General Organic Chemistry

The Breaking and forming of Bonds:Organic reactions usually involve the fission and
formation of covalent bonds. The covalent bond is often represented as a dash (––) and the
movement of a pair of electrons is shown by a curved arrow (↷), where as the movement of a
single electron is a shown by fish hook arrow .

There are two ways in which a covalent bond may be broken.

i) Homolytic Fission:Suppose the atoms X and Y are bonded through a covalent bond.
When a bond breaks such that each of the atoms retains one of the bonding electrons, the
process is called homolytic bond cleavage (or) homolysis. Homolytic fission results in the
formation of free radicals.

X − Y 
→X + Y
Free radicals

ii) Heterolytic Fission:When more electronegative atom remains attached with less
electronegative atom, then the bonded pair of electrons moves towards more
electronegative atom, there by more electronegative atom gets negative charge and less
electronegative atom gets +ve charge such type of fission is known as heterolytic fission
i.e. this fission occurs by a shifting of bonded pair of electrons from less electronegative
atom to more electronegative atom.

The ions of carbon, known as carbanions and carboniumions, are of special importance in
organic chemistry.

Homolytic chemistry is the chemistry of the odd electron; Heterolytic chemistry is the
chemistry of the electron pair. Where homolytic chemistry deals with the neutral particles
called free radicals, heterolytic chemistry deals with positive and negative charges, with
cations and anions. Homolytic reactions are typically carried out in the gas phase, or in
solvents whose principal function is to provide an inert medium in which the reacting
molecules can move about. Heterolytic reactions are typically carried out in solution in
polar solvents, because of the greater ease of separation of charges therein and very often
because of the stabilization of the resultant ion pairs through solvation.

Electron Displacement in Organic Molecules: In organic molecules different

reactions depend on the electron density in their molecules. Since majority of attacking reagents
are polar, i.e. nucleophilic (or) electrophilic, hence in organic compounds permanent (or)
temporary polarity is developed by temporary (or) permanent electron displacements.

The different electronic effects which operates in covalent bonds are

i) Inductive effect
ii) Mesomeric and resonance effect
iii) Electromeric effect and
iv) Hyper conjugation
i) Inductive Effect:In a covalent single bond between unlike atoms, the electron pair
forming the σbond is never shared absolutely equally between the two atoms; it tends to
be attracted a little more towards the more electronegative atom of the two. Thus in an
alkyl chloride, the electron density tends to be greater nearer chlorine than carbon, as the
former is the more electronegative; this is generally represented as in
−
δ+ δ
Cl Cl

If the carbon atom bonded to chlorine is itself attached to further carbon atoms, the effect
can be transmitted further . For example C2H5 – Cl.
δδ+ δ+ δ−
CH 3 CH 2 Cl
2 1
a-I group, will draw electrons.

a slightly positive charge a polarization of this bond

on the C2 atom.
Electron displacement along the chain
In ethyl chloride the effect of the chlorine atom, partial appropriation of the electrons of
the carbon chlorine bond is to leave C1 slightly electron deficient this it seeks to rectify by
in turn, appropriating slightly more than its share of the electrons of the σ bond joining it
to C2, and so on down the chain. The effect of C1 on C2 is less than the effect of Cl on C1.
However it decreases as the distance from source (more electronegative atom) increases.
From practical point of view, it may be neglected after third carbon atom.

Inductive effect is denoted by the symbol I and represented by a straight arrow (→), the
arrow head pointing towards the source.

The inductive effect causes certain degree of polarity in the bond which in term renders
the bond much more liable to be attached by other charged atoms (or) group.

Thus inductive may be defined as the permanent displacement of electron forming a

covalent bond towards the more electronegative element or group.

Atoms (or) groups which attract electrons more strongly than hydrogen are called
attracting (or) withdrawing groups and produce –I effect. The following is the order of
decreasing –I effect.

NR 3+ , SR +2 , NH 3+ , NO2, SO2R, CN, COOH, F, Cl, Br, I, OAr, COOR, OR, OH, C6H5,
CH2 = CH2, H.

Atoms (or) groups which attract electrons less strongly than H are called as electron
releasing or repelling groups and produce +I effect. Following is the decreasing order of
+I effect.
C6H5O–, COO–, R3C, CHR2, CH3, H

Applications of Inductive Effect

a) Dipole moment:Since, inductive effect leads to a dipolar character in the molecule,
it develops some dipole moment in the molecule, which increases with the increase in
the inductive effect.

CH 3 I CH 3 Br CH 3 Cl
1.648D 1.79D 1.83D
Increasing dipole moment

b) In Bond Length:With increase in inductive effect, the bond length usually

decreases because of increased ionic character,

CH 3 F CH 3 Cl CH 3 Br CH 3 I
1.38Å 1.78Å 1.94Å 2.14Å

c) Strength of Fatty Acids:As the number of alkyl groups attached to –COOH

group increases, the acid strength decreases. Thus formic acid is stronger acid than
acetic acid which is stronger than propionic acid and so on, due to increasing +I effect
of alkyl groups.

O O H3C

H H3C O

O H O H O H
(Formic acid) (Acetic acid) (Propanoic acid)

d) Strength of Substituted Acids:Chlorinated acetic acids are stronger than acetic

acid due to the –I effect of chlorine atom.
O
O
H3C Cl H
+I O
-I
O
H (mono chloro acetic acid)
(Acetic acid)

Larger the number of chlorine atoms, the greater will be –I and the stronger will be
the acid.
Cl Cl

Cl COOH COOH Cl H3C COOH

Cl Cl COOH

The relative strength of the different halogen substituted acids is

FCH2COOH > ClCH2COOH > BrCH2COOH > ICH2COOH

e) Reactivity of Alkyl Halides:The carbon-halogen bond in tertiary alkyl halides is

most reactive while it is least reactive in primary alkyl halides. This can be explained
on the basis of greater +I effect in t-alkyl halides which pushes the –I effect; hence the
bond becomes highly polar and most weak.
 CH3 H3C

H3C Cl Cl H3C H3C Cl

H3C Cl
CH3

ii) Mesomeric Effect or Resonance:Special properties are associated with systems in

which a π-bond is conjugated either with a second π-bond (or) with an atom which
possesses a pair of electrons in a p-orbital. These are: stabilization energy, single bond
lengths which are shorter than those in non-conjugated compounds, and (in some cases)
the modification of dipolar properties.

a) π-bond-π bond conjugation: The simplest example is butadiene,CH2=CH–

CH=CH2. This is symmetrical molecule and conjugation does not lead to the
appearance of a dipole. In valence bond language, contributions from the ionic
+ − − +
structures C H 2 − CH = CH − C H 2 and C H 2 − CH = CH − C H 2 are necessarily equal
and their dipoles therefore, nullify each other. This is not true, however, when π-
bonds of different types are in conjugation. For example in an α, β unsaturated
carbonyl compound such as butenal the contribution of structure (A) is greater than
that of (B) because oxygen significantly more electronegative than carbon the
carbonyl group thus polarizes the C = C bond.

H3C O H3C O
[A] {B}

A group such as carbonyl which withdraws electrons from an adjacent group via the
π-bonding frame work is described as having a – M effect, the –ve sign indicating
electron withdrawal and M standing for mesomeric. Other groups of –M type include
ester, nitrile and nitro etc., and the curved arrows in the representations denote the
direction of the mesomeric effect.
C C C
+
O N N O
O

b) π-bond-p-orbital conjugation:In vinyl chloride (chloroethene) the p-orbital on the

carbon which is attached to chlorine can overlap with both the p-orbital on the second
carbon atom and one of the filled p-orbitals on chlorine three delocalized MO’s are
established of which the two of lowest energy are occupied. Since the p-orbital on
chlorine is initially filled, its participation in the delocalized π system leads to the
partial removal of electrons from chlorine and the appearance of a dipole moment
directed from chlorine towards carbon. This is opposed to the dipole established in C
– Clσ bond as a result of the –I effect of chlorine, with the overall result that the
dipole moment of vinyl chloride (1.44D) is considerably smaller than that of ethyl
chloride (2.0D) in which the –I effect is operative. The capacity of chlorine for
donating electrons into a molecular π-system is described as a +M effect.
 H
H
H H
C
H H2C
Cl
+
Cl H2 C Cl
[A] [B] [C]

In VB terminology, vinyl chloride is described as a hybrid of the structures (B) and (C), the latter
symbolizing the +M effect of chlorine. Both descriptions also indicate that C—Cl bond should be
shorter than in a saturated alkyl chloride, as is found.

Other elements with unshared p-electrons which take part in forming delocalized π -systems
include other halogens, oxygen and nitrogen, e.g.,

CH 2 = CH− OCH 3 CH 2 = CH − N(CH3 )2

In each case the substituent has a + M effect.

Two further points should be noted. First, bond strength is dependent on the extent of the overlap
of the combining atomic orbitals, so that in these conjugated systems the more nearly equal in
size the p-orbitals are, the more effective is the π -orbital overalp. Hence fluorine is more
effective than chlorine in conjugating with carbon, and oxygen is more effective than sulphur.
Secondly, as the nuclear charge in an atom is increased, so also is the hold of the nucleus on the
surrounding electrons so that, for comparably sized atoms, the ability to conjugate decreases as
the atomic number increases. Hence the order of +M effects is

— NR 2 > — OR > — F

+M effect possessing groups are:

—OH, — OR, — NH 2 , — NHR, — NR 2 , — SR, — X
etc.

–M effect possessing groups are:

—CHO, = CO, — CN, — NO 2 , — SO3 H etc.

The low reactivity of halogens bonded to unsaturated carbon is due to the +M effect of the
halogen. The C—Br bond in vinyl bromide has a partial double-bond character due to the +M
effect of bromine with consequent low reactivity of bromine.

CH 2 = CH — Br ←
→ CH 2 — CH = Br

The acidity of phenol is due to the +M effect of OH group. The mesomeric transfer of the lone
pair on the oxygen atom of phenol to the π electrons of the benzene ring results in several
resonance structures with positive charge on the oxygen atom. This aids the hydrogen atom of
OH group to leave as proton.
 OH OH OH OH O

←
→ ←
→ ←
→ H2O
+ H 3O +

The ionization is specially aided due to the formation of the relatively more stable phenoxide ion.
The charge delocalization in phenoxide ion affords greater stability over phenol in which charge
separation occurs in the canonical forms.

O O O O

←
→ ←
→ ←
→

Hence, phenol prefers to ionize, i.e. it is acidic.

Resonance
If a molecule or ion can be shown by two (or) more structures differing only in the distribution of
electrons, but none of these structures truly explains all the properties of that molecule (or) ion,
these structures are called resonating (or) contributing or canonical structures and this
phenomenon is called resonance.

For example, CO 2 molecule can be shown by the following three contributing forms:

O = C = O ←
→ O—C≡O ←
→ O≡C—O

The actual structure of the molecule is a resonance hybrid. This fact is proved from the C—O
bond distance. The actual bond distance is 1.15Å while it should be 1.20Å. The bond shortening
is attributable to the triple bond formation as shown above.

Rules for Drawing valence Bond Resonance Structues

We have already said that resonance effects are encountered mainly in molecules with multiple
(i.e. π) bonds. Except in a few special molecules, the σ -bond framework is not involved in
significant resonance interactions.

This fact can be rationalized by noting that electrons in π bonds are higher in energy than those
in σ bonds, making the π -bonding electrons more reactive and also more polarizable than σ -
bonding electrons.

When a species contains multiple bond(s) it may have several resonance contributors for
example, even a molecule as simple as ethylene has several resonance.
But not all resonance structures contribute equally to the hybrid’s properties. For example, here
are four structures we might write for ethylene:
H H H H H H H H
C C ←
→ C C ←
→ C C ←
?
→ C C
H H H H H H H H
(I) (II) (III) (IV)

The first structure (I) is by far the main contributor. Structure II and III are minor contributors for
three reasons: the π bond has been broken, there are charge separations not present in the major
contributor, and the valence of the +vely charged carbon is unsatisfied. Structure IV does not
contribute at all not only are both carbons’ valences unsatisfied, but previously paired electrons
have become unpaired. From considerations such as these we can devise a list of rules that will
help us determine if a given resonance contributor has a valid structure, and how important its
relative contribution is.

1. In going from one resonance structure to an other no nuclei can change position; only
electrons (bonds) can move.

2. No atom in any resonance structure can ever have more electrons around it than will fill
its valence shell; that is, there should be no more than eight electrons around any second
period element.

3. Most organic structures have no unpaired electrons. But if there are unpaired electrons,
the no. of unpaired electrons cannot change from one structure to the next.

4. The most important resonance contributor’s are those with the maximum no. of covalent
bonds and the minimum number of charge separations.

5. When Zwitterionic charges are present negative charges prefer to be on the

electronegative atoms, with positive charges on the more electro positive atoms. Rules 1,
2 and 3 determine whether a structure is “legal”, while rules 4 and 5 determine the
relative contribution by a resonance structure.

Electromeric Effect
On the close approach of a reagent, the electronic system of an unsaturated molecule is
deformed. when the reagent is removed without allowing the reaction to takes place, the
electronic system reverts to the original ground state of the molecule. This kind of polarizability
of multiple bonds is known as electromeric effect.

Electromeric effect causes complete transfer of the loose π electrons from one carbon to the
other consequently, one end is positively charged and the other negatively charged which aid the
reagent to attack. The shift of the electrons is shown by a curved arrow (↷) indicating the
direction of the electron shift.

C=C →
Re agent
C−C
The effect is temporary since the electrons revert to the original state on removing the reagent.

C=C C−C
Reagent added
Re agent removed

When the multiple bond is between two dissimilar elements the shift of electrons takes place
towards the more E.N of the two. Inductive effect may also determine the direction of the shift of
electrons e.g.,

CH 3 → CH = CH 2

Hyperconjugation
Unlike the usual delocalization which involves electrons, a different type called hyper
conjugation involves σ electrons. This another type of resonance (hyper conjugation) is often
invoked to account for the stabilizing and electron donating effect of an alkyl group. Hyper
conjugation involves deloocalization of C—H sigma electrons into an adjacent pi system. Thus
propene may be described as a hybrid of structures I and II. In canonical forms which involve
hyper conjugation there is no bond between the carbon and hydrogen and therefore this effect has
also been called no bond resonance [sacrifical hyper conjugation, since in II, there is one less real
bond]. Alternatively, the molecular description is that this effect arises from the overlap of σ
orbitals in the alkyl group with the π system.

The evidence for hyper conjugation is that in propene e.g., the C—C single bond is slightly
shorter than in ethane. Thus it is reasoned that C—C single bond in propene acquires some
double bond character. Moreover the heat of hydrogenation of propene (30.1 Kcal/mol i.e., 126
kJ/mol) is less than that of ethene (32.8 kcal/mol i.e., 137 kJ/mol). Hyper conjugation is however,
no longer believed to make any significant contribution to the stability of substituted alkenes. In
fact at present the evidence is against hyper conjugation in the ground states of neutral molecules.
Evidence is there to show that hyper conjugation is indeed important and significantly accounts
for the stability of carbocations and free radicals.
H H+
CH 2 CH = CH 2 ←
→ CH 2 = CH — CH 2
I II

Sacrificial hyper conjugation

H

Hyperconjugation in an alkene: overlap

between σ and π orbitals.

Thus in hyperconjugation in the ground state of neutral molecules, the canonical forms invoke
not only no-bond resonance but a charge separation as well which however not possessed by the
main form.

Effects of Hyperconjugation
1. Stability of Carbonium ions: The order of stability of carboniuim ions is as follows
(CH3)3C+ > (CH3)2CH+> CH3CH2+
above order of stability can be explained by hyper conjugation. In general greater the
number of hydrogen atoms attached to α -carbon atoms, the more hyper conjugative
forms can be written and thus greater will be the stability of carbonium ions.
H
CH3
+
H C H
H3C C 3° carbonium ion
H3C C
CH3
CH3
(9 equivalent forms)

H
CH3
+
H C H
H3C C+
2° carbonium ion
H3C C
H
(6 equivalent forms) H
H
CH3 +
H C H
H C+
H C 1° carbonium
H
H
(3 equivalent forms)

2. Stability of free radicals: Stability of free radicals can also be explained as that of
carbonium ions.

(CH3 )3 C > (CH3 ) 2 CH > CH3CH 2 > CH3

3. Bond lengths: The bond length in a molecule changes if there is hyper conjugation, e.g.,
3 2 1
in propene C H 3 — C H = C H 2 , the C1 — C 2 bond length is found to be more than 1.34Å
while the C2 — C3 bond distance is less than 1.54Å (C—C single bond length).

4. Dipole moment: since hyper conjugation causes the development of charges, it also
affects the dipole moment of the molecule.

5. Orientation influence of methyl group: The O, p directing influence of the methyl group
in methyl benzenes is attributed partly to inductive and partly of hyper conjugation effect.
CH3

[Orientation influence of the methyl group due to +I effect]

The role of hyper conjugation in O,P directing influence of methyl group is evidence by the fact
that nitration of P-isopropyl toluene and p-tert-butyl toluene from the product in which — NO2
group is introduced in the ortho position with respect to methyl group and not to isopropyl or t-
butyl group although the latter groups are more electron donating than methyl groups i.e. the
substitution takes place contrary to inductive effect. Actually this constitutes an example where
hyper conjugation overpowers inductive effect.
H H
H C H H C H

H C CH3 H3C C CH3

CH3 CH3

Reactive Intermediates
A great majority of organic reactions are multistep processes involving intermediates whose life
time are usually very short. An understanding of the structures and properties of these
intermediates which are normal covalent compounds, ions or radical’s is of paramount
importance to an understanding of organic reaction mechanisms. As we shall see in the energy
profile diagrams, intermediates possess sufficiently low energy to be formed under the reaction
conditions, but in most of the cases are not stable enough to permit isolation. This is especially
true of those intermediates in which carbon has fewer than four covalent bonds. A brief
description of some common kinds of intermediates is given below.

Carbocations
Carbocations are the key intermediates in several reactions and particularly in nucleophilic
substitution reactions.

Structure:Generally, in the carbocations the positively charged carbon atom is bonded to three
atoms and has no lone pairs on carbon.

Carbon has six valence electrons.

It is sp2 hybridized with a planar structure and bond angles of about 120°.
R

C
R R
Orbital picture of carbocation
+
There is a vacant unhybridized p orbital which e.g., in the case of C H 3 lies perpendicular to the
sp2 hybridised plane..

Formation: Carbocations can be generated in a variety of way’s some of the reactions in which
carbocations are formed are summarized below.
1. Solvolyis of C—X bond (X = halogens, OBs, etc]
→ R ⊕ + X–
R — X 

2. Deamination of amines by nitrous acid.

R — NH 2 
HNO 2
→ RN ⊕2 
→ R ⊕ + N2

3. Protonation of alcohols followed by dehydration

⊕ ⊕
R — OH →
H
→ R ⊕ + H 2O
R O H 2 

Stability:There is strong evidence, both physical and chemical, that alkyl groups are more
electron-donating than hydrogen. It, therefore, follows that when these groups are attached to the
electron-deficient carbon of the carbocation, they tend to release electrons and partially
compensate for the electron-deficiency of the positive carbon. The positive charge thus gets
dispersed over all the alkyl groups and this dispersal of charge increases the stability of the whole
system. Accordingly, tertiary carbocations are more stable than secondary ones which in turn are
stabler than primary carbocations.

R H H H

R C > R C > R C >H C

R R H H

The greater stability of alkyl substituted carbocations is sometimes partly ascribed to the
phenomenon of hyperconjugation. According to this, the σ electrons of an α C—H bond can be
delocalized into the unfilled p orbital of the positive carbon atom, thus spreading the charge over
all such bonds. For an alkyl-substituted carbocation, several hyperconjugative resonance forms
can be written each having the same number of covalent bonds as the first structure.
H H H H

H C CH2 H C CH2 H C CH2 H C CH2

H H H H

In case of a secondary carbocation, more equivalent structures can be written than for a primary
carbocation whereas still greater number of such structures can be written for a tertiary
carbocation.

H H

H C H H C H
Five more eqivalent
H3C C H3C C structures

H H
 H H

H C H H C H
Eight more eqivalent
H3C C H3C C structures

CH3 CH3

Resonance is an important factor that enhances the stability of a carboaction by delocalization of

its charge in systems like allyl and benzyl carbocations.

CH 2 = H — CH ⊕2 ←
→ CH ⊕2 — CH = CH 2

CH2 CH2 CH2 CH2

←
→ ←
→ ←
→

Triphenyl carbocation is so stable that when triphenylmethyl bromide is placed in liquid sulphur
dioxide (a solvent with which carbocation does not react) it is possible to determine it
quantitatively by measuring the electrical conductivity of the solution.

C6 H 5 C6 H 5

H 5 C6 C Br 
liquid SO2
→ H 5 C6 C + Br

C6 H 5 C6 H 5

CPh2 ←
→ CPh2 ←
→ CPh2

etc. ←
→ CPh2

Steric effects also play key role in the ease of formation and stabilityofcarbocations derived from
highly substituted substrates. The stability of such carbocations is attributed to the steric relief. In
substrates such as tri-isopropyl chloride, the three bulky isopropyl groups are pushed together
due to sp3 angle of 109.5°. This pushing together results in a strain called B strain (or back
strain). When this ionizes, the angle expands from 109.5° ( sp3 ) to 120° ( sp 2 ) resulting in the
relief of this strain due to increase in space between the alkyl groups.
CH3 H3C CH3
H3C HC CH
109.5°
Cl H3C C
H3C CH 109.5° CH 120° CH
CH3
°

CH
9.5

H3C
10

H3C CH3
H3C CH3
Such a carbocation would resist addition of a nucleophle as it would result in the crowding of
bulky groups together.

Carbanions
Carbanions are anions of carbon, generated by the removal of one of the groups attached to a
carbon without removing the bonding electrons. Thus, every carbanion possesses one unshared
pair of electrons and three pairs of bonding electrons around the central carbon atom which is
sp3 hybridized.
R
R' C
R"

We know that the non-bonding electron pair repels the bonding pair more than the bonding pairs
repel each other and because of this, there is reduction of the angle between bonding pairs to a
value slightly lesser than the tetrahedral value of 109.5°. The configuration of simple carbanions
such as the methyl anion thus appears to be pyramidal just like that of ammonia with which the
methyl anion is isoelectronic. With this picture of carbanion, one can infer that if the three
substituents are different, the carboanion should be asymmetric and consequently there should be
retention of configuration in the reactions involving a carbanion intermediate. However, it could
not be demonstrated experimentally as the unshared pair and the central carbon rapidly oscillate
from one side of the plane to the other. This rapid equilibrium between enantiomeric pyramidal
structure thus explains the loss of optical activity associated with the asymmetric carbanions.

R R H
R' C C R' H N
R" R" H

Formation:As there is little difference between the electro negativities of carbon and hydrogen
(2.5 and 2.1, respectively) the polarity of the C—H bond is very small. The heterolytic fission of
this covalent bond to form an anion and a proton should then be a very difficult process. In other
words, a hydrogen atom bound to an sp3 carbon atom shows negligible acidity. However, the
presence of electron attracting substituents such as nitro, cyano or carbonyl groups on the same
carbon renders the hydrogen relatively acidic. The increase in acidity is not only due to the
electron-withdrawing ability of these substituents, but also due to their ability to delocalize the
negative charge of the anion. Thus hydrogens on the carbon atom alpha to nitro, cyano or
carbonyl groups have acidic character and can be removed as protons leaving resonance
stabilized anions.

O O O
⊕

H3C N 
–H
→ H2C N ←
→ H2C N

O O O
⊕
CH3 — C ≡ N 
–H
→ CH 2 — C ≡ N ←
→ CH 2 = N = N 
 O O O
⊕
H3C C H 
–H
→ H2C C H ←
→ H2C C H

Carboanions are also formed when a nucleophile adds to a carbon-carbon double bond.

C 2 H 5 OCH 2 — CH — C ≡ N 
→ 
C2 H 5 O + CH 2 = CH — C ≡ N  b


 C 2 H 5OCH 2 — C = C = N 

Stability:As we have already seen, carboanions are stabilized by electron-withdrawing

substitutents. Generally speaking, a carbanion is stabilized by resonance if a double bond is
located α to the anionic carbon. This explains the stability of the allyic and benzyliccarbanions.

R — CH = CH — CH 2 R — CH — CH = CH 2

CH2 CH2 CH2 CH2

Ready conversion of triphenylmethane to the triphenylmethylcarbanion can be similarly

explained.

(C 6 H 5 )3 CH 
Na
→ (C6 H 5 )3 C Θ : Na ⊕

(C6H5)2 C (C6H5)2 C etc

The order of stability of the simple carbanions is:

methyl> primary > secondary > tertiary

Another factor that contributes to the stability of carbanions is the extent of s-character of the
bonding orbitals of the carboanionic carbon. Carbanion stability, thus, has been found to be in the
order: RC ≡ CΘ > R 2 C = CH Θ > R 3C — CH Θ2 . We have already seen that the carbon atom in
acetylene is sp hybridized (50% s character) and hence hydrogen atom attached to it should be
more acidic than that of ethylene where the carbon is sp 2 hybridized (33% s character).

An interesting example is cyclopentadiene which readily loses a proton to form the

cyclolpentadienyl anion.
  → ≡
–
CH 3O

H H
H H

The unusual stability of cyclopentadienyl anion is explained by the fact that althought it has only
four π electrons, two more electrons become available to it by the heterolysis of the C—H bond
thus forming a system of six electrons. These electrons are spread over all the five carbon atoms
like the delocalized aromatic system of benzene ring, thus conferring on it stability so
characteristic of the aromatic compounds.

Free Radicals
There are two possible structures for simple alkyl radicals. Either a free radical may be a planar
species (A) in which the carbon atom bearing the odd electron in sp 2 hybridized (as in
carbocations) and the odd electron remains in the p-orbital, or it could have a shape resembling a
shallow pyramid (B) which is neither planar nor tetrahedral and the orbital containing unpaired
electron is some sort of a hybrid between a p and an sp3 orbital.

R' R" R R
fast
C or R' C C R'
R" R"
R
(A) (B)

The question as to whether free radicals exist in a planar configuration or in a rapid equilibrium
between the two pyramidal forms (B) is difficult to answer with certainty. However, available
evidence indicates that the unpaired electron is in a p orbital. Resonance stabilized free radicals
certainly exist in planar configuration.

Formation:Free radicals are often produced when a molecule is supplied with sufficient
energy—thermal or photochemical—to cause homolysis of a covalent bond. In addition
oxidation-reduction reactions involving the gain or loss of a single electron can also generate
radicals. Some typical reactions producing free radicals are given below:
∆
(CH3 ) 4 Pb  → 4CH3 + Pb
∆
CH3 — N = N — CH3  → 2CH3 + N 2
∆
C6 H5CO — O — OCOC6 H5  → 2C6 H5COO 
→ 2C6 H5 +2CO2

CH3COCH3 
hv
→ CH3 +COCH3 
→ CH3 + CO
O O

R C O 
anode
– e–
→ R C O 
→ R + CO 2
Stability:In general, it has been found that the stability of alkyl radicals is in the order
(CH3)3C•> (CH3)2CH•> CH3 – CH2• . The reason for the stabilizing influence of alkyl groups is
not far to seek if we consider that in going from methyl to t-butyl, there is increasing tendency
for electron release due to hyperconjugation. As we have seen that the carbon atom carrying an
unpaired electron has a half-filled orbital that gives the radical its characteristic unstability; the
hyperconjugative mechanism tends to fill this orbital and thus stabilizes the radical to some
extent. Various hyperconjugative contributing forms of tert-butyl radical are given below :
CH3 CH 2 H CH3

C C C etc
H3C CH3 H3C CH3 H3C CH 2 H

Allyl and benzyl radicals are particularly stable because of resonance involving π electrons of
the double bond or aromatic ring.
CH 2 = CH — CH 2 ←
→ CH 2 — CH = CH 2
IX

CH 2 CH2 CH2

Another factor that is responsible for the increased stability of tertiary radicals may be steric.
Formation of a tert-butyl radical by the removal of a hydrogen atom from isobutane, (CH 3 )3 CH ,
is favoured as the steric repulsion between the methyl groups is relieved to a certain extent by an
increase in bond angles from 109.5° to about 120°. Clearly this steric relief should be the greatest
in the formation of a tertiary radical.

Carbenes
Carbenes can be defined as neutral, divalent carbon intermediates in which a carbon is covalently
bonded to two atoms and has two non-bonding orbitals containing two electrons between them.
Theoretical considerations suggest that there are two possible kinds of carbenes, singlet and
tripletcarbenes. In the singlet state, a carbon atom is presumed to approximate sp 2 hybridization.
Two of the three sp 2 hybrid orbitals are utilized in forming two covalent bonds whereas the third
hybrid orbital contains the unshared pair of electrons. The unhybridized p orbital remains vacant.
Thus singlet carbene (A) resembles a carbocation very closely. On the other hand, carbon atom
of a triplet carbene (B) is sp hybridized and it is a linear or near-linear species. These two hybrid
orbitals are involved in the bond formation with two groups and the two electrons are placed one
each, in the equivalent, mutually perpendicular p y and p z orbitals. Since these electrons have
parallel spins, a carbene with this structure is said to be in a triplet state.
 R R
C C
R' R'

(A) (B)

At first sight, it appears that a singlet carbene has lower energy as the unshared electron pair is in
a sp 2 hybrid orbital; but the considerations of the electron repulsion energy that must be
overcome to pair two electrons in a single orbital places it at the higher energy level than a triplet
structure. It is, therefore, reasonable to believe that the triplet state of a carbene is more stable
than the singlet state and should be expected to be the ground state.

Formation:Photochemical or thermal cleavage of cyclopropanes and oxiranes is a common

method for the generation of carbenes.
H5C6 CH2
C CH2 →
hv
or ∆
H 2 C + C6 H 5 CH = CH 2
H

H5C6 O O
C CH 
hv
→ C6 H5 HC + HC — C6 H 5
H C6 H 5

Stability:Carbenes in which the carbene carbon is attached to two atoms, each bearing an
unshared pair of electrons, are somewhat more stable due to resonance.

R2 N R2 N R2 N
C ←
→ C ←
→ C
R2 N R2 N R2 N

Nitrenes
Nitrenes are electron-deficient monovalent nitrogen species in which the nitrogen atom has a
sextet of electrons in its outer shell. There are two possible forms in which a nitrene can exist, the
singlet and triplet states.

R—N R—N
singlet triplet

Arynes
Arynes may be defined as aromatic compounds containing a formal carbon-carbon triple bond.
The best known aryne is benzyne which may be regarded as the aromatic counterpart of
acetylene or in other words, it is benzene minus two orthohydrogens and can also be called as
dehydrobenzene.

The benzyne bond is not like the triple bond of acetylene where the two carbons form a σ bond
using sp orbitals and the remaining p orbitals are used to form π bonds. Such a structure is not
possible in benzyne because of the hexagonal geometry associated with the benzene ring. Most
probably the new bond of benzyne is formed by the overlap of sp 2 orbitals belonging to two
neighbouring carbon atoms. These sp 2 orbitals are orthogonal to the π molecular orbital of the
benzene ring.

Formation:Benzyne has been shown to be intermediate in several important organic reactions.

For example, in the presence of a strong base, aryl halides eliminate HX from 1, 2-positions to
produce benzyne which then rapidly reacts with the available nucleophile to regenerate the
aromatic system.

Br
+ NH 2 
→ + NH 3 +Br
H

NH3 NH2
+ NH 3 
→ 
→

Stability:The new bond of benzyne, formed by the overlap of sp 2 orbitals belonging to two
neighbouring carbon atoms in unstable, and therefore benzynes are extremely reactive chemical
species.

Isomerism
Different organic compounds with the same molecular formula but different physical and
chemical properties are called isomers and the general phenomenon is known as isomerism. It is
classified as follows.
 ISOMERISM

Stereoisomerism
Structural
(constitutional)
Isomerism

Chain Position Functional Metamerism Ring Chain Tautomerism

Optical Geometrical

Structural Isomerism
Compounds which possess the same molecular formula but differ in bonding arrangement of
atoms (or) groups within the molecule i.e. differ in structure [A structural formula for a
compound conveys which atom is directly linked to which other atom. It, however, tells nothing
about the shape of the molecule but indicates the groups of elements present which provide clues
to the properties of the substance], are structural isomers and this phenomenon is known as
structural isomerism.

i) Chain or Nuclear Isomerism:In this type the isomers differ in the variation of the
carbon chain (or) skeleton of the molecule. The same molecular formula may represent a
straight chain of carbons as well as a branched chain. The molecular formula C4H10
stands for two isomers namely n-butane and isobutane.
H3 C CH3
CH
CH 3CH 2 CH 2 CH 3 ≡ and ≡
n − Bu tan e
CH3
isobutane (2 methyl propane)

C5H12 stands for three chain isomers

i) CH 3CH 2 CH 2 CH 3CH 3 ≡
(n-pentane)
ii) CH3

CH CH3
≡
H3C CH2
isopentane
iii) CH3
H3C C CH3 ≡
CH3
neopentane (2,2-dimethyl propane)

Cyclohexane and methyl cyclopentane are nuclear isomerism

 CH3
CH2
H2C CH2 CH
H2C CH2
H2C CH2 H2C CH2
CH2

C4H10O
CH3

OH
H3C OH and H3C
butan-1-ol 2-methylpropan-1-ol

Illustration 1: Give the possible chain isomers of C5H12.

CH3
|
Solution:
CH3 – CH2-CH2 – CH2-CH3, CH 3 − C H − CH 2 − CH 3 , CH 3 − C − CH 3
| |
CH 3 CH3
n-pentane isopentaneneopentane

Illustration 2: Give the possible chain isomers for C5H13N

Solution: NH2
H 3C CH3

H 3C NH2 H 3C

CH3 NH2
CH3

ii) Position Isomerism:In it, the isomers differ in the attachment of the functional
group (or) substituents to the carbon chain. This is illustrated by the following examples.

i)
CH 3CH 2 CH = CH 2 ≡ and CH 3 − CH = CH − CH 3 ≡
but-1-ene but-2-ene

ii) Cl
Cl and H3C
H3C
1-chloropropane CH3
2-chloropropane
 iii) CH3

H3 C CH3 and H3 C CH3

3-methylpentane
CH3
2-methylpentane
Illustration 3: Give the possible positional isomers of xylene

Solution: CH3
CH3
CH3
CH3

CH3 CH3
o-xylene m-xylene p-xylene

Note: In the aromatic series, the disubstitution products of benzene also exhibit isomerism due to
different relative positions occupied by the two substituents on the benzene ring.

iii) Functional Isomerism:If the molecules have the same molecular formula but differ
in the type of the functional group, then it is known as functional group isomerism. A few
examples of functional isomers are:
a) Molecular p-alcohol s-alcohol t-alcohol Ethers
formula
H3C H3C O
C 2 H6 O –– ––
OH CH3
ethanol dimethyl ether

C 3 H8 O OH H3C –– H3C O
H3C
OH CH3
H3C
OH CH3
C4H10O H3C OH H3C O CH3
CH3 CH3 H3C CH3 O
H3C H3C CH3
OH OH
H3C O
H3C
CH3
H3C
b) Monocarboxylic acids and esters are functional isomers
H3C O

OH and H3C

O O
propanoic acid
H3C
methyl acetate

c) Aldehydes, ketones, unsaturated alcohols and alkene oxides are functional isomers.
i) H3 C H 2C O
C2H4O OH
O Ethylene oxide
Ethanal Vinyl alcohol
 ii) O
H3C H2C
H3C OH
C3H6O
O CH3 Allyl alcohol
Propanal Propanone

iii) Cyanides are isomeric with isocyanides

RCN (Alkyl cyanide) RNC (alkyl isocyanide)

iv) Nitroalkanes are isomeric with alkyl nitrites

O
R O
R N
N O
O
Nitroalkane Alkyl Nitrite

v) Aromatic alcohols may be isomeric with phenols

OH
CH3

OH

phenylmethanol o-cresol

vi) Sometimes a double bond containing compound may be isomeric with a triple
bond containing compound. This is also called as functional isomerism. Thus
butyne is isomeric with butadiene (Molecular formula C4H6)
H3C H2C

CH CH2
but-1-yne buta-1,3-diene

vii) Primary, secondary and tertiary amines of some molecular formula are also the
functional isomers.
CH3
H 3C H3C NH
H3C N
NH2 C 2H5
CH3
propan-1-amine N-ethyl-N-methylamine N,N,N-trimethylamine

Illustration 4: Give the functional isomer for acetic acid

Solution: O O

H3C H

OH O CH3
acetic acid methyl formate
Monocarboxylic acids and Ester’s are functional isomers.
Illustration 5: Give the functional isomer of nitropropane

Solution: CH3 – CH2 - CH2 – O – N = O

propane nitrite
Nitro and nitrite both are functional isomer.

Illustration 6: Give the functional isomers for C4H8O

O
||
Solution: CH3 – CH2 – CH2 – CHO, CH 3 - CH 2 - C- CH 3 , CH2 = CH – CH2 – CH2OH

iv) Metamerism:It arises when different alkyl radicals are joined with the same divalent
functional group present in the molecule, e.g. ethers, thioethers, secondary amines,
ketones, esters etc.
a) H C O H 3C O
3 O CH 3 H 3C CH3
CH3
diethyl ether 1-methoxypropane
H3C
2-methoxypropane
b) S H3C S
H 3C S CH3 H 3C CH3
CH3
(ethylthio)ethane 1-(methylthio)propane
H 3C
2-(methylthio)propane

Illustration 7: Give the metamers of C4H10O

Solution: CH3 – CH2−CH2− O – CH3, CH3 – CH2 – O – CH2 - CH3

1-methoxypropane ethoxyethane

Solution: O

O CH3 CH3
H3C H3C O
propyl acetate
O
ethyl propionate

v) Ring Chain Isomerism:This type of isomerism is due to difference in way of

linking of carbon atoms and the isomers may have either open chain (or) closed chain
structure e.g. alkenes and cycloalkanes.

a) C3H6
H3C
CH2
cyclopropane
prop-1-ene

b) C4H8
 CH2
H 3C H 3C
H3C CH3
CH2 CH3
CH3 cyclobutane methylcyclopropane
but-1-ene but-2-ene
2-methylprop-1-ene

c) C6H12

H3C CH3
CH2
hex-1-ene
cyclohexane methylcyclopentane
Note: Ring chain isomers are always functional isomers.

Tautomerism
It is a special type of functional isomerism in which the isomers are readily interchangeable and
maintain a dynamic equilibrium with each other. Hence, the name dynamic isomerism. Both the
isomers represent one and a single substance. This isomerism is caused by the oscillation of a
hydrogen atom between two polyvalent atoms with necessary rearrangement of linkage.

This type of isomerism in which a substance behaves as if it has two different structures is known
as tautomerism and different forms are called as tautomers. Tautomerism is also known as
desmotropism (Desmos = bond, tropos = turn)

Structural requirement for tautomrism

i) Compound should have electronegative atom bonded with multiple bond (i.e. N and O).

ii) Compound should have atleast one acidic hydrogen present on α-carbon of the molecule.

It is two conditions are fulfilled then compound will show tautomerism. For example.
O O
α Electronegative atom α Electronegative atom
H3C H3C

H CH3
α Electronegative atom
N Electronegative atom
H 3C
α
N O H3C
CH3
O

These compounds fulfill both the conditions, hence these will show tautomerism.

CH3 O C 6H 5 O C 6 H5

H 3C H3C N H5 C 6

α CH3 H α C 6 H5 O α CH3 N
In these compounds electronegative atom is bonded with multiple bond but compound has no
hydrogen on α-carbon hence these compounds will not show tautomerism.

If compound has active methylene group (or) active methyne group then α-carbon for
tautomerism is always carbon of active methylene (or) methyne group. For example
O
α
H 3C
α O CH 2 O O α CN
CH 2 HC
α
NC CH 2
H5C 2OOC CH3 CH3 H 3C CH3
CN
active methylene group active methylene group active methylene group

These compounds will also show tautomerism because these compounds fulfill both structural
requirements.

Cause of tautomerism:Migration of acidic hydrogen from α-carbon to electronegative

atom which is bonded with multiple bond is the cause of tautomerism and this phenomenon is
known as tautomerism.
OH
CH3 H2C
H
CH3
O
(I) (II)

i) Both (I) and (II) are isomers known as tautomers.

ii) Tautomers are always in equilibrium state.
iii) Number of sigma, pi and lone pair of electrons in both tautomers are always same.
iv) Tautomerism is a chemical phenomenon which takes place only in liquid state.
v) Tautomersim is catalysed by acid as well as base.
vi) Tautomers are always reversible functional groups, functional isomers.

Tautomerism is of several types the two important types are dyad and triad systems.

a) Dyad System:It involves the oscillation of H atom between two polyvalent atoms, e.g..,
hydrogen cyanide (I) and hydrogen isocyanide (II).

H N H N C
(I) (II)

In the above example the H atom vibrates between carbon and nitrogen atoms. The alkyl
derivatives of (I) are called cyanides while those of (II) isocyanides.

b) Triad System:In it one H atom oscillates between three polyvalent atoms.

i) Keto-enoltautomerim:In this case the polyvalent atoms are one oxygen and two
carbon atoms, e.g. aceto acetic ester, acetyl acetone, benzoyl acetone, acetaldehyde,
acetone, phenol etc.
The form containing keto (oxo) group is called keto while that having alkene and –ol
functions is called an enol form.
H
H 3C O
O O
C 2 H5
C 2 H5
OH O
CH3 O
keto form enol form
H 3C CH3 H 3C CH3

O O OH O
keto form enol form
H5 C 6 CH3 H 5C 6 CH3

O O OH O
keto form enol form

the conversion of a keto form into enol form is known as enolization. It is catalysed
by the presence of acid (or) alkali. This dynamic isomerism is shown only by those
aldehydes, ketones or esters which have at least one labile α-hydrogen atom. For
example, benzaldehyde and benzophenone do not have labile α-hydrogen, hence these
do not show tautomerism.
O O

H5 C 6 H 5C 6 (absence of α-H atom)

H C 6H 5

On other hand, acetophenone contains α-H atoms, hence exhibits tautomerism.

O OH

H5 C 6 H5 C 6
α
CH3 CH2
Keto form Enol form
Enolization is in the following order:

CH3COCH3< CH3COCH2COOC2H5 < C6H5COCH2COOC2H5

< CH3COCH2CHO < CH3COCH2COCH3

In compounds whose molecules have two carbonyl groups separated by one –CH2 –
group (called β-dicarbonyl compounds), the amount of enol present at equilibrium is
far higher e.g.
OH O
O O

H 3C CH3
H 3C CH3
(76%)
(24%)

the greater stability of the enol form of β-dicarbonyl compounds can be attributed to
stability gained through resonance stabilization of the conjugated double bonds and
(in a cyclic form) through hydrogen bonding.
 H H
O O O O

H 3C CH3 H 3C CH3

H H

Percentage of enolic contents of some common compounds in decreasing order is given below:
O O O O O

H5C 6 CH3 H3C CH3

O O
O O
O O

H3C CH3 H3C

H3C
H3C O

C 2H5

Percentage Composition of Tautomeric Mixture: Percentage of enol contents of

some compounds is given below in the table.
Enol content of some compounds
Compound Enol Percentage Compound Enol Percentage
O O
O
H3C 0.00025 31.00
H3C O
CH3
CH3 CH3
O
O O
CH3 0.0056 80.4
H3C
H3C CH3
O
O O
O O

H3C O 4.8 89.0

H5C 6 CH3
CH3
O O O

7.7
H 3C O 99.99
C 2H 5

The conversion of a keto form into an enol form is known as enolisation and the enolisation of a
compound has been found to depend upon various factors such as structural factor, temperature
and nature of solvent. However, the most important is the structural factor (resonance and
hydrogen bonding).

i) Ketonic form predominates in simple monocarbonyl compounds like acetaldehyde,

acetone and cyclohexanone. This is due to the greater bond strength of C = O {>C = O,
365 kJ/mole) present in keto form than the carbon-carbon double bond (C = C, 250
kJ/mole) present in enolic form.

ii) Enolic form predominates in β-di ketones due to intramolecular hydrogen bonding and
resonance. Intramolecular hydrogen bonding stabilizes enol form by 7 kcal/mole and
resonance stabilizes enol form by 15 kcal/mole. Thus enol form is more stable than keto
form by 22 kcal/mole in 1,3-diketones.
O O
H H
O O O O
H3C CH3
H3C CH3 H 3C CH3

H H H H
O O O O O O O O

H 3C CH3 H 3C CH3 H3C CH3 H 3C CH3

ii) Triad System containing Nitrogen

a) Nitrous acid exists in two tautomeric forms:

O
H O
H N
N O
O
Nitrite form
Nitro form

The alkyl derivatives of nitro form and nitrite form are called as nitro alkanes and
alkyl nitrites, respectively.

b) Primary and secondary nitroalkanes have liable α-H atom, hence exhibit nitro-aci
nitro type of tautomerism.

H3C
α H3C

N O N OH

O O
Nitro form (I) Aci form (II)

c) Nitroso-isonitro System: In this system one tautomer exits as nitroso while the other
tautomer exists as an isonitroso (oxime) form.

OH
O
H3C N
H3C N
Nitroso form Isonitroso form

d) Imine-Enamine System

H3C H3C
NH NH2
Imine Enamine

Mechanism of tautomerism:Acid catalysedtautomerism is a two step process.

i) Proton transfer from the acid catalyst, H—A, to the carbonyl oxygen forms the conjugate
acid of the aldehyde (or) ketone.

O O H

H 3C C CH3 + H — A
fast
H 3C C CH3 + : A
(conjugate acid of ketone)

ii) Proton transfer from the α -carbon to the base, A Θ gives the enol and generates a new
molecule of the acid catalyst, H—A.
 O H OH

H3C C CH2 H
slow
H3C C CH2 + H — A
Enol form

with unsymmetrical ketones, enolization may occur in either of two directions.

OH O OH
α α
H2 C C CH2 CH3 H3 C C CH2 CH3 H3 C C CH2 CH3
but-1-en-2-ol 2-Butanone but-2-en-2-ol

the ketone is by far the most abundant species present at equilibrium. Both enols are also
present, but in very small concentrations. The enol with the more highly substituted
double bond is themore stable of the two enols and is present in higher concentration than
the other.

* Percent enol content α conjugation

α /Temperature
α /Hydrogen bonding
α /Base strength
Stereoisomerism: When isomer’s have the same structural formula but differ in relative
arrangements of atoms or groups in space within the molecule, these are known as stereosiomers
and the phenomenon as stereoisomerism
Stereo isomers can be configurational isomers or conformation isomers.
The fixed relative spatial arrangement of atoms in the molecule is known as configuration.
A particular orientation (or arrangement) of atoms in a molecule, differing from other possible
orientations by rotation around single bonds is known as conformation.

Configurational isomer’s can be geometrical isomers (or) optical isomers.

Geometrical Isomerism: Configurational stereo isomer’s arising due to different

arrangements around carbon-carbon double bond are known as geometrical isomers. Those
stereoisomer having same structural formula but differing in spatial arrangement of the group
around the double bond are known as geometrical isomers and the phenomenon as geometrical
isomerism.

Since the presence of pi ( π) bond above and below the plane of sigma (σ) bond lock’s the
molecule in a fixed position, hence alkene derivatives of the formula abc=cab can be written by
two spatial arrangement.
a c b a c b

a c b b c a
I (cis) II (trans)
In spatial arrangement (I) similar groups are present on the same side of double bond, while in
(II) the similar groups are present on the opposite side of the double bond. Hence spatial
arrangement (I) is called cis, whereas (II) as the trans-isomer. Such type of geometrical is called
as cis-trans isomerism.

Reason of Occurrence of geometrical Isomerism: When the two atoms are joined
together by a double bond (>C=C<), one pi and one sigma, free rotation about the carbon-carbon
double bond becomes restricted (hindered) hence the spatial arrangements of atoms (or) groups
attached with these carbon atoms becomes fixed in space and it represents two different isomers.
Thus lack of free rotation about carbon-carbon double bond gives rise to geometrical isomersm.

In general the necessary and sufficient conditions for the occurrence of geometrical isomersm are
(i) restricted (hindered) rotation of the carbon-carbon double bond and (ii) both the doubly
bonded carbons should have different substituents.

Van’t Hoff explained the occurrence of cis-trans isomers on the basis of tetrahedral conception of
carbon atom. According to him a double bond may be created by placing the two tetrahedrons
edge-to-edge; such an arrangements would be rigid and free rotation around the double bond
would be restricted.

Thus for a compound of the general formula abc=cab, two spatial models can be constructed
where free rotation would be impossible.

The simple examples showing geometrical isomerism are given below.

H3C CH3 H3C H

2-Butene
H H H CH3
cis-2-butene trans-2-butene

H H H CH2 CH3

3-Hexene
H3C CH 2 CH 2 CH3 H3C CH2 H
cis-3-Hexene trans-3-Hexene

H C COOH H C COOH
Maleic and
H C COOH HOOC C H
Fumaric acids
Malic acid (cis) Fumaric acid (Trans)

Geometrical isomerism in the compounds containing C=N: Oximes of aldelydes

and unsymmerical ketones, i.e., aldoxines and unsymmetrical ketoximes are the best examples of
the occurrence of such geometrical isomerism.

Benzaldoxime (C6 H 5 — CH = NOH) has the following two geometrical isomers.

 H 5 C6 C H H 5 C6 C H

N OH HO N
syn anti

Geometrical isomerism in the compounds containing N=N: The simplest

example is that of azobenzene

N N
It has following two geometrical isomers.

C6H5 C6H 5
N N

N N
C6H5 H 5C6
syn anti

Geometrical Isomerism in Cyclic Compounds: In cyclic compounds there can be no

free rotation about carbon-carbon single bonds because rotation would break the bonds and break
the ring system. for example, 1,2-dimethyl cyclopropane exists in two isomeric forms.
H H H3C H

CH3 CH3 H CH3

cis-1,2-dimethylcyclopropane trans-1,2-dimethylcyclopropane

Stability of cis, Trans (or) Geometrical isomers: The trans isomers of alkenes are
usually more stable than their corresponding cis isomers.

A B
A C B C

A C B C
B A
cis-isomer

The reason for this becomes clear if we consider the cis and trans-isomers of the alkene
ABC=CAB in which `A’ is a bulky group as compared to `B’ (e.g., CH3 — HC = CH — CH3 ) .
In the cis isomer, the two bulky `A’ groups are very close to each other. The repulsion due to the
overlapping of the electron clouds of the two bulky `A’ groups will make this isomer less stable
than trans isomer in which the bulky `A’ groups are far apart [being on the opposite sides of the
double bond].

Number of Geometrical isomers

a) In compounds containing more than one double bond, the number of geometrical isomers
(N) is given by the formula
 N = 2n
where n = no. of double bonds with different substituents at each end.
For example, R—CH=CH—CH=CHR has 4 isomers.

b) When the ends of an alkene are the same and n is the no. of double bonds, then the no. of
geometrical isomers is given as :
N = 2 n –1 + 2p–1
n
where p = when n is even
2
n +1
and p = when n is odd.
2
For example: CH 3 — CH = CH — CH = CH — CH = CH — CH 3 , has the no. of
geometrical isomers.
N = 23–1 + 22–1 = 22 + 2 = 4 + 2 = 6

E and Z nomenclature of geometrical isomers: If all the four groups/atoms’

attached to C=C double bond are different, then cis and trans nomenclature fails in such cases
and a new nomenclature called E and Z system of nomenclature replace it.
H I higher H I higher
priority C priority
C

C C
higher Br Cl Cl Br higher
priority priority
E Z
I II
The group/atom attached to carbon-carbon double bond is given to higher rank, whose atomic
weight is higher. If two higher ranked group are across, it is called E form (E stands for the
German word entgegen meaning there by opposite) and the two higher ranked groups are on the
same side, they are called Z-form (Z stands for German word Zusummen meaning there by on
the same side.)

If the first atom is common in the groups, then the priority is given to the second atom in the
group.

Optical Isomerism:Certain substances possess the property to rotate the plane of polarized
light. such substances are called optically active substances and this phenomenon is called optical
activity.

Optical Activity:Light is propagated by a vibratory motion of the `ether’ particles present in

the atmosphere. Thus in ordinary light vibrations occur in all planes at right angles to the line of
propagation. In plane polarized light the vibrations take place only in one plane, vibrations in
other planes being cut off. Plane polarized light can be obtained by passing ordinary light through
a Nicol prism.
 Ordinary light Nicol prism Plane polarized waves
waves vibrating in vibrating in one direction
all directions

Plane rotated Plane polarized Plane rotated

to the right light to the left

Certain organic compounds, when their solutions are placed in the path of a plane polarized light,
have the remarkable property of rotating its plane through a certain angle which may be either to
the left (or) to the right. this property of a substance of rotating the plane of polarized light is
called optical activity and the substance possessing it is said to be optically active.

The observed rotation of the plane of polarized light [determined with the help of polarimeter]
produced by a solution depends on: (a) the amount of the substance in tube; (b) on the length of
the solution examined; (c) the temperature of the experiment; and (d) the wavelength of the light
used.

The instrument used to measure angle of rotation is called polarimeter. The measurement of
optical rotation is expressed in terms of specific rotation [α ]Dt ; this is given by the following
relation:

α obs
[α ]Dt =
l×c
where α = observed angle of rotation
[α ]Dt = specific rotation determined at t°C, using D-line of sodium light.
l = length of solution in decimeters
C = concentration of the active compound in grams per milliliter.

For example, the specific rotation of amyl alcohol [2-methyl-1-butanol] at 25°C for D-line of
sodium light is given by.
°
[α ]25
D = –5.756°

The sign attached with the angle of rotation signifies the direction of rotation. Negative sign (–)
indicates that the rotation is towards the left, while positive (+) sign means that the direction of
rotation is toward right.

The rotation may be different in different solvents and this needs to be mentioned while reporting
the specific rotation. Thus,
°
[α ]25
D = +24.7° (in chloroform)
Asymmetric carbon (or) Chiral Carbon: If all the four bonds of carbon are satisfied by
four different atoms/groups, it is chiral. Chiral carbon is designated by an asterisk (*).

Optical isomerism in bromochloroiodo methane: The structural formula of

bromochloroiodomethane is

Br

H C Cl

I
The molecule has one chiral carbon as designated by star. So molecule is chiral. It is non-super
imposable on its mirror image.

According to Van’t Hoff rule.

Total number of optical isomers should be = 2 n .
where n is number of chiral centre.

The fischer projections of the two isomers are

Br Br

H I I H

Cl Cl
(i) (ii)

These are optically active, which are non-super imposable mirror image of each other and can
rotate plane of polarized light.

Stereosiomers which are mirror-image of each other are called enantiomers (or) Enantimorphs.
(i) and (ii) are enantiomers. All the physical and chemical properties of enantiomers are same
except two:

i) They rotate PPL to the same extent but in opposite direction. One which rotates PPL in
clockwise direction is called dextro-rotatory (dextro is Latin word meaning thereby right]
and is designated by d (or) (+). One which rotates PPL in anti-clockwise direction is
called laevo rotatory (means towards left] and designate by l (or) (–).

ii) They react with optically active compounds with different rates.

Optical isomerism in compounds having more than one chiral carbons: If

an organic molecule contains more than one chiral carbons then the molecule may be chiral (or)
achiral depending whether it has element of symmetry or not.

Elements of symmetry: If a molecule have either.

a) a plane of symmetry, and/or

b) centre of symmetry, and/or
c) n-fold alternating axis of symmetry.

If an object is super imposable on its mirror image; it cannot rotate PPL and hence optically in
active. If an object can be cut exactly into two equal halves so that half of its become mirror
image of other half, it has plane of symmetry.
COOH

H C OH (I)
Mirror Plane

H C OH (II)

COOH
(I) and (II) are mirror images, hence plane of symmetry is present in the molecule.
COOH

H C OH (I)
Mirror Plane

HO C H (II)

COOH

(I) and (II) are not mirror images, hance plane of symmetry is absent in the molecule.

Centre of Symmetry:It is a point inside a molecule from which on travelling equal distance
in opposite directions one takes equal time.

A centre of symmetry is usually present only in an even numbered ring. For example, the mole of
trans-2, 4-dimethyl-cyclobutane-trans-1, 3 dicarboxylicacid has a centre of symmetry.
CH3 COOH

H
H
H H

COOH CH3

Thus, if an organic molecule contains more than one chiral carbon but also have any elements of
symmetry, it is super imposable on its mirror-image, cannot rotate PPL and optically inactive. If
the molecule have more than one chiral centres but not have any element of symmetry, it must be
chiral.

Stereoisomerism in Tartaric Acid: Compounds which contain two asymmetric carbon

atoms and are of the type Cabc–Cabcexist in only three isomeric forms. Two of these are non-
superimposable mirror images of each other and are optically active and the third, a
diastereomerof the first two, contains a plane of symmetry, is super imposable on its mirror
image, and is not optically active, e.g.,
OH CO2H
OH
OH CO2H
H C OH
CO2H HO2C
HO2C HO2C
CO2H OH
OH H C OH
OH
l (-) tartaric
acid d (+) tartaric CO2H
Mesotartaric
acid acid

The inactive diastereomer is usually described as a meso form. As with other examples of
diastereomers, the properties of meso forms are different from those of the isomeric mirror-image
pairs; for example, mesotartaric acid melts at a lower temperature [140°C] than the d and l
isomers [170°C], and is less dense, less soluble in water, and a weaker acid.

Compounds with two asymmetric carbon atoms in which at least one substituent in not common
to both carbons occur in four optically isomeric forms, e.g., the four isomers of structure.

H H

H3C C C CH2 CH3

Br Br
2,3-dibromopentane
CH3 CH3 CH3 CH3

H C Br Br C H H C Br Br C H

H C Br Br C H Br C H H C Br

H2 C CH3 H3C CH2 H2C CH3 H3C CH2

(i) (ii) (iii) (iv)

In general, a compound possessing n distinct asymmetric carbon atoms exists in 2 n optically

active forms.

It should be noted that, whereas (i) and (ii) and (iii) and (iv) are mirror-image pairs and therefore
have identical properties in a symmetric environment, neither of the (i) and (ii) bears a mirror-
image relationship to either of those (iii) and (iv). These and other stereoismers which are not
enantiomers are described as diastereomers (or diastereo isomers) and, unlike enantiomers, they
differ in physical and chemical properties.

Calculation of number of optical isomers:The number of optical isomers of an

organic compound depends on its structure and number of asymmetric carbon atoms. thus, the
number of optical isomers may be determined from the knowledge of the structure of the
compound as follows:

1. When the molecule is unsymmetrical

No. of optically active isomers, a = 2 n
 Number of meso forms (m) = 0
a
Number of racemic mixtures, r =
2
∴ Total no. of optically active isomers = (a + m) = 2n

2. When the molecule is symmetrical and has even no. of asymmetric carbon atoms.
No. of optically active isomers, a = 2(n –1)
No. of meso forms, m = 2[n / 2–1]
a
No. of racemic mixtures, r =
2
∴ Total no. of optically active isomers = a + m.

3. When the molecule is symmetrical and has an odd no. of asymmetrical carbon atoms.
no. of optically active isomers, a = 2(n –1) – 2(n / 2–1/ 2)
1
(n / 2– )
No. of meso forms, m = 2 2

∴ Total no. of optically active isomers = (a + m) = 2(n –1)

Optically active compounds having no asymmetric carbon:

1. Allenes:Ansp-hybridized carbon atom possesses one electron in each of two mutually

perpendicular p orbitals. When it is joined to two sp2-hybridized carbon atoms, as in
allene, two mutually perpendicular π -bonds are formed and consequently the π-bonds to
the sp2-carbons are in perpendicular planes. Allenes of the type abC=C=Cab (a ≠ b) are
therefore not superimposable on their mirror images and despite the absence of any
asymmetric atoms, exist as enantiomers and several optically active compounds have
been obtained. (e.g. a = phenyl, b = 1-napthyl)
py px
b a a b
C C C C C C

pz a b b a
pz
Molecular orbital
diagram of allene

2. Any molecule containing an atom that has four bonds pointing to the corners of a
tetrahedron will be optically active if the groups are different.
16
O

CH2 S CH3

18O

3. Alkylidenecyclo alkanes:The replacement of one double bond in an allene by a ring

does not alter the basic geometry of the system and appropriately substituted compounds
exist in optically active forms.
 H CO2H

H3C H

Related compounds in which sp2-carbon is replaced by nitrogen have also been obtained
as optical isomers.

H OH
N
CO2H

Difference between Racemic mixture and Meso compound: A racemic mixture

contains equimolar amounts of enantiomers. It is optically inactive due to external compensation.

External compensation: If equimolar amounts of d and l-isomers are mixed in a solvent, the
solution is inactive. The rotation of each isomer is balanced (or) compensated by the equal but
opposite rotation of the other. Optical inactivity having this origin is described as due to external
compensation. Such mixtures of (+) and (–) isomers (Racemic mixtures) can be separated into
the active components.

A meso compound is optically in active due to internal compensation.

Internal compensation: In meso tartaric acid the inactivity is due to effects within the
molecule and not external. The force of rotation due to one of the molecule is balanced by the
opposite and equal force due to the other half. The optical inactivity so produced is said to be due
to internal compensation. It occurs whenever a compound containing two (or) more asymmetric
carbon atoms has a plane (or) point of symmetry. Since the optical inactivity of such a compound
arises within the molecule, the question of separating into active components does not arise.
Solved Problems
Objective

Problem 1: In which of the following alcohols C – O bond breaks (heterolytically) with

greatest ease:
CH3
(a) CH3CH2CH2OH (b)
CH3 – CH – OH
CH3 CH3
(c) CH3 – C – OH (d) CH3 – C – CH2 – OH
CH3 CH3

Solution: Breaking of C – O bond results in formation of most stable tertiary

carbocation.
∴ (c)

Problem 2: Which of the following carbocation is least stable

+
CH2
+
(a) (b) C H = CH 2

CH3
+
(c) CH 2 = CH − C H 2 (d) CH3 – C+
H

Solution: Positive charge is on sp hybridized carbon.

∴ (b)

Problem 3: A compound contains 2 dissimilar asymmetric carbon atoms. The number of

optical isomers is:
(a) 2 (b) 3
(c) 4 (d) 5.

Solution: a = 2n , where n is no. of dissimilar asymmetric carbon atoms.

∴ (c)

Problem 4: Which of the following carbocations is expected to be most stable?

CH3 CH3

(a) (b)

X H X H
 CH3 CH3

(c) (d)
H H

X X

Solution: Here in the given problem, carbocation (b) is stabilized most, as the CH 3 (e–
releasing group) group is attached to the carbon bearing positive charge.
∴ (b)

Problem 5: keto-enol isomerism is observed in

O O
(a) (b)
C6H 5 C H C6 H5 C CH3
O CH3
O
(c) (d) C 6 H5 C C C6H5
C 6H 5 C C 6H 5
CH3

Solution: For a compound to exhibit keto-enol isomerism, presence of α -hydrogen is

necessary. This is satisfied only by acetophenone.
∴ (b)

Problem 6: Which of the following has the most acidic hydrogen?

(a) 3-hexanone (b) 2, 4-hexanedione
(c) 2, 5-hexanedione (d) 2, 3-hexanedione.

Solution: (a) H 3C CH3 (b) H3C CH2 CH2

C C CH3

O O O
(c) O (d) O
H3C CH2 C CH3
C CH2 CH3 H3 C
O O
*
The most acidic hydrogen is the H attached to the C in (b) as the negative
charge on it after removal of proton is extensively delocalized as compared to
the all other due to the two carbonyl groups which are adjacent to this carbon.
∴ (b)

Problem 7: Of the following order of reactivity of Cl with AgNO3, which one is correct?
(a) CH2 = CH –CH2Cl > CH3CH2CH2Cl > CH3CH = CHCl
(b) CH2 = CH – CH2Cl > CH3CH2CH2Cl < CH3CH = CHCl
(c) CH2 = CHCH2Cl < CH3CH2CH2Cl > CH3CH = CHCl
(d) CH2 = CHCH2Cl < CH3CH2CH2Cl < CH3CH = CHCl.

Solution: CH 2 = CHCH 2 Cl is an allylic chloride that reacts with AgNO3 in the cold to
give a white precipitate of AgCl.
 CH 3CH 2 CH 2Cl gives a precipitate on warming.
CH 3CH = CHCl is a vinylic chloride which is inert even when heated.
∴ (a)

Problem 8: Nitrophenol, C6H4(OH) (NO2) can have:

(a) No isomer ( only a single compound is possible)
(b) Two isomers
(c) Three isomers
(d) Four isomers

Solution: o-,m- and p-isomers, i.e., position isomers

∴(c)

Problem 9: Geometrical isomerism is possible in:

(a) Butene-2 (b) Ethene
(c) Propane (d) Propene

Solution: H H

H3C CH3
If either of the two doubly bonded carbon atoms has same group or atoms
attached on it, it will not show geometrical isomerism.
∴ (a)

Problem 10: Which of the following statement is correct?

+
(a) Allylcarbonium ion (CH2=CH– C H2 ) is more stable than propyl
carbonium ion
(b) Propyl carbonium ion is more stable than allylcarbonium ion
(c) Both are equally stable
(d) None
Solution: Allylcarbonium ion undergoes resonance stabilization.
∴(a)

Problem 11. Number of unhhybridised orbitals in vinyl acetylene are

(a) 2 (b) 3
(c) 4 (d) 6
[RPMT 1999]

Solution : (d)Vinlyl acetylene there are 6 unhybridised orbitals.

CH 2 = CH2
− C ≡ CH 2
sp2 sp sp sp
1 2 2
1

(no. of unhybridised orbitals)

Problem 12. Number of σ and π bonds present in 1-butene –3-yne respectively are
(a) 7σ, 3π (b) 5σ, 2π
(c) 8 σ, 3π (d) 6σ, 2π
 [RPMT 1999, MP PET 2000; DCE 2000]
Solution : (a) CH 2 = CH − C ≡ CH
7σ ,3π

Problem 13. Which is an acidic hydrocarbon

(a) CH3CH2CH2CH3 (b) CH3C ≡ CCH3
(c) CH3C ≡ CH (d) CH2 = CH – CH = CH2
[AMU 2000]

Solution : (c)Propyne has one acidic hydrogen

Problem 14. Which of the following is a polar compound

(a) C2H6 (b) CCl4
(c) HCl (d) CH4
[MH CET 2003]

Solution : (c) We know that there is more difference in the electro negativities of hydrogen
and chlorine. Therefore HCl is a polar compound.

Problem 15. Which of the following is the most stable compound

+ +
(a) Ph 3 C (b) Ph 2 C H
+ +
(c) Ph 3 C H 2 (d) Ph C H 2
[BHU 2004]

Solution : (a)Triphyenyl methyl cation has three benzene resonating ring so it is most
stable compound.

Problem 16. The order of decreasing stability of the carbanions

.. − .. − .. − .. −
(1) (CH 3 )3 C (2) (CH 3 ) 2 C H (3) CH 3 C H 2 (4) C6 H 5 C H 2
(a) 1 > 2 > 3 > 4 (b) 4 > 3 > 2> 1
(c) 4 > 1 > 2 > 3 (d) 1 > 2 > 4 > 3
[KCET 1996]

Solution : (b) C6 H5 − CH..2 > CH3CH..2 > (CH3 ) 2CH.. > (CH3 )3C..

Problem 17. Heterolysis of carbon-chlorine bond produces

(a) Two free radicals (b) Two carbonium ions
(c) Two carbanions (d) One cation and one anion
[MLNR 1986 ; MP PET/PMT 1998]
−
Solution : (d) C – Cl Heterolytic
bond fission
→ C + Cl
+

Problem 18. An aromatic compounds among other things should have a π-electron cloud
containing electrons where n can’t be
 (a) 1/2 (b) 3
(c) 2 (d) 1
[J & K 2005]
Solution : (a) According to Huckel rule, all aromatic compounds must have (4n + 2)π
electrons where n is an integer , i.e. n = 0, 1, 2, 3, . . . . and possess unusual
stability due to the complete delocalisation of π-electron.

Problem 19. Which of the following is an electrophile

(a) H2O (b) SO3
(c) NH3 (d) ROR
[J & K 2005]

.. .. ..
Solution : (b) H − O − H , N H 3 , R − O − R, nucleophiles and SO3 electron deficient
.. ..
center (a reagent which can accept an electron pair in a reaction, is called an
electrophile)

Problem 20. An alkyl halide may be converted into an alcohol by

(a) Elimination (b) addition
(c) substitution (d) Dehydrohalogenation
[Pb. PMT 2000]

Solution : (c) nucleophile can substituted by another nucleophile by substitution reaction

Problem 21. Which of the following compounds displays geometrical isomerism?

(a) ClFC = CBrI (b) CH2 = CBr2
(c) ClCH = CHBr (d) Br2C = CCl2

Solution: (a), (c)

For alkene to show geometrical isomerism the two groups at the doubled
bonded carbon atom should be different.

Problem 22. In the alkylation of benzene, stable σ-complex can be:

H H
CH3 CH3
(a) (b)

H H
CH3 CH3
(c) (d)

Solution: (a), (b), (c), (d)

All the four are stable resonating structure

Problem 23. Hydroboration oxidation and acid hydration will yield the same product in case
of:
(a) (b)

(c) CH2 = CH2 (d) CH3CH = CHCH3

Solution: (b), (c), (d)

b, c, d all are symmetrical alkene, hence they will give same alcohol both by
Markovnikov’s and anti-Markovnikov’s rule.

Problem 24. Which of the following pairs of compounds are diasteriomers?

CH3 CH3 CH3 CH3
H OH H OH HO H HO H
(a) HO H
and
H OH
(b) H OH
and
HO H
CH3 CH3 CH3 CH3
CH3 CH3 CH3 CH3
H OH HO H H OH HO H
(c) HO H
and
H OH
(d) HO H
and
HO H
CH3 CH3 CH3 CH3

Solution: (a), (b), (d) :Diasteriomers are not mirror image each other. Whereas enantiomers
are non-supperimposable mirror image.

Problem 25. Which of the following compounds is/are optically inactive

(a) (CH3)2 CHCH2OH (b) CH3CH2OH
(c) CCl2F2 (d) CH3CHOHC2H5

Solution: (a), (b), (c)

(a, b, c) does not contain chiral carbon that’s why they are optically inactive,
whereas (d) contains one chiral carbon atom. Hence it is optically active

Problem 26: Match the column- I with column – II

Column – I Column- II
O O (p) Positional isomers
|| ||
(a) CH 3 − C − O − H & H − C − O − CH 3
O (q) Tautomers
H3C CH3 & H C CH3
3
(b) O
O OH (r) Functional Isomers

&
(c)
(d) CH3—CH2—N=O and (s) Metamers
CH3—CH = N—OH

Solution : (a – r), (b – ps), (c – qr), (d – qr)

Write–up - I

A little thought should convince you that the net specific rotation of any mixture of the d and l
isomers of a given chiral compound is equal to the weighted average of the rotation due to both
isomers. Expressed mathematically.
[α]net = fd[αd] + fl[αl]
Whereas fd and fl are the fraction of d and l isomers. While [αd] and [αl] are the specific rotation
of pure d and l isomers respectively. Since fl = 1 – fd and
[αl] = –[αd] we can revise
[α]net = fd[αd] + (1 – fd) (–[αd])
= [αd] (2fd – 1)
= [αl] (2fl – 1)
i.e. (enantiomeric excess = (2fl – 1) = 2fd – 1
α
we know [α ]Tλ =
lC
Where l = length of the polarimeter tube or solution column (dm) and
C = concentration of solution (g/dm3)
The pure d-isomers of a certain chiral compound are [α ]25
D = +55° . A non-racemic dl mixture of

this compound has a net [α ]25

D of -11°C.

1. Which enantiomers are predominates in this mixture.

(a) d-isomers (b) l-isomers
(c) both are in equal (d) None of these

2. What is enantiomeric excess?

(a) 30% (b) 20%
(c) 50% (d) 70%

3. What is fraction of both isomers in the mixture?

(a) 60%, 40% (b) 70%, 30%
(c) 80%, 20% (d) 90%, 10%

4. The [α ]25
D for R = – 22.5°C, then what is observed rotation of its enantiomer in a solution of
concentration 2g/mL filled in a polarimeter tube of length 0.5 dm?
(a) + 22.5° (b) – 22.5°
(c) 68.5° (d) – 68.5°

Solution :

1. (b) Since the net rotation of mixture is –ve so l isomers predominated.

−11 1
2. (b) i.e. = 2f l − 1 = = = 20 = 20%
−55 5
3. (a) fl –1 = 20
0.20 + 1
fl = = 0.60 = 60%
2
fd = 1 – fl = 1 – 0.60 = 0.40 = 40%
4. (a) robs = l.c. [α ] = 0.5 × 2 × (+ 22.5)
= + 22.5

Write–up - II
Aromatic compounds are those that meet the following criteria:
i) The structure must be cyclic, containing some number of conjugated pi bonds.
ii) Each atom in the ring must have an unhybridized p orbital. (The ring atoms are usually sp2
hybridized or occasionally sp hybridized.)
iii) The unhybridized p orbitals must overlap to form a continuous ring of parallel orbitals. In
most cases, the structure must be planar (or nearly planar) for effective overlap to occur.
iv) Delocalization of the pi electrons over the ring must lower the electronic energy.
An antiaromatic compound is one that meets the first three criteria, but delocalization of the pi
electrons over the ring increases the electronic energy.
Hückle’s Rule: If the number of pi electrons in the cyclic system is:
(4N + 2), the system is aromatic
(4N), the system is antiaromatic
where N is an integer.
A cyclic compound that does not have a continuous, overlapping ring of p orbitals cannot be
aromatic or antiaromatic. It is said to be non-aromatic,
Heterocyclic compounds, with rings containing sp2 hybridized atoms of other elements, can also
be aromatic. Nitrogen, oxygen, and sulfur are the most common heteroatoms in heterocyclic
aromatic compounds. Following four compounds are all aromatic :
4
5 3 4 3 4 3 4 3

6 2 5 2 5 2 5 2
N N1 O S
1 1 1
H
Pyridine Pyrrole Furan Thiophene

If we examine these structures, we shall see that pyridine is electronically related to benzene, and
that pyrrole, furan, and thiophene are related to the cyclopentadienyl anion.
The nitrogen atoms in molecules of both pyridine and pyrrole are sp2 hybridized. In pyridine the
sp2 hybridized nitrogen donates one bonding electron to the π system. This electron, together
with one from each of the five carbon atoms, gives pyridine a sextet of electrons like benzene.
The two unshared electrons of the nitrogen of pyridine are in ansp2 orbital that lies in the same
plane as the atoms of the ring. This sp2 orbital does not overlap with p orbitals of the ring (it is,
therefore, said to be orthogonal to the p orbitals). The unshared pair on nitrogen is not a part of
the π system, and these electrons confer on pyridine the properties of a weak base.
In pyrrole the electrons are arranged differently. Because only four π electrons are contributed by
the carbon atoms of the pyrrole ring, the sp2 hybridized nitrogen must contribute two electrons to
give an aromatic sextet. Because these electrons are part of the aromatic sextet, they are not
available for donation to a proton. Thus, in aqueous solution, pyrrole is not appreciably basic.
Furan and thiophene are structurally quite similar to pyrrole. The oxygen atom in furan and the
sulfur atom in thiophene are sp2 hybridized. In both compounds the p orbital of the heteroatom
donates two electrons to the π system. The oxygen and sulfur atoms of furan and thiophene carry
an unshared pair of electrons in ansp2orbital that is orthogonal to the π system.

1.
(I) (II) (III) (IV)

Which of the following statement is correct?

(a) (I) and (II) are aromatic (b) Only III is antiaromatic
(c) (I) and III are non aromatic (d) (I) and (III) are antiaromatic.

2. Which of the following is aromatic?

(a) (b)

(c) (d)


H
→
+

H
→
3. N NH2
N NH
H
I II III IV
Which of the following statement is true regarding the aromatic character of the four
species?
(a) All the four are aromatic (b) I and III are aromatic
(c) I, III and IV are aromatic (d) I, II and III are aromatic
 H3C CH2
4.
Ha Hb Hc Hd

All the hydrogen’s marked (Ha, Hb, Hc and Hd) are attached with a sp3hybridised carbon.
Which among these is most acidic?
(a) Ha (b) Hb
(c) Hc (d) Hd
6
5 N
6 4 4 5 7 5 N
8 1

N N N N H
5. 1 2 3 3 2 1 N
4 2

9 N
3
H
pyrimidine imidazole purine

Among the following which statement is false?

(a) Both the nitrogens of pyrimidine are basic
(b) In imidazole protonation takes place on nitrogen (marked 3)
(c) Purine has three basic nitrogens
(d) In imidazole protonation can takes place on N (marked 1) as well as on N (marked 3)
with equal ease.

Solution:
1. (d) 2. (a) 3. (c) 4. (b) 5. (d)

Subjective
O O
|| ||
Problem 1: Why CH3 – C– CH2 – C – CH3 is known as active methylene compound?
Solution: The – CH2 – group (methylene group) is acidic in nature i.e. these hydrogen’s
can be easily lost as H+, on action of a base because the resulting carbanion
can be resonance stabilized.
O O O– O
|| || ||
CH3 – C – CH – C – CH3 ←→ CH3 – C = CH – C – CH3
Oδ Oδ
– –
O O
||
←→ CH3 – C – CH = C – CH3 ≡ CH3 – C –––– CH –––– C – CH3

Problem 2: Give the order of stability of the following carbocations.

CH 3+ ,CH 3CH +2 , CH 3CH 2CH +2 , CH 3CH + CH 3 (CH 3 )3 C +
Solution: The decreasing order of stability
(CH 3 )3 C + > CH 3CH + CH 3 > CH 3CH 2 CH +2 > CH 3CH +2 > CH 3+ . In CH 3CH 2+ ,
CH 3 group donates electron’s by +I effect. As the no. of CH 3 group increases
distribution of charge and hence the reduction of charge density on C bearing
 +ve charge is more effective. So (CH 3 )3 C + is most stable-most no. of alkyl
groups-most stable.

Problem 3: Give the relative order of solubility of carbanions.

– – – –
CH 3 , CH 3CH 2 , CH 3CH CH 3 ,(CH 3 )3 C

Solution: The decreasing order is CH 3– > CH 3CH 2– > CH 3CH – CH 3 > (CH 3 )3 C – . The
order is opposite to that proposed for cations +I effect of alkyl group increases
the –ve charge on C.
Electron releasing groups destabilize anions.

Problem 4: Which among the following most acidic

a) H3C COOH

F
b) F

H3 C
CH2COOH
c) H3C COOH

F
d) COOH
F
Solution: As the inductive effect of fluorine decreases with distance, (A) will be most
acidic, because the carboxylate ion which results after the loss of H + can be
stabilized by electron withdrawing nature of fluorine (—I effect) which is
strongest in which fluorine atom is at α carbon.

Problem 5: Write the following Alkenes in increasing order of their stability with
explanation
R2C = CR2, R2C = CHR, R2C = CH2, RCH = CH2, CH2 = CH2.

Solution: Let R = CH 3
a) CH 2 = CH 2 (no. α – H . no. Hyperconjugation)
b) H3C H
C C
H H ( 3α – H , 3-Hyperconjugative structure)
c) H3C H
C C
H3C H
( 6α – H , 6H-structures)
d) H3 C CH3
C C
H3 C H
( 9α − H , 9H-structures)
 e) H3C CH3
C C
H3C CH3
( 12α − H , 12 H structures)

Problem 6: Write all possible structural isomers of the compound with molecular formula
C4H10O.

Solution: Total number of structural isomers = 7

CH3 — CH 2CH 2CH 2 — OH H3 C CH CH2 OH

(i) CH3

(ii)
H3 C CH CH2CH3 CH3

OH H 3C C OH
(iii) CH3
(iv)

CH 3CH 2 — O — CH 2CH3 CH 3 — O — CH 2 — CH 2 — CH3

(v) (vi)

H3C O CH CH3

CH3
(vii)

Problem 7: In phenol, almost 100% enol form exists. Why?

Solution: OH O
H
H

enol keto
In phenol, there is almost 100% enol form, because it retains the aromaticity
of the ring but in keto form the aromaticity of the ring gets ruptured.
Problem 8: Arrange the following species in increasing order of dipole moment.
cis − 2,3 − dichloro − 2 − butene cis − 1, 2 − dichloroethene
(i) (ii)

cis − 1, 3 − dibromo − 1, 2 − dichloroethene trans − 1, 2 − dichloroethene

(iii) (iv)

Solution: H3C Cl H Cl Br Cl Cl H

H3C Cl H Cl Br Cl H Cl
(I) (II) (III) (I)

Resultant vector Resultant vector Resultant vector None resultant vector

In I, there is addition of vector

In II, there will neither be addition nor subtraction of vector
In III, there is subtraction of vector
 In IV, the vectors almost cancel each other. So the increasing order of dipole
moment is IV < III < II < I.

Problem 9: Identify the 1,2- and 1-4 addition products of Free Radical addition of CBrCl3
to 1,3-butadiene.
Solution: CH2
Cl HC
CH2
H2C 
CCl3
→ Cl
Cl
Br
(I)
CH2
Br CH2 Cl
Cl
Cl
Cl
Cl
Cl
1,2-addition product Br
Cl
Cl
Cl
1,4-addition product

Problem 10: Write all possible structural isomers of the compound with molecular formula
C5H12O.
Solution: Total number of structural isomers = 7
i) ii) CH3
H3C OH
OH
H3C
iii) iv) CH3
HO CH3
H3C OH
CH3
v) vi) O
H3C O CH3 H3C CH3
vii) O OH
H3C
CH3
KVPYNMents (New Pattern)
1. Geometrical isomerism is not exhibited by – (2007)
(C)
(A) (B) (D)

2. (S)-lactic acid is (2008)

(A (B (C (D
) ) ) )

3. The configuration at C-2 and C-5 in the following compound, respectively, are (2008)

(A) 2R and 5R (B) 2S and 5S (C) 2R and 5S (D) 2S and 5R

4. Identify the stereoisomer pair from the following choices (2010)

(A) CH3CH2CH2OH and CH3CH2OCH3
(B) CH3CH2CH2Cl and CH3CHClCH3
H
|
(C) CH3 − C = C− CH3 and CH3 − C− C− CH3
| | |
H H H
CH3

(D)
and

5. The structure of cis–3–hexene is (2013)

(A) (B) (C) (D)

6. Optically pure 3-bromopent-1-ene upon addition of 1 mole of Br2 produces a tribromo compound. The
number of stereoisomers in the product is (2007)
(A) 2 (B) 4 (C) 6 (D) 3

7. The acid strength of o-nitrophenol (I), m-nitrophenol (II) and p-nitrophenol (III) follows the order. (2007)
(A) I < II = III (B) II < I < III (C) III < I < II (D) I < II < III
8. The order of increasing stability of carbanions in compound I-IV is – (2007)
(I)

(A) III, IV, I, II (B) IV, II, I, III (C) III, I, IV, II (D) II, IV, I, III

9. You have been given four bottles marked A, B, C and D each containing one of the organic
compounds given below (2010)

The following observation were made.

(i) The compound in the bottle A did not dissolve in either 1 N NaOH or 1 N HCl.
(ii) The compound in the bottle B dissolved in 1 N NaOH but not in 1 N HCl
(iii) The compound in the bottle C dissolved in both 1 N NaOH and 1 N HCl
(iv) The compound in the bottle D did not dissolved in 1 N NaOH but dissolved in 1 N HCl
(Fill up the blanks)
(a) Indicate the compounds in : bottle A : III ,bottle B: II,bottle C- IV and bottle D –I
(b) The compound with the highest solubility in distilled water is IV

10. Among (2011)

the compound which is not aromatic is

(A) i (B) ii (C) iii (D) iv
2
11. The number of sp hybridized carbon atoms in (2013)
O
||
HC ≡ C − CH2 − C− CH2 − CH = CH2 ' is
(A) 3 (B) 5 (C) 4 (D) 6

12. The number of isomers which are ethers and having the molecular formula C4H10O, is
(2014)
(A) 2 (B) 3 (C) 4 (D) 5

13. The number of isomers which are ethers and having the molecular formula C4H10O, is
(2014)
(A) 2 (B) 3 (C) 4 (D) 5
14. The amonia evolved from 2g of a compound in Kjeldahl’s estimation of nitrogen neutralize 10 mL of
2M H2SO4 solution. The weight percentage of nitrogen in the compound is
(A) 28 (B) 14 (C) 56 (D) 7
15. is (2008)
The IUPAC name of

(A) (3Z)-hept-3-en-1-ol (B) (3E)-hept-3-en-1-ol

(C) (3Z)-hept-4-en-7-ol (D) (3E)-hept-4-en-7-ol

16. Among the following compounds (2011)

2, 3-dimethylhexane is
(A) i (B) ii (C) iii (D) iv

17. Which of the following molecules has no dipole moment? (2013)

(A) CH3Cl (B) CHCl3 (C) CH2Cl2 (D) CCl4

18. is (2008)
The IUPAC name of

(A) (3Z)-hept-3-en-1-ol (B) (3E)-hept-3-en-1-ol

(C) (3Z)-hept-4-en-7-ol (D) (3E)-hept-4-en-7-ol

Answer Key:

1:A 2:B 3:A 4:C 5:C

6:B 7:B 8:B 9.No solution
10.: B 11:A 12:A 13:B 14:A
15:A 16:B 17:D 18:A
Assignments (New Pattern)

SECTION – I Single Choice Questions

LEVEL - I

1. Arrange given compounds in order of decreasing acidity:

(1) CH3 — NO2 (2) NO 2 — CH 2 — NO2
O2N CH NO 2
(3) CH3 — CH 2 — NO 2 (4)
NO2
(a) 4>2>1>3 (b) 4 > 2 > 3 > 1
(c) 3>1>2>4 (d) 3 > 1 > 4 > 2.

2. 2-Methylpenta -2, 3 diene is achiral because it has:

(a) acentre of symmetry (b) a plane of symmetry
(c) a C2 axis of symmetry (d) both centre and a plane of symmetry.

3. The following compound can exhibit

H3C H
C C H
H3C C
H3C COOH
(a) geometrical isomerism (b) geometrical and optical isomerism
(c) optical isomerism (d) tautomerism.

4. Which of the following carbon free radical is the most stable?

(a) Vinyl carbon free radical (b) benzyl carbon free radical
(c) Tertiary carbon free radical (d) Secondary carbon free radical.

5. What is the decreasing order of stability of the ions?

+ + +
H3C HC H3C HC H3C HC

CH3 O CH3 CH3

(I) (II) O (III)
(a) I > II > III (b) II > III > I
(c) III > I > II (d) II > I > III

6. How many optically active stereoisomers are possible for butane-2, 3-diol:
(a) 1 (b) 2
(c) 3 (d) 4
7. A solution of (+) -2-chloro-2-phenylethane in toluene racemises slowly in the presence of
small amount of SbCl5 , due to the formation of:
(a) carbanion (b) carbene
(c) free-radical (d) carbocation.

8. Which of the following has the highest nucleophilicity:

(a) F – (b) OH –
(c) CH 3– (d) NH 2– .

9. Which of the following, has the most acidic hydrogen:

(a) 3-hexanone (b) 2, 4-hexanedione
(c) 2, 5-hexanedione (d) 2, 3-
hexanedione.

10. The number of isomers for the compound with molecular formula CBrClFI is:
(a) 3 (b) 4
(c) 5 (d) 6.

11. The most reactive positions for electrophilic substitution reaction of anthracene are
8 9 1
7 2

6 3
5 10 4

(a) 1&4 (b) 1 & 2

(c) 2&3 (d) 9 & 10.

12. Fischer projection indicates

(a) Horizontal substituents above the plane
(b) Vertical substituents above the plane
(c) Both horizontal and vertical substituents below the plane
(d) Both horizontal and vertical substituents above the plane

13. Allylisocyanide has:

(a) 9 sigma bonds and 4 pi bonds
(b) 9 sigma bonds, 3 pi bonds and 2 non-bonding electrons
(c) 8 sigma bonds and 5 pi bonds
(d) 8 sigma bonds, 3 pi bonds and 4 non-bonding electrons

14. The percentage of `s' character of the hybrid orbital of carbon in ethane, ethene and
ethyne respectively are
(a) 25, 33, 50 (b) 20, 50, 33
(c) 25, 50, 75 (d) 33, 66, 99

15. The compound which has one isopropyl group is :

(a) 2,2,3,3 -tetramethyl pentane (b) 2,2 - dimethyl pentane
(c) 2,2,3 - trimethyl pentane (d) 2-methyl pentane
16. Cl Cl

are ....... isomer

Cl Cl
(a) position (b) optical
(c) geometrical (d) none of these

17. Resonating forms of phenoxide ion is:

(a) O (b) O

(c) O (d) O

18. Which has no acidic H?

OH
(a) H3C (b) OH
O
O
(c) (d) NaNH2
H3C CN

19. C – C and C = C bond lengths are equal in:

(a) 1,3-buta-di-ene (b) cyclopentene
(c) 1,3-cyclohexa-di-ene (d) none

20. Functional isomer of ester is :

(a) carboxylic acid (b) anhydride
(c) aldehyide (d) ketone

LEVEL - II

1. Which among the following carbocations is most stable:

C
⊕
(a) (b) C6 H 5 — C H 2

⊕ H3C C CH3
(c) C6 H 5 — C H — C6 H 5 (d)
CH3
2. Consider the following compounds:
NH2 NH2 NH2 NH2

NO2 CN CH3
(1) (2) (3) (4)
Arrange these compounds in decreasing order of their basicity:
(a) 1 > 2 > 3 > 4 (b) 2 > 3 > 1 > 4
(c) 4 > 1 > 3 > 2 (d) 4 > 1 > 2 > 3.
3. Which one of the following compounds has maximum enol content in solution:
O O
(a) (b)
H3C C CH2 COOC2H5 H3C C CH2 CN
O
(c) (d) O
H3C C CH3

4. The number of optically active isomers observed in 2, 3-dichlorobutane is:

(a) 0 (b) 2
(c) 3 (d) 4.

5. Most unstable carbanion among the following is

(a) H5C6 CH2 (b) F3C CH2
H2 C
(c) (d) C 6H 5
CHO

6. In the following compounds,

OH OH OH OH

NO 2
CH3 NO 2
(1) (2) (3) (4)

Arrange these compounds in decreasing order of their acidity.

(a) 3 > 4 > 1 > 2 (b) 1 > 4 > 3 > 2
(c) 2 > 1 > 3 > 4 (d) 4 > 3 > 1 > 2.

7. The optically active tartaric acid is named as D –(+) – tartaric acid because it has a
positive:
(a) optical rotation and is derived from D-glucose
(b) pH in organic solvent
(c) optical rotation and is derived from D – (+) – glyceraldehydes
(d) optical rotation only when substituted by deuterium.
 +
8. N H3 NH3
Z Y
COOH
X
Arrange in order of increasing acidic strength
(a) X > Z > Y (b) Z < X > Y
(c) X > Y > Z (d) Z > X > Y.

9. The correct order of basicities of the following compounds is:

NH O

H 3C C CH 3 — CH 2 — NH 2 (CH 3 ) 2 NH H 3C C NH2
NH2
2 3 4
1
(a) 2>1>3>4 (b) 1 > 3 > 2 > 4
(c) 3>1>2>4 (d) 1 > 2 > 3 > 4.

10. Which of the following structures are super imposable?

H Br Br Me
Br Me H Me Me H Br H
HO Et Et OH Et Me HO Et

Me Me OH Me
(1) (2) (3) (4)

(a) 1 and 2 (b) 2 and 3

(c) 1 and 4 (d) 1 and 3

SECTION – II May be more than one choice

1. Which of the following order(s) is/are correct as indicated?

- - - -
(a) H3C CH2 > NH2 > H2C CH > HO (Basic strength)
O

O
(b) R NH2 < R < NH (Acidic strength)
NH2

O
H3C > H3C > H3C
(c) NH2
(Basic strength)
NH N
(d) PhOH< H2CO3<PhCOOH< HCOOH (Acidic strength)

2. which is/are correct statements?

P Q

(a) P is cis- and Q is trans- (b) P is Z and Q is E

(c) P is R and Q is S (d) P and Q are same structure
3. Which can show tautomerism?
H3C
(a) NO2
(b) O

(c) (d) HCN

CH3

4. Which will show geometrical isomerism?

H3C
(a) (b)
N OH
H3C
HO N
(c) N (d)
N OH
H3C OH

5. Which is/are less acidic than phenol?

OH
(a) CH3OH (b)
CH3

OH
(c) (d) H2O
NO2

6. Which have active methylene group?

O O
(a) (b) H3C NO2
H3C CH3
O
O
(c) CN (d)
H3C
NC

7.

N N

H NH2
pyrrole I pyridine II aniline III
Which is/are correct statements?
(a) I is more basic than II (b) II is more basic than I and III
(c) III is more basic than II (d) all are aromatic bases
8. Which is/are true statements(s)?
(a) Protonation increases electrophilic nature of carbonyl group
(b) CF3SO3− is better leaving group than CH 3SO 3−
(c) Benzyl carbonium ion is stabilized by resonance
Cl OH
(d) Cl is stable
Cl OH

9. Which of the following will show hyperconjugation:

H3C H3C
(a) (b)
H3C CH3
H3C
(c) (d)
H3C CH3

10. Which shows aromatic character?

(a) (b)

(c) (d)

SECTION – III Comprehension Type Questions

Write-up I
The conversion of a keto form into enol is enolisation. It depends on structural factor,
temperature and nature of solvent. Resonance and hydrogen – bonding increases enol
content.Enolic form of phenol is more stable than keto form by –13 kcal/mol of energy
hence phenol exist exclusively as an enol. Enolic tautomer is less polar due to
4intramolecular hydrogen bonds than the corresponding keto form. Any polar solvent
would decrease the enolisation and favourketo form intramolecular hydrogen bonding
stabilized enol form by 7kcal/mol and resonance stabilizes enol form by 15 kcal/mole

1. The enol content of ethyl acetoacetate is maximum in

(a) Water (b) acetic acid
(c) ethanol (d) hexane

2. Which one of the following compounds has maximum enolcontent

(a) CH3COCH2COOCH3 (b) CH3COCH2COOC2H5
(c) CH3COCH2COCH3 (d) C6H5COCH2COC6H5

3. Ketonic form predominates in

(a) CH3 – CO – CH3 (b) C6H5COCH2COCH3
(c) CH3 – CO – CH2 – COCH3 (d) CH3COCH2COOC2H5
 Write-up II
Carbocations are species in which central carbon carries positive charge. If the charge on
the carbocations gets concentrated or localized the carbocation becomes unstable. The
two factors which account for stability of carbocations are inductive effect and hyper
conjugation (no bond resonance). Inductive effect is minor factor and hyper conjugation
is major factor.

4. Which is most stable carbocation

+ +
(a) C H 3 (b) CH 3 C H 2
+ +
(c) (CH 3 ) 2 C H (d) (CH 3 )3 C
5. n-propyl carbocation rearranges to isopropyl carbocation by shift of
(a) proton (b) Hydride ion
(c) electron (d) None of these
6. Hybridisation of carbon in carbocation is
(a) sp (b) sp2
(c) sp3 (d) dsp2

7. Which is most stable carbocation

+ +
(a) C H3 (b) CH 3 C H 2

+
CH2
(c) CH 3CH 2 C H (d)

Write-up III

Substituents (Y) in the benzene ring with +M and/or +I effect coupled with
hyperconjugative effect increases the e– density in the ring and thus activate the ring
towards electrophilic substitution. Substituents (Y) with –M and –I effect deactivates the
ring towards electrophilic substitution. Ring activating substituents are o– and p-
orienting while ring deactivating substituents are m- orienting. When two substituents are
present it is the more activating group or the activating substituent of the other one is
deactivating decides the orientation.

8.
OH 
Br2 / CHCl3
→P

The major monobrominated product (P) is:

OH
(a) (b) Br OH

Br
Br Br

(c) OH
(d) OH
 O
9.
N 
Cl2 / Fe
→Q

The major monochlorinated product (Q) is:

O Cl O

(a) N (b) N

Cl
Cl
O O

(c) N Cl
(d)
N Cl

SECTION - I

Level - I

1. (a) 2. (c) 3. (c) 4. (b)

5. (d) 6. (b) 7. (d) 8. (c)
9. (b) 10. (d) 11. (d) 12. (a)
13. (b) 14. (a) 15. (d) 16. (c)
17. (b) 18. (d) 19. (a) 20. (a)

LEVEL - II

1. (a) 2. (c) 3. (d)

4. (b) 5. (d) 6. (d)
7. (c) 8. (a) 9. (b)
10. (d)

SECTION - II

1. (b), (c), (d) 2. (a), (b) 3. (a), (b), (c), (d)

4. (a), (b), (d) 5. (a), (b), (d) 6. (a), (b), (c), (d)
7. (b),(d) 8. (a), (b), (c), (d) 9. (a), (b), (c)
10. (a), (b)

SECTION - III

1. (d) 5. (b) 9. (c)

2. (d) 6. (b)
3. (a) 7. (d)
4. (d) 8. (a)