CHAPTER TWO

HYDROCARBONS
 Introduction
 The structural features that make it possible to classify
compounds into families are called functional groups.
 A functional group is a group of atoms within a molecule that
has a characteristic chemical behavior.
 A hydrocarbon is a compound composed of only carbon and
hydrogen.
 Alkanes are members of a larger group of organic
compounds called hydrocarbons ( aliphatic hydrocarbons).
 Alkanes are a class of saturated hydrocarbons with the
general formula CnH2n+2. That is, they contain only carbon-
carbon single bonds.
 Saturated means that each carbon has the maximum number
of hydrogen's bonded to it.
 Cont.…
 Cycloalkanes are saturated cyclic hydrocarbons with the
general formula CnH2n.
 In contrast to open-chain alkanes, where nearly free rotation
occurs around C−C bonds, rotation is greatly reduced
(Restricted) in cycloalkane.
 Cycloalkanes are named by adding the prefix “cyclo” to the
alkane name that signifies the number of carbon atoms in the
ring.
 Cycloalkane has two fewer hydrogen's than an acyclic alkane
with the same number of carbons.
 Nomenclature of alkanes
A. Branched-chain alkanes:
 A chemical name typically has four parts in the IUPAC system
of nomenclature: prefix, parent, locant, and suffix.

 To name branched-chain alkanes and learn some general

rules that are applicable to all compounds.
STEP 1: Find the parent hydrocarbon.
a). Find the longest continuous chain of carbon atoms in the
molecule.
 Cont.…
b). If two different chains of equal length are present, choose the
one with the larger number of branch points as the parent.

STEP 2: Number the atoms in the longest chain.

a). Begin at the end nearer the first branch point, number each
carbon atom in the parent chain.
 Cont.…
b). If there is branching an equal distance away from both ends
of the parent chain, begin numbering at the end nearer the
second branch point.

STEP 3: Identify and number the substituents.

a). Assign a number, or locant, to each substituent to locate its
point of attachment to the parent chain.
 Cont.…
b). If there are two substituents on the same carbon, give both the
same number. There must be as many numbers in the name as
there are substituents.

c). If the same substituent numbers are obtained in both

directions, the first group cited receives the lower number
(alphabetically).
 Cont.…
STEP 4: Write the name as a single word.
 Use hyphens to separate the different preixes, and use
commas to separate numbers.
 If two or more different substituents are present, cite them in
alphabetical order.
 If two or more identical substituents are present on the parent
chain, use one of the multiplier prefixes di-, tri….
 Cont.…
B. Cycloalkanes
 Cycloalkanes are named by adding the prefix “cyclo” to the
alkane name that signifies the number of carbon atoms in the
ring.

a). In the case of a cycloalkane with an attached alkyl

substituent, the ring is the parent hydrocarbon unless the
substituent has more carbon atoms than the ring.
 In that case, the substituent is the parent hydrocarbon and the
ring is named as a substituent.
 There is no need to number the position of a single
substituent on a ring.
 Cont.…
Examples:

 If the ring has two different substituents, they are cited in

alphabetical order and the number 1 position is given to the
substituent cited first (alphabetical).

 If there are more than two substituents on the ring, they are
cited in alphabetical order.
 Cont.…
 The substituent given the number 1 position is the one that
results in a second substituent getting as low a number as
possible.
 Properties of Alkanes
 Alkanes containing 1 to 4 carbons are gases at room To.
 Those containing 5 to 17 carbons are colorless liquids.
 High-molecular-weight alkanes (those with18 or more
carbons) are white, waxy solids.
 Alkanes are sometimes called to as paraffin's (Less reactive).
 Alkanes show regular increases in both boiling point and
melting point as molecular weight increases.
 Due to dispersion forces increase as molecule size increases.
 Branched alkanes have lower boiling point and melting point
because they will show steric hindrance resulting low contact
within a molecule consequently have smaller dispersion
forces.
 Cont.…
 The reaction of an alkane with Cl2 occurs when a mixture of
the two is irradiated with ultraviolet light (UV).
 Depending on the relative amounts of the two reactants and
on the time allowed, a sequential substitution of the alkane
hydrogen atoms by chlorine occurs, leading to a mixture of
chlorinated products.
 The typical reaction of alkane is substitution reaction.
 They can be prepared by reduction of alkenes & alkynes.
 Alkenes and Alkynes
Alkenes:
 An unsaturated hydrocarbon contains one or more carbon-
carbon double because they have fewer than the maximum
number of hydrogen's.
 An alkene, sometimes called an olefin.
 They have general formula CnH2n.
 They have two fewer hydrogen's than an alkane with the
same number of carbon atoms.
 They are non-polar molecules & aliphatic Hydrocarbons.
 Nomenclature of Alkenes
 Step 1: Name the parent hydrocarbon. Find the longest
carbon chain containing the double bond.

 Step 2: Number the carbon atoms in the chain. Begin at the

end nearer the double bond, if the double bond is equidistant
from the two ends, begin at the end nearer the first branch
point. This rule ensures that the double-bond carbons receive
the lowest possible numbers.
 Cont.…
 Step 3: Write the full name. Number the substituents
according to their positions in the chain, and list them
alphabetically.
 Indicate the position of the double bond by giving the number
of the first alkene carbon and placing that number directly
before the parent name.
 If more than one double bond is present, indicate the position
of each and use one of the suffixes -diene, -triene, and so on.
 Cont.…
 Cyclo-alkenes:
 In naming cyclo-alkenes, the carbon atoms of the ring double
bond are numbered 1 and 2 in the direction that gives the
substituent encountered first the smaller number.
 Preparations of alkenes
 The preparation of alkenes is dominated by elimination rxns.
 The two most common elimination reactions are
dehydrohalogenation (the loss of HX from an alkyl halide)and
dehydration (the loss of water from an alcohol).
 Cis–trans isomerism in alkenes
 Because the two p orbitals that form the bond must be parallel
to achieve maximum overlap, rotation about a double bond
does not readily occur.
 If rotation were to occur, the two p orbitals would no longer
overlap and the bond would break.

 Alkene such as 2-butene can exist in two distinct forms.

 The isomer with the hydrogen's on the same side of the
double bond is called the Cis-isomer. Cis–trans works only
with disubstituted alkenes.
 Cont.…
 The isomer with the hydrogen's on opposite sides of the
double bond is called the trans isomer.
 A pair of isomers such as cis-2-butene and trans-2-butene is
called Cis–trans isomers or geometric isomers.

 Cis-trans isomers are not possible for an alkene that has

identical substituents attached to one of the double-bonded
carbons.
 E, Z nomenclature of alkenes
 With trisubstituted and tetrasubstituted double bonds, a more
general method is needed for describing double-bond
geometry.
 The method used for describing alkene stereochemistry is
called the E,Z system.
 Rule 1: Considering each of the double-bond carbons
separately, look at the two substituents attached substituent
with higher atomic number ranks higher than an atom with
lower atomic number.
 Rule 2: If a decision can’t be reached by ranking the first
atoms in the two substituents, look at the second, third, or
fourth atoms away from the double-bond until the first
difference is found.
 Cont.…
 Once the two groups attached to each double-bonded carbon
have been ranked as either higher or lower. If the higher
ranked groups on each carbon are on the same side of the
double bond, the alkene is said to have Z geometry.
 If the higher-ranked groups are on opposite sides, the alkene
has E geometry
 Reactions of alkenes
A. Addition of Hydrogen Halides
 In the addition of HX to an alkene, the H attaches to the
carbon with fewer alkyl substituents and the X attaches to the
carbon with more alkyl substituents (Markovnikov’s rule).
 The addition of HCl to propene is highly regioselective and
that 2-chloropropane is the major product of the reaction.
 A regioselective reaction is a reaction in which one direction
of bond forming or breaking occurs in preference to all other
directions.
 Cont.…
 When both double-bonded carbon atoms have the same
degree of substitution, a mixture of addition products results.

 Carbocation rearrangement can also be observed in some

reactions.
 Cont.…
B. Addition of Water: Acid-Catalyzed Hydration
 When water is added to an alkene, no reaction takes place,
because there is no electrophile present to start a reaction by
adding to the nucleophilic alkene.
 The OH bonds of water are too strong and water is too weakly
acidic to allow the hydrogen to act as an electrophile for this
reaction.

 However, an acid (e.g., or HCl) is added to the solution, a

reaction will occur because the acid provides an electrophile.
 The product of the reaction is an alcohol. The addition of
water to a molecule is called hydration.
 Cont.…
 In the addition of HX, H2O, or ROH to an alkene, hydrogen
adds to the carbon of the double bond having the greater
number of hydrogen (Markovnikov’s rule).
 Alkynes
 An alkyne is a hydrocarbon that contains a carbon–carbon
triple bond.
 They are unsaturated aliphatic hydrocarbon.
 Acetylene, C2H2, the simplest alkyne, was once widely used in
industry as the starting material for many compounds.
 Alkyne has four fewer hydrogen's than the corresponding
alkane.
 The general molecular formula for an acyclic (noncyclic)
alkyne is a CnH2n-2.
 For a cyclic alkyne CnH2n-4.
 Nomenclature of Alkynes
 Naming of alkyne follows the general rules for hydrocarbons.
 The suffix -yne is used, and the position of the triple bond is
indicated by giving the number of the first alkyne carbon.
 Numbering the main chain begins at the end nearer the triple
bond so that the triple bond receives as low a number as
possible.

 Compounds with more than one triple bond are called diynes,
triynes.
 Cont.…
 Compounds containing both double and triple bonds are
called enynes (not ynenes).
 Numbering of an enyne chain starts from the end nearer the
first multiple bond, whether double or triple.
 When there is a choice in numbering, double bonds receive
lower numbers than triple bonds.
 Preparation of Alkynes
 Elimination Reactions of Di-halides.
 Alkynes can be prepared by the elimination of HX from alkyl
halides in a similar manner as alkenes.
 Treatment of a 1,2-dihaloalkane (called a vicinal dihalide)
with an excess amount of a strong base such as KOH or
NaNH2 results in a twofold elimination of HX and formation
of an alkyne.
 Reactions of Alkynes:
 Addition of Alkyl Halide (HX).
 As a general rule, electrophiles undergo addition reactions
with alkynes much as they do with alkenes.
 Halogen adding to the more highly substituted side of the
alkyne bond and hydrogen adding to the less highly
substituted side (Markovnikov’s).
 Cont.…
 Bromine and chlorine also add to alkynes to give addition
products, and trans stereochemistry again results.
 Cont.…
 Hydration of Alkynes
 Alkynes can be hydrated by either of two methods. Direct
addition of water catalyzed by mercury(II) ion yields the
Markovnikov product.(Hydroboration as Reading)
 Mercury(II)-Catalyzed Hydration of Alkynes
 Alkynes don’t react directly with aqueous acid but will
undergo hydration readily in the presence of mercury(II)
sulfate as a Lewis acid catalyst.
 Cont.…
 The actual product isolated from alkyne hydration is not a
vinylic alcohol, or enol (ene-ol), but is instead a ketone.
 Although the enol is an intermediate in the reaction, it
immediately rearranges into a ketone by a process called
keto–enol tautomerism.
 The individual keto and enol forms are said to be tautomers
 Cont.…
 Mechanism of the mercury(II)-catalyzed hydration of an
alkyne to yield a ketone.
 The reaction occurs through initial formation of an
intermediate enol, which tautomerizes to the ketone.
 Cont.…
Here
 Cont.…
 A mixture of both possible ketones results when an
unsymmetrically substituted internal alkyne is hydrated.
 The reaction is therefore most useful when applied to a
terminal alkyne because only a methyl ketone is formed.
 Aromatic Hydrocarbons
 In the early days of organic chemistry, the word aromatic was
used to describe such fragrant substances.
 However, that substances grouped as aromatic differed from
most other organic compounds in their chemical behavior.
 We now use the word aromatic to refer to the class of
compounds that contain special ring structure became known
as a benzene ring.
 Aromatic compounds containing a benzene ring became part
of a larger family of compounds now classified as aromatic
on the basis of their electronic structure rather than their
odor.
 It does not undergo the addition, oxidation, and reduction
reactions characteristic of alkenes and alkynes.
 Cont.…
 Naming Aromatic Compounds
 Monosubstituted benzenes are named systematically in the
same manner as other hydrocarbons, with -benzene as the
parent name.

 Alkyl-substituted benzenes are named in different ways

depending on the size of the alkyl group.
 If the alkyl substituent is smaller than the ring (six or fewer
carbons), is referred to as an alkyl-substituted benzene.
 If the alkyl substituent is larger than the ring (seven or more
carbons), the compound is referred to as a phenyl-substituted
alkane.
 Cont.…
 The name phenyl is used for the -C6H5 unit when the
benzene ring is considered a substituent.

 Disubstituted benzenes are named using the prefixes ortho

(1,2), meta (1,3), or para (1,4) relationship on the ring.
 Cont.…
 Benzenes with more than two substituents are named by
choosing a point of attachment as carbon 1 and numbering
the substituents on the ring so that the second substituent has
as low a number as possible.
 If ambiguity still exists, number so that the third or fourth
substituent has as low a number as possible, until a point of
difference is found. The substituents are listed alphabetically
when writing the name.
 Cont.…
 Aromaticity and the Hückel 4n +2 Rule
 Criteria for Aromaticity were recognized in the early 1930s by
Erich Hückel, a German chemical physicist.
 His calculations demonstrated that monocyclic, planar
molecules with a closed loop of 2, 6, 10, 14, 18, . . . p
electrons in a fully conjugated system should be aromatic.
 These numbers are generalized in the (4n+2) p electron rule,
where n is a positive integer (0, 1, 2, 3, 4, . . . .)
 Conversely, monocyclic, planar molecules with 4n p
electrons (4, 8, 12, 16, 20, . . .) are especially unstable and are
said to be anti-aromatic.
 Cont.…
 To be aromatic, a compound must:
 Be cyclic.
 Have one 2p orbital on each atom of the ring
(conjugation).
 Be planar overlap of all 2p orbitals of the ring.
 Have a closed loop of (4n +2) p electrons.
 Cont.…
 Cyclooctatetraene is not planar, but tub shaped. Because the p
orbitals cannot overlap, each pair of electrons is localized
between two carbons instead of being delocalized over the
entire ring of eight carbons (not aromatic).

 Cyclobutadiene has four p electrons and is anti-aromatic. The

p electrons are localized in two double bonds rather than
delocalized around the ring.
 Cont.…
 According to Hückel’s criteria, [10] annulene should be
aromatic; it is cyclic, has one 2p orbital on each carbon of the
ring, and has 4(2)+2 = 10 electrons in its p system.
 It has been found, however, that this molecule shows reactions
typical of alkenes and therefore is classified as nonaromatic.
 Heterocyclic and Aromatic Ions
 Heterocyclic Aromatic compounds:
 Aromatic character is not limited to hydrocarbons; it is found
in heterocyclic compounds as well.
 Pyridine and pyrimidine are heterocyclic analogs of benzene.
 In pyridine, one CH group of benzene is replaced by
nitrogen, and in pyrimidine, two CH groups are replaced by
nitrogen.
 Cont.…
 The five-membered ring heterocyclic compounds such as
thiophene, pyrrole, and imidazole are also aromatic.
 Aromatic Ions
 Any neutral monocyclic unsaturated hydrocarbon with an
odd number of carbons in the ring that have at least one CH2
group in the ring and therefore cannot be aromatic. Examples
of such hydrocarbons are cyclopropene, cyclopentadiene, and
cycloheptatriene.

 Cyclopropene has the correct number of p electrons to be

aromatic, namely 4(n) + 2 = 2, but it does not have a
continuous closed loop of 2p orbitals.
 Cont.…
 If the CH2 group becomes a CH+ group in which the carbon
atom is sp2 hybridized and has a vacant 2p orbital. The
cyclopropenylcation should be aromatic.
 To form an aromatic ion from cyclopentadiene, it is necessary
to convert the CH2 group to a -CH2 group in which the carbon
becomes sp2 hybridized and has two electrons in its
unhybridized 2p orbital. The resulting cyclopentadienyl anion
is aromatic.

End