KIMIA ORGANIK

Tutorial VII

Cycloalkanes/Sikloheksana
S Rusdi
Program Studi Teknik Kimia
Uiversitas Islam Indonesia

Overview

 Because of their cyclical nature, cycloalkanes do not have the freedom of rotation
that regular alkanes possess.
Stereochemistry plays a very important role in both the limitations of movements,
but also, in some instances the limitations of reactions that can take place. Often
these limitations are due less to the cyclical nature itself so much as the lack of
freedom of rotation found in such alkanes.
A good example is the restrictions placed on E2 elimination reactions, which we'll
cover later in the book.
Cycloalkanes are hydrocarbons containing one or more rings.
(Alkanes without rings are referred to as aliphatic.)

Drawing Cycloalkanes

H2
Under certain reaction conditions, propane can be transformed into cyclopropane. (H2
comes off as a sideproduct.)

First four simple cycloalkanes

The above image of the first four simple cycloalkanes shows that each carbon has
2 hydrogens attached.
As you can see, the other 2 bonds are to adjacent carbons. While the shapes
show the basic 2-dimensionaly, top-down shape, only cyclopropane and
cyclobutane have all of their carbons on a plane.
Cylcopentane and cyclohexane, as well as higher cycloalkanes, all have a 3dimensional geometry. Cyclohexane is particularly important and it will be
discussed separately.

Cyclopentane and cyclohexane without atoms labeled

More often, cycloalkanes, like many other organic structures, are drawn such that
their carbons and hydrogens aren't labeled. Cyclopentane and cylohexane (see
above) are generally drawn as a pentagon and a hexagon, respectively.

Naming of Cycloalkanes
Naming of cycloalkanes is similar to alkanes. The smallest cycloalkane is
"Cyclopropane", so as you might imagine, this is a ring of 3 carbons. If the
number of carbons on the cycloalkane is higher than the number of carbons on
any of its substituents (that is, carbon chains attached to carbons on the
cycloalkane), then the base name is prefixed with "cyclo" and the rest of the
name the same as an alkane with the same number of carbons.

Not, 1-ethylbuthylcyclopentane
If, as in the above image, the cycloalkane has fewer carbons than a carbon chain
it's connected to, then the longest carbon chain is the primary and the cyclic
portion receives the substituent "-yl" ending and prefixes the primary name. Thus
the name 1-ethylbutylcyclopentane, while technically an accurate description, is
not the correct name.

 Numbering of carbons in substituted cycloalkanes is fairly straight-forward. If

there is only one substituent, it is the 1-carbon.
If there are more than one, then numbering proceeds, clockwise or counterclockwise, such that the lowest number after 1 goes to the least (or a least)
substituted carbon.
I know that sounds tricky, so we'll look at the example on the left, 3-chloro-1,1dimethylcyclohexane. the carbon with the chlorine bond is the least substituted
carbon, so it gets the lowest number after 1 and 1 goes to the nearest carbon
with more than 1 substituent. So, the 1 is applied to the methyls. Substituents are

still placed in alphabetic order, as you can see from the second example, 2bromo-3-chloro-1,1-dimethylcyclohexane.

Substituents
If a cycloalkane has only one substituent, it is not necessary to assign that
substituent a number. If there is more than one substituent, then it is necessary
to number the carbons and specify which substituent is on which carbon.

Methylcyclopentane

1,2-dimethylcyclopentane

1,1-dimethylcyclopentane

1,3-dimethylcyclopentane

The organic compound

could be named and numbered

1-cyclopropyl-5-ethyl-2-methylcyclohexane
and should be named

2-cyclopropyl-4-ethyl-1-methylcyclohexane
because it produces a lower numbered name (1+5+2=8 vs. 2+4+1=7).

In the following example, notice that the longer chain is the parent and the
cycloalkane is the substituent.

2-Cyclopropylbutane

1,5-dicyclopropylpentane

Multicyclic alkanes
Multicyclic alkanes are hydrocarbons that have more than one bonded cyclic ring.
These abound in biology as all kinds of hormones, steroids, cholesterol,carbohydrates,
etc.

They are named as bicycloalkanes, tricycloalkanes, etc.

They are named slightly differently than singularly cyclic alkanes.

Bicyclo[2.1.0]pentane

Multicyclic alkanes are found frequently in living beings:

Part of Cholesterol

Other Cyclohexane

Boat conformation

Chair conformation

Note: In the above models, the straight lines represesnt single bonds, the lumps
represent carbon atoms, and the open ends represent hydrogen atoms.
The chair conformation (can you see how it looks like a chair?) is lower in energy than
the boat conformation. This is because the two ends of the molecule are farther apart
and avoid steric hinderance.
Hydrogen atoms in a cyclohexane can be divided into two types:
1. Axial, that point towards the top and bottom, and
2. Equitorial, that point out away from the edge of the molecule
When hydrogens are replaced with other, bulkier groups, it becomes apparent that the

axial positions are less energetically favored than the equitorial positions. That means
that, if given a choice, bulkier groups will tend to bond to cyclohexane in equitoral
positions, as this reduces their steric hinderance and potential energy.

Ring Strain in Cycloalkanes

Carbons with 4 single bonds want the bonds to be at a tetrahedral angle of
109.5. In 1885, Adolf von Baeyer proposed that since carbons prefer this angle,
that only rings of 5 and 6 members should be possible.
Baeyer made the mistake of thinking in 2-dimensions and assuming that all rings
are planar. In fact, only cyclopropane and cyclobutane are flat, resulting in their
bond angles of 60 and 90, respectively.
But for some time, it was believed that these smaller cycloalkanes could not be
created and that ones of more than 6 carbons would have strain because their
angles would be too far in excess of the 109.5 preferred angle.
*

Cyclopropane (unstable, lots of ring strain)

Cyclobutane (ring strain)

*
Cyclopentane (little ring strain)
no ring strain)
*

Cyclohexane (Next to

Cyclodecane

First four simple cycloalkanes in 3-dimensional stick representation

In the above figure, the first four simple cycloalkanes are again represented, but
this time the 3 dimensional representations are shown. Notice how cyclopentane
has 4 carbons on a plane and the 5th is slightly off the plane, giving it the shape
of an open envelope.

 In fact, rings larger than 3 carbons have 3 dimensional shapes that relieve this
bond strain, but it's important to note that bond strain does affect stability.

o For cyclopropane and cyclobutane, the strain energy is about 110 kJ/mol.
Cyclobutane can enter a "puckered" formation that slightly relieves some
torsional strain.

o Cyclopentane, which is non-planar can remove some of the strain and has
only about 25 kJ/mol of strain.

o Cyclohexane, because of its chair conformation, can maintain perfect

tetrahedral angles, resulting in no strain.

 As the ring size goes up further, angle strain can be avoided at the cost of
introducing some eclipsing strain, and vice versa, so that some strain exists, but
the most strained of these, cyclononane, has only about 50 kJ/mol of strain. Ring
strain pervades for ring sizes up to 13 members. After that, there are enough
carbons that ring strain is removed completely.

Cyclopentane in a 3-dimensional stick representation

But angle strain isn't the only issue involved in ring strain. Torsional strain is also
a factor. When the hydrogen bonds in a ring eclipse each other, this creates
additional strain. In the case of cyclopropane the hydrogens eclipse each other,
greatly adding to the strain.
In fact, this is the cause of most of the strain found in cyclopentane.

 Cyclopentane has bond angles very close to 109.5, but because 4 of its
carbons are planar, there it has torsional strain that makes it less stable.
Looking at the cyclopentane along 2 of the bonds on the plane, with the nonplanar carbon closest to us, in the figure above, one can see that the bend in the
bonds allows the hydrogens to move slightly out eclipse, reducing the torsional
strain somewhat.
Cyclohexane is the lowest membered ring that's able to have both 109.5
bond angles and maintain a staggered conformation, allowing it to be strain
free.
Rings with thirteen or more carbons have virtually no ring strain.

Conformations of Cyclohexane
There are 3 main conformations of Cyclohexane, the chair, the reverse chair and
the boat. The chair conformations have no angular, torsional or steric strain.

However the boat conformation does have steric strain, as the hydrogens at the
high points on the front and back of the boat are slightly overlapping.

Conformations of Mono- and Di-substituted Cyclohexane

The Effect of Conformation on Reactions with Cyclohexane
Different conformations of cyclohexane can react differently for certain reactions.
For example, the E2 elimination reaction, which we'll cover later in this book,
requires that a halogen atom and a hydrogen atom be on adjacent carbons and
coplanar from each other, or 180 (anti).
In cyclohexanes with multiple substituents attached to its carbons, it's possible
for that the hydrogen and halogen can be on adjacent carbons, but never be
coplanar, thus preventing the reaction from occurring.
In other reactions, steric interference from adjacent substituents, for example, a
large alkyl group on an adjacent carbon, can prevent a nucleophile from attacking
a desired location. For these, and other reasons, it's important to understand the

3-dimensional geometry and structure of the reactants as well as the mechanisms

of the reactions that are taking place.

Large Ring Systems

Polycyclic Ring Systems

In some compounds, two or more rings are fused together in the same molecule.
This can occur in both aliphatic and aromatic compounds.
If the two rings meet at a single carbon atom, where that carbon atom is part of
both rings, the compound is called a spiro compound. The two rings are roughly
(but not exactly) perpendicular to each other because of the usual tetrahedral
bonding of four ligands around carbon.
If the two rings are bridged at two or more carbon atoms, the carbon atoms form
part of a bridge, and the compound is a bicycloalkane (for two rings) or a
polycycloalkane (for three or more rings).
An aromatic bicyclic compound is naphthalene (C10H8), which is a pair of benzene
rings fused across a carbon-carbon bond. An aliphatic (non-aromatic) bicyclic

compound is decalin (C10H18), formally known as decahydronaphthalene, which is

a pair of cyclohexane rings fused across a C-C bond.

Naming conventions for bicyclic rings

A bicyclic alkane ring system is composed of three parts:
1. The longer carbon chain (a)
2. The shorter carbon chain (b)
3. The carbon-carbon bridge (c)

Note that Failed to parse (<math_output_error>): a >= b >= c

always.

A bicyclic ring is named according to the total number of carbons in the following
form:
bicyclo[a.b.c]alkane

 In this formula, substitute [a.b.c] with the lengths of the carbon chains, and
substitute "alkane" with the total number of carbons (heptane, octane, nonane,
etc.).
A famous example of a bicyclic compound is norbornane (see image below). The
formal name for norbornane is bicyclo[2.2.1]heptane. There are two carbons to the
left of the bridge, two carbons to the right of the bridge, and one carbon on the bridge
itself. Therefore, the numbers in the brackets are [2.2.1]. Note that the two carbons at
the base of the bridge are not counted in the brackets.

Introduction to Heterocyclic Compounds

A sampling of single-ring heterocylic compounds

Heterocyclic compounds are cyclic compounds that contain atoms other than
carbon in their ring. The figure above shows just a few single-ring heterocyclic
compounds. The ones shown are simply 5 and 6 membered rings. There are
smaller and larger rings and there are also multiple ring heterocycles.

 Heterocyclic compounds play a big role in organic chemistry and because they
have different electron configurations from carbon, they react differently from
carbon rings and differently from each other. Later in this book we will discuss
several specific heterocyclic compounds that are very commonly used in organic
chemistry and we'll discuss their individual characteristics.