RB’S FAST TRACK

SERIES
CHAPTER : GOC
GOC Basics

General Components of an Organic Reaction

A typical reaction mechanism proceeds in the following manner:

Reactants + Catalyst or Energy → Intermediate (Transition State) → Product

Adequate reaction conditions facilitate the formation of an intermediate from the

chemical reaction between the reactants. These intermediates are generally
unstable and quickly react further to yield a product.

The reactants of an organic reaction can be classified as follows:

 Reagents – Reactive chemical species that trigger the reaction by attacking another
species.
 Substrate – The species that is attacked by a reagent in an organic reaction.

The site of the reagent attack can vary based on the nature of the reagent
(electrophilic or nucleophilic):
Electrophiles – They are electron-deficient species that attack the substrate at a
region where the electron density is high.

Nucleophiles – They are electron-rich species that tend to donate their

electrons. Nucleophiles generally attack the reagent at a region where the electron
density is low.

Cleavage of Bonds and Reaction Intermediates

Chemical reactions generally involve the breakage of existing chemical bonds and
the formation of new ones. A covalent bond can break in two different ways:

Homolytic Fission – The covalent bond is cleaved in such a manner that each
participating atom leaves with one unpaired electron. The chemical species that are
created as a result of homolytic fission are called free radicals. They are highly
reactive (due to their unstable electron configurations).

Heterolytic Fission – The covalent bond is cleaved in such a manner that one atom
retains both the electrons and the other retains none. Heterolytic fissions feature the
formation of an ion pair – a positively charged cation and a negatively charged anion.

Inductive Effect
(Main Article: Inductive Effect)

The introduction of an electron-rich or electron-deficient species to a carbon chain

results in the formation of a permanent dipole. This effect is called the inductive
effect since the dipole is induced by the difference in the electronegativities of the
atoms in the molecule.

The direction of the dipole moment depends on the electronegativity of the attacking
species (relative to the carbon atom it bonds with). Note that the partial charge
(positive or negative) gained by the carbon atom is relayed through the carbon chain,
as illustrated below.

 In this example, the electronegativity of chlorine is higher than that of carbon, causing the
bond pair of electrons to shift closer to the chlorine atom.
 This results in the formation of a permanent dipole where the chlorine has a partial
negative charge (since the electron density around it is high), and the carbon atom has a
partial positive charge (since the electron density around it is low).
 Since the alkyl group is an electron-donating group, the partial positive charge on the
chlorine-bonded carbon is stabilised by the rest of the chain. Therefore, the inductive
effect propagates through sigma bonds.
 Eventually, the partial charge propagates through the entire carbon chain.

Important Note: The magnitude of the partial charge decreases down the carbon chain. Its magnitude can
be neglected from the 4th carbon atom in the chain.

Salient Features of the Inductive Effect

 1. It is a permanent effect.
2. It is dependent on distance (its magnitude decreases as the distance between the atoms
increases).
3. It is relayed through sigma bonds.

Types of Inductive Effects

+I effect: The positive inductive effect (abbreviated to +I effect) involves the
transmission of a negative charge through the chain. It occurs when an electron-
donating group is introduced to a chain of atoms. Example of +I species: Alkyl
group.

-I effect: The -I effect, also known as the negative inductive effect, occurs when an
electron-withdrawing group is introduced to a chain of atoms. This results in the
transmission of a positive charge through the chain. Example of -I
species: Halogens, such as fluorine and chlorine.

Gauging the Stability of Molecules with the Inductive Effect

(Solved Example)
Question: Which of the following compounds is the most stable?

Answer: The compound with the methyl functional group (bottom) is the most stable
since the CH3 group is a +I species, which increases the stability of the carbocation.
Since fluorine and chlorine are electron-withdrawing -I groups, they decrease the
stability of the carbocation by increasing the magnitude of the positive charge on it.
However, the compound containing fluorine is less stable than the one containing
chlorine (because fluorine is more electronegative and, therefore, more electron-
withdrawing).
Important Note: electron-donating species decrease the stability of carbanions and increase the stability
of carbocations due to the +I effect. Electron-withdrawing species increase the stability of carbanions and
decrease the stability of carbocations due to the -I effect.

Gauging the Acidity or Basicity of a Compound with the

Inductive Effect (Solved Example)
Question: Which of the following compounds has the highest acidity?

Answer: The order of acidity is F-CH3COOH > CH3COOH > O–-CH3COOH

Explanation:

 The acidity of an acid is directly proportional to the stability of the corresponding

conjugate base.
 The acidic part of these molecules is the carboxyl group (COOH group), whose conjugate
base is the carboxylate ion (COO–).
 A +I group will increase the negative charge on the conjugate base, thereby decreasing
its stability and, consequently, decreasing the acidity of the parent acid.
 A -I group will stabilize the negative charge of the conjugate base due to its electron-
withdrawing nature. This increases the stability of the conjugate base and the acidity of
the parent acid.
 Since O– is an electron-donating group (or a +I group), it will decrease the acidity of the
compound.
 Since F is an electron-withdrawing group, it will increase the acidity of the compound.
 Therefore, the compound at the bottom is the most acidic, and the one on the top right is
the least acidic.

Remember:
  -I Groups (electron-withdrawing groups) increase acidity and decrease the basicity.
 +I Groups (electron-donating groups) decrease acidity and increase basicity.

Electromeric Effect
(Main Article: Electromeric Effect)

The electromeric effect involves the complete transfer of pi electrons to one of the
bonded atoms in an organic compound. It is a temporary effect that occurs due to
the presence of an attacking reagent (an electrophile or nucleophile that triggers the
formation of a dipole in the organic compound). The electromeric effect subsides
when the attacking reagent is removed from the system.

Types of Electromeric Effects

+E Effect: When the attacking reagent is an electrophile, the pi electrons shift
towards the attacking reagent, which binds to the atom that retains the bond pair
(and is negatively charged).

For example, the +E effect can be observed during the protonation of alkenes
(illustrated below).

-E Effect: When the attacking reagent is a nucleophile, the pi electrons shift away
from the attacking reagent, which binds to the atom that lost its pi-electron (and is
positively charged). For example, the -E effect can be observed during the addition
of a nucleophile (such as a cyanide ion) to the carbonyl group of a carbonyl
compound (illustrated below).

Remember:
  Electrophiles are +E groups
 Nucleophiles are -E Groups
 +E and -E effects are temporary, and their presence is entirely dependent on the attacking reagent.

Hyperconjugation
Carbocations are stabilised by adjacent sigma bonds that donate electrons to vacant
p-orbitals. This effect is a permanent effect and is called hyperconjugation (also
called no-bond resonance). Here, the delocalization of the positive charge increases
the stability of the compound.

The stability added by hyperconjugation is directly proportional to the total number of

hyper-conjugating structures, which is, in turn, directly proportional to the total
number of alpha hydrogens.

Gauging the Stability of Carbocations with Hyperconjugation

(Solved Example)
Question: Rank the following carbocations in increasing order of stability.
Answer: The total number of alpha-hydrogens is proportional to the stability of the
carbocation (due to hyperconjugation). Therefore, the bottom-left and the top-left
compounds are the most stable, and the top-right compound is the least stable.

Mesomeric Effect
The mesomeric effect involves the delocalization of electrons over a network of pi
bonds. The polarity that arises in organic compounds due to the interactions
between two pi bonds (or a pi bond and a lone pair) is a consequence of the
mesomeric effect. This effect can stabilize both negative and positive charges.

Types of Mesomeric Effects

+M Effect: It involves the donation of electrons by a pi-system. Electrons typically
move away from +M groups. An illustration detailing the +M effect in a methoxy ether
molecule is provided below.

Examples of +M groups: O–, NH2, and OH groups. These groups usually contain a
lone pair or a pi bond.

-M Effect: It involves the acceptance of electrons by a pi-system. Electrons typically

move towards -M groups, as illustrated below.

Examples of -M groups: CHO and NO2 groups.

Mesomeric Effect in Phenol (Example)

The OH group in a phenol molecule exhibits a +M effect, resulting in the
delocalization of a lone pair of electrons (belonging to the oxygen atom) over the
aromatic system (illustrated below).
From the illustration, it can be observed the electron densities are particularly high at
the ortho and para positions of the aromatic ring. This makes the phenol molecule
particularly susceptible to electrophilic substitutions at the ortho and para positions.

Comparison between Inductive and Mesomeric Effects

 Inductive effects are typically weaker than mesomeric effects.
 The stability offered by a +M group to an anion is generally greater than that offered by a
+I group.
 The distances over which mesomeric effects are effective are much greater than the
distances over which inductive effects are effective. This is because mesomeric effects
are dependent on the positions of the +M and -M groups in the molecule.

Resonance Effect
(Main Article: Resonance Effect)

The resonance effect involves the delocalization of pi electrons and lone pairs over
molecules. This results in several hypothetical molecular structures known as
resonance structures. It occurs at an intramolecular level and does not alter the
structural arrangement of atoms in the molecule (the arrangement of electrons can
vary).

The stabilization offered by resonance is greatest when an equivalent resonating

structure (known as a resonance hybrid) can be drawn for the molecule. An
illustration detailing the resonance of an ozone molecule is provided below.

Types of Resonance Effects

+R Effect: It occurs when a lone pair of electrons is released into a molecule. +R
effects usually involve the transmission of a negative charge throughout the
molecule due to the delocalization of a lone pair of electrons. The electron-donating
agent obtains a positive charge when its lone pair undergoes delocalization.

-R Effect: It occurs primarily due to electron-withdrawing species or species with

vacant p or d orbitals. -R effects usually feature the transmission of a positive charge
through the molecule (the electrons are delocalized into the electron-withdrawing
group from the rest of the molecule).

Isomerism
Isomerism is a phenomenon in which multiple compounds have the same chemical
formula but feature different chemical structures. The chemical compounds that
exhibit isomerism are called isomers.

Isomerism can be broadly classified into two categories:

1. Structural isomerism
2. Stereoisomerism

Structural isomerism, also known as constitutional isomerism, features molecules

with the same chemical formulae but differently arranged atoms.

Stereoisomerism is the phenomenon in which multiple molecules have the same

chemical formulae but different three-dimensional orientations of the atoms.

An illustration detailing the different types of isomerism is provided below.

ISOMERISM
IUPAC & GOC
In the study of organic chemistry we come across many cases when two or more
compounds are made of equal number of like atoms. A molecular formula does not
tell the nature of organic compound; sometimes several organic compounds may
have same molecular formula. These compounds possess the same molecular
formula but differ from each other in physical or chemical properties, are called
isomers and the phenomenon is termed isomerism (Greek, isos = equal; meros =
parts). Since isomers have the same molecular formula, the difference in their
properties must be due to different modes of the combination or arrangement of
atoms within the molecule. Broadly speaking, isomerism is of two types.

 Structural Isomerism
 Stereoisomerism

(i) Structural isomerism: When the isomerism is simply due to difference in the
arrangement of atoms within the molecule without any reference to space, the
phenomenon is termed structural isomerism. In other words, while they have same
molecular formulas they possess different structural formulas. This type of isomerism
which arises from difference in the structure of molecules, includes:

 Chain or Nuclear Isomerism;

 Positional Isomerism
 Functional Isomerism
 Metamerism and
 Tautomerism

(ii) Stereoisomerism: When isomerism is caused by the different arrangements of

atoms or groups in space, the phenomenon is called Stereoisomerism (Greek,
Stereos = occupying space). The stereoisomers have the same structural formulas
but differ in the spatial arrangement of atoms or groups in the molecule. In other
words, stereoisomerism is exhibited by such compounds which have identical
molecular structure but different configurations.

Stereoisomerism is of two types:

(a) Geometrical or cis-trans isomerism; and

(b) Optical Isomerism.

Thus various types of isomerism could be summarized as follows.

STRUCTURAL ISOMERISM

Chain or Nuclear Isomerism

This type of isomerism arises from the difference in the structure of carbon chain
which forms the nucleus of the molecule. It is, therefore, named as chain, nuclear
isomerism or Skeletal isomerism. For example, there are known two butanes which
have the same molecular formula (C4H10) but differ in the structure of the carbon
chains in their molecules.

While n-butane has a continuous chain of four carbon atoms, isobutane has a
branched chain. These chain isomers have somewhat different physical and
chemical properties, n-butane boiling at -0.5o and isobutane at -10.2o. This kind of
isomerism is also shown by other classes of compounds. Thus n-butyl alcohol and
isobutyl alcohol having the same molecular formula C4H9OH are chain isomers.

It may be understood clearly that the molecules of chain isomers differ only in
respect of the linking of the carbon atoms in the alkanes or in the alkyl radicals
present in other compounds.

Positional Isomerism
It is the type of isomerism in which the compounds possessing same molecular
formula differ in their properties due to the difference in their properties due to
difference in the position of either the functional group or the multiple bond or the
branched chain attached to the main carbon chain. For example, n-propyl alcohol
and isopropyl alcohol are the positional isomers.

OH

CH3–CH2–CH2–OH CH3–CH–CH3

n-propyl alcohol isopropyl alcohol

Butene also has two positional isomers:

CH2=CH–CH2–CH3 CH3–CH=CH–CH3

1-butene 2-butene

1-Chlorobutane and 3-Chlorobutane are also the positional isomers:

Methylpentane also has two positional isomers:

In the aromatic series, the disubstitution products of benzene also exhibit positional
isomerism due to different relative positions occupied by the two substituents on the
benzene ring. Thus xylene, C6H4(CH3)2, exists in the following three forms which
are positional isomers.

Functional Isomerism
When any two compounds have the same molecular formula but possess different
functional groups, they are called functional isomers and the phenomenon is termed
functional isomerism. In other words substances with the same molecular formula
but belonging to different classes of compounds exhibit functional isomerism. Thus,

(1) Diethyl ether and butyl alcohol both have the molecular formula C4H6O, but
contain different functional groups.

C2H5–O–C2H5 C4H9–OH

diethyl ether butyl alcohol

The functional group in diethyl ether is (–O–), while is butyl alcohol it is (–OH).

(2) Acetone and propionaldehyde both with the molecular formula C3H6O are
functional isomers.

CH3–CO–CH3 CH3–CH2–CHO

acetone Propionaldehyde

In acetone the functional group is (–CO–), while in propionaldehyde it is (–CHO).

(3) Cyanides are isomeric with isocyanides:

(4) Carboxylic acids are isomeric with esters.

(5) Nitroalkanes are isomeric with alkyl nitrites:

(6) Sometimes a double bond containing compound may be isomeric with a triple
bond containing compound. This also is called as functional isomerism. Thus, butyne
is isomeric with butadiene (molecular formula C4H6).

(7) Unsaturated alcohols are isomeric with aldehydes. Thus,

(8) Unsaturated alcohols containing three or more carbon atoms are isomeric to
aldehydes as well as ketones:

(9) Aromatic alcohols may be isomeric with phenols:

(10) Primary, secondary and tertiary amines of same molecular formula are also the
functional isomers.

(11) Alkenes are isomeric with cycloalkanes:

Such isomers in which one is cyclic and other is open chain, are called ring-chain
isomers. Alkynes and alkadienes are isomeric with cycloalkenes.

Metamerism
This type of isomerism is due to the unequal distribution of carbon atoms on either
side of the functional group in the molecule of compounds belonging to the same
class. For example, methyl propyl ether and diethyl ether both have the same
molecular formula.

CH3–O–C3H7 C2H5–O–C2H5

methyl propyl ether diethyl ether

In methyl propyl ether the chain is 1 and 3, while in diethyl ether it is 2 and 2. This
isomerism known as Metamerism is shown by members of classes such as ethers,
and amines where the central functional group is flanked by two chains. The
individual isomers are known as Metamers.

Examples:

Tautomerism

It is the type of isomerism in which two functional isomers exist together in

equilibrium. The two forms existing in equilibrium are called as tautomers. For
example, the compound acetoacetic ester has two tautomers – one has a keto group
and other has an enol group:

Out of the two tautomeric forms, one is more stable and exists in larger proportion. In
above, normally 93% of the keto form (more stable) and only 7% of the enol form
(less stable i.e. labile) exist.

The equilibrium between the two forms is dynamic, i.e., if one form is somehow
removed by making a reaction, some of the amount of the other form changes into
the first form so that similar equilibrium exists again. Thus, whole of the acetoacetic
ester shows the properties of both ketonic group as well as the enolic group. Thus, it
adds on HCN, NaHSO3 etc. due to the presence of •C=O group and it decolourises
bromine water and gives dark colouration with FeCl3 due the presence of >C—OH
group. Due to the presence of keto and enol form this type of tautomerism is known
as keto-enol tautomerism. It is the most commonly observed type of tautomerism.

Keto-enol tautomerism is generally observed in those compounds in which either a

methyl

(CH3—), methylene (—CH2—), or a methyne ( ) group is present adjacent to a

carbonyl
(—CO—) group as in acetoacetic ester above. In other words, it can be said that
keto-enol tautomerism is possible in only those carbonyl compounds in which atleast
one α-hydrogen atom is present so that it may convert the carbonyl group to enol
group.

Another example of keto-enol tautomerism is:

It is found that if the α-hydrogen atoms are present on both the carbons attached to
carbonyl group, more stable is the enol form and hence more its content. Thus,
larger the number of α-hydrogens in a ketone, more is enol content. Also, if number
of α-hydrogen containing carbonyl groups is more, again more is the enol content.
Thus the order of enol content is:

CH3CHO • CH3COCH3 • CH3COCH2CHO • CH3COCH2COCH3

CH3COCH2COH3 has about 75% enol content. Moreover, the enol form shows acidic

nature due to the tendency to liberate proton (H+) from the enol ( C—OH)
group. This H is the α-hydrogen in keto – form. Therefore, α-H in carbonyl compound
is acidic in nature. More the enol content, more is the acidic nature of α-hydrogens in
a carbonyl compound. Thus above is also the increasing order of acidity of α-
hydrogens.

An interesting observation about the enol content in acetoacetic ester is the fact that
above mentioned percentage ratio (93:7) is in its aqueous solution. In liquid state this
ratio is nearly 25 : 75. It is because in liquid state the enol form is much stabilised
by intramolecular H-bonding.

In aqueous solution the intermolecular H-bonding with water takes place and it
dominates the intramolecular H-bonding, resulting in lower enol content.

Keto-enol tautomerism exists in cyclic carbonyl compounds also if they fulfil the
condition of presence of α-H. Thus, we have
Tautomerism is also termed as desmotropism (desomo= bond, tropis = turn)
because in tautomers the bonding changes.

Every compound having skeleton has its tautomer skeleton

e.g., in the preparation of a very small amount of enol

isomers also forms which can be isolated. The two exist in

equilibrium with each other and can be separated by suitable methods.

A hydroxy group attached to a carbon which is itself attached to another carbon atom
by a double bond is known as enolic (en for double bond, ol for alcohol). Its nature
becomes acidic as in phenol and unlike OH group in alcohol which is neutral or only
very slightly acidic (C2H5OH + Na → C2H5ONa + 1/2H2). In the above two examples
migration of a proton from one carbon atom to another takes place with simultaneous
shifting of bonds.

Hydrocyanic acid, H – C ≡ N and Isohydrocyanic acid H — N ≡ C are also tautomeric

isomers or tautomers.

Difference between Tautomerism & Resonance

(a) In tautomerism, an atom changes place but resonance involves a change of

position of pi-electrons or unshared electrons.
(b) Tautomers are different compounds and they can be separated by suitable
methods but resonating structures cannot be separated as they are imaginary
structures of the same compound.

(c) Two tautomers have different functional groups but there is same functional
group in all canonical structures of a resonance hybrid.

(d) Two tautomers are in dynamic equilibrium but in resonance only one compound
exists.

(e) Resonance in a molecule lowers the energy and thus stabilises a compound and
decreases its reactivity. But no such effects occur in tautomerism.

(f) In resonance, bond length of single bond decreases and that of double bond
increases e.g. all six C—C bonds in benzene are equal and length is in between the
length of a single and a double bond.

(g) Resonance occurs in planar molecule but atoms of tautomers may remain in
different planes as well.

(h) Tautomers are indicated by double arrow in between the two isomers but
double headed single arrow ←⎯→ is put between the canonical (resonating)
structures of a resonating molecule.

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