What Is Organic Chemistry?

Organic chemistry is the branch of Chemistry that involves the scientific study

of organic compounds (compounds that contain covalently bonded carbon

atoms). This branch of chemistry primarily deals with the structure and

chemical composition of organic compounds, the physical and chemical

properties of organic compounds, and the chemical reactions undergone by

these compounds. Advancements in the field of organic chemistry have made

numerous contributions to human society, such as the synthesis of several

drugs, polymers, and other natural products. Synthetic organic chemistry is an

important application of organic chemistry that deals with the design and

construction of organic compounds for practical purposes.

The term ‘organic’ was coined because the field of organic chemistry was

initially finite to compounds that were produced by living organisms. This was

attributed to some ‘vital force’ that was present in organic substances as they

had something that inanimate substances lacked. The above theory was

debunked when Urey Miller synthesised urea from inorganic substances, but

the classification is still in use.

Organic chemistry is a vast science due to one key property exhibited by the

element carbon, which is called carbon catenation. Carbon has the

exceptional ability to form very stable bonds with other carbon atoms, giving it

the ability to form stable molecules with relatively complex structures.

Catenation is the ability of an element to form bonds with an atom of the same

kind. Hence, the vastness of organic chemistry can be attributed to this

property of carbon.

Table of Contents

• Cleavage of Bonds
• Reaction Intermediates
• What Are Carbenes?
• What Are Free Radicals?
• Carbanions and Carbocations
• Transition State in Organic Reactions
• Reagents in Organic-Chemistry
• Types of Reactions in Organic Chemistry
• Field Effect
• Resonance Effect
• Role of Steric Hindrance
• Stability of Intermediates
The importance of organic chemistry in the present age is as immense as it

has been since its inception. It plays an important role in our everyday life

because food, medicines, paper, clothes, soap, perfumes, etc., are

indispensable to us for proper living. The study of organic chemistry is

important for chemists and pharmacists in synthesising medicines for the

alleviation of human suffering.

The reactions in organic chemistry occur between organic compounds. Let us

now study the different terminologies, classifications, field effects, types of

reagents, the stability of intermediates, and properties in detail.

Cleavage of Bonds

The reactions in organic chemistry occur through the breaking and making of

bonds. Bonds can cleave in either of two ways:

• Homolytic cleavage
• Heterolytic cleavage

What Is Homolytic Cleavage?

If the covalent bonds between two elements break in such a way that each of

the elements gets its own electrons, it is called homolytic cleavage. That is,

each element gets an electron. Homolytic cleavage results in the formation

of free radicals.

Homolytic Cleavage of Covalent Bond

In the above figure, we have used an arrow to show the movement of

electrons. Here, in this case, the arrow used is called the fish-hook arrow, as

it signifies that there is a movement of only one electron.

Also Read:
• Purification of Organic Compounds
 • Organic Chemistry for Class 11
• Name Reactions
• Qualitative Analysis of Organic Compounds
• Lassaigne’s test
• Victor Meyer’s Method

What Is Heterolytic Cleavage?

If the covalent bonds between two elements break heterolytically, i.e.,

unequally, it results in the formation of charged species. This type of bond

breaking, where the electrons are unevenly distributed, is called heterolytic

cleavage.

Heterolytic Cleavage of Covalent Bond

In the above figure, we have used arrows to signify the movement of

electrons, a regular arrow signifies that two electrons are being moved.

Reaction Intermediates in Organic Chemistry

Intermediates can be understood as the first product of a consecutive

reaction. For example, in a chemical reaction, if A→B and B→C, then B can be

said to be the intermediate for reaction A→C. The reactions in organic

chemistry occur via the formation of these intermediates.

What Are Carbenes?

Carbenes (H2C) are neutral and reactive species that have six electrons in

the outer shell of carbon, making them electron deficient. Since carbenes are

species having two odd electrons, we can classify carbenes based on their

spin states.

Singlet Carbene

The electrons are present in different orbitals with opposite spins. The

electrons are paired in sp 2 hybridized orbitals and behave as paired electrons.

Spin state= (2S + 1), S for singlet carbene is zero, as the electrons are

antiparallel.

Therefore, spin state = (2 × 0 + 1) = 1

Triplet Carbene

Both electrons are present in different orbitals, and they possess the same

spin.

Spin state = (2S + 1), S for triplet carbene is 1, as both electrons have the same

spin.
Therefore, spin state= (2 × 1 + 1) = 3

Hybridization of Singlet and Triplet Carbene

Singlet carbene hybridization: They are sp2 hybridized with a bent shape.

They have a bond angle of 103° and a bond length of 112 pm.

Hybridization of Singlet Carbene

Triplet carbene hybridization: They possess a sp hybrid orbital with a linear

shape. They have a bond angle and bond length of 180° and 103 pm,

respectively.
Why Is Triplet Carbene More Stable than Singlet?

Triplet carbene has lower energy than singlet carbene because, in singlet

carbene, there are more inter-electronic repulsions as both the electrons exist

in the same orbital, whereas in triplet carbene, the two electrons exist in

different orbitals, making it possess less energy.

What Are Free Radicals?

Free radicals in organic chemistry are formed by the homolytic cleavage of

carbon bonds. The shape of the species formed is planar, and the carbon is

sp3 hybridized with an odd electron being placed in the p-orbital. If the free

radical is relatively stable, then it may possess a planar structure.

Planar Structure of Free Radicals

Carbanions and Carbocations

What Are Carbanions?

They are generated by heterolytically cleaving a group attached to carbon

without removing the bonded electrons. This makes the carbon have a pair of

electrons, thereby imparting a negative charge on the carbon. CH 3– is

isoelectronic with NH3, and it is sp3 hybridized, and the shape is pyramidal

owing to the presence of a lone pair of electrons.

Formation of Carbanions and Carbocations

What Are Carbocations?

Carbocations have a sextet of electrons on the carbon-containing positive

charge and are hence termed ‘cations’. It is sp2 hybridized and has an empty

p-orbital. The shape is planar. It is generally formed by heterolytic cleavage

of a carbon-heteroatom bond.

Transition State in Organic Reactions

We saw the intermediates that could be formed in an organic reaction; now,

let us look into transition states and the difference between an intermediate

and a transition state.

The intermediates in organic chemistry are formed in a multi-step reaction,

but some reactions can occur in a single step without having to form an

intermediate. These reactions will occur by going through a transition state.

This can be clear by looking at the energy profile diagram for a reaction,

R→P.
The transition state corresponds to the highest energy in the reaction, after

which it can give either the products or, in the case of a reversible reaction,

the reactants.

Consider a reaction, A→D with the following steps, A→B, B→C, and C→D

The energy profile for this reaction is given below:

We can see that B and C are the products of a reaction, and hence they are

termed intermediates. The highest energy of a particular reaction should be

the transition state.

Conclusion:

From the above example, we can show that the intermediates are isolable,

that is, they can be isolated. On the other hand, the transition state is not

isolable because we assume the reaction to take place via a transition state

cannot be isolated.
Reagents in Organic Chemistry

Reagents are the chemicals that we add to bring about a specific change to

an organic molecule. Any general reaction in organic chemistry can be

written as follows:

Substrate + Reagent → Product

Where the substrate is an organic molecule to which we add the reagent.

Based on the ability to either donate or abstract electrons, the reagents can

be classified as follows:

• Electrophiles
• Nucleophiles

Electrophiles

Electrophiles are electron-deficient organic reagents. It can be generalised

that all the positive charge-containing species are electrophiles. For

example, H+, NO2+, CH3+, Cl+

Check: Electrophilic Substitution Reaction

Neutral molecules that are electron deficient can also act as electrophiles.

Lewis acids like AlCl3 and BF3 are examples of neutral electrophiles.
Nucleophiles

Nucleophiles are electron-rich organic reagents. They seek bonding centres

with other nuclei and hence the name nucleophile. It can be generalised that

negative charge-containing species are nucleophiles. For example, H –, CH3–,

and Cl–.

Neutral molecules with a lone pair of electrons on the heteroatom can act as

a nucleophile. For example, H2O, NH3, and CH3OH.

Types of Reactions in Organic Chemistry

Organic reactions are reactions that occur between organic compounds. The

reactions in organic chemistry are broadly classified into six categories. Let us

study in detail these different types of reactions and their products.

Substitution Reactions

R-X + Y → R-Y +X

Where R-X is the substrate, Y is the reagent (which can be electrophilic or

nucleophilic), and X is called the leaving group. The term substitution means

one group is replacing the other group.

Types of Substitution Reaction:

 1. Nucleophilic Substitution ( SN1, SN2, SNi)
2. Electrophilic Substitution (SE)
3. Nucleophilic Aromatic Substitution (SNAr)
4. Addition Reactions
Addition reactions can be further classified into:

1. Electrophilic Addition
2. Nucleophilic Addition
3. Elimination Reactions

Elimination Reactions

These reactions can be said to be the reverse of an addition reaction, wherein

a simple molecule (HX, H2O) is removed from the substrate, i.e., a molecule is

said to be eliminated from the substrate. Elimination reaction can be

classified further into E1, E2, and E1CB.

1. Oxidation and reduction reactions

2. Pericyclic reactions
3. Molecular rearrangements

Field Effect in Organic Chemistry

Inductive Effect

It is an electron delocalisation effect via σ bonds that arises due to the

difference in electronegativities. For example, in a σ bonded organic

compound like C-C-C-Cl, the carbon attached to the chlorine atom can be
referred to as the α-carbon, and the one adjacent to that carbon as the ß-

carbon and so on.

Now, since chlorine is more electronegative than carbon, it withdraws the

electrons that are present via the σ bond toward itself, thereby making Cα

fractionally positive. Since it is devoid of electrons, Cα, now being slightly

electropositive than Cß, pulls the sigma-bonded electrons of Cα-Cß bond

toward itself, and in this process, it makes Cß slightly electropositive.

The electron-withdrawing effect of the chlorine atom is transmitted through

the carbon chain via the σ bonds. This transmission of charges decreases

rapidly with the number of intervening σ bonds. We can practically ignore this

effect beyond Cß.

The arrow is pointed more towards the electronegative atom. If a group

withdraws the electron from carbon, it makes carbon slightly electropositive.

Such groups are called -I groups, and the effect is termed -I effect. For

example, -Cl, -Br, -CN and -NO2 are -I groups.

Groups that release electrons towards carbon are termed +I groups, and the

effect is termed as +I inductive effect in organic chemistry. For example, alkyl

groups like -CH3 are +I groups.

Electromeric Effect

It is the temporary delocalisation of π-electrons in a compound containing

multiple covalent bonds. It is important to note that it is only a temporary

effect, that is, it occurs only when a reagent is added. The Electromagnetic

Effect in organic chemistry can be classified into two types:

• Positive Electromeric Effect

• Negative Electromeric Effect

Positive Electromeric Effect

When the π-electrons are given to the attacking reagent, for example, the

reactions alkenes and alkynes mostly occur via +E, this reaction is also called

electrophilic addition.
 Positive Electromeric Effect
The proton adds at C-1 as the π-electrons were given to the attacking

reagent (H+). This results in the formation of a carbocation.

Negative Electromeric Effect

When the π-electrons are shifted to a more electronegative atom (O, N, S)

joined via multiple bonds, it is called the negative electromeric effect. For

example, the reactions of aldehydes and ketones occur predominantly by the

-E effect. It is also called nucleophilic addition.

Negative Electromeric Effect

The CN- ion adds to the C atom of the carboxy group opposite to the

movement of the π-electron cloud.

Mesomeric Effect

Molecules possessing sigma bonds and pi-bonds alternatively exhibit the

mesomeric effect. The effect is exhibited due to the permanent delocalisation

of π-bonds. This increases the number of resonating structures which

makes the molecules of organic chemistry more stable. Such kind of a

system, where there are alternative sigma and pie bonds, is called

conjugated.

Types of Mesomeric Effect

• Positive mesomeric effect

• Negative mesomeric effect:

Positive Mesomeric Effect

This effect is exhibited when the direction of the delocalisation of electrons is

away from the position where the group is attached. Normally, groups having

a lone pair of electrons attached to a conjugated system push electrons into

the conjugated system, that is, away from them.

Groups in organic chemistry showing positive mesomeric effect (+M) effect

are -OH, -OR, -NH2, -SH, -X, etc.

Negative Mesomeric Effect

This effect is exhibited when the direction of the delocalisation of electrons is

towards the position where the group is attached. These are generally

electron-withdrawing groups of organic chemistry.

Resonance Effect

For certain molecules like carbonate ion (CO 32-), one single Lewis structure

would not be enough to explain all of the properties. In that case, the

molecule is said to have more than one structure.

Each of those structures can explain some of the properties but not all of the

properties. The actual structure of the molecule is a hybrid of all the possible

structures (canonical forms). This phenomenon is called resonance in

organic chemistry. If resonance occurs, each bond would be both a single

bond and a double bond at the same time, i.e. the bond order would lie

between one and two.

Resonating structures should fulfil the following criteria:

1. All atoms should have the same positions in all the structures.
2. There should have the same number of paired and unpaired electrons.
3. The structures should have almost the same energies.
Note: Canonical forms do not have any existence in reality.
Resonance Energy

The energy difference between the most stable canonical form and the

resonance hybrid is known as Resonance Energy. The more the resonance

energy, the more the stability.

Rules for finding out the most stable canonical form:

1. The canonical form with no charges is the most stable

2. The canonical form with more number of covalent bonds is more stable
3. The canonical form where unlike charges are in close proximity are more stable
4. If they are to be charged, the negative charge should be on an electronegative
atom. Then, this canonical form is said to be more stable.

Role of Steric Hindrance

The structure and reactivity of many compounds in organic chemistry are

greatly dictated by the presence of bulky groups or constituents in the

molecule. This is called steric hindrance. It arises because of inter-electronic

repulsions due to spatial crowding amongst bulky groups. Using steric

factors, we can conclude that trans-2-butene is more stable than cis-2-

butene.
 Steric Hindrance in Organic Chemistry

Stability of Intermediates

Carbocations

The stability of carbocations can be explained by the Inductive Effect.

CH3++CH2(CH3) +CH(CH3)2+C(CH3)3, i.e., Methyl Primary (1°) Secondary (2°)

Tertiary(3°)

We know that alkyl groups of organic chemistry are +I groups, that is, they

release electrons through the sigma bonds.

Since the carbon is deficient in electrons, we can say that as the number of

methyl groups increases, the stability of the carbocation increases, as the

electropositive carbon is satiated by the electrons given by the methyl groups

via the +I effect.

Therefore, the stability order of carbocations in organic chemistry is of the

order 3° > 2° > 1° > Methyl carbocation.

Hyperconjugation

When a C-H σ-bond is in conjugation with a carbocation, this effect is

observed. A carbocation has a vacant p-orbital. The bonded σ-electron pair

of the C-H bond is displaced towards the vacant p-atomic orbital. This

increases the electron density in the empty p-AO.

It is, therefore, a resonance effect, where a C-H bond breaks and the σ-

electron pair is delocalised to the vacant p-AO of the carbonation. Since the
bond between C and H is broken, it is also called ‘no bond resonance’. It is

also referred to as the Baker-Nathan effect.

The more the number of α-hydrogens in a carbonation, the more

hyperconjugated structures would be possible. The more the number of

structures, the more the stability of the species.

Stability of Carbanions

The stability of carbanions can be explained using the inductive effect.

CH3 — CH2(CH3) — CH(CH3)2 — C(CH3)3 i.e. Methyl Primary (1°) Secondary (2°)

Tertiary (3°)

Since alkyl groups are electron-releasing by nature through induction, we can

say that the more the number of methyl groups attached to the carbon

having a negative charge, the less its stability would be.

This is because the carbon already has a negative charge, to which the

methyl groups push electrons via induction. This results in inter-electronic

repulsions and destabilises the species.

Therefore, the stability order for carbanions is as follows:

3°< 2°< 1°< Methyl carbanion

Stability of Free Radicals

The stability of free radicals in organic chemistry follows the same trend as

that of carbocations.

CH3–CH2(CH3)–CH(CH3)2–C(CH 3)3 i.e. Methyl Primary (1°) — Secondary (2°) —

Tertiary(3°)

Therefore, the stability order of free radicals is of order: 3° > 2° > 1° > methyl

carbocation.
This can be explained with the help of the Hyperconjugation that we saw, but

there would be an overlap between the σ-bond of C-H and the odd electron

in the p-orbital of carbon.