ORGANIC CHEMISTRY

FORMULA BOOKLET - GYAAN SUTRA

ALKANE
Wurtz reaction :
e.g., R1 X + R2 X + 2Na  R1 – R2 + 2NaX

Decarboxylation :
H 
General reaction RCOONa  R – H + Na2CO3

O
– O
–

..

Mechanism R–C  R + C H
 R – H
O O

The thermal decarboxylation of free acids may be :

O
–
O–H
+
R–C  H +R–C 
O O
+ –
..

H + R + CO2 R – H + CO2

ALKYL HALIDE
Nucleophilic substitution Reaction (SN1, SN2)
SN1 reaction : R – OH + HX  R – X + H2O
(R may rearrange)

Reactivity of HX : HI > HBr > HCl

Reactivity of ROH : allyl, benzyl > 3° > 2° > 1° (Carboocation)

Carbocation formed

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 
H
Mechanism R –OH 

H O 
R–X
 R  O H2 2
  R

e.g. CH3CHCH3 CH3 CHCH 3

| |
OH Br
Isopropyl alcohol Isopropyl bromide

SN2 reaction :
Alkylhalide are hydrolysed to alcohol very solwly by water, but rapidly by
silver oxide suspended in boiling water.
RX + KOH  ROH + KX

– –
Mechanism R – X  H O ....R .... X  HO – R + X
—
HO
—

a a a
– –
C H O.... C.... X C
HO— +   + X—
b d X b d HO d b
Williamson’s synthesis :
It is the reaction in which sodium or potassium alkoxide is heated with an
alkyl halide (SN2).

– –
R1O– + R2–X R 1 O........R 2 ....... X  R1OR 2  X – ( g)
This method is particularly useful for preparing mixed ethers.

GRIGNARD REAGENTS
R1H + Mg(OH)X  H2O 1 R2OH 1 2
 R MgX   R H + Mg(OR )X
The majority of Grignard reactions fall into two groups

(i) Addition of the Grignard reagent to a compound containing a multiple -

bond group e.g.
C=O ;–CN; C = S ; —N = O ; S=O

(ii) Double decompsition with compounds containing an active hydrogen

atom or a reactive halogen atom.

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 H2O R2OH
R1H + Mg(OH)X   R1MgX   R1H + Mg(OR2)X

Important chemical synthesis by Grignard reagent

H
1. Hydrocarbons : RMgBr + H2O 
 RH + Mg(OH)Br
H
RMgBr + RNH2 
 RH + RNHMgBr
2. Alcohols :
(a) Primary alcohols

O 3 H O
RMgX  2 RMgX
 RO2MgX 
  2ROMgX   2ROH
(b) Secondary alcohols
OMgX
1 H O
R1CHO + R2MgX  RCH 3 R1CHOHR2
2
R
(c) Tertiary alcohols :

R
1
R
1 OMgX H O R
1 OH
3
C = O + R MgX  2
C
3
3 2
C
3
R
2 R R R R
3. Ethers :
R1OCH2Cl + R2MgX  R1OCH2R2 + MgXCl

4. Aldehydes :

H OMgX
H H O
C= O + RMgX  C 3 RCHO
R
EtO E+O

5. Ketones :
3 H O
R1C (OC2H5)3 + R2MgX R1R2C (OC2H5)x + Mg (OC2H5)x 
R1COR2
R1CN + R2MgX
 R1R2C

3 H O H O
3 R1COR2 + NH3
= NMgX   [R1R2C = NH]
Ketimine
6. Acids :

O O H O
RMgX + C  R — C 3 RCO2H
O OMgX

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7. Esters :
Cl Cl OMgX H O
C=O + RMgX  C 3 RCO2Et
EtO EtO R

8. Alkyl Cyanides :
RMgX + (CN)2  RCN + Mg(CN)x

9. Primary amines :
H3O 
RMgX + RONH
2
RNHMgX + RH + Mg(OCH3)Cl
  RNH2 (40-90%)
RMgX + ClNH
2
 RNH 2
+ MgxCl

ALKENE & ALKYNE

Electrophilic addition reactions :
Mechanism
Step 1 : Attack of the electrophile on  bond forms a carbocation.
+ | +
C=C + E –C–C
|
E
+ on the more substituted carbon
Step 2 : Attack by a nucleophile gives the product of ad-
dition.
| + | |
–C–C + Nu: CC
| | |
E E Nu

e.g. (a) Addition of water + H2 O

(b) Addition of hydrogen halides (where HX = HCl, HBr, HI)

H X
HX HX | |
R – C  C – R  R  CH  CX  R  R  C  C  R
(Markovniko v addition ) | |
H X

Page # 140
 AROMATIC COMPOUNDS
Electrophilic aromatic substitution :
(a) Bromination of Benzene : Bromination follows the general mecha-
nism for electrophilic aromatic substitution. Bromine itself is not suffi-
ciently electrophilic to react with benzene, but a strong Lewis acid such
as FeBr3 catalyzes the reaction.
Step 1 : Formation of a stronger electrophile.
: :  

: :

: :

:
: :
:Br – Br : + FeBr3 :Br – Br – FeBr3

Step 2 : Electrophilic attack and formation of the sigma complex.

H
H H +
: :

: :

:Br – Br: FeBr3

  +
H H
H

FeBr4¯
Step :2 Loss of a proton gives the products.
H
H Br
+ HBr + FeBr3
H H
H
bromobenzene

T .S1
reactants T .S2
+ Br2
+ FeBr3
H
energy Br¯FeBr4
+
intermediate products
Br + HBr
-10.8 kcal/mol + FeBr 3

reaction coordinate

(b) Nitration

H3 O  +

Page # 141
 H
+
NO2 NO2
+
(-complex)
( - complex)

H+ +

(c) Sulphonation :
The electrophilic reagent, SO3, attacks the benzene ring to form the inter-
mediate carbocation.
2H2SO4 SO3 + +

(d) Friedel Craft reaction :

Alkylation mechanism

(i)

(ii)

(iii) + AlCl4¯

Page # 142
Acylation mechanism
Acylation of benzene may be brought about with acid chlorides or anhy-
drides in presence of Lewis acids.
Step 1 : Formation of an acylium ion.
:O : :O:
|| .. || ..
+ -
R – C – Cl:
.. + AlCl3 R – C – Cl
.. – AlCl 3

acylchloride
complex

+ .. +
- [R – C = O R – C  O:]
AlCl4 + ..
acylium ion
Step 2 : electrophilic attack.
O
O ||
|| C
C+ R
H
| +
H
R
sigma complex

Step 3 : Loss of a proton. Complexation of the product.

....
O
O ||
|| .. - C
C :Cl R
R .. – AlCl3
+ H
H acylbenzene
sigma complex

O CH3
O C
|| (1) AlCl3
e.g. + CH3 – C – Cl
CH2CH3
(2) H2O
ethylbenzene acetyl chloride
CH2CH3
p-ethyl-acetophenone
(70 – 80%)

Note : Friedal - Crafts acylations are generally free from rearrangements

and multiple substitution. They do not go on strongly deactivated rings.

e.g.

Page # 143
Chemical Reactions of Benzene :
Conc. HNO 3
     
H2SO 4 + H2 O

Conc. H2SO 4  SO 3
        + H2 O

Cl
 2
 + HCl
FeCl3

RCl
  
 + HCl
AlCl3
Friedel-Crafts alkylation

RCOCl
   
AlCl3 + HCl
C6 H6
Friedel-Crafts acylation

D / D2O + H+
 

HNO 2 + H2 O
   

N=N – Ar
 –
ArN2 X + HX
  

Nucleophilic Aromatic Substitution :
The reaction is second-order in which nucleophilic sbustitution occurs on
benzene ring. It is generally accepted that the reaction proceeds via an
intermediate -complex, the benzenonium carbanion (or the pentadienyl
anion), e.g.,
- –
Cl OH Cl OH Cl OH
Cl OH

OH +– slow –   – fast + Cl–


 
1. 2. 3.
Page # 144