GOC1

Introduction :
The effect which appears due to electronic distribution is called electronic effect.
Classification :
1. Inductive effect
The normal C–C bond has no polarity as two atoms of same electronegativity (EN) value are connected to
each other. Hence the bond is nonpolar. Consider a carbon chain in 1-Chloro butane, here due to more EN of
Cl atom C – Cl bond pair is slightly displaced towards Cl atom hence creating partial negative ( –) charge
over Cl atom and partial positive (+) charge over C1 atom.
Now since C1 is slightly positive, it will also cause shifting of C1 – C2 bond pair electrons towards itself
causing C2 to acquire small positive charge. Similarly C3 acquires slightly positive charge creating an induction
of charge in carbon chain. Such an effect is called inductive effect.
Diagram showing I effect
The arrow shows electron withdrawing nature of – Cl group.

Thus inductive effect may be defined as a permanent displacement of  bond pair electrons due to a dipole.
(Polar bond)
Some important points are:
(a) It can also be defined as polarisation of one bond caused by polarisation of adjacent bond.
(b) It is also called transmission effect.
(c) It causes permanent polarisation in molecule, hence it is a permanent effect.
(d) The displacement of electrons takes place due to difference in electronegativity of the two atoms involved
in the covalent bond.
(e) The electrons never leave their original atomic orbital.
(f) Its magnitude decreases with distance and it is almost negligible after 3rd carbon atom.
(g) The inductive effect is always operative through  bond, does not involve  bond electron.
Types of inductive effects :
(a) – I Effect : The group which withdraws electron cloud is known as – I group and its effect is called
– I effect. Various groups are listed in their decreasing – I strength as follows.
> – > – > – NO2 > –SO2R > –CN > – CHO > – COOH > – F > – Cl >
– Br > – I > – OR > – OH > – C  CH > – NH2 > – C6H5 > – CH = CH2 > – H.
(b) + I effect : The group which release electron cloud is known as + I group and effect is + I effect.
> > – C(CH3)3 > – CH (CH3)2 > – CH2 – CH3 > – CH3 > – D > – H
The hydrogen atom is reference for + I and – I series. The inductive effect of hydrogen is assumed to be zero.
GENERAL ORGANIC CHEMISTRY (GOC)-I # 1

Ex. Since – NO2 is – I group it pulls or withdraws electron from cyclohexane ring making it electron deficient
Ex. Let us consider effect of COOH & – COO– in carbon chain
(a) (b)
Due to e¯ donating nature of carbon chain has become partially negative but – COOH is – I group
therefore carbon chain has become partially positive.
Ex. Direction of electron displacements
1. -OOC CH2 CH2 CH3 2. HOOC CH2 CH3 3.
CN
4. 5. 6.
+ + –
7. 8. 9. CH 3 CH CH NO2
2. Resonance
Resonance is the phenomenon in which two or more structures involving in identical position of atom, can be
written for a particular species, all those possible structures are known as resonating structures or canonical
structures.
Resonating structures are only hypothetical but they all contribute to a real structure which is called resonance
hybrid. The resonance hybrid is more stable than any resonating structure.


Resonance hybrid
The most stable resonating structure contribute maximum to the resonance hybrid and less stable resonating
structure contribute minimum to resonance hybrid.
Conjugation:
A given atom or group is said to be in conjugation with an unsaturated system if:-
(i) It is directly linked to one of the atoms of the multiple bond through a single bond.
(ii) It has π bond, positive charge, negative charge, odd electron or lone pair electron.

Types of Conjugation :
1. Conjugation between C = C and C = C (  )
2. Conjugation between +ve charge and C = C (  )
3. Conjugation between lone pair and C = C (  )
4. Conjugation between odd electron and C = C (CH2 = CH –  – CH = CH2)
5. Conjugation between negative charge and C = C (  )
Resonance Energy:
The P.E. difference between the most stable resonating structure and resonance hybride is called resonace
energy. The stability of molecule is directly proportional to resonance energy.
The difference in energy between the hybrid and the most stable canonical structure is referred as the
resonance energy. (as shown in Fig.2)
Fig.2
The resonance energy of a resonance hybrid is the difference between the theoritical and experimental value
of heat of hydrogenation of the compound.
Catalyst
+ H2    + (–28.6 Kcal/mol)
Cyclohexene
Accordingly,
Catalyst
+ 3H2    + 3 × 28.6 = (–85.8 Kcal/mole)
Therefore, benzene has [–85.8 – (–49.8)] Kcal/mol less energy than expected for a typical compound with
three double bonds. Hence resonance energy of benzene molecule is– 85.8 + 49.8 = –36.0 Kcal/mole.
The Rules of Resonance :

(a) All the canonical forms (resonating structure) must have proper lewis structure. For instance none of
them may have a carbon atom with five bonds.

(b) The positions of the nuclei of the atoms must remain the same in all of the structures. Structures 3 is not
a esonance structure of 1 or 2, for example, because in order to form it we would have to move a
hydrogen atoms and this is not permitted :
(c) All atoms taking part in the delocalisation must lie in a plane so that orbitals overlaping become parallel
to each other.

 i.e. 
 z
(d) All canonical forms must have the same number of unpaired electron.
(e) The energy of actual molecule is lower than of any form. Therefore delocalisation is a stabilizing
phenomenon.
(f) All canonical forms do not contribute equally to the true molecule. The more stable structure is the greater
contributor to its resonance hybrid.
Relative stability of the canonical form :

(a) Nonpolar (uncharged) structure are most stable. Charge separation decreases stability. Separating opposite
charges requires energy. Therefore, structures in which opposite charges are separated have greater energy
(lower stability) than those that have no charge separation.
: :
CH2 – CH = Cl +
: :
: :
CH2 = CH – Cl
(I) (II)
(b) Structures with more covalent bonds are more stable than other structures
(c) Structures in which all of the atoms have a complete valence shell of electrons (i.e., the noble gas
structure) are especially stable and make large contributions to the hybrid.
Ex. (II is more stable than I)
(d) Structure that carry negative charge on a more electronegative atom and positive charge on less
electronegative atom are comparatively more stable.

Ex.  is more stable than )
3. Mesomeric effect (or Resonance effect)

Mesomeric effect is defined as permanent effect of  electron shifting from multiple bond to atom or from
multiple bond to single bond or from lone pair to single bond. This effect mainly operates in conjugated
system of double bond. So that this effect is also known as conjugate effect.
Ex.
Types of Mesomeric effects :

(a) Positive Mesomeric effect (+M effect) :
When the group donates electron to the conjugated system it shows + M effect.
Relative order of +M groups (usually followed) :
– O > –NH2 > –NHR > –NR2 > –OH > –OR > –NHCOR > –OCOR > –Ph > –F > –Cl > –Br > –I > –NO
Ex. (I)
(II) .. - +
H2C = CH – CH = CH – NH2 H2C – CH = CH – CH = NH2
(III)
(IV)
(b) Negative Mesomeric effect (–M effect) :

When the group withdraws electron from the conjugated system, it shows – M effect
Relative order of –M groups (usually followed) :
— –
–NO2 > –CHO > C=O > –C–O–C–R > –C–O–R > –COOH > –CONH2 > –C–O
— || || || ||
O O O O
+ –
Ex. (I) (II) H 2C = CH – C N: H 2C – CH = C = N:
..
– + – + . .– – + ..
O – N = .O: O – N – .O:
. O – N = O:
.
(III)

Note :
1. When a +M group and –M group are at meta-positions with respect to each other then they are not in
conjugation with each other, but conjugation with benzene ring exists.
etc.
2. +M group increases electron density in benzene ring while –M group decreases electron density in the
benzene ring.
Ex. Write electron density order in the following compound.
(a)
(b)
Ans. (a) I > II > III > IV (b ) III > I > II > IV
4. Hyperconjugation
It is delocalisation of sigma electron with p-orbital. Also known as -conjugation or no bond resonance. It
may takes place in alkene, alkynes, carbocation, free radical, benzene nucleus.
Necessary Condition : Presence of at least one hydrogen at saturated carbon which is  with respect to
alkene, alkynes, carbocation, free radical, benzene nucleus.
(i) Hyperconjugation in alkene
(ii) Hyperconjugation in carbocation
(iii) Hyperconjugation in radical

(iv) Hyperconjugation in toluene
(a) The effect of electron displacement due to this type of resonance is called hyperconjugative effect.
(b) Since canonical forms of this resonance may not contain any bond between H and C so hyperconjugation
is also known as no bond resonance.
(c) These resonating structures only suggest that
* There is some ionic character between C – H bond.
* Carbon - carbon double bond acquires some single bond character.
(d) Number of no bond resonating structures due to hyperconjugation = Number of -hydrogens (In aliphatic
systems)
Applications of hyperconjugation
(a) Stability of Alkenes : More is the number of hyperconjugative structures more stable is the alkene.
"More alkylated alkenes are more stable".
Stability of alkenes no. of hyperconjugative structures.
H3C CH3 H3C H3C

C=C > C = CH – CH3 > C = CH2
Ex.
H3C CH3 H3C H3C
(b) Heat of hydrogenation : Greater the number of  hydrogen results greater stability of alkene.
Thus greater extent of hyperconjugation results lower value of heat of hydrogenation
1
Stability of alkenes no. of hyperconjugative structures 
HHydrogenat ion
Ex. CH2 = CH2 > CH3 – CH = CH2 > CH3 – CH = CH – CH3 (HHydrogenation)
(c) Bond Length : Bond length is also affected by hyperconjugation
Ex. 
(i) Bond length of C(II) – C(III) bond is less than normal C–C bond.
(ii) Bond length of C(II) – C(I) bond is more than normal C=C bond.
(iii) C–H bond is longer than normal C–H bond.
(d) Dipole moment : Since hyperconjugation causes the development of charge, it also affects the dipole
moment of the molecule.
Ex. (i) CH2 = CH2 < CH3 – CH = CH2 (Dipole moment)
(ii) H–CH=O < CH3–CH=O < CH3–CH=CH–CH=O (Dipole moment)
(e) Stability of carbocation : More the extent of hyperconjugation more is the stability.
Ex. (i) < CH3 < CH3 CH3 < (CH3)3

CH3
(ii) CH3 – > CH3 – CH2 – CH2 – > – > CH3 C –
CH3
(due to resultant of inductive effect and hyperconjugation)
(f) Stability of free radical : Greater the number of -hydrogen results greater stability of carbon free radical

Ex. (i) < CH3 – < CH3 – – CH3 < CH3 –
(ii) CH3 – > CH3 – CH2 – > >
(due to resultant of inductive effect and hyperconjugation, both operates in same direction)
5. Electromeric effects
It is a temporary effect. The organic compound having a multiple bond ( double or triple bond) show this effect
in the presence of an attacking reagent only. It is defined as the complete transfer of a shared pair of -
electrons to one of the atoms joined by a multiple bond on the demand of an attacking reagent. It is represented
by E and the shifting on the electrons is shown by a curved arrow. There are two types of eletromeric effect.
(i) +E effect : In this effect -electron of the multiple bond are transferred to that atom to which the reagent
gets attached.
– CH2 – E
(ii) – E effect : In this effect the -electron of the multiple bond are transferred to that atom to which the
attacking reagent does not get attached + NC

Note : When inductive and electromeric effects operate in opposite directions then the electromeric effect dominates.
6. Aromatic character [The Huckel 4n + 2 rule]
The following rules are useful in predicting whether a particular compound is aromatic or non–aromatic.
Aromatic compounds are cyclic and planar. Each atom in an aromatic ring is sp2 hybridised. The cyclic 
molecular orbital (formed by overlap of p-orbitals) must contain (4n + 2)  electrons, i.e., 2, 6, 10, 14 ........ 
electrons. Where n = an integer 0, 1, 2, 3,..............
Aromatic compounds have characteristic smell, have extra stability and burn with sooty flame.
Comparision between aromatic, anti aromatic and non-aromatic compounds.
Characteristics Aromatic Anti Aromatic Non-Aromatic
compounds (A) compounds (B) compounds (C)
Example
1. Structure Cyclic, planar all Cyclic, planar all Cyclic or acyclic

atoms of ring sp2 atoms of ring sp2 planar,or non planar
hybridised hybridised sp or sp2 or sp3
3. MOT Unpaired e¯s in B.M.O. B.M.O. / Non-bonding

M.O.
4. Overlapping Favourable over Unfavourable over Simple overlaping
lapping of p orbital lapping of p orbital like alkenes
5. Resonance Very high Zero 4-8 kcal/mol

energy (R.E.) R.E. > 20-25 kcal/mol like alkenes
6. Stability Unstable Normal stability
not-exist at like a conjugated
room temperature system
7. Characteristic Electrophilic Dimerisation Electrophilic addtion
Reactions substitution Reaction reaction to attain reaction like alkenes
stability
Stability of compounds : Aromatic > Non-Aromatic > Anti-Aromatic

7. Comparision between electronic effects :
Inductive effect Mesomeric effect Hyperconjugative effect
(1) It is found in saturated and (1) It is found in unsaturated (1) It is found in carbocation,
unsaturated compounds. compounds especially having carbon free radical and
conjugated system. unsaturated compounds.
(2) It involves partial shifting of (2) It involves complete shifting (2) It involves partial shifting
sigma electrons. of pi-electrons of pi-bonds or of sigma-electrons into
lone pair of electrons. adjacent p-orbital.
(3) The electron pair is slightly (3) The electron pair is (3) The electron pair is
displaced from its position and completely transferred and partially transferred.
thus partial charges are thus full positive and negative
developed. charges are developed.
(4) It is transmitted over a quite (4) It is transmitted from one (4) It is transmitted from one
short distance. The effect end to other end of the chain end to other end of the chain
becomes negligible after third provided conjugation is provided conjugation is
atom in the chain (distance present. It is distance present. It is distance
dependent). independent. independent.
Important points :
(a) If any group has more than one  bond in conjugation, then only one  bond will take part in delocalisation.
CH2  CH – C  CH

Out of two  bonds only one  bond will take part in delocalisation.
(b) If any conjugate position has more than one lone pair then only one lone pair will take part in the
delocalisation.
..
CH 2 = CH – .O. – CH 3

Out of the two lone pair ’s only one will take part in delocalisation.
(c) If any conjugate position has  bond and any of the positive charge, negative charge, odd electron,
lone pair electrons then only  bond will take part in delocalisation on priority.
.N.

Nitrogen has  bond as well as lone pair, but only  bond of nitrogen will take part in delocalisation.
(d) Electrons of negative charge or lone pair behave as 2 electrons if it is in conjugation to bond.
; ;
8. Applications of electronic effects

(a) Stability of reaction intermediates :
(i) Stability of carbocation  + M, + I groups.
(ii) Stability of carbon free radical  + I groups.
(iii) Stability of carbanion  – M, – I groups.
(b) Stability of Alkene :
More substituted (Branched) Alkenes are more stable due to hyperconjugation.
Note : Resonance effect or delocalisation of electrons increases the stability of over all system.
For example carbocation, carbon free radical, carbanion & Alkenes.
(c) Acidic & Basic strength of organic compounds :
(i) Acidity (Ka)  – M, –I groups.
(ii) Basicity (Kb)  + M, +I groups and solvation effect in aqueous solution.

9. Reaction Intermediates
Reactive, shortlived, high energy, unstable species, those are formed in the course of organic reactions are
called reaction intermediates.
Reaction intermediates generally formed after bond breaking and before bond formation.
A covalent bond can get cleaved either by :
(i) Heterolytic cleavage, or (ii) Homolytic cleavage.
Homolytic fission of Covalent Bonds :

The bond may break in such a way that each fragment takes away one of the electrons of the bond. This
process called homolysis, produces fragments with unpaired electrons called radicals.
Heterolytic fission of Covalent Bonds :

The bond may break in such a way that one fragment takes away both electrons of the bond, leaving the
other fragment with an empty orbital. This kind of cleavage called heterolysis, produces charged fragments
or ions.
Heterolysis of a bond normally requires that the bond be polarised.
Polarisation of a bond usually result from different electronegatives of the atoms joined by the bond. The
greater the difference in electronegativity, the greater the polarisation. In the given instance, atom B is more
electronegative than A.
(A) Carbocation :
Definition : A carbon intermediate which contain three bond pair & a positive charge on it is called carbocation.
Hybridisation : Carbocation may be sp2 & sp hybridised
Hybridisation Example
sp 2 , , ,
sp H2C = , HC 
Carbocations are electron deficient. They have only six electrons in their valence shell, and because of this,
carbocations act as Lewis acids. Most of the carbocations are short-lived and highly reactive, they occur as
intermediates in some organic reactions. Carbocations react with Lewis bases or ions that can donate the
electron pair, that they need to achieve a stable octet of electrons (i.e., the electronic configuration of a noble
gas):

Because carbocations are electron seeking reagents, chemists call them electrophiles. All Lewis acids,
including protons, are electrophiles. By accepting an electron pair, a proton achieves the valence shell
configuration of helium; carbocations achieve the valence shell configuration of neon.
Stability : Carbocations are stabilised by

(i) + I effect (ii) + m effect (iii) Hyperconjugation (iv) delocalisation of charge
General stability order :
> > > >
> > >
Ex. > >
t-Butyl carbocation has +I effect of three Me–groups and also Hyperconjugation effect which makes it most
stable.
Ex. > >
In Benzyl cation, Extensive Resonance is seen which stabilises .

In Ethyl carbocation + I and Hyperconjugation of Me – group stabilizes carbocation.
In vinyl carbocation stability decreases rapidly since carbon of (CH2) is sp2 hybridized which is slightly more
electronegative hence acts as – I group which increases (+) charge density.
Rearrangement :
Whenever an Intermediate carbocation is formed in reaction it may rearranges.
Only those carbocation will rearrange which can produce more stable species. It can be done either by
(i) Shifting of H, alkyl, aryl, bond (1, 2 shifting)
(ii) Ring expansion (more strained ring to less strained ring)
(iii) Ring contraction

(i) Shifting of H, alkyl, aryl, (1, 2 shift)
1,2 H
(A) 

Shifting

(B) 1
,2 Me

Shifting
1,2 Ph 
(C)  
Shifting
+
CH
– 2 1,2 Bond
(ii) Ring expansion :  
Shifting
1,2 Bond
(iii) Ring contraction :  
Shifting
Note : The unique stabilisation of cyclopropyl methyl carbocation due to  electrons overlapping with vacant p-
orbital of carbocation carbon is seen. cyclopropyl methyl carbocation (more stable than
Benzyl)
Q. Rearrange (if applicable) the following carbocations into more stable form :-
CH3
+
(a) CH3 – CH2 – CH2 (b) (c) CH3 – C – CH – CH3
+
CH3
CH3
– CH3
– –
(d) CH3 (e) (f)
+ +
(B) Carbanion :
Definition : A carbon intermediate which contain three bond pair and a negative charge on it, is called
carbanion.
Hybridisation : Hybridisation of carbanion may be sp3, sp2 & sp.
Hybridisation Example
sp 3 , CH3– , , ,
sp 2 H2C= , CH2=CH– ,
sp HC 
Stability of carbanion : Carbanions are stabilised by electron withdrawing effect as

(i) – I effect (ii) – m effect (iii) Delocalisation of charge

Carbanions are Lewis bases. In their reactions they seek a proton or some other positive centre to which
they can donate their electron pair and thereby neutralize their negative charge.
Example of stability order :
Ex. (a) CH3 CH 3 CH2 CH 3 CH2 CH3 CH3 C CH3 (Stability order : 1 > 2 > 3 > 4)
CH3
(b) CH  C .. (Stability order : 1 > 2 > 3)
1
.. .. ..
CH2
(c) (Stability order :1 > 2 > 3)
  
••
(d) CH2  CH – C H2 C 6H5 – C H2 ( C 6H 5 ) 3 C (Stability order : 1 < 2 < 3)
Rearrangement : Generally carbanions do not undergo rearrangement.

(C) Free Radicals :
Homolysis of covalent bond results into free radical intermediates possess the unpaired electrons.
It is generated in presence of Sun light, Peroxides or High temperature
Free Radical : An uncharged intermediate which has three bond pair and an unpaired electron on carbon.
Note : (i) It is Neutral species with odd e¯
(ii) It is paramagnetic in nature due to odd e¯
(iii) No rearrangement is observed generally.
(iv) Carbon atom having odd electron is in sp2 hybridised state
(v) Any reaction if it is carried out in the presence of sunlight, peroxide or high temperature it generally
proceeds via free radical intermediate.
 Stability of free radical : It is stabilised by resonance, hyperconjugation and + I groups.
  
Ex. (H3C)3C > H3 C – C H – CH3  H3 C – C H2  C H3 (Stability order)
  
Ex. (C 6H5 )3 C > (C 6H5 )2 C H > C 6H5 – C H2 > CH2  CH – C– CH3 (Stability order)
|
CH3

(D) Carbenes (Divalent Carbon intermediates) :
Definition : There is a group of intermediates in which carbon forms only two bonds. These neutral divalent
carbon species are called carbenes. Most carbenes are highly unstable that are capable of only fleeting
existence. Soon after carbenes are formed, they usually react with another molecules.
Methods of preparation of carbene :
CHCl3 + : CCl2 CH2I2 + Zn : CH2
CH2N2 N2  + : CH2 CH2 = C = O : CH2 + CO
Types of carbene Singlet Triplet
Shape Bent Linear

2
Hybridisation sp sp
Nature of reaction stereospecific None
State Excited state Ground state
Magnetic Diamagnetic Paramagnetic
Nature Paired electrons Diradical
(E) Nitrenes :
The nitrogen analog of carbenes are nitrenes. They are very much reactive since in them octet of N is
incomplete. In nitrenes only one valencies of N are satisfied.
(F) Benzyne :
The benzene ring has one extra C – C  bond in benzyne
Clearly, we can see that the newly formed  bond cannot enter in resonance with other  orbitals of ring. since
it is in perpendicular plane.
It is also important to note that hybridisation of each carbon involved in 'Benzynic bond' is sp2 since the
overlap between these sp2 hybrid orbitals is not so much effective.

Type (I) : Very Short Answer Type Questions : [01 Mark Each]
1. What is a homolytic cleavage? The homolytic fission of C–C bond in ethane produces :
2. What is a carbocation?
3. What are free radical reactions?
4. The central carbon atom of a free radical, carbocation and carbanion containing electrons in outermost shell
respectively.
5. Give reason why the following two structures I and II cannot be the major contributors to the real structure of
CH3COOCH3.
6. Identify electrophilic centre in the following :

(i) CH3CH=O (ii) CH3CN (iii) CH3I (iv) CH3COOH
Type (II) : Short Answer Type Questions : [02 Marks Each]

7. Write resonance structures of CH2=CH–CHO. Indicate relative stability of the contributing structures.
8. Arrange the following carbocation in increasing order of their stability with reason.
9. Explain why alkyl groups act as electron donors when attached to a -system.
10. Write a stable resonating structure for each of the following compounds :
(i) CH2=CH–CH=CH–CN (ii) (iii) (iv)
11. Draw all the hyperconjugating structures of toluene.
12. Relative stabilities of the following carbocation will be in order.
13. Arrange the following carbocations in increasing order of their stability with reason.

Type (III) : Long Answer Type Questions : [03 Marks Each]
14. Draw the resonance structures for the following compounds. Show the electron shift using curved arrow
notation.
(a) C6H5OH (b) C6H5NO2 (c) CH3CH=CHCHO (d) C6H5–CHO
(e) C6H5– (f) CH3CH=
15. What are hybridisation states of each carbon atom in the following compounds ?
CH2=C=O, CH3CH=CH2, CH2=CHCN, C6H6 , (CH3)2CO, HCONH2
16. For the following bond cleavages, use curved-arrows to show the electron flow and classify each as homolysis
or heterolysis. Identify reactive intermediate produced as free radical, carbanion and carbocation.
(a) (b)
(c)
CH3

|
17. CH3  C C  CH3 The given carbocation rearranges into :
| |
H3 C OH
Type (IV) : Very Long Answer Type Questions: [05 Marks Each]
18. Draw all the resonating structures of the following compounds :

(a) Benzene (b) Naphthalene
(c) Anthracene (d) Phenanthrene
PART - I : SUBJECTIVE QUESTIONS

Section (A) : Inductive effect
A-1. Show the direction of inductive effect in following compounds
(1) (2) (3)
(4) (5) (6)
(7) (8) (9)
(10) (11) (12)

(13) (14) (15)
(16) (17) (18)
(19) (20)
Section (B) : Resonance Concepts, Conditions, Resonating Structures & Conjugation

B-1. Which of the following compounds have delocalized electrons ?
O
||
(P) CH 2  CHCCH 3 (Q) (R) (S) CH3CH2NHCH = CHCH3
B-2. Number of  electrons in resonance in the following structure is.
Section (C) : Stability of Resonating Structures and different species

C-1. In the following sets of resonating structure, label the major and minor contributors towards resonance
hybrid.
(P)
(Q)
(R)
(S)

C-2. Write the stability order of following resonating structures :
I II I II
(P) (Q)
(R) (S)
Section (D) : Mesomeric Effect

D-1. Arrange the following groups in the increasing order of +m :
(i) I, Cl, F, Br (ii) –NH2, –OH,
D-2. Arrange the following groups in the increasing order of –m :
(i) –NO2, –COOR, –CHO, –CN, –COR (ii) , ,
D-3. Classify the following groups as +m, –m, ±m, +I, –I ?

(i) –NO2 (ii) –OH (iii) –ONO
(iv) –NO (v) (vi) –SO3H
D-4. Classify the following groups as +m, –m, ±m, +I, –I ?

(i) –S–R (ii) (iii)
(iv) –Cl (v) –CF3 (vi) –B(OH)3
D-5. How many groups (attached with benzene ring) show + M effect?
Section (E) : Steric Inhibition of Resonance (SIR Effect)

E-1. Explain the SIR effect.
E-2. Compare the SIR effect between orthochloro benzoic acid, orthobromobenzoic acid and orthoiodo benzoic
acid.

Section (F) : Hyperconjugation
F-1. Define hyperconjugation by taking an example of propene.
F-2. In which molecules or ions hyperconjugation effect is observed and write the number of hyperconjugable
hydrogen atoms.
(A) C6H5 – CH = CH2 (B) CH3 – CH2 – CH = CH2 (C) CH2 = CH2 (D)
CH3 C 2H5 CH3

|  | |
(E ) (F) CH3 — C — C H2 (G) C 2H5 — C  (H) CH3 — C
| | |
CH3 C 2H5 CH3
(I) (J) (K) (L)
Section (G) : Applications of electronic effects

G-1. The correct decreasing order of electron density in aromatic ring of following compounds is :
O O O
|| || ||
C–H O–C–H NH – CH3 C – NH – CH3
(I) (II) (III) (IV)
G-2. Correct dipole moment order is
(p) (q) (r)
G-3. Identify the relation between given pairs :
(a) , (b) ,
(c) , (d) CH3–CH=CH–CH3 ,
G-4. Find the total number of the position where positive charge can be delocalized by true resonance
. (Excluding the given position)

Section (H) : Concept of Aromaticity
H-1. What is aromaticity ?
H-2. Classify the following as aromatic, antiaromatic and nonaromatic compounds.
(a) (b) (c) (d) (e)
(f) (g) (h) (i) (j)
(k) (l) (m) (n)
H-3. Why cyclooctatetraene is nonplanar.
Section (I) : Carbocations

I-1. Arrange the following carbocations in decreasing order of their stability :
(I) (II) (III) (IV)
   
(P) CH3—CH2— CH2 CH3 — CH — CH2 CH3 — CH — CH2 CH3 — CH — CH2
| | |
F Br Cl
   
(Q) CH3 – CH2 – C H2 CH3 – C H – CH2 – CH3 (CH3 )3 C C H3
(R)
I-2. Write the stability order of following carbocations with proper reason.
I II III IV
I-3. Which of the following carbocation is more stable and why ?
(I) (II)
I-4. Draw the structures of P and Q.

Section (J) : Carbanions
J-1. Arrange the following in decreasing order of stability.
(a)
(b)
J-2. Arrange the following in decreasing order of stability.

..
.. CH3
–
(a) ..
..
–
CH3
1 2 3 4
(b)
.. ..
(c) CCl3 CF3
1 2
Section (K) : Carbon free radicals

K-1. Rank the following free radical in increasing order of their stability and give appropriate reasons.
K-2. Arrange the following free radical in decreasing order of stability :

 
CH3 – CH2 CH3
I IV
PART - II : OBJECTIVE QUESTIONS

* Marked Questions may have more than one correct option -
Section (A) : Inductive effect
A-1. Inductive effect involves :
(A) Delocalisation of  - electrons (B) Partial displacement of  - electrons
(C) Delocalisation of  - electrons (D) Displacement of lone pair electrons.
A-2. Select correct statement about I effect?
(A) I effect transfers electrons from one carbon atom to another.
(B) I effect is the polarisation of  bond electrons.
(C) I effect creates net charge in the molecule.
(D) I effect is distance independent.
A-3. Which of the following group shows +I-effect :

(A) –Br (B) –COOH (C) –OR (D) –COO–
A-4. Which of the following alkyl groups has the maximum +I effect ?
(A) (CH3)2CH– (B) (CH3)3C– (C) CH3CH2– (D) CH3–

A-5. Decreasing –I effect of given groups is :
(i) CN (ii) NO2 (iii) NH2 (iv) F
(A) iii > ii > i > iv (B) ii > iii > iv > i (C) iii > ii > iv > i (D) ii > i > iv > iii
A-6. Which of the following is the strongest -  group :
  
(A) – N (CH3)3 (B) – N H3 (C) – S (CH3)2 (D) – F
A-7. In which of the following species, incorrect direction of Inductive effect is shown ?
CH3 O O
-
C – OH C O
(A) (B) (C) (D)
CH3
Section (B) : Resonance Concepts, Conditions, Resonating Structures & Conjugation
B-1. The notation for relating two resonating structures is :
(A) (B) (C) (D)
B-2. Resonance is delocalisation of :

(A)  electrons (B)  electrons (C)  electrons (D) None
B-3. Resonance effect involves :
(A) Delocalization of –electrons along a conjugated system.
(B) Delocalization of lone pair along a conjugated system.
(C) Delocalization of negative charge along a conjugated system.
(D) All are correct.
B-4. During delocalization, which statement is incorrect :
(A) Net charge remains same (B) Number of paired electrons remain same
(C) Number of unpaired electrons remain same (D) Energy of resonating structures always remains same
B-5. Which of the following statements is incorrect ?

(A) The energy of resonance hybrid is always less than that of any resonating structure.
(B) The resonance energy is the difference between the enthalpies of formation of the molecule and the
resonating structure having maximum energy.
(C) The resonance structures are hypothetical structure and they do not represent any real molecule.
(D) In delocalized structure of benzene the -charge cloud is spread equally above and below the plane of
molecule.
B-6. Which of the following statement regarding resonance is NOT correct ?
(A) the different resonating structures of a molecule have fixed arrangement of atomic nuclei.
(B) the different resonating structures differ in the arrangement of electrons.
(C) the hybrid structure has equal contribution from all the resonating structures always.
(D) None of the individual resonating structure explains all characteristics of the molecule.
B-7. Resonance energy is :
(A) The potential energy difference between most stable resonating structure and resonance hybrid
(B) The potential energy difference between the least stable resonating structure and resonance hybrid.
(C) The potential energy difference between the least stable and most stable resonating structure.
(D) None
B-8. Resonance structure of the molecule does not have
(A) higher energy than their hybrid structure.
(B) identical arrangement of atoms.
(C) the same number of paired electrons.
(D) always equal contribution to the resonance hybrid.

B-9. Which of the following species can not show resonance?
(A) (B) (C) (D)
B-10. Resonance is not possible in :
(A) (B) (C) CH2=CH–Cl (D)
B-11. Which does not have conjugate system ?
(A) CH2 = CHCl (B) CH2 = CHCHO (C) CH3CH = CH2 (D)
B-12. The compound which is not resonance stabilised
(A) CH2=CH–Cl (B) (C) CH2=CH–CH2–Cl (D)
B-13. Which of the following is not acceptable as resonating structure :
(A) (B) (C) (D) None of these
B-14. Which of the following pair is not pair of resonating structures?


(A) & (B) CH2 = CH – O– & CH2 – CH  O
   
(C) CH2 = CH – O – CH3 & CH2 – CH  O – CH3 (D) CH3 – C  O & CH3 – C  O
B-15. Which of the following structures constitute resonance structures ?
(A) & CH3 – O – N = O (B) &
(C) (CH3)2 CO & (D) CH3 – CH = CH – CH3 & CH3 – CH2 – CH = CH2
B-16. Among the given sets, which represents the resonating structure ?
(A) and (B) and
(C) and (D) and
B-17. In which of the following resonance is not possible?

(A) CH2 = C = CH2 (B) CH2 = C = CH (C) CH2 = C = CH (D) CH2 = C =

Section (C) : Stability of Resonating Structures and different species
C-1. In which of the following first resonating structure is more stable than the second ?
(A)  (B) 
(C) CH2=CH–NH2  (D) 
C-2. Which one of the following is least stable resonating structure ?
(A) (B)
(C) (D)
C-3. Which of the following resonating structure of 1-Methoxy-1,3-butadiene is least stable ?

+ +
(A) CH2 – CH = CH – CH = O – CH3 (B) CH2 = CH – CH – CH = O – CH3
+ +
(C) CH2 – CH – CH = CH – O – CH3 (D) CH2 = CH – CH – CH – OCH3
C-4. Which of the following resonating structure is the least contributing structure ?
(A) (B)
(C) (D)
C-5. HNCO (isocyanic acid) has following resonating structures :
HN  C  O  

I
The order of stablity is :
(A) I > III > II (B) I > II > III (C) II > III > I (D) II > I > III
C-6. The correct stability order of the following resonance structures is :
(A) (IV) > (I) > (III) > (II) (B) (II) > (IV) > (I) > (III)
(C) (III) > (II) > (IV) > (I) (D) (I) > (IV) > (III) > (II)
C-7. Which of the following is least stable resonating structure ?
(A) (B)
(C) (D)
C-8. Which is the most stable resonating structure ?
(A) (B) (C) (D)

C-9. The correct stability order of given resonating structures is :
(A) I > II > III > IV (B) IV > III > II > I (C) I = II = III = IV (D) II = III > I = IV
C-10. Which of the following is incorrect for stability of structures.
O¯ O¯
| | 
(A) CH3  CH  CH  CH2 > CH3  C  CH  CH3 (B) CH2  CH  CH  CH  C H2 >
(C) > (D) <
C-11. In which of the following pairs of first species is more stable than second.
(A) , (B) ,
(C) , (D) ,
Section (D) : Mesomeric Effect

D-1. Which of the following group show +m effect?
(A) –CN (B) –O–NO (C) –CCl3 (D) –CHO
D-2. Which of the following group show –m effect?
(A) –CMe3 (B) (C) (D)
D-3. Which of the following group show +m and –I effect ?

(A) (B) (C) –O (D) –OH
D-4. Which of the following group show +m > –I effect ?
(A) –F (B) (C) (D) –COOH
D-5. Which of the following group show –m and –I effect ?

(A) –NO2 (B) –NH2 (C) –OH (D) –Cl
D-6. Identify which of the following group acts as +m as well as –m ?

(A) –F (B) –NH2 (C) –Cl (D) –OH
D-7. +m and +I both effects are shown by :

(A) (B) (C) (D) – C (CH3)3
D-8. The weakest + m group of the given species is :
(A) – OCH3 (B) – F (C) – I (D) – N (CH3)2

Section (E) : Steric Inhibition of Resonance (SIR Effect)
E-1. Maximum extent of steric inhibition of resonance can be expected in
(A) (B) (C) (D)
E-2. Select the correct statement about this compound.
NO2
3
1 5
NO2 NO2
Br
(A) All three C–N bond length are same.

(B) C1–N and C3–N bonds length are same but shorter than C5–N bond length.
(C) C1–N and C5–N bonds length are same but longer than C3–N bond length.
(D) C1–N and C3–N bonds length are different but both are longer than C5–N bond length.
E-3. The longest C — N bond length in the given compound is :
(A) x (B) y (C) z (D) w
Section (F) : Hyperconjugation

F-1. In hyperconjugation there is overlap between :
(A) p- and -orbitals (B) 2  - orbitals (C) d-and--orbtial (D) -and p - orbitals
F-2. Which of the following cannot exhibit hyperconjugation -


(A) CH3 C H2 (B) (C) CH3CH = CH2 (D)
F-3. Which of the following alkenes will show maximum number of hyperconjugation forms ?
(A) CH2 = CH2 (B) CH3–CH=CH2 (C) CH3–CH2–CH=CH2 (D)
F-4. Arrange the stability of following
I II III
(A) I < II < III (B) II < I < III (C) I < III < II (D) II < III < I
F-5. The order of heat of hydrogenation in following compound is :
(I) (II) (III) (IV)

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

F-6. does not involve :
(A) –p overlap (B) – overlap (C) p–p overlap (D) p–d overlap
F-7. Which one of the following has inductive, mesomeric and hyperconjugation effect ?
(A) CH3Cl (B) CH3–CH=CH2
(C) CH3CH= CH – C – CH3 (D) CH2 = CH – CH = CH2

||
O
Section (G) : Applications of electronic effect

G-1. The decreasing order of electron density on the ring is :
(A) III > II > I (B) II > III > I (C) I > III > II (D) III > I > II
G-2. Correct dipole moment order is
(p) (q) (r)
(A) p > q > r (B) r > q > p (C) q > r > p (D) p > r > q
G-3. Arrange following compounds in decreasing order of their dipole moment.

I II III IV
CH3—CH2—NO2 CH3—CH2—NH2 CH3—CH2—F CH3—CH2—CN
(A) IV > III >I > II (B) IV > I > III > II
(C) I > III > IV > II (D) I > IV > III > II
G-4. The decreasing order of bond length of C = C bond in the following compounds is:
I II III IV
(A) II > I > IV > III (B) III > I > II > IV
(C) IV > II > I > III (D) IV > I > II > III
G-5. Decreasing order of bond length of C = C bond in the following compound?
(A) p > q > r (B) r > q > p

(C) p > r > q (D) q > r > p

G-6. In which of the following C = C bond length is minimum :
(A) (B) C=CH2 (C) CH2 = CH – N (D)
G-7. Which of the following is correct about the following compound
(Naphthalene)
(A) All the C-C bond length are same
(B) C1–C2 bond length is shorter than C2–C3 bond length
(C) C1–C2 bond length is greater than C2–C3 bond length
(D) All the C-C bond length are equal to C-C bond length of benzene
G-8. The stability order of alkene in following compounds is :
(I) (II) (III) (IV)

(A) I < II < III < IV (B) II < I < III < IV (C) II < III < I < IV (D) II < IV < I < III
G-9. Observe the following statements and choose the correct option.
S1 : Inductive effect is more powerful than mesomeric effect.
S2 : The bond polarity order of bonds a, b, and c in the given molecule (I) is c > a > b
b CH2–CH=CH2
Ph–CH2 a CH
c CH2–CCH
(I)
S3 : The hybrid structure has always have equal contribution from all the resonating structures.
S4 : shows inductive effect, resonance, hyperconjugation & intramolecular hydrogen bonding.
(A) TFTF (B) FTFT (C) FTTF (D) TTFF
Section (H) : Concept of Aromaticity

H-1*. Conditions of aromaticity is/are :
(A) Compound must be cyclic
(B) Compound must be planar
(C) Each member of the ring must have p-orbital perpendicular to plane of the ring.
(D) Total number of -electrons must be equal to 4n + 2, where n = 0, 1, 2.....
H-2 . Which out of the following is aromatic hydrocarbon ?
(A) (B) (C) (D)
H-3. Identify the aromatic compound ?
(A) (B) (C) (D)

H-4. Number of  electrons in conjugation for these compounds
, , & will be respectively :
(A) 8, 6, 6, 6 (B) 6, 4, 6, 6 (C) 6, 6, 6, 6 (D) 6, 6, 8, 6
H-5. The hybridisation of nitrogen in (pyrrole) is :
(A) sp3 (B) sp2 (C) sp (D) Cann't be predicted
Section (I) : Carbocations

I-1. The most unstable carbocation is :
   
(A) CH3 C H2 (B) Cl – CH2 – C H2 (C) C H2 – CHO (D) C H2 – O – CH3
I-2. The most stable carbocation is :
(A) (B) (C) (D)
I-3. Which of the following is the correct stability order for given carbocations ?


(A) (B) (C) (D)



(E)
(A) E > D > B > A > C (B) C > D > B > A > E
(C) C > E > B > A > D (D) A > C > E > D > B
I-4. Write correct stability order of following compounds :
(1) (2) (3) (4)
(A) 2 > 4 > 3 > 1 (B) 4 > 2 > 3 > 1 (C ) 2 > 3 > 1 > 4 (D) 1 > 2 > 3 > 4
I-5. The stability order of following carbocation is
(i) (ii) (iii) (iv)

(A) i > ii > iv > iii (B) iii > i > ii > iv
(C) iv > ii > iii > i (D) ii > iv > iii > i

I-6. Which of the following shows the correct order of decreasing stability ?

(A) > > > CH3 – C H2

(B) > > > CH3 – C H2

(C) > > > CH3 – C H2

(D) > > CH3 – C H2 >
I-7. Which of the following is the rearranged more stable carbocation of the given species ?
CH3
| 
CH3 – C – C H  CH3 
|
CH3
CH3 CH3
| | 
(A) CH3 – C – C H – CH3 (B) CH3 – C – C H2 – C H2
|  |
CH3 CH3
CH3 CH3 CH3

| | | 
(C) CH3 – C — CH – CH3 (D) CH3 – CH – CH  C H2
 |
CH3
I-8. Which of the following is the rearranged more stable carbocation of the given species ?

CH2 


(A) CH2 (B)  CH3 (C) CH3 (D)  CH2
I-9. The given carbocation rearranges into :
(A) (B)
(C) (D)

Section (J) : Carbanions
J-1. Which of the following is the least stable carbanion ?
(A) HC  C– (B) (C6H5)3C– (C) (CH3)3C– (D) CH3–
J-2. The most stable anion is :
(A) (B) (C) (D)
J-3. In which of the following pairs of carbanion the first one is more stable than second.
(A) (B)
(C) (D)
J-4. Arrange the following carbanions in decreasing order of stability :
I II III IV
(A) III > I > IV > I (B) III > II > I > IV
(C) I > III > II > IV (D) III > I > II > IV
Section (K) : Carbon free radical
K-1. Among the following, the paramagnetic species is :
(A) Free radical (B) Carbonium ion (C) Carbanion (D) All the three
K-2. The stability of given free radicals in decreasing order is :
  
(i) CH3– C H2 (ii) CH3– C H –CH3 (iii) (iv) C H3
(A) iii > iv > i > ii (B) i > ii > iii > iv
(C) iii > ii > iv > i (D) iii > ii > i > iv
K-3. Which of the following is the correct order of stability of free radicals?
(A) benzyl > allyl > 2º > 1º (B) allyl > benzyl > 2º > 1º
(C) allyl > 2º > 1º >benzyl (D) benzyl > 2º > 1º > allyl
K-4. Most stable radical among the following is :
(A) (B) (C) (D)
K-5. Arrange the following radicals in decreasing order of their stability.
(I) (II) (III) (IV)
(A) IV > I > III > II (B) IV > III > II > I
(C) I > II > III > IV (D) IV > III > I > II

PART - III : ASSERTION / REASONING
Each question has 5 choices (A), (B), (C), (D) and (E) out of which ONLY ONE is correct.
(A) STATEMENT-1 is true, STATEMENT-2 is true and STATEMENT-2 is correct explanation for STATEMENT-1.
(B) STATEMENT-1 is true, STATEMENT-2 is true and STATEMENT-2 is not correct explanation for STATEMENT-1.
(C) STATEMENT-1 is true, STATEMENT-2 is false.
(D) STATEMENT-1 is false, STATEMENT-2 is true.
(E) Both STATEMENTS are false.
1. Statement-1 : Carbon–oxygen bonds are of equal length in acetate ion.
Statement-2 : Bond length decreases with the multiplicity of bond between two atoms.
2.
Statement- : Carbocation (II) is more stable than carbocation (I).

Statement-2 : Carbocation (II) has less positive inductive effect of –CD3 group as compared to –CH3 group.
3. Statement-1 :
I and II are resonating structures and III is resonance hybrid.

Statement-2 : The resonance hybrid is the hypothetical structure that is considered to be a ‘blend’ of the
real contributing structures.
PART - I : SUBJECTIVE QUESTIONS

1. The central carbon-carbon bond in 1, 3-butadiene is shorter than that of n-butane. Why ?
2. Write decreasing order of electron density in aromatic ring in following compounds.
3. Identify the number of compounds in which positive charge will be delocalised ?

4. In how many of the following cases, the negative charge is delocalised?
.. – CH3
..
5. Observe the following compound and write the number of hydrogen atom involved in hyperconjugation ?
6. Write that resonating structure of given carbocation in which all atoms have complete octet.
7. Write rearranged carbocation obtained by 1, 2-Methyl shift.
8. Which one of the following cation is most stable. Give reason ?
(I) (II) (III) (III)
9. Find the number of carbon atoms including the given structure which can have negative charge in resonating
structures. (The structures with charge separation are not acceptable).
10. Arrange the following carbanions in decreasing order of stability :
I II III IV
PART - II : OBJECTIVE QUESTIONS
Single choice type
1. What is NOT-True for inductive effect but True for Resonance effect (During their functioning)
(Inductive effect) (Resonance effect)
(A) electron pair is delocalised -electron pair delocalized
(B) electron pair is localized -electron pair is localized
(C) Bond angle does not change -electron pair is localized
(D) Hybridisation of atoms changes -electron pair is localized
2. The most unlikely representation of resonance structures of p-nitrophenoxide ion is:
(A) (B) (C) (D)
3. In which delocalisation of positive charge is possible ?

–
NH H H OH O
3 2
N 

(A) (B) (C) (D)
4. Resonance stabilized cation is :
(A) (B) (C) (D)
5. Which of the following is not the correct resonating structure of C6H5NH2 ?
(A) (B) (C) (D)
6. Decreasing order of potential energy of the folowing cations is :
(I) (II) (III)

(A) II > I > III (B) I > II > III (C) III > II > I (D) II > III > I
7. Stability order of the following species ?
(A) > >  (B) > >  (C) > >  (D) > > 

8. Least contributing resonating structure of nitroethene is :
(A) (B) (C) (D)
9. The least and most stable resonating structure respectively are :
(1) (2) (3) (4)

(A) 2, 1 (B) 2, 3 (C) 3, 1 (D) 1, 2
10. Which of the following species does not have equally contributing resonating structures ?
(A) (B) CH2=CH–CH=CH2 (C) (D) CH2=CH–CH2
11. Which of the following group show +m and +I effect ?
(A) (B) –NH (C) (D) –F
12. The correct order of + m effect of ‘N’ containing functional group on benzene ring, amongst the given compounds
is
(A) I > II > IV > III (B) II > I > III > IV (C) I > II > III > IV (D) IV > III > II > I
13. In which case the -bond pair and  bond pair of electrons both are attracted in the same direction, (towards
same atom.) :
(A) H2C = CH — Cl (B) CH3 – CH2 – NH2 (C) H2C = CH – CH = O (D) H2C = CH – OCH3
14. Which of the following group has the maximum hyperconjugation effect when attached to bezene ring ?
(A) CH3– (B) CH3CH2– (C) (CH3)2CH– (D) (CH3)3C–
15. Hyperconjugation is possible in :
(A) (B)
(C) (D)
16. Stability of -bond in following alkenes in the increasing order is :

CH3–CH = CH – CH3
(I) (II) (III) (IV)

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

17. The correct heat of hydrogenation order of
(A) III > I > II > IV (B) I > III > II > IV
(C) II > I > IV > III (D) III > IV > II > I
18. The minimum magnitude of heat of hydrogenation per mole of molecule is of :
(A) (B) (C) (D)
19. The correct order of electron density in aromatic ring of following compounds is :
I II III IV
(A) IV > III > II > I (B) I > II > III > IV
(C) IV > II > I > III (D) IV > II > III > I
20. The decreasing order of electron density on the ring is :
(A) x > w > y > z (B) z > y > w > x

(C) x > z > y > w (D) y > z > w > x
21. The decreasing order of electron density on the ring is :
(I) (II) (III) (IV)
(A) (II) > (III) > (IV) > (I) (B) (IV) > (I) > (II) > (III)
(C) (IV) > (I) > (III) > (II) (D) (I) > (III) > (IV) > (II)
22. The least polar compound is :
(A) (B) (C) (D)

23. Correct dipole moment order is :
CH2  CH  Cl CH3  CH2  Cl CH2  CH  CN
(p ) (q) (r )
(A) r > q > p (B) r > p > q (C) q > r > p (D) p > r > q
24. Which of the following statement is correct ?
(A) In the dianion , all the C – C bonds are of same length but C – O bonds are of different length
(B) In the dianion, all C – C bonds are of same length and also all C – O bonds are of same lengths
(C) In the dianion, all C – C bond lengths are not of same length
(D) None of the above
25. The decreasing order of bond length of double bonds is :
(A) c > a > b > d (B) d > c > a > b (C) b > c > a > d (D) a > b > d > c
26. If the given compound is planar. Select the correct statement.
(A) The boron is sp2 hybridized and the p–orbital contains an unshared pair of electron
(B) The boron is sp2 hybridized and a hybrid orbital contains an unshared pair of electron.
(C) The boron in sp2 hybridized and hybrid orbital is vacant
(D) The boron is sp2 hybridized and the p–orbital is vacant
27. Aromatic compounds burn with sooty flame because :

(A) They have a ring structure of carbon atoms. (B) They have a relatively high percentage of hydrogen.
(C) They resist reaction with oxygen of air. (D) They have a relatively high percentage of carbon.
28. In the following carbocations, the stability order is :
(A) III > II > IV > I (B) IV > I > II > III (C) IV > III > II > I (D) III > IV > II > I
29. Which of the following is most stable carbocation ?

   
(A) CH3 – C H2 (B) C H – CH Cl (C) C H2 – CH2 – Cl (D) C H2 – CCl3
2 2
(A) CH3 (B) CH3 (C) CH3 – (D)

31. The most stable carbocation is :
(A) (B)
+ +
(C) + (D) +
32. The most stable carbocation is :
(A) (B) (C) (D)
33. Arrange the following carbanions in decreasing order of stability :
(A) III > II > IV > I (B) III > II > I > IV
(C) III > I > II > IV (D) II > III > I > IV
34. The stability order of the following anions :
(A) IV > III > II > I (B) I > II > III > IV (C) I > II > IV > III (D) I > III > II > IV
35. Give the stability order of following radicals :
(I) (II) (III) (IV)
(A) III > IV > II > I (B) IV > III > II > I (C) I > II > III > IV (D) IV > II > III > I
More than one choice type
36. Which statement is/are true about resonance ?
(A) It decreases the energy of system.
(B) The hybridisation of atoms do not change due to resonance
(C) Resonance hybrid is more stable than any resonating structure.
(D) Resonanting structures can not be isolated at any temperature
37. Which of the following statement is incorrect about resonance ?
(A) The most stable structure explains all the characteristics of a species.
(B) All resonating structures remain in equilibrium.
(C) Resonance hybrid has maximum similarity with most stable resonating structure.
(D) Resonance hybrid is real.
38. The correct number of p-electrons have been mentained in :
(A) ; (4) (B) ; (6)
(C) ; (3) (D) ; (6)

39. Which of the hybrid species are correct?
(A) (B)
(C) (D)
40. In which of the following pairs of resonating structures first resonating structure is more stable than second?
(A)  (B) 
(C)  (D) 
41. In which of the following pairs of compounds will second structure have more contribution to resonance
hybrid than first ?
(A) & (B) &
(C) & (D) &
42. Which of them are correct for magnitude of resonance energy ?
(A) < (B) <
(C) < (D) <
43. The correct orders for bond length are :
(A) (a > a) (B) (b = b)
(C) (c > c) (D) (d > d)

PART - III : MATCH THE COLUMN
1. Match the following
Coulmn - I Coulmn - II
(Compounds) (Characteristics)
(A) (p) Mesomeric effect / resonance
(B) Ph–CH=CH–CH3 (q) Inductive effect.
(C) (r) Hyperconjugative effect
(D) (s) Nonpolar
(t) Polar
2. Column-I Column-II
(Stability order) (Responsible effect)
(A) (p) Inductive effect
(B) > (q) Resonance
(C) CH3–CH2– > (r) Hyperconjugation
(D)  > CH3–CH2 (s) Mesomeric effect
PART - IV : COMPREHENSION
Comprehension # 1
Identification of +m & –m groups : If the first atom of the group has lone pair or negative charge shows +m
effect. If the group has vacant p-orbital or vacant d-orbital on first atom. Also a multiple bonded group in which
second atom is more electronegative than the first then it shows –m effect.
1. Identify which of the following does not show + m effect.

O O

|| ||
(A) –NH2 (B) –O (C)  NH  C  CH (D)  C  NH  CH
3 3
2. Identify which of the following cannot show – m effect.


(A) –CH = O (B)  P(CH ) (C) –F (D) –B(CH3)2
3 3

3. Decreasing + m-power of given group is :
(I) – NH2 (II) – OH (III) (IV) – NH – CO – CH3
(A) I > III > IV > II (B) III > II > I > IV
(C) III > I > II > IV (D) II > I > IV > III
Comprehension # 2
Hydrogenation of unsaturated hydrocarbons is an exothermic reaction. Due to hyperconjugation and resonance
the stability of unsaturated hydrocarbons increases and the increase in stability is more due to resonance.
Compound with same number of -bonds and more stability has lower heat of hydrogenation.
Heat of formation is defined as the energy evolved when a molecule is formed from its atoms. For isomers the
more stable compound has higher heat of formation.
4. The correct heat of hydrogenation order is :
(p) 1, 3-Pentadiene (q) 1, 3-Butadiene
(r) 2, 3-Dimethyl-1, 3-butadiene (s) Propadiene
(A) p > q > r > s (B) s > q > p > r
(C) q > s > p > r (D) s > p > q > r
5. The order of heat of formation of the following molecules is :
(A) I > II > III > IV (B) II > III > IV > I (C) IV > II > III > I (D) IV > III > II > I
Comprehension # 3
Reaction intermediates : Reaction intermediates are short lived species and are highly reactive. They are
formed by heterolytic and homolytic bond fission. There are various types of reaction intermediates in which
the most important are carbocation, carbanion and free radical.
Carbocation is an organic species in which carbon have positive charge and six electrons in its
outermost shell. The stability of carbocation can be increased by positive inductive effect, hyperconjugation
and delocalisation. If -atom with respect to carbocation has one or more lone pair of electrons then lone pair
of electron strongly stabilises the carbocation due to octet completion.
Species in which carbon have negative charge is called carbanion. Carbanion carries three bond
pairs and one lone pair. The stability of carbanion can be increased by negative inductive effect, negative
mesomeric effect and delocalisation.
Free radical is a species which have seven electrons in its outermost shell. The stability of free
radical can be increased by hyperconjugation and delocalisation.
6. Which of the following is the most stable carbanion intermediate ?
(A) (B)
(C) (D)

7. The stability order of following free radicals is :
(A) I > II > III > IV (B) II > III > I > IV
(C) I > III > II > IV (D) III > II > I > IV
8. The stability order of following carbocations is
(A) I > II > III (B) II > I > III

(C) III > I > II (D) II > III > I
PART - I : IIT-JEE PROBLEMS (LAST 10 YEARS)

* Marked Questions may have more than one correct option.
1. Write resonating structure of the compound . [JEE-03(S), 2/60]
2. The correct stability order for the following species is : [JEE-04, 2/60]
(A) (II) > (IV) > (I) > (III) (B) (I) > (II) > (III) > (IV)
(C) (II) > (I) > (IV) > (III) (D) (I) > (III) > (II) > (IV)
3. Explain why 7-bromo-1, 3, 5-cycloheptatriene exist as an ion while 5-Bromo-1, 3-cyclopentadiene does not
form any ion even in the presence of Ag+ . Explain why ? [JEE 2004, 4/60]
4. Explain the following observations [JEE 2005, 2/84]
but not
5. Which will be the least stable resonating structure : [JEE-05(S), 3/84]


(A) CH2 = CH – – – O – CH3 (B) C H2 – – CH = CH – OCH3

(C) C H2 – CH = CH – CH = – CH3 (D) CH2 = CH – – CH = – CH3

6. Among the following, the least stable resonating structure is : [JEE-07, 3/162]
 O
+
(A) (B) +
N
O

 O
+
(C) + N (D)
O

7. Hyperconjugation involves overlap of the following orbitals : [JEE-08, 3/163]

(A) – (B) –p (C) p – p (D)  – 
8. The correct stability order of the following resonating structures is : [JEE-09, 3/160]
(A) (I) > (II) > (IV) > (III) (B) (I) > (III) > (II) > (IV)
(C) (II) > (I) > (III) > (IV) (D) (III) > (I) > (IV) > (II)
9. In the following carbocation; H/CH3 that is most likely to migrate to the positiviely charged carbon is
[JEE-09, 3/160]
(A) CH3 at C-4 (B) H at C-4 (C) CH3 at C-2 (D) H at C-2
10. The total number of contributing structures showing hyperconjugation (involving C–H bonds) for the following
carbocation is [JEE-11, 4/180]
11.* Which of the following molecules, in pure form, is (are) unstable at room temperature ? [JEE-12, 4/136]
(A) (B) (C) (D)
12.* The hyperconjugative stabilities of tert-butyl cation and 2-butene, respectively, are due to
(A)  p (empty) and  * electron delocalisations. [JEE(Advanced)-2013, 4/120]
(B)  * and   electron delocalisations.
(C)  p (filled) and   electron delocalisations.
(D) p (filled)  * and  * electron delocalisations.

PART - II : AIEEE PROBLEMS (LAST 10 YEARS)
1. In the following benzyl/allyl system R – CH = CH2 and (R is alkyl group)
Then decreasing order of inductive effect is : [AIEEE-2002]

(A) (CH3)3 C— > (CH3)2CH— > CH3CH2— (B) CH3CH2— > (CH3)2CH— > (CH3)3C—
(C) (CH3)2CH— > CH3CH2— > (CH3)3C— (D) (CH3)3C— > CH3CH2— > (CH3)2CH—
2. The increasing order of stability of the following free radicals is : [AIEEE-2006, 3/220]
• • • •
(A) (C6H5)3 C < (C6H5)2 C H < (CH3)3 C < (CH3)2 C H
• • • •
(B) (C6H5)2 C H < (C6H5)3 C < (CH3)3 C < (CH3)2 C H
• • • •
(C) (CH3)2 C H < (CH3)3 C < (C6H5)3 C < (C6H5)2 C H
• • • •
(D) (CH3)2 C H < (CH3)3 C < (C6H5)2 C H < (C6H5)3 C
3. The electrophile, E  attacks the benzene ring to generate the intermediate -complex, which of the following
-complex have lowest energy ? [AIEEE-2008, 3/105]
NO2 NO2 NO2

H
H
+ E +
(A) (B) + E (C) + (D)
H
E
H E
4. Arrange the carbanions, (CH3)3 C , C Cl3 , (CH3)2 C H, C6H5 C H2 in order of their decreasing stability :
[AIEEE-2009, 4/144]
(A) (CH3)2 C H > C Cl3 > C6H5 C H2 > (CH3)3 C (B) C Cl3 > C6H5 C H2 > (CH3)2 C H > (CH3)3 C
(C) (CH3)3 C > (CH3)2 CH > C6H5 CH2 > CCCl3 (D) C6H5 CH2 > CCl3 > (CH3)3 C > (CH3)2 CH
5. The order of stability of the following carbocations : [JEE(Mains)-2013, 4/120]
; ; is :
(A) III > II > I (B) II > III > I (C) I > II > III (D) III > I > II

BOARD LEVEL EXERCISE : HINT & SOLUTIONS
1. In homolytic cleavage one of the electrons of the shared pair in a covalent bond goes with each of the
bonded atoms. Thus in this movement of a single electron takes place instead of an electron pair. The
homolytic fission of C–C bond in ethane produces radicals.
2. A species having a carbon atom possessing a sextet of electrons and a positive charge is called a carbocation.
For example methyl carbonium ion +CH3.
3. Organic reactions that proceed by homolytic fission are called free radical reactions.
4. The central carbon atom of a free radical, carbocation and carbanion containing electrons in outermost shell
respectively 7, 6 and 8.
5. Structure I and II have charge separation, so less stable than the neutral structure, hence less contributors
to the real structure.
6. (i) (ii) (iii) (iv)
7. (Stability order : 1 > 2 > 3)
8.
9. sp3 hybrid carbon atoms and hydrogen atoms are less electronegative as compare to sp2 and sp hybrid
carbon and other  systems so alkyl group act as electron donor.
10. (i) (ii) (iii) (iv)
11.

12. Order : IV < II < III < I (Electron releasing groups (+m, +I) increases stability of carbocations and electron
withdrawing groups (–m, –I) decreases the stability of carbocations.)
13. +I and hyperconjugation effect of methyl groups stabilize the carbocation.

(CH3)3C+ has 9 hyperconjugative hydrogen, (CH3)2CH+ has 6 hyperconjugative hydrogen, CH3CH2+ has 3
hyperconjugative hydrogen. Stability order is
14. Refer Notes
15. , , , , ,
16. (a) [Homolysis of peroxy bond produces radicals]

Free radical
(b) [Hetrolysis of bond produces ions]
Carbanion
(c) [Hetrolysis of bond produces ions]

Carbocation
17.
+ M effect of —OH group stablises carbocation (Complete octet).
18. ;
Benzene has two Naphthalene has three
Anthracene has four
Phenanthrene has five resonating structures

EXERCISE - 1
PART - I
A-1. (1) (2) (3)
(4) (5) (6)
(7) (8) (9)
(10) (11) (12)
(13) (14) (15)
(16) (17)
(18) (19) (20)
B-1. (P), (R), (S) B-2. 8
C-1. (P) I – minor II – major (Q) I – minor II – major

(R) I – minor II – major (S) I – minor II – major
C-2. (P) I > II ; (Q) II > I ; (R) I > II ; (S) II > I
D-1. (i) +m : I < Br < Cl < F ; (ii) +m : –OH < –NH2 <
D-2. (i) –m : –COOR < –COR < CHO < CN < NO2 ; (ii) –m : < <
D-3. (i) –m, –I (ii) +m, –I (iii) +m, –I (iv) ±m, –I (v) –m, –I (vi) –m, –I
D-4. (i) ±m, –I (ii) –m, –I (iii) +m, –I (iv) +m, –I (v) –I (iv) +I

D-5. 6
E-1. SIR effect is combined effect of steric hindrance, crowding and electronic effect in ortho subsitituted benzoic
acid normally.
E-2. SIR effect increases with the size of ortho group. The order of SIR effect is o-iodo benzoic acid > o-bromo
benzoic acid > o-chloro benzoic acid.
F-1. It is delocalisation of sigma electron with p-orbital. It may takes place in alkene, alkynes, carbocation, free
radical, benzene nucleus.
Necessary Condition : Presence of at least one hydrogen at saturated carbon which is  with respect to
alkene, alkynes, carbocation, free radical, benzene nucleus.
Propene 
F-2. (A) 0 (B) 2 (C) 0 (D) No hyperconjugation

(E ) 0 (F) 0 (G) 6 (H) 9
(I) 3 (J) 10 (K) 0 (L) 10
G-1. (III) > (II) > (IV) > (I)
+ m group increases electron density and – m group decreases electron density in aromatic ring.
G-2. p>q>r
G-3. (a) Resonating structure (Conjugation of -bonds). (b) Resonating structure (+M effect of –NH2 group)
(c) Functional isomers. (d) Hyperconjugative structure.
G-4. 2
H-1. Those molecules are aromatic which have very high resonance energy. Only those molecules has sufficiently
high amount of resonance energy to become aromatic which
(a) are cyclic
(b) are planar
(c) contains (4n +2) number of  -electrons in ring.
(d) must have cyclic resonance between (4n + 2) number of -electrons
Where n = 0,1,2,3,4 ..........
H-2. Aromatic : (a), (b), (c), (d), (e), (f), (h), (m) ; Antiaromatic : (g), (i), (j), (l), (n) ; Nonaromatic : (k)
H-3. Cyclooctatetraene is nonplanar due to avoid its anti aromaticity and it becomes tub-shaped structure.
I-1. (P) I > III > IV > II (Q) III > II > I > IV. (R) III > II > IV > I
I-2. IV > III > II > I

I-3. (II) is more stable carbocation due to extented conjugation
I-4. (P) = ; (Q) =
J-1. (a) 1 > 2 > 3 ; (b) 1 > 2 > 3

J-2. (a) 2 > 1 > 3 > 4 ; (b) 1 > 2 > 3 ; (c) 1 > 2
K-1. Stability order : - IV > III > II > I
IV is most stable being 3º and delocalised but III is 2º and delocalised.
K-2. III > II > I > IV

PART - II
A-1. (B) A-2. (B) A-3. (D) A-4. (B) A-5. (D)
A-6. (A) A-7. (D) B-1. (B) B-2. (A) B-3. (D)
B-4. (D) B-5. (B) B-6. (C) B-7. (A) B-8. (D)
B-9. (A) B-10. (A) B-11. (C) B-12. (C) B-13. (B)
B-14. (A) B-15. (B) B-16. (B) B-17. (A) C-1. (C)
C-2. (C) C-3. (D) C-4. (B) C-5. (A) C-6. (D)
C-7. (D) C-8. (B) C-9. (D) C-10. (A) C-11. (A)
D-1. (B) D-2. (D) D-3. (D) D-4. (B) D-5. (A)
D-6. (C) D-7. (C) D-8. (C) E-1. (C) E-2. (C)
E-3. (D) F-1. (D) F-2. (D) F-3. (B) F-4. (C)
F-5. (B) F-6. (D) F-7. (C) G-1. (A) G-2. (B)
G-3. (D) G-4. (B) G-5. (A) G-6. (B) G-7. (B)
G-8. (A) G-9. (B) H-1*. (A,B,C,D) H-2 . (C) H-3. (B)
H-4. (C) H-5. (B) I-1. (C) I-2. (B) I-3. (A)
I-4. (A) I-5. (D) I-6. (B) I-7. (C) I-8. (B)
I-9. (D) J-1. (C) J-2. (A) J-3. (B) J-4. (D)
K-1. (A) K-2. (D) K-3. (A) K-4. (C) K-5. (B)
PART - III
1. (B) 2. (E) 3. (C)
EXERCISE - 2
PART - I
1. 1, 3-Butadiene shows delocalisation.
CH2 = CH – CH = CH2 – CH = CH –
So bond between second & third C-atoms show partial double bond character. Hence bond length is shorter
than C – C bond in n-butane.
2. III > I > II > IV 3. 5 4. 5 5. 9
6. 7. 1,2Methyl shift
    
8. (III) Maximum number of convalent bond (complete octet). 9. 6.
10. IV > III > II > I

PART - II
1. (A) 2. (C) 3. (D) 4. (C) 5. (C)
6. (A) 7. (A) 8. (C) 9. (C) 10. (B)
11. (B) 12. (C) 13. (C) 14. (A) 15. (A)
16. (A) 17. (D) 18. (D) 19. (D) 20. (B)
21. (C) 22. (C) 23. (A) 24. (B) 25. (D)
26. (D) 27. (D) 28. (A) 29. (A) 30. (C)
31. (A) 32. (D) 33. (B) 34. (B) 35. (B)
36. (A,B,C,D) 37. (A,B) 38. (A,B,C,D) 39. (A,B,C,D) 40. (B,C)
41. (A,B,C) 42. (A,B) 43. (A,B,D)
PART - III
1. (A - p,q,t) ; (B - p,q,r,t) ; (C - p,q,r,t) ; (D - p,q,s) 2. (A - s) ; (B - p, q, r) ; (C - p) ; (D - p, r)
PART - IV
1. (D) 2. (C) 3. (C) 4. (B) 5. (C)
6. (D) 7. (D) 8. (A)
EXERCISE - 3
PART - I
1.
2. (I) +m effect of ‘O’ and hyperconjugative effect of 2-CH3 groups.

(II) is a simple 2º–carbocation
(III) +m effect of ‘O’ and hyper conjugation of one –CH3 groups.
(IV) is a simple 1º–carbocation.
3. 7-bromo-1, 3, 5-cycloheptatriene on ionisation gives tropylium ion which is aromatic & highly stable,
but ionisation of 5-bromo-1, 3-cyclopentadiene gives 1, 3-cyclopentadienyl cation which is anti aromatic
& unstable. (non existent)
4. In the formation of first product the antiaromaticity due to the presence of three “ ” rings of the reactant is
finished and the product becomes more stable.While in 2nd case the product is thermodynamically less
stable.
5. (A) Negative charge and lone pair on adjacent atom will increase potential energy and decrease stability.
6. (A) 7. (B) 8. (B) 9. (D) 10. 6
11.* (B, C) 12.* (A)
PART - II
1. (A) 2. (D) 3. (A) 4. (B) 5. (D)

PART - I : OBJECTIVE QUESTIONS
Single choice type
1. Which is the incorrect order of electron density in aromatic ring ?
(A) > > >
(B) > > >
(C) < < <
(D) > > >
2. Which of the following pairs are resonating structures.
(A) & CH3 – O – N = O (B) &
(C) (CH3)2 CO & (D) CH3 – CH = CH – CH3 & CH3 – CH2 – CH = CH2
3. Polarization of electrons in acrolein may be written as :

–  – 
(A) C H2  CH – C H  O (B) C H2  CH – C H  O
–  –   –
(C) C H2  CH – C H  O (D) C H2  CH – C H  O
4. Which allylic carbocation is most stable ?

 
(A) CH3  CH  CH  C H2 (B) CH3  CH  CH  C H  CH3

(C) CH3  CH  CH  C CH3 (D) All have same stability
|
CH3

(A) (B)
(C) (D)
6. Give the stability order of the following compounds.
OCH3 OCH3 NH2 NH2

+ +
+ +
y H
H y y H y
(I) (II) H (III) (IV)
(A) I > II > III > IV (B) IV > I > II > III
(C) IV > I > III > II (D) IV > II > I > III
7. The following carbocation rearranges to
CH3 CH3
|  |
CH2  C  C  C H  CH  CH3
| |
CH3 CH3
(A) (B)
CH3 CH3
|  |
(C) (D) CH2  C  C  CH  CH  CH3
| |
CH3 CH3
More than one choice type

8. Which of the following is a conjugated system ?
(A) CH2=CH–CH=CH2 (B) CH2=C=CH2
(C) CH2=CH–CH2–CH=CH2 (D) CH2=CH–CH=O

9. The acceptable resonating structure(s) of the following molecule is/are :
(A) (B)
(C) (D)
10. In which cases delocalisation of charge is possible?
– –  –
(A) (B) O — P(CH3)2 (C) O — P (CH3)3 (D) O — B(CH3)2
PART - II : SUBJECTIVE QUESTIONS

1. Identify total no. of compounds which have correct direction of Inductive effect.
(i) CH3 – CH2 K (ii) CH3 – CH2 MgBr (iii) (iv)
(v) (vi)
2. Draw all the contributing structures of (i) Aniline (ii) Benzaldehyde ?

3. Find the total number of the position where positive charge can be delocalized by true resonance
(Excluding the given position)
4. Find the number of carbon atoms including the given structure which can have negative charge in resonating
structures. (The structures with charge separation are not acceptable).

5. Which of the following has the highest dipole moment. Explain briefly.
(a) (b) (c)
6. CH2 = CH — Cl CH3 — CH2 — Cl

(I) (II)
Compare the above molecules with respect to :

(P) C — Cl bond length (Q) Dipole moment
(R) C — C bond length of (I) with respect to ethene
7. Identify total no. compound which contains equal C–O bond length and Explain why
(i) (ii) (iii) (iv)
8. Write all possible hyperconjugative structures of propene (CH3–CH=CH2)

9. Which of the following carbocation can undergo rearrangement :
(a) (b) (c) (d)
(e) (f) (g) (h)
(i) (j) (k) (l) (n)
10. Stability order of following carbocations is :

CH3 CH3
|  |
(I) CH3 – O – CH2 CH2  CH  CH2 (II) CH3 – O – CH2 CH2  C  CH3

CH3 CH3
 |  |
(III) CH3 – O – CH2 CH  CH  CH3 (IV) CH3 – O – C H CH 2  CH  CH3
11. Arrange the following carbocations in decreasing order of their stability :
(I) (II) (CH3CH2)2 (III) (CH3CH2)3 (IV)

12. Arrange the following carbanions in order of decreasing stability.
, , , , ,
13. Write the number of hyperconjugable hydrogen atoms of the following species :
(P) (Q)
(R) (S)
14. Find the molecule which are Aromatic, Antiaromatic or nonaromatic in nature.
+ +
(a) (b) (c) (d)

+
H H
Cyclopropenyl Cyclobutenyl
cation di-cation
(e) (f) (g) Tropylium cation (h)

(Cycloheptatrienyl
cation)
H
H H
(i) (j) (k) H
H
H
[18] Annulene
15. How many of the given molecules have all carbon atoms in one plane :
16. How many species out of the following are aromatic ?

PART - I
1. (D) 2. (B) 3. (D) 4. (C) 5. (D)
6. (C) 7. (D) 8. (A,D) 9. (A,B) 10. (B,C,D)
PART - II
1. 4
2. (i)
(ii)
3. 10 4. 7
5. c, due to –M effect of NO2.
6. (P) I < II (C – Cl bond length) (Q) I < II (dipole moment) (R) I has bigger bond length
7. 3 (i, ii, iv) equal contributar resonating structures.
8.   
9. (b) 1
, 2H shift
 (c) 1
, 2  bond shift
  (d) 1
, 2H shift

(e) 1
, 2H shift
 (g) 1
, 2H shift
 (i) 1
, 2H shift

(j) (k) 1

, 2CH3 shift
 (n) 1
, 2H shift


10. IV > III > II > I 11. (IV) > (III) > (II) > (I)
12. 4>6>5>1>2>3
13. (P) 2 (Q) 1 (R) 4 (S) 6
14. Aromatic – a, c, g, h, i, j, k ; Antiaromatic – b, d, e ; Nonaromatic – f
15. 7 [1, 2, 3, 4, 6, 7 and 9. have all carbon atoms in one plane.]
16. 5
PART - I
1. On the basis of electronic effect.
2. (B)
  –
3. (D) C H2  CH – C H  O Due to inductive effect.
4. (C) Due to maximum number of hyperconjugation and delocalisation.
5. (D) More stable carbocation due to delocalisation and hyperconjugation.
7. (D) 1, 2-methyl shift results into more stable carbocation which is stable due to delocalisation and
hyperconjugation.
8. CH2=CH–CH=CH2 and CH2=CH–CH=O have alternate multiple bond so these are conjugated system.
9. A & B are proper resonating structures while C & D violate octet rule.
10. (nitrogen does not have empty p/d orbitals)

PART - II
3.
4.
The negative charge is delocalised on the marked carbon atoms (1 - 7).
10. – OCH3
This carbocation is stabilize by +M effect of H3CO- group and resonance with benzene ring.
14. Aromatic cyclic, planner, conjugated system having (4n + 2)electrons.

Antiaromatic  Cyclic, Planner, conjugated system having 4n electrons.
16. Aromatic species are

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Introduction :

The arrow shows electron withdrawing nature of – Cl group.

GENERAL ORGANIC CHEMISTRY (GOC)-I # 1

Ex. Let us consider effect of COOH & – COO– in carbon chain

GENERAL ORGANIC CHEMISTRY (GOC)-I # 2

1. Conjugation between C = C and C = C (  )

2. Conjugation between +ve charge and C = C (  )

3. Conjugation between lone pair and C = C (  )

4. Conjugation between odd electron and C = C (CH2 = CH –  – CH = CH2)

5. Conjugation between negative charge and C = C (  )

The Rules of Resonance :

GENERAL ORGANIC CHEMISTRY (GOC)-I # 3

Relative stability of the canonical form :

Ex. (II is more stable than I)

GENERAL ORGANIC CHEMISTRY (GOC)-I # 4

3. Mesomeric effect (or Resonance effect)

Types of Mesomeric effects :

(b) Negative Mesomeric effect (–M effect) :

GENERAL ORGANIC CHEMISTRY (GOC)-I # 5

(i) Hyperconjugation in alkene

(ii) Hyperconjugation in carbocation

(iii) Hyperconjugation in radical

GENERAL ORGANIC CHEMISTRY (GOC)-I # 6

H3C CH3 H3C H3C

Ex. (i) < CH3 < CH3 CH3 < (CH3)3

GENERAL ORGANIC CHEMISTRY (GOC)-I # 7

(ii) CH3 – > CH3 – CH2 – > >

attacking reagent does not get attached + NC

1. Structure Cyclic, planar all Cyclic, planar all Cyclic or acyclic

3. MOT Unpaired e¯s in B.M.O. B.M.O. / Non-bonding

5. Resonance Very high Zero 4-8 kcal/mol

Stability of compounds : Aromatic > Non-Aromatic > Anti-Aromatic

GENERAL ORGANIC CHEMISTRY (GOC)-I # 8

8. Applications of electronic effects

GENERAL ORGANIC CHEMISTRY (GOC)-I # 9

Homolytic fission of Covalent Bonds :

Heterolytic fission of Covalent Bonds :

Heterolysis of a bond normally requires that the bond be polarised.

GENERAL ORGANIC CHEMISTRY (GOC)-I # 10

Stability : Carbocations are stabilised by

General stability order :

> > > >

> > >

Ex. > >

Ex. > >

In Benzyl cation, Extensive Resonance is seen which stabilises .

GENERAL ORGANIC CHEMISTRY (GOC)-I # 11

Stability of carbanion : Carbanions are stabilised by electron withdrawing effect as

GENERAL ORGANIC CHEMISTRY (GOC)-I # 12

Example of stability order :

Rearrangement : Generally carbanions do not undergo rearrangement.

It is generated in presence of Sun light, Peroxides or High temperature

GENERAL ORGANIC CHEMISTRY (GOC)-I # 13

Methods of preparation of carbene :

CHCl3 + : CCl2 CH2I2 + Zn : CH2

CH2N2 N2  + : CH2 CH2 = C = O : CH2 + CO

Types of carbene Singlet Triplet

Shape Bent Linear

GENERAL ORGANIC CHEMISTRY (GOC)-I # 14