INTRODUCTION TO ORGANIC CHEMISTRY

 Living things are made of atoms covalently bonded to form molecules of

organic compounds.
 All these molecules are based on carbon compounds.
 The complexity of life requires a great variety of different compounds.
 The great variety of organic compounds is possible because every carbon atom
can bond with other carbon atoms to form chains and rings.
 These chains and rings are often found bonded to atoms of other elements,
such as hydrogen, oxygen and nitrogen.
 This explains the millions of organic compounds that exist.
 Note that not all carbon compounds are classified as organic compounds. The
oxides of carbon and compounds containing carbonate and hydrogencarbonate
ions are classed as inorganic compounds .
 Importance of Carbon in
Organic Chemistry
 In organic chemistry, carbon (C) is the most important
element.
 It has remarkable properties, which allow carbon a great
diversity of combinations and bonds with other molecules.
 Carbon has four valence electrons. This means that it can
make four covalent bonds with other molecules.
 Also, it has a moderate electronegativity and a rather small
(right) size. So, it can bond to other molecules easily and to
itself and make infinite structures.
 Double bonds or even triple bonds are also possible with
 Definition of an organic
molecule
 An organic molecule consists of many carbons and hydrogen atoms,
which form bonds with the carbons.
 In addition, it has functional groups attached to the whole complex.
 The carbon-hydrogen bonds are assumed to be neutral as the difference
in electronegativity is practically neutral anyway.
 Functional groups make up the polar part of an organic molecule.
 Compounds that only contain carbon and hydrogen are called
hydrocarbons.
 They are classified as aliphatic or aromatic.
 Aromatic compounds contain one or more arene rings. They have
distinctive, usually pleasant smells.
 All the other organic compounds are aliphatic. For example, all alkanes
and alkenes are aliphatic and benzene is an aromatic compound
Different types of hydrocarbon molecules

 Aromatic hydrocarbon: These are hydrocarbon rings, which

have double or triple bonds.
 Saturated hydrocarbon: The formula of the hydrogen-carbon
ratio is given by: CnH2n+2 , assuming a non-cyclic (ring) structure.
Saturated hydrocarbons only consist of single bonds and the
very easiest appearance of a saturated hydrocarbon is an
alkane.
 Unsaturated hydrocarbon: The ratio of hydrogen and carbon
is given by: CnH2n , where again a non-cyclic structure is
assumed. Unlike saturated hydrocarbons, it has double bonds
and the simplest appearance of an unsaturated hydrocarbon is
an alkene.
There is a second type of unsaturated hydrocarbons which has
the rational formula given by: CnH2n + 2.
 REPRESENTING ORGANIC MOLECULES

 We can represent organic molecules by a variety of

different types of formula.
 The empirical formula gives us the least detail.
 Ittells us the simplest ratio of the different types of
atoms present in the molecule.
 For example, an organic compound called butane, has
the empirical formula C2H5.
 This tells us that it has twice as many hydrogen atoms
as carbon atoms in its molecules.
 Themolecular formula shows us the actual numbers of
each type of atom in a molecule.
 Tofind this we need to know the relative molecular mass
of the compound. The relative molecular mass of butane
is 58.
 We know that its empirical formula is C2H5; this C2H5 group
of atoms has a relative mass of 29, as the relative atomic
mass of C = 12 and H = 1.
 Bydividing the relative molecular mass by the relative
mass of the empirical formula (58/29 = 2), we see that
there must be (2 . C2H5) atoms in a butane molecule.
 So its molecular formula is C H
 Chemists can give more detail about a molecule by
giving its structural formula.
 This tells us about the atoms bonded to each
carbon atom in the molecule.
 The structural formula of butane is CH3 CH2 CH2
CH3.
 This tells us how many hydrogen atoms are bonded
to each carbon atom.
 all the bonds within a molecule are shown in its
displayed formula.

 H
 The Skeletal /line formulae is a simplified representation of an
organic molecule that concentrates on the carbon ‘backbone’ of a
molecule, together with any functional groups.
 Bonds to hydrogen atoms are not normally shown, unless they form
part of a functional group.
 The skeletal formula for butane is
 FUNCTIONAL GROUPS
 There are many classes of organic compound, some
 Within a class of compounds all the compounds consist of
molecules with a particular atom, or grouping of atoms, called a
functional group.
 Different classes of compounds/homologous series have different
functional groups.
 The functional group determines the characteristic chemical
properties of the compounds that contain that specific functional
group.
 The functional group in an alkene is the C = C double bond. The
functional group in a carboxylic acid is the -COOH group.
 HOMOLOGOUS SERIES
 Homologous series: a series of compounds of
similar structures which:
• contain the same functional group
• all share same general formula.
• formula of homologue differs from
neighbour by CH2
• similar chemical properties
• gradual change in physical properties as
Mr increases
CLASS OF ORGANIC NAME OF FUNCTIONAL GROUP STRUCTURE
COMPOUNDS Single bond -C-C-
Alkanes

Alkenes double bond =C=C=

Alkynes triple bond -CΞC-

Halogens halogen - X ( F,Cl,Br,I )

Alcohols hydroxyl -OH

Aldehydes aldehydic(formyl) -CHO

Carboxylic acids carboxyl -COOH

Acid amides amides -CONH2

Primary amines amino - NH2
NAMING ORGANIC COMPOUNDS
 Chemists have a system of naming organic
compounds that can be applied consistently.
 This means that they can communicate with each
other clearly when referring to organic compounds.
 The class of hydrocarbons called alkanes provide
the basis of the naming system.
 The stem of each name indicates how many carbon
atoms are in the longest chain in one molecule of
the compound.
 The table below shows the names of the first ten
alkanes and the stems used in naming other
molecules.
NUMBER OF MOLECULAR N NAME OF STEM USED
CARBON FORMULAR ALKANE IN NAMING
ATOMS

1 CH4 methane meth-

2 C2H6 ethane eth-

3 C3H8 propane prop-
4 C4H10 butane but-
5 C5H12 pentane pent-
6 C6H14 hexane hex-
7 C7H16 heptane hept-
8 C8H18 octane oct-
 NOMENCLATURE
 Select longest chain as the main chain
  Other carbon chains as substituent alkyl groups
  Give lowest number C in main chain to substituent
  If different alkyl groups present on identical position,
give simpler alkyl smaller number
  Two or more alkyl groups present, order alphabetically
  If same substituent repeated use di, tri, tetra prefix
  If ring of carbon present, use prefix cyclo
  Write position of double bond in alkene e.g. but-1-ene
 ISOMERISM IN ORGANIC COMPOUNDS
 We have seen how a compound’s molecular formula tells us the
number and type of each atom in one molecule of the compound.
 However, for a given molecular formula there may be different
ways of arranging these atoms.
 This means different molecules can be formed, with different
structures, resulting in different compounds.
 Such compounds with the same molecular formula but different
structural formulae are called structural isomers.
 There are three types of structural isomerism:
1 position isomerism
2 functional group isomerism
3 chain isomerism.
 1. Position isomerism
 In position isomerism, it is the position of the functional group that
varies in each isomer.
 An example is provided by the compound with the molecular formula
C3H7Br.
(i) In one of them the bromine atom is on the end of the chain, whereas in
the other it's attached in the middle.

Another similar example occurs in alcohols such as C4H9OH

 2 Functional group isomerism
 In functional group isomerism there are different
functional groups present. For example, given the
molecular formula C3H6O we can draw both an
aldehyde and a ketone.
 3 Chain isomerism
 Chain isomers differ in the structure of their carbon‘ skeleton’.
 For example, there are two isomers of butane, C4H10.
 In one of them, the carbon atoms lie in a "straight chain"
whereas in the other the chain is branched.

 Butane 2-
methylpropane
 STEREOISOMERISM
 In stereoisomerism we have compounds whose molecules have
the same atoms bonded to each other but with different
arrangements of the atoms in space.
 There are two types of stereoisomerism:
 1 cis–trans isomerism
 2 optical isomerism.
 1 Cis–trans isomerism
 Unlike a C-C single bond, there is no free rotation about a C=C
double bond.
 This results in the possibility of a different type of isomerism in
unsaturated organic compounds.
 For example, but-2ene, CH3CH=CHCH3 has 2 cis-
trans isomers.
 ORGANIC REACTIONS – MECHANISMS
 Chemists find it useful to explain organic reactions by summarising
the overall reaction in a series of steps called a reaction mechanism.
 Like all chemical reactions,organic reactions involve the breaking and
making of chemical bonds.
 There are two ways in which covalent bonds can break: homolytic
fission and heterolytic fission.
1. Homolytic fission
 In this type of bond breaking, both the atoms at each end of the bond
leave with one electron from the pair that formed the covalent bond.
 The species produced when a bond breaks homolytically are called
free radicals.
 We can show the formation of free radicals by using an equation:

H Cl H• +Cl•
 H• and Cl• are free radicals. All free radicals have an unpaired
electron (represented by the dot) and are very reactive.
2. Heterolytic fission
 The second type of bond breaking involves the ‘uneven’breaking of
a covalent bond.
 In heterolytic fission the more electronegative atom takes both the
electrons in the covalent bond.
 Again we can use hydrogen chloride to illustrate this
H Cl H+ +Cl-
 The heterolytic fission of a bond can involve a C-X bond,where X is
an atom more electronegative than carbon.
 For example HC3 Cl HC3+ +Cl-
 In this case, as the bond breaks, the Cl atom takes
both the shared electrons, forming a chloride anion
(a negatively charged ion).
 This leaves the methyl group one electron short,
resulting in the formation of a positively charged
ion. This type of alkyl ion is called a carbocation.
 Thus heterolytic fission results in formation of +ve
and –ve ions
 If +ve charge on C, its called carbocation or
carbonium
 If –ve charge on C, its called carbanion
 TYPES OF ORGANIC REAGENTS
 Two types of reagents: nucleophilic and electrophilic.
 Nucleophilic reagent (nucleophile): donator of pair of electrons
 Must have lone pair of e-s
 Attack centre of +ve charge (positive pole)
 Reaction with nucleophile called nucleophilic reactions
 Examples: CH-, Cl-, NH3, H2O, CN-
 Electrophilic reagent (electrophile): acceptor of pair of
electrons
 +ve ions or e- deficient molecules
 Attack regions of high e- density
 Examples: Br+, CH3+, AlCl3
 TYPES OF ORGANIC REACTION
 Addition reactions, which involve 2 molecules combining to make only
one new molecule. For example, if ethene and steam is passed over a hot
phosphoric acid catalyst, ethanol is produced
CH2= CH2(g) + H2O (g) CH3CH2OH (g)
 Elimination reactions result in the removal of a small molecule from a
larger one. An example is the dehydration of an alcohol by concentrated
sulfuric acid
CH3CH2OH (g) CH2=CH2(g) + H2O (g)
 Substitution reactions involve the replacement of one atom, or a group
of atoms, by another.

CH3CH2Br (l) + OH- (aq) CH3CH2OH (aq) + Br- (aq)

 Hydrolysis is the breakdown of a molecule by water.
 This type of reaction is often speeded up by acid or alkali.
 For example, the hydrolysis of a halogenoalkane by water to give an
alcohol.
 CH3CH2Br (l) + H2O (l) CH3CH2OH (aq) + HBr (aq)
 Oxidation is defined as the loss of electrons from a species.
 However, in organic reactions it is often simpler to think of oxidation
reactions in terms of the number of oxygen and/or hydrogen atoms before
and after a reaction.
 Oxidation is the addition of oxygen atoms to a molecule and/or the removal
of hydrogen atoms from a molecule.
 An example is the partial oxidation of ethanol to ethanol using acidified
potassium
 C2H5OHdichromate(VI)
+[O] CH3solution
CHO +H2O

 before the reaction ethanol contains one O atom and six H atoms
 Reduction
 This is the opposite of oxidation and, in general, applies to
compounds containing a C=O group.
 Reduction may be brought about by several reducing agents
including tin and dilute hydrochloric acid, sodium in ethanol and
lithium aluminium hydride.
 In organic reduction reactions, the reducing agent is usually
represented by [H], as shown in the example below:
 CH3CO2H + 4[H] → CH3CH2OH + H2O
 A condensation reaction is a reaction in which two large
molecules combine and form one larger molecule and a very small
molecule, usually water is eliminated.
CH3COOH(aq) +CH3CH2OH(aq) CH3COOCH2CH3(aq) +H2O(l)
 Acid-base reactions involves the reaction of an acid with a base to
give a salt.
 CH3COOH (aq) + NaOH (aq) CH3COONa (aq) + H2O (l)
 An esterification reaction is a special type of condensation
reaction in which a carboxylic acid reacts with an alcohol to form an
ester and water
 THE HYDROCARBONS
 Crude oil is our main source of hydrocarbons.
 Hydrocarbons are compounds containing carbon and hydrogen
only.
 They provide us with fuels such as petrol, diesel and kerosene.
 Hydrocarbons are also the starting compounds we use to make
many new compounds, such as most of the plastics we meet in
everyday life.
THE HOMOLOGOUS GROUP OF ALKANES
 The homologous series of the alkanes have the following properties:
 They have a general formula of CnH2n+2
 They are non-polar molecules with only C-H and C-C bonds so can
not be attacked by nucleophiles or electrophiles.
 All the C-C bonds are single bonds so the alkanes are described as
saturated hydrocarbons.
 The alkanes are generally unreactive compounds. This can be
explained by the very small difference in electronegativity between
carbon and hydrogen.
 They have no partial positive charges on any of their carbon atoms
to attract nucleophiles, neither do they have areas of high electron
density to attract electrophiles
 However, the alkanes do react with oxygen in combustion reactions
and also undergo substitution by halogens in sunlight.
 COMBUSTION OF ALKANES
 Alkanes are often used as fuels. We burn them for many
reasons:
■■ to generate electricity in power stations
■■ to heat our homes and cook our food
■■ to provide energy needed in industrial processes
■■ to provide power for ships, aeroplanes, trains, lorries,
buses, cars and motorbikes.
 Ifan alkane is burnt in plenty of oxygen, it will undergo
complete combustion.
 The carbon will be oxidised fully to form carbon dioxide and
the hydrogen will be oxidised to form water:
 alkane + oxygen carbon dioxide + water
SUBSTITUTION REACTIONS OF ALKANES
 Alkanes react with halogens: 𝐶𝑙2 and 𝐵𝑟2 in sunlight. For example:
 CH4 + Cl2 CH3Cl + HCl
 In this reaction a hydrogen atom in the methane molecule gets replaced by a
chlorine atom.
 However, the reaction does not take place in darkness.
 So what role does the sunlight play in the mechanism of the substitution reaction?
 Initiation step
 The first step in the mechanism is the breaking of the Cl Cl bond by ultraviolet
light from the Sun. This is an example of homolytic fission of a covalent bond .
 This is called the initiation step in the mechanism:
Cl2 2Cl•
As the Cl - Cl bond breaks, each chlorine atom takes one electron from the pair of
electrons in the Cl Cl bond.
 Two Cl atoms are formed. These Cl atoms, each with an unpaired electron, are
called free radicals.
 Highly reactive 𝐶𝑙 ∙ collides with a 𝐶𝐻4 molecule forming a
 Propagation:

new free radical; 𝐶𝐻3 ∙



 𝐶𝐻4 + 𝐶𝑙⋅→ 𝐶𝐻3⋅ +𝐻𝐶𝑙

 𝐶𝐻3⋅ +𝐶𝑙2 → 𝐶𝐻3𝐶𝑙 + 𝐶𝑙⋅
 This can then react with another 𝐶𝑙2 and process
 repeats if sufficient 𝐶𝑙2 present until all 𝐻 are replaced
 Termination steps
 Whenever two free radicals meet they will react
with each other. A single molecule is the only
product.
 As no free radicals are made that can carry on the
reaction sequence, the chain reaction stops.
Examples of termination steps include:
 𝐶𝐻3 ⋅ +𝐶𝑙 ⋅→ 𝐶𝐻3𝐶𝑙
 𝐶𝐻3 ⋅ +𝐶𝐻3 ⋅→ 𝐶2𝐻6