GOC Allen

Read more at www.puucho.
com JEE – MAIN
REACTION MECHANISM
 Reaction : Breaking of old bond and formation of new bond is known as chemical reaction
A B + X Y A X + B Y
Old bonds New bonds
A sequential account of each step, describing details of electron movement, energetics during bond cleavage
and bond formation, and the rates of transformation of reactants into products (kinetics) is referred to as reaction
mechanism.
Species on which reagent is attacking is known as substrate or reactant.
Species which attack on substrate, is known as reagent.
 Type of cleavage of bond :
(A) Heterolytical cleavage/fission.
(B) Homolytical cleavage/fission.

C + × Z
|V Ionic cleavage
or
C .× Z C × + ZW
 | Heterolytic fission
Un Ionic cleavage
C + × Z or
Homolytic fission
Reaction
intermediate
(A) Cleavage in which unequal distribution of electrons takes place during the bond cleavage is known as
heterolytical cleavage. Due to unequal distribution of electrons, ions are formed. That’s why it is also
known as ionic cleavage or heterolytical cleavage.

C + × Z
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C ×Z

C × + Z
(B) Cleavage in which equal distribution of e–s takes place during the chemical reaction is known as homolytical
cleavage.
C × Z C + × Z
 Due to equally distribution of electrons, without charge unpaired electrons species is formed, which is
known as free radical and cleavage is known as unionic cleavage/homolytical fission.
 By both cleavage [ionic/non ionic] three type of species are formed [One carrying positive charge, other
carrying negative charge and third one is neutral with unpaired electrons] is known as reaction intermidiate.
 If reagent compound is organic, then reaction intermediate are -
(
i
) Carbocation
(ii
) Carbanion
(iii) Carbon free redical
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Chemistry
 Carbocation :
Carbon on which positive charge is present is called carbocation.
 It is electrons defficient species.
 It is incomplete octet species also because it has six electron in outer most shell.
 It'shybridisation state is sp2.
 It's Geometry is Trigonal planner.
 Bond angle is of 120°.
 Due to electron deficiency it act as a electrophile and always attack on electron richer site.
 Carbocation are of three types :
(i) 1º or primary, (ii) 2º or secondary, (iii) 3ºortertiary
(i) 1º or primary : When positive charge present on 1º or primary carbon.
 
Example : CH3 CH2 CH3  CH2  CH2
ethyl carbocation n–propyl carbocation
 
CH3  CH2  CH2  CH2 CH2  CH  CH2
n–butyl carbocation Allyl carbocation Benzyl carbocation

(ii) 2° or secondary carbocation : When positive charge present on 2° or secondary carbon.
 
Example : CH3 CH CH3 CH CH2 CH3
CH3 Sec. butyl carbocation
iso-propyl carbocation

CH

CH 3 CH CH2 CH2 CH3

Active secondary pentyl carbocation diphenyl methyl carbocation
(iii) 3° or tertiary carbocation : when positive charge present on 3° or tertiary carbon.
CH3
Example : CH3 C
CH2 CH3
Tertiary butyl carbocation Tertiary pentyl carbocation
Triphenyl methyl carbocation

 Carbanions :
 Carbon on which the negative charge is present is called carbanion.
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JEE – MAIN
 It has eight electron in outermost shell so it is complete octet species.
 It is an electron richer species because it has extra electron.
 It has non bonding electron pair.
 It's Geometry is pyramidal.
 Bond angle is of 107°.
 Due to presence of non bonding electron it act as a nucleophile also.
 On the basis of presence of negative charge on carbon atom it is of three types -
(i) 1º or primary (ii) 2º or secondary (iii)3º ortertiary
(
i
) 1° or Primary carbanion : When negative charge present on primary carbon like,
CHCH
3 2
CH2
ethyl carbanion
3 2 2
n-propyl carbanion benzyl carbanion

Other example of primary carbanion are same as that of carbocation only negative charge will be
present on carbon instead of positive charge.
(ii) 2° or secondary carbanion : When negative charge present on secondary carbon. Other example
of secondary carbanion are same as that of carbocation only negative charge will be present on carbon
instead of positive charge.
CH
CH3–CH–CH3
(iii) 3° or tertiary carbanion : When negative charge present on tertiary carbon.

C
CH3 CH CH3 ,
CH3
 Free Radical :
 Carbon on which a unpaired electron is present and also electrically neutral then it is known as carbon
free radical.
 It is always formed by the homolytical fission of bond or it is form when reaction occurs in the presence
of U.V.
 light or reaction occurs at high temperature or reaction occurs in presence of non polar solvent.
 It has seven electron or odd electron in outermost shell.
 It is incomplete octet species so it is also electron deficient species.
 Geometry is trigonal planner.
 Bond angle is 120°.
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Chemistry
 On the basis of presence of unpaired electron on carbon. It is also of three types :
(i) 1° or primary free radical (ii) 2° or secondary free radical (iii) 3°or tertiary free radical
(
i
) 1° or primary free radical : When an unpaired electron present on primary carbon.
Examples :
. . .
CH3 CH2 , CH3CH2 CH2 , CH3 CH CH2
CH3
(ii
) 2° or secondary free radical : When unpaired electron present on secondary carbon.
. .
CH3CH CH3 , CH3CH CH2CH 3
(iii) 3° or tertiary free radical : When unpaired electron present on tertiary carbon.
Examples :
. .
CH3 C CH3 , C
CH3
 CARBENES (CH2:) :
Carbenes are neutral carbon species in which the carbon atom is bonded to two monovalent atoms or groups
and carries two electrons.
 It is Bivalent radical.  6 e– in outermost shell.
 It is neutral.  4 e are bonded and two are nonbonded e–.
–
 Carbenes are of two types :

(A) Singlet carbene : Carbene in which both non-bonded e– lies in same orbital with opposite spin.
H empty unhybridized p–orbital
103° C lone pair of e–

2
sp hybridized carbon
H
Orbital structure of singlet carbene
Characteristic of singlet carbene :

 Both non-bonded e– lies in one orbital with opposite spin.  Hybridization – sp2
 It is electron deficient so acts as electrophilic reagent.  It is diamagnetic in nature.
 Geometrical shape – bent or V-shape or angular shape.

(B) Triplet carbene : Carbene in which both non-bonded e– lies in two different orbitals with same spin.
C
sp carbon
two unhybridized p–orbital

Orbital structure of triplet carbene
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JEE – MAIN
Characteristic of triplet carbene :
 Both non-bonded e– lies in two different orbitals with same spin.  Hybridization – sp
 Geometrical structure – linear  It is paramagnetic in nature.
 It is also electron deficient so acts as electrophilic reagent.
 Triplet carbene is more stable than singlet carbene
ATTACKING REAGENTS
The species which attack on a substrate molecule or intermediate and form a product is called as attacking
reagent. These are of two types :
(A) Electrophilic reagent or electrophiles:
Electrophilic (electro + philic)
(electron + loving)
The reagent which attacks on the negative of the molecule or loves electrons are called electrophiles.
Electrophiles may be positively charged or electron deficient molecule (molecule with sextet or septet).
(i) Positively charged electrophiles :
         
H , S O 3 H , NO , NO 2 , C, CH2
, X , R , C 6 H 5 N2 , C H 2 OH CH3 CH
O
(ii) Neutral electrophiles :- Which possess a electron dificiency.

(a) All Lewis acids as :
BF3, AlCl3, SO3, ZnCl2, BeCl2, FeCl3, SnCl2, CO2, SnCl4.
(b) The neutral atom that accept electrons from the substrates :
*N
*OCl, R – * – X, * – Cl, CH – C
* = O, R C
> C Mg I 3
The star (*) indicates the atom that accept electrons.

(c) Free radicals, carbenes & nitrene acts as electrophiles.
(B) Nucleophilic reagent or nucleophiles :
Which attack on the positive site of the substrate or loves nucleus.
Nucleophilic (Nucleo + philes)

(Nucleus + loving)
Nucleophiles may be negatively charged ions or possess a lone pair of electron or donate an unshared electron
pairs.
(
i
) Negatively charged nucleophiles.
              
H, OH, OR, CN, X, R, R – COO, NH2, CH2 – COR, SH, HSO4, NO3, RS, CO3, CH2 = CH
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Chemistry
(
ii
) All Lewis base which contains lone pairs :
        
H2 O ,R  O H ,R  O  R , N H 3 , R  N H 2 , R3 N , R S

H, R  S

 R , H2 S
   
(iii)
*
R * , CH – CN
* – Li, LiAlH
– Mg – X, R *
*, NaBH
4 3 4
The star (*) indicates the atom which donates electrons to the substrate.
Ambident nucleophile : Nucleophiles which have two sites of electron rich centre or in which two or more
atoms bear an unshared pair of electrons.
Example : K—O—N O, N H 2— O H

CH2 C R  CH2 C R
O O
Resonating structures are also abmbident nucleophile.
S .No . Electro phile Nucleo phile
1 Accep ts the electron p air Sup p lies the electron p air

2 Electron de ficient Ele ctron rich
3 Attacks the p oints of high electron density Attacks the p oint of low electron density
4 Lewis acid Lewis base
Posse ss an emp ty orbita l to receive the Possess an e lectron p air which is loose ly held a nd
5
ele ctron p a ir can be sup p lied easily
6 Usually p ositively charged sp ecie s Usually ne gatively charged sp ecies

7 Forms an extra bond with the nucleop hile Increa ses its covalency by one unit

 ELECTRONIC EFFECTS :
There are four effect which affect the chemical reaction are –
(1) Inductive effect (2) Mesomeric effect
(3) Hyper conjugation (4) Electromeric effect
1. INDUCTIVE EFFECT :
 Polarity developed in Carbon–chain due to the shifting of  bond electron by the group or atom
present on carbon-chain is known as inductive effect,.
 Discovered by scientist Ingold.
 It is effective upto 3 or 4 carbons. After 3 or 4 carbons it becomes neutralized.
1
So Magnitude of I effect ∝
dis tance
 Inductive effect is measure with respect to hydrogen atom that means inductive effect of hydrogen is
always zero.
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JEE – MAIN
 It is a permanent effect.
 Some atoms or groups have a greater tendency to attract the shared electron of the covalent bond. Such
atoms or groups acquire partial negative charge by receiving electron density from the covalent bonds
of the chain. Therefore, these are classified as the groups exerting negative inductive (– I) effect.
 If shifting of electron takes place from carbon chain to group or away from the carbon chain or towards
the group , then it is known as (–) I effects.
   
C– C C C Z
3 2 1
(I)
C1() > C2 () > C3 ()

 Due to –I effect positive charge develops over carbon chain or carbon chain becomes electron deficient
such type of carbon chain will be more reactive towards nucleophile or less reactive will be towards
electrophile.
Group which shows (–)I are -
The decreasing order of negative inductive effect of some important atoms and groups is given below
  
Order of – I effect OR2 > –NR3 >–NH3 > –NO2 > –SO3H > –CN >
–COR > –X > –OH > –OR > –NH2 > –C6H5 > –H
 Some groups are electron donor and therefore acquire partial positive charge by increasing electron
density in the covalent bonds of a chain. Such groups exert positive inductive (+ I) effect.
 Or if shifting of electron takes place from group to carbon chain or away from the group or towards
the carbon chain then it known as (+) I effect
   
C– C C C Z
3 2 1
(II)
C1() > C2 () > C3 ()

 Due to +I effect electron density increase on carbon chain or negative charge comes on carbon chain
such type of carbon chain will be more reactive towards electrophile or will be less reactive towards
nucleophile.
Group which shows +I effect are.
O
||
– O, – O – C, all alkyl groups
 In alkyl groups megnitude of +I effect  size of alkyl group

– CH3 < – CH2CH3 < –CH2CH2CH3 < –CH2CH2CH2CH3
In isomeric alkyl group megnitude of +I effect  number of branches.
CH3
–CH2CH2CH2CH3 < –CH2–CH–CH3 < –C–CH3
CH3 CH3
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Chemistry
 APPLICATION OF I-EFFECT
(1) Stability of carbocation :
(a) If number of + I groups increases then stability of carbocation increases.
(b) If number of –I groups decreases then stability of carbocation increases.
(c) Therefore
1
Energy  charge 
stability
Stability of Carbocation  No. of  Igroups
1
Stability of carbocation 
No.of  Igroups
CH3
   
Question : Stability order : CH3 C   CH3 CH     CH CH    CH3
3 2
CH3 CH3
3° 2° 1°
Ans. Reason : More no. of +I group.

more stable carbocation.
(2) Stability of carbanion :
(a) If number of – I groups increases then stability of carbanion increases.
(b) If number of +I groups decreases then stability of carbanion increases.
(c) Therefore
Stability of Carbanion  No.of  I groups
1
Stability of Carbanion 
No.of  I groups

CH3
   
Example: (1) CH3 C (2) CH CH3 (3) CH3 CH2 (4) CH3
CH3 CH3
3° 2° 1°
More No. of +I group.

Less stable carbanion.
So stability order 1 < 2 < 3 < 4
  
Example : (1) CH2 CH CH2 CH3 (2) CH2 CH2 CH CH3 (3) CH2 CH2 CH2 CH2 F
F F
Minimum distance of –F.
Maximum –I of –F.
Minimum negative charge.
Maximum stable.
So stability order 1 > 2 > 3
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JEE – MAIN
Acidic and basic strength :

 Acidic strength :
+
H donar
Acid
e– acceptor
(
i
) If No. of – I groups increases then acidic strength increases.
(ii
) If No. of + I groups increases then acidic strength decreases.
1
acidic s tre ngth  No . o f - I g ro ups 
No . o f + I gro ups
Example :
(
i
) CH3 C OH Cl CH2 C OH
O 
O
–H 
 –H 
CH3 C O Cl CH2 C O
O O
+I of –CH3 –I of –Cl, so anion is more stable
so anion is less stable and corresponding acid is more acidic.
(ii
) CH3 CH2 CH COOH > CH3 CH CH2 COOH > CH2 CH2 CH2 COOH
F F F
minimum distance of F
from –COOH maximum –I
of F. So maximum acidic.
 Basic strength :
–
OH donar
Base
e– donar
+
H acceptor
(
i
) If No. of + I groups increases then basic strength increases.
(ii
) If No. of – I groups increases then basic strength decreases.
1
Bas ic s tre ngth  No . o f + I g ro ups 
No . o f – Igro ups
Example :
CH3
CH3 C OH > CH3 CH OH > CH3 CH2 OH

CH3 CH3
Maximum +I.
Maximum tendency to donate l.p.
Maximum basic.
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Chemistry
Question : Explain— Basicity order in aqueous solution and in liquid phase. Et2 NH > Et3 N > Et NH2
Ans. Due to steric hindrance in 3° amine, it is less basic, than 2° amine.
Steric hindrance of three –C2H5 group protect the lone pair of nitrogen from the attack of H.
H H H H
C HH C
H C C H
H .. H
N
H C H
H C H
H
In solution or in aqueous phase basic order is R2N > R–NH2 > R3N > H–NH2
But in gaseous phase basic order is R3N > R2N > R–NH2 > H–NH2
Some other basic order of different amine if alkyl group would be change
Alkyl groups (R–) Relative base strength
(
i
) CH3 – R2NH > RNH2 > R3N > NH3
(ii
) C2 H 5 – R2NH > RNH2 > NH3 > R3N
(iii) (CH3)2CH – RNH2 > NH3 > R2NH > R3N
(iv) (CH3)3C – NH3 > RNH2 > R2NH > R3N
Question : Ethyl amine is more basic then aniline, why ?

Ans. Due to the + I effect of ethyl group.
Question : Cl–NH2 is less basic then methyl amine, why ?
Ans. Due to – I effect of –Cl group and p–d conjugation.
Question : Correct basic order of the following different amine in chlorobenzene medium is -

N N
(A) CH3 – CH2 – NH2 (B) (C) (D) |
CH3 H
Ans. C > D > B > A
Question : Which is most basic among the following :

(A) CH3NH2 (B) CH3CH2NH2 (C) NH3 (D) (CH3)2CHNH2
Ans. (D)
Question : Which is most acidic compound –
OH OH OH
OH
(A) NO2 (B) (C) (D)
NO2
NO2
Ans. (B)
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JEE – MAIN
2. MESOMERIC EFFECT OR RESONANCE EFFECT
 Polarity developed in conjugate system by the complete transfer of non–bonding electron or –bond electron
due to the group or atom attach with conjugate system is known as mesomeric effect.
 If transfer of pi-bond electron takes place from conjugate system to group then it is known as negative mesomeric
(–M) effect.
O

CH2 CCH CC C 
O
 O
CH2 C C C C CH
O
 O
CH2 = C C CC C 
O
 O
CH2 CH C CH C CH 
O
 For –M effect, group should have either be positive charge or should have vacant orbital.
 Due to –M effect positive charge comes over conjugate system or due to –M effect electron density decrease
in conjugate system, such type of conjugate system will be more reactive towards nucleophile or will be less
reactive towards electrophile.
 Group which shows –M effect are -
–NO2 , –CN, –SO3H , – CHO, –COR, –COOH, –COOR , –COX, –CONH2 etc.
 If transfer of non bonding electron takes place from group to conjugate system then it is known as positive
mesomeric (+M) effect.
..
CH2 ==CH – CH = CH – CH = CH – NH2

CH2 = CH – CH = CH – CH — CH = NH2

CH2 = CH – CH – CH = CH – CH = NH2

CH2 – CH = CH – CH = CH – CH = NH2
 For +M effect, group should have either be lone pair of electron or should have negative charge.
 Due to + M effect negative charge comes over conjugate system or electron density increase on conjugate
system such type of conjugate system will be more reactive towards electrophile or will be less reactive towards
nucleophile.
 Group which shows + M effect are -
– O , –NH, –NR2 , –NHR, –NH2 , – OH, –OR, –SH – SR, – F, – Cl, – NHCOR , –O–COR etc.
 In mesomeric effect polarity or charge migrate from one end to another end. During charge transfer, energy
releases from the conjugate system which increase the stability of conjugate system also.
 Due to charge transfer compound form more then one structure. without change in atomic orientation these
structures are known as resonating structures.
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Chemistry
 These structures are helpful in explanation of chemical reactivity or the chemical reaction of the compound
thats why we can say resonance phenomenon is the result of mesomeric effect or delocalisation.
(
i
) Resonating structure are not the real structures of conjugated compounds.
(
ii
) The real structure of conjugated compound is a hybrid of all resonating structures. This phenomenon is
known as resonance, mesomerism or delocalisation.
(iii) Thus resonance is nothing but hybridisation of resonating structures and resonance phenomenon will take
place in conjugated compounds.
(iv) Conditions of Resonating Structures : Resonance structures should fulfil following conditions :
(a) All resonating structures must have the same arrangement of atomic nuclei. Resonance differs from
tautomerism in this very important aspect.
O O
|| | 
: :
R – C – O –H R – C = O –H
Positions of atomic nuclei in (I) and (II) are same.
3 3
O OH
|| |
CH3 – C – CH3 CH3 – C = CH2
1 1
(I) (II)
Position of hydrogen nuclei in (I) and (II) are different, hence (I) and (II) are not resonating structures, they
are tautomer.
(b) The resonating structures must have the same numbers of paired and unpaired electrons. However, they
differ in the way of distribution of electrons.
•• • •• •• • ••
O=N—•O• •• •
•O— N=O
•• •• 
••
Total number of Total number of

paired electrons = 16 paired electrons = 16
unparied electron =1 unparied electron =1
 The energy of the different resonating structures must be the same or nearly the same.
 All atoms that are part of the delocalisation system must be in a plane or be nearly planar.
(v) All atoms of the resonating structure should follow the octet rule.
For Example: All atoms follow octet rule.

NH3 NH3
 Nitrogen does not follow its octet rule
hence (II) is not resonating structure (I)
I II
 CONDITIONS FOR RESONANCE :

1. If there are two bonds at alternate position then e– of one bond are transferred towards another bond.
(According to I–effect).
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JEE – MAIN
Example :
   
(
i
) CH2 CH CH CH2  CH2 CH CH CH2  CH2 CH CH CH2

(ii
) CH2 CH C H  CH2 CH C H

O O
 
(iii) CH3 CH CH CH CH2 CH3 CH CH CH CH2
2. If there is one lone pair or a negative charge and one  bond are at alternate position then e– of lone pair
or negative charge are transferred towards  bond.
Example :
..  
(
i
) CH2 CH OH  CH2 CH OH
 
CH CH2  CH2 CH CH2
(ii
)
CH2
..  
(iii) CH2 CH O CH3  CH2 CH O CH3
 
CH O  CH2 CH O
(iv)
CH2
3. If there is one positive charge and one  bond are at alternate position then e– of  bond are transferred
towards positive charge.
 
Example : CH2 CH CH2  CH2 CH CH2

Note : CH2 C H does not show resonance because due to more EN of oxygen, e– are always
O
transferred towards oxygen.
4. If there is one free e– and one  bond are at alternate position.

Example :
. .
(
i
) CH2 CH CH2  CH2 CH CH2
(ii
) . .
CH3 CH CH CH2  CH3 CH CH CH2
5. If there is one lone pair or negative charge and one positive charge are at adjacent atoms then e– of lone
pair or negative charge are transferred towards positive charge.
 .. 
Example : CH2 OH  CH2 OH
 Characteristics of Resonance :
(
i
) In resonance only e– are transferred not atoms.
(ii
) The number of e– or number of unpaired or paired e– in all resonating structures should be same.
(iii) The energy of resonating structures is almost same.
(iv) It is permanent effect.
(v) All the resonating or canonical structures must confirms to Lewis structures.
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Chemistry
 Hybrid resonating structure :
   
CH2 CH CH CH2  CH2 CH CH CH2  CH2 CH CH CH2
1 2 3 4 1 2 3 4 1 2 3 4
I II I
In the structure I C1—C2 has double bond while in II and III C1—C2 has single bond, so C1—C2 shows bond
length in between single and double bond similarly in structure I C2—C3 has single bond. While in structure
II and III C2—C3 has double bond, so C2—C3 shows bond length in between single and double bond.
So hybrid resonating structure from all its resonating structures is :
CH2 CH CH CH2 Hybrid structure
Example :
 
..    
(
i
) CH2 CH OH  CH2 CH OH CH2 CH OH
I II
(Resonating structure) (Hybrid structure)
  – –
(ii
) CH2 CH CH2  CH2 CH CH2 CH2 CH CH2
1 2 3 1 2 3
(Resonating structure) (Hybrid structure)
 RESONANCE ENERGY :
The difference in the experimental and calculated energies (heat of hydrogenation) by which the compound
is stable, is known as the resonance or delocalization energy. Higher the value of resonance energy, greater
is the resonance stabilization.
 RESONANCE ENERGY (R.E.) OF BENZENE :


The Resonance energy of benzene is calculated from the heat of hydrogenation as given below :
+ H2  + 28.6 Kcal.
+ 3H2  + 3 ×28.6 Kcal. (=85.8)
but experimental value is 49.8 Kcal. so,
Resonance energy = Calculated value – Experimental value
= 85.8 – 49.8 = 36 Kcal.
76 E
JEE – MAIN
 APPLICATION OF R OR M-EFFECT
 Stability of carbocation :
(a) Stability of carbocation is increased by resonance.
(b) Aromatic compound are more stable than non aromatic compound.
Example : Compare stability order of :-
  
(
i
) CH2 CH CH2 > CH3 CH2 CH2 > CH2 CH CH CH2
stable by resonance +I of Alkyl group –I of Alkenyl group
 
(ii
) CH2 <  < CH3
1° 2° 3°
  
(iii) CH2 CH2 CH2

Re sonance increases, stability increases


  
(iv) , ,
(I) (II) (III)

stable by resonance more resonance localized ve charge
stability order II > I > III
 Stability of carbanion :
(a) Stability of carbanion is increased by resonance.
Example : Compare stability order of :

  
(
i
) CH2 CH CH2 , CH2 CH , CH3 CH2
stable by resonance – ve charge on more EN atom
stability order I > II > III
 
(ii
) , ,
(I) (II)
stable by resonance more resonance
stability order II > I.
  
(iii) CH2 — N O 2 CH2 —CH 2—NO 2 C H 3 — CH — N O 2
stable by resonance no resonance stable by resoncance, but +I of CH3
stability order I > III > II
 Stability of free radicals :

(a) Stability of free radicals is increased by resonance.
Example : Compare stability order of :

. . .
(
i
) CH2 CH CH2 CH2 CH CH2 CH CH CH CH2
less resonance no resonance more resonance
stability order III > I > II
E 77
Chemistry
. . .
(
ii
) , ,
resonance more resonance localized
stability order II > I > III
Equal resonating structures : Resonating structures in which there is same charge on same atom.

Example : H C O  H C O are equal R.S.

O O
Unequal resonating structures : Resonating structures in which there is same charge on different atom
or different charge on same atom or different charge on different atom.
 
Example : CH2 CH O CH2 CH O are unequal R.S.
 .. 
CH2 OH  CH2 OH
Note : Equal resonating structures are more stable than unequal resonating structures.
 Acidic and Basic strength :
(a) Acidic strength :
1 1
Acidic stre n gth   M   I  
M I
Question : Carboxylic acids are more acidic than phenols, why ?
Ans. R C OH OH
O


 
–H –H


R C O R C O O O


 
O O

2, equal R.S. more stable anion 5, unequal R.S. less stable anion
so corresponding acid is more acidic
Question : Phenol is more acidic than alcohols why ?
Ans. Ph OH R OH


 
–H –H
Ph O R O
stable by resonance no resonance.

So, it is more acidic.
(b) Basic strength order :-
If there is more resonance of lone pair or negative charge then it will be more stable, means less basicity.
1 1
Basic strength   M   I  
M –I
78 E
JEE – MAIN
Example : Give basic strength order :

.. .. ..
NH2 CH2 NH2 NH CH3
(
i
)
l.P. is stabilized by no resonance of l.p. l.p. is stabilized by resonance

resonance so maximum basic stabilized and +I of CH3
basic order — II > III > I
NH2
(ii
) .. ..
N N
H
stable by localized
resonance l.p. on more EN
basic order — III > II > I
Question : Give basic strength order for :
.. .. ..
NH NH2 CH2 NH2
(
i
)
diphenyl amine benzyl amine

more resonance no resonance
Ans. 3 > 2 > 1
Question : Aniline is less basic than alkyl amine, why ?
Ans. Due to delocalization of l.p. of nitrogen in aniline, aniline is less basic.
Question : Which is weakest base :
(i) C6H5—CH2—NH2 (ii) C6H5—CH2—NH—CH3
(iii) O2N—CH2—NH2 (iv) CH3—NH—CHO
Ans. (iv) due to resonance of l.p.
7. Reactivity of benzene : Characteristic reaction of benzene is electrophilic substitution (ESR)

  
E -H
 H  (product)
E E
In benzene ring due to more electron density first attack will be of electrophile.
8. Rules for stability of resonating structure (R.S) :
(
i
) Non-polar R.S. is more stable than polar resonating structures.
(ii
) In polar R.S. complete octet is more stable than incomplete octet.
(iii) For incomplete R.S. positive charge on more EN is less stable.
Example : Arrange the following for stability order.

   
(
i
) CH2 CH Cl CH2 CH Cl CH2 CH Cl
non-polar complete octet incomplete octet

stability order : 1 > 2 > 3
E 79
Chemistry
 
(ii
) R C OH  R C O H  R C OH
 
O O O
non-polar complete octet incomplete octet

 
(iii) R C O < R C O
incomplete octet complete octet

(Acylium ion)
 
(iv) CH2 CH O > CH2 CH O
negative charge on negative charge on

more EN less EN
Example : Give stability order of :
   
CH2 CH2 CH2 CH2
(
i
)
NO2 Cl CH3 OCH3
–M –I +I M
charge charge  charge  charge 
So stability order IV > III > II > I
 
 
CH2 CH2 CH2 CH2
(ii
)
NO2 Cl CH3 OCH3

–M –I +I M
charge  charge  charge  charge 
Stability order I > II > III > IV

  CH2
CH2 CH2 CH2
(iii) NO2
NO2
NO2
–M and M = 0 –M and
more –I only –I less–I
charge is minimum
So stability order I > III > II > IV
80 E
JEE – MAIN
Question : Give acidic strength order for :
OH OH OH OH
NO2 Cl CH3 OCH3

–M –I +I +M
Ans. So acidic order is I > II > III > IV
Question : The mixture of ortho-nitrophenol and para-nitrophenol can be separated by steam distillation why
and which can be distilled out ?
Ans. Ortho-nitrophenol is distilled out due to less B.P. of ortho-nitrophenol it is more volatile
Example : Give acidic strength order for
(
i
)
OH OH OH OH
CH3
CH3
CH3




   
–H –H –H –H
 
O O

O O

CH3
CH3
CH3
more +I and H= 0 less +I and maximum stable anion
H-effect of CH3 ,So only +I H-effect so corresponding acid is
anion is minimum stable maximum acidic
Acidic order 4 > 2 > 3 > 1
OH
OH
NO2 OH OH
NO2 NO2 NO2
(ii
)
NO2
NO2
maximum –M and –I
so maximum acidic
Acidic order 1 > 2 > 3 > 4
Example : Give basic strength order for :
NH2 NH2 NH2 NH2
(
i
)
NO2 Cl CH3 OCH3
–M –I +I +M
So basic strength order IV > III > II > I
Question : What is the increasing order of resonance stabilization of benzene, naphthalene and anthracene.
Ans. The values of resonance energy for benzene, naphthalene and anthracene are 36, 76 and 85 Kcal per
mole respectively. It is clear from these values that the resonance stabilisation of naphthalene is more
than that of benzene and less than that of anthracene. Thus, the increasing order of resonance stabilisation
isasfollows.
E 81
Chemistry
3. HYPERCONJUGATION EFFECT (H-EFFECT)
 H-EFFECT :
Complete transfer of e– of –C–H bond towards bond or positive charge or free electron is called as
H-effect (permanent effect). It is also called as non-bonded resonance and given by Nathen and Baker.
 CONDITIONS OF H-EFFECT :
1. If there is one C–H bond and one positive charge are at alternate position

H H H H
 
H C CH2  H C CH2  H C CH2  H C CH2

H H H H
all are called as hyperconjugation structures or canonical structures.

Carbon which is attached to positively charged carbon is called as  –C and H which is attached to
–C are called as – H. So if number of – H are more then there will be more number of hyperconjugation
structures, so more stable carbocation.
2. Carbon which is attached to sp2 C is called as –C and H which are attached to -C are called as -H.
If there is one –C–H bond and one free e– are at alternate position then there will be H-effect.
.
H H H H
 . .
H C CH2  H C CH2  H C CH2  H C CH2
.
H H H H
3. If there is one –C–H  bond and  bond are at alternate position then there will be
H-effect.

H H H H
    
H C CH CH2  H C CH CH2  H C CH CH2  H C CH CH2
1 2 3 1 2 1 3 2 3 1 2 3
 H
H H H
Special point :
(
i
) H3 C CH CH2

1 2 3
C1—C2 bond length = 1.54 Å

C2—C3 = 1.34 Å.
but in propene the actual bond length is 1.54 > b.l. > 1.34 Å
It can be explained by H-effect. So C–C bond length order of
CH2 CH—CH CH2 C H 3— C H CH2 CH3 – CH3
is III > II > I
Due to resonance bond length is shortest in I.
(ii
) The effectivity order of M, H and I effect
M > H > I
Note : If there is one —C—H  bond and one negative charge at alternate position then there will be no
H-effect.
H

H C CH2 (No H - effect)
H
no shifting of —C—H  bond, because anion have complete octet. (8e–)
82 E
JEE – MAIN
 APPLICATION OF H-EFFECT
 STABILITY OF CARBOCATION :
 Stability of carbocation can be explained by M, I and H-effect.

 If more hyperconjugation structures (more -H) then more stable cation.
 Stability of carbocation  No. of canonical structures  No. of  H.
Example : Give stability order for :-
CH3
  
(
i
) CH3 C > CH3 CH > CH3 CH2 > CH3
CH3 CH3
9 -H 6 -H 3 -H Zero -H
Maximum stable
 
CH3 
CH2
(
ii
) > >
 Stability of carbon free radicals :

 Stability of carbon free radical is explained by M and H-effect.
 More hyper conjugation structures (more -H) more stable free radical.
Example : Give stability order for :-
CH3
. . . .
CH3 C CH3 CH CH3
(
i
) CH3 CH2
CH3 CH3
3° 2° 1°
9 -H 6 -H 3 -H Zero -H
Maximum stable
Stability order I > II > III > IV
 Stability of alkenes : More hyperconjugation structures (more -H) more stable alkene.
(
i
) C H 3— C H CH2 > CH 2 CH 2
3 -H Zero -H
more stable
(
ii
) Stability order of alkenes will be
CH3 CH3 CH3 CH3 CH3 H CH3 H

C C C C C C C C
CH3 CH3 CH3 H CH3 H H CH3
CH3 CH3 CH3 H H H

C C C C C C
H H H H H H
Question : which of the following alkene is maximum stable.

(i) R2C CR2 (ii) R—CH C—R2 (iii) R—CH CH—R (iv) R—CH CH2
Ans. (i) due to more substituted alkene.
E 83
Chemistry
 Heat of hydrogenation :
R—CH CH2 + H2 R—CH2—CH3 + H (Heat of hydrogenation)
Heat evolved when any unsaturated hydrocarbon are hydrogenated is called heat of hydrogenation (H)
If alkene is more reactive towards hydrogen then it will evolve more H.
1 1
So, Heat of hydrogenation  
stability of alkene number of  H
Question : Which of the following has minimum heat of hydrogenation.

(i) ethene (ii) Propene (iii)cis-2-butene (iv) trans-2-butene
Ans. (iv) maximum stable alkene means minimum reactive.
Question : If Heat of hydrogenation of 1-butene is 30 Kcal then heat of hydrogenation of 1,3-butadiene is ?
(i)30 (ii)60 (iii)57 (iv) 25
Ans. (iii) 1,3-butadiene requires two moles of hydrogen so heat of hydrogenation should be 60 Kcal but
1,3-butadiene is stabilized by resonance than propane so heat of hydrogenation of 1,3-butadiene
will not be twice of 30.
Actual H - 60 > H > 30 Kcal.
Question : Which of the following is maximum stable.
(
i
) Conjugated alkadiene (CH2 CH—CH CH2)
(ii
) Isolated alkadiene (CH2 CH—CH2—CH CH2)
(iii) Cumulated alkadiene (CH2 C CH2)
(iv) All are equal.
Ans. (
i
) Due to resonance conjugated alkadiene is maximum stable. Isolated is more stable than cumulated
alkadiene due to H-effect.
 Reactivity of Benzene : H-effect of R groups increases electron density in benzene ring.

H H

C H  C H
H 
H
due to CH3 group there is more e– density at ortho and para position so CH3 is ortho/para directing and
activating group.
If H-effect is more than e– density will be more.
Example : Give electrophilic sustitution reaction order :
Maximum -H.
So maximum H-effect
So maximum e– density
So maximum reactive
ESR order I > II > III > IV
84 E
JEE – MAIN
4 ELECTROMERIC EFFECT : (E Effect)
It is a temporary effect. The organic compounds having a multiple bond (a 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. The effect is annulled
as soon as the attacking reagent is removed from the domain of the reaction. It is represented by E and the
shifting of the electrons is shown by a curved arrow ( ). There are two distinct types of electromeric effect.
(
i
) Positive Eelctromeric Effect (+ E effect) : In this effect the  -electrons of the multiple bond are
transferred to that atom to which the reagent gets attached. For example :

C = C + H+ C–C
(attacking H
reagent)
(ii
) Negative Electromeric Effect (-E effect) : In this effect the - electrons of the multiple bond are
transferred to that atom to which the attacking reagent does not get attached. For example.
C = O + CN C–O
(attacking CN
reagent)
HCN   
CH3 C H  CH3 C H H2O
CH3 C N  CH3 C N
,

O O
TYPE OF REACTIONS
Mainly reactions are of four types :
1. Substitution reactions. 2. Addition reactions.
3. Elimination reactions. 4. Rearrangement reactions.
1. SUBSTITUTION REACTIONS : Reactions in which one atom or a group of substrate is replaced by other
atom or group are called as substitution reactions.
on the basis of attacking species, substitution reaction is also of three types :
(a) Free radical substitution reactions
(b) Electrophilic substitution reactions
(c) Nucleophilic substitution reactions
(a) Free radical substitution reactions :- These reactions are brought about by the attack of free radicals.
Example : (
i
) Halogenation of alkane :
h
CH4 + Cl2   CH3Cl + HCl
Mechanism : reaction occurs in three steps :
I Chain initiation step :
 
h
Cl2  C l  C l
E 85
Chemistry
I Chain propagation step :
 
CH 4  C l  C H 3  HCl
 
C H 3  Cl2  CH 3  Cl  C l
(major product)
III Chain termination step :
 
C l  C l Cl2
 
C H 3  C H 3 CH3 – CH3 (minor)
 
C H 3  C l CH3 – Cl
(ii
) Allylic or benzylic substitution by NBS or by Br2/h.
Br2 CH2 CH CH2 + HBr

CH3 CH CH2 
h
Mechanism : Br
 
h
Br2   Br + Br
 
CH3—CH CH2 + B r  C H 2 —CH CH2 + HBr (stable by resonance)
 .
C H 2 —CH CH2 + Br2  CH2 CH CH2 + Br
Br

(Product)
(b) Electrohilic substitution reactions (ESR) :- These are brought about by the attack of a electrophiles.
Example : (i) Nitration of benzene.
(ii) Reaction of Grignard reagent with active –H.
(i) Nitration of benzene :- formation of nitrobenzene
conc HNO + conc H SO

NO2

3 2 4
(Nitrating mixture or nitrating agent)
Mechanism :
(i) Formation of electrophile :

..  
HO NO2 + H H2SO4 H–O NO2  H2O + NO2
H electrophile or attacking species.
86 E
JEE – MAIN
(ii) Attack of electrophile (E+) on benzene :
H  NO2
NO

2
H

intermediate
(iii) Removal of H+ :
NO2  NO2
H 
–H

 In nitration attacking species is nitronium ion (NO2+).
 In nitration H2SO4 is Bronsted acid while HNO3 is Bronsted base.
(c) Nucleophilic substitution reactions (NSR) : These are brought about by the attack of a nucleophile.
In nucleophilic substitution reaction a weaker nucleophile is replaced by stronger nucleophile.

Example : OH 
R X  R OH + X
 
weaker stronger
nucleophile nucleophile
NSR are of two types
(i) SN1 : In these reaction the rate of reaction depends only upon concentration of the substrate and not
upon the attacking nucleophile.
CH3 CH3

OH 
Example : CH3 C Cl  CH3 C OH + Cl
(hydrolysis)
CH3 CH3
Mechanism : SN1 reaction occurs in two steps :

(a) Formation of carbocation :
CH3 CH3
Slow step 
CH3 C Cl  CH3 C + Cl

Example : (Rate determination step)
CH3 CH3
(b) Attack of OH on C:
CH3 CH3
  fast step CH3 C OH
Example : CH3 C + OH 
CH CH3
3
 Rate of reaction  concentration of 3° halides.

 Order of reaction is 1, so reaction called as SN1
 In SN1 reaction intermediate is carbocations so rearrangement can take place.
CH2 Cl SN
1 OH
– CH3
OH
 In SN1 reaction intermediate is carbocations so if substrates has chiral carbon atom (optically
active) then product will be racemic mixture, (opitically inactive).
E 87
Chemistry
(ii) SN2 : Bimolecular subsitution reaction.

 
CH3—Cl + OH CH3—OH + Cl
Mechanism : SN reaction occurs in one steps :
2
H H break H
 
HO + C Cl  H C Cl  OH C
Example : 
H H form H H H H
Transition stage

 Rate of reaction  [OH] [1° halides].
 Order of reaction is 2, so reaction called as SN2
AROMATIC NUCLEOPHILIC SUBSTITUTION :
(i) Decomposition of diazonium salts in polar medium and formation of various products in presence of various
nucleophiles.
 
N N + N2
HO

2
Ph OH
 
Cl
 Ph Cl

CN
 Ph CN
(ii) Aryl halides activated by strong electron withdrawing groups from o– or p– positions undergo substitution
reaction by nucleophile.
Cl OH


OH
 + Cl
[NaOH]
high temp.
NO2 NO2

Mechanism :
Cl
Cl OH

OH 
+ 
slow step
O N O O N O
There is very much positive Stable by resonance by
charge on carbon due to –M NO2 group
of NO2 and –I of Cl.
OH
Cl OH
 fast

 + Cl
O N O O N O
If there is no strong –M group (like NO2) on benzene ring then displacement is carried out only in presence
of very strong bases such as NaNH2/liq. NH3.
 
C6H5Cl + NH2 
liq. NH 3
 C6H5NH2 + Cl
88 E
JEE – MAIN
NSR in Acid derrivatives :
Example : Hydrolysis of acid derrivatives :
Nu
 
Nu –Z
R C Z  R C Z  R C Nu

O O O
Where Z —Cl, —OR, —NH2, O C R

O
here Z is a good leaving group then H and R as in carbonyl compounds, so carbonyl compound
does not shows NSR.
2. ADDITION REACTIONS : It is also of three types :

(a) Free radical addition reactions
(b) Electrophilic addition reactions
(c) Nucleophilic addition reactions
(a) Free radical addition reactions :- Addition of HBr on alkene or alkyne in presence of peroxide.
HBr( )
CH3—CH CH2 
ROOR CH3 CH CH2
H Br
Mechanism :

R—O—O—R 
 2R O
 
R O + HBr ROH + B r
. . .
CH3 CH CH2 + Br  CH3 CH CH2 + CH3 CH CH2
Br Br
2° (more stable) 1° (less stable)

. .
CH3 CH CH2 + HBr   CH3 CH CH2 + Br
Br H Br
(major)
Anti-Markovnikoff's Rule/Anti M.K. Rule/Kharash effect/peroxide effect
 In presence of peroxide negative part of a reagent attack on the sp2 –C which have more H.
 Only HBr shows peroxide effect. Other H-X shows electrophilic addition reaction in presence of peroxide.
Reason :
 Reactivity order of H-X HI > HBr > H-Cl > HF
 Bond energy order H-F > H-Cl > HBr > HI
In case of HCl :
 .
CH3—CH CH2 + C l  CH3 CH CH2
Cl
E 89
Chemistry
. .
CH3 CH CH2 + H Cl  CH3 CH CH2 + Cl
Cl H Cl
Strong weak (endothermic step)
bond bond
In case of Hl :
 
R O + Hl ROH + I

CH3—CH CH2 + I X (No reaction)
 More activation energy  endothermic step.
Question : CH3—CH CH2 
HCl
ROOR
 CH3 CH CH3
Cl
Ans. no effect simple EAR
(b) Electrophilic addition reaction :- Characteristic reaction of alkene is EAR. Due to more e density
in alkene first attack will be of electrophile. There is unsaturation in alkene so there will be addition.
E
  Nu 
>C C  >C C<  >C C<
E Nu E
intermediate addition product
I M
e  philic addition reaction  e – density  
I M
Question : Give reactivity order towards EAR.

(a) (i) CH2 CH2 (ii) CH3—CH CH2
(iii) C H 3 — C H CH—CH3 (iv) CH3 C CH CH3
CH3
reactivity order IV > III > II > I

OH Cl CH3
(b) (i) (ii) (iii) (iv)
reactivity order II > IV > I > III

Cl
Cl2
Example : CH3 CH CH2  CH3 CH CH2
FeCl3
Cl
Mechanism :
 
Cl2 + FeCl3  C l + FeCl4
Cl
 
CH3 CH CH2  CH3 CH CH2  CH3 CH CH2
:Cl 
Cl
• Complete octet
• More stable
• Cyclic halonium ion
• Intermediate
90 E
JEE – MAIN
Cl
+ FeCl
CH3 CH CH2  CH3 CH CH2 + FeCl3
4
+
Cl Cl
 In this reaction intermediate is cyclic halonium ion. So there will be no rearrangement.
Br
Br
Question : CH3 CH CH CH2 
2
CH3 CH CH CH2
CH3 CH3 Br
Anti addition
Marcovnikoff's Rule :- (Old rule) only for unsymmetrical alkene (without rearrangement).
 In addition of alkene negative part of a reagent attacks on the sp2 carbon which have less H.
 In EAR attack of a nucleophile on the sp2 carbon which have less hydrogen.
New Rule :- If there is carbocation as intermediate than nucleophile attack on more stable carbocation (with
rearrangement, only for unsymmetrical alkene).
Question : Which of the following does not follow M.K. rule ?

(i) CH2 CH2 (ii) CH3—CH CH2 (iii) CH3—CH CH—CH3 (iv) CH 3—CH CH—CH 2—CH 3
Ans. (iii) it is symmetrical alkene.
(c) Nucleophilic addition reactions :
 NAR in alkynes
 NAR in carbonyl compounds
Example : Addition of HCN.
H/ R
weak base
R–C + HCN
OH–  H2O
O – +
CN+H
(Nucleophile)
H/ R H/ R H/ R
R–C R–C–CN R–C–CN

+ –
O O H +OH OH
3. ELIMINATION REACTIONS : These reactions are brought about elimination of small molecule from the substrate
Elimination
.–elimination –elimination –elimination

or 1, 1–elimination or 1, 2–elimination
-Elimination (1, 1-Elimination) : Removal of H and X from one C-atom
Example : KOH
CHCl3   :CCl2 (dichloro carbene)
Mechanism :
Cl OH
  Cl
H C Cl 
(KOH)
C Cl + H2O
(acidic H) Cl Cl
E 91
Chemistry
..
Cl
.. –Cl

C ..Cl  :CCl2


Cl
, Elimination (, elimination) : Removal of H and X from adjacent C-atoms
E1 unimolecular elimination

E2 bimolecular elimination
(a) Unimolecular elimination (E1) :-
CH3 CH3
CH3 C Cl + KOH CH3 C + KCl + H2O

CH3 CH2
Mechanism : occurs in two steps –

Step-I Formation of Carbocation :
CH3 CH3
 
slow step
CH3 C Cl 
Rate det er min ation step
 CH3 C + Cl
CH3 CH3
Step-II Abstraction of proton (H+) by base (KOH) :

CH2 H CH2

 OH
CH3 C  CH3 C
–H2O
CH3 CH3
Fast step (Alkene)
 Rate of reaction  (3° halide)
 Order of reaction = 1 (So reaction is called as E1)
 In E1 reaction intermidiate carbocation is formed.
Special point : All the reaction in which intermidiate is carbocation. There will be rearrangement of carbocation

to get more stable carbocation (if possible)
 hydride shifting (H ) 

Example :  CH3 CH CH2  CH3 CH CH3
H
1° (less stable) 2° (more stable)

CH3 CH3

Example : CH3 C CH2 
methylide shifting
 CH3 C CH2 CH3

CH3
1° 3°
H
 
Example : CH C
3 CH2  CH3 C CH3
CH3 CH3
1° 3°
92 E
JEE – MAIN
H H
  
Example : CH CH CH CH  CH3 C CH CH3  CH3 C CH2 CH3
3 2
CH3 CH3 CH3
1° 2° 3°
CH3 H CH3 CH3

  
Example : CH3 C CH CH2  CH C CH CH  CH3 C CH CH3
3 3
CH3 CH3 CH3
1° 2° 3°
(b) Bimolecular elimination (E2) : In this reaction strong bases are used (more than KOH).
Example : Alcoholic KOH/sodamide/Alc. NaOH. + NaOH

R—OH + KOH  R— OK + H2O
 
RO is stroger base than OH due to +I of R.

Alc. KOH
Example : CH3—CH2—Cl + R— O    CH2 CH2
Mechanism :
H
 
CH2 CH2 +RO  CH CH2 + Cl + ROH
Rate det er min ation step 2
Cl
 Rate of reaction 1° halide [RO–]

 Order of reaction = 2 (So reaction is E2)
 In E2 reaction intermediate (carbocation) is not formed. So there will be no rearrangement.
CH3 CH CH3 

Alc.

(KOH )
CH 2 CH—CH 3
Cl
Alc.
C H 3 —CH 2 —C H 2 —C H 2 — C l    C H 3— C H 2— C H CH2
(KOH )
RO 
CH3 CH CH2 CH3  CH 3 — CH C H— CH 3 + C H 2 C H— CH 2 — CH 3
(major) (minor)
Cl
Saytzef's rule : If there are 2 or more alkenes are formed than more substituted (more stable) alkene
is major product.
E1
Example : CH3 CH CH CH3  CH3 CH C CH3
CH3 Cl CH3
E2
 CH3 C CH CH3
CH3
Zn
– Elimination : Cl—CH 2 —CH 2 —CH 2 —Cl 
 ZnCl

2
E 93
Chemistry
4. REARRANGEMENT REACTIONS :These reactions involve migration of a group from one atom to another
in the same molecule.
For example : carbocation rearrangement to form more stable carbocation.
CH3

Example : CH3 C CH2 OH 

H
 (CH ) C CHCH3
3 2
CH3
Mechanism :
CH3 CH3 CH3

H   
Example : CH3 C CH2 OH   CH3 C CH2 H2 O
OH    CH3 C CH2
CH3 CH3 H CH3
CH3 CH3
 H  
methylide
CH3 C CH2   CH3 C CH2 CH3   (CH3)2 C CH—CH3
shifting
CH3 3°
1°
OTHER REACTIONS :
1. CONDENSATION REACTIONS : In these reactions, two different or same organic reactions unite to give
a product with or without elimination of another simple molecule.
For example : Aldol condensation.
(i ) NaOH
2CH 3CHO    CH 3—CH CH—CHO + H 2O
(ii ) 
Mechanism :

H

OH 
CH2 C H 
–H O
CH2 C H
2
O O
CH2 CHO CH2 CHO

 
CH3 C H + CH2 CHO  CH3 C H H
 CH3 C H

O O OH

CH3 CH CH2 CHO  C H 3— C H CH—CHO
H 2 O
OH (Aldol)
94 E
JEE – MAIN
2. ISOMERIZATION REACTIONS : These reaction involves the interconversion of one isomer into the another
isomer.
For example :
(
i
) CH 3 —CH 2 —CH 2 —CH 3 
AlCl3
 CH3 CH CH3
 HCl
CH3
(ii
) CH 3 —CH 2 —CH CH 2 Al (SO )

2 4 3
 CH3 C CH2 + CH3 CH CH CH3
CH3
NaNH
(iii) CH 3 —CH 2—C CH Alc.KOH
 
 CH3 C C CH3  CH3 CH2
2
C C Na
REACTION AT A GLANCE :
S .N. Cla s s o f c o m p o u nd s Typ e s o f re a c tio ns

(i) Alka ne Fre e ra dica l substitution
(ii) Alke ne , a lkyne Ele ctrop hilic a ddition
(iii) Alkyl ha lide Nucle op hilic substitution
(iv) Alde hyde , ke tone Nucle op hilic a ddition
(v) Acid a nd the ir de riva tive s Nucle op hilic substitution
(vi) Arom a tic com p ounds Ele ctrop hilic substitution
E 95

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Read more at www.puucho.

com JEE – MAIN

Old bonds New bonds

n–butyl carbocation Allyl carbocation Benzyl carbocation

CH3 Sec. butyl carbocation

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Tertiary butyl carbocation Tertiary pentyl carbocation

Triphenyl methyl carbocation

n-propyl carbanion benzyl carbanion

(iii) 3° or tertiary carbanion : When negative charge present on tertiary carbon.

 Carbenes are of two types :

H empty unhybridized p–orbital

103° C lone pair of e–

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Orbital structure of singlet carbene

Characteristic of singlet carbene :

 Geometrical shape – bent or V-shape or angular shape.

two unhybridized p–orbital

 Geometrical structure – linear  It is paramagnetic in nature.

 It is also electron deficient so acts as electrophilic reagent.

 Triplet carbene is more stable than singlet carbene

(ii) Neutral electrophiles :- Which possess a electron dificiency.

The star (*) indicates the atom that accept electrons.

Resonating structures are also abmbident nucleophile.

S .No . Electro phile Nucleo phile

1 Accep ts the electron p air Sup p lies the electron p air

6 Usually p ositively charged sp ecie s Usually ne gatively charged sp ecies

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C1() > C2 () > C3 ()

C1() > C2 () > C3 ()

 In alkyl groups megnitude of +I effect  size of alkyl group

In isomeric alkyl group megnitude of +I effect  number of branches.

–CH2CH2CH2CH3 < –CH2–CH–CH3 < –C–CH3

Stability of Carbocation  No. of  Igroups

Ans. Reason : More no. of +I group.

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More No. of +I group.

Acidic and basic strength :

CH3 C OH > CH3 CH OH > CH3 CH2 OH

Question : Ethyl amine is more basic then aniline, why ?

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Ans. C > D > B > A

Question : Which is most basic among the following :

Positions of atomic nuclei in (I) and (II) are same.

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 CONDITIONS FOR RESONANCE :

4. If there is one free e– and one  bond are at alternate position.

CH2 CH CH CH2 Hybrid structure

(Resonating structure) (Hybrid structure)

(Resonating structure) (Hybrid structure)

 RESONANCE ENERGY (R.E.) OF BENZENE :

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+ H2  + 28.6 Kcal.

+ 3H2  + 3 ×28.6 Kcal. (=85.8)

but experimental value is 49.8 Kcal. so,

Resonance energy = Calculated value – Experimental value

= 85.8 – 49.8 = 36 Kcal.

(I) (II) (III)

Example : Compare stability order of :