 :

A B + X Y A X + B Y

 :

(A)

(B)


C + × Z
|V
C .× Z C × + ZW
 |

C + × Z

(A)


C + × Z
C ×Z

C × + Z

(B)

C × Z C + × Z

 [ ] [

1
 (Attacking reagents)

(A)
Electrophilic (electro + philic)
(electron + loving)

(i)

         
H , SO3 H , NO , NO2 , C, CH2
, X , R , C6 H5 N2 , C H2 OH CH3 CH
O
(ii)
(a)
BF3, AlCl3, SO3, ZnCl2, BeCl2, FeCl3, SnCl2, CO2, SnCl4.
(b)

* = O, R C
> C *N
* OCl, R – * – X, * – Cl, CH – C
Mg I 3

(*)
(c)
(d) Reasent with electrophilie centre :
• • • • • • •
H , (H–F, H–Cl, H–Br, H–I), H–O–Cl, H–O–Br, O=N–Cl, O=N–Br, Br–Cl, I–Br
(B)

Nucleophilic (Nucleo + philes)


(Nucleus + loving)

(i)
                 
H, OH, OR, CN, X( I, Br, Cl, F), R, R– COO, NH2 , CH2 –COR, SH, HSO4 , NO3 , RS, CO3 ,
   
CH2= CH, N=N=N.
(ii)

        
H2 O ,RO H,RO  R , N H3 , R  N H2 , R3 N , R S

H, RS

 R , H2 S
   

(iii)
*
R * , CH – CN
* – Li, LiAlH
– Mg – X, R * , R
* , NaBH * CuLi , R
* Zn, R * Cd, Bu *
* AlH
4 3 4 2 2 2 2

(*)

2
 (Ambident nucleophile) :

  ••
Examples :- K—O—N O, NH2—OH, K CN

CH2 C R  CH2 C R

O O

(Amphiphile) :

Examples :-
>C O CH3 C N

1.

2.

3.

4.

5.

6.

7.

 (Electronic effects) :

(1) (2) (3) (4)

 :
 

 3 4 3 4
1
I ∝

H 3
 

(– I)
 (–) I

   
C– C C C Z
3 2 1
(I)

C1() > C2 () > C3 ()

 (–) I

 –I

  
–I OR2 > –NR3 >–NH3 > –NO2 > –SO3H > –CN >
–COOH > –X > –OH > –OR > –NH2 > –C6H5 > –H

(+ I)


(+) I
   
C– C C C Z
3 2 1
(II)
C1() > C2 () > C3 ()
 +I

+I
O
||
– O, – O – C ,

 +I 
– CH3 < – CH2CH3 < –CH2CH2CH3 < –CH2CH2CH2CH3
+I 
CH3

–CH2CH2CH2CH3 < –CH2–CH–CH3 < –C–CH3

CH3 CH3
 I- (Application of I-effect) :
(1)
(a) +I
(b) –I

4
H
 (c)

 

 +I

1

–I

Example : :

CH3
   
CH3 C   CH3 CH   CH CH2   CH3
3

CH3 CH3
3° 2° 1°

+I

(2)
(a) –I
(b) +I
(c)
 I
1

I

CH3
   
Example: (1) CH3 C (2) CH CH3 (3) CH3 CH2 (4) CH3
CH3 CH3
3° 2° 1°

+I

1 < 2 < 3 < 4

  
Example : (1) CH2 CH CH2 CH3 (2) CH2 CH2 CH CH3 (3) CH2 CH2 CH2 CH2 F
F F

–F
F –I
,
1 > 2 > 3

H 5
 :
 :

+
H

e–

(i) –I
(ii) +I
1
 -I 
+I
Example :
(i) CH3 C OH Cl CH2 C OH
O 
O
–H 
 –H 
CH3 C O Cl CH2 C O
O O
–CH3 +I –Cl –I

(ii) CH3 CH2 CH COOH > CH3 CH CH2 COOH > CH2 CH2 CH2 COOH
F F F
–COOH F
F –I
 :
–
OH

e–
+
H

(i) +I
(ii) –I

1
 +I 
–I
Example :

CH3

CH3 C OH > CH3 CH OH > CH3 CH2 OH

CH3 CH3

+I

6
H
 Ex. : Et2 NH > Et NH2 > Et3 N
Sol. 3°
3°

H

H H H H
HH C
C
H C C H
H .. H
N
H C H
H C H
H

   
R3N >R2NH > RNH2 > NH3
( )
(R–)
(i) CH3 – R2NH > RNH2 > R3N > NH3
(ii) C2H5 – R2NH > R3N > RNH2 > NH3

Ex.
Sol. +I
Ex. Cl–NH2
Sol. Cl –I p–d
Ex. -

N N
(A) CH3 – CH2 – NH2 (B) (C) (D) |
CH3 H

Sol. C > D > B > A

Ex.
(A) CH3NH2 (B) CH3CH2NH2 (C) NH3 (D) (CH3)2CHNH2
Sol. (D)
Ex.

OH
OH OH OH
(A) NO2 (B) (C) (D)
NO2 NO2

Sol. (B)

H 7
 (Mesomeric effects) :

 (–M)

 O
CH2 =CH — N
O

 O

CH2 —CH = N
O

 –M

 –M –M

 –M -

–NO2, –CN, –SO3H, – CHO, –COR, –COOH, –COOR, –COX, –CONH2

 (+M)

..
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

 +M

 +M

 +M

– O , –NH , –NR2 , –NHR, –NH2 , – OH, –OR, –SH – SR, – F, – Cl, – NHCOR , –O–COR

8
H
 

(i)

(ii)

(iii)

(iv)

(a)

O O
|| | 
: :

R – C – O –H R – C = O –H
(I) (II)

3 3
O OH
|| |
CH3 – C – CH3 CH3 – C = CH2
1 1
(I) (II)

(I) (II) (I) (II)

(b)

•• • •• •• • ••
• •
O=N—•
O • O—N=O
•
•• 
• 
•• ••
Total number of Total number of
paired electrons = 16 paired electrons = 16
unparied electron =1 unparied electron =1

(v)

Example :


NH3 NH3
 Nitrogen does not follow its octet rule
hence (II) is not resonating structure (I)

I II
 (Conditions for Resonance) :
1.  –  (I–
)

H 9
 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. 

Example :
..  
(i) CH2 CH OH  CH2 CH OH

 
CH2 CH CH2  CH2 CH CH2
(ii)

..  
(iii) CH
2 CH O CH3  CH2 CH O CH3

 
CH O  CH2 CH O
(iv)
CH2

3.  
 
Example : CH2 CH CH2  CH2 CH CH2

Note : CH2 C H EN 
O
4. 
Example :
. .
(i) CH2 CH CH2 CH2 CH CH2

(ii) . .
CH3 CH CH CH2  CH3 CH CH CH2

5.

 .. 
Example : CH2 OH  CH2 OH
 :
(i)
(ii)
(iii)
(iv)
(v)

10
H
  :

..     ..
OH OH OH OH OH
1.  
  


5-

 
 CH2 CH2 CH2
CH2  CH2
2.    


5-

  
CH2 CH2 CH2 CH2 CH2
3.  
 
 

5-


C H C H C H C H C H
4.        
O O O O O

5-

. . .
. CH2 CH2 . . CH2 . .CH2 CH2
5. .  . . .   
.

5-

 

6. ..        ..

   
N N N N
N N
H H H
H H H

6-


..  NH2  ..
NH2 NH2 NH2 NH2
7.      


5-
 :
   
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 III
I C1 – C2 II III C 1 – C2 C 1 – C2
I C2—C3 II III C2—C3 C2—C3

H 11
 CH2 CH CH CH2
Example :
 
..    
(i) CH2 CH OH  CH2 CH OH CH2 CH OH
I II
 
   
(ii) CH2 CH CH2  CH2 CH CH2 CH2 CH CH2
1 2 3 1 2 3

 (Resonance energy) :

 (Resonance energy (R.E.) of Benzene) :



+ H2  + 28.6 Kcal.

+ 3H2  + 3 ×28.6 Kcal. (=85.8)

= 49.8 Kcal.
R.E. = –
= 85.8 – 49.8 = 36 Kcal.
 (Application of M- effect or Resonance effect) :
:
(a)
(b)
Example : :-
  
(i) CH2 CH CH2 > CH3 CH2 CH2 > CH2 CH CH CH2
+I –I
 
(ii) CH2 <  < CH3

1° 2° 3°
  
(iii) CH2 CH2 CH2


Re sonance increases,stability increases



  
(iv) , ,

II > I > III

12
H
  :
(a)
Example : :-
  
(i) CH2 CH CH2 , CH2 CH , CH3 CH2
EN
I > II > III

 
(iii) , ,

II > I

  
(v) CH2—NO2 CH2—CH2—NO2 CH3— CH—NO2
CH3 +I
I > III > II

(a)
Example : :
. . .
(i) CH2 CH CH2 CH2 CH CH2 CH CH CH CH2

III > I > II

. . .
(ii) , ,

II > I > III

:


Example : H C O  H C O

O O

 
Example : CH2 CH O CH2 CH O

 .. 
CH2 OH  CH2 OH

Note :

H 13
 :
(a) :-
1 1
 M   I  
M I

Ex.

Sol. R C OH OH
O




 
–H –H



R C O R C O O O


 
O O

Ex.

Sol. Ph OH R OH



 
–H –H

Ph O R O

(b) :

1 1
 M   I  
M –I

Ex. :
.. .. ..
NH2 CH2 NH2 NH CH3
(i)

CH3 +I
— II > III > I

NH2
(ii) .. ..
N N
H

EN
— III > II > I

14
H
 Ex. :
.. .. ..
NH NH2 CH2 NH2
(i) (ii) (iii)

Sol. iii > ii > i

Ex. ?

Sol.

Ex : :
(i) C6H5—CH2—NH2 (ii) C6H5—CH2—NH—CH3 (iii) O2N—CH2—NH2 (iv) CH3—NH—CHO
Sol. (iv)

7. : (ESR)

  
E -H
 H  (product)
E E

8. :

(i)

(ii)

(iii) EN

Example :
   
(i) CH2 CH Cl CH2 CH Cl CH2 CH Cl

– 1> 2 > 3

 
(ii) R C OH  R C O H  R C OH
O  
O O

 
(iii) R C O < R C O

(Acylium ion)
 
(iv) CH2 CH O > CH2 CH O

EN EN

H 15
Ex : :–
   
CH2 CH2 CH2 CH2

(i)

NO2 Cl CH3 OCH3

–M
–I +I M
   

IV > III > II > I

   
CH2 CH2 CH2 CH2

(ii)

NO2 Cl CH3 OCH3

–M M
–I +I
   

I > II > III > IV


  CH2 
CH2 CH2 CH2
(iii) NO2
NO2
NO2

–M M = 0 –M

–I –I –I

I > III > II > IV

Ex : :

OH OH OH OH

NO2 Cl CH3 OCH3

–M –I +I +M
Sol. I > II > III > IV

Ex.

Sol.

16
H
 Ex.
(i)
OH OH OH OH
CH3
CH3
CH3







   
–H –H –H –H

 
O O

O O


CH3
CH3
CH3
+I H = 0 +I
CH3 H- +I H-

4>2>3>1

OH
OH
NO2 OH OH
NO2 NO2 NO2
(ii)

NO2 NO2

–M

–I

1 > 2 > 3 > 4

Ex. :

NH2 NH2 NH2 NH2

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

NO2 Cl CH3 OCH3

–M –I +I +M

IV > III > II > I

Ex.
Sol. 36 76
85

H 17
 Phenol : 9.98/1.10 × 10 –10 pKa/K a value
Sub tituent O– M– P–

(i) Me 10.28/0.63 × 10–10 10.08/0.98 × 10–10 10.14/0.67 × 10–10

(ii) NO2 7.23/600 × 10–10 8.40/50 × 10–10 7.15/690 × 10–10

(iii) F 8.81/15 × 10–10 9.28/5.2 × 10–10 9.98/1.1 × 10–10

(iv) Cl 8.48/77 × 10–10 9.02/16 × 10–10 9.38/6.3 × 10–10

(v) CH3–O 9.98/1.05 × 10–10 9.65/2.24 × 10–10 9.38/0.62 × 10–10

(vi) OH 9. 4 8 9.44/3 × 10–10 9.96

(vii) NH2 9.71/2.0 × 10–10 8.16/68 × 10–10 10.30

(viii) Br 41 × 10–10 14 × 10–10 5.6 × 10–10

(ix) I 34 × 10–10 13 × 10–10 6.0 × 10–10

(x) 2.4- dinitrophenol 4. 0 0

(xi) 2,4,6-trinitro phenol pKa = 0.71 10.50 × 10–2

OH
Me Me
10. 6 0

OH
Me Me
7. 2 2
NO2

OH

10. 1 7
Me Me

OH

Me 8. 2 5
Me
NO2

18
H
 pK a/Benzoic acid  4.20

Substituent pK a – O– M– P–

H 4.20 4.20 4.20 4.20

Me – 3.91 4.27 4.37

NO2 – 2.17 3.48 3.43

F – 3.27 3.87 4.14

Cl – 2.94 3.83 3.98

Br – 2.85 3.81 4.00

OMe – 4.09 4.09 4.47

OH – 2.98 4.08 4.58

NH2 – 4.92 4.72 4.98

–COOH – 2.98 3.46 3.56

H–COOH 3.77

CH3–COOH 4.76

CH3–CH2–COOH 4.88

HOOC–COOH 1.23

HOOC–CH2–COOH 2.83

HOOC–(CH2)2–COOH 4.19

Maleic acid 1.92 (pKa1) 6.23 (pKa2)

Fumaric acid 3.02 (pKa1) 4.38 (pKa2)

CHC–COOH 1.84

CH2=CH–COOH 4.25

F–CH2–COOH 2.57

Cl–CH2–COOH 2.86

Br–CH2–COOH 2.90

I–CH2–COOH 3.16

O2N–CH2–COOH 1.68

Me3N+ –CH2–COOH 1.83

NC–CH2–COOH 2.47

EtOCOCH2COOH 3.35

MeO–CH2–COOH 3.58

H 19
 pK a /K a value-Aniline  4.62
Sub tituent O– M– P–

Me– 4.39 4.69 5.12

Me–O 4.49 4.20 5.29
NH2 4.47 4.20 6.08
NO2 –0.29 2.50 1.02
Cl 2.64 3.34 3.91
Br 2.60 3.51 3.91
OH 4.72 4.17 5.30

O
••
–NH–CH3 4.85 CH–C–NH2 ~0.5

O
CH3 C
–N shown some
CH3 5.06 N–H
C acidic nature
O

–NH–C2H5 5.11

C2H5 NH2
Ph–N 6.56 NH=C 13.6
C2H5 NH2

Ph2NH 0.9

NH
Ph–NH–AC 0.4 CH3–C 12.4
NH2

NH2
Me Me
5.69 (C2H5)2NH 10.93

Et3N 10.88
Et–NH2 10.67
H3C CH3
N
HO2C NO2
4.60 NH3 9.25
NO2
Me3N 9.80
Me2N 10.77
Me–NH2 10.64

20
H
 10.50 Bu3N 9.87
N
Bu2NH 11.28
BuNH2 10.61

NH–CMe3
7.1 5.23
N

N –0.27 N 11.22
H H

N 2.53 4.94
N
H N

N
N 7.03 5.2
N
H

 (Hyperconjugation effect or H-effect) :

–C–H   H–

 H- :

1. C–H  H–


H H H H
 
H C CH2  H C CH2  H C CH2  H 
C CH2

H H H H

 –C  –C  – H
–H
2. sp2 C –C -C -H
C–H  H-

.
H H H H
 . .
H C CH2  H C CH2 H C CH2  H C CH2
.
H H H H

H 21
3. –C–H   H-


H H H H
    
H C CH CH2  H C CH CH2  H C1 CH
2
CH2  H C CH CH2
3 1 2 3
1 2 3 1 2 3
 H
H H H

(i) H3 C CH CH2
1 2 3

C1—C2 = 1.54 Å
C2—C3 = 1.34 Å.
1.54 > b.l. > 1.34 Å
H
CH2 CH—CH CH2 CH3—CH CH2 CH3—CH3 ,
III > II > I
I
(ii) M, H I
M > H > I
Note : –C–H  H-

H

H C CH2 (No H - effect)
H

C–H 
 (Application of H-effect) :
(Stability of carbocation) :
 M, I H-
 ( -H)
   -H

Ex.

CH3
  
(i) CH3 C > CH3 CH > CH3 CH2 > CH3
CH3 CH3

9 -H 6 -H 3 -H Zero -H

 
CH3 
CH2
(ii) > >

22
H
  (Stability of carbon free radicals) :

 M H-

 (-H )

Ex :

CH3
. . .
CH3 CH .
(i) CH3 C CH3 CH2 CH3
CH3 CH3
3° 2° 1°
9 -H 6 -H 3 -H Zero -H

I > II > III > IV

 (Stability of alkenes) : -H )

(i) CH3—CH CH2 > CH2 CH2
3 -H ( -H
(ii)

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

Ex :
(A) R2C CR2 (B) R—CH C—R2 (C) R—CH CH—R (D) R—CH CH2
Sol. (i)

 (Heat of hydrogenation) :
R—CH CH2 + H2  R—CH2—CH3 + H

1 1
H  
 –H

Ex :

(i) (ii) (iii) -2- (iv) -2-

Sol. (iv)

H 23
Ex : 1- 30 Kcal 1, 3-
(i) 30 (ii) 60 (iii) 57 (iv) 25

Sol. (iii) 1,3- 2 60 Kcal

1,3- 60 Kcal
60 Kcal 30 Kcal

okLrfod H - 60 > H > 30 Kcal.

Ex :

(i) (CH2 CH—CH CH2)

(ii) (CH2 CH—CH2—CH CH2)

(iii) (CH2 C CH2)
(iv)
Sol. (i) H-

 (Reactivity of Benzene) : R H- (ed)


H H
C H  C H
H 
H

—CH3 H–
CH3

H- (-H )
Ex. :

-H
H-
e–

I > II > III > IV

 (E– ) :

24
H
 (i) +E 
:


C = C + H+ C–C
( H
)

(ii) –E 

C = O + CN C–O
( CN
)
HCN   
CH3 C H  CH3 C H H2O
CH3 C N  CH3 C N
,

O O
 (Aromaticity) :

 

(36 / 151
/ )

(a) p
(b) p 
(c)

(i)  (  )

 p
 p p

(ii)  
H 25
 p 


 1931
4n + 2
 (4n + 2) 
n 2(n = 0), 6(n =1), 10 (n =2), 14
(n = 3), 18 (n = 4), 
1, 3, 5, 7, 9, 




135°
sp2 120°

cyclobutadiene benzene [6] cyclooctatetraene

[4]-annulene -annulene [8]-annulene

? p
sp2 sp p

+ –
:

Cyclopropene Cyclopropenyl cation Cyclopropenyl anion

p 
  
( )
+ +

+
resonance contributors for the cyclopropenyl cation

+ +

+
resonance hybrid

26
H
  ( )
p sp3
 ( ) p

cycloheptatriene cyclopentadiene

(5- ), (7- ) (9- )

naphthalene
phenanthrene chrysene

::
::
:

N N O S
:

H
Pyridine pyrrole Furan Thiophene

(4n + 2) - sp3
sp3
6 -
 (Reaction Intermediates) :
:
(i) (ii)
(iii) (iv)
(v) (v)
 : 'C'

Classical Non classical

Note :
 
IUPAC CH3, CHCH
3 2 (
 
) CH3, CHCH
3 2

( )
H 27
 (carbenium ion) :

1. :

sp2 'p'

120°

C
2
sp

2. : :

(i) + I (ii) + M (iii) -


3. –C ( ) :

(a) :( )

Cl  
 –Cl
(i) (CH3)3Cl (CH3)3C + Cl 1
(ii) CH2=CH–CH2  CH2=CH–CH2

(b) :

H  H 
(i) –CH=CH–  –CH CHCH –CH2–

H

••
H
(ii) >C=O
••

••

–C–O
••


H
(iii) –CN
••

–C=N–H
(c) :

 –H2O 
••
H
(i) R–CH2–O–H
••
R–CH2–O–H R–CH2
H

R R

H
(ii) R–O R–O–H R + H–O–R


O O O

H 
(iii) R–C–O–R R–C–O–R R –C+H–O–R
H

(d) :

AlCl3   –AlCl 
(i) CH3–CH2–Cl CH3–CH2–Cl......AlCl3 4
CH3–CH2

O
    
AlCl3 –AlCl ••
(ii) R–C–Cl R–C–Cl......AlCl3 4
R–C=O R–CO
••

••

28
H
 (e) :


(i) CH3–N2 – Cl CH3+N2 + Cl




N2Cl


(ii)  +N2 + Cl

(f) :


FSO3H–SbF5
H –H2
(i) CH3–H + H+ CH3 CH3 + H2
H

Methonium ion (Classical) C

FSO3H  SbF5
(ii) CH3–CH3 + H+   C2H5+ + H2


CH3 CH3
FSO3H
H + H   CH3
+ +
(iii) CH3 C  SbF5
C + H2

CH3 CH3

4. ( ) :

(a) :

H
+
(i) H
+ –H
C CH2 H C = CH2

H H

(b) :

–Nu
R ––– CH2 R ––– CH2–– Nu

Cl
–
Cl
(i) CH3 ––– CH2 CH3 – CH2

(c) :
(i) CH3 + CH2 = CH2  CH3 – CH2 – +CH2
+

CH3 CH3 CH3 CH3

(ii) CH3 –– C = CH2 + +C –– CH3 CH3 –– C — CH2 —C –– CH3

+

CH3 CH3

H 29
 (d) :

H
 
(i) : CH3––CH––CH2 CH3 –– CH –– CH3

CH3 CH3

(ii) : CH3 –– C –– CH2 CH3 –– C — CH2 –– CH3


CH3

Ph CH3
(iii) : (CH3)2C –– CH
2 CH3 –– C –– CH2


Ph- > > Me-

(e) :

CH3 CH3 CH3 CH3 CH3 CH

 
CH3 –– C –– CH2 –– C H –– C –– CH3 CH3–– C –– CH2 –– CH + C –– CH3

CH3 CH3 CH3 CH3 CH3 CH3

 (Carbanion) :
(1)

eg : CH3 ,

CH3 – CH2 ,

(CH3 )2 CH

(2) :

(a) (sp3) ( )

C
C

(b) (sp2) (–ve  )

2
sp 120°
C

'p'

30
H
 Example :
–
sp2

(i) CH CH – CH (ii)
2 2

sp2
O
–
–
(iii) CH2 (iv) CH2 –– C – H
sp2
sp2

(3) :

(a) –I
(b) –M
(c)
(d)
 (Generation of Carbanion) :
 C–H :
C–H :

(1) C—x = y 'H' (E.N. y > x)

H


O O O
–H2O
R—CH—C—R  R—CH—C—R R—CH C—R
OH
H

(2)  C—H :


NH2 
(i) CH C—H CH C
–NH3

 
NH2
(ii) CH3 – C C – H CH3 —C C
–NH3

 :

O

R – CH2 –– C R – CH2 + CO2
O

 :
S– S  S
Mg/ether
(i) CH3 – Cl C H3 M gCl C H3  M gCl
Cd
(ii) 2CH3 – CH2 – Cl (CH3 – CH2)2Cd

H 31
 Zn
(iii) 2CH3CH2 – Br (CH3 – CH2)2Zn + ZnBr2
Li
(iv) 2CH3 – CH2 – I CuI
(CH3 – CH2)2CuLi ( )

O O
 
(v) Br –– CH2 –– C –– O – C2H5 Br Zn CH2 –– C –– O – C2H5
Et2O

 (Reactions of Carbanion) :
(1) H+ :
1
CH3 + H  CH4
(2) :

X

C—C 

X
–
––C–––C ––C=C––+ X–

(3) :
:

– – +
O O – MgBr O– H
OH
H – OH
C –
CH3Mg Br + — C – CH3 — C – CH3 + Mg



Br
(4) :
(i) :

O O O O OH


H – C – CH2 OH H
H – C – CH2 C – CH3 H – C – CH2 – CH – CH3

H H
O

OH
 H – C – CH= CH – CH3

Shot cut :

O H O H

H OH
H – C – CH H – C – CH= C – CH3
H O = C – CH3 

(ii) :
O O O O O

EtO 
CH3 – C – EtO EtO – C – CH2 C – CH3 EtO – C – CH2 – C – CH3

OEt OEt
O O

CH3 – C – CH2 – C – OC2H5

32
H
 ( iii ) :

H O H O
O
H – +
CH3–C–ONa
C=O CH – C C – CH3 C = C – C – OH
H
O O H

(iv) :

O
H N
(C2H5 – O – C)2C O = C – Ph Ph – CH = C(COOC2H5)2
H
H

(v) :

O O
– +
Et O Na
Ph — CH2 – C – CH2 Ph — CH2 — CH2 — C — OEt
Cl

(vi) :

O O O O O
– –
Et O Na OH/HO
EtO – C – CH2 – Br + Ph – C – H Ph – CH — CH – C – OEt H/
2
Ph – CH2 – C – H

( vi i ) :

H O OH
KCN
C=O EtOH C – CH Benzoin

( vi ii) :

O OH O
  –
EtO
CH2 = CH – C – CH3+ CH2(COOEt)2 EtOH
CH2 — CH = C – CH3 CH2 — CH2 – C – CH3
CHCOOEt CH(COOEt)2

( i x) :

CH3 CH3
DM SO
CH3 – C = O CH2 = PPh3 CH3 – C = CH2 + Ph3P = O

(x) :

OH O O
NaOI NaOH – +
CH3 — CH — R' CH3 — C — R' I2
CHI3 + R' — C — ONa

H 33
 ( xi ) :

O H OH O
Zn/Et2O
CH2 — C — OEt + Ph — C = O Ph – CH – CH2 – C – OEt
NH4Cl/H2O

Br
O
Ph – CH = CH– C – O – Et

( xi i) :

O O O
HCl
CH3 – C – CH2 – H + CH2 – + H–NR2 [CH3 – C – CH2– CH2– CH2–NR2] HCl

(xiii) :

O
 
C – OEt EtONa
O
C – OEt C – OEt
O O

 (Carbon free Radical) :

(1)
(CARBON FREE RADICAL)

– C–

(2) :
, sp3
; sp2
Note :

(3) :
(a) ( ) :
• •
(i) CH3 + CH2CH2–CH3 CH3 CH2CH2–CH3
• •
(ii) CH3 – CH2 + CH2 – CH3  CH3 – CH2 – CH2 – CH3

(b) :

H
• •
(i) CH2 – CH2 + CH3 – CH2 CH2 = CH2 + CH3 – CH3

•
(ii) 2CH3 – CH – CH3  CH3 – CH = CH2 + CH3 – CH2 – CH3

(c) :

(i) CH•3  H – H  CH4  H•

34
H
 •
(ii) CH3 – C H2  H – H  CH3 – CH 3  H•

(d) :
•
(i) CH•3  CH2  CH2  CH 3 – CH2 – C H2
• •
(ii) CH3 – CH  CH2 
C H2
 CH3 – C H – CH2 – CH 3

(e) :

•
(i) CH3+Zn Zn CH3
CH3


(ii) C H 3  Hg  (CH 3 )2 Hg


(iii) C H3  Sb  (CH3 )3 Sb

(f) :

  
CH2 CH2
CH3 + CH2 = CH2 CH3 – CH2 – CH 2   CH3 – CH2 – CH2 – CH2 – CH 2

CH2 CH2 CH2 CH2
  CH 2 – CH2 – CH2 – CH2 – CH2 – CH2 – CH3  

 (Carbene) :

(1) :

( )
(2) : ,

(i) (—C—)

(ii) (—C—)

(a) :

(i) sp2

(ii) sp2

sp2
C

(iii)
(iv)
(v) M = 2S + 1
S = (+1/2) + (–1/2) = 0 M = 2 × 0 + 1 = 1
H 35
 (vi)
(b) :
(i) 'p'
(ii) 'sp'

(iii)
(iv)

µ= n(n  2) = 2(2  2) = 2 2 Bohr magnaton.

(v) M = 2S + 1 = 2 (+1/2 + 1/2) + 1 = 3

(vi)
(3) :

(i) CH2  N  N  

 : CH2


(ii) CH2  C  O   : CH2

R R

(iii) C=C=O C:
R R

(iv)

Cl Cl
–
OH
Cl C —H –H2O
Cl C– Cl – C – Cl
Cl Cl
(v) CCl4 + LiR –  R – Cl + LiCCl3, LiCCl3  Cl – C – Cl
(vi) CH2Cl2 
LiR
 : CHCl
(4) :
(i) :

H O O
•• ••
H–OH –HCl OH2
••

Cl – C – Cl Cl – C – Cl H – C – Cl H— C — Cl

O– H O– H
O O H


OH –HCl
H– C– O H– C– O– H

36
H
 Cl – C– – Cl H H
H–NH2 NH3 NH3
(ii) Cl – C – Cl H— N+ — H Cl — C — Cl Cl — C = N H—C N
H N– H H
H

(5) CAR :

 CCl 
(i) : R – NH2 
 2
CHCl3 / KOH

 R–NC

O O
SOCl2 H2O
(ii) : R – C – OH R – CH = C = O Ag2O R – CH2 – C – OH
CH2N2

OH OH O

CCl2 C–H
( iii ) : CHCl3/KOH

 (Benzyne) :

(1) :

(2) :

(i) sp2

(ii) sp2  

(3) :

(i) :

Cl Cl
–NH3
–NH2 ––
H

(ii) :

Cl
Li
+ Li Br + LiCl
Br

H 37
 O
C — O–
( iii ) +
N N

O
C — O–

+
+ N2 + CO2
N N

(4) :

–
NH2 – NH2
NH2 –NH2
(a) –– H –NH2

O – CH3 O – CH3

(b) NaNH2
NH3
NH2

CH3 CH3
OH
(c) NaOH
H–OH

 (Nitrene) :
(1)
(unidogeh), ,

H– N R– N

(2) :
hv
(i) H – N3 N2 + R – N
O
(ii) hv
R – C – N3 N2 + R – C – N
hv
(iii) H– N= C=O CO + H – N

(3) :
(i) :

(a) CH2=CH2
H– N CH2 —— CH2
N
H

(b) H– N N– H

38
H
 (c) C2H5 – C = CH2 C2H5 — C — CH2
N N

(i) :

O O O
H H
Br2

OH –
R– C – N R– C —– N R– C —– N — Br
H Br

(ii) (HCLS ):

O
H2N–OH H3O
( iii ) : R– C – Cl AcCl
R– N = C = O R– NH2

O

H2SO4 H3O
(iv) : R– C – OH R– N = C = O R– NH2
H–N3

(b) : R – N3 :

O O O
NaN3  H2O/H+
R– C – Cl R– C – N3 –N2
R– C – N R– N = C = O –CO2
R– NH2

(c) :

R R R
–N2
 ••
N
N3 N

( iii ) :

O O O H
(a)  H–CH2–R
C2H5 – O – C – N3 –N2
C2H5 – O – C – N C2H5 – O – C – N – CH2 – R

O O O H
(b)  H–CH2–CH2–CH3
C2H5 – O – C – N3 C2H5 – O – C – N C2H5 – O – C – N – CH2 – CH2 – CH3
–N2

O H
+ C2H5 – O – C – N – CH– CH3

CH3

–N2 H
(c)

N3 N N
H

H 39
 (iv) :

Ph Ph Ph Ph
N3 N N=N
–N2


 (Types of Reactions) :

(I)

(II)

(III)

(IV)

(I) (Substitution Reaction) :

 (Electrophilic Substitution Reactions) :

COOH
H E
–H+ E+ CO2
+
AlCl3

NO2
C – Cl
NO+2 COCl2
O
HNO3 + H2SO4 AlCl3

SO3H O = CH

SO3 CO + HCl
H2SO4 or H2SO4 +SO3 AlCl3

Cl CHO

Cl
+
BEN ZEN E HCN + HCl + ZnCl2
+
Cl2 + AlCl3 H3O

O
CH3
+ I C – NH2
CH3 +
CH3Cl+ AlCl3 I Cl – C – NH2/AlCl3
CuCl2 + I2
O
I2 + 2Cu 2I +2Cu
2+ + +

O = C – CH3 or I2/HNO3 ; HIO3 or H2O2 O O = C – Ph

+
CH3 – C = O Ph – C – Cl + AlCl3
CH3–C–Cl+AlCl3
O CH2–Cl
HCHO+HCl+ZnCl2

40
H
  (Nucleophilic Substitution Reaction) :
SN1 SN2 , :

(1) SN2 : -
  1
CH3Br + OH CH3OH + Br = K [CH3Br] [OH ]
 – –
HO–C–Br –Br
HO–C–Br HO–C– + Br –

C6H13 C6H13
H–C–Br NaOH
HO–C–H (RI > RBr > RCl > RF)
SN2
RI
CH3 CH3

(–) 2- ( ).
SN2

SN2 DMF DMSO SN2

CH3OH, C2H5OH

H H Br CH3
H–C–Br CH3–C–Br CH3–C–CH3 CH3–C–Br
H H H CH3
–2 –4
37 1.0 2 ×10 8 ×10

SN2 1° > 2° > 3°

1 1  1
– HO  R – X  [HO .....R.......X  HO – R  X(.g)

• SN2
 
DMF
R–Br+Cl RCl + Br

CH3 CH3
- CH3CH2Br > CH3CHCH
2 2Br > CH3–CH–CH2–Br > CH3–C–CH2–Br

CH3
–6
1.0 0.69 0.33 6 ×10

 SN2 :

(i) 1°

(ii) 2, =1

(iii) DMF DMSO.

(iv)

(v) RI

(vi)

(2) SN1 :
CH3 CH3
 
CH3–C–Br + OH CH3–C–OH + Br
CH3 CH3
H 41
 = K [RBr]
 1
: R–X  R  X
 1
: R  OH ROH

H2O

C6H13 C H
CH3

C6H13 C6H13
HO–C–H H–C–OH
CH3 CH3
(a) (b)

 SN1 :
(i) = K[RX]

= ,

(ii)

(iii)

(iv) 3° > 2° > 1°.

(v) , RI
SN1 SN2

RI > RBr > RCl > RF RI > RBr > RCl > RF

R3CX > R2CHX > RCH2X > CH3X CH3X > RCH2X > R2CHX > R3CX

; ; 100

42
H
 (II) (Elimination reactions) :

- -

X

–HX
–C–C–

–C=C–
H H
- 1, 2,-

 - :

- E1 ( ) E2 ( )

E2 : :

CH3CH2Br + C2H5O1  CH2= CH2 + C2H5OH + Br1

= K [CH3CH2Br] [C2H5O1]

-
-

s– s+
 H H C2H5O — H H
C2HO
5

H – C —C – H H — CH CH2 C2H5OH + H — C C — H + Br
Brs
–
H Br H

E1 CB : 1, 1, 1 –2, 2
-
C2H5OD  Cl
CF3—CHCl2 CF3—C CF3—CDCl2
Cl

CF2=CCl2
E1 : :

(" ")

H H

–C—C– –C—C–

+X
X
H

–C—C–

–C C– + H
H
=k –C C–
X
H 43
 -

(a) (Saytzeff Rule) : ( )

E1 E2
CH3
CH3 CH3
H2O
CH2=C—CH2CH3 (20%)
CH3–C–CHCH
2 3 E1
CH3–C–CHCH
2 3
 CH3—C=CHCH3 (80%)
Br
CH3

C2H5O1 + CH3CH2 CHCH3  

C2 H5 OH
CH3CH=CHCH3 + CH3CH2CH=CH2
Br
(80% ) (20% ) +

-
:
R2C = CR2 > RCH = CR2 > RCH = CHR > RCH = CH2 > CH2 = CH2

(b) (Hofmann Rule) :

 
( NR3, SR2 ) -

H H

(i) CH3 – C – CH2 – N – CH2 – C – H CH3CH2CH2N —CH3 + CH2 = CH2 + H2O
H H3C CH3 H CH3
OH
H
(ii) KOH
CH3 — CH2 — CH — CH2 C2H5OH
CH3 — CH2 — CH CH2
F

(III) (Addition Reaction) :

A B
A–B
C=C C–C

:
(i) CH2 = CH2 
H2
 CH3 – CH3
Cl
(ii) CH3 – CH = CH2 
HCl
 CH3– CH – CH3

44
H
 Br
(iii) CH3 – CH = CH2 
 CH3– CH2– CH2 HBr
Peroxide

H OH
(iv) CH2 = CH2 
H–OH
H
 CH2– CH2

H OH
H2O  Cl
(v) CH2 = CH2 
 CH2– CH2
HOCl

 (Mechanism of addition reaction) :

(A)

(B)

 ( ):

H
H
H
(i) CH2 = CH2 CH2– CH2  CH2 – CH2
Cl
Cl

 CH3 Cl CH3
C(CH3)3 
Cl
(ii) CH2 = CH2 CH2– CH2–C– CH3 CH2–CH2– C– CH3
CH3 CH3

 :

Br Br H
•
(i) Br• H–Br
CH2 = CH2 CH2 – CH2 CH2 – CH2
–Br•

Br H Br
•
Br• H–Br
(ii) CH3 – CH = CH2 CH3 – CH – CH2 CH3 – CH– CH2
–Br•

Br H Br
•
Br• H–Br
(iii) CH3 – C  CH CH3 – C = CH CH3–C=CH

Br Br Br H
•
•
(vi) Br
•
Br
•
H–Br
•
–Br

 ( ):

 
O O MgCl O– H
(i) H
CH3 – C – H CH3MgCl
 CH3 – C – H CH3 – C – H
CH3 CH3

H 45
 O O O– H
(ii) H
CH3 – C – H CH3 – C – H CH3 – C – H
CN
CN CN
O O – AlH3 O– H
H
(iii) CH3 – C – H CH3 – C – H CH3 – C – H
AlH
3

H H H

Hg2+
Hg2+ H
2+
Hg –Hg
2+

(iv) CH CH CH= CH –CN

CH= CH H
CH= CH
CN CN
Hg2+
 
O O O OH
H •• H
(v) CH3 –C– H CH3 – CH– N H CH3 –CH– N– H CH3 – CH– N– H
:N H
H

H
H H H

H H H

H ••
CH2 =CH–CH=O CH2 – CH=CH– O CH2 – CH=CH– O CH2 – CH– C=O

••
(vi)
Cl
Cl Cl H Cl

 :
CH2
(i) CH2= CH2
:CH 2
CH2– CH2

CCl2
(ii) CH3 – CH= CH – CH3 Cl CH3 – CH– CH – CH3
:C Cl

Cl LiR
(iii) Cl
C Cl
:C Cl

 :

Cl

Cl Cl
Cl
 
(i) Cl2 Cl Cl
CH2 = CH2 CH2 – CH2 CH2 – CH2 CH2 – CH2
CCl4
Cl
Cl

Cl Cl
Cl2 Cl

Cl
 H Cl
(ii) CH  CH CH= CH CH = CH C=C
CCl4 Cl H
(Trans)

H BH2
BH2
H–BH2
(iii) CH2 = CH2 CH2 —CH2 CH3 – CH2

46
H
 H BH2
H–BH2 H BH2
(iv) CH  CH CH —CH C C
H H

CH2 O O CH2–O O CH2–OH

H
(v) + Os Os
CH2 CH2–O CH2–OH
O O O

(IV) (Rearranement reaction) :

 (Beckmann rearrangement) :
H
R R' R R' R' H – O R' HO R' O R'

C  C C ••
C  C C

••
H /H2SO4 H2O –H
N N  N N N N–H
OH O– H R R R R
••

••
••

••

H
H2SO4( .)

 (Bayer-villiger rearrangement) :


O OH O O
OH O OH
 
F3CCO3H O–O–C–CF3 –F3C–C–O
C C CH3 – C–O– O– C– CF3 CH3 – C – O
–F3C–C–OO
CH3 O CH3


OH OH O

CH3 – C – O – –H
CH3 – C – O – CH3 – C– O–


: 3° > 2° > 1° > CH3°

CH3–O– – > CH3– –> – > Cl– – > O2N– –

 :

Me Me Me CH3
O2 H  H ••
Ph–C–H 60°C
Me–C–O–O–H conc. H2SO4
Me–C–O–O –H2O Me–C–O–

H
Me

H2O

OH
O Me H Me
–H
Me– C– Me + Me– C—O – Me–C–O–
–H  +H
••

H– O
•• O

H H

H 47
 (Benzylic acid rearrangement) :

O Ph Ph Ph Ph

KOH
– C– C=O – C– C– O – C– C=O – C – C= O
  
O OH O OH OH O–K
 (Fries rearrangement) :

AlCl3 o- p-
COOCH3 OH OH
AlCl3(Anhydrous) COCH3
+
Heat

COCH3
o- p-

 (Claisen rearrangement) :

200°C
-
O–CH2CH=CH2 OH
CH2CH=CH2
200°C
(Diphenyl ether)

o-

O–CH2CH=CH2 OH
H3C CH3 H3C CH3
200°C

CH2CH=CH2

 :

(i) (Meerween ponndorf verley reduction) :

Al(OPr)i 3
=O i –OH
Pr OH

(ii) (Oppenauer oxidation) :

Al(OBut.)3
–OH (CH ) C=O =O
32

(iii) (Tischenko Reaction) :

O O
Al(OEt)3
CH3 – C – H CH3 – C – O – CH2 – CH3

(iv) (Cannizzaro reaction) :


O O O O O O
50%  
H– C–H NaOH
H– C–H C–H H– C–OH+H– C– H H– C–ONa +CH3 –OH
OH H H

48
H
 SOLVED EXAMPLES

Ex.1 If CH3 CH CHO :

CH3

CH2 CH3 CH3

(A) CH CHO (B) CH CHO (C) C CHO (D)
CH3 CH2 CH3

Sol. : Ans.(C)

H3C H3C
C CH O C CH O
H3C H3C

Ex.2 :

 •
(A) BrCH2CH2 C H2 (B) CH3– CH– C H2
Br

(C) CH3– CH –CH2Br (D) Ans. ( C )

Ex.3 :
(A) RCOOH RCOO–
(B) RCOO– RCOOH
(C) RCOOH RCOO –

(D)
Sol. RCOO– RCOOH Ans.(B)
Ex.4 –
(A) –CN (B) –NH2 (C) –NHR (D) –NHCOR
Sol. –CN
N– Ans.(A)
Ex.5 -

(A) CH2 NO2 (B) CH2 CHO (C) CH2 CH3 (D) CH3

Sol. CH2 CH3 CH3 +I Ans.(C)

O O

Ex.6

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

Sol. Ans.(C)

H 49
 + 
Ex.7 CH2 O H  CH2= O –H. I II -

I II

(A) I > II (B) II > I (C) I = II (D)

Sol. IInd Ans.(B)

   
Ex.8 (I) CH4  C H3 + H (II) C H3  :CH2 + H (I) (II) :


(A) C H3 :CH2 (B) (II) > (I)

(C) C H3 :CH2 (D)
Ans.(C)

Sol. C H3 :CH2

Ex.9
(A) R2C CR2 (B) R—CH CR2 (C) R—CH CH—R (D) R—CH CH2 Ans.(D)

Sol. (D)

Ex.10 :

OH OH OH OH

(A) (B) (C) (D) Ans.(A)

NO2 Cl CH3 OCH3

50
H