General Organic Chem

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General Organic
Chemistry
This chapter is about an overview of organic chemistry. Here well discuss the entire framework within which the
concepts of this subject will be built. A good feel of general organic chemistry is very necessary if you wish that the
myriad of information available in this field stays coherently connected in your mind. As we progress along the
study of organic chemistry, youll begin to understand that grasping a small number of guiding principles can be
used to explain a vast array of existing disparate information and also to make predictions about previously
unknown reactions and compounds.
Keeping this in mind, you should strive hard to really understand the underlying basic principles of organic
chemistry.
Section - 1
THE CARBON ATOM : HYBRIDISATION
Since organic chemistry is all about the study of carbon compounds we should have a good understanding of the
chemistry of carbon atom.
Consider the ground state electronic configuration of the carbon atom.
We see that there are two half-filled orbitals in the 2p level. Thus, only two unpaired electrons might indicate that
carbon atom is divalent.
The following visual will help you form a mental picture of what the second level orbitals of carbon look like.
(Recall from the chapter on Atomic Structure that orbitals actually represent probability density distributions).
Chemistry / General Organic Chemistry
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z
z
y
x
2s
x
2py
2px
2pz
The four second-level orbitals (observe their orientations)

z
y
The three p-orbitals shown on the same axes

Fig -01
Coming back to the question of carbons valency, although the ground state configuration of carbon indicates that
carbon should be divalent, carbon is actually tetravalent in an overwhelming majority of its compounds (In fact,
compounds in which carbon is divalent exist but they are very unstable; an example of such a compound is CCl2).
[ METHANE ]
Consider one of the simplest possible compounds of carbon as an example : methane (CH4). The carbon atom
exhibits tetravalency in this compound. Not only that, each carbon-hydrogen bond length is precisely the same;
whereas if we have one 2s and three 2p orbitals in the valence shell of carbon, we should expect the four bond
lengths to be different. How do we explain all these facts about carbons bond formation ? The answer is
hybridisation.
It is clear that for the carbon atom to exhibit tetravalency, we cant just do with two unpaired electrons; we need
four. This can happen if one of the 2s electrons can be excited to the empty 2p orbitals, which would result in four
unpaired electrons.
Excite one of
2s2
2p1x
2p y1
Ground state
the 2s electrons
2s1
2p1x
2p y1
2p 1z
Excited state
This is how the tetravalency is explained : carbon atom undergoes bond formation with other atoms not in its
ground state (where it has only two unpaired electrons) but in its excited state (where it has four unpaired electrons).
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But even now a problem remains. A carbon atom still cannot bond in the configuration 2 s1 2 p1x 2 p1y 2 p1z of the
excited state even though it has four unpaired electrons. This is because if the carbon atom were to do so, it would
lead to the formation of three directed bonds with the three 2p orbitals (which would be mutually at right angles)
and one different non-directed bond with the spherical 2s orbital. However, as already stated earlier for the case
of methane, the four carbon-hydrogen bonds are of identical lengths and lie symmetrically; the angle between any
two bonds being 10928' (the four hydrogen atoms lie at the four vertices of a regular tetrahedron). It is this
symmetry that hybridisation explains.
What hybridisation says is that before undergoing bond formation (in methane, for example) the 2s and the three
2p orbitals are hybridised (mixed) to yield four new identical orbitals which are capable of forming stronger bonds.
These four orbitals point towards the four vertices of a regular tetrahedron. These orbitals are referred to as sp3
hybrid orbitals.
Hybridisation
2s1
2p1x
2p y1 2p 1z
Four new sp3 hybrid

orbitals
To form a visual picture in your mind, refer to the next figure which shows on the right hand side the four new sp3
hybrid orbitals that are identical in all respects. The angle between any two hybrid bonds in 10928'.
Fig - 02
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The next figure shows these four hybrid orbitals in the same figure, which should make it clear how these bonds are
symmetrically oriented:
The four symmetrically oriented

sp3 hybrid orbitals
C
Fig - 03
Hybridisation is actually a mathematical process that is carried out on the electron - wave functions
(which represent the orbitals) and is not something that physically occurs like we have put it here. It is
a tool used to understand the behaviour of different atoms in bond formation. The full significance of
these concepts will become clear in advanced courses at university level.
Once we have four sp3 hybrid orbitals at our disposal, we can easily explain bond formation in a molecule like
methane:
H
C
+4 H
add 4
mix
H-atoms
H
H
H
C
H
C
1s and sp3
H
H
C
H
H
H
H
H
H
H
-bonded methane
Fig - 04
From the figure above, observe that each sp3 hybrid orbital of carbon overlap with the 1s orbital of a hydrogen
atom to form a sp3 s carbon - hydrogen sigma bond ( bond), These four bonds, being tetrahedrally placed
with respect to each other, explain the symmetric structure of methane. (The significance of the term - bond
is as follows : whenever the overlap of two atomic orbitals takes place along their major axis, the resulting (bonding
molecules) orbital is the - bonding orbital. Any such bond will be referred to as a - bond .)
[ ETHANE ]
Let us consider another simple compound of carbon : C2H6 called as ethane
Each carbon in ethane is sp3 - hybridised. The following figure depicts in detail the bond formation process in
ethane:
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H
H
H
H
H
H
H
a C C bond
H
H
H
H
(wedge-shaped three dimensional

representation will be learnt soon)
Fig - 05
As depicted in the figure above, two sp3 hybrid orbitals, one from each carbon, undergo a head - on overlap to
form a carbon-carbon - bond. The other six sp3 hybrid orbitals, three on each carbon, undergo - bond
formation with the 1s orbitals of the hydrogen atoms. Note that both the carbon atoms are still in the tetrahedral
configuration.
It has been found that free rotation is possible about a carboncarbon single bond. Thus, an infinite variety of
structures are possible according to the relative positions of the groups attached on the two carbon atoms. Such
structures which are obtainable by free rotation about a carboncarbon bond are called conformations. (In
other words, they are different arrangements of the same group of atoms that can be converted into one another
without the breaking of any bonds.) Consider ethane. We will discuss two extreme conformations of ethane: One
in which all the hydrogen atoms are aligned and one in which they are oppositely aligned.
These two conformations are known by the names Eclipsed and Staggered conformations.
There are two ways that we can use to represent conformations, as done in the following figure:
Fig - 06
The two extreme conformations of ethane
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Observe that in the staggered conformation, the hydrogen atoms are as far apart from each other as they can
possibly be, so this would be a minimum repulsion configuration. On the other hand, the eclipsed form is the
conformation with the maximum possible crowding and hence the maximum repulsion. Hence the staggered form
should be the most stable while the eclipsed form is the least stable.
However, although there is a difference in stability since the hydrogen atoms are very small, this difference in
stability is negligible to an extent that even at room temperature conversion from one conformation to the other
easily takes place with the help of ordinary thermal motions.
Later on we will encounter molecules where such differences in stability of the conformations are more pronounced.
Well discuss the properties of - bonds soon enough. Right now, let us see organic compounds containing
carbon atoms in a state of hybridisation different than sp3.
[ ETHENE ]
Ethene has the molecular formula C2H4. Each carbon is bonded to only three atoms: two hydrogens and the other
carbon atom. How can we use hybridisation to explain the structure of ethene?
This is how hybridisation takes place : only three orbitals undergo hybridisation (the 2s and two of the three 2p
orbitals) to yield three new identical sp2 hybrid orbitals placed symmetrically in a plane at 120 to each other, while
the remaining 2p orbital stays unhybridised.
2s1
2px
2py
2pz
2pz
Three new identical
2
sp hybrid orbitals
sp hybridisation
y
2s
x
in xy
plane
Hybridisation
x
2px
in x-y
plane
x
along the
y-axis
2py
Three new identical sp2 hybridised orbitals

(They have a planar configuration)
Fig - 07
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The next figure shows two views of how the three sp2 hybrid orbitals and the fourth unhybrid 2p orbital are placed
z
unhybridised
orbital
y
120
120
x
120
Hybrid orbital
Side-view
Top-view
The three hybridised sp2 orbitals
symmetrically placed at 120 to
each other. The fourth unhybridised
2p orbital is perpendicular to the
plane of paper (not shown here). z axis
is coming out of the plane of paper
The unshaded lobes, lying in the

same plane correspond to the three
sp2 hybrid orbitals while the
fourth (shaded) orbital along the
z-axis is the unhybridised 2p orbital.
(Minor lobes have not been shown)
Fig - 08
The bond formation/structure of ethene can now be explained using two such sp2 hybridized carbon atoms
Side-way overlap
Observe the following:
H
H
Two sp2 hybrid orbitals of each

C-atom overlap with two 1s H
orbitals forming a total of 4 CH
bonds.
Head-on overlap
-bond
H
-bond
-bond
Fig - 09
Head-on overlap occurs between

two sp2 hybrid orbitals (one from
each of the two C-atoms) oriented
along the internuclear axis, thus,
forming a CC bond (refer
Fig 09 below.
The remaining p orbital on each

C-atom mutually overlap
side-ways to form a molecular
orbital representing the bond.
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We thus see that two sp2 hybrid orbitals, one from each carbon, overlap head-on to form a C C - bond.
Similarly, the remaining four sp2 hybrid orbitals are used to form - bonds with the four hydrogen atoms.
However, notice how the unhybridised 2p orbitals overlap. Since these two 2p orbitals are parallel to each other,
they overlap side-ways resulting in an (bonding) orbital that spreads over both the carbon atoms and is situated
above and below the plane containing the two carbon and the four hydorgen atoms. Such a bond is referred to as
a -bond (pi - bond).
Thus, from now on, we can visualise the ethene molecule as containing an electron cloud (due to the - bond)
above and below the plane containing the six atoms.
We can represent an ethene molecule conveniently as
-cloud (bond)
H
C
or
H
C
H
H
-bond
C
H
The double-line indicates a -bond

and a -bond
Fig - 10
From Fig - 8, it should be intuitively obvious that this sideways overlap will be the maximum when the two
unhybridised 2p orbitals are exactly parallel to each other (or equivalently, when the six atoms of ethene are
coplanar)
If one tries to cause rotation about the carbon carbon double bond, it is obvious that ethene will deviate from
its state of maximum overlap leading to a lesser stable configuration (a decrease in strength of the bond). Thus, any
such attempt to cause rotation about the double bond will be resisted.
Thus, in the ethene molecule (and any other molecule containing a double bond), free rotation about a carbon
carbon double bond is not possible and thus the question of conformations as in ethane, does not arise.
Observe that due to the cloud , the carbon carbon double bond is a spatial region of high negative charge
density so it will favour an attack on itself by electron-seeking reagents. Well have to say more about this later.
[ ETHYNE ]
Ethyne has the molecular formula C2H2. Each carbon is bonded to only two atoms : one hydrogen and the other
carbon atom.
Hybridisation in ethyne takes place as follows : only two orbitals undergo hybridisation ( the 2s and one of the
three 2p orbitals) resulting in two new sp hybrid orbitals placed symmetrically in a linear fashion, while the remaining
two 2p orbitals stay unhybridised
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2p 1x
2s1
2p y1
2p 1z
2p y1 2p y1
Two new identical
sp hybrid orbitals
sp hybridisation
y
x
Hybridisation
y
x
Two new identical sp hybridised orbitals

(They have a linear configuration)
Fig - 11
The following figure shows two views of how the two sp hybrid orbitals and the remaining two unhybrid
2p orbitals are placed.
Unhybridised
orbitals
y
180
C
sp hybrid orbital
Side-view
The unshaded lobes, lying along the x-axis
correspond to the two sp hybrid orbitals
while the two orbitals (shaded) lying along
the y-axis and the z-axis are the two unhybrid
2p orbitals. (Minor lobes have not been shown)
Fig - 12
Top-view
Two sp hybrid orbitals lie in a linear
fashion, at 180 to each other. The
two unhybrid orbitals lie along the y
and z axis (not shown here)
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10
The bond formation in ethyne takes place using two sp-hybridised carbon atoms:
z
Sideways overlap
Head-on overlap
-cloud (bond) due to

overlap of pz orbitals
-cloud (bond) due to
overlap of py orbitals
H
C
-bonds
Fig - 13
Observe carefully that two sp hybrid orbitals, one from each carbon, overlap head-on to form a CC
- bond. The remaining two sp hybrid orbitals are used to form - bonds with the two hydrogen atoms.
There are two pairs of unhybridised 2p orbitals, one pair parallel to the y-axis and one to the z-axis. These pairs
overlap sideways resulting in two - bonds (these - bonds lie in planes at right angles to each other)
Due to these two - bonds, the ethyne molecule can be effectively considered as having a cylindrical region of
negative charge along the carbon-carbon - bond.
bond
-bond
H
An approximate
representation
H of ethyne
cloud of negative charge
Fig - 14
The ethyne molecule can be represented as
H
A triple line indicates one

- bond and two -bonds
We have thus seen three valid ways in which the orbitals of carbon can be hybridised, resulting in the following
hybrid orbitals: sp3, sp2 or sp. (Other valid modes of hybridisation are also possible but we shall not discuss them
here.) The following figure summarizes the structures, bond lengths and bond angles in ethane, ethene and ethyne.
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11
H
C
C
109.28
1.54
1.10
C
H
H 118 H
1.20
1.34
1.09
ethane
C 180
121
ethene
1.06
H
ethyne
Fig - 15
You must understand why hybridisation takes place at all and what is the advantage gained out of it.
It is a universal law of nature that any natural system will tend to take up a configuration where its total instrinsic
energy is minimum. Hybridisation lets the molecule take up a minimum energy configuration because hybrid orbitals
can form stronger bonds; also, hybrid orbitals ensure that the other atoms bonded to the hybridised atom remain
as far apart from each other as possible. Thus, the process of hybridisation is energetically favoured.
BONDING CHARCTERISITICS
We know why atoms hybridize. Let us now see how hybridization affects various bond characters of molecule.
We will be discussing the following three characteristics:
(i)
Bond length
(ii) Bond angle
(iii) Bond strength (energy)
Before that, let us first calculate the percentage s (or p) character in a hybrid orbital and after this calculation, we
will see its effect on the above characteristics of a bond.
Percent of s(or p) character =
No. of s(or p) orbitals mixed

100
Total no. of orbitals mixed
Thus, % s character in:

1
sp3 = 100 = 25%
4
1
sp 2 = 100 = 33.33%
3
1
sp = 100 = 50%
2
Percentage s-character has two effects on the bond characteristics:

I.
Orbital containing more s-character is closer to the nucleus and hence, forms shorter bonds. We know
that, the shorter the bond, the stronger it is.
II.
s-character also affects the electronegativity of carbon. Carbon atoms having hybrid orbitals which posses
high s-character are more electronegative.
Thus, increasing order of electronegativity of the hybrid orbitals is:
sp3 < sp 2 < sp
% s-character:
25
33.33
50
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12
Thus, we can summarize:
More s character
Closer to nucleus + More electronegative
Shorter bond
Stronger bond
High bond energy
Now let us study the characters one by one.

(i)
BOND LENGTH: Experimental measurements indicate that similar bonds have fairly constant bond
lengths. eg. carbon-carbon bond length in ethane, propane, cyclohexane, isobutane etc. is approximately
the same.
However, the bond length decreases as % s-character increases.
Hybridization :
% s character :
Bond length() :
C C C == C C C
sp
sp3
sp 2
50
25
33.33
1.18
1.53
1.31
Apart from increase in s-character, there is one more reason for shortening of bond as we move from
C C to C == C and finally to C C. The reason is:
C C contains only one sigma bond.
C == C contains one sigma bond and an additional bond which shortens the distance between
the two carbon atoms.
C C contains one sigma bond and two additional bonds which further shorten the distance
between carbon atoms.
In molecules like
C CH CH C , it has been observed that the C C single bond length is
only 1.48. The shortening of bond length is because this single bond is formed between two sp hybrid
carbon atoms (having more s-character than sp).
Thus, for a molecule like C C C C, the carbon-carbon single bond length is even shorter, 1.38
because here, the single bond is formed between two sp hybrid carbon atoms (50% s-character).
In addition to CC bond, it has also been observed that CH bond length depends on the hybridization
of carbon atom.
CH 3 CH 3
CH 2 = CH 2
Hybridization of Carbon
% s-character
CH bond length
sp3
25
1.09
Similar is the case for other bonds: C O, C N, C S, C X etc.
sp 2
33.33
1.08
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13
Example 1
Which has a shorter C = O bond length: formaldehyde or carbondioxide?
H
Solution:
H
C
Hybridization of carbon :
% s-character:
OCO
O
sp2
33.33
sp
50
Thus, CO2 will have a shorter C = O and length than formaldehyde.
(ii)
Experimental values: Formaldehyde
CO 2
C = O bond length
1.16
1.21
BOND STRENGTH: The strength of a bond can be measured by measuring the energy of the bond. It
can be expressed in two ways:
Dissociation energy (D).
Bond energy (E).

D is the energy needed to cleave a bond to constituent radicals. Let us consider the example of a water
molecule. For the process,
H 2 O
H + OH,
However, for the process,
OH
H + O,
D = 118 kcal/mol.
D = 100 kcal/mol.
We can see that it has two different values of D for the same bond.
Thus, the bond energy of OH bond is taken to be the average of the two (D) values, which is called the
bond energy, E and is equal to 109 kcal/mol for H2O.
Obviously, for diatomic molecule, D = E.
We know, the shorter the bond, the stronger it is. Or we can say, larger amount of energy is required to
cleave a shorter bond.
Let us summarize it:
short bond
strong bond
High bond energy

Always keep in mind that in a given group of the periodic table, the bond weakens on moving down the
group. Thus, CS bond is weaker than CO bond.
Similarly, the carbon-halogen bond strength decreases in the order: C F > C Cl > C Br > C I
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(iii)
14
We have seen that C C is a shorter and thus, a stronger bond than C=C and even more stronger than
CC. But we should keep in mind that C=C is not twice as strong as CC because C=C consists of 1
bond and 1 bond. We know that extent of overlap in bond is less than that in bond. Thus bonds
stronger than bonds. Hence, C=C is not twice as strong as CC.
Hence, CC bond dissociation energy will be maximum for ethyne.
BOND ANGLE: Bond angle depends upon the hybridization of the central atom.
When the central atom is sp hybridized, the bond angle is normally 10928', where all the four groups
attached to the central atom are identical.
Similarly, when the central atom is sp hybridized, the bond angle is 120 and for sp hybridized central
atoms, the bond angle is 180.
However, the measure of angle deviates when different groups are attached to the central atom. eg.
Although carbon is sp hybridized, the CCBr bond angle in CH3 CH CH3 is 114.2
|
Br
Hetero Bonds
Carbon-oxygen and carbon-nitrogen bonds: Carbon can bond to oxygen through single or double bonds.
Consider the electronic configuration of oxygen atom:
Hybridisation in the oxygen atom can take place in two ways: sp3 or sp2
Thus, observe that two of the four hybridised orbitals will be used to accomodate the two lone pairs on oxygen
while the other two can be used in bond formation with other groups. For example, consider a class of organic
: :
compounds called ethers, which have a C O C linkage. The oxygen atom here is sp3 hybridised.
There are two lone pairs accomodated in two of the four sp3 orbitals of oxygen while the other two hybrid orbitals
are used to form bonds with the carbon atoms which are themselves sp3 hybridised. Oxygen atom can also
1s2
2s2
2p 2x
2p y1
sp2 hybridisation
2p 1z
1s2
2p 1z
Three new sp2
Unhybridised
hybridised orbitals p orbital
: :
be sp2 hybridised. For example, we consider a class of organic compounds called ketones, which have a
linkage. Observe that the carbon atom is sp2 hybrdised. The oxygen atom is also sp2 hybridised:
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15
Observe that two of the three sp2 hybrid orbitals are used to accomodate the two lone pairs on oxygen. The third
half-filled hybrid orbital forms a bond with the sp2 hybridised carbon. The unhybridised p orbital on oxygen
overlaps sideways with the unhybridised p-orbital on carbon to form a carbon-oxygen bond
Sideways overlap
forming a bond
-bond
Carbon-oxygen -bond
Fig - 16
An approximate sketch showing the carbon-oxygen double bond. is depicted in Fig 16 .Carbon can bond to
nitrogen using single, double and triple bonds. Consider the valence shell electronic configuration of nitrogen
2s
2px
2py
2pz
Nitrogen can undergo hybridisation in three ways: sp3, sp2 or sp:
(i)
1
2s
2px
2py
2pz
sp hybridisation
Four new sp hybridised orbitals
The lone pair is accomodated into one of the sp3 hybrid orbitals while the remaining three orbitals can be
used in bond formation. An example would be the following compound:
:
CH3 N CH3
CH3
The nitrogen atom is

3
sp hybridised and
has a lone pair
(ii)
1
2s2
2px
2
2py
sp hybridisation
2pz
2pz
Three new sp2
hybridised orbitals
Unhybridised
p orbital
The lone pair is accomodated into one of the three sp2 hybrid orbitals. The remaining two sp2 hybrid orbitals
can be used in the formation of bonds . The unhybridised 2p orbital will form a bond . An example
of this case is the following compound:
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16
CH3
CH3
N
C
H
CH3
CH3
The carbon and nitrogen atoms are both

sp2 hybridised. The lone pair on nitrogen
is accomodated into one of the sp2 hybrid
orbitals. The unhybridised 2p orbitals on
carbon and nitrogen form a p-bond.
Carbon and nitrogen are bonded

by a double bond.
Fig -17
(iii) We finally consider the case when nitrogen is sp hybridised.
2s2
2px
2py
2pz
2py
2pz
Two new sp
hybridised orbitals
sp hybridisation
The lone pair is accomodated into one of the sp hybridised orbitals. The other hybrid orbital can be used to
form a bond . The two unhybridised 2p orbitals can form two bonds. Let us consider an example:
Lone pair
CH3
CH3
The carbon and nitrogen atoms are both sp

hybridised. The lone pair on nitrogen is
accomodated into one of the sp hybrid
orbitals. The other hybrid orbital forms a
-bond with an sp hybrid orbital of carbon.
The two unhybridised 2p orbitals on
carbon and nitrogen each form two -bonds
The drawing depicts an approximate

electronic charge distribution in the spatial
region of the carbon nitrogen bond. As in
ethyne, here also a cylindrical region of
negative charge density will envelop the
carbon-nitrogen bond region
Fig - 18
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17
Section - 02
CLASSIFICATION OF ORGANIC COMPOUNDS
On the basis of structure and the type of atoms present, different terms have been designated to organic compounds:
hydrocarbons, saturated, unsaturated, alicyclic, aromatic etc.
Let us see what these terms mean.
HYDROCARBONS:
The term hydrocarbon refers to compounds containing only carbon and hydrogen atoms. These include alkane,
alkene, alkynes and aromatic hydrocarbons.
Alkanes: are hydrocarbons that contain only single bond and no multiple bonds. They are also referred to as
saturated compounds because they contain maximum number of hydrogen atoms that the carbon compound can
possess.
CH 3
|
eg. CH 3 , CH 3 CH 3 , CH 3 C CH 2
|
|
CH 3 CH 3
Alkenes are the hydrocarbons that contain carbon-carbon double bond. eg. CH 2
= CH 2 , CH 2 CH = CH 2
Alkynes are the carbon-carbon triple bond containing hydrocarbons. eg. HC CH , CH 3 C CH

Aromatic compounds are organic compounds containing multiple bonds and possessing special ring structure.
Benzene and its derivations are called benzenoid.
CH3
eg,
hydrocarbons which do not contain a benzene ring are called non-
benzenoid compounds.
e.g.
In aromatic compounds , if atoms, other than carbon (eg O, N, S etc.) constitute the ring, then aromatic compounds
are not classified as hydrocarbons. They are called heterocylic aromatic compounds.
e.g.
,
N
,
N
H
Alkenes, alkynes and aromatic compounds are referred to as unsaturated compounds (compounds containing
multiple bonds) because they have fewer number of hydrogen atoms than the maximum number the carbon compound
can possess. Thus, they can react with hydrogen under suitable conditions.
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18
ACYLIC COMPOUNDS:
Organic compounds may exist as long chain or branched chain. These compounds are referred to as acyclic or
open chain or aliphatic compounds.
CH3
e.g.
CH 3 CH 3 , CH3 CH CH2 CH3 , CH3 C OH etc.
ALICYCLIC COMPOUNDS:
Sometimes the long chain organic compounds may form a loop and arrange to form a ring-like structure. These
compounds are referred to as alicyclic or closed chain or ring compounds.
If only carbon atoms constitute the ring, it is called homocyclic.
eg.
If atoms other than carbon (heteroatoms eg. O, S, N etc.) form the ring, the cyclic compounds are called heterocyclic.
[Heteroatoms are atoms that form covalent bonds and have unshared electron pairs].
eg.
N
H
We will study each of these class of compounds in later chapter. Let us now try to summarize.
O
ORGANIC COMPOUND
_______________|______________
Acyclic
Cyclic
or
or
Open chain or Aliphatic compounds Closed chain or Ring compounds
_
____________|_____________
Homocyclic
Heterocyclic
______|_______
______|_______
Alicyclic
Aromatic
Alicyclic
Aromatic
_________|________
Benzenoid
Non Benzenoid
MAJOR FUNCTIONAL GROUPS
Most of the organic compounds concerning us also contain atoms such as oxygen, nitrogen, etc. Such an atom or
group of atoms or an exclusive kind of chemical bond gives exclusive properties to the carbon compound. In other
words, it determines the structure and properties of a family of organic compounds. Such an atom or group of
atoms or special kind of bond is called a functional group as it determines the overall function of the organic
compound.
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19
Now, let us consider an example. In the following compound:

CH3 Cl
the halogen atom, here chlorine, is the functional group as it determines the overall chemical properties of the
compound. It should be noted here that the carbon portion, i.e. CH3 , of the molecule, under suitable conditions,
undergoes the reactions typical of the class of compounds with C C single bonds ( called as alkanes - details
would be covered later). However, the set of reactions that characteristically determine the family of compounds
R X (here X is a halogen atom and R is an alkyl group) are the reactions that occur at the halogen atom. Let us
take another example:
CH3 OH
Here, OH (read as hydroxyl group) determines the characteristics of the family of compounds represented as
R OH. Hence OH is the functional group.
Let us now go on to examine a few very important functional groups that we will frequently encounter in the rest of
organic chemistry. What you are expected to do while going through the following discussion is to learn to identify
the functional groups wherever they appear in molecular or structural formulae of organic compounds. Also, your
job would be to learn their names. This would ease your understanding of assigning names to organic compounds
which we would discuss later. Apart from the names of functional groups, sometimes special names are assigned
to classes of compounds containing particular functional groups. For example, functional group OR (where R is
a hydrocarbon framework or can be called as an alkyl group) called as alkoxy functional group when present in a
class of compounds R1OR2 (R1, R2 may be two different alkyl groups) gives it the general class name ether.
Now, we move on to discuss the major functional groups as follows:
C double bond in alkenes
(1) C
Alkenes, sometimes also called as olefins, contain carbon-carbon double bonds imparting exclusive reactivity to
the alkene molecule. Hence, the double bonds are treated as functional groups. In case you are finding it awkward
to classify a kind of bond (here , C
C double bond) as a function group, please recall the definition of functional
group. An atom or group of atoms or any special feature of an organic molecule that imparts it a characteristic
reactivity has been discussed as a functional group. Since C
C double bond too attributes special reactive
nature to the organic compound in which it is present, hence this too is treated as a functional group.
Example 2
CH CH3
H3C H2C HC
C C double bond is a functional group and the class of

compounds in which it is present is called as alkenes
(2) C C triple bonds in alkynes

Carbon-carbon triple bonds also impart special kind of reactivity to the compounds in which they are present.
Hence, such triple bonds are considered as functional groups and the corresponding class of compounds are
called as alkynes.
Example 3
H3C C
C CH3
triple bond as a functional groups.
LOCUS
20
Note : Alkanes (simplest class of organic compounds) do not contain any functional group. They simply consists
of C C single bonds and attached hydrogen atoms as shown below. Hence, they are extremely unreactive.
Example 4
CH3 CH2 CH2 CH3
no functional group, hence very less reactive
(3) Hydroxyl (OH) group in alcohols

The functional group represented as OH attached to a carbon atom is known as hydroxyl group. The class
of organic compounds containing this group is called as alcohols. They are usually represented as R OH
where R is the hydrocarbon (alkyl) group.
Example 5
CH3 OH
'hydroxyl' functional group
(4) Alkoxy (OR) group in ethers

Ether is a class of compound consisting of two alkyl groups (usually denoted as R', R2, etc.) mutually connected
through an oxygen atom. The functional group here is OR (called as alkoxy) where R is smaller of the two alkyl
groups.
Example 6
alkoxy functional group
(here R of OR is 'CH3' group)
CH3 O C2H5
(5) Nitro group (NO2) in nitro compounds

The functional group nitro (NO2) is present in a class of compounds represented as RNO2 and called as nitro
compounds.
Example 7
CH3 NO2
nitro functional group
Note: Observe the following structural representation of the nitro group. It will assume major significance as we
move into organic reactions later.
O
O
N
R
N
O
correct structural formula

of NO2 group
incorrect structural formula as

nitrogen cannot have five bonds
LOCUS
21
(6) Halogen functional groups present in alkyl halides

Atoms such as fluoro, chloro, bromo and iodo are present as functional groups in R F, R Cl, R Br and
R I respectively. The class of such compounds R X (where X denotes a halogen atom) is called as alkyl
halide.
Example 8
CH3CH2 Cl
CH3 F
functional
group: chloro
(7)
CH3CH2 Br
functional
group: fluoro
functional
group: bromo
Carbonyl group ( C O ) in aldehydes and ketones
The presence of carbonyl functional group, structurally represented as C O , gives rise to the following two
classes of compounds:
H
(i) aldehydes, structurally represented as
CO
R
1
(ii) ketones, structurally represented as
CO
R
Note: The only difference between the above two structural representations is that aldehyde always has at least
one hydrogen atom attached to the carbonyl carbon atom, while ketone has alkyl groups (R1 and R2, say) as the
two substituents on the carbonyl carbon.
Example 9
two alkyl groups (and no H atom) on
carbonyl carbon, hence ketone
at least one H atom on carboxyl

carbon, hence aldehyde
H
CO
CH3
CO
CH3
C2H5
CO
CH3
CO
CH3
Carbonyl functional group

(8) Carboxyl group (COOH) in carboxylic acids
The carboxyl functional group imparts to its class of compounds, carboxylic acids the special reactivity of acids as
the name carboxylic acids itself suggests. Structurally, the functional group is represented as follows:
O
RC
OH
Carboxyl functional
group
is the acidic proton that imparts acidic nature to

the functional group and hence to the compound
(note that 'R' could be H atom too).
LOCUS
22
Example 10
O
HC
O
CH3 C
OH
OH
Carboxyl functional group
(9) Carboxyl group with an additional alkyl group (COOR) in esters.

This functional groups is written by replacing H atom ( of carboxylic OH) with alkyl group R. Structurally, the
functional group being discussed here is represented as (note that R1 is not a part of the ester functional group):
functional group (obtained from carboxyl
group) characteristic of esters
O
1
R COR
alkyl group replacing the acidic H atom of the

corresponding carboxyl functional group.
Example 11
functional group characterising esters
O
CH3 C O CH3
alkyl group replacing the acidic H atom

of the carboxyl functional group.
(10) Functional group (COCl) present in acyl chlorides.

Structurally, the functional group is represented as
O
functional group in acyl chlorides.
RC
Cl
It is written by replacing the OH in carboxylic acid with the chloro groupCl.

Example 12
O
O
replace OH
CH3 C
OH
carboxyl
functional group
by Cl
CH3 C
Cl
functional group
in acyl chlorides
LOCUS
23
(11) CONH2, CONHR or CONR1R2 functional groups in amides.

The class of compounds called as amides may contain any of the following functional groups.
RC
R C
or
R C
or
N
R
possible functional groups
These are written by replacing the OH of the carboxyl group by the following respective groups:
O
or
RC
or
R C
OH
R C
OH
replace 'OH'
by 'NH2'
OH
replace 'OH'
1
by 'NHR '
replace 'OH'
1 2
by 'NR R '
RC
R C
R C
NH R
NH2
NR R
The dashed region shows the possible functional groups present in amides.
Example 13
O
functional group
CH3 C
alkyl group on N atom is not
a part of the functional group.
(12) Amino (NH2) group in amines.

Here, the amino functional group NH2 is present on a carbon atom of the hydrocarbon framework, R. It is
represented as R NH2 and the NH2 group imparts a basic (contrary to acidic nature of carboxyl functional
groups) character to the compound.
LOCUS
24
Example 14
CH3CH2 NH2
amino functional group
hydrocarbon framework,
represented above as 'R'
Note: Compare the slight difference in the names of the two classes of compounds amides (in discussion (11)
above) and amines (in discussion (12) above). The structural difference between the two classes of compounds,
as you must have noticed by now, is that the amide class of compounds have carbonyl functional group present in
them, while amines do not have any carbonyl group.
(13) Cyano group ( C N) in cyanides.
Cyanide compounds are also called as nitriles or nitrile compounds. This class of compounds is represented as
R CN.
Example 15
CH3 C N
cyano functional group.
(14) Acetal class of compounds

Acetals are those compounds that have two oxygen atoms singly bonded to the same carbon atom of the organic
compound. Structurally, we can represent it as follows:
CH3
C2H5
R1
R2
functional group characterising the

class of compounds called as acetals
Example 16
CH3
CH3
CH3
CH3
characteristic functional group.
C
the carbon atom to which the two
oxygen atoms are singly bonded
The following table enlists a general formula for various classes of compounds and corresponding functional
groups. Note that subscript n stands for number of carbon atoms present in the compound.
LOCUS
25
Table 1 : Functional groups and general formula

Class of compound
Functional group
General formula ( n = no. of Catoms)
Alkenes
C
C double bond
Cn H 2 n
Alkynes
C C triple bond
Cn H 2 n 2
Alcohols
OH (hydroxyl)
Cn H 2 n + 2 O
Ethers
OR (alkoxy)
Cn H 2 n + 2 O
Aldehydes
O (carbonyl)
Cn H 2 n O
Ketones
O (carbonyl)
Cn H 2 n O
Carboxylic acids
Cn H 2 nO2
COOH (carboxyl)
O
Esters
Cn H 2 nO2
C O (carboxyl with an additional

alkyl group on saturated oxygen atom)
Section - 3
REPRESENTATION OF ORGANIC COMPOUNDS
Let us now devise a method to conveniently represent organic molecules on paper. This would improve our
approach to deal with those organic molecules whose structures appear complex. We will here focus upon the
central chain of carbon atoms that runs through the entire molecule. This may even form a ring structure. Observe
the following compounds:
H H
C
H
H
CCC
H
H
H
H
C C
|
|
CC
|
|
H H
CH3 CH2 CH3 or C3H8
C5H10
(1)
(2)
H
H
H
Note that with increasing number of carbon atoms, it becomes increasingly inconvenient to draw the structures.
Also, the C-atoms forming the skeleton practically do not exist in straight lines. On the other hand, let us draw
them in a zig - zag fashion to realise their practical way of existence and also increase our comfort at drawing the
molecules. Study the following example.
LOCUS
26
H
H
H
C
simple
representation
H
(3)
(4)
Here, the zig - zag pattern (4) is very clear to comprehend and it eliminates any confusion between the hydrogen
atoms attached to the various carbon atoms. However, the following aspects of arriving at diagram (4) from
diagram (3) should be kept in mind.
(i)
Every kink in representation (4) and the two ends of the line show a C-atom.
(ii)
Hydrogen atoms bonded to C-atoms are not shown; not even the bonds between hydrogen and carbon
atoms. Even without drawing them their presence is implied. Any carbon atom in representation (4) whose
four bonds are not explicitly shown is assumed to have as many hydrogen atoms as needed to satisfy the
valency of carbon which is 4.
(iii)
Most important is the rule that C atoms are not shown explicitly by writing C.
Study the following figure for complete understanding of the above stated rules:
end of line represents
a C-atom
every kink in the chain (bond-line diagram)

represents a C-atom
OH
this H-atom is shown

because it is bonded
to oxygen: a hetero atom
(atom other than C or H)
O
this C-atom must
also carry 3H-atoms
because only 1 bond
is shown attached
to it
these 2 C-atoms
should also carry
1 H-atom because
only 3 bonds are
shown for each
C-atom
each of these 2
C-atoms have two
bonds shown, hence
each should also
carry 2 H-atoms
this C-atom has all

its 4 bonds shown,
hence no H-atoms
are implied
Fig - 19
Here, it is noteworthy that all hetero atoms are explicitly shown; even H atom(s) bonded to such hetero atoms are
shown. We will now consider some examples.
Example 17
H H H H
|
|
|
|
HCCCCH
|
|
H
H
represented
as
these C-atoms carry
1 H atom each
LOCUS
27
Example 18
OH
CH3 CH CH COOH
represented
as
C atom has
no H atom
C-atom has
3 H atoms
Example 19
OH
|
CH
OH
represented
OH
COOH
as
C
||
O
CH3
sometimes, C-atom, being part of the

functional group, may be clearly shown
Example 20
O
represented
CH3
OH
as
OH
Example 21
CH3
CH2
represented
NH2
NH2
as
H atoms bonded to hetero

(here, nitrogen)atom is shown
Example 22
CH2
CH2
CH2
CH2
CH
N
represented
as
N
lone pair of electrons on
N-atom is shown here
From the above examples we can conclude that the basic purpose of highlighting the functional group(s) should be
served. At times, we may even show hydrogen atom(s) bonded to the carbon skeleton or we may even show a
lone pair of electrons (a pair of electrons not involved in a chemical bond). The core idea is that any molecular site
which is participating in a given reaction should be explicitly shown.
LOCUS
28
Also, you can draw the bond-line diagrams in any other convenient orientation. For example:
Example 23
CH3
OH
|
CH
OH
represented
COOH
or
COOH
as
OH
OH
For further convenience and to focus our attention only on the reactive part of the organic compound, we put a
curvy line which is nothing but a pictorial indication of an incomplete structure. Observe the following representation:
curvy (wiggy) line to indicate
rest of the compound
represented
as
The curvy line within the dashed space above simply denotes that we are, for the time being, not concerned with
the non-carboxylic part of the molecule. This approach not only reduces our efforts to repeatedly draw irrelevant
molecular portion but also prevents us from unnecessarily thinking about it.
Note: If we want to represent the three dimensional (spatial) orientation of organic molecules on paper, we
proceed as follows:
(i)
Show one of the substituents on the carbon atom as coming out of the plane of the paper towards us, and
the other substituent going away from us, into the plane of the paper.
COOH
(ii)
The coming-out-of-the-paper bond can be shown using a bold-wedged diagram:
(iii)
The going-into-the-paper bond can be shown using a dashed-wedged (or non-wedged) diagram fading
away from us: dashed-wedged
or dashed (not wedged)
(iv)
The other bonds attached to the carbon atom can be depicted using straight lines as if in the plane of the
paper.
Observe the following representation:
bond going into
the paper
CO2H
NH2
H2N
three-dimensionally
represented as
CO2H
H
bond coming out

of the paper
other two bonds in

the plane of the paper
While drawing such diagrams, prefer showing the functional groups as coming-out-from or going-into the plane
of the paper but retain the basic carbon skeleton in the plane of the paper.
LOCUS
29
Example 24
OH I
OH
drawn
as
I and OH are respectively

shown 'coming-out' and 'going-into'
the plane of the paper
Let us now study the various types of carbon atoms on the basis of number of neighbouring carbon atoms to which
it is bonded. Following five types of carbon atoms can be arrived at:
(1)
Methyl carbon
CH3 OH
Here, the carbon atom is not bonded to any other carbon atom.
neighbouring
C-atom
(2)
Primary carbon or 1 carbon.

OCH3
Here, the carbon atom is attached to only one neighbouring carbon atom.
(3)
Secondary carbon or 2 carbon
OH
two neighbouring C-atoms.
The carbon atom is attached to two neighbouring carbon atoms.
(4)
Tertiary carbon or 3 carbon
Cl
3 neighbouring
C-atoms.
Here, the carbon atom is attached to three neighbouring carbon atoms.

(5)
Quaternary carbon or 4 carbon
OH
The carbon atom is attached to four neighbouring carbon atoms.

Section - 4
CONJUGATED SYSTEMS
Certain organic compounds exhibit conjugation which well discuss in this section. Conjugated systems are of so
much importance to organic chemistry that they merit a separate section for their discussion.
LOCUS
30
A system is said to be conjugated if it contains alternate single and multiple bonds. For example, the following
compounds are conjugated:
CH2 CH CH CH2
CH3 CH CH CH CH CH CH CH3
Such compounds in which the bonds are conjugated are found to be slightly more stable than the compounds in
which these bonds are isolated. For example, consider the following two compounds which have the same molecular
formula.
CH2 CH CH2 CH CH2
CH3 CH CH CH CH2
(i)
(ii)
Even though these two compounds appear to be the same except for the positioning of one of the double bonds,
it is found that compound (i) is thermodynamically more stable than compound (ii).
The fact that conjugated compounds are slightly more stable than their corresponding non-conjugated counterparts
is experimentally provable:
(i) Conjugated molecules exhibit a lower heat of combustion
(ii) They exhibit a lower heat of hydrogenation
(iii) It is found that isolated double bonds can be made to migrate under certain conditions quite easily to form
conjugated system. This shows that conjugated systems are more stable.
As an example, consider the following reaction which takes place easily under alkaline conditions. Observe how
the double bond migrates to form a conjugated system which is stabler:
|
CH CH CH2 C O
Base
Non-conjugated system
|
CH2 CH CH C O
Conjugated system
Now the question that arises is: Why should conjugated systems be more stable?
In organic chemistry, a very powerful rule of thumb can be used to explain a lot of phenomenon regarding stability
of molecules : the greater the delocalisation (spread) of charge on the molecules surface (or surroundings), the
more stable that molecule tends to be. This is intuitively appealing: if we try to localise charge on some region of
the molecule, that region would tend to get destablised because of the high concentration of charge in a small
region. However, spreading the charge will result in lower local charge density and hence more stability. A complete
justification of this rule has its basis in Molecular Orbital Theory which we will not delve into here.
We can now use this rule to explain why conjugated systems are stabler. In particular, well discuss why compound
(i) above is stabler than compound (ii). First visualise the orbital picture for compound (ii), and observe that it has
two localised bonds , these being at the two ends of the carbon chain:
H2C CH CH2 CHCH2
Orbital picture of compound (ii)
Fig - 20
In this figure, only the uhybridised

2p orbitals used in the -bond
formation are being emphasised
LOCUS
31
Now visualise the orbital picture for compound (i) :
Here too, only the unhybridised

2p orbitals are being emphasised
CH3 CH CH CH CH2
Orbital picture of compound (i)
Fig - 21
Can you notice the difference between the orbital pictures of the two compounds?
If we number the carbon atoms from left to right, notice that in compound - (i), a sideways overlap is possible even
for the 2p orbitals on the third and fourth carbon atoms. This overlap is depicted using the dashed curve in the
figure. This means that sideways overlap can take place between all the four 2p orbitals on the adjacent carbon
atoms. This overlap will result in a (molecular) orbital delocalised over all the four carbon atoms as shown below:
A very approximate picture
showing the delocalised molecular
orbital due to adjacent overlap of
four 2p orbitals in compound (i)
CH3 CH CH CH CH2
Fig - 22
Such an extended delocalisation, which is not possible with compound (ii), is the reason that compound (i) is more
stable.
Benzene: A highly conjugated system
As another example of conjugation, well discuss in brief here the orbital picture of benzene, which exhibits a high
degree of conjugation.
The molecular formula for benzene is C6 H6 and the structure of benzene is known to be planar. The six carbon
atoms are connected in a hexagonal ring. This implies that each carbon atom must be sp2 hybridised: two of the
three hybrid orbitals will be used in bonding with two other adjacent carbon atoms in the benzene ring while the
third hybrid orbital will be used to bond with the hydrogen atom. The fourth unhybridised 2p orbital on each
carbon remains perpendicular to the plane of the ring
4
6
In this approximate orbital

picture of benzene, the
unhybridised 2p orbitals
have been emphasised.
Note that the carbon atoms
have been numbered
Fig - 23
Sideways overlap of the 2p orbitals could take place in one of the two possible ways, leading to two possible
structures which are represented below:
LOCUS
32
1 2, 3 4, 5 6
1 6, 2 3, 4 5
Fig - 24
The two possible structures so formed are called the Kekule structures of benzene.
However, no such Kekule structures exist as such. The fact that overlap does not take place has been described
in the figure above. Note that in the benzene ring, the bonds are conjugated. Therefore, what actually happens is
that all the six adjacent porbitals overlap. Well not discuss in detail what exactly happens when these six
porbitals overlap (actually six new Molecular Orbitals will be formed; this is part of Molecular Orbital Theory).
It will suffice to say for now that the overlap of all these six p-orbitals will result in the formation of an annular
electron cloud, above and below the plane of the benzene ring.
Fig - 25
This figure should make it clear to you that the benzene molecule is a highly conjugated system (the 2p electrons
are delocalised all over the ring). This explains the fact that benzene exhibits a very high thermodynamic stability.
Well discuss more about the stability of benzene in a question later on.
Section - 5
RESONANCE
In the last section, we discussed about the two possible (theoretical) structures of benzene, called the Kekule
structures. However, as mentioned there only, these Kekule structures actually do not exist. The actual structure of
benzene involves a molecular orbital delocalised over the entire ring.
We can say that the actual structure of benzene is a hybrid of the two Kekule structures. The figure below depicts
this relation between the two thoretical Kekule structures and the real benzene molecule which is a hybrid of
these two structures.
LOCUS
33
The real benzene molecule

in which the molecular
orbital is delocalised over
the entire ring
The two (theoretical) Kekule

structures of benzene
On the left hand side above, we have used curved arrows in the first Kekule structure. You must understand very
carefully that these curved arrows do not represent an actual movement of electrons . (In fact, as already
mentioned, this Kekule structure does not even really exist). The curved arrows are just a representation tool that
we use to link one Kekule structure to the other (in other words, the curved arrows in the Kekule structure tell us
how to obtain the other Kekule structure; they do not in any way represent a real movement of electrons).
Such a phenomenon in which different theoretical structures can be written for a molecule, and the actual structure
of the molecule is a hybrid of all the theoretical structures, is called resonance. The various theoretical structures
are called the canonical forms of the molecule under consideration while the actual structure is the resonance
hybrid of these canonical forms.
Thus, for example, benzene exhibits resonance. It has two canonical forms given by the two Kekule structures
while the actual benzene molecule is a resonance hybrid of these two Kekule structures.
You should understand this carefully that resonance is a way of representing molecules, that cannot be represented
adequately by a single structure, by a combination of two or more classical structures (the canonical forms). These
structures can be related to one another through curved arrows as already used for benzene: the tail of the curved
arrow indicates where an electron pair moves from and the head of the curved arrow indicates where it moves to
in the molecule. To emphasize again there is no such movement of electron pairs in reality. You should not visualise
the canonical forms as interconvertible structures that are rapidly oscillating from one form to another. What exists
in reality is a single, stable structure that can be said to be a hybrid of the various (nonreal) canonical forms.
Let us consider another example of a molecule which exhibits resonance. Consider the acetate anion, CH 3COO ,
whose theoretical structure is represented below:
O
CH3 C
O
This figure indicates that the two carbonoxygen bonds should turn out to be of different lengths since one is a
single bond while the other is a double bond. However, this is not the case. Experiments prove that the two
carbon-oxygen bonds in the acetate anion are of exactly the same length; in other words, it is impossible to
distinguish between the two oxygen atoms.
This is explained as follows: the actual structure of the acetate anion is a hybrid of the two canonical forms
possible.
O
CH3 C
O
O
CH3 C
O-
The two (theoretical) canonical

forms of the acetate anion
CH3 C
The real acetate anion is a

resonance hybrid of its two
canonical forms
LOCUS
34
Observe that in the real (hybrid) acetate anion, the negative charge is delocalised over both the oxygen atoms (and
not just one). This explains the fact that the two oxygen atoms are indistinguishable.
As another example, observe carefully how resonance takes place in the following ion (which is allyl carbocation
(discussed later)):
+
CH2 CH CH2
CH2 CH CH2
CH2 CH CH2
The actual structure of this ion shows how the positive charge is spread (delocalised) over the entire molecule
rather than on just one carbon atom as in the theoretical canonical forms.
What physical significance does resonance have? Observe carefully that what resonance actually implies is
delocalisation of charge. Thus resonance in a compound implies increased stability due to delocalisation. In general,
the more the canonical structures that can be written for a compound, the greater should be the delocalisation of
electrons, and the more stable the compound will turn out to be.
Let us now list down some general rules pertaining to the writing of canonical forms for a given compound. The
justifications of these rules are straight forward:
(a)
(b)
(c)
(d)
(e)
In each canonical form, the constituent atoms of the compound must occupy the same relative positions.
All the canonical forms must contain the same number of paired electrons.
The various canonical forms should not differ too much in their energy content. If such a case occurs, the
canonical forms with higher energy content will contribute very little to the hybrid; their contribution to the
hybrid will be irrelevant.
For canonical forms that have the same energy content (for example, the two forms for the acetate anion),
the stabilising effect of resonance is more pronounced. Thus, we should expect benzene molecule, acetate
anion and allyl carbocation to be stable entities.
Structures which have charge separation will be of a higher energy content than structures which dont, and
hence the former will contribute lesser to the stability of the hybrid
+
(f)
CH2 CH CH2
CH2 CH CH2
(i)
(ii)
In the figure above, the contribution of carbocation (ii) in the stability of the hybrid allyl carbocation will
be negligible since it has high degree of charge separation.
Delocalisation (resonance) occurs most effectively when the atoms attached to the carbon atoms involved
in multiple bonds lie the same plane (or nearly in the same plane). In such a case, the lateral overlap of the
unhybridised 2p orbitals is the most effective.
As a concluding example, consider the stabilising effect of resonance in the following anion:
OH
OO
O
O
-
Canonical forms
Actual Structure
In the actual structure, the negative charge is not concentrated only on the oxygen atom. It is also delocalised
over the entire ring due to resonance.
LOCUS
35
Example 25
The C O double bond energy is significantly less than twice the CO single bond energy. What could be the
possible reason?
Solution: The oxygen atom in C O is sp2 hybridised with its two lone pairs of electrons present in sp2 hybrid
orbitals (120 apart). On the other hand, the oxygen atom in CO is sp3 hybridised (as in
CH 3 O CH 3 , for example) implying presence of lone pairs of electrons in tetrahedral (109
apart) hybrid orbitals. Hence, lone pairs on oxygen are initially more distant in
than in CO
due to reduced electrostatic repulsion amongst the lone pairs.
Further, no such lone pair is available on carbon atom. Hence, the
double bond energy (of
1 and 1 bond) is significantly lower than twice the CO single bond energy (one bond).
Example 26
In the spectroscopic analysis of dienes, it is observed that simple dienes absorb in the ultra-violet region of the
spectrum while as the extent of conjugation increases, the absorption moves towards the visible range of the
spectrum. Thus, highly conjugated dienes are colored. Justify this observation.
Solution: As the extent of conjugation increases, the delocalisation of bonding electrons also increases, thus
imparting extra stability to the excited states of dienes. Their extra stability implies lowering the energy
level of the dienes excited states. It leads to reduction in energy gap between ground and excited
states of conjugated compounds, in comparison to compounds containing isolated double bonds. The
overall effect is that with increasing conjugation, energy gap goes on decreasing, implying lower amount
of energy (and hence higher wavelength radiation) for exciting a ground state electron. Thus, dienes
with increasing extent of conjugation increasingly absorb in the visible range (higher wavelength)
compared to simple dienes absorbing in the ultra-violet region (lower wavelength). Hence, highly
conjugated dienes are coloured.
Example 27
Draw the possible canonical forms of the following compounds and also represent their respective resonance
hybrid.
O
(a)
CH3 C CH2
(b)
CH3 CH CH CH O
Solution: Canonical forms and corresponding resonance hybrids are drawn as below:
CH3 C CH2
CH3 C CH2
(a)
O
CH3 C
CH2
canonical forms
reronance hybrid
LOCUS
36
(b)
CH
CH3
CH
CH
CH3
CH
CH
CH
CH
O-
CH3
CH
CH
Example 28
Is delocalization possible in allene, CH2 C CH2 ? Explain with reasoning.
Solution: CH2 C CH2 (called as allene) has its central C-atom doubly bonded to two other C-atoms
(of methylene groups, CH2). There is no single bond separating the two double bonds. Hence, no
conjugation is possible, leading to a complete absence of delocalisation of electrons.
Let us understand with the help of orbital picture as to why delocalisation cannot occur. In the following
figure, it is easy to see that 2C is sp hybridised while 1C and 3C are sp2 hybridised. Further, the two
bonds are mutually perpendicular. Absence of their coplanarity prevents delocalisation of electrons.
sideways
overlap
H
2
C
H
H
1
H
in horizontal plane
(or plane of C-skeleton)
C C and C C bonds (formed

as a result of overlap of p orbitals
along mutually perpendicular axes)
are at right angles to each other
1
C
H
in vertical plane (or plane

perpendicular to C-skeleton)
Here, along with the two -bonds, the two terminal

CH2 (methylene) groups are perpendicularly oriented (as shown
by the horizontal and vertical planes)
Fig - 26
LOCUS
37
TRY YOURSELF - I
1
Q. 1 Consider the compound C H3 C H C H C H C H2 explain the following observations.

(i) The C3 C4 bond length is shorter than a C C single bond.
(ii) There is significant restriction on rotation about the C3 C4 single bond.
Q. 2 Consider the following enthalpies of hydrogenation:
(i)
+ H2
H = 120 kJ / mol 1
(ii)
+ 2H2
H = 232 kJ / mol 1
(iii)
+ 3H2
H = 208 kJ / mol 1
Observe that enthalpy of hydrogenation of the cyclic diene in (ii) is almost twice of cyclohexene in (i). Thus, if
benzene were to exist as a kekule structure (with three double bonds), we could expect the enthalpy of hydrogenation
of this hypothetical structure to be three times that of cyclohexene, i.e., approximately 3x ( 120 kJmol1)= 360
kJ mol1.
However, the actual enthalpy of hydrogenation, for the real benzene, is only 208 kJ mol1, as given in (iii).
Thus, real benzene is thermodynamically more stable than the hypothetical cyclohexatriene by 208 ( 360)
= 152 kJ mol1.
On the other hand, a conjugated diene is more stable than a non-conjugated diene by only around 17 kJ mol1.
Explain why benzene exhibits such high stability.
Q. 3 Mention the possible reason(s) that phenol, PhOH, exhibits acidic behavior, while aliphatic alcohol, of the
general form ROH, does not.
Q. 4 Draw possible canonical forms and corresponding resonance hybrids of the following compounds:
+
(i) CH2 CH2 CH2
(ii) CH2 CH CH CH2
(iii)
Q. 5
(iv) CH3 CH CH CH NH2
Given below are pairs of resonating structures Predict which one would contribute most to the hybrid and
explain your answers.
O
CH2 C CH3 (ii) H C
(i) CH2 C
CH3
(iii) CH3 CH OH
Q. 6
Q. 7
O
HC
OH
OH
CH3 CH OH
Though cyanic acid ( H O C N ) and isocyanic acid ( H N = C = O ) yield the same anion
on losing a proton, the two acids are not regarded as resonance structures of each other. Explain
Which has a shorter carbon-nitrogen bond length: methylamine or formamide?
LOCUS
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Section - 6
MECHANISM IN ORGANIC REACTIONS
A general organic reaction may be depicted as:

Attacking
reagent
Substrate
[Intermediate]
Products(s) + By-products(s)
As we can see, there are two reactants: substrate and reagent. Substrate is the reactant that supplies carbon to the
newly formed bond. The other reactant is called the reagent.
In case, both reactants supply carbon to the new bond, the molecule on which attention is focussed is arbitrarily
chosen as the substrate.
Mechanism is the actual process by which the reaction takes place. It tells us which bonds are broken, which new
bonds are formed, the order in which bond fission-formation takes place, the steps involved etc.
In most of the organic reactions that we will encounter, bonds are broken. This can occur in either of two ways:
(i) Homolytic fission
(ii) Heterolytic fission
Bond fission leads to formation of reactive intermediates and the natue of these intermediates depends on the
mode of bond cleavage. In other words, what type of intermediate species (carbocation, carbanion etc.) are
formed will depend upon the way a particular bond breaks.
Futher, reagents and intermediates, together, decide the type of reaction a given substrate will undergo e.g. addition,
substitution etc.
(a) BOND CLEAVAGE
A knowledge of how bond cleavage takes place in molecules is important to understand the various transient
intermediate structures formed during reactions. There are three ways in which a covalent bond can be broken:
(i)
A B
A +B
This sort of cleavage is termed homolytic fission because each group separates with one electron. The
entities so formed are very reactive and are known as radicals. Such cleavage generally occurs in the gas
phase or in non-polar solvents. It can be catalysed by light (as in the substitution of methane which will be
discussed suitably under free radical reactions) or by the addition of other radicals
(ii)
AB
A: + B
(iii)
AB
A: + B
In the process of cleavage, it could happen that one group separates with both the electrons of the covalent
bond. This will result in the formation of an ion pair. Note that it can happen in two ways as in (ii) and (iii)
above. Such cleavage is termed heterolytic fission. This generally occurs in solution in polar solvents.
There are two reasons for this.
(a) a polar solvent aids in the separation of charge (by favouring the bond cleavage process)
(b) the resultant ion pair so formed can be stabilised through solvation (by the molecules of the polar
solvent.)
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39
In the context of carbon compounds, a carbocation is a positive ion in which a carbon carries the positive charge
while a carbanion is a negative ion in which a carbon atom carries the negative charge.
The three transient intermediates discussed here may be formed in an actual reaction for only very short durations
and in very low concentrations, but they are the prime controlling factors that determine the outcome of the
reaction. Finally, other reaction intermediates also exist. Well discuss about them in later chapters. However, free
radicals, carbocations and carbanions are the intermediates mostly encountered in organic reactions.
(b) REACTION INTERMEDIATES
Carbocations: As we have already understood that carbocation is simply a positively charged organic ion
where the positive charge is present on the C-atom. In other words, the C-atom is electron-deficient as it is
bonded to three other atoms, thus amounting to a total of only 6 electrons (2 electrons less than octet) in the
valence shell. The positively charged C-atom is sp2 hybridised yielding three sp2 hybrid orbitals lying in the same
plane as that of the C-atom, and are directed towards the corners of an equilateral triangle. Let us analyse the
following diagram of the simplest possible carbocation - the methyl cation:
empty p orbital
H
C
H
H
or
H
or
H
H
sp s bond
2
planar trigonal
shape due to 3 bonds
structural representation
orbital representation
(a)
(b)
Fig - 27
Notice here that the planar trigonal shape due to 3 bonds (involving 3 sp2 orbitals of the positively charged
C- atom and three 1s orbital of the H atom) is flat. However. Fig. (b) shows an empty (and unhybrid) p orbital
lying perpendicular to the plane of the three bonds. This empty p orbital imparts, to the entire carbocation,
reasons to be unusually stable or unstable. There are various factors that contribute to increase or decrease in
carbocation stability. The degree of stability attained by a carbocation is mainly determined by how well it
accommodates the positive charge. Electrostatically, a charged system is more stable if the charge is dispersed
over more atoms. Thus, it can be concluded that any phenomenon which encourages the spread of positive
charge and disperses it over the rest of the ion stabilizes the carbocation.
Consider a case when the positively charged C-atom has a substituent, say A, in place of a H-atom. Relative to the
H-atom, this substituent A may either withdraw electrons or release electrons. An electron-releasing A would
reduce the positive charge at the C-atom; As electron-releasing tendency would impart slight positive charge to A
itself, thus overall a dispersal of the positive charge would occur imparting stability to the carbocation. Observe the
following figure:
H
H
H
H
C
electron-releasing substituent :
dispersal of charge; stabilizes
cation
electron-withdrawing substituent :
intensification of charge; destabilizes
cation
(a)
(b)
Fig - 28
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40
Further, an electron-withdrawing substituent intensifies the positive charge on the already electron-deficient
C-atom, making it less stable. Refer Fig.... (b) above.
Hence, we can say that the higher is the number of electron-releasing substituents, more stable is the carbocation.
Such a phenomenon of availability (release or withdrawal) of electrons at the reaction site is called as polar
effect.
Carbanions: We shall now move onto another kind of transient intermediates carbanions. As the name itself
suggests, this kind of intermediate has a negative charge being carried by the C-atom. This negatively charged
C-atom could be either sp3 hybridised (resulting into a pyramidal configuration Fig... (a)) or sp2 hybridised (yielding
planar trigonal arrangement, Fig.... (b)). Examine the following possible configurations.
unhybrid p orbital
containing the ve charge
R3
or
C
R1
R2
R3
R2
R1
smaller lobe of the orbital

is not shown here
(a)
(b)
Fig - 29
In the above figure, R (R1, R2, R3) is any hydrocarbon group. Now, of the two possible configurations shown in
Fig...., which one actually exists in a given organic reaction depends on the nature of R1, R2 and/or R3. For the time
being, it is sufficient for you to understand that a carbanion may have any of the two possible configurations. In
fact, the actual configuration may be intermediate between the two.
The stability of a carbanion is judged on grounds similar to those applicable to carbocations. The higher the
number of electron-withdrawing substituents on the negatively charged C-atom, the more is the dispersal of the
negative charge and hence, increased stability of the carbanion.
Free Radicals: We now move onto understand free radicals one of the most reactive transient intermediates. By
definition, an atom or group of atoms having an odd electron (an electron which is not paired; it does not have a
partner of opposite spin) is called a free radical. Its symbolic representations includes a dot () to indicate an odd
electron. Further, when a free radical participates in a reaction, the movement of the single electron (or even in
cases where no free radical is innolved, but we need to exclusively depict the movement of one single electron and
not one pair of electrons) is indicated by a single - barbed curved arrow, as shown below:
A : B
homolysis
A + B
single-barbed curved
arrow denotes movement
of a single electron
Note: Movement of a pair of electrons in an organic reaction is shown by the normal double - barbed curved
arrow as drawn below:
heterolysis
A: + B
A : B
ion pair
normal double-barbed curved arrow
denotes movement of an electron pair
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41
Structurally, the case of a free radical is somewhat similar to that of carbanions as far as location of the odd
electron is concerned. Two configurations are possible: one, the unpaired electron is present in an unhybrid
p orbital (with rest of the sp2 hybrid orbitals forming planar trigonal configuration); and second, the odd electron
could be present in a sp3 hybrid orbital (thus giving a pyramidal shape to the radical). The two possibilities are as
shown below:
R3
120
R1
120
R2
C
120
sp3 hybrid orbital

containing the odd
electron
unhybrid p orbital
containing the odd
electron
or
R3
R2
R1
sp2 hybrid C-atom
sp3 hybrid C-atom
(a)
(b)
Fig - 30
Experimentally, it has been found that most simple alkyl radicals are planar trigonal at the carbon having the
unpaired electron. The simplest alkyl radical is CH3 called as methyl radical. However, an experimentally observed
exception is that of CF3 which has essentially sp3 hybrid C-atom. Hence CF3 has a pyramidal geometrical
shape.
Let us now discuss the stability aspects relating to a free radical. Although alkyl radicals are uncharged, the carbon
that bears the odd electron is electron-deficient (as its octet in the valence shell is not complete). Hence,
electron-releasing substituents (recall polar effects) bonded to such a C-atom would stabilize it, and the more
such substituents are, the more stable the radical would be.
Carbenes: Carbenes are neutral species in which carbon atom forms only two bonds (C is bonded to only 2
atoms) and has only 6 valence electrons. Out of these 6 electrons, 2 are present in each bond and the remaining
2 are non-bonding electrons.
A carbene may be represented as:
R1
:C
R2
Carbenes are very reactive species and have a lifetime of less than 1 second. They can only be isolated by trapping
them in matrices at low temperature.
Generation of carbenes:
(i)
-elimination: In these types of eliminations, both leaving groups are from the same atom. e.g. When
chloroform is treated with a base, it leads to the formation of dichlorocarbene.
Cl
Cl C H + OH
Cl
very acidic proton
due to presence of
three electron
withdrawing Cl atoms
Cl
Cl C
Cl
Cl
C
Cl
Cl
loss of Cl
leads to formation
of carbene
dichloro carben
LOCUS
42
e.g. Decarboxylation of sodium trichloro acetate.

O
Cl
Cl
> 80C
Cl C C
O Na
Cl
CO2
Cl
C
Cl
Cl
Loss of CO2, leaving

behined the electron
pair
(ii)
Cl C
Cl
Cl leaves with bonding

pair of electron, leading to
formation of carbon
dichloro carbene
Disintegration of compounds containing certain types of double bonds.

R
R
C = Z
C : + !Z
e.g. Decomposition of diazomethane.
CH2 N N
hv
CH2 + N N
loss of N2 leads to
formation of carbene
Types of carbenes:
There are two types of carbenes: (i) Singlet (ii) Triplet.
Both singlet and triplet carbenes are sp2 hybridised and the two differ only in the way the non-bonded electrons
occupy the orbitals.
(i)
Singlet carbene: In case of singlet carbenes, the two non-bonded electrons are present in the sp2 hybridized orbital. The unhybridized p-orbital remains vacant.
unhybridized
p-orbital empty
H
smaller
bond angle
(100-110)
C
H
Sp2 hybridized orbital

contains non bonding
electrons
2 electrons cause
more repulsions
(ii).
Triplet carbene: The two non-bonding electrons in triplet carbenes occupy different orbitals. One electron
is present in sp2 hybrid orbital and the other is present in unhybridized p-orbital
LOCUS
43
unhybridized p-orbital
contains one nonbonding
electron
H
Larger
bond angle
(130-150)
sp hybridized orbital
contains one non-bonding
electrons
C
H
only 1 electrons
less repulsions
All carbenes can exist either as singlet or triplet. However, most carbenes are stable as triplet states
because the energy that can be gained by bringing the electron to more stable sp2 orbital is insufficient to
overcome the repulsion that arises due to pairing of electron.
Section - 7
ELECTRONIC EFFECTS IN MOLECULE
A number of factors operate in molecules that govern the charge density available at different sites in the molecule.
We will discuss these effects in the context of organic molecules in particular.
(a)
INDUCTIVE EFFECT:
This effect takes place whenever two atoms/groups of different electronegativities are bonded to each other.
The more electronegative atom/group of the two will tend to draw the shared electron pair more towards
itself, resulting in a skewed rather than a symmetrical electron charge distribution.
Consider two atoms A and B bonded to each other, with B being more electronegative. B will tend to pull the
electron pair of the covalent bond towards itself. This means that overall, the electron pair of the covalent
bond will spend more time near B than A, resulting in a slight negative charge ( ) on B and a slight positive
charge (+ ) on A:
+
A
B is more electronegative than A, so its

pull on the electron pair is greater than A
+
A
An approximate orbital picture showing the

skewed electron charge density between A and B
Fig - 31
Consider the compound CH 3Cl (methyl chloride). Chlorine is more electronegative than carbon. Thus,
methyl chloride shows the inductive effect : electron density is greater near the chlorine atom
H
H
+
C
Cl
H
Inductive effect in
methyl chloride
H
H
Cl
H
An approximate orbital picture showing the skewed
charge distribution between carbon and chlorine
Fig - 32
+
C
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44
Thus, it should be noted that inductive effect in a molecule is a state of permanent polarisation of the molecule.
This will show up in the physical properties of the molecule like its dipole moment.
Inductive effect can be propagated down a chain. Consider the following carbon chain, with chlorine at one
end. Observe how the inductive effect propagates down the chain:
+ + +
Cl
It should be clear that the strength of the inductive effect falls as we proceed down the chain. For all
purposes, the transmission of the inductive effect after the second carbon atom is negligible.
C
3
+
C
2
+
C
1
Cl
Decreasing skewness of charge

distribution along the C-skeleton
A crude orbital picture showing how the

inductive effect dies down along the chain
Fig - 33
Inductive effect is abbreviated as the I-effect

Further, any atom or group which attracts electrons more strongly than hydrogen, is said to be showing I
(negative-inductive / electron - withdrawing) effect. On the other hand, any atom or group attracting electrons less
strongly than hydrogen is said to be showing +I (positive inductive / electron-releasing) effect. Following are two
sequences in decreasing order of their effects:
+
I groups :
(CH 3 )3 N > NO2 > CN > F > COOH > Cl > Br > I > CF3 > OH > OCH 3 > C6 H 5 > H
+I groups :
(CH 3 )C > (CH 3 )2 CH > CH 3CH 2CH 2 > CH 3CH 2 > CH 3 > H
(b)
MESOMERIC EFFECTS:
Consider an organic compound in which the linkage C = O is present. We can write two canonical forms
for this linkage so that the actual linkage will be a hybrid of these two canonical forms :
C O
(i)
CO
(ii)
(iii)
You might say that (ii) is not a stable canonical form since it involves the separation of charge and therefore
will be of a higher energy content. However, the negative charge being on electronegative oxygen atom will
stabilise this form to an extent. Thus, (ii) will not have a negligible contribution to the hybrid (iii).
Thus, we should actually expect that the linkage will be in a state of permanent polarisation due to the
resonance possible. There will be an electron withdrawing inductive effect of the oxygen atom too, but since
the electrons are much less polarisable than the electrons, we can expect the polarisation in (iii) to be
mostly due to the electrons.
Lets see another example in which such redistribution is possible. We consider a conjugated system in which
the C = O linkage is conjugated to a carbon - carbon double bond. For this compound, we can write
two canonical forms, and the actual structure will be a hybrid of these two forms:
LOCUS
45
H
|
CH C
O
CH
H
|
*
CH CH C O
H
|
*
CH CH C O
+
Thus, the actual structure is in a state of permanent polarisation, with the oxygen atom being slightly negatively
charged and the (starred) carbon atom being slightly positively charged. Notice that this polarisation has
been transmitted through the electrons only.
Having seen these two examples, we can now properly define the mesomeric effect : it is essentially an
electron redistribution that can take place in unsaturated systems (especially in conjugated systems) via the
orbitals.
Since transmission of this effect occurs via the orbitals while inductive effect operates through the sigma
orbitals (which are much less polarisable than the orbitals), the mesomeric effect suffers much less
attenuation in its transmission, with the result that this effect can operate across long carbon chains
(the polarity of adjacent carbon atoms will alternate along the chain due to this effect). Electron-donating
mesomeric effect is represented as the +M effect while the electron withdrawing mesomeric effect is
represented as M effect.
Consider the following two examples:
C C C C NH CH3
C2H5 C C C O
shows an electron-donating
(+M) mesomeric effect
carbonyl group shows

-M mesomeric effect
Following is a list of +M and M atom or group of atom:

+M groups: Cl,Br,I ,NH2 ,NR2 ,OH,OCH3
M groups:
Like the inductive effect, mesomeric effect is a permanent polarisation state of the molecule and would thus,
show up in physical properties of the molecule like its dipole moment. For the sake of emphasis, inductive
and mesomeric effects have been compared in the table below:
Table-2: Comparison between inductive and mesomeric effects
Inductive effects
1. Operate in both saturated and
unsaturated compounds
2. Involve bond electron s
3. Can be transmitted only over
very short distances due to low
polarisability of the orbitals
(c)
Mesomeric effects
Operate only in unsaturated compounds
(and especially in conjugated compounds)
Involve electrons and orbitals
Can be transmitted across large carbon chains
(provided, of course, that conjugation is present
across the carbon chain)
HYPERCONJUGATION:
In part (a), we discussed the inductive effect as an electron donating or withdrawing effect of a group
depending on the relative electronegativity of the other group with which it is bonded.
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46
It is known that alkyl groups have the following order of electron donating inductive effect (which well
denote as +I effect):
CH3
CH3 C
CH3
CH3
CH
CH3 CH2
CH3
CH3
(i)
(ii)
(iii)
(iv)
Thus, tertiary alkyl groups as in (i) above have the highest +I effect while methyl group (in (iv)above) will
have the lowest +I effect.
However, this order of electron donating effect does not hold true when the alkyl group is attached to an
unsaturated system like a double bond or a benzene ring. In some cases, this order might even be reversed,
so that the methyl group will have the highest and the tertiary alkyl group the lowest electron releasing effect.
Obviously, some other mechanism of electron donation is at work when alkyl groups are connected to
unsaturated systems. This mechanism is termed hyperconjugation and is a sort of an extension of the mesomeric
effect. In hyperconjugation, the delocalisation of electrons occurs through - overlap of orbitals.
Let us discuss this effect in detail in the case of CH3 CH CH2 . First, let us understand the physical
picture of how the - overlap occurs. Then well understand how to represent the process of
hyperconjugation on paper, through canonical forms.
Consider the following approximate orbital picture of CH3 CH CH2 .
H
C
Only one of the three carbon-hydrogen molecular

orbital has been drawn. Note that in addition to the
2p-2p unhybridised orbital overlap, an overlap can
also take place of the carbon-hydrogen orbital with
the orbital system of the double bond. This is
represent ed by t he three dotted l ines
H
C
C
H
H
Fig - 34
As is evident in the figure above, (each of) the carbon hydrogen sigma molecular orbital can overlap with the
-orbital system of the carbon-carbon double bond, resulting in a sharing of electron charge density of the
carbon-hydrogen single bonds with the carbon-carbon double bond. This explains the electron donating
effect of the methyl group when attached to a double bond (or any unsaturated system). We can represent
hyperconjugation in this case using canonical forms as follows:
H
|
H C CH CH2
|
H
H
H C CH CH2
|
H
H
|
C CH CH2
|
H
H
H
C
H
C CH2
H
|
H C CH CH2
H
In the actual structure, the carbonhydrogen orbitals charge density

is shared with the carbon-carbon
double bond.
LOCUS
47
We can now explain the observed reversal of the electron donating effects of alkyl groups when attached to
unsaturated systems using hyperconjugation
H
|
H C CH CH2
|
H
(i)
H
|
H C CH CH2
|
CH3
H
|
CH3 C CH CH2
|
CH3
CH3
|
CH3 C CH CH2
|
CH3
(iii)
(iv)
(ii)
In (i), we have three hyperconjugable hydrogen atoms, because all three of the carbon-hydrogen orbitals
can overlap with the molecular orbital system. In (iv), for example, there is no hyperconjugable H-atom
and thus electron-donating effect of the alkyl group, here, through hyper conjugation is the lowest.
Hyperconjuation explains a lot of phenomenon which could not otherwise be explained. It tells us, for
example, why (A) is thermodynamically more stable than (B) below:
CH3
CH3
|
|
CH CH3
CH3 C
CH3 CH2 C
CH2
(A)
(B)
(A) has nine hyperconjugable H-atoms while (B) has only five. Thus, the effective delocalisation of charge is
more in (A) than in (B) (due to hyperconjugation) and hence (A) is more stable.
(d)
TIME VARIABLE EFFECTS (ELECTROMERIC EFFECT) :

The three effects discussed above are permanent in the sense that they represent permanent polarisations in
the compound. They would thus show up in the physical properties of the molecule, like its dipole moment.
Molecules can also show time-variable effects, which occur only on some external stimuli, like the approach
of a reagent, for example.
We will discuss here one of the more important time variable effects, the electromeric effect. This effect
occurs via - electrons. On the approach of some external reagent, the - electron pair shifts entirely to the
more electronegative atom. Consider the following example
C O + Nu
(A nucleophile ;
CO
we'll discuss more

about these soon)
The approach of Nu above causes the - electron pair to shift entirely to oxygen. Electromeric effect is a
temporary effect. If the attacking reagent is removed, the molecule will revert back to its ground state. Thus,
this effect will not show up in the physical properties of the molecule.
Electromeric effect is the time-variable counterpart of the mesomeric effect. Like wise, theres a
time-variable inductomeric effect which corresponds to the (permanent) inductive effect
LOCUS
48
Example 29
Draw the hyperconjugation possible in toluene (Ph CH3) by sketching various possible canonical forms.
Solution: Following canonical forms depict hyperconjugation in toluene:
H
HCH
H C H
HC
H
H
HC
H
.... so on
for the other two H atoms on the C atom bonded to the phenyl group. Hence, there would be a total
of 10 such canonical forms.
Note: While writing such canonical forms, try to explicitly show all hyperconjugable H atoms(s) so that you dont
miss out drawing any possible canonical form.
Example 30
A student represents the hyperconjugation possible in propane as follows:
H
H
H C CH CH2
H
H C CH CH2
H
Can we infer from the second canonical form that a proton separates from the main carbon chain? What is the
significance of this second structure?
Solution: No, the second canonical form does not imply that a proton becomes free. Separation from the main
carbon chain would mean movement of the proton from its original position - a situation inhibiting
delocalisation whose basic pre-requisite is that all the constituent atoms must occupy essentially the
same relative positions in each canonical form.
(The significance of the second structure lies in clarifying how alkyl groups here), CH3 are capable
of giving rise to electron release, thus, enabling delocalisation.
TRY YOURSELF - II
Q. 1
Explain why reactions involving ionic intermediates take place more easily in solution in polar solvents than
in non-polar solvents.
Q. 2
Which carbocation is expected to be more stable:
CH3 CH2 C H2 or CH2
Q. 3
= CH C H2
What should be the direction of the inductive effect exerted on carbon by magnesium in the compound
H 3C MgX where X is a halogen atom? (This compound is an example of a Grignard reagent which we
will encounter later in organic chemistry).
LOCUS
49
Section - 8
TYPES OF REAGENTS
In this section we will formally categorise the types of reagents that we encounter in the course of our study of
organic chemistry.
(a)
Electrophiles (electron-seeking reagents)

These are species which tend to attack electron rich sites. For example, a site like the oxygen atom in the
C = O linkage will tend to be attacked by an electrophile. Substitution on the benzene ring will be almost
always by an electrophile because of the high electron charge density on the ring.
(b)
Electrophiles can be positively charged cations like NO2 . They might also be species that are actually not
cations but posess an atom or centre that is electron deficient and will tend to react with an electron rich site.
For example the sulphur atom SO3 will act as an electrophile, due to the electron deficient sulphur atom,
(even though SO3 is not a full blown cation):
O
O
S +++
O
Nucleophiles (nucleus - seeking reagents)
These are reagents which will tend to attack electron deficient sites. For example, in the following compound
| +
C
Cl
|
the carbon atom acquires a slightly positive charge due to the I effect of the chlorine atom. This carbon
atom will tend to be attacked by nucleophiles.
As in electrophiles, nucleophiles can either be negatively charged anions like OH, Cl etc, or they can be
species which are not actually anions but which posess an atom or a centre that is electron rich. For example,
the nitrogen atom in ammonia , NH3 , will tend to act as a nucleophile.
(c)
Free radicals
These are highly reactive reagents (intermediates) which are not charged, and thus they are much less prone
to variations in electron density in the substrate (which they attack) than reactions which involve polar
intermediates ( electrophiles or nucleophiles). An example of a free radical is the chlorine free radical, which
can be formed by the action of sunlight on the chlorine molecule :
Cl2
sunlight
Cl + Cl
We will discuss more about the properties of these reagents (like their hybridisation states etc) as and when
we encounter them. For the time being, this introduction should suffice.
Example 31
Classify the following as electrophiles or nucleophiles.
(i) NO +2
(iv) AlCl3
(ii) RO
(v) SO3
(iii) OH
(vi) CO2
(Note that electrophilicity of Al, S and C atoms are being refered to wherever present)
LOCUS
50
Solution: Electron-seeking reagents or electrophiles are as follows:

NO +2 , AlCl3, SO3, CO2
Nucleophiles are: RO and OH.
Section - 9
TYPES OF REACTIONS
The reactions of organic compounds can be classified into four major categories:
(a) Substitution
(b) Addition
(c) Elimination
(d) Rearrangement
(a)
Substitution reactions are those in which a group attached to a carbon atom is substituted by another
group.
A classic example of a substitution reaction is the nucleophilic substitution in alkyl halides :
|
C X + Nu
|
|
C Nu + X
|
The Nu (a nucleophile)anion displaces the halide ion. (This reaction will be discussed in some other
context ).
Substitution is, of course, not limited to nucleophilic reagents. It can be electrophilic as well as radical
induced.
(b)
Addition reactions occur in unsaturated systems. As the name suggests, an addition reaction is one in
which two molecules add; a good example is the addition of a hydrogen halide, HX, to the carbon-carbon
double bond
|
|
CC
|
|
H Br
Addition reactions too can be electrophilic, nucleophilic or radical-induced, depending on what entity initiates
the addition reaction. In general, addition to carbon-carbon double bonds is electrophilic or radical induced,
while addition to, say carbon oxygen double bond would be usually nucleophilic. (More on this later)
+ H Br
(c)
C C
Elimination reactions are the reverse of addition reactions; a molecule is lost/eliminated/ subtracted
from the original molecule. The most common elimination reactions are those in which there is a loss of a
hydrogen atom and another atom or group from adjacent carbon atoms. The dehydrohalogenation of alkyl
halides in the presence of a base is a good example of this class of reactions:
H
C
HX
X
(d)
Rearrangement reactions under certain reaction conditions, a molecule may rearrange its structure to
another form which might be thermodynamically more stable (in having a lower energy content). Carbocation
rearrangement is an example of this class of reactions ( the reason why it happens will be discussed here)
LOCUS
51
H
|
CH3 C CH2 OH
|
CH3
H
|
CH3 C CH2 OH2
|
CH3
H2O
CH3 C CH3
|
CH3
H
|
hybride
CH3 C CH2
shift
|
(a rearrangement)
CH 3
3 carbocation
1 carbocation
This example illustrates that rearrangements do take place. Details of this reaction will be dealt with later.
Rearrangements can also proceed through intermediates that can be cations (electrophiles), anions
(nucleophiles) or radicals. The most common intermediates in rearrangements are carbocations.
Section - 10
ACIDS AND BASES
(A) DEFINITIONS
We will, in our course of the study of organic chemistry, frequently encounter acids and bases. Questions
might be posed as to which of a given set of organic compounds is the most acidic or most basic, and so on.
It is thus of significant importance to study the concept of acidity and basicity, the various theories involved
and the factors influencing acidity and basicity.
The three theories of acidity / basicity that well discuss are as follows in increasing order of generality :
(i) Arrhenius definition
Acids are compounds that yield hydrogen ions (H +) in solution. Bases are compounds that yield hydroxide
ions (OH ) in solution. This was one of the first definitions proposed and it sufficiently covers reactions
in which water is the reaction medium.
As an example of an Arrhenius acid and base, you can think of HCl which would be an acid since it can
yield H + ion in solution ; NaOH is a possible base since it can yield OH in solution. However, this
definition cannot account for acidity and basicity in certain compounds and thus it has become more
generalised.
(ii) Bronsted definition
Acids are proton (H +) donors while bases are proton acceptors. For example, consider the following
reaction:
+
HCl + H2O:
Cl
+ H3O
Acid
Base
Conjugate
base
Conjugate
acid
Observe that HCl acts as a Bronsted acid since it can denote an H + ion to the water molecule; it thereby
gets converted into Cl which is termed its conjugate base. H2O acts as a Bronsted base since it can
accept the H + ion from HCl; doing so converts H2O into H3O+ which is its conjugate acid.
The Bronsted definition is an improvement over the Arrhenius definition in terms of more generality, but
it can be further generalised to include even more compounds. This is what the Lewis definition does.
LOCUS
52
(iii) Lewis definition

Acids are molecules or ions which can co-ordinate with unshared electron pairs provided to them by
other molecules or ions. Bases are molecules or ions which have unshared electron pairs available for
co-ordination with other molecules or ions.
To understand how this definition is more generalised, consider the following reactions
Me3N: + BF3
Me3 N : BF3
Cl2 + AlCl3
Cl + AlCl4
In these reactions, there is no involvement of protons (H+ ions)/ hydroxide ions (OH ions). Even then,
we can use the Lewis definition to say that BF3 and AlCl3, for example, are Lewis acids because each
of them are capable of co-ordinating with (accepting) an unshared electron pair.
(B) ACID - BASE REACTIONS
Can we predict whether a given pair of acid and base will react to give appreciable amounts of products or
not?
Let us see how to do so. It is said that initially acid-base reactions exist in equilibrium .
Conjugate Pairs
Strong +
Acid
Strong
Base
Weak + Weak
Base
Acid
Conjugate
The products of the reaction are determined by the position of equilibrium. We know that equilibrium
reactions always favour formation of most stable species. Since weaker acids and bases are more stable
than stronger acids and bases, the equilibrium shifts towards formation of weaker acid and base.
Thus, we should always keep in mind the following rule: Acid-base reactions always favour the formation
of weaker acid and weaker base.
(C) MEASURE OF ACIDITY/ BASICITY
As has been discussed in the chapter on equilibrium, the strength of acids and bases is measured in terms of
pKa and pKb respectively (We will be concerned with only proton acids and bases for the time being)
Ka and Kb are equilibrium constants for the following equilibrium (considered in an aqueous solution)
Acids
!!" H 3O + + A
HA + H 2O : #!!
[ H 3O + ][ A ]
Ka =
[ HA]
pK a = log10 K a
...(i)
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53
Bases
!!" BH + + OH
B : + H 2O #!!
[ BH + ][OH ]
Kb =
[ B :]
pK b = log10 K b
...(ii)
It is evident from these relations that stronger acids/ bases imply higher corresponding values of Ka/Kb and
therefore lower corresponding values of pKa/pKb. Thus, for example, an acid with a pKa of 1 will be
stronger than an acid with a pKa of 2. A similar analogy would hold for such a pair of bases.
Conventionally, the strength of bases is also described in terms of Ka (and pKa) instead of Kb and (pKb).
Doing so will result in a single scale/measure for the strength of both acids and bases and will thus be more
convenient. To do so, we consider, instead of the reaction (ii), the following reaction as our reference
reaction for bases :
!!" B : + H 3O +
BH + + H 2O : #!!
For this reaction, we can write the Ka (and pKa) as :
Ka =
[ B :] [ H 3O + ]
[ BH + ]
pK a = log10 K a
Thus, Ka (pKa) here would be a measure of the strength of the conjugate acid BH+ of the base B : . A lower
pKa value will imply a stronger conjugate acid BH + and thus a weaker conjugate base B:. Similarly, a higher
pKa value implies a stronger base B :
Lower pK a value Stronger acid BH + Weaker base B:
Higher pK a value Weaker acid BH + Stronger base B:
For example, NH3 has a pKa value of 9.25 while CH3NH2 has a pKa value of 10.64. Thus, CH3NH2 is a
stronger base.
One point must be emphasised here : the pKa scale is logarithmic and you must appreciate this. Thus, an acid
with a pKa value of 2 will be 10 times weaker than an acid with a pKa value of 1. In fact, acids with pKa >
16 will not even be detectable as acids at all in water, because their ionisation will be less than the autolysis
of water itself.
For very stronger acids, full ionisation will be achieved in water, and thus all strong acids will appear to be of
the same strength in water. This levelling effect of water will be reduced to an extent in case the solvent is
other than water and is a weaker base than water ( because for a weaker base, ionisation of the acid will be
100% complete).
This means that relative strengths of strong acids can be compared in a solvent that is a weaker base than
water. Similarly, relative strengths of very weak acids can be compared in bases stronger than water.
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54
(D) FACTORS AFFECTING ACIDITY

In this section, we will discuss the factors which affect the strength of acids in the form of HA. If HA gives up
its proton easily, it will be a stronger acid than in the case when it is reluctant to give up the proton.
Also, the acid which gives up its proton easily results in formation of a weaker have than when it is reluctant
to give up the proton.
The factors which can affect acidity/basicity are:
(i)
Strength of H A bond : The general rule is: The stronger the H A bond, the weaker the acid.
Amongst the compound, of the same group of the periodic table, bond strength to proton decreases on
moving down the group.
pKa
Acidity
H Cl
H Br
Increases
Decreases
HF
HI
This is because, as we move down the group, the effective overlap between hydrogen and the halogen atom
decreases. Thus, overlap is minimum in HI which results in formation of weaker H I bond. Weaker bond
implies stronger acid.
Now let us compare the basic strength of the conjugate bases of these acids. Since HI is the strongest acid
amongst them, its conjugate base (I) will be the weakest one. On the other hand, F will be a stronger
base because it is the conjugate base of a weaker acid (H F).
The same holds true for compounds of other groups of periodic table.
pKa
H2O
H2S
Increases
Decreases
(ii)
Acidity
H2Se
Here, H2O is the weakest acid and H2Se is the strongest one.
Electronegativity: On moving left to right across a periodic table, bond strength varies but the predominant
factor is the increase in electronegatvity. Recall that electronegativity is a measure of an atoms attraction for
electrons. The higher the electronegativity, the greater the attraction.
Electronegativity has the following two effects on the acidity
LOCUS
55
(a) Polarity of the bond.

(b) Stability of the anion formed (conjugate base) after the loss of proton
High electronegativity increases the polarity of the bond. Let us examine the compounds of any one period.
e.g. CH4, NH3, H2O, HF.
Increases
electronegativity
C N OF
Thus, we can say, F being most electronegative causes most polarization of the H F bond. In other
words, H acquires maximum positive charge in HF and least in CH4. Thus, HF can readily lose a proton to
a base and hence, is most acidic.
H3C H
H2N H
HO H
FH
Increases
Polarity
Decreases
pKa
Increases
Acidity
Now let us compare the strength of their conjugate bases.

HF being the strongest acid forms the weakest have F. This is because fluorine is most electronegative and
can most readily accommodate the negative charge. Thus, F is most stable and least reactive and hence,
least basic.
(iii)
On the other hand, CH4 is the weakest acid so leads to formation of strongest base CH3. Carbon being the
least electronegative atom is least ready to accept the negative charge and is most unstable and reactive.
Thus, it is most basic.
Hybridization: We have already studied about the effect of hybridization on the acidity of the molecule.
Recall that more s-character increases the electronegativity. Thus,
Increases
pK4
H
H C C H
H
CC
HCCH
H
H
Acidity
Decreases
(iv) Inductive effect: We studied about inductive effect and the types of inductive effects in section-7. We
know that a + I group (electron releasing group) increases the electron density around the atoms to which it
is attached. If it is attached to a base, it will increase the electron density around it making it more unstable
and henc, more reactive or more basic.
LOCUS
56
On the other hand, I group (electron withdrawing group) decreases the electron density around the atom
to which it is attached. I group attached to a base decreases electron density of the base making it less
reactive and less basic.
I groups attached to an acid facilitate release of proton by withdrawing electrons. On the other hand, +I
groups have an opposite effect on acidity ie. they decrease acidic character.
Acidic nature Basic nature
+I effect
Decreases
Increases
I effect
Increases
Decreases
e.g. CH3 C OH
CH2 C OH
Cl
(I)
O
(II)
Amongst the two compounds, (II) will be more acidic because of presence of a I group at -carbon.
NH2
NH2
NH2
(I)
CH3
(II)
NO2
(III)
e.g .
The increasing order of basicity of the above compounds is:

NH2
NH2
<
NO2
(III)
NH2
<
(I)
CH3
(II)
(III) is least basic because it has an electron withdrawing (I group) attached which decreases basicity. On
the other hand, (II) has an electron-donating (+I group) which increases basicity.
Inductive effect: We studied about inductive effect in Section -7. The application of inductive effect and its
influence on acidity of a molecule is explained using example 37.
LOCUS
(v)
57
Effect of stability of A with respect to HA: This factor is very important in determining the strengths of
acids. If the conditions are such that A (the conjugate base of HA) can be stabilised with respect to HA
itself, we will find that HA will tend to be more acidic.
The reason for this is clear. A stable conjugate base A because of its stability, will be reluctant to gain a
proton to form back the acid HA. Thus, a stable A will be a weak base and consequently, HA will be a
strong acid. You can think of it this way : if A can be stabilised somehow, it will be energetically favorable
for HA to give up a proton to form A can ; thus, HA will lose its proton with ease, and will therefore be a
strong acid.
All factors that can possibly stabilise A will have something to do with dispersion/delocalisation of charge.
Let us consider the various factors through examples :
Example 32
The order of acidity of the hydrogen halides in aqueous solution is HF < HCl < HBr < HI . Explain.
Solution: Observe this order carefully. Do you realise that this order is contrary to what we should expect due
to the affect of electronegativity described earlier ? For example, since fluorine is the most electronegative
of all the halides, we should expect HF to be the strongest acid. However, as it turns out, it is the
weakest. (Before proceeding on, one point requires attention here. The order of acidity is being
talked about in water as a solvent, since this is the most common solvent used for organic reactions).
One factor to which we can attribute the reversal of the expected acidity order is the relative stability
order of the halide anions (the conjugate bases) formed on the loss of a proton. This stability order is
as follows:
F < Cl < Br < I
Order of stability
The reason for this stability order is that the larger the atomic radius of an anion, the more the volume
of the region over which the negative charge can spread and thus more stable that anion will be. Since
atomic radii of the halide atoms are in the order F < Cl < Br < I, stability of the anions will also
follows this order. Consequently, as described earlier, acidity of the hydrogen halides will also follow
this order.
Example 33
The compound HCOOH is by organic standards, a moderately strong acid. It has a pKa of of 3.77 (The name of
this compound is methanoic acid). Explain.
Solution: We must again look into the possibility of the conjugate base of this acid being somehow stabilised.
A minor reason for this compound showing acidity is the fact that the
carbonyl group
C O is electron withdrawing, so it increases the
electron affinity of the oxygen atom of the OH group (which contains

the acidic hydrogen atom.)
The major reason for methanoic acid showing strong acidity is that the conjugate base is resonance
stabilised.
O
O
O
H C
H C
H C
O
O
O
methanoate anion
LOCUS
58
The delocalisation of the negative charge is in fact extremely effective since the two canonical forms
are of identical energy content. Thus, the methanoate anion is quite stable.
Observe that although delocalisation through resonance can take place in methanoic acid itself, it will
not be really effective since it will involve charge separation in the canonical forms.
O
O
H C
H C
O H
O+ H
This structure has a
high energy content
Thus, resonance will tend to stabilise the methanoate anion with respect to the methanoic acid, which
results in the acidity of the latter.
Example 34
The alcohol ROH (where R is an alkyl group) is a much weaker acid than phenol, PhOH, altough both contain the
same functional group ( OH). Explain.
Solution: Again, we look into factors stabilising the conjugate base of phenol and which do not work for the
alcohol
Consider the conjugate base of phenol, PhO. Observe that there is a possibility of resonance
stabilisation in this anion :
O
The 'actual'
phenoxide anion
Observe that in the phenoxide anion, the negative charge is delocalised over the entire benzene ring
and thus this anion is stabilised.
Resonance can occur in the undissociated phenol molecule also but that will involve charge separation
and will therefore be less effective than resonance in the conjugate base.
This discussion justifies why phenol shows an acidity stronger than alcohols (where no such resonance
stabilisation is possible in the conjugate base RO ).
As an example, the pKa of CH3OH is 16 while that of phenol is around 10, indicating that phenol is a
considerably stronger acid than CH3OH.
Example 35
Phenol (PhOH) is a considerably weaker acid that the carboxylic acids (in which the acidic part is the functional
O
group C
) . Explain.
OH
LOCUS
59
Solution: As discussed in the previous case study, the phenoxide anion PhO is stabilised by resonance and thus
PhOH is acidic. Here we need to look into how carboxylic acids should be even stronger acids.
Consider the conjugate base of a general carboxylic acid (RCOOH) and observe that it will be resonance
stabilised too:
O-
O
RC
O-
RC
O
RC
Carboxylate anion
However, resonance stability in the carboxylate anion will be much more than that in the phenoxide
anion. This is due to two reasons:
(i) For the carboxylate anion, both the canonical forms are of identical energy content
(ii) In the canonical forms of the carboxylate anions, the negative charge is on the highly electronegative
oxygen atoms and therefore we can expect these forms to be stable.
In the canonical forms of the phenoxide anion drawn earlier, there is a negative charge on a carbon
atom in three of the four structures, and hence these forms are likely to be of a higher energy content
(and therefore less stable) than the structure in which the negative charge is on oxygen.
These two reasons justify which carboxylic acids are stronger acids than phenol. As an example, the
O
pKa of phenol is around 10, while that of methanoic acid, CH3 C
is 4.76.
OH
Note:The inductive effect of the groups connected to the acidic group in a molecule can have a significant effect
on the acidic properties of that molecule. We first discuss as an example, inductive effects in carboxylic acids.
Consider a general carboxylic acid of the form G - COOH, where G could be any group. If G has an electron
withdrawing inductive effect, it will tend to stabilise the carboxylate anion by aiding in the disperson of charge on
the COO group. On the other hand, a + I effect of G would tend to distabilise the carboxylate anion.
O
G
I effect of G will
stabilise the conjugate
base of GCOOH
+I effect of G will
destabilise the conjugate
base of GCOOH
We can thus conclude that groups with I effect will increase the acidity of the carboxylic acid while groups with
+I effect will decrease the acidity. This is what is actually observed, as the data in the table below proves.
Methanoic acid, HCOOH (pKa = 3.77) has been used as a reference. On the left hand side are carboxylic acids
weaker than methanoic acid due to the +I effect of the group attached to the carboxylic group; on the right hand
side are carboxylic acids stronger that methanoic acid due to the I effect of the group attached to the carboxylic
group.
LOCUS
60
These acids have been arranged in increasing order of acidity.

Table 3 : Major acids in increasing order of acidity
Acids weaker than
methanoic acid
Acids stronger than

methanoic acid
pKa
CH3
(1) CH3
pKa
O
||
3.35
5.05
(12)
4.88
(13)
4.86
(14) Br
CH2
COOH
2.90
4.82
(15) Cl
CH2
COOH
2.86
4.76
(16)
CH2
COOH
2.57
(6) CH2CH2CH2 COOH

|
Cl
4.52
(17) NC
(7) CH2 CH COOH
4.25
(18) (CH3)3 N
(8) CH3 CH CH2COOH

|
Cl
4.06
(19) NO2
(9) HO
3.83
COOH
CH3
(2) CH3CH2
COOH
(3) CH3 CH
|
CH3
COOH
(4) CH3CH2CH2
(5) CH3
COOH
COOH
CH2 COOH
CH2
COOH
CH2
COOH
CH2
CH2
COOH
COOH
Cl
CH
(20)
COOH
3.16
2.47
1.83
1.68
1.25
Cl
Cl
O
||
(10)
(11) CH3 O CH2
3.58
COOH
3.53
(21) Cl
COOH
0.65
Cl
*Data quoted from Peter Sykes : A Guidebook...
LOCUS
61
You are urged to go through this table and observe carefully how the pKa varies as the group attached to the
carboxylic group is varied.
It would in fact be a good exercise to compare two different compounds of the same (or similar) molecular
formula or similar structure and try to reason out why their acidities differ. We will now do this in a few examples.
As mentioned at the end of casestudy 1, here also the justification of the acidity order based
only on the inductive effect is only partially complete. The actual scenario requires a more
detailed and complete justification. You can refer to the appendix for that prupose. However,
for our current needs, the justification provided above would suffice.
Example 36
(a)
Why is F CH2 COOH a stronger acid than I CH2 COOH ?
(b)
Why is
Cl
a stronger acid than Cl CH2 COOH ?
CH COOH
Cl
Solution : You should find this question very straightforward since it requires simple reasoning based on the
inductive effect.
(a) F is more electronegative than I ; the electron withdrawing inductive effect (I effect) of F will
therefore be more than I, and thus stabilisation of conjugate bases will be greater in the case of F
than in the case of I. This explains the observed greater acidity of F CH2 COOH.
(b) The I effect of two chlorine atoms will obviously be more than that of just a single chlorine atom.
This explains why the dichloro-substituted acid is stronger.
Example 37
CH COOH a stronger acid than CH3 CH2 COOH ?
Why is CH2
Solution : The - carbon (the C-atom immediately next to the carboxylic C-atom) in the first compound is sp2
hybridised. Electrons in an sp2 hybrid orbital will be drawn closer to the carbon nucleus than in an sp3
hybrid orbital. The reason for this has already been discussed. sp2 orbitals contain a greater s-character.
Thus, an sp2 hybridised carbon atom will be less electron donating than an sp3 hybridised carbon
atom.
Thus, the +I effect on the carboxylic group will be lesser in the case of the first compound than in the
second in which the -carbon is sp3 hybridised. This explains why CH2 CH COOH is a stronger
acid
Note: Let us now understand the effect of inductive/mesomeric electron withdrawal/donation on acidity in aromatic
compounds.
Inductive and mesomeric effects can have significant influence on acidity in aromatic compounds too, as in the
case of aliphatic compounds.
LOCUS
62
For a start, well discuss acidity in substituted phenols. Our reference compound for discussion will be phenol
(pKa = 9.95). The conjugate base of phenol is phenoxide anion which is stabilised by resonance :
O
Although resonance to an extent delocalises the negative charge over the benzene ring, any group which has an
electron withdrawing effect, when attached to the benzene ring, will further increase the stability of the phenoxide
anion by aiding in further delocalisation of the negative charge. Such a substituted phenol will be more acidic than
phenol itself.
On the contray, any group which has an electron donating effect, when attached to the benzene ring, will tend to
destabilize the phenoxide ion, and hence the substituted phenol will be less acidic than phenol itself.
*
If the substituted group has an inductive effect, we can expect the inductive influence of this group to fall
off with distance as we go from ortho meta para substituted phenol.
If the substituted group has a mesomeric effect, it will have an influence when the group is attached to the
ortho or para position but not at the meta position. This will become clear when we draw the canonical
structures possible for each of the three positions and observe that only if the group is at the ortho or the
para position can it promote ionisation by stabilisation of the anion.
We do this as an example for NO2 attached at para position, i.e., for p-nitrophenoxide ion.
O
N
+
N
+
N
+
N
+
(A)
(B)
Observe the form (A) (B) and note that it was because of the fact that the nitro group is at the p-position that it
could exert M effect and aid in the stabilisation of the phenoxide anion.
This would not have been possible had the nitro group been on the meta position, as should be evident from the
following canonical forms:
OO
O
O
NO2
NO2
NO2
NO2
LOCUS
63
In the canonical forms above, the negative charge never appears at the meta position ; therefore, the nitro group
does not have a possibility of delocalising the negative charge over itself through its M effect.
Let us now discuss other cases of acidity through examples.
Example 38
Justify the following observed values of pKa :
COOH
COOH
COOH
COOH
Cl
Cl
4.20
2.94
Cl
3.99
3.83
Solution: We must first of all focus our attention on the substituent which is Cl here. Cl has a power I effect
because of its high electronegativity. However, Cl can also exert a +M effect due to the lone pair when
attached at the ortho or para position. This means that there are two opposing effects here : Cl will
tend to stabilise the system by its I effect but at the same time tend to destabilise the system by its +M
effect
*
ochlorobenzonic acid is the strongest of the four given acids because of the extremely short
distance over which the powerful I effect of Cl operates (this more than compensates for the +M
effect of Cl). As we go from o m p chlorobenzoic acid, the strength of this I effect
falls off very quickly.
* pchlorobenzoic acid is weaker than m-chlorobenzoic acid due to a weaker I effect in the
former (because of the larger distance) and the possibility of the +M effect due to chlorine being
at the para position.
Example 39
Explain the observed values of pKa for the following nitro-substituted phenols (phenol itself has a pKa of 9.95) :
OH
OH
OH
NO2
OH
NO2
OH
NO2
NO2
NO2
NO2
7.23
8.35
NO2
7.14
4.01
NO2
1.02
Solution: Here we present a point - by - point analysis of these observed values of pKa.
*
*
All nitro-substituted phenols are stronger acids than phenols due to the I effect of NO2 and M
effect of NO2 if it is at the ortho or para position
o and pnitrophenol are stronger acids than m-nitrophenol due to the M effect the NO2can
exert at the ortho and para positions
LOCUS
64
Although in o-nitrophenol, the I effect of NO2 operates over a shorter distance than in p-nitrophenol
(and we should therefore expect o-nitrophenol to be stronger than p-nitrophenol), it actually turns
out that p-nitrophenol is the stronger acid (albeit only marginally). This happens because there are
a lot of (complicated) factors contributing to acidity, like the solvation patterns etc (and which we
do not consider here for the sake of simplicity).
* 2, 4 - dinitrophenol will obviously be a still stronger acid due to two reasons : the powerful I
effect of the two nitro groups and also their M effect since they are at the ortho positions.
* 2,4,6 - trinitrophenol is a very strong acid due to the effect of the three nitro groups which will
exert both I effect and M effect to stabilise the conjugate base to a large extent.
Example 40
2, 6-dihydroxybenzoic acid is found to be highly acidic by organic standards (pKa = 1.30)
COOH
OH
COO
OH
OH
OH
H+
(A)
(B)
Such high acidity cannot be accounted for by the I effect of the OH groups alone. What could be the other
possible factors ?
Solution : This is an example of a general trend : the behaviour of ortho - substituted acids many times turns out
to be significantly greater than expected because of direct interaction possible between the adjacent
groups.
It turns out that here a direct interaction is possible between the carboxylic group (COO) and the
two hydroxyl groups (OH) in the form of hydrogen bonding, which stabilises the anion (B) to a very
large extent.
This stability is the reason that the acid (A) readily gives up its acidic proton to form the anion (B). It
should be pointed out here that intramolecular Hbonding will also be possible in the undissociated
acid (A) itself but it will not be as effective as in (B) in which there is a negative charge and hence
stronger H-bonding.
(iv) Effect of solvent: A mention was made earlier about the levelling effect of water. All strong acids get
100% dissociated in water and thus appear to be equally strong in water. To compare the relative
strengths of these strong acids, a base weaker than water can be used as the solvent. This is one of the
many examples which show that the nature of the solvent can have a profound determining effect on the
acidity of the solvent. As the example above shows, this is particularly the case when water is the
solvent.
LOCUS
65
We can divide organic solvents into two broad classes :

(a) polar solvent
- like water
(b) non-polar solvent
- like toluene (methylbenzene)
We might find cases where a particular molecule shows acidic properties in a particular solvent but is
totally non-acidic in another. The next example considers this scenario.
Example 41
HCl is a very strong acid in water. In fact, it exists almost fully dissociated in water. In alcohols also, like methanol
(CH3OH) for example, HCl is a moderately strong acid. However, in a non-polar solvent like toluene (methyl
benzene), HCl is almost totally non-acidic i.e. it occurs almost totally undissociated in toluene. Justify these
observations.
Solution: For any acid, the stronger the solvent as a base, the more the dissociation of that acid in the solvent
will be observed and correspondingly, the weaker the solvent as a base, the lesser the dissociation of
that acid will be observed. Water and alcohol are good solvents in this sense. In fact, water is a very
good polar solvent :
(a) it has a high dielectric constant which aids in the formation of the ion pairs from the acid
(b) it aids in the stabilisation of the ion pair because it has a very strong ion-solvating power due to its
ability to form hydrogen bonds.
Alcohols share these properties to an extent and thus HCl is found to be a moderately strong acid in
methanol also.
However, toluene is non-polar (and non-basic) and has none of the ion-pair stabilisation abilities that
water and alcohol have. Thus, it it energetically unfavorable for the HCl molecule to dissociate in
toluene. This explains the observations.
(D) FACTORS AFFECTING BASICITY
As discussed earlier, the reference reaction for bases is the following equilibrium :
!!" B : + H 3O +
BH + + H 2O #!!
with Ka and pKa now being given by
Ka =
[ B :][ H 3O + ]
[ BH + ]
pK a = log10 K a
Thus, higher the pKa, stronger is the base B: In physical terms, the strength of a base is the measure of ease
with which B: can accept a proton, or equivalently, the measure of the availability of the unshared electron
pair on B. Factors which increase this availability of electrons will tend to increase the basicity of B: while
factors which decrease this availibity of electrons will tend to reduce its basicity.
However, as in acidity, the solvent also has an effect on the basicity. We will now discuss the various factors
through examples.
LOCUS
66
Example 42
The basicity order of ammonia (NH3) and alkyl-substituted ammonia (amines) in a non-polar solvent is found to be
in the following order
NH3
R NH2
R NH
1 amine
2 amine
R
R N
R
3 amine
Explain.
Solution: The basicity order being talked about has been measured in a non-polar solvent which means that we
can safely neglect any effects of solvent molecules on the basicity order (such as H-bonding) and
concentrate only on structural reasons that give rise to this order.
Recall that basicity will increase as the unshared electron pair availability on the nitrogen atom increases.
Recall also that alkyl groups have a + I effect.
This is the reason behind the observed basicity order. As we go from 1 amine to 3 amine, the
increasing +I effect of the substituted alkyl groups increases the electron pair availability on nitrogen,
causing an increase in basicity :
R
R
NH3
R NH2
NH
N
R
R
R
Example 43
The basicity order of NH3 and the amines in water follows the order:
R
R N
R
This means that basicity increases up to the 2 amine but then decreases in the 3 amine! Explain.
NH3
R NH2
R
NH
R
Solution: Obviously, apart from the +I effect of the alkyl groups, theres another factor at work now, which must
be due to the solvent, water. This factor is that water due to its polar nature, has the ability of ion
solvation. The amine, after the uptake of a proton, can become solvated by water molecules through
hydrogen bonding and can thus get stabilised.
If you observe the structures of the amines carefully, you will realise that after protonation, a 1 amine
is capable of forming 3 H-bonds, a 2 amine can form 2 H-bonds while a 3 amine can form only 1 Hbond :
H2O
H
|
R NH
|
H
OH2
H OH2
|
R N H OH2
|
R
OH2
OH2
H
|
R NR
|
R
Decreasing stabilisation due to solvation

by water molecules
Thus, while progressing along the series
NH3 RNH2 R2NH R3N

LOCUS
67
the inductive effect increases the basicity but lesser stabilisation of the cation formed after protonation
by the water molecules through solvation decreases the basicity. The net result is that the effect of
introducing alkyl groups becomes progressively smaller and from 2 3 amine, a reversal takes
place because the solvation factor becomes stronger than the inductive factor.
This explains the observed basicity order. As an example, consider the following pKa values which
clearly confirm this trend :
CH3
CH3
NH2
NH CH3 N
NH3 CH3
CH3
CH3
9.25
10.64
10.77
9.80
Example 44
$$ ( pK = 4.62) is a very weak base compared to ammonia, NH
$$ ( pK = 9.25) . Explain.
Aniline, PhNH
2
a
3
a
Solution: We must look into the factors affecting the unshared electron pair availability on the nitrogen atom.
Obviously, for aniline to be a weaker base, there must be a factor (s) at work which is reducing the
e - pair
availability on nitrogen. If we analyse the structure of aniline, well be able to identify two such factors:
(a) The unshared electron pair on nitrogen can interact with the -molecular orbital system on the
benzene ring, and get delocalised over the benzene ring to an extent, reducing its availability for
protonation :
Thus, it would be energetically unfavorable for aniline to gain a proton since then the lone pair will
no longer be available for delocalisation
(b) Nitrogen atom is attached to an sp2 - hybridised carbon atom, which also plays a role (how
significant is difficult to say) in making the unshared pair lesser available for protonation.
Example 45
Nitro-substituted anilines are extremely weak bases. This should be evident from the following pKa vallues
Aniline
NH2
m-nitroaniline
NH2
o-nitroaniline
NH2
p-nitroaniline
NH2
NO2
NO2
4.62
Explain.
0.28
2.45
NO2
0.98
LOCUS
68
Solution: As discussed earlier, the NO2 group will have two effects :
(a) A I effect which decreases with distance as o m p.
(b) A M effect which operates if NO2 is at the o or the p positions.
The point (b) explains why o and pnitro aniline are weaker bases than m-nitro aniline. For the sake
of emphasis, let us draw the canonical forms for p-nitro aniline and see the M effect of the NO2
group:
+
NH2
NH2
NH2
NH2
N
+
N
+
N
+
N
+
Forms (A) (B) should make it clear to you how NO2 exerts a M effect being at the pposition.
The point (a) partially explains why o-nitroaniline is a much weaker base than p-nitroaniline. Another
reason is the stabilising effect of the intra-molecular H-bonding possible between the NO2 and NH2
groups when NO2 is at the o position.
Example - 46
Amides, of the general structural form R C NH2 , are very weak bases. Justify.
||
O
Solution: One possible reason for this observation is that the nitrogen atom is bonded to a group with an overall
electron-withdrawing inductive effect through the sp2 - hybridised carboxyl carbon :
O
||
RC
O
||
-I effect of the R C
NH2
group will reduce the unshared
e -pair availability on the N-atom
O
||
A more significant reason is that the R C group can give rise to an electron-withdrawing mesomeric
effect (M effect ) :
O
O
||
|
+
R C NH2
R C NH2
Thus, amides are weak bases for these two reasons. As an example, consider the pKa of acetamide :
CH3 C NH2
||
O
acetamide
pKa = 0.5
LOCUS
69
Example - 47
Guanidine, with the structure:
HN
NH2
|
C
NH2
is an extremely strong organic base, with a pKa of 13.6. Explain.
Solution: Observe that the guanidine molecule exhibits a certain sort of symmetry. This symmetry is more evident
when we consider the protonated form of guanidine. For the protonated cation, we find that three
identical canonical forms (of equal energy content) can be drawn :
+NH
NH2
|
+ C
NH2
H2N
H2N
||
C
NH2
H2N
NH2
|
C +
NH2
The outcome of the fact that three identical canonical forms can be drawn is that this cation is extremely
stable, with the positive charge being delocalised over the entire molecule. Thus, it is energetically
favorable for the guanidine molecule to accept a proton, which justifies its strong basicity.
Observe that the non-protonated guanidine molecule will also show resonance but not as effective as
that possible in the protonated cation.
Example 48
Compare to aniline, the pKa values of the OH substituted anilines are found to be as follows:
NH2
NH2
NH2
NH2
OH
OH
(An)
4.62
(oAn)
4.72
(mAn)
4.17
OH
(pAn)
5.30
Explain.
Solution: Let us first discuss what effect(s) the substitutent OH can have :
(a) a base strengthening +M effect from the ortho and para positions
(b) a base weakening I effect which falls off with distance as o m p.
In mAn, there can be no base strengthening +M effect. However, the I effect operates and this
explains why mAn is a weaker base than An.
Both oAn and pAn are stronger bases than An due to the +M effect possible in these two molecules.
However, between oAn and pAn, oAn is a weaker base because of
(a) powerful I effect of OH which is a short distance away from NH2 in oAn.
(b) other steric and polar effects possible in oAn due to direct interaction between NH2 and OH
group.
LOCUS
70
TRY YOURSELF - III

Q. 1
Explain the following observed pKa values :
Q. 2
CH
C COOH
4.88
1.84
4.25
2, 4, 6-trinitrophenol (below) is a very strong acid. Explain the possible reason(s).
CH2 CH COOH
CH3 CH2 COOH
OH
O2N
NO2
pKa = 1.02
NO2
Q. 3
Explain the following observed pKa values:

COOH
Q. 4
Q. 5
COOH
COOH
COOH
COOH
COOH
CH3
NO2
Cl
OH
4.87
4.20
4.34
3.43
3.99
4.58
The following compound is found to be non-basic even though it contains a nitrogen atom
CF3
N CF3
CF3
Explain.
Ethanamidine (drawn below) is an extremely basic compound, with pKa = 12.4. What is (are) the possible
reason(s)?
CH3
C
HN
Q. 6
NH2
Consider the following two compounds:

H
H
NO2
O2N
NO2
(A)
CH3
CH3
NO2
O2N
NO2
(B)
It is observed that (B) is about 40000 times more basic than (A). What could be the possible reason(s)?
LOCUS
71
Section - 11
(i)
DIPOLE MOMENT
Polarity of bond: We know that a covalent bond is formed by sharing of electrons between two atoms.
The electrons are shared equally when the two atoms forming the covalent bond have, approximately, the
same tendency to attract electrons. However, when one of the atoms, forming the covalent bond, is more
electronegative than the other, the electron cloud shifts towards the atom with higher attracting power.
This results in increase in electron density around one atom and a decrease in electron density around the
other making the bond negative at the electronegative end and positive at the other. Or we can say, there
develops a positive and a negative pole. In other words, the molecule constitutes a dipole due to separation
of two opposite poles in space.
It is symbolyzed as:
+ve
end
ve
end
Such bonds are said to be polar and they possess polarity. Polarity is indicated using symbols + and
which imply partial (or slight) positive and negative charge.
+
HF
Cl
Remember, the greater the difference in electronegativities of the atoms forming covalent bonds, the more
polar the bond will be.
The polarity of bond affects various physical and chemical properties of the molecule like solubility, melting
point, boiling point, the type of reaction that it undergoes etc.
Dipole moment is a physical property which can be measured experimentally. It may be defined as the
product of magnitude of charge (in electrostatic units, esu) and the distance between the charges (in cm).
Dipole moment = charge distance
= e d
Thus, its unit will be esu cm.
Since the charge of most molecules is of the order 1010 esu and separation between them is approximately
108 cm, ( = 1010 esu 108 cm = 1018 esu cm) for convenience 1018 esu cm is taken to be one debye,
D.
So far we have only discussed diatomic molecules. We concluded that any diatomic molecule in which
two atoms have different electronegativities will be polar and will necessarily have a dipole moment.
(ii)
What if a molecule consists of more than one polar bond? Will it necessarily be polar? We will see that it
may or may not be polar. Lets see how.
Polarity of molecule: As an example, we will discuss the polarity of the carbon dioxide molecule. We
know carbon and oxygen have appreciable difference in electronegativity values. Thus, carbon-oxygen
bond will be polar with slight positive charge on carbon and slight negative charge on oxygen. Hence, we
should expect CO2, having two polar bonds, to be polar.
But actually, CO2 has zero dipole moment. If we look at the structure of CO2, we see that it is linear
(carbon being sp hybridized). The two carbon-oxygen bonds are definitely polar but the two dipoles act
in opposite direction.
OCO
LOCUS
72
Since the individual dipoles are equal in magnitude, they cancel each other and result in no net dipole
moment.
Let us take another molecule CCl4. Obviously, the CCl bond will be polar due to large difference in
electroegativities of carbon and chlorine. But just like CO2, CCl4 also doesnt possess any dipole moment
and is non polar.
This is because CCl4 is tetrahedral and if we consider the direction of individual bond moments, we will
see that they cancel each other.
Cl
Cl
C
Cl
Cl
Cl
Cl
Cl
Cl
If on the other hand, we consider another molecule CH3Cl, we will find that it possesses considerable
amount of dipole moment. This is because it has three carbonhydrogen bonds which have negligible
individual dipole moments (C and H have nearly the same electronegativities). However, the carbonchlorine bond is highly polar and accounts for the dipole moment of CHCl3
Cl
H
H
Example 49
Predict whether the given molecules will possess net dipole moment or mot:
C (CH 3 ) 4 , SO2 , H 2O, NH 3
Solution: (i) C (CH 3 ) 4
This case is similar to CCl4. Being a symmetric molecule, it doesnt possess any overall dipole
moment.
CH3
C
CH3
CH3
CH3
(ii) SO2
According to VSEPR theory, the shape of SO2 molecule is angular (Unlike CO2 which has linear
as geometry).
Resultant
O
O
Thus, it possesses dipole moment.
LOCUS
73
(iii) H2O
Water also has angular shape with two lone pair of electrons on oxygen. Lone pairs contribute
more to the dipole moment because they are not bonded to any atom.
Resultant
O
H
H
(iv) NH3
Like H2O, NH3 also possesses dipole moment. The shape of NH3 is pyramidal with one lone pair
on nitrogen.
Resultant
N
H
H
Example 50
Predict whether the following molecules possess net dipole moment or not. Also give the direction of net dipole
moment for the molecule.
(i) cis CHCl = CHCl
(ii) trane CHCl = CHCl
(iii) CH 2 = CBr2
Solution: (i) cis CHCl = CHCl

H
CC
Resultant
Cl
Cl
(ii) trans CHCl = CHCl
Resultant
Cl
CC
Zero
Cl
Br
C C
(iii)
Resultant
Br
Br
Br
Br
C C
(iv)
Br
Br
Resultant
Zero
(iv) CBr2
= CBr2
LOCUS
74
TRY YOURSELF - IV
1.
Indicate the direction of dipole moment if any.

CH3
CH3
(i) diethyl ether
(v)
(ix)
NO2
OH
NO2
(ii) N(CH3)3
(vi)
(x)
CH3
(iii) ICl
(vii)
CH3
CH3
CH3
(iv) Methanol
(viii)
LOCUS
75
EXERCISE
Q. 1
Given that benzene contains an annular electron cloud above and below the plane of the ring. what type of
reagents are expected to attack benzene most readily?
Q. 2
What are the important criteria for delocalisation of electrons through orbital overlap to take place ?
Q. 3
Explain how conjugation takes place in the following compound (draw the possible canonical forms):
Q. 4
CH3
CH
CH
CH
Classify the following as electrophiles or nucleophiles :

(ii) RC C
(i) O3
(iii) H
(iv) H +
(A starred atom means electrophilicity / nucleophilicity is being talked about for that particular atom )
Q. 5
What do you expect should happen when the following compound is treated with an acid ?
CH3 CH3
H
CH3 C C CH3
OH OH
Think as freely as you can, and remember that one of the most important factors driving a reaction is the
stability of its end products.
Explain the following observed pKa values :
Cl
Q. 6
4.82
2.84
CH2 CH2 CH2 COOH
CH3 CH CH2 COOH
CH3 CH2 CH COOH
CH3 CH2 CH2 COOH
Cl
Cl
4.06
4.52
Q. 7
Which of the following compounds will be more acidic?

OH
OH
or
CH3
LOCUS
Q. 8
76
Explain why o-hydroxybenzoic acid is found to be much more acidic than p-hydroxybenzoic acid.
COOH
OH
COOH
OH
p-hydroxy benzoicacid
o-hydroxy benzoicacid
Q. 9
Explain the following observed pKa values:

H COOH
CH 3COOH
C6 H 5COOH
3.77
4.76
4.17
HOOC COOH
1.23
HOOC CH 2 COOH
2.83
Q. 10 The basicity of butyl amines in chlorobenzene is found to follow the following order:
BuNH2 < Bu2NH < Bu3N

while in water, it follows the following order:
Bu3N < BuNH2 < Bu2NH
Explain
Q. 11 Consider the following compound (which is known as phthalimide):
O
H
N
O
Do you expect this compound to be acidic or basic?
Q. 12 The compound diphenylamine, Ph2NH, is an extremely weak base, with pKa = 0.8. Explain the possible
reason.
Q. 13 Do you expect the following compound to be extremely basic
NH2
NO2
O2N
NO2
Q. 14 Explain the following observed pKa values:
NH2
NH2
NH2
NH2
OCH3
OCH3
4.62
4.49
4.20
OCH3
5.29
LOCUS
77
[ ANSWER ]
TRY YOURSELF - I
1.
(a) Hint: C3 C4 bond has a partial double bond character

(b) Hint: delocalisation of electrons would require the four p atomic orbitals to be essentially parallel, thus,
restricting rotation about the C3 C4 single bond.
2.
Benzene being flat has an aromatic character due to cyclic overlap of p orbitals and fulfillment of the
4n + 2 electrons as per the Hckels rule. Aromaticity imparts extra stability than the hypothetical
cyclohexatriene.
3.
The conjugate base PhO of PhOH is resonance stabilised while it is not so in case of an aliphatic alcohol
of the general form ROH.
4.
Resonance hybrids are as follows:

+
(i) [ CH2 CH2 CH 2 ] `

+
(ii) [ CH2 CH2 CH2 CH 2 ]
(iii)
(iv)
CH3 CH CH CH NH2
(i)
CH2
because negative charge on highly electronegative atom makes the structure more
CH3
stable.
O
(ii)
because charge separation decreases stability. Also, more covalent bonds a structure
H
OH
has, more stable it is
(iii) CH 3 CH
6.
=OH
because all atoms have a complete octet of electrons.
Cyanic acid and isocyanic acid differ in position of hydrogen atom

Loss of proton from.
Cyanic acid yield. O C N
and from isocyanic acid yields: N C = O

They are resonating structures.
OCN
OCN
H
7.
(I) Methylamine CH3 NH2
(II) Formamide
CO
NH2
Carbon in (I) is sp hybridized and in (II) is sp hybridized. Thus, carbon in (II) has more s-character than
in (I) and hence forms a shorter and a stronger bond with nitrogen.
3
LOCUS
78
TRY YOURSELF - II
1.
Hint: due to greater ease of separation of charge and stabilisation of the resultant ion pairs through
solvation.
2.
CH2 CH CH2 is more stable
3.
H 3C
Mgx
TRY YOURSELF - III

1.
Higher is the degree of s-character in the hybridization of the -carbon atom, more closely electrons are
held to the carbon nucleus. Hence, sp hybridised -carbon is less electron-donating (thus, corresponding
carboxylic acid is more acidic) than sp2 and similar order of decreasing electron-donation follows from
sp2 to sp3 hybridized -carbon atom.
2.
Due to the following reasons:

M effect of nitro substituents in the ortho and para positions
I effect of all the three nitro groups (though it falls off rapidly with distance on moving from
o m p ).
the pattern of negative charge increases stability of the anion via solvation.
Use the following hints to explain the pKa values:
phenyl group has lower +I effect (than a saturated C-atom) due to the sp2 hybridized C-atom to which the
carboxyl group is attached.
+I substituents (e.g. alkyl groups) decrease acidity
M groups at o and p position (e.g. NO2) increase acidity
Groups with I but +M effect when located at o and ppositions (here, OH, Cl) have an overwhelming
electron-donating mesomeric effect, thus reducing the acidity.
3.
4.
Hint: presence of three powerful electron-withdrawing CF3 groups.
5.
Delocalisation stabilises both the neutral (given) molecule as well as the cation resulting from its protonation.
Further unlike the given neutral molecule, the cation has two exactly equivalent canonical forms, thus,
making protonation energetically profitable.
6.
The NMe2 group sterically interferes with the two very large NO2 groups at o-position, thus, preventing
the p orbitals of the N-atom from being parallel to the p orbitlas of the ring-carbon atoms, Hence +M
effect of NMe2 is inhibited. Also, M effect of NO2 groups does not take place and their baseweakening influence is restricted to their inductive effects. Thus, N-atom in NMe2 is more electron-rich
than that in NH2.
LOCUS
79
TRY YOURSELF - IV
1.
(i) diethyl ether

Resultant
O
C2H5
(ii) N(CH3)3
C2H5
Resultant
N
CH3
CH3
CH3
(iii) I Cl
Resultant
(iv) Methanol
Resultant
O
H
CH3
CH3
NO2
Resultant
(v)
Resultant
(vi)
CH3
CH3
Resultant
(vii)
Resultant
CH3
(viii)
Zero
CH3
CH3
OH
Resultant
Resultant
(ix)
(x)
NO2
LOCUS
80
EXERCISES
[ ANSWER ]
1.
Electron-seeking or electrophilic reagents.
2.
For delocalisation, all participating atomic orbitals should essentially be parallel by virtue of planarity of the
molecule. This planarity may get effected due to steric factors. Further, a large increase or decrease in
compounds energy content and/or charge separation discourages delocalisation.
+
3.
CH
CH
CH3
CH
CH
O
CH3
CH
CH
CH
CH3
CH
CH
4.
Electrophiles : O3, H
Nucleophiles : RC C, H
5.
The product (mechanistic details would be learnt later under pinacol-pinacolone rearrangement) is as
shown below:
(CH3)3 C C CH3
O
6.
Farther located is the halogen atom from the carboxyl group, its I effect dies down more rapidly along a
saturated chain. Hence, the negative charge in carboxylate anion becomes progressively spread.
7.
8.
C6H5OH is more acidic.

Formation of intramolecular hydrogen bonding stabilises the anion from o-hydroxybenzoic acid by
delocalising its charge. This is not possible in p-hydroxybenzoic acid.
9.
Ponder upon the following hints:

the I effect of carboxylic group as a substituent falls off rapidly with saturated C-atom(s) separating the
two COOH groups
phenyl group has lower electron-donating nature than saturated -carbon as in CH3 group.
10.
In solvents such as water where stabilisation by solvation via the hydrogen-bonding can occur, introduction
of a second alkyl group increases the basic strength. However, the introduction of a third alkyl group
decreases the basic strength as it is also determined by the extent to which the cation, formed by uptake
of a proton, can be solvated and hence, stabilised.
In a solvent such as chlorobenzene where there is no scope for hydrogen-bonding, the higher the number
of alkyl groups, the more is the basicity of the butylamines as here, basicity is determined exclusively by
electron availability on the nitrogen atom.
11.
Compound is acidic as loss of proton would lead to the following resonance stabilised anion.
O
LOCUS
81
12.
Reasons are as follows:

N-atom is bonded to two sp2 hybridised C-atom
Unshared electron pair on nitrogen get protonated, the resultant cation does not have unshared electron
pair for delocalisation. Thus, the neutral molecule is stabilised with respect to the cation (or protonation of
the neutral molecule is energetically unfavorable).
13.
The given compound has very low basicity due to effective +M effect of NH2 group (hardly any steric
repulsion as NH2 is a sufficiently small group) and hydrogen bonding between the oxygen atoms of the oNO2 groups and the hydrogen atoms of the NH2 group (this hydrogen-bonding assists in holding the
groups in the required planar orientation).
14.
Use the following hints:

OMe group has +M effect (at o- and p- position) and I effect.
o-substituent has both steric and polar effects apart from the usual +M and I effect

General Organic Chem

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LOCUS

THE CARBON ATOM : HYBRIDISATION

Chemistry / General Organic Chemistry

The four second-level orbitals (observe their orientations)

The three p-orbitals shown on the same axes

Four new sp3 hybrid

Chemistry / General Organic Chemistry

The four symmetrically oriented

these concepts will become clear in advanced courses at university level.

(wedge-shaped three dimensional

Three new identical sp2 hybridised orbitals

The unshaded lobes, lying in the

Observe the following:

Two sp2 hybrid orbitals of each

Head-on overlap occurs between

The remaining p orbital on each

The double-line indicates a -bond

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Two new identical sp hybridised orbitals

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-cloud (bond) due to

cloud of negative charge

A triple line indicates one

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No. of s(or p) orbitals mixed

Thus, % s character in:

Percentage s-character has two effects on the bond characteristics:

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Thus, we can summarize:

Closer to nucleus + More electronegative

High bond energy

Now let us study the characters one by one.

C C contains only one sigma bond.

C CH CH C , it has been observed that the C C single bond length is

Thus, CO2 will have a shorter C = O and length than formaldehyde.

Experimental values: Formaldehyde

Dissociation energy (D).

Bond energy (E).

High bond energy

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Nitrogen can undergo hybridisation in three ways: sp3, sp2 or sp:

Four new sp hybridised orbitals

The nitrogen atom is

The carbon and nitrogen atoms are both

Carbon and nitrogen are bonded

The carbon and nitrogen atoms are both sp

The drawing depicts an approximate

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CLASSIFICATION OF ORGANIC COMPOUNDS

Alkynes are the carbon-carbon triple bond containing hydrocarbons. eg. HC CH , CH 3 C CH

hydrocarbons which do not contain a benzene ring are called non-

CH 3 CH 3 , CH3 CH CH2 CH3 , CH3 C OH etc.

Now, let us consider an example. In the following compound:

C C double bond is a functional group and the class of

(2) C C triple bonds in alkynes

triple bond as a functional groups.

no functional group, hence very less reactive

(3) Hydroxyl (OH) group in alcohols

'hydroxyl' functional group

(4) Alkoxy (OR) group in ethers

(5) Nitro group (NO2) in nitro compounds

nitro functional group

correct structural formula