04-General Organic - Sandeep Final - CW

JEE MAINS - VOL - IV GENERAL ORGANIC CHEMISTRY
GENERAL ORGANIC CHEMISTRY

SYNOPSIS Homolytic Cleavage
(Equal cleavage of covalent bond)
 Reaction mechanism involves the sequential  In homolytic bond fission, a covalent bond is
account of each step, describing the detailed cleaved in such a way that each atom separates
electron movement,Energy changes during bond with one electron forming highly reactive entities
breaking and bond formation and the rates at called free radicals.
A : B  A.  B.
which reactants are converted into products i.e.
kinetics of reaction.
 Mechanism of a reaction is hypothetical,This Cl : Cl  Cl.  Cl.
helps in understanding the reactivity of
H 3C : H  H 3C.  H.
compounds and in planning the synthesis of the
compounds.By knowing the mechanism, it shall  Free radicals are highly reactive due to their
be more easy to adjust the experimental unpaired electrons.
conditions as to improve the yield of the products  Homolytic fission usually occurs in non-polar
or even the course of reaction to get different bonds when the linked atoms have nearly the
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products. same E.N & it occurs in vapour phase and

 In organic reactions the reactant also called as generally initiated by high temperature
the substrate, this reacts with an attacking reagent (  5000 C ) Electricity,U.V radiations &by the
and forms one or more intermediates which finally presence of organic peroxides or catalysts.
forms products & byproducts.
Heterolytic Fission
Substrate + reagent  [Intermediate] 
Product (Unequal cleavage of covalent bond)
 In Heterolytic bond fission, a covalent bond is
 cleaved in such a way that both the electrons of
By Product shared pair are carried away by one of the atoms
leading to the formation of negative and positive
 To understand clearly the mechanism of various ion pair.
organic reactions, it is essential to have a
 If positive charge is present on the carbon then
knowledge of
cation formed is termed as Carbocation, if
i) Cleavage (fission or Breaking) of covalent
negative charge is present on the carbon then
bonds,
the anion is called Carbanion.
ii)Nature of attacking reagents
 The electron pair is carried away by the atom
iii) Electronic displacements in covalent bonds
which is more E.N.
Fission of a Covalent Bond
 Depending upon the nature of the given A : B  A  B  (A is more E.N.)
compound,the nature of attacking reagent & A : B  A  B  (B is more E.N.)
reaction conditions bond cleavage occurs in two
different ways,  Heterolytic fission mostly occurs in polar covalent
(i) Homolytic cleavage or homolysis bonds and is favoured by polar solvents like
(ii) Heterolytic cleavage or heterolysis water alcohol and is influenced by the presence
of acid &base catalysts.
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GENERAL ORGANIC CHEMISTRY JEE MAINS - VOL - IV
Reaction Intermediates (3) A free Radical after loosing a neutral molecule
 Short lived ( 106 to a few seconds) fragments and forming another free radical

called reaction intermediates result from CH 3COO   CH 3  CO2
homolytic and heterolytic bond fission. They are  The structure of carbon free radicals may not be
produced during the reaction but are lost before predicted, they may have from planar to
the reaction is complete. pyramidal geometry based on the groups and
 The important reaction intermediates are free atoms attached to carbon atom having odd
radicals, carbocations, carbanions, carbenes, electron. for example: In
nitrenes, benzyne flouro substituted alkyl radical ‘S’ character of
Free Radicals orbitals increases therefore the shape changes
 A free radical may be defined as an atom or group
to pyramidal in CF3
of atoms which contains an unparied electron.
They are formed by homolysis. If the unpaired 
CH 3  planar shape
electron is on carbon atom, they are c a l l e d 
alkyl free radicals. Free radicals are highly CF3  pyramidal shape
reactive due to their unpaired electrons Relative Stability of Free Radicals
 Chemical reaction which occurs in the presence  Alkyl radicals are classified as primary, secondary
of Heat (  500o C ), Electricity,Light and tertiary radicals on number of carbon atoms
(sunlight, h ), Peroxide,Radical is known as attached to radical.

Free radical reaction.  Stability of alkyl free radicals can be explained
Characteristics of Free Radicals by hyperconjugation and number of resonating
 (i) Free radicals are Electrically neutral and are structures due to hyperconjugation, The
highly unstable decreasing order of stability of alkyl free
(ii) They are short lived & highly reactive due to 
radicals is 30 > 20 > 10 > CH3
unpaired electrons.
(iii) The free radicals are planar and the central CH 3 H H
carbon atom is in sp2 hybridisation (attached to | | |
3 atoms or groups). The unhybridised 2p orbital H 3C  C   H 3C  C   H 3C  C   H 3C 
of the central carbon atom contains the unpaired  | | |
CH 3 CH 3 H
electron. 30  alkyl 20  alkyl 10  alkyl methyl
H  Benzyl,allyl free radicals are resonance stabilised
C H
hence they are more stable than alkyl free radical
H
M e th y l fre e r a d ic a l
(iv) They are paramagnetic in nature.

 Three types of reactions are observed in Free
Radicals,
(1) Reactions between two Free Radicals
forming neutral molecule.
CH3.  Cl.  CH 3  Cl
(2) Reaction between Free radical & Neutral
molecule leading to the formation of another free
radical CH 4  Cl.  CH 3  Cl  H .
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 
Alkyl carbonium ions are classified as primary,
H 2 C  CH  C H 2  C H 2  CH  CH 2 secondary and tertitary carbonium ions based on
Allyl free radical resonance structures carbon having positive charge attached to
number of alkyl or aryl groups.

 C6 H5 3 C   C6 H5 2 CH   C6H5 CH 2  H 2C CH C H 2

 
(i) Number of resonating structures decreasing
(ii) Decreasing stability
 Both electron-withdrawing groups such as

carbonyl, cyano, and electron-donating groups
like methoxy & dimethyl amino have stabilising
effect on a radical at an adjacent carbon due to
resonance.
 Stability of various free radicals can be
compared from their bond dissociation energies
(energy required for homolytic cleavage to form
free radicals), the smaller the bond energy more
is the stability of free radicals.
 Stability of same type of alkyl free radicals 

Number of carbons in alkyl free radical
Stability of various free radicals in Charateristics of carbocations
decreasing order;  The positively charged carbon atom in
 thecarbocation is sp2 hybridised. This part of the
 C6 H5 3 C   C6 H5 2 CH   C6 H5  CH2 
 H2C  CH  C  CH3  2 
carbocation is planar and the vacant p- orbital is
  O
H2C  CH  CH   CH3   H2C  CH  CH2  3 alkyl free radical  perpendicular to this plane. The shape of methyl
O O
2 alkyl free radical  1 alkyl free radical  Methyl free radical
carbocation is trigonal planar.
 Examples of free radical reactions (i) Wurtz

reaction giving alkanes,(ii) Kolbe’s electrolytic H
reaction,(iii) substitution reactions of C H
alkanes.(iv) Anti markownikoff’s addition or
H
peroxide / Kharausch effect.
Ca Methyl carbonium ion
Carbocations (Carbonium ions)  Carbon atom carrying positive charge has six
 Carbocation may be defined as a group of electrons in its valence shell, i.e., 2 electrons less
atoms that contains a carbon atom bearing than octet.
postive charge and having only six electrons  They are highly reactive and react with
in its valence shell. These are formed by the nucleophilic reagents to fulfil their octet
heterolytic cleavage and are also known as configuration
carbonium ions. Stability of Carbonium ions
 Stability of alkyl carbocations is influenced by
C X C + X resonance, hyperconjugation and inductive effect.
 An alkyl group attached to positively charged
carbon of a carbocation releases electrons
towards that carbon ( + I effect). Therefore more
the number of alkyl groups, greater the dispersal
of postive charge, more is the stability of
carbocation.
 
H2C  CH  CH2  CH2  CH  CH2  Allyl
Among allyl and benzyl carbocations. Benzyl
carbocation is more stable due to more
resonationg structures and cyclopropyl methyl
carbocations are more stable than benzyl
carbocations.Their stability increases with
additional cyclopropyl group.
 Stability decreases as +I effect decreases

 
CH 3CH 2CH 2 C H 2  CH3CH 2 C H 2
 
 CH 3 C H 2  C H 3
 If  - position with respect to carbocationic
carbon has an atom with one or more lonepair
of electrons, it strongly stabilises the carbocation
due to resonance or delocalisation.  NH2  and
alkoxy  OR  groups are important substituents

Relative stability of carbocations are
for such type of carbocations 1) phenyl > benzyl >allyl >alkyl > methyl
30 > 20 > 10 30 > 20 > 10 30 > 20 > 10
30 > 20 > 10
 
 C6 H5 3 C   C6 H5 2 C H   CH3 3
  
2) C  C6 H 5 C H 2  CH 2  CH  C H 2 
   
Allyl and benzyl carbocations are more stable  CH3 2 CH  CH3 C H 2  C H3  HC  C
due to resonance
The groupslike  NO 2 ,  CN,  Br etc (electron
attracting) have -I effect and reduces stability of
carbonium ions. Reactions involving carbonium
ions:
i) Elimination reactions of alcohols and alkyl halides  The groups having +I effect decreases while
to form alkenes groups having -I effect increases the stability of
ii) Electrophilic addition reactions of alkenes, carbanions
alkynes and alkadienes
iii) S N1 reactions of alkyl halides and diazonium salts
iv) Molecular pinacol - pinacolone rearrangement
Carbanions
 Carbanion may be defined as a group of atoms
that contains a carbon atom bearing negative
charge and having six bonding and two
nonbonding electrons in its valence shell. These
are formed by the heterolytic cleavage in which
shared pair remains with carbon atom.
__ C  Y  __ C  + Y +
 Carbanions are classified as10 , 20 and 30 based

on nature of carbon atom bearing the negative  Greater the number of alkyl groups on the carbon
charge atom carrying the negative charge, greater would
Characteristics & structure of be the intensity of the negative charge on carbon
Carbanions and hence, less stable would be the
 In carbanions, the carbon carrying negative carbanion. Order of stability of carbanions
charge is sp3 hybridised. Its shape is pyramidal 1    2    3 
0 0 0
or tetrahedral with one lone pair.

 Allyl and benzyl carbanions are stable due to
resonance.
Relative stability of carbanions
C
H H
H
Methyl carbanion  i  Aromatic  benzyl  allyl 
 
 The carbon carrying the negative charge contains CH  C  CH 2  C H  alkyl
8 electrons in the valence shell, i.e.,complete octet  pri  sec   tert  
 They are highly reactive because in them the  
carbon carrying the negative charge is electron  ii  C6 H 5 3 C   C6 H 5 2 C H 
rich and can donate its non bonding pair of 
electrons to some other group for sharing. Hence, C6 H 5 C H 2  CH  CH 2  HC 
carbanions behave as nucleophiles and readily  
attacked by electrophiles C  H 2C  C H 
 
 Carbanions are diamagnetic
C H3  CH 3 C H 2   CH 3  2
Stability of Carbanion  
 The stability of carbanions is influenced by C H   CH 3 3 C
resonance, inductive effect and s-character of
orbitals.

iii) Stability of carbanion increases with increase
in s-character of orbitals : CF2 : CCl 2 : CBr2 : Cl 2  sin glet
  
R  C  C  R 2 C  C H  R 3C  C H 2   
50% s 33% s 25% s :C  F:  C  F :

 
groups like | |
 NO 2 , CN, COOC2 H 5 ,  C  O , F F
halogens and C6H5  (electron attracting groups)  Due to presence of vacant ' p ' orbital in singlet
increases the stability of carbanions carbenes backbonding can occur. As the size
Carbenes of halogen increases backbonding tendency
 Carbenes are neutral species in which carbon decreases and hence stability decreases.
atom has six electrons in the outer shell, out of Types of Reagents
which two are non bonding and four are bonding.  Most of the attacking reagents carry either a
 The carbene,:CH2 is reactive and short lived. positive or a negative charge. The fission of the
Carbon is in sp2 or sp hybridisation.Carbenes substrate molecule to create centres of high or
are generally produced in situ and can be low electron density is influenced by attacking
generated by photolysis of diazomethane or species
ketene.
 The reagents can be classified into nucleophiles,

  electrophiles and free radicals.
U.V
CH 2  N  N    CH 2 + N 2 Electrophiles
CH 2  C  O  U.V 
 CH 2 + CO  Electrophiles means electron seeking species.

Electrophiles are the reagents that attack a point
 on the basis of spin of lone pair of electrons
of high electron density or negative site.
carbenes are of two types, singlet carbene and
 Electrophiles are electron deficient species.
triplet carbene
 They are either positively charged or neutral,
 If lone pair of electrons of carbene is paired it is
and attack regions of high electron density in
known as singlet and if it is unpaired it is known
substrate molecule.
as triplet carbene
 They act as lewis acids.
Charged electrophiles
Singlet carbene Triplet carbene H+, Cl+, Br+, I+,
NO2 , R3C+ and other carbocations,
H NH 4 , NO+, C6H 5N 2
C H C H
H
Neutral electrophiles
SO3 , BF3 , AlCl3 FeCl3 , ZnCl2 , BeCl2
Nucleophiles
 Singlet carbene is diamagnetic with bent shape  Nucleophile means nucleus seeking or electrons
due to lp-bp repulsion and behave as cation hating species. Nucleophiles are the reagents
 Triplet carbene is paramagnetic with linear shape( that attack a site of low electron density or
bp-bp repulsion) and behave as biradical positive centres.
 Triplet carbene is more stable than singlet because  Nucleophiles are electron donat ing
of less (lp-bp) repulsion, Halocarbenes are more species.They are either negatively charged or
stable in singlet state rather than triplet neutral molecules with a free electron pair to
donate. They act as Lewis bases.
decreases as the distance from ‘Cl’ increases. It
Charged Nucleophiles
may be neglected after C3.
Cl–, Br–, I–  NH 2 ,  NHR,  NR2  Inductive effect is denoted by I and represented
by a straight arrow (  ),the arrow leading
OR, RCOO R 3 C,CH 3 COCH 2 ,OH
towards the more electronegative element.
CN  , N 3 ,SH, HSO3 Types of Inductive effect:
Neutral Nucleophiles -I Effect (Electron withdrawing
    groups);
R 3 N H 2 O,

R O H, R O R  Atoms or groups which attract electrons more
strongly than hydrogen are called electron
   withdrawing groups and produce - I effect.
H 2 S, R S H, R S R
  The order of electron withdrawing groups in the
 Molecules having multiple bonds between similar decreasing - I effect.
atoms like C2H4, C2H2 and C6H6 also act as
nucleophiles.
Free Radicals
 Free radicals are neutral species having an
    
unpaired electron. eg. Cl,
Br, OR, R, CH 3  -I effect decreases with decrease in the

Electron Displacements in covalent electronegativity
Bond Inductive Effect i) F > Cl > Br > I
 The electron donating or electron withdrawing ii) - F > - OR > - NR2 > - CH3
effect of a group or an atom that is transmitted iii) - F > - OH > - NH2  CH3
by the polarisation of electrons in  bonds is iv) - OR > - SR  SeR
+
called Inductive effect. v) - O+R2 > - N R 3
Characteristics of Inductive effect vi) = O > = NR; = O > - OR
 It is denoted by I  with a decrease in the percentage of ‘s’ character
 It is a permanent effect of hybrid orbital, electro negativity of hybrid
 In a covalent single bond between unlike atoms orbital decreases and hence-I effect decreases.
the electron pair forming the  bond never vii)  N  NR
shared equally between the two atoms. The more
viii) - C  CR  CR  CR2
electronegative atom tends to attract the shared
pair more towards itself. ix) C  CH  CH  CH2
 In CH3 - CH2 - CH2 - Cl, the chlorine atom + I effect(Electron-donating groups)
attract the shared electron pair towards itself. It  Atoms or groups which attract electrons weaker
is represented as than H are called as electron releasing groups
C  Cl or C Cl and produce +I effect.
 If the carbon atom bonded to chlorine atom is  Alkyl groups are considered as weakly electron
itself attached to other carbon atoms, the effect donating. O  COO   alkyl.
is transmitted further,  The decreasing order of +I effect is
     
CH3  CH 2  CH2   Cl
CH 3 CH 3
 The effect of polarisation of C1 and C2 bond is
C CH3 CH CH 2CH3  CH 3  T  D  H
less than the effect in Cl - C1 bond and it
CH3
CH 3
Applications of Inductive Effect EX-1:
Stability of carbocations    
C H 3  CH3  C H 2  CH3  C H  CH3  CH3  C  CH3
 To stabilise a positive charge, electron donating |
groups are needed .Therefore more the no of CH3

Alkyl groups with +I effect are present, more is Decreasing stability
the stability of Carbocation  I Group  Stability of Carbanoins
Stability of Carbocation  + I power EX-2:
Stabilityof Carbocation  Ipower
EX-3:
 
F3 N  CH 2  C H 2  Cl3C  CH 2  C H 2 

Decreasing Carbocation Stability N  C  CH 2  C H 2  Decreasing Stability

EX:4
      
C H3  R  C H 2  R  C H  R  R  C  R  CH3  C H2  H2 C  C H  HC  C  Increasing Stability
| S%=25% S%=33.3% S%=50%
 R
Increasing Carbocation stability.
Reactivity of alkyl Halides
 The presence of halogen atom in the molecule of
alkyl halide creates a centre of low electron
 Magnitude of positive charge on carbon is density which is readily attacked by the negatively
increased by -I groups. Hence more the number charged reagents.
of -I groups, lesser the stability of carbocation.
Eg : CH 3 Cl is more reactive than CH4 as inductive
1
 I groups  effect is present in CH3Cl and no inductive effect
Stability of Carbocation
in methane.
   In case of alkyl halides reactivity order is
CH 3  C H 2  Cl  CH 2  C H 2 
30  20  10  methyl
 
 Cl 2 CH  C H 2   Cl 3 C  C H 2 Strength of carboxylic acids
decreasing stability of carbocations  Any group or atom showing +I effect decreases
the acid stength as it increases the negative charge
   
on the carboxylate ion which holds the hydrogen
O2 N  C H 2  N  C  C H 2  Cl  C H 2  F  C H 2  firmly
Decreasing stability Eg: HCOOH  CH3COOH  C2H5COOH  C3H7COOH
Stability of carbanion  The group or atom having -I effect increases the
 Magnitude of negative charge is increased by +I acidic strength as it decreases the negative charge
groups, Hence more the number of +I groups on the carboxylate ion.
,lower the stability of carbanion. Order of acidic strength:
Eg 1: FCH2COOH  ClCH2COOH  BrCH2COOH  ICH2COOH
1
 IGroups  Eg 2: CCl3COOH  CHCl2COOH  CH2ClCOOH  CH3COOH
Stability of Carbanion

 If both inductive effect and electromeric effect
CH3  CH(N H3 )  COOH  CH3  CH(NO2 )  COOH  operate in opposite direction, then electromeric
Eg 3:
CH3  CH(CN)  COOH  CH3  CH(F)  COOH effect predominates.
Eg4: Cl  CH2  COOH  CH3 COOH   CH3 3 C COOH Mesomeric Effect
 As compared to water ,phenol is more acidic (-  The electron pair displacement caused by atom
I effect) but ethyl alcohol is less acidic or group along a chain by a conjugative
(+I effect ) mechanism is called the mesomeric effect of that
atom or group.
ii) in which C-C bond of CH 3CH 2CH 2 Br the  It is denoted by M
inductive effect is expected to be the least?  Lone pairs and  electrons are involved and
Sol: Magnitude of inductive effect diminishes as the operate through conjugative mechanism of
number of intervening bonds increases.hence the electron displacement
effect is least in the bond between carbon-2 and  It influence the physical properties, reaction rates
carbon-3. etc.
Electromeric Effect + M effect
 It is defined as the complete transfer of a shared  Groups which tend to increase the electron
pair of  electrons to one of the atoms joined by density of rest of the molecule are said to have
a multiple bond on the demand of an attacking +M effect.These groups possess lone pair of
reagent. electrons.
 It is denoted by E  Down the group electron density decreases due

 It is a temporary effect. to increase in size as result + M effect decreases
 It is observed in organic compounds containing -F > - Cl > - Br > - I ;
multiple bonds in the presence of attacking OH  SH  SeH
reagent. - OR > - SR > SeR
 This effect is not observed when the attacking  With decreasing the basic strength, electron
reagent is removed from the domain of the releasing tendency , as result + M effect
reaction. decreases.
 It involves lone pairs,  electrons in conjugative  NR2  OR  F ,
mechanism of electron displacement.
- NH2 > - OH > - F ;
 If  electrons of multiple bond shift to that atom
- O > - OR.
to which the attacking reagent bonded is called
- M effect
+E effect.
 Groups which had to decrease the electron
density of rest of the molecule are said to have -
M effect.
 Group exhibiting - M effect possess multiple
bond and -M effect can be compared based on
electronegativity
 If  electrons of multiple bond shift towards = O > = NR > = CR2
that atoms where the attacking reagent is not 
= NR2  NR
forming bond is called - E effect.
 N  CR .
NO ,COOH,CHO,HSO & CONH also have (-
2 3 2
M ) effect.
 Halogens have - I effect but with lone pairs they
have +M effect. These two operate in opposite
directions.
Charaterstics of mesomeric effect: 2) all atoms in the molecule are in the same plane
1) it is a permanent effect present in the molecule 3) the total number of paired or unpaired electrons
in the ground state. should be same in any structure;
2) This effect is distance independent 4) the canonical structures should have as far as
3) + M and - M groups are always in conjugation possible nearly equal energy;
in ortho and para positions of the benzene ring. 5) more stable resonance structures contributes
Thus, +M groups will give electrons to the ring more to the actual molecule;
at ortho and para position. Similarly -M groups 6) more the delocalisation more is stability;
will withdraw electrons from ortho and para 7) more the covalent bonds, more is the stability.
position of the benzene ring. + M and -M groups 8) The canonical structure in which negative charge
have no effect on meta position. on more electronegative atom is more stable.
4) Mesomeric effect is dominant over inductive 9) Lesser the charge separation, more will be the
effect stability of canonical structure.
e) in case of halogen -I effect is more effective Resonance Effect
than + M effect  It is the polarity produced in a molecule by the
Resonance interactions of two  bonds or between a
 If a molecule or ion can be shown by two or  bond and a lone pair of electrons present on
more structures differing only in the distribution adjacent atoms
of electrons, but none of these structures truely  It is denoted by R
explains all the properties of that molecule or ion,  If the transfer of electrons are away from the
these structures are called resonating or canonical atoms or substituent group attached to the
structures and this phenomenon is called conjugated systems then the molecule gets high
electron density at one of the position and it is
resonance.
denoted by ( +R). X, - OH, -OR, - NH2, -
O NHR, -NR2 - NHCOR, shows + R effect.
||
 If the structure of urea is H2N  C  NH2 . it should  If the transform of electrons are towards the atom
or substituent group it is ( -R) effect. This is
behave as
observed in nitrobenzene.
1) dibasic acid
2) should not have dipole moment COOH,-COOR,CHO,  C  O,  CN,  NO
2
3) C - N should be equal to single covalent bond shown - R effect.
 It was observed that urea is  Resonance effect and mesomeric effect both
1) mono acidic base appear as the same but they are different.
2) has dipole moment  Mesomeric effect involves only electrons and
3) C-Nbond length is inbetween C-N&C= N. mainly in conjugate system where as
 To explain the above variations in the properties resonance effect involves even ‘  ’ electrons.
of urea the following structures are suggested Resonance Energy
 It is the difference in energy between the actual
energy of the molecule and that of the most stable
canonical forms.
 The real structure of the molecule is not possible i) Write resonance structure of CH 3COO  and
to denote with one structure and it only a
show the movement of electrons by curved
hypothetical structure known as resonance
arrows.
hybrid.
sol : First. write the structure and put unshared pairs
 Characteristics of resonance structures
of valence electrons on appropriate atoms. then
1) it involves only displacement of electrons without
draw the arrows one at a time moving the
disturbing the nuclei;
electrons to get the other structures.
 The  electrons of C -H bond of the alkyl group
enter into the partial conjugation with the attached
..
..
O: unsaturated system sp 2 or with the unshared p-
O: ..
orbital .
CH3 C CH3 C
..
..  Hyper conjugation is a permanent effect
O:
O: Condition for hyperconjugation
..
(1) Compound should have atleast one sp 2 -hybrid
ii) Write resonance structures of
carbon
CH 2  CH  CHO , indicates relative
(2)  -carbon with respect to sp 2 -hybrid carbon
stability of the contributing structures.
sol : should be sp3 ,
(3)  -carbon should have atleast one hydrogen.
 In CH 3CH 2 ( ethyl cation) the positively
charged carbon atom has empty p - orbital . One
stability order is II>III>I of the C -H bonds of methyl group can align in
Reason the plane of the empty p - orbital and the
II: more stable,more number of covalent bonds, electrons constituting the
C - H bond in the plane with this p - orbital can
each carbon and oxygen atom has an octet and

no separation of opposite charge delocalised in to the empty p - orbital.
III) negative charge on more electronegative  This type of overlap stabilises the carbocation
atom because electron density from the adjacent 
I) does not contribute as oxygen has positive bond helps in dispersing the positive charge
charge and carbon has negative charge.hence
least stable
iii) Explain why the following two structures, I and
II cannot be the major contributors to the real
structure of CH 3COOCH 3
 In general, greater the number of alkyl groups
attached to a positively charged carbon atom,
.. ..
greater is the hyperconjugation interaction
:O: :O:
..  and greater is the stabilisation of cation.
CH 3  C  O  CH 3 
 CH 3  C  O  CH 3  The relative stability of carbocations is
 .. ..
I II
CH 3 CH 3 H
| | |
Sol : the two structures are less important H 3C  C   H 3C  C   H 3C  C   H 3C 
contributors as they involve charge | | |
CH 3 H H
separation.Additionally , structure I contains a 30  alkyl 2 0  alkyl 10  alkyl methyl
carbon atom with an incomplete octet.
Hyper Conjugation  Hyperconjugation is also possible in alkenes and
 Hyperconjugation is a general stabilising alkylarenes
interaction.  There are various ways of looking at the
 It involves delocalisation of  electrons of C- hyperconjugative effect. One of the way is to
H bond of an alkyl group directly attached to regard C -H bond as possessing partial ionic
character due to resonance
an atom of unsaturated system sp 2 or to an
atom with unshared p - orbital
CONCEPTUAL
FISSION OF COVALENT BOND
1. In organic reactions the reactant is called

as
1) intermediate 2) product
 The hyperconjugation may also regarded as no 3) substrate 4) by product
bond resonance. 2. Heterolysis of C-Cl bond produces
 Structure derived from hyperconjugation known 1) Two free radicals
as hyperconjugative structures(HS) 2) Two carbonium ions
3) Two carbanions
No.of hyperconjugative structures 
 4) One cation and one anion
No.of   Hydrogens  1 3. Heterolysis of propane gives
Reverse hyperconjugation 1) Methyl and ethyl free radicals
 The phenomenon of reverse hyperconjugation is 2) Methylcarbocation and ethyl free radicals
also observed in the system given below 3) Methyl anion and ethyl carbocation
4) Methylfree radical and ethylcarbocation
X
4. Removal of hydride ion from a methane
C C C molecule will give a
(x=Cl) 1) Methyl radical 2) Carbonium ion
in the sysytem the effect operates in reverse 3) Carbanion 4) Methyl group
direction.Hence, it is known as reverse
hyperconjugation. REACTION INTERMEDIATES

i) Explain why  CH 3  C is more stable than
3 5. The shape of carbonium ion is
  1) Planar 2) Linear
CH 3 C H 2 and C H 3 is the least stable 3) Pyramidal 4) Tetrahedral
cation. 6. The shape of methyl free radicals is
 1) Planar 2) Pyramidal
sol : Hyperconjugation interaction in  CH 3  C is
3 3) Tetrahedral 4) Linear
 

greater than in CH 3 C H 2 as the  CH 3  C 7. The reaction,  CH 3 3 C  Br   CH 3 3 C  Br  is an
3
example of

has nine C-H bonds.In C H 3 vacant p orbital is 1) Homolytic fission 2) Heterolytic fission
3) Cracking 4) All the above
perpendicular to the plane in which C-H bonds 8. Which of the following contains only three

lie: hence cannot overlap with it.thus C H 3 lacks pairs of electrons
1) Carbocation 2) Carbanion
hyperconjugative stability
3) Free radical 4) All of these
9. Which of the following species is
paramagnetic
1) A carbonium ion 2) A free radical
3) A carbanion 4) All of these
10. In carbonium ion the carbon bearing the 18. Electrophiles are
positive charge is 1) Lewis bases 2) Lewis acids
1) sp hybridized 2) sp 2 hybridized 3) Amphoteric 4) All of these
19. Electrophiles are
3) sp 3 hybridized 4) un hybridized
1) Electron loving species
11. Due to its sextet (having six electrons), the 2) Electron hating species
carbonium ions are 3) Nucleus loving reagents
1) unstable 2) very stable 4) Nucleus hating reagents
3) negatively charged 4) all of these 20. Nucleophiles are
12. Among the following the true property 1) Electron loving 2) Electron hating
H3C
+
3) Nucleus loving 4) Nucleus hating
about C CH3 is 21. Which of the following statement is false
H3C
about an electrophile?
1) non - planar 1) Electron - deficient species
2) C+ is sp2 - hybridised 2) An acidic reagent
3) Electrophile can attack on C+ 3) A reagent which attacks an electron-deficient
4) Does not undergo hydrolysis site in a molecule
13. The geometry of a methyl carbanion is likely 4) A species which seeks a pair of electrons
to be 22. Methyl carbonium ion is
1) Pyramidal 2) Tetrahedral
1) Nucleophile 2) Lewis base

3) Planar 4) Linear 3) Electrophile 4) Both ‘a’ and ‘b’
14. Due to the presence of an unpaired electron 23. Which of the following reaction
free radicals are intermediates are electrophilic in character?
1) Cations 2) Anions a) Carbocation b) Carbanion
3) Chemically inactive 4) Chemically reactive c) Free radicals d) Carbenes
15. Which of the following is the intermediate 1) only ‘b’ 2) ‘a’ and ‘c’
species formed on heterolysis of Grignard 3) ‘a’, ‘c’ and ‘d’ 4) ‘a’, ‘b’, ‘c’ and ‘d’
reagent? 24. Ammonia molecule is
1) Carbanion 2) Carbocation 1) A nucleophile
3) Alkyl radical 4) Free radical 2) An electrondeficient
3) A electrophile
TYPES OF REAGENTS 4) An acid
25. Which of the following pairs is / are correctly
16. Which of the following statements are matched?
correct for nucleophile I. Carbocation : electrophile
1) All negatively charged species are nucleophiles II. Free radical : paramagnetic
2) Nucleophiles are Lewis bases III. Carbene: Incomplete octet
3) Alkenes, alkynes, benzene and pyrrole are IV. Carbanion: Incomplete octet
nucleophiles Select the correct answer using the codes
4) All are correct given below:
17. Which one of the following statement is not 1) Only I 2) I and II
correct for electrophile 3) I, II, III and IV 4) I, II and III
1) Electron deficient species are electrophiles 26. Methyl carbanion is
2) Electrophiles are Lewis acids 1) Electrophile
3)All positively charged species are electrophiles 2) Lewis acid
4) AlCl3 and SO3 are electrophiles 3) Both (1) and (2)
4) Nucleophile
33. Reaction mechanism describes
ELECTRON DISPLACEMENT 1) sequential account of each step describing the
IN COVALANT BOND details of electron movement
2) energy changes during bond breaking and
27. Which of the following statements is correct bond formation
about inductive effect 3) kinetics of the reaction
1) Implies the transfer of lone pair of electrons 4) all of these
from more electronegative atom to lesser 34. Substitution reactions may be
electronegative atom in a molecule 1) Free radical substitution
2) Implies the transfer of lone pair of electrons 2) Nucleophilic substitution
from lesser electronegative atom to the more 3) Electrophilic substitution
electronegative atom in a molecule 4) All are correct
35. CH 3  CH 2  X  KOH  alc   CH 2  CH 2  KX  H 2 O
3) Increases with increase in distance
4) Implies the atoms ability to cause bond is
polarization 1) addition reaction
28. The displacement of electrons in a multiple 2) substitution reaction
bond in the presence of attacking reagent is 3) elimination reaction
called 4) molecular rearrangement
1) inductive effect 2) electromeric effect 36. hv
is an
CH 4  Cl2   CH 3Cl  HCl

3) resonance 4) Hyper-conjugation
example for
29. The electromeric effect in organic
1) free radical substitution reaction
compounds is a
2) electrophilic substitution reaction
1) Temporary effect
3) nucleophilic substitution reaction
2) Permanent effect
4) nucleophilic addition reaction
3) Temporary or permanent effect
hv
4) All the above 37. C6 H 6  3Cl2   C6 H 6 Cl6 is an example
30. Which of the following is not the correct for
condition for resonance? 1) free radical substitution reaction
1) The positions of all the atomic nuclei in the 2) electrophilic addition reaction
resonating structures may be differ 3) free radical addition reaction
2) The resonating structures must have the same 4) nucleophilic addition reaction
number of unpaired or paired electrons
3) The molecules exhibiting resonance must be KEY
planar in nature
CONCEPTUAL
4) The resonating structures must have nearly the
same energies 1)3 2)4 3)3 4)2 5)1
31. Resonance is due to 6)1 7)2 8)1 9)2 10)2
1) delocalisation of sigma electrons 11)1 12)2 13)1 14)4 15)1
2) migration of H atoms 16)4 17)3 18)2 19)1 20)3
3) migration of proton 21)3 22)3 23)3 24)1 25)4
4) delocalisation of pi electrons 26)4 27)4 28)2 29)1 30)1
32. Resonance in benzene is accompanied by 31)4 32)4 33)4 34)4 35)3
delocalization of   electrons. Each  36)1 37)3
electron is attached with
1) 4 carbons 2) 2 carbons
3) 3 carbons 4) 6 carbons
HINTS 6. + R power of the given groups


1)  O 2) - NH2
CONCEPTUAL 3) - OH 4) - NHCOCH3
in decreasing order is
 
3) C H 3 , C2 H 5 are stable due to inductive effect. 1) 1 > 2 > 3 > 4 2) 4 > 3 > 2 > 1
3) 1 > 3 > 2 > 4 4) 1 > 4 > 3 > 2
 
4) 7. Which of the following substituents when
CH 4  C H 3  H
present on the benzene ring, exhibits
  mesomeric effect opposite to that of the
15) RMgX  R  Mg X
remaining three?
LEVEL - I 1)  SH 2) Cl
3) COOH 4) OH
ELECTRONIC DISPLACEMENT
OF COVALENT BOND 8. In pyridine; Number of conjugated
N
electrons are:
1. Which one of the following orders is correct 1) 6 2) 8 3) Zero 4) 5
regarding the -I effect of the substituents? 9. In hyper conjugation, the atom involved is
1)  NR2  OR   F 1)   H atom 2)   H atom

2)  NR2  OR   F 3)   H atom 4) All
3)  NR2  OR   F 10. The correct resonance hybrid of carboxylic
acid is
4)  NR2  OR   F
2. Decreasing - I power of given groups is
1) CN 2)-NO2
1) 2)
3) NH3 4) F
1) 2> 1> 4> 3 2) 2 > 3 > 4 > 1
3) 3 > 2 > 4> 1 4) 3 > 2 > 1 > 4
3. Which of the following belongs to -I group?
1) C6 H 5 2) CH 3 3) 4)
3) CH 2CH 3 4) C  CH 3 3
4. Which of the following functional group 11. Hyperconjugation involves overlap of the
shows +R -effect ? following orbitals
1) -CHO 2)  NO2 1)  - 2)  -p 3) p-p 4) π-π
12. +I effect is shown by
3) -CN 4)  NR2
1)  NO 2 2) Cl
5. Hyper conjugation is
1)    conjugation 3)  Br 4) CH3
2) Due to delocalization of  and  bonds 13. Zero inductive effect is exerted by
3) No bond resonance 1) C6 H 5  2) -H
4) All of these
3) CH 3  4)- Cl

14. Hyperconjugation is most useful for
stabilizing which of the following
carbocations?
3) 4)
1) neo - Pentyl 2) tert -Butyl
3) iso - Propyl 4) Ethyl
15. Hyperconjugation phenomenon is possible 19. Arrange the following groups in order of
in decreasing - R ( or -M) power
1) H 2 C  CH 2 a) NO2 b) SO3H
c)CF3 d) CHO
2) CH3 CH 2  CH  CH 2 1) a > c > b > d 2) a > b > c > d
3) C6 H 5CH  CH 2 3) a > d > c> b 4) d > c> b > a
20. The reaction intermediate produced by
4)  CH 3 3 C  CH  CH 2 homolytic cleavage of bond is called
1) carbocations 2) carboanions
3) free radicals 4) carbenes
REACTION INTERMEDIATES 21. Most stable carbocation is
 
16. Among the following carbocations which is 1) CH 3  C H 2 2) C H 2 CHCl2
more stable
 
3) C H 2 CH 2 Cl 4) C H 2  CH 2 NO 2
+ 22. Carbocation is a reaction intermediate in
1)  C6 H 5 3 C  2)
which of the following reactions
1) E1 reactions
+
2)Electrophilic addition reactions of alkenes and
alkynes

3) 4) CH 2  C H 3) S N1 reactions 4) All of the above
23. Halogenation of an alkane takes place
through the intermediate
17. The compound which gives the most stable 1) carbocation 2) carbanion
carbonium ion on dehydration 3) carbon free radical 4) carbene
1) CH 3  CH  CH 2OH
|
CH 3 FISSION
CH 3
|
H 3C  C  OH 24. Which free radical is the most stable
2) |
 
CH 3 1) C6 H 5  C H 2 2) CH 2  CH  C H 2
3) CH 3  CH 2  CH 2  CH 2OH 

4) CH 3  CH  CH 2  CH3 3) CH 3  C H  CH 3 4) CH 3  C  CH 3
| |
OH C H3
18. Which carbocation is most stable
25. The most stable carbonium ion is
1) Methyl carbonium ion
2) Primary carbonium ion
1) 2) 3) Secondary carbonium ion
4) Tertiary carbonium ion
26. Stability of which intermediate is not govern R  X  OH aq  
 R  OH  X aq  is an
34.
by hyperconjugation?
1) carbon cation 2) carbon anion example for
3) carbon free radical 4) carboniumion 1) addition reaction
2) substitution reaction
27. In CH 3CH 2 OH , the bond that undergoes
3) elimination reaction
heterolytic cleavage most readily is 4) molecular rearrangement
1) C  C 2) C  O
3) C  H 4) O  H
ATTACKING REAGENTS 35. is
28. The ion with highest nucleophilicity is

1) F  2) OH  3) CH 3 4) NH 2
29. Which one is the characteristic feature of an example for
a free radical ? 1) addition reaction
1) Presence of negative or postive charge 2) substitution reaction
2) Presence of unpaired electron 3) elimination reaction
3) Presence of even number or electrons 4) molecular rearrangement

4) Association with high stability Fe
36. C6 H 6  Cl2   C6 H 5Cl  HCl is an
30. An elctrophilic reagent is
1) Electron - rich species example for
2) electron-deficient species 1) Free radical substitution reaction
3) a Lewis base 2) Electrophilic substitution reaction
4) negatively charged species 3) Nucleophilic addition reaction
31. Which of the following is an electrophilic 4) Nucleophilic substitution reaction
reagent ? 37. The following reaction is an example of
1) H 2 O 2) OH 
O OH
3) NO 2  4) all of these + HCN

H
H
32. In a Freidel - Craft’s reaction, the
electrophile is
1) Nucleophilic substitution
1) Cl or X  2) Electrophilic substitution
2) CH 3  or CH 3CO  3) Electrophilic addition
4) Nuclephilic addition
3) CH 3Cl 4) CH 3COCl 38. Alkenes readily undergo
1) Substitution reactions
TYPES OF REACTIONS 2) Addition reactions
3) Elimination reactions
33. CH 2  CH 2  Br2   CH 2 Br  CH 2 Br is 4) Rearrangement reactions
39. Nitration of benzene is
an example for
1) nucleophilic substitution
1) addition reaction
2) substitution reaction 2) nucleophilic addition
3) elimination reaction 3) electrophilic substitution
4) molecular rearrangement 4) free radical substitution
40. The reaction HINTS
H2 O
 CH3 3 C  Br 
  CH 3 3 C  OH is
1) elimination reaction LEVEL - I
2) substitution reaction
3) free radical reaction 1. Based on order of negative inductive effect
4) displacement reaction 8. If lone pair and  bond is present on key
41. Which of the following is a free radical atom(N),  bond is involved in conjugation.
substitution reaction? 17. Tertiary butyl alcohol forms stable carbonium ion
42. It is electron releasing group
1) CH 3CHO  HCN  CH 3CH  OH  CN
CH2 Cl CH 2 NO2 LEVEL - II
2) + AgNO 2 
ELECTRONIC DISPLACEMENTS
OF COVALENT BOND
CH 3
1. Inductive effect involves
3) + CH Cl 
3
Anhy.AlCl3
1) displacement of  - electrons
2) delocalisation of  - electrons
3) delocalisation of  - electrons
CH 3 CH 2 Cl 4) displacement of  - electrons
Boiling 2. Hyperconjugation involves overlap of the
4) + Cl2  following orbitals
1)    2)   p
42. Decreasing -I power of given groups is: 3) p  p 4)   
a) CN b) NO 2 3. Which among the following statements are

true with respect to electronic displacement
c) N H 3 d) F in a covalent bond
1) b  a  d  c 2) b  c  d  a a) Inductive effect operates through a  - bond
b) Resonance effect operates through a  -
3) c  b  d  a 4) c  b  a  d
bond
c) Inductive effect operates through a  - bond
KEY d) Resonance effect operates through a  -
LEVEL - I bond
e) Resonance and inductive effects operate
1) 3 2) 4 3) 1 4) 4 5) 4
through  - bond
6) 1 7) 3 8) 1 9) 2 10) 1
1) a and b 2) a and c
11) 2 12) 4 13) 2 14) 2 15) 2
3) b and c 4) c and d
16) 1 17) 2 18) 1 19) 1 20) 3
4. Compound which shows positive mesomeric
21) 1 22) 4 23) 3 24) 1 25) 4
effect
26) 2 27) 4 28) 3 29) 2 30) 2
31) 3 32) 2 33) 1 34) 2 35) 4 1) H 2C  CH  Cl
36) 2 37) 4 38) 2 39) 3 40) 2 2) C 6 H 5  N O 2
41) 4 42) 4
3) H 2C  CH  CH 2 Cl
4) Both 2 & 3

10. Which is most stable carbocation?
REACTION INTERMEDIATES 1) n - propyl cation
2) iso - propyl cation
3) Ethyl cation
5. The reaction intermediate carbenes are
4) Triphenylmethyl cation
produced from
11. Which of the following is the most stable
1) diazo methane
compound?
2) ketene

3) CHCl3 / C2 H 5ONa 1) Ph3C  2) Ph2 C H
4) All of these  
6. The stability order in the following 3) Ph2 C H 2 4) Ph C H 2
carbocations, 12. Which one of the following carbanions is
 least stable ?
CH 3CH 2  I  ,  CH 3 2
 1) CH 3CH 2 2) HC  C 

C H  II  ,  CH 3 3 C  III  
3)  C6 H 5 3 C  4)  CH 3  C
1) I > IV > III > II 3
2) I > II > III > IV

3) III > IV > I > II ATTACKING REAGENT
4) III > II > I > IV

7. Consider the following carbocations
13. Among the following, the strongest
 
I) C6 H 5 C H 2 II) C6 H 5CH 2 C H 2 nucleophile is

1) C2 H5SH 2) CH 3COO 

III) C6 H 5 C HCH 3 IV) C6 H 5 C  CH 3 
2 3) CH 3 NH 2 4) NCCH 2
the order of stability is
1) II < I < III < IV 2) II < III < I < IV
3) III < I < II < IV 4) IV < III < I < II TYPES OF REACTIONS
8. The arrangement of
14. Identify the correct order of reactivity in
 CH 3 3 C ,  CH 3 2 CH , CH 3CH 2  w h e n electrophilic substitution reactions of the
attached a benzene or an unsaturated group following compounds
in increasing order of electron releasing
CH 3 Cl NO 2
tendency is
1)  CH 3 3 C    CH 3 2 CH   CH 3CH 2 
2) CH 3CH 2    CH 3 2 CH    CH 3 3 C  1 2 3 4
1) 1 > 2 > 3 > 4 2) 4 > 3 > 2 > 1

3)  CH 3 2 CH    CH 3 3 C   CH 3CH 2 
3) 2 > 1 > 3 > 4 4) 2 > 3 > 1 > 4
4)  CH 3 3 C   CH 3CH 2    CH 3  2 CH  15. Which of the following is least reactive in a
9. Due to the presence of an unpaired electron, nucleophilic substitution reaction?
free radicals are 1)  CH 3 3 C  Cl
1) Chemically reactive
2) Chemically inactive 2) CH 2  CHCl
3) anions 3) CH 3CH 2Cl
4) cations
4) CH 2  CHCH 2 Cl
16. Nucleophilic addition reaction will be most 2. The correct stability order for the following
favoured in species is
1) CH 3CH 2 CHO 2) CH 3CHO
O
||
3)
CH 3CH 2CH 2  C  CH 3
4)  CH 3  2 C  O
KEY
LEVEL - II
1) 1 2) 2 3) 4 4) 1 5) 4
6) 4 7) 1 8) 1 9) 1 10) 4
11) 1 12) 4 13) 1 14) 3 15) 2
16) 2
1) II > IV > I > III
LEVEL - III
2) I > II > III > IV

3) II > I > IV > III
ELECTRONIC DISPLACEMENTS 4) I > III > II > IV
3. Which statement is correct for inductive
effect:
1. Which of the following carbocations is more 1) It is a permanent effect
stable ? 2) It is the property of single bond
3) It causes permanent polarisation in the
NO2
molecule
NO 2 4) All are correct
 4. Which statement is correct for electromeric
effect:

1) 2) 1) It is a temporty effect
H 2) It is the property of  bond
X 3) It takes place in presence of
H X reagent,electrophile or nucleophile
4) All are correct
5. Consider the following carbanions:
NO2
H X  
(a) CH 3  C H 2 (b) CH2  C H
O2 N

  (c) CH  C
3) 4)
H Consider order of stability of these
X carbanions in decreasing order is
1) a  b  c 2) b  a  c
3) c  b  a 4) c  a  b

6. The number of delocalised  electrons in 12. Which one of the following statements is
not correct for electrophile:
1) Electron deficient species are electrophiles
2)Electrophiles are Lewis acids
3) All +ve charged species are electrophiles
the given compound is
4) AlCl3 , SF6 , IF7 and SO3 are electrophiles
13. Which among the following species is an
1) 4 2) 6 3) 8 4) 2 ambident nucleophile?

1) CH 3  C H 2 2) C H 2  C H 2
7. Hyper conjugation effect is not possible in

which of the following species 
4) NH
3) CN 3

1) 14. In each of the following pairs of species
CH3 CH2 which species is an electrophile:
1) BF3, NO  2) N 3 , R O H
2) C H  C H
6 5 3
3)H 2O, RSH 4)ROR , BF3
3) CH2  CH2 15. Which among the following compounds
behave both as an electrophile as well as a
CH 3 nucleophile
| 
a) CH 2  CH 2 b) CH 2  CH  C H 2
CH 3  CH  CH  C  CH 3
4) O O
|
CH 3 || ||
c) CH 3  C  CH 3 d) CH 3  C  Cl
8. CH3 group of toluene is o,p -directing group
due to the 1) Only a 2) a and b
1) Hyperconjugation 2) Resonance 3) c and d 4) b,c and d
3) Inductive effect 4) Electromeric effect 16. Which of the following reaction
9. Which among the following species is an intermediates are electrophile in character?
ambident nucleophile. a) Carbocation b) Carbanion
1) Ethene 2) benzene c) Free radicals d) Carbenes
3) Cyanide ion 4) Acetone 1) only b 2) a and c
10. Which one of the compound behaves as an 3) a,c and d 4) a,b,c and d
electrophile as well as nucleophile. 17. Which of the following reaction would
1) Acetone generate an electrophile?
2) Cyanide ion I)  CH3 3 CBr  AnhyAlCl3
3) nitrite ion

4) Sulphite ion II)  CH3   CH  CH2  H
3
11. Which one of the following species is a

nucleophile: III) C6 H5 COOH  H 3 O
1) NH4 2) FeCl3
IV) HNO3  H 2SO4
3) R O R 4) SO3 1) I, II and IV 2) I,II and III
3) I,II,III,IV 4) II,III and IV
18. Which allylic carbocation is the most stable
carbocation : KEY
 LEVEL - III
1) CH 3  CH  CH  C H 2
1) 1 2) 4 3) 4 4) 4 5) 3

2) CH 3  CH  CH  C H  CH 3 6) 2 7) 3 8) 1 9) 3 10) 1
11) 3 12) 3 13) 3 14) 1 15) 3
 16) 3 17) 3 18) 3 19) 1 20) 3
3)CH 3  CH  CH  C CH 3
|
HINTS
CH3
4) All have same stability LEVEL-III
19. Consider the following carbanions:

 2. Stability of carbanion ( when hybridization of
I) H3CO C H2 
C is different ) is directly proportional to percent

 S character
II) O 2 N C H2  
6. C  N : it has two nucleophilic centers.

III)  7. Organic compound in which electronegative
C H2 atom is bonded with carbon by multiple bond
 behaves as both

IV) H 3C C H2 
Correct decreasing order stability is : O O

1) II  III  IV  I 2) III>IV>I>II || |
3) IV>I>II>III 4) I>II>III>IV CH 3  C  CH 3  CH 3  C CH 3

20. Rank the following free radicals in order of
decreasing stability: polar structure behaves as electrophile as well
 as nucleophile
I) C6 H5 C HC6 H 5 8.
 9. Positive charge species in which central atom has
II) C6 H5  C H  CH  CH 2 complete octet is not electrophile. for example
  
III) CH  C H  CH
3 3 N a, N H 4 .

IV) C6 H 5  C H  CH 3 ` 13. All have incomplete octet

 14. C6 H 5COOH  H3 O  no reaction
V) CH 3CH  CHCH 2 C H 2
15. It is stabilised by resonance as well as by + I

effect of two methyl groups
VI)CH3  CH2 C CH3
16.
|

 
C H2
CH3 C H2 C H2
1) I>II>III>IV>V>VI
2) VI>V>IV>III>II>I
CH 3
3) I>II>IV>VI>III>V OCH 3 NO 2
Stabilized by-R and - I effect De stabilized by
De stabilized by + R effect
4) I>IV>III>I hyper conjugation and + I effect

19. + R power of OH group is maximum. 6. STATEMENT - I Singlet carbenes have
hence + R power highly dominates over -I opposite spin (antiparallel) .
power of OH. STATEMENT -II Singlet carbene is
diamagnetic
LEVEL-IV 7. STATEMENT - I Tertiary carbocations are
generally formed more easily than primary
carbocation.
STATEMENT TYPE STATEMENT -II Hyperconjugation as well as
1) Statement - I is true, Statement- II is true; inductive effect due to additional alkyl groups
Statement - II is a correct explanation for stabilize tertiary carbocations.
Statement - I 8. STATEMENT - I: Heterlolytic fission involves
2) Statement -I is true, Statement - II is true ;
the breaking of a covalent bond in such a way
Statement-II is not a correct explanation for
that both the electrons of the shared pair are
Statement - I
carried away by one of the atoms.
3) Statement - I is true, Statement - II is false
STATEMENT -II : Heterlolytic fission occurs
4) Statement - I is false, Statement - II true
1. STATEMENT-I: The order of acidic character readily in polar covalent bonds.
of the following compounds
COMPREHENSION TYPE
PASSAGE : 1
An atom or group which attracts electrons more
strongly than Hydrogen is said to have a
STATEMENT:II : -I and -R effect of the group
negative inductive effect   I  . An atom or
stabilizes the conjugate base decreasing the -ve
charge. Where as +I effect of the group group which attracts electrons less strongly than
destabilises the conjugate base by intensifying the Hydrogen is said to have positive
charge inductive effect   I  .
2. STATEMENT - I: Tropylium cation is more
9. Strong acid among the following is
stable than  CH3 3 C 1) HCOOH
STATEMENT -II: Tropylium cation has 2) CH 3COOH
aromatic character
3. STATEMENT - I : - NO2 ,-CN, -CNO act as 3) CH 3CH 2COOH
ambident nucleophiles 4) C6 H 5COOH
STATEMENT -II : These consist atoms of 10. The alkyl halide which has more dipole
same period moment is
4. STATEMENT - I : Cation carries, e.g:H-Br,
Cl-OHand Br-Br and oxididing agents such as 1)  CH 3 2 CHBr 2) C2 H 5 I
O3 and R-O-O-R,etc. act as electrophilic 3)  CH 3 3 CBr 4) (CH 3 )3 Cl
reagents. 11. The dissociation constant (or) acidic nature
STATEMENT -II : Electrophilic are Lewis is more for
acids 1) n - Butyric acid
5. STATEMENT - I : inductive and eletromeric 2)  - Mono chloro butyric acid
effects require polar nature in the molecule.
STATEMENT -II : Polar nature in inductive 3)  - mono chloro butyric acid
effect is a must but not necessarily in eletromeric 4)  - Mono chloro butyric acid
effect.
PASSAGE : 2 17. hybridisation of carbon in carbocation is
Carbene is an important intermediate and can 1) Sp 2) Sp 2
be formed in many reactions. One of these
is   elimination of gem dihalide by active metal. 3) Sp3 4) dSp3
Carbon is divalent in carbene highly reactive. The 18. Which is most stable carbocation
two non-bonding electrons decide the shape and + +
the bond angle of this intermediate. One of these 1) C H3 2) CH 3 C H 2
is called singlet carbene (single orientation in
magnetic field) and other is called triplet carbene +
3) CH3CH2 CH2 4)
(three orientations in magnetic field). Carbon of
carbene is electron deficient and will try to get
stabilized by reactions such as insertion reactions
in alkanes and cyclo-addition reactions in PASSAGE : 4
alkenes. When an electron withdrawing or releasing group
12. Which one of the following singlet carbene attached to carbon chain,polarity is induced on
is most stable ? the carbon atom and on the
substituent attached to it this permanent polarity
1) : CH 2 2) : CF2
is due to electron
3) : CHF 4) : CCl2 displacement due to difference in
13. Which carbene will have greater bond angle? electronegativities, this is called inductive effect .
1)Singlet 2)Triplet Inductive effect is classified into two types
3)Both have similar bond angle (1) + I effect (2) - I effect
4)Bond angle cannot be measured
19. inductive effect is maximum in
14. When triplet carbene : CFCl  reacts with
1) FCH 2COOH 2) ClCH 2COOH
cis 2-butene, how many products are
possible ? 3) BrCH 2COOH 4) ICH 2COOH
1) 1 2) 2 3) 3 4) 4
 NO2 ,  CN ,  COOH
PASSAGE : 3 20. Among these
I II III
Carbocations are species in which central carbon
groups, which of the following orders is
carries positive charge. If the charge on the
correct for the magnitude of their -I
carbocation gets concentrated or localized the
effect ?
carbocations becomes unstable. The two factors
which accounts for stability of carbocations are 1)I > II > III 2)I > III > II
inductive effect and hyperconjugation (no bond 3)III > II > I 4)II > I > III
resonance). Inductive effect minor factor and 21. Write the stability order of carbanion
hyper-conjugation is major factor  
15. Which is most stable carbocation (I)FCH 2 C H 2 (II)F2 CH C H 2
+ +
1) C H3 2) CH 3 C H 2 
(III)F3C C H 2
+ +
3)  CH 3  2 C H 4)  CH 3 3 C
1)III>II>I 2)II>I>III
16. n-propyl carbocation rearranges to isopropyl 3)II>III>I 4)I>II>III
carbocation by shift of
1) proton 2) hydride ion
3) electron 4) all of these
PASSAGE : 5 PASSAGE : 6
Delocalisation of electrons takes place in An organic reaction occurs by using reagents
alternate single and multiple bonds involving called electrophiles and nucleophiles via the
carbon atoms. formation of some reactive intermediates called
Delocalisation may also occur in a carbocations,carbanions, free radicals,carbenes
conjugated system involving carbon atom and , nitrenes,radical cations and radical anions.
atom other than the carbon. There are also 25. Which of the following contains nuleophiles
examples in which pi orbital and ‘p’ orbital only?
(vacant or half-filled ) overlap. Thus delocalisation
are of the following types : 1) PH3 , ROH , CH 2  CH 2
(i) delocalisation by  ,  overlap and
2) SnF4 , BeF2 , NH 3
(ii) delocalisation by  , p overlap
Delocalisation makes system stable. More is the 
number of resonating structures more is the 3) Cr 3 , N H 2 , H 2 O
stability of the system.  
22. In which of the following compounds 4) : C C l 2 , I , H
delocalisation is not possible :
1) 1, 4-pentadiene 2) 1, 3-butadiene 26. Which of the following contains electrophiles
3) 1, 3, 5-hexatriene 4) benzene only?
23. Which one of the following anion is most 1) Br  , PH 3 , H 2 O

stable due to the delocalisation ?
2) NO 2  ; CBr2 , SO 3
OH 3) NH 3 , H 2 O, AlBr3
1) C6H5 O 2) 4) AlCl3 , CH 2  CH 2 , SO3
NO2
27. The most stable carbanion is:

OH 1) p hC H 2 C H 2
O

3) NO2 4) 2) p h C H 2
NO 2
24. Which one of the following cabocation is

most stable due to the resonance ?
3)
1) C6H5 CH C6H5
2) C6H5 CH2
3) 4)
4) C6H5 C C6H5
CH3

28. The most stable carbanion is: PASSAGE-7

1) p h C H 2 Hyperconjugation describes the orbital
interactions between the  -systems and
adjacent bond of the substituent group(s) in
organic compounds. Hyperconjugation is also
2) called as Baker and Nathan effect. The nesessary
and sufficient conditions for the hyperconjugation
are:
(i) Compound should have at least one SP 2 -
hybrid carbon of either alkene , carbocation or
3)
alkyl free radical
(ii)  -carbon with respect to SP 2 -hybrid
carbon should have at least one hydrogen.
Hyperconjugation are of three types:
4) (i)  (C-H),  -conjugation

(ii)  (C-H),  - positive charge conjugation
(iii)  (C-H),  - odd electron conjugation

29. The most stable free radical is:
 
31. Hyperconjugation is possible in which of the
1) phCH 2 C H 2 2) Me C H 2 following species?
 
3) Me 2 C H 2 4) ph C HMe 1) CH 3  CH 2
30. The least stable carbocation is: 2) C6 H 5  CH 3

3) H 2 C  CH 2
1) O 2 N C H2
CH 3
|

CH 3  C  CH  CH 2
2) Cl C H2 4)
|
CH 3

Me C H2
3)

MeO C H2
4)

32. Which of the following carbocations will 34. Which of the following alkenes will show
show highest number of hyperconjugative maximum number of hyperconjugation
forms? forms?
CH 3 1) H 2 C  CH 2
| 2) CH3  CH  CH 2
1)
CH 3  CH  CH  CH 2 3) CH 3  CH 2  CH  CH 2
CH 3

CH 3  C H 4) |
| CH3  CH  CH  CH 2
2)
CH 3 35. Stability of alkyl carbocations can be
explained by:
1) inductive effect
CH3
2) hyperconjugation
| 3) both inductive effect and hyperconjugation
 4) electrometric effect
CH 3  c
3) MATRIX MATCHING
|
CH3 36. Column I Column II
A) Inductive effect p) Deloclisation of  e 

CH 3
B) Electromeric effect q) Displacement of  e 
|
C) Resonance r)   H  atoms

CH 3  CH 2  c D) Hyperconjugation s) Influence stability of
4) carbocation
|
t) Complete transfer of  e 
CH 3
37. Column I Column II
33. Which of the following free radicals will not
show the phenomena of hyperconjugation? A) CCl2 p) sp2 -hybridized

1) C H 3 CH3
B) CH q) Electrophile by nature
2) CH 3  CH 2  CH 2 CH3
*
3) CH 3  C H 2 CH 3
C) CH r) 6  H  atoms
CH3 CH 3
|
4)
CH3  CH
 D)
CH3 .
CH s) sp 3 -hybridised
CH3

38. Column-I Column-II
A) Stability order: 30  20  10 p) Methyl carbocation

B) Stability order: 10  20  30 q) Alkyl carbocation
C) No hyperconjugation r) Carbanion
D) Two unshared pair of s) Nitrene
electrons
KEY
LEVEL - IV
1) 1 2) 1 3)2 4)2 5)4
6)2 7)1 8)2 9) 1 10)3
11) 2 12) 2 13) 2 14) 2 15)4
16) 2 17) 2 18) 4 19) 1 20)1
21) 1 22) 1 23) 3 24) 3 25)1
26)2 27)3 28)2 29)4 30)1
31)2 32)3 33)1 34)2 35)3

36) A-q,s;B-t;C-p,s;D-p,r,s
37) A- p,q; B-p,q,r; C-r,s; D-p,r
38) A-q,B-r,C-p,D-s
HINTS
LEVEL -IV
1. -m groups increse the acidic charachter

7. Stability order of carbo cation
   
H 3 C   CH 3  C H 2   CH 3  2 C H   CH 3 3 C
9. -I  acidic strength
11. -I  acidic strength  Ka
15. +I effect  stability of carbocations
18. Carbocation stability  resonance effect
1
19. -I effect  stability of carbocation
1
30. -I effect  stability of carbocation

04-General Organic - Sandeep Final - CW

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JEE MAINS - VOL - IV GENERAL ORGANIC CHEMISTRY

GENERAL ORGANIC CHEMISTRY

products. same E.N & it occurs in vapour phase and

NISHITH Multimedia India (Pvt.) Ltd., 91

(sunlight, h ), Peroxide,Radical is known as attached to radical.

(iv) They are paramagnetic in nature.

 C6 H5 3 C   C6 H5 2 CH   C6H5 CH 2  H 2C CH C H 2

 Both electron-withdrawing groups such as

 Stability of same type of alkyl free radicals 

 Examples of free radical reactions (i) Wurtz

 Stability decreases as +I effect decreases

alkoxy  OR  groups are important substituents

 Carbanions are classified as10 , 20 and 30 based

or tetrahedral with one lone pair.

NISHITH Multimedia India (Pvt.) Ltd., 95

50% s 33% s 25% s :C  F:  C  F :

 The reagents can be classified into nucleophiles,

Br, OR, R, CH 3  -I effect decreases with decrease in the

groups are needed .Therefore more the no of CH3

Decreasing Carbocation Stability N  C  CH 2  C H 2  Decreasing Stability

 It is denoted by E  Down the group electron density decreases due

each carbon and oxygen atom has an octet and

FISSION OF COVALENT BOND

1. In organic reactions the reactant is called

1) Nucleophile 2) Lewis base

CH 4  Cl2   CH 3Cl  HCl

HINTS 6. + R power of the given groups

1)  NR2  OR   F 1)   H atom 2)   H atom

NISHITH Multimedia India (Pvt.) Ltd., 105

ATTACKING REAGENTS 35. is

28. The ion with highest nucleophilicity is

3) Presence of even number or electrons 4) molecular rearrangement

3) NO 2  4) all of these + HCN

108 NISHITH Multimedia India (Pvt.) Ltd.,

2) I > II > III > IV

4) III > II > I > IV

1) 1 > 2 > 3 > 4 2) 4 > 3 > 2 > 1

2) I > II > III > IV

110 NISHITH Multimedia India (Pvt.) Ltd.,

Correct decreasing order stability is : O O

112 NISHITH Multimedia India (Pvt.) Ltd.,

23. Which one of the following anion is most 1) Br  , PH 3 , H 2 O

24. Which one of the following cabocation is

NISHITH Multimedia India (Pvt.) Ltd., 115

4) (i)  (C-H),  -conjugation

(iii)  (C-H),  - odd electron conjugation

30. The least stable carbocation is: 2) C6 H 5  CH 3

116 NISHITH Multimedia India (Pvt.) Ltd.,

CH3 36. Column I Column II

A) Inductive effect p) Deloclisation of  e 

NISHITH Multimedia India (Pvt.) Ltd., 117

38. Column-I Column-II

A) Stability order: 30  20  10 p) Methyl carbocation

31)2 32)3 33)1 34)2 35)3

1. -m groups increse the acidic charachter

118 NISHITH Multimedia India (Pvt.) Ltd.,

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