the carbon atoms have four bonds, all of the bonds are single bonds, and
the bond angles are close to tetrahedral.
The methane molecule is CH4 and the four bonds to
carbon are directed toward the corners of a
tetrahedron. Valence bond theory is based on the in-
sp3 Hybridization and Bonding in Methane
phase overlap of half-filled orbitals of the connected
atoms. But with an electron configuration of 1s2 2 s2
In the 1930s Linus Pauling offered an ingenious
2px 1 2 py1 carbon has only two half-filled orbitals
solution to this puzzle !!!!

The electron configuration of a carbon bonded to other atoms need not be the same as a free
carbon atom. By mixing (“hybridizing”) the 2 s 2px 2 py , and 2 pz orbitals, four new orbitals
are obtained. These four new orbitals are called sp 3 hybrid orbitals because they come
from one s orbital and three p orbitals.

1. All four sp 3 orbitals are of equal energy .

2. The axes of the sp 3 orbitals point toward the
corners of a tetrahedron .
3. Bonds involving sp 3 hybrid orbitals of
carbon are stronger than those involving
unhybridized 2s or 2p orbitals .
Isomeric Alkanes: The Butanes

Methane is the only alkane of molecular formula CH4 , ethane the only one that is
C2H6 ,and propane the only one that is C3H8 . Beginning with C4H10 , however,
constitutional isomers are possible; two alkanes have this particular molecular formula.
In one, called n - butane, four carbons are joined in a continuous chain. The n in n –
butane stands for “normal” and means that the carbon chain is unbranched. The second
isomer has a branched carbon chain and is called isobutane.

The C5H12 Isomers

Three isomeric alkanes have the molecular formula C 5 H 12 . The unbranched isomer
is n -pentane. The isomer with a single methyl branch is called isopentane . The third
isomer has a three-carbon chain with two methyl branches. It is called neopentane .
 Physical Properties of Alkanes and Cycloalkanes
Boiling Point. Methane, ethane, propane, and butane are gases at room temperature. The
unbranched alkanes pentane (C5H12 ) through heptadecane (C17H36 ) are liquids,
whereas higher homologs are solids.

The boiling points of unbranched alkanes increase

with the number of carbon atoms.

that the boiling points for 2-methyl-branched

alkanes are lower than those of the unbranched
isomer.

By exploring at the molecular level the reasons for the

increase in boiling point with the number of carbons and
the difference in boiling point between branched and
unbranched alkanes, we can continue to connect structure
with properties.

A substance exists as a liquid rather than a gas because attractive forces between molecules
(intermolecular attractive forces) are greater in the liquid than in the gas phase. Attractive forces
between neutral species (atoms or molecules, but not ions) are referred to as van der Waals forces
and may be of three types:

1. dipole–dipole (including hydrogen bonding)

2. dipole/induced-dipole
3. induced-dipole/induced-dipole
It might seem that two nearby molecules A and
B of the same nonpolar substance would be
unaffected by each other.

In fact, the electric fields of both A and B are

dynamic and fluctuate in a complementary
way that results in a temporary dipole moment
and a weak attraction between them.

An alkane with a higher molecular weight has more atoms and electrons and,
therefore, more opportunities for intermolecular attractions and a higher boiling point
than one with a lower molecular weight.
Branched alkanes have lower boiling
points than their unbranched isomers.
Isomers have, of course, the same
number of atoms and electrons,
but a molecule of a branched alkane
has a smaller surface area than an
unbranched one.
sp 2 Hybridization and Bonding in Ethylene

Ethylene is planar with bond angles

close to 120°; therefore, some
hybridization state other than sp3 is
required. The hybridization scheme is
determined by the number of atoms to
which carbon is directly attached.

In ethylene, three atoms are attached to each carbon, so three equivalent hybrid orbitals
are needed. These three orbitals are generated by mixing the carbon 2s orbital with two of
the 2p orbitals and are called sp2 hybrid orbitals.

The three sp2 orbitals are of equal

energy; each has one-third s character
and two-thirds p character. Their axes
are coplanar, and each has a shape
much like that of an sp3 orbital. The
three sp2 orbitals and the unhybridized p
orbital each contain one electron.
Each carbon of ethylene uses two of its sp2 hybrid orbitals to form bonds to two
hydrogen atoms. The remaining sp2 orbitals, one on each carbon, overlap along
the internuclear axis to give a bond connecting the two carbons.

Each carbon atom still has, at this point, an

unhybridized 2p orbital available for
bonding. These two half-fi lled 2 p orbitals
have their axes perpendicular to the
framework of σbonds of the molecule and
overlap in a side-by-side manner to give a
pi (π) bond.

Electrons in a bond are called π electrons.

The probability of finding a electron is
highest in the region above and below the
plane of the molecule. The plane of the
molecule corresponds to a nodal plane,
where the probability of finding a electron is
zero.
sp Hybridization and Bonding in Acetylene

The structure of acetylene with its bond

distances and bond angles. Its most
prominent feature is its linear geometry.

Because each carbon in acetylene is bonded to two other atoms, the orbital
hybridization model requires each carbon to have two equivalent orbitals available for
σ bonds.

According to this model the

carbon 2 s orbital and one of its 2
p orbitals combine to generate
two sp hybrid orbitals, each of
which has 50% s character and
50% character p.
The two carbons of acetylene are connected to each other by a 2 sp –2 sp
σ bond, and each is attached to a hydrogen substituent by a 2 sp –1 s σ
bond.

The unhybridized 2p orbitals on

one carbon overlap with their
counterparts on the other to form
two π bonds. The carbon–carbon
triple bond in acetylene is viewed
as a multiple bond of the σ + π + π
type.
Alkanes and Cycloalkanes:
Conformations and cis–trans
Stereoisomers
Structures A, B, and C represent different conformations of hydrogen peroxide.
Conformations are different spatial arrangements of a molecule that are generated
by rotation about single bonds. Although we can’t tell from simply looking at
these structures, we now know from experimental studies that C is the most stable
conformation.

Conformational analysis is the study of how conformational factors affect the

structure of a molecule and its properties. In this chapter we’ll examine the
conformations of various alkanes and cycloalkanes, focusing most of our attention
on three of them: ethane, butane, and cyclohexane.
Ethane is the simplest hydrocarbon that can have distinct conformations. Two, the
staggered conformation and the eclipsed conformation.

• In the staggered conformation, each CH bond of one carbon bisects an HCH angle of
the other carbon.
• In the eclipsed conformation, each CH bond of one carbon is aligned with a CH bond
of the other carbon.

The staggered and eclipsed conformations

interconvert by rotation around the CC
bond, and do so very rapidly.

Among the various ways in which the

staggered and eclipsed forms are
portrayed, wedge-and-dash, sawhorse, and
Newman projection drawings are especially
useful.
 In a Newman projection, we sight down the C-C bond, and represent the
front carbon by a point and the back carbon by a circle. Each carbon has
three other bonds that are placed symmetrically around it.

Illustrate the spatial relationship between

bonds on adjacent carbons. Each H-C-C-H
unit in ethane is characterized by a torsion
angle or dihedral angle, which is the angle
between the H-C-C plane and the C-C-H
plane.

The torsion angle is easily seen in a

Newman projection of ethane as the angle
between C-H bonds of adjacent carbons.

• Eclipsed bonds are characterized by a

torsion angle of 0°.
• When the torsion angle is
approximately 60°, we say that the
spatial relationship is gauche.
• When it is 180° we say that it is anti.

Staggered conformations have only gauche or anti relationships between

bonds on adjacent atoms.
 Of the two conformations of ethane, the staggered is 12 kJ/mol (2.9 kcal/mol)
more stable than the eclipsed. The staggered conformation is the most stable
conformation, the eclipsed is the least stable conformation.

Two main explanations have

been offered for the difference in
stability between the two
conformations.

• The repulsions between

bonds on adjacent atoms
destabilize the eclipsed
conformation.
• Better electron delocalization
stabilizes the staggered
conformation.

Ethane has an infinite number of

conformations that differ by only tiny
increments in their torsion angles. Not
only is the staggered conformation more
stable than the eclipsed, it is the most
stable of all of the conformations; the
eclipsed is the least stable.
Three equivalent eclipsed conformations and three equivalent
staggered conformations occur during the 360° rotation; the
eclipsed conformations appear at the highest points on the
curve ( potential energy maxima), the staggered ones at the
lowest ( potential energy minima).
 Both staggered conformations are equivalent
and equal in energy, but for one staggered
conformation to get to the next, it must first
pass through an eclipsed conformation and
needs to gain 12 kJ/mol (2.9 kcal/mol) of
energy to reach it. This amount of energy is
the activation energy (Eact ) for the process.

The point of maximum potential energy encountered by the reactants as they proceed to
products is called the transition state. The eclipsed conformation is the transition state for
the conversion of one staggered conformation of ethane to another.

As with all chemical processes, the rate of

rotation about the carbon–carbon bond
increases with temperature. Most of the
molecules in a sample have energies that are
clustered around some average value; some
have less energy, a few have more. Only
molecules with a potential energy greater than
Eact, however, are able to go over the transition
state and proceed on.
Conformational Analysis of Butane
The methyl groups are gauche to each other in one, anti in the other. Both conformations are
staggered, so are free of torsional strain, but two of the methyl hydrogens of the gauche
conformation lie within 210 pm of each other and there is a repulsive force between them.

The destabilization of a molecule that results when

two of its atoms are too close to each other is called
van der Waals strain, or steric hindrance, and
contributes to the total steric strain.

The staggered conformations are more stable than the eclipsed. At any instant, almost all the
molecules exist in staggered conformations, and more are present in the anti conformation than in
the gauche. The point of maximum potential energy lies some 25 kJ/mol (6.1 kcal/mol) above the
anti conformation.
 Small Rings: Cyclopropane and Cyclobutane

Conformational analysis is far simpler in cyclopropane than in any other

cycloalkane. Cyclopropane’s three carbon atoms are, of geometric necessity,
coplanar, and rotation about its carbon–carbon bonds is impossible

Strong sp3 – sp3 σ bonds are not possible for

cyclopropane, because the 60° bond angles of
the ring do not permit the orbitals to be properly
aligned for effective overlap. The less effective
overlap that does occur leads to what chemists
refer to as “bent” bonds.

Cyclobutane has less angle strain than

cyclopropane and can reduce the torsional
strain that goes with a planar geometry by
adopting the nonplanar “puckered”
In addition to angle strain, cyclopropane is destabilized
conformation.
by torsional strain. Each C—H bond of cyclopropane is
eclipsed with two others.

Which hydrogen atoms are twisted away from one

another. The eclipsing interactions are decreased
in the puckered form!!!
Cyclopentane

Angle strain in the planar conformation of cyclopentane is relatively small because

the 108° angles of a regular pentagon are not much different from the normal
109.5° bond angles of sp3 -hybridized carbon.

• The torsional strain, however,

is substantial, because five
bonds are eclipsed on the top
face of the ring, and another
set of five are eclipsed on the
bottom face.

• Some, but not all, of this

torsional strain is relieved in
nonplanar conformations.
Two nonplanar conformations
of cyclopentane, the
envelope and the half-chair,
are of similar energy.

In both the envelope and the half-chair conformations, in-plane and out-of-plane
carbons exchange positions rapidly. Equilibration between conformations of
cyclopentane is very fast and occurs at rates similar to that of rotation about the
carbon–carbon bond of ethane.
Conformations of Cyclohexane
The most stable conformation of cyclohexane is called the chair conformation. With C-C-C
bond angles of 111°, the chair conformation is nearly free of angle strain. All its bonds are
staggered, making it free of torsional strain as well.

The cyclohexane chair is best viewed from the

side-on perspective, which is useful for
describing its conformational properties.

The nonplanar conformation called the boat is much

less stable. This conformation has bond angles that are
approximately tetrahedral and is relatively free of angle
strain. It is, however, destabilized by the torsional strain
associated with eclipsed bonds on four of its carbons.

Both sources of strain are reduced by rotation about the

carbon–carbon bond to give the slightly more stable
twist boat, or skew boat, conformation

The various conformations of cyclohexane are in rapid equilibrium with one another,
but at any moment almost all of the molecules exist in the chair conformation.
 The conformational studies of cyclohexane show
that its 12 hydrogen atoms can be divided into two
Axial and Equatorial Bonds in Cyclohexane groups. Six of the hydrogens, called axial and
equatorial hydrogens.

• Axial hydrogens, have their bonds parallel to a vertical axis that passes
through the ring’s center. These axial bonds alternately are directed up and
down on adjacent carbons.

• Equatorial hydrogens, are located approximately along the equator of the

molecule.

Notice that the four bonds to each

carbon are arranged tetrahedrally,
consistent with an sp3
hybridization of carbon.

The conformational features of six-membered rings are fundamental to organic

chemistry, so it is essential that you have a clear understanding of the directional
properties of axial and equatorial bonds and be able to represent them accurately.
Conformational Inversion Rotation around the central carbon–carbon bond in
butane occurs rapidly, interconverting anti and gauche
in Cyclohexane conformations. Cyclohexane, too, is conformationally
mobile. Through a process known as ring inversion, or
chair–chair interconversion, one chair conformation is
converted to another chair.

In the first step, the chair conformation is converted to a skew boat. In this step, cyclohexane
passes through a higher-energy half-chair conformation.
The energy of activation is the difference in
energy between the chair and half-chair
conformations. The skew boat
conformations are intermediates. The boat
and half-chair conformations are transition
states.

The half-chair conformations are highest

in energy because they have the most
eclipsing interactions. The difference
in energy between the chair and half-
chair conformations is the activation
energy for
the chair–chair interconversion, which is
45 kJ/mol.

The most important result of ring inversion is that any

substituent that is axial in the original chair conformation
becomes equatorial in the ring-inverted form and vice versa.
Conformational Analysis of Monosubstituted Cyclohexanes
Ring inversion in methylcyclohexane differs from that of cyclohexane in that the two chair
conformations are not equivalent. In one chair the methyl group is axial; in the other it is
equatorial.
When two conformations of a molecule are in
equilibrium with each other, the one with the lower
free energy predominates. Why is equatorial
methylcyclohexane more stable than axial
methylcyclohexane?

Methyl group is less crowded when

it is equatorial than when it is axial.

The conformational preference for an equatorial methyl

group in methylcyclohexane to the conformation of
butane. The zigzag arrangement described by each
path mimics the anti conformation of butane. When the
methyl group is axial, each path mimics the gauche
conformation of butane.

Disubstituted Cycloalkanes: cis–trans
Stereoisomers
Both terms come from the Latin, in which cis
means “on this side” and trans means “across.”
When a cycloalkane bears two substituents on
different, these substituents may be on the same or
on opposite sides of the ring. When substituents
are on the same side, we say they are cis to each
other; if they are on opposite sides, they are trans
to each other.
The cis and trans forms of 1,2-dimethylcyclopropane are
stereoisomers. Stereoisomers are isomers that have
their atoms bonded in the same order—that is, they have
the same constitution, but they differ in the arrangement
of atoms in space. Stereoisomers of the cis–trans type
are sometimes referred to as geometric isomers.
We can measure the energy difference between cis
- and trans -1,2-dimethylcyclopropane by comparing
their heats of combustion. The two compounds are
isomers, and so the difference in their heats of
combustion is a direct measure of the difference in
their energies.

Conformational Analysis of
Disubstituted Cyclohexanes
The heats of combustion reveal that trans -1,4-dimethylcyclohexane is 7
kJ/mol (1.7 kcal/mol) more stable than the cis stereoisomer. It is
unrealistic to believe that van der Waals strain between cis substituents
is responsible, because the methyl groups are too far away from each
other. To understand why trans -1,4-dimethylcyclohexane is more stable
than cis -1,4-dimethylcyclohexane, we need to examine each
stereoisomer in its most stable conformation.

cis -1,4-Dimethylcyclohexane can adopt either of two

equivalent chair conformations, each having one axial
methyl group and one equatorial methyl group. The two
are in rapid equilibrium with each other by ring
interconversion. The equatorial methyl group becomes
axial, and the axial methyl group becomes equatorial.

The most stable conformation of trans-1,4-

dimethylcyclohexane has both methyl groups in
equatorial orientations. The two chair conformations of
trans -1,4- dimethylcyclohexane are not equivalent. One
has two equatorial methyl groups; the other, two axial
methyl groups.

It is worth pointing out that the 7 kJ/mol (1.7 kcal/mol) energy difference between cis
– and trans -1,4-dimethylcyclohexane is the same as the energy difference between the
axial and equatorial conformations of methylcyclohexane
 trans -1,2-dimethylcyclohexane has a lower heat of combustion
and is more stable than cis -1,2-dimethylcyclohexane. The cis
stereoisomer has two chair conformations of equal energy, each
containing one axial and one equatorial methyl group.

Both methyl groups are equatorial in the most stable conformation of trans -1,2- dimethylcyclohexane.

As in the 1,4-dimethylcyclohexanes, the 6 kJ/mol (1.5

kcal/mol) energy difference between the more stable
(trans) and the less stable (cis) stereoisomer is attributed to
the strain associated with the presence of an axial methyl
group in the cis stereoisomer.
Unlike the 1,2- and 1,4-dimethylcyclohexanes, in which the trans stereoisomer is more
stable than the cis, we fi nd that cis -1,3-dimethylcyclohexane is 7 kJ/mol (1.7 kcal/mol)
more stable than trans -1,3-dimethylcyclohexane.

The most stable conformation of cis -1,3-

dimethylcyclohexane has both methyl
groups equatorial.

The two chair conformations of trans -1,3-dimethylcyclohexane are equivalent to

each other. Both contain one axial and one equatorial methyl group.

Thus the trans stereoisomer, with one axial

methyl group, is less stable than cis -1,3-
dimethylcyclohexane where both methyl
groups are equatorial.