HYDROCARBONS

Alkanes
Simplest family of hydrocarbons.

Contain C-H and C-C single bonds.

Comprised of only sp3 hybridized C

bonded to H atoms by sigma bonds.

Tetrahedral geometry
Alkanes
Saturated - have the maximum
possible number of H atoms

Relatively unreactive

Undergoes substitution reactions

Gen Formula: Cn H2n+2

Naming Alkanes
NUMBER OF C ATOMS NAME
1 Meth
2 Eth
3 Prop
4 But
5 Pent
6 Hex
7 Hept
8 Oct
9 Non
10 Dec
11 Undec
12 Dodec
 Prefixes to indicate number of
substituents
NUMBER PREFIX

2 Di

3 Tri

4 Tetra

5 Penta

6 Hexa

7 Hepta
 Naming Alkanes
1.Find the longest continuous chain of C
atoms (may not be written in a straight
line).
2. Give chain the appropriate alkane name
3. Find the substituents and name each with
the appropriate group name.
4. Number the carbon atoms such that the
substituents have the lowest number.
5. List the groups alphabetically in front of the
alkane.
6. Precede each substituent with a prefix
indicating how many of them are present in
the molecule
Alkyl Groups
Alkyl groups part of the alkane that
remains when a H is removed.

Alkyl groups are named by replacing the

ane of the parent alkane with yl
Use of Commas and
Hyphens
Use hyphens to separate different
prefixes

Use commas to separate numbers when

there are more than one.
Name the Alkanes
Name the Alkanes
Name the Alkanes
 Cycloalkanes
Cycloalkanes - contain C-H bonds and C-
C single bonds joined up in a ring.

They do not fit the alkane general formula,

CnH2n+2- because 2 H atoms are lost by
joining the carbon atoms in a ring.

The general formula for a cycloalkane is

CnH2n
Cycloalkanes
C and H are not explicitly shown in these
structures

C atom is understood to be present at

every junction

When cycloalkane functions as a

substituent, it is referred to as cycloalkyl
 Structural Isomers
Compound having the same molecular
formula but different structural
arrangement.

All alkanes with 4 or more C atoms can

show structural isomerism.

C4H10 - butane and 2-methylpropane.

C5H12
REACTIONS OF ALKANES
Reactions of Alkanes
Saturated - have the maximum possible
number of H atoms
Relatively unreactive

Alkanes have very weak induced dipole -

induced dipole forces.

As a result, alkanes tend to have low mp and

bp and very low solubility in polar solvents
(like dissolve like).
 CHEMICAL REACTIVITY

Alkanes do not have any significant

amount of positive or negative charge
which other compound might be attracted
to.

As a result alkanes have a fairly restricted

set of reactions.
Alkane Reactions
Substitution/ Halogenation

Combustion (oxidation)

Pyrolysis (cracking- thermal and

catalytic)
Combustion
Combustion: burning in the presence of oxygen.
Alkanes burn with a clean, blue flame
forming CO2, H2O and heat.

CH4 + 2O2 CO2 + 2H2O

Using balanced equations, show the

reactions for the combustion of
(i) propane
(ii) butane
(iii) pentane
 Pyrolysis (cracking)

Alkane + 400-600oC smaller alkanes +

alkenes + H2

Used to increase the yield of gasoline from

petroleum.

Higher boiling fractions are cracked into

lower boiling fractions that are added to the raw
gasoline.
 Halogenation/Chlorination
CH4 +Cl2 CH3Cl + CH2Cl2 + CHCl3 + CCl4 + HCl

Reaction halogenation

Mechanism - free radical substitution mechanism

Reactions vs Mechanisms
Chemical reaction chemical changes involving
the transformation of reactants into product(s).

Maybe represented with chemical equations

showing the reactants, the end product(s). Any
intermediate or the reaction conditions may also
be included.

Reaction mechanism sequence of events that

defines the pathway from reactants to products.
 Using Curved Arrows
Curved arrows in mechanisms show the flow of e-s and not the
movement of atoms.

There are two types of curved arrows:

1. for pairs of electron-s (double-headed arrow)

2. for single electron(single-headed , fish hook arrow)

Curved arrows move from e- rich to e- poor (i.e. nucleophile to

electrophile)

Nucleophile- species that donates an electron-pair to an electrophile

to form a chemical bond in a reaction. A Lewis base is a nucleophile.

Electrophile- species that accept electrons. Lewis acids.

Using Curved Arrows
Curved arrows must start from either e-
lone pairs or bonds

If the curved arrow starts from a lone pair

then the charge on that atom will become
more +ve

If the curved arrow starts from a bond then

e-s are being taken out of that bond, so the
bond is broken
Using Curved Arrows
Curved arrows must end either between
a pair of atoms or on an atom

If the curved arrow ends between a pair of

atoms, a new bond is formed

If the curved arrow ends on an atom then

the charge on that atom will become
more -ve
Free Radical Substitution
Alkane and halogen do not react unless
exposed to UV light or heat.

Consider methane and chlorine

UV light contains sufficient energy to

break the weaker Cl-Cl bond(58kcal/mole)
but insufficient energy to break the
stronger C-H bond (104 kcal/mole).
Free radical substitution
This leads to two highly reactive chlorine
free radicals (Initiation).

A free radical is an atom or group that

has a single unshared electron.
Covalent Bond Cleavage
Homolysis - the covalent bond is broken in
such a way that each resulting species
gets its own electron.

The factor which favours homolysis is

that the difference in electronegativity is
less than or equal to zero

Covalent Bond Cleavage

Heterolysis - the covalent bond is broken in such a way
that one species (i.e., less electronegative) is deprived
of its own electron, while the other species gains both
the electrons.

Thus formation of opposite charged species takes place.

In case of organic compounds, if positive charge is

present on the carbon then the cation is termed
ascarbocation.

If negative charge is present on the carbon then the

anion is termed ascarbanion.
Halogenation of Ethane
ALKENES
Alkenes
Hydrocarbons that contain one or more
C=C

Unsaturated fewer H atoms per C than

corresponding alkanes

Reactive

Undergoes addition reactions

Gen. formula: CnH2n

alkenes
A bond is not as strong as a bond and is
more easily broken

Alkene are more reactive than alkanes

Each C-H bond comprises the overlap of an

sp2 hybrid orbital with the 1s orbital of an H
atom.

Trigonal planar geometry

Nomenclature of alkenes
1. Select the longest continuous chain that contains the
C=C

2. Change the ending "-ane" of the corresponding

alkane name to "-ene".

3.Indicate the position of the double bond in the parent

chain numbering from the end of the chain nearest
the double bond.

4. Indicate the substituents attached to the parent

chain.
Naming Alkenes
Nomenclature of
Dienes/Triene
Find the longest chain that contains both double
bonds.

Use the corresponding alkane name but replace

the ne with diene.

Note that a will now be apart of the alkanes

name.

1,3-butadiene
1,3,6-heptatriene
Geometric (cis/trans)
isomerism
Chemical compounds have the same molecular
formula but different geometric configuration, as
in different spatial arrangement on either side of
a bond or ring.

When two similar groups are bonded to carbons

on the same side of the double bond -cis isomer.

If similar groups are on opposite sides of the

double bond -trans isomer

Rigidity and lack of rotation of the carbon-carbon

double bond gives rise to cis-trans isomers
Geometric isomerism
Geometric isomerism

Cis-2-pentene Trans-2-pentene
Geometric isomerism

Not all alkenes can show geometric

isomerism.

If any of the C=C bond has two identical

groups then the molecule cannot have cis-
trans isomerism.

Can 3,4-dimethyl-3-heptene exhibit

geometric isomerism?
Reactions of Alkenes
The following are general rxns of
akkenes:
Combustion
Halogenation
Hydrogenation
Hydrohalogenation
Hydration
Oxidative cleaveage
Hydroxylation
 Reactivity of C=C
42

Electrons in pi bond are loosely held.

Electrophiles are attracted to the pi electrons.

Carbocation intermediate forms.

Nucleophile adds to the carbocation.

Net result is addition to the double bond.

43
Electrophilic Addition

Step 1: Pi electrons attack the electrophile.

E
+
C C + E C C +

Step 2: Nucleophile attacks the carbocation.

E E Nuc
_
C C+ + Nuc: C C
Electrophilic addition of
hydrogen halide
 Addition of HX (1)
45

Protonation of double bond yields the most

stable carbocation. Positive charge goes
to the carbon that was not protonated.
CH3
CH3 C CH CH3
CH3 +
H
CH3 C CH CH3 _
+ Br
H Br X CH3
CH3 C CH CH3
+
H
 Addition of HX (2)
46

CH3 CH3
_
CH3 C CH CH3 CH3 C CH CH3 + Br
+
H
H Br

CH3 CH3
CH3 C CH CH3 CH3 C CH CH3
+
H Br H
_
Br
 Markovnikovs Rule:
47

The proton of an acid adds to the

carbon in the double bond that already
has the most Hs. Rich get richer.

In an electrophilic addition to an alkene,

the electrophile adds in such a way as
to form the most stable intermediate.

HCl, HBr, and HI add to alkenes to form

Markovnikov products.
Halogenation
 Oxidative Cleavage
49

Hot alkaline KMnO4.

Both the pi and sigma bonds break.

C=C becomes C=O.

 Cleavage with Hot KMnO4-
50

Permanganate is a strong oxidizing agent.

Disubstituted carbons become ketones.

Monosubstituted carbons become

carboxylic acids.

Terminal =CH2 becomes CO2.

 Example
51

H CH3
H CH3 KMnO4
C C H3C C C CH3
CH3 CH3 (warm, conc.)
OH OH
H CH3
H3C C + C CH3
O O

OH
H3C C
Chapter 8 O
ALKYNES
alkynes
Hydrocarbons that contain C-C triple bonds

Molecular formula CnH2n-2

An alkyne where theC-C triple bond comes

at the end is called a terminal alkyne

If the triple bond is located other than the

end it is called an internal alkyne
alkynes
Terminal alkynes are more acidic than
other hydrocarbons.

The acidity of the C-H bond varies with

its hybridization, increasing with
increasing s character

sp3<sp2<sp
Reactions of Alkynes
Hydrogenation

Also catalyzed by Ni or Pt

Catalytic hydrogenation of an alkyne using a

catalyst such as Pt or Ni yields an alkane

Reaction can be controlled so that only the

alkene is produced: use of Lindlars catalyst
Pd/CaCo3
To prevent hydrogenation of the alkene, a less active catalyst must be employed.
Lindlar catalyst, which is a mixture of Pd, CaCO3, is the catalyst of choice in
catalytic hydrogenation of alkynes to give alkenes.
Alkynes Nomenclature
Find the longest chain of carbon atoms
that include the triple bond.

Change ane of the parent alkane to yne

Number the chain from the end closest

to the double bond.

Indicate substituents and their location

 AROMATIC
HYDROCARBONS
Aromatic Hydrocarbons
Refers to hydrocarbons containing an
aromatic ring

Simplest is benzene, C6H6

Methylbenzene( toluene) Ethylbenzene

Substituted Aromatic
Compounds
H has been replaced by an atom or group of atoms

-Benzoic acid phenol

benzaldehyde
aminobenzene (aniline)
nitrobenzene
chlorobenzene
Substituted Aromatic
Compounds
May also be disubstituted

m-nitrobenzoic acid

m-bromophenol

Substituted group will affect the position of the

new group

Ortho-para directors: -OH, NH2, R

Meta directors: -NO2, -COOH

Mechanism
The most important mechanism involved
in reactions of aromatic compounds is
electrophilic aromatic substitution

Benzenes pi electrons are in a stable

aromatic system but are available to
attack a strong electrophile to give a
carbocation
 Reactions of Aromatic
Hydrocarbons
Undergo electrophilic aromatic substitution

1. Nitration(concHNO3/concH2SO4):
electrophile: NO2+

2. Halogenation(X2/FeX3): electrophile: X+
Side Chain Reactions
Halogenation (X2/heat or light energy or
X2/FeX3)

Oxidation(KMnO4) benzoic acid

Benzene
An alkene decolourizes KMnO4 to form a
glycol, and a ppt of MnO2 forms

No rxn occurs when KMnO4 is added to

benzene.

Most alkenes decolourize bromine but no

rxn occurs with benzene.
Benzene
If a catalyst such as ferric bromide is added the
mixture of bromine and benzene, the bromine colour
will slowly disappear. HBr gas is evolved but the
expected addition of bromine does not take place.

Instead the organic product results from the

substitution of a bromine atom for a hydrogen and
all 3 double bonds are retained.

Benzene reluctance to undergo typical alkene

reactions suggest that it must be unusually stable
Bromination of toluene(in the
presence of sunlight)
Bromination of
nitrobenzene
Chlorination of Toluene
(Sunlight)
Nitration of benzene