CHAPTER 3 ALKANES, CYCLOALKANES, ALKYNES AND FUNCTIONAL

GROUPS

3.1 NAMING ALKANES

We will begin our study of alkenes by looking at their structures and how they are named.
Then we will examine a reaction of an alkene, paying close attention to the steps by which
the reaction occurs and the energy changes that accompany them.

Alkenes are hydrocarbons that contain a carbon-carbon double bond. Alkenes play many
important roles in biology. For example, ethene (H2C "CH2), the smallest alkene, is a plant
hormone-a compound that controls growth and other changes in the plant's tissues. Among
other things, ethene affects seed germination, flower maturation, and fruit ripening. Many of
the flavors and fragrances produced by plants also belong to the alkene family.

3.2 ALKANE NOMENCLATURE

The IUPAC system uses a suffix to denote certain functional groups. The double bond is the
functional group of an alkene; its presence is denoted by the suffix "ene." Therefore, the
systematic (IUPAC) name of an alkene is obtained by replacing the "ane" ending of the
corresponding alkane with "ene." For example, a two-carbon alkene is called ethene, and a
three carbon alkene is called propene. Ethene also is frequently called by its common name:
ethylene.

Most alkene names need a number to indicate the position of the double bond. The longest
continuous chain that contains the functional group (i this case, the carbon- carbon double
bond) is numbered in the direction that gives the functional group suffix the lowest possible
number. For example, 1-butene signifies that the double bond is between the first and second
carbons of butene; 2-hexene signifies that the double bond is between the second and third
carbons of hexene.
3.2 ALKANNES, CYCLOALKANES AND BICYCLIC COMPOUNDS

Alkanes are organic compounds that consist entirely of single-bonded carbon and hydrogen
atoms and lack any other functional groups. Alkanes have the general formula CnH2n+2 and
can be subdivided into the following three groups: the linear straight-chain alkanes, branched
alkanes, and cycloalkanes.

Cycloalkanes have their own names under IUPAC rules, and their properti are generally
different from those of their noncyclic (also called acyclic) analogs with the same number of
carbons. We will see that they also exhib a kind of isomerism unique to cyclic molecules.

Hydrocarbons containing single-bonded carbon atoms arranged in rings an known as cyclic

alkanes, carbocycles or cycloalkanes. The majority of organic compounds occurring in nature
contain rings. Indeed, so many fundamental biological functions depend on the chemistry of
ring containing compounds that life as we know it could not exist in their absence. Radicals
derived from cycloalkanes by abstraction of a hydrogen atom are cycloalkyl radicals.

Bicyclic molecule (bi = two, cycle = ring) is a molecule that features two joined rings. Bicyclic
structures occur widely, for example in many biologically important molecules like a-thujene
and camphor. A bicyclic compound can be carbocyclic (all of the ring atoms are carbons), or
heterocyclic (the rings atoms consist of at least two elements), like DABCO. Moreover, the
two rings can both be aliphatic (e.g. decalin and norbornane), or can aromatic (e.g.
naphthalene),combination of aliphatic(e.g tetralin)
Three modes of ring junction are possible for a bicyclic compound:

Spirocyclic compounds, the two rings share only one single atom, the spiro atom, which is
usually a quaternary carbon.[4] An example of a spirocyclic compound is the photochromic
switch spiropyran.

In fused bicyclic compounds, two rings share two adjacent atoms. In other words, the rings
share one covalent bond, i.e. the so-called bridgehead atoms are directly connected (e.g. a-
thujene and decalin).

In bridged bicyclic compounds, the two rings share three or more atoms, separating the two
bridgehead atoms by a bridge containing at least one atom. For example, norbornane, also
known as bicyclo[2.2.1]heptane, can be viewed as a pair of cyclopentane rings each sharing
three of their five carbon atoms. Camphor is a more elaborate example.

The root of the compound name depends on the total number of atoms in all rings together,
possibly followed by a suffix denoting the functional group with the highest priority.
Numbering of the carbon chain always begins at one bridgehead atom (where the rings meet)
and follows the carbon chain along the longest path, to the next bridgehead atom. Then
numbering is continued along the second longest path and so on. Fused and bridged bicyclic
compounds get the prefix bicyclo, whereas spirocyclic compounds get the prefix spiro. In
between the prefix and the suffix, a pair of brackets with numerals denotes the number of
carbon atoms between each of the bridgehead atoms.

3.3 CONFORMATION OF ALKANES

In the organic chemistry, it is found that you can rotate a single bond of a molecule to change
the arrangement of atoms, without changing the chemical formula of the compound. So
isomers of a compound can be created by different forms of rotation about one single bond. So
the different arrangements of atoms due to such rotations of bonds are known as
conformations.

Conformation of Alkanes deals with the isomers of alkanes that form due to slight changes in
their structure, especially in their carbon-carbon bonds. The conformations start with ethane
and occur in all alkanes higher than ethane.

3.4 Naming and Conformation of Cycloalkanes

Overall ring strain decreases in cycloalkane rings that are large enough to allow the carbon-
carbon bonds to rotate away from planar structures. Configuration of a molecule denotes three-
dimensional arrangement of atoms in space. The infinite number of different arrangements of
atoms in space that is a result of rotation about a single bond is called Conformational isomers,
conformers or conformations. Yet another less common term is rotamers.

Ring-containing structures are a common occurrence in organic chemistry. We must, therefore

spend some time studying the special characteristics of the parent cycloalkanes. Cyclical
connectivity imposes constraints on the range of motion that the atoms in rings can undergo.
Cyclic molecules are thus more rigid than linear or branched alkanes because cyclic structures
have fewer internal degrees of freedom (that is, the motion of one atom greatly influences the
motion of the others when they are connected in a ring). In this lesson we will examine
structures of the common ring structures found in organic chemistry. The first four
cycloalkanes are: Cycloprane, Cyclobutane, Cyclo pentane and Cyclohexane.
The amount of energy stored in a strained ring is estimated by comparing the experimental heat
of formation to the calculated heat of formation. The calculated heat of formation is based on
the notion that, in the absence of strain, each -CH2- group contributes equally the heat of
formation, in line with the behavior found for the acyclic alkanes (i.e., open chains). Thus, the
calculated heat of formation varies linearly with the number of carbon atoms in the ring.
Except for the 6-membered ring, the experimental values are found to have a more positive
heat of formation than the calculated value owning to ring strain. The plots of calculated and
experimental enthalpies of formation and their difference (i.e., ring strain) are seen in the
Figure. The 3-membered ring has about 27 kcal/mol of strain. It can be seen that the 6-
membered ring possesses almost no ring strain. possesses alm

Carbon atoms prefer to adopt tetrahedral geometry, meaning that ideal bond angles are close to
109°. The 3-membered cyclopropane ring has C-C-C bond angles that are 60° and thus bent
about 50° from the ideal angle. Cyclopropane is a known compound; at room temperature it
exists as a gas that can be stored for long periods without decomposition. Obviously, molecules
such as cyclopropane deform far from their ideal geometry.
The potential energy as a function of bond angle for propane gives an estimate of how much
energy is stored in deforming the molecule to make the 60° angle required of the 3-membered
ring. Notice that the lowest energy for propane is at an angle slightly more open than 109°.
This is probably because the methyl groups are larger than hydrogen, and to minimize
crowdedness, the bond angle deforms ever so slightly away from 109". Notice also that the
bond angle can be opened or closed several degrees without costing much energy.

3.4 ALKANE REACTIONS

alkanes are not very reactive, but that they do undergo several types of transformations. These
processes, of which combustion is one example, do not involve electrophile-nucleophile
chemistry. Instead, they are called radical reactions. Although we shall not explore radical
reactions in great depth in this course, they play significant roles in biochemistry (such as
aging and disease processes), the environment (destruction of the Earth's ozone layer), and
industry (manufacture of synthetic fabrics and plastics).

Radical reactions begin with the breaking of a bond, or bond dissociation. The majority of the
topic will deal with halogenation, a radical reaction in which a hydrogen atom in an alkane is
replaced by halogen. The importance of halogenation lies in the fact that it introduces a
reactive functional group, turning the alkane into a haloalkane, which is suitable for further
chemical change. mechanisms are needed to describethe very large number of reactions in
organic chemistry. Mechanisms enable us to understand how and why reactions occur, and
what products are likely to form in them.
Radicals are formed by homolytic cleavage In our example, the bond breaks in such a way that
the two bonding electrons divide equally between the two participating atoms or fragments.
This process is called homolytic cleavage or bond homolysis. The separation ofthe two
bonding electrons is denoted by two single-barbed or "fishhook" arrows that point from the
bond to each of the atoms.

When these species are composed of more than one atom, they are called radicals. However,
radicals and free atoms are present in low concentration as unobserved intermediates in many
reactions, such as the production of polymers and the oxidation of fats that leads to the
spoilage of perishable foods an alternative way of breaking a bond, in which the entire bonding
electron pair is donated to one of the atoms. This process is heterolytic cleavage and results in
the formation of ions.

3.5 NAMING AND PREPARING ALKYNES

Parkinson's disease is a neurodegenerative disease, because the symptoms are caused by the
degeneration of neurons (brain cells). The neurons most affected by the disease are located in a
region of the brain called the substantia nigra. When these neurons die, they cease to produce
dopamine, a neurotransmitter used by the brain to regulate voluntary movement. The
symptoms described above begin to appear when 50-80% of dopamine producing neurons have
died. There is no known cure for the disease, which is progressive. However, the symptoms
can be treated through a variety of methods. One such method utilizes a drug called selegiline,
whose molecular structure contains a C=C bond the presence of the triple bond plays an
important role in the action of this drug. The properties and reactivity of compounds are
together with C=C bonds called alkynes. Indeed, alkynes are similar to alkenes in their ability
to function either as bases or as nucleophiles.

Alkynes are less common in nature than alkenes, although more than 1000 different alkynes
have been isolated from natural sources. One such example is histrionicotoxin, which is one of
the many toxins secreted by the South American frog, Dendrobates histrionicus, as a defense
against predators. For many centuries, South American tribes have extracted the mixture of
toxins from the frog's skin and placed it on the tips of arrows to produce poison arrows.

3.6 alkyne reaction

Like alkenes, the main pathway found in the reactions of alkynes is "addition" - that is,
breaking the C-C п bond and forming two new single bonds to carbon. The product of an
addition reaction to an alkyne is an alkene - and, as we just mentioned, alkene reactions
undergo addition reactions too. The upshot of this is that since alkynes possess two п bonds,
one must always be alert to the possibility of two addition reactions occurring. Furthermore,
should only one addition occur, the stereochemistry of the addition should be well noted, as it
can lead to the formation of geometric isomers (i.e. E/Z isomers). Finally, there is an additional
complexity in certain alkyne reactions that is not found in the reactions of alkenes. When water
is added across an alkyne, the resulting product is an "enol". And enols, tend to be fairly
unstable species. Through a process calledtautomerism, they convert to their constitutional
isomers containing carbonyl (C=O) groups such as aldehydes and ketones.

Another reaction not present in the reactions of alkenes is deprotonation. Alkynes are
unusually acidic hydrocarbons, with a pKa of about 25 (compare that to alkenes (pka = 43) and
alkanes (pKa = 50). The deprotonation of alkynes leads to its conjugate base, an "acetylide",
which is an excellent nucleophile. The reaction of acetylides with alkyl halides is one of the
few carbon-carbon bond forming reactions, which makes it arguably the most important
reaction to learn.

Finally, alkynes also undergo oxidative cleavage reactions. Treatment of alkynes with either
ozone or KMnO4 leads to carboxylic acids [terminal alkynes give carbonic acid, which
decomposes to CO2 and water].

3.7 Synthesis using alkynes

The simplest alkyne, acetylene (H-C=C-H), is a colorless gas that undergoes combustion to
produce a high-temperature flame (2800°C) and is used as a fuel for welding torches.
Acetylene is also used as a precursor for the preparation of higher alkynes.

In addition to the alkynes found in nature, many synthetic alkynes (prepared in the laboratory)
are of particular interest. One such example is ethynylestradiol, found in many birth control
formulations. This synthetic oral contraceptive elevates hormone levels in women and prevents
ovulation. The presence of the triple bond renders this compound a more potent contraceptive
than its natural analogue, which lacks a triple bond. The effect of the triple bond is attributed to
the additional structural rigidity that it imparts to the compound.

3.8 FUNCTIONAL GROUPS

The functional group in an alkene is a carbon-carbon double bond. The functional group in an
alkyne is a carbon-carbon triple bond. Aromatics are cyclic strcutures that are planar, fully
conjugated and that possess an odd number of electron pairs in the n bonding system.

Cycloalkanes are alkanes with carbon atoms attached in the form of a closed ring. functional
groups: An atom or groups of atoms that substitute for a hydrogen atom in an organic
compound, giving the compound unique chemical properties and determining its reactivity.

SUMMARY:

Alkenes are hydrocarbons that contain a carbon-carbon double bond. The double bond is the
functional group of an alkene; its presence is denoted by the suffix "ene." Therefore, the
systematic (IUPAC) name of an alkene is obtained by replacing the "ane" ending of the
corresponding alkane with "ene. Most alkene names need a number to indicate the position of
the double bond. The longest continuous chain that contains the functional group (in this case,
the carbon-carbon double bond) is numbered in the direction that gives the functional group
suffix the lowest possible number.

Hydrocarbons containing single-bonded carbon atoms arranged in rings are known as cyclic
alkanes, carbocycles or cycloalkanes. The majority of organic compounds occurring in nature
contain rings. The Bicyclic structures occur widely, for example in many biologically
important molecules like a-thujene and camphor. There are three modes of ring junction are
possible for a bicyclic compound: 1. Spirocyclic compounds, 2 fused bicyclic compounds and
3. bridged bicyclic compounds.
Conformation of Alkanes deals with the isomers of alkanes that form due to slight changes in
their structure, especially in their carbon-carbon bonds. The conformations start with ethane
and occur in all alkanes higher than ethane. Overall ring strain decreases in cycloalkane rings
that are large enough to allow the carbon-carbon bonds to rotate away from planar structures.
Configuration of a molecule denotes three-dimensional arrangement of atoms in space. The
infinite number of different arrangements of atoms in space that is a result of rotation about a
single bond is called conformational isomers, conformers or conformations.

Alkynes are less common in nature than alkenes, although more than 1000 different alkynes
have been isolated from natural sources. One such example is histrionicotoxin, which is one of
the many toxins secreted by the South American frog, Dendrobates histrionicus, as a defense
against predators.