ORGANIC

CHEMISTRY

Nomenclature
Number of carbon atoms in the parent chain Root word

1 Meth

2 Eth

3 Prop

4 But

5 Pent

6 Hex

7 Hept

8 Oct

9 Non

10 Dec
Number of carbon atoms in the parent chain Root word

11 Undec

12 Dodec

13 Tridec

14 Tetradec

15 Pentadec

16 Hexadec

17 Heptadec

18 Octadec

19 Nonadec

20 Icos
Under this IUPAC nomenclature of organic chemistry, there is a set of rules that every
chemist must follow to name compounds belonging to particular groups.
There are various ways to modify the root name of a compound according to its
functional group. These are –
● Substitutive: Functional groups of the highest priority modify the suffix. On the other
hand, other groups or substituents adds prefixes to root names.
● Functional Groups: Here, substances are named according to their highest priority
conditional groups. For instance, ketone, alkyl halide, alcohol, etc.
● Replacement: This process indicates when a carbon atom is getting replaced by
another atom.
● Conjunctive: It is used for combining named subunits.
● Trivial: Due to their widespread use, some compounds are registered under IUPAC
nomenclature according to their trivial names.
Functional Group
Priority order
 I U PA C R u l e s f o r A l k a n e N o m e n c l a t u r e

8. If both ends
of the root chain
have
equidistant
substituents:
6. The prefixes (i) begin
5. Assemble the di, tri, tetra etc., 7. If there are numbering at
3. Number the 4. Designate
name, listing used to two or more
1. Find and chain the location of the end nearest
2. Identify and groups in designate longest chains of
name the consecutively, each substituent
name groups alphabetical several groups of equal length, the a third
longest starting at the group by an
attached to this order using the the same kind, one having the
continuous end nearest a appropriate are not
substituent, if
chain. full name (e.g. largest number
carbon chain. substituent number and cyclopropyl considered of substituents is one is present
group. name.
before isobutyl). when chosen. (ii) begin
alphabetizing.
numbering at
the end nearest
the first cited
group
(alphabetical
order).
 What are stereoisomers?
In stereoisomerism, the atoms making up the isomers are joined up in the same order, but still manage to have a
different spatial arrangement. Geometric isomerism is one form of stereoisomerism.

Geometric (cis / trans) isomerism

How geometric isomers arise
These isomers occur where you have restricted
rotation somewhere in a molecule. Think about what
happens in molecules where there
is unrestricted rotation about carbon bonds - in other
words where the carbon-carbon bonds are all single.
The next diagram shows two possible configurations
of 1,2-dichloroethane. These two models represent
exactly the same molecule. You can get from one to
the other just by twisting around the carbon-carbon
single bond. These molecules are not isomers.
If you draw a structural formula instead of using
models, you have to bear in mind the possibility of this
free rotation about single bonds. You must accept that
these two structures represent the same molecule:
 Lets take now the case of 1,2-dichloroethene.
These two molecules in the figure aren't the same.
The carbon-carbon double bond won't rotate and
so you would have to take the models to pieces in
order to convert one structure into the other one.
That is a simple test for isomers. If you have to
take a model to pieces to convert it into another
one, then you've got isomers. If you merely have
to twist it a bit, then you haven't got the isomer.

In the model, the reason that you can't rotate

a carbon-carbon double bond is that there
are two links joining the carbons together.
In reality, the reason is that you would have
to break the pi bond. Pi bonds are formed by
the sideways overlap between p orbitals. If
you tried to rotate the carbon-carbon bond,
the p orbitals won't line up any more and so
In one, the two chlorine atoms are locked on opposite sides of the double
the pi bond is disrupted. This costs energy
bond. This is known as the trans isomer. (trans : from latin meaning "across"
and only happens if the compound is heated - as in transatlantic).
strongly. In the other, the two chlorine atoms are locked on the same side of the
double bond. This is know as the cis isomer. (cis : from latin meaning "on
Geometric isomerism in cyclic compounds
Geometric isomers can only occur where there is restricted rotation about a bond.
If you have a ring of carbon atoms there will also be no possibility of rotation about any of the carbon-carbon bonds.

1, 2 dibromo Cyclohexane

The shape around each carbon atom is tetrahedral, and there are two
different ways the bromine atoms can arrange themselves. They can
both lie above the ring, or one can be above the ring and the other
below.
If you swapped the hydrogen and bromine atoms around on one of the
carbon atoms, then both bromines would be on the same side - a cis
form.
 How to recognise the possibility of geometric isomerism

• You need to have restricted rotation somewhere in the molecule. Compounds containing a carbon-
carbon double bond have this restricted rotation.
• Ring compounds also have a possibility of geometrical isomers.​
• You won't have geometric isomers if there are two groups the same on one end of the bond - in this
case, the two pink groups on the left-hand end.

• there must be two different groups on the left-hand carbon and two different groups on the right-hand
one. The cases we've been exploring earlier are like this:
 Optical isomerism
Characteristics:
• Optical isomers are named like this because of their effect on plane polarised light.
• Simple substances which show optical isomerism exist as two isomers known as enantiomers.
• A solution of one enantiomer rotates the plane of polarisation in a clockwise direction. This enantiomer is known as
the (+) form.
• A solution of the other enantiomer rotates the plane of polarisation in an anti-clockwise direction. This enantiomer is
known as the (-) form
• If the solutions are equally concentrated the amount of rotation caused by the two isomers is exactly the same - but
in opposite directions.
• When optically active substances are made in the lab, they often occur as a 50/50 mixture of the two enantiomers.
This is known as a racemic mixture or racemate. It has no effect on plane polarised light.
Optical isomerism

The examples of organic optical isomers contain a carbon atom joined to

four different groups.​

Let's try them to align by rotating one of the molecules? The diagram
on side shows what happens if you rotate molecule B.

They still aren't the same - and there is no way that you can rotate them so
that they look exactly the same. These are isomers of each other.
They are described as being non-superimposable
Organic Reactions
 Alkanes - Free Radical Substitution
Covalent bonds can break in two ways: The breaking of a bond is called fission.

Heterolytic fission - bond breaks unevenly and Homolytic fission - bond breaks evenly and each
both electrons from the bond go to one atom. bonded atom gets one electron, forming free-
radicals.

• Free radicals are species that have an unpaired electron and they are highly reactive.
• Halogens can react with alkanes in free-radical substitution reactions, the mechanism occurs as a ‘chain’ reaction with three
stages:
• Initiation - U.V. light is needed to start the reaction and cause homolytic fission of the halogen molecule, creating two halogen
radicals.
• Propagation – radical species react with the alkane and get substituted into the molecule, creating further radicals.
• Termination – two radical species combine to create a covalent bond and terminate the chain as the product is not a free
radical.
Alkanes - Free Radical Substitution with Halogens
 Alkenes - Electrophilic Addition Reactions
• Alkenes react by electrophilic addition reactions.
• Electron deficient species (electrophiles) -- Electron deficient species are called electrophiles; they are attracted to the
electrons within the carbon-carbon double bond and can accept a pair of electrons---- are attracted to the pi-bonded
electrons in a carbon-carbon double bond.
• In electrophilic addition, an electrophile causes the carbon-carbon double bond to break, and a new bond is formed between
the electrophile and one of the carbon atoms.
• A carbocation (positively charged carbon atom) intermediate is formed that a negatively charged species forms a bond with.
• Primary carbocations are less stable than secondary and tertiary carbocations because they experience less of an inductive
effect, meaning they aren’t as likely to form during electrophilic addition.
•Major and minor products of electrophilic addition reactions are determined by the stability of the intermediate carbocation
that forms.
 Oxidation of Alcohols
•In organic chemistry, oxidation is a carbon atom gaining a bond to an oxygen atom and/or losing a bond to a hydrogen atom.

•To oxidise an alcohol, an oxidising agent (usually acidified potassium dichromate) is used and the alcohol is heated.

• Primary alcohols can be oxidised to an aldehyde, then to a carboxylic acid.

• To isolate the aldehyde, the products must be distilled from the reaction mixture.
• If a carboxylic acid is desired, the mixture must be heated under reflux conditions.

•Secondary alcohols can only be oxidised to form ketones.

• Fehling’s solution and Tollens’ reagent are used to distinguish between aldehydes and ketones.
• Aldehydes react to form a brick red precipitate with Fehling’s solution and a silver solid (silver mirror) with Tollens’ reagent.
Ketones do not react with either.

•Teritary alcohols cannot be oxidised.

 Elimination Reactions
Important Methods of Elimination Reaction
Normally, elimination reactions are distinguished by the kind of atoms or groups of atoms that leave the
molecule. Due to this, there are two main methods involved in this type of reaction;

Dehydration

Dehydrohalogenation
 Nucleophilic Substitution Reactions
• A nucleophile, a species with an unshared electron pair (lone-pair electrons), reacts with an alkyl halide (substrate) by
replacing the halogen substituent (leaving group).
• In nucleophilic substitution reactions, the C–X bond of the substrate undergoes heterolysis, and the lone-pair electrons of
the nucleophile is used to form a new bond to the carbon atom.
 Nucleophilic Substitution Reactions
In nucleophilic substitution reactions, the reactivity or strength of nucleophile is called its nucleophilicity.
So, in a nucleophilic substitution reaction, a stronger nucleophile replaces a weaker nucleophile from its
compound.
A nucleophile addition is an addition reaction in which a nucleophile adds to a pi bond of a compound. As a result, two new
sigma bonds are formed. This reaction is essential in organic chemistry because it enables carbonyl compounds to form new
products having various functional groups.
Carbonyl compounds undergo nucleophilic addition reactions because of the C=O bond’s polarity. The polar bond allows partial
charges on the carbon and oxygen atoms, making it easy for the nucleophile to attack at the 1,2-positions.
Nucleophilic addition reaction will be most favored in aldehydes and ketones. It differs from nucleophilic substitution reactions
since neither aldehydes nor ketones have a leaving group.
Hydrolysis, also known as hydrolysis reaction, is a type of Dehydration synthesis, also known as a
decomposition reaction in which a molecule is broken dehydration reaction, is a chemical reaction that
down into components by adding water. The entire involves forming a new compound accompanied
molecule changes its structure as new bonds are formed. by removing water from the product. Some
It is the reverse of dehydration synthesis or condensation commonly used dehydrating agents are
reaction, where molecules combine to form larger concentrated phosphoric acid, concentrated
molecules. sulfuric acid, and alumina. When the synthesis
occurs in the presence of heat, it is known as
thermal dehydration