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ORGANIC REACTIONS: AN INTRODUCTION

Introduction

The wide variety of functions and their combination in different skeletal frameworks
implies an even wider variety of possible reactions. In fact, most times, different
reactions occur simultaneously and it is just the skill in controlling the experimental
conditions, what will finally lead to the required products and the yield of the process.

Organic reactions constitute a vast jungle of chemical changes, but nevertheless they
can be classified using some simple criteria; this allows a high school approach to this
fascinating field of chemistry.

Attacking Species and Substrates

The reactants in a chemical reaction can be further classified. In organic chemistry the
substrate is the organic substance that will suffer the change and the attacking
species the inorganic agent that is acting on it. In many chemical reactions both
reactants are organic; in these cases the substrate is the reactant on which we focus
our attention. For instance, when an alcohol and an acid react to form an ester, any of
the two can be considered the substrate depending whether we are studying the
reactions of acids or the reactions of alcohols.

THE CLASSIFICATION OF ORGANIC REACTIONS

Organic reactions are classified based in both the nature of the attacking species and the
changes that the substrate undergoes. As organic reactions are very frequently multi-
stage processes, they are also classified according to how many species (molecules,
ions, etc.) are involved in the rate determining step. A reaction can be thus classified
(for instance) as a monomolecular nucleophilic substitution (SN1 type of reaction) or an
bimolecular electrophilic addition (AN2 type of reaction).

Organic Reactions According to the Attacking Species

 Free Radicals and Homolytic Reactions

According to the nature of the attacking species, organic reactions are said to be
homolysis (or free radical) or heterolytic (either nucleophilic or electrophilic).The
attacking species can be classified (and accordingly the reactions in which they
intervene) as free radicals, nucleophiles and electrophiles. Free radicals are formed if
a bond splits evenly - each atom getting one of the two electrons. The name given to
this is homolytic fission. Homolytic reactions are frequently triggered by light or
peroxides (substances showing -O-O- bonds that easily break homolytically)
To show that a species (either an atom or a group of atoms) is a free radical, the symbol
is written with a dot attached to show the unpaired electron. For example:

a chlorine radical Cl
a methyl radical CH3
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Free radical attack gives way to what is known as a free radical or better a homolytic
reaction.

 Electrophiles and Electrophilic Reactions

An electrophile is something which is attracted to electron-rich regions in other

molecules or ions. Because it is attracted to a negative region, an electrophile must be
something which carries either a full positive charge, or has a slight positive charge
on it somewhere. The electrophile is normally the slightly positive ( +) end of a
molecule like hydrogen bromide, HBr.

Other frequently found nucleophiles are very unstable species formed in the reacting
mixtures. Some examples are shown here.

The NO2+ cation is called the nitronium ion and is the attacking species in the
preparation of nitrocompounds (T.N.T. for example). The CH3+ and the CH3CO+ cations are
examples of carbocations. These reactive species are not isolated but have been proved
to be the active intermediates in many reactions. Metallic cations are not electrophiles
because they do not “want” to take any electros. They have already lost them to become
stabilised

Reactions in which the key stage involves an electrophile are called electrophilic
reactions.

 Nucleophiles and Nucleophilic Reactions

A nucleophile is a species (an ion or a molecule) which is strongly attracted to a region

of positive charge in something else.
Nucleophiles are either fully negative ions, or else have a strongly - charge
somewhere on a molecule. Common nucleophiles are hydroxide ions, cyanide ions,
water and ammonia.

Notice that each of these contains at least one lone pair of electrons, either on an atom
carrying a full negative charge, or on a very electronegative atom carrying a substantial
- charge. The negative methyl group is the simplest example of a carbanion.
Of course reaction involving nucleophiles are named nucleophilic reactions.

Organic Reactions According to the Substrate’s Changes

 Substitution reactions

These are reactions in which one atom in a molecule is replaced by another atom or
group of atoms. In these reactions a σ bond is broken and a new σ bond is formed.
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Simple examples of substitution are the reaction between methane and chlorine in the
presence of UV light (or sunlight) and the reaction of a haloalkane with hot water.

Notice that in the first example one of the hydrogen atoms in the methane has been
replaced by a chlorine atom and in the second one, bromine has been replaced by a
hydroxyl group. That's substitution.

 Addition Reactions

In addition reactions a π bond is broken to form two σ bonds, generally one for each
of the two atoms involved in the original π bond.
For example, adding hydrogen bromide (HBr) to a double bond in an alkene to form a
haloalkane and the addition of hydrogen cyanide (HCN) to an aldehyde to give a 2-
hydroxi-nitrile

An addition reaction is a reaction in which two molecules join together to make a bigger
one. Nothing is lost in the process. All the atoms in the original molecules are found in
the bigger one.

 Elimination Reactions

Elimination reactions are formally the reverse of addition reactions: two σ bonds
disappear and one π bond is formed instead. Simultaneously a (generally) small
molecule is formed.
The dehydration of ethanol by the action of hot concentrated sulphuric acid is a typical
example.

The acid is not written into the equation because it serves as a catalyst. You could
eventually write, for example, "conc. H2SO4" over the top of the arrow.

 Condensations and Addition / Elimination Reactions

These two types of reaction are closely related: in fact some times the names are
interchanged. In both cases an addition occurs to molecule bearing a C=O grouping and
this addition is followed by the elimination of a (generally) small molecule. The
difference stands in the way the elimination occurs.
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When the C=O belongs to either a ketone or an aldehyde, the double bond will be
changed generally into a C=C or C=N bond. A double bond (σ/π pair) is changed into
a new double bond (σ/π pair) and a water molecule is formed. These reactions are
condensation reactions. The reaction of any ketone with hydroxylamine to form an
oxime is an example:

The C=O bond has been replaced by a C=N- bond.

In case the C=O is part of an ester amide or the so called “acid derivatives” a different
route is followed: the original double bond is regenerated and the “other” part of the
function is substituted: the result is just a substitution (σ / σ) at an unsaturated carbon
(carbon bearing a double bond). These are preferably named addition
/eliminations. The acid catalysed formation and hydrolysis of an ester such as ethyl
ethanoate belong to this class. These are in fact reversible reactions.

The –OH group (hydroxy) of the acid has been replaced by an –OCH 2CH3 (ethoxy)
group.

 Rearrangement Reactions

In rearrangement reactions a C-C bond (mostly) in the chain is broken and part of the
chain shifts to a new position . The isomerisation of alkanes is good example. It is used
particularly to change straight chains containing 5 or 6 carbon atoms into their branched
isomers. For example:

In order to raise the octane rating of the molecules found in petrol (gasoline) and so
make the petrol burn better in modern engines, the oil industry rearranges straight chain
molecules into their isomers with branched chains.

Hydrocarbons used in petrol (gasoline) are given an octane rating which relates to how
effectively they perform in the engine. A hydrocarbon with a high octane rating burns
more smoothly than one with a low octane rating.
Molecules with "straight chains" have a tendency to pre-ignition. When the petrol / air
mixture is compressed they tend to explode, and then explode a second time when the
spark is passed through them. This double explosion produces knocking in the engine.
Octane ratings are based on a scale on which heptane is given a rating of 0, and 2,2,4-
trimethylpentane a rating of 100.

 Organic Acid / Base reactions

Organic acids behave just like any other acid. Carboxylic acids are generally from
weak to very weak although there are some pretty strong acids as trichloro-ethanoic
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acid and methanoic acid. But there are other acids as the sulphonic acids that are as
strong as their inorganic partners. Sulphonic acids belong to this class. They can be
considered as derivatives of sulphuric acid in which one of the –OH groups has been
replaced by an organic chain

Amines are the bases in organic chemistry. They can be considered as derivatives of
ammonia in which one, two or all three hydrogen atoms have been replaced by organic
chains. Consequently amines are weak bases although generally slightly stronger than
ammonia. The lone pair on the N atom can coordinate to several groups (a Lewis base)
most frequently accepting a positive hydrogen ion (a Bronsted base).

CH3CH2CH2NH2 (CH3)2NH (CH3)3N

Propylamine or Dimethylamine Trimethylamine
1-aminopropane

 Organic Red-Ox Reactions

All organic compounds can be burnt to form water and carbon dioxide.
Boiling potassium permanganate (manganate(VII)) in acidic or alkaline solution or
chromic acid (Chromium (VI) oxide dissolved in sulphuric acid) will completely
destroy almost any organic compound turning it into CO2 and H2O too. Obviously in
these cases organic compounds behave all as reducing agents.
There are many reactions in which hydrogen linked to a carbon atom is replaced by a
more electronegative atom (the chlorination of methane for instance) that can be
considered from the red-ox point of view.
But when organic chemists talk about “oxidation” and “reduction” they generally refer
to the old good “gain / loss of oxygen” concept.
A carbon atom in an alkane gets oxidised when it is part of the C-OH group (alcohols).
Alcohols can be oxidised to aldehydes and ketones (the C atom is bonded twice to
oxygen). Further oxidation of aldehydes leads to carboxylic acids. Ketones are broken
into two different chains (cleavage of the molecule). Alkenes are readily oxidised and
broken down too. There is a vast range of redox reactions in organic chemistry that can
include additions, substitutions, eliminations etc. We will not discuss them in this
course.

Organic Reactions According to the Molecularity of their Rate Determining Step

As mentioned before, organic reactions are complex multistage processes. The rate
determining step in these reactions may be:
 Monomolecular that is, involve just one of the reaction species (e.g. the
spontaneous unassisted cleavage of the C-Cl bond in some hydrolyses of
haloalkanes).
 Bimolecular: two reacting species are involved in the rate determining step
(e.g. the addition of bromine to an alkene).
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The essentials of this classification can be found summarised in the chart at the
end of the chapter

SOME SPECIFIC EXAMPLES OF ORGANIC REACTIONS

Homolytic Substitution

The reaction we are going to explore is the first example of the previous paragraph
between methane and chlorine in the presence of ultraviolet light - typically sunlight.
This is a good example of a photochemical reaction (a reaction brought about by
light).
CH4 + Cl2 CH3Cl + HCl
The organic product is chloromethane.
This is a substitution reaction (sigma bond replaced by sigma bond) and a homolytic or
free radical reaction (started by chlorine atoms with an unpaired electron)

The mechanism involves a chain reaction. During a chain reaction, for every reactive
species you start off with, a new one is generated (it means that a reactant is
regenerated in the process) and this keeps the process going.
A chain reaction involves three sets of processes or reactions:
 Initiation
The chain is initiated (started) by UV light breaking a chlorine molecule into
free radicals.
Cl2 2Cl
 Propagation
These are the reactions which keep the chain going.
CH4 + Cl CH3 + HCl
CH3 + Cl2 CH3Cl + Cl
 Termination
These are reactions which remove free radicals from the system without
replacing them by new ones.
2Cl Cl2
CH3 + Cl CH3Cl
CH3 + CH3 CH3CH3
It’s worth mentioning that free radical reactions are not necessarily chain reactions
although many of them do.
It is also important to highlight that a chain reaction is not necessarily an explosive
event!. Nuclear chain reactions can lead to devastating explosions because they are
triggered by a neutron and in one of the propagation steps three neutrons are formed!
That means that for just one neutron to begin with, after three cycles (some
milliseconds) you will have 27 neutrons all reacting at the same time! This fact puts the
reaction out of any control and the energy is released “all of a sudden”.

Electrophilic addition

An electrophilic addition reaction is an addition reaction which happens because what

we think of as the "important" molecule (the substrate) is attacked by an electrophile.
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The substrate has a region of high electron density which is attacked by something
carrying some degree of positive charge. What follows is a detailed analysis of an
electrophilic addition.

It is very unlikely that any two different atoms joined together will have the same
electronegativity. We are going to assume that Y is more electronegative than X, so that
the pair of electrons is pulled slightly towards the Y end of the bond. That means that
the X atom carries a slight positive charge.

The slightly positive X atom is an electrophile and is attracted to the

exposed pi bond in the ethene. Now imagine what happens as they
approach each other.

You are now much more likely to find the electrons in the half of the pi bond nearest the
XY. As the process continues, the two electrons in the pi bond move even further
towards the X until a covalent bond is made.

The electrons in the X-Y bond are pushed entirely onto the Y to give a negative Y- ion.

In the final stage of the reaction the electrons in the lone pair on the
Y- ion are strongly attracted towards the positive carbon atom. They
move towards it and form a co-ordinate (dative covalent) bond
between the Y and the carbon.

The movements of the various electron pairs are usually shown using
curly arrows.
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In the examples to follow we will use this kind of electron shifting diagrams

Nucleophilic Substitution: Bimolecular and Monomolecular Reaction Paths

If a haloalkane is heated with a solution of sodium or potassium hydroxide, the halogen

is replaced by -OH and an alcohol is produced.

For example, using bromoethane as a typical primary haloalkane (the Br is attached to

the end of the chain forming -CH2-Br) :

The bromine in the haloalkane is simply replaced by an -OH group hence it is a

substitution reaction.
On the other hand OH- is a nucleophile and the C-Br bond is polarised with the negative
end on the Br side rendering the C atom slightly positive. That’s why the reaction is a
nucleophilic reaction.

This is an example of a bimolecular nucleophilic substitution.

Because the mechanism involves collision between two species in the slow step (in this
case, the only step) of the reaction, it is known as an SN2 reaction. We can figure that
the OH- anion attacks the substrate from the rear end. During the collision the intrusion
of the OH- will strain the molecule to a very unstable situation: 10 electrons around the
C atoms, the OH- bond about being formed and simultaneously the Br atom being
expulsed with together with the bonding electron pair. This is the transition state, a very
unfavourable situation for the system! Finally if the collision is successful, the Br - will
be finally expelled and the OH- will be attached to C atom to form an alcohol. Notice
that the bonds in the molecule have inverted the configuration turning inside out as an
umbrella on a windy day.
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The facts of the reaction are exactly the same as with primary haloalkanes. If the
haloalkane is heated under reflux with a solution of sodium or potassium hydroxide in a
mixture of ethanol and water, the halogen is replaced by -OH, and an alcohol is
produced.

For example:

Or if you want the full equation rather than the ionic one:

This mechanism involves an initial ionisation of the haloalkane:

followed by a very rapid attack by the hydroxide ion on the carbocation (carbonium ion)
formed:

This is an example of a monomolecular nucleophilic substitution. The difficult step

(the ionisation of the covalent haloalkane) only involves one species and is not affected
by the presence of the nucleophile. This one will stick to the reactive carbocation as
soon as it is available. It is known as an SN1 reaction. Notice that in this case the C
atom will be attacked by any of the two sides. The carbocation is planar because of the
central atom having just three groups attached to it.

QUESTIONS AND PROBLEMS

1- Classify the following species as free radicals, nucleophiles or electrophiles.

State which are formed by homolysis and which by heterolysis.
H+ H2O NH3 Cl· OH- Cl+ Na+ CH3CH2+

2- Wurtz’s reaction was formerly used to prepare hydrocarbons. It consists in the

reaction of a haloalkane with metallic sodium as shown below. “R” stands for
any possible C chain. Classify this reaction according to what is shown in
equation (b).
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3- The following sequence shows the polymerisation of styrene to form the very
well known (poly) styrene polymer.
a- Classify it according to the different criteria
b- Compare it with Wurtz’s reaction.
c- Is it a chain reaction? Explain.

4- The equations corresponding to the different steps in the bromination of toluene

(a free radical chain reaction) are shown below but jumbled. Write them in the
proper sequence and tell which belong to the different stages of a chain reaction.

Overall reaction (just for you to see

reactants and products)

Jumbled equations (to sequence properly)

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5- The following diagrams show an energy-reaction course profile for an SN1 and
an SN2 reaction: which corresponds to which? Explain your choice

6- Inspect the following organic reactions (and classify them (neglect molecularity)

a-

b-
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c-

d-

e-

f-

g-

ORGANIC
REACTIONS

Are classified according to

The substrate’s (main The attacking species
organic molecule) point point of view
of view
HOMOLYSIS: reactant splits forming two
species with one non-paired electron each
ADDITION:
A : B → A∙ + B∙
A π bond is changed into two σ A∙ and B∙ are called FREE RADICALS
bonds

HETEROLYSIS: reactant splits

ELIMINATION: asymmetrically forming an anion A:-
Two σ bonds are changed to one π (NUCLEOPHILE)) and a cation B+
bond (ELECTROPHILE
A:B → A:- + B+ (Nitrogen with a lone pair of
electrons is also a nucleophile

SUBSTITUTION:
σ REARRANGEMENT:
One σ bond is broken and another
A C-C bond in the chain is broken
σ bond is formed and part of a chain shifts to a new
position

CONDENSATION:
A double bond (σ/π pair) is
changed into a new double bond
(σ/π pair) and a water molecule is
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ADDITION / ELIMINATION:
A two step substitution on a double
bond. Reactant adds and then the
double bond is regenerated

ACID / BASE: REDOX:

As studied for inorganic chemistry. As studied in inorganic chemistry.
Amines are the bases in Org. Alkane►Alcohol►Aldehyde►Acid
Chem. but other bases can also Double bonds can be split
react. Acids are either carboxylic

How many species are involved during the rate determining

(most difficult) step

MONOMOLECULAR
BIMOLECULAR