General Organic Chemistry 1

CHAPTER

1
General Organic Chemistry

1.1 Introduction:
Organic reactions involve the breaking and making of covalent bonds. The breaking and making of covalent
bonds usually occurs in several descrete steps before transformation into product. The detailed sequential
description of all steps of the transformation into products is called the mechanism of a reaction.
Complete information regarding all the steps is seldom obtained. However, a good deal of data can be
gathered from the following
(a) study of kinetics of the reactions
(b) isolation of intermediate, if isolable.
(c) study of reactions in the presence of other similar substrate.
(d) study of the isotopically labelled atom in the reactants.
(e) trapping of free radicals
(f) crossover experiments
(g) stereochemical aspects etc.

Reaction mechanism containing following tools

solvent
Reactant  
temperature/light
pressure
 Product


(i) Reactant :
Reactants are classified into substrate and reagents
(A) substrates  species at which reagent attack.
(B) Reagents  attacking species (more reactive species)

Case-I: If reaction occurs between organic and inorganic species, organic species act as substrate and inor-
ganic species act as reagent.
Organic species  Inorganic species 
 Product
 substrate   reagent 
Case-II: If reaction takes place between organic species then higher charge species act as reagent, other
species act as substrate.
Organic species  Organic species 
 Product
 less charge   excess charge 
 substrate   reagent 
 2 General Organic Chemistry

Example:
H3C CH2 CH2 Br + KOH H3C CH2 CH2 OH + KBr
substrate reagent product
(organic) (inorganic)

O O
OH O
C C H3O+ CH3
H3C C H + H2C CH2 CH3 CH C
H3C
H2 H2C CH2 CH2
(substrate) (reagent)

1.2. Electrophiles :
(Electron loving species) electrophiles are electron-deficient species and tend to attack the substrate at a site of
high electron density. They may be neutral species as examplified by Lewis acid (such as BF3, AlCl3, ZnCl2),
carbene and carbocations.

H + OH O
Proton as electrophiles H H
hydroxide ion water
as nucleophile
Classification of electrophiles:
(a) Species having positive charge

Example : H  , R  , Cl , NO  , NO 2 , C6 H 5  N 2 , H 3C  C  O etc.
(b) Neutral species having vacant p-orbitals
Example : BF3, BCl3, BBr3, carbene, etc.
(c) Species having vacant d-orbital
Example : FeCl3, FeCl2 etc.
(d) Species having low lying  -antibonding molecular orbital.
Example : Br2, Cl2, I2 etc.
(e)  -bonding molecule:
O
O
Example : SO3, CO2, , R C N , , etc.

(f) Element in their atomic state :

Example : O, S etc.
1.3. Nucleophiles:
(Nucleus-loving species) Nucleophiles are electron donar species. Nucleophilic reagents tend to attack the
electron deficient species (electrophiles).
Classification of Nucleophiles:
(a) Negative charge species:
OH  , OR  ,SH  ,SR  , R  ,Cl , Br  , I etc
(b) Organometallic reagent:
R  MgX, R  Li, R 2 CuLi, R 2 Cd, R 2 Zn etc
(c) Lone pair containing species:

H2 O , R O H , NH3 , H2S , etc

N
General Organic Chemistry 3

(d)  -bonded molecules:

OR OH
Alkene, Alkyne, Benzene, , , etc
N
Note: Some species behave as the electrophiles as well as nucleophiles
Example : Br2, Cl2, I2, etc.

Ambidentated nucleophile : Those nucleophile which posses more than one site for E+ attack but at the
same time only one side is used to form bond with electrophile. It is called ambidented nucleophile, such type
of ambidentated nucleophile are regioselective.

O O
C H2C C
Example : H2C H H

O O R
Aprotic
solvent
+ R X + X
e.g. DMF

O O
Protic R
solvent
+ R X + X
e.g. ROH

Note:
Decreasing order of nucleophilicity
[Electronegativity  % of S-character]
Note : Electron Displacement Effects:
Effect occuring due to displacement of electron in organic compound is called Electron Displacement
Effect or electron delocalisation effect.
Electron displacement effect is of mainly two types.

Electron Displacement Effect

Permanent effect Temporary effect

(Polarization effect) (Polarizability effect)

Inductive Hyper Resonance or Mesomeric Inductomeric Electromeric

effect conjugation effect effect effect
 4 General Organic Chemistry
Other Effect:
(a) Steric inhibition of resonance (b) Ortho effect.
1.4. Inductive effects:
In a covalent bond between two different atoms, the electrons in the   bond are not shared equally. The
electrons are attracted towards the most electronegative atom. An arrow drawn above the line representing the
covalently bonded electrons shifts towards higher electronegative atom can show this. Electrons are pulled in
the direction of the arrow.
When the atom (X) is more When the atom (Z) is less
electronegative than carbon electronegative than carbon

electrons attracted to X electrons attracted to carbon

 
C X C Z

negative inductive positive inductive

effect (–I effect) effect (+I effect)

–I groups +I groups
X=Br, Cl, NO2, OH, OR, SH, Z=R(alkyl or aryl),
SR, NH2, NHR, NR2, CN, CO2H, metals (e.g. Li or Mg), anions (e.g. O)
CHO, COR
The more electronegative the atom(X), The more electropositive the atom (Z),
the stronger the –I effect the stronger the +I effect.

Pauling electronegativity scale The inductive effect of the atom rapidly

diminishes as the chain length increases
K = 0.8 I = 2.5
C = 2.5 Br = 2.8
   
N = 3.0 Cl = 3.0
O = 3.5 F = 4.0 H3C CH2 CH2 CH2 Cl
Higher the value, more
electronegative will be atom experiences a experiences a
negligible –I effect strong –I effect

The overall polarity of a molecule is determined by the individual bond polarities, formal charges and lone pair
contributions, and this can be measured by the dipole moment (µ). Higher the dipole moment (measured in
debyes (D)), more polar will be compound.
1.5. Hyperconjugation:
A   bond can stabilise a neighbouring carbocation (or positively charged carbon) by donating electrons to
the vacant p-orbital. The positive charge is delocalised or ‘spread out’, and this stabilising effect is known as
hyperconjugation or “no-bond resonance”.
H
C–H The electrons in the -bond
a -bond spend time in the vacant p-orbital

vacant p-orbital
Points to Remember :
Number of  hydrogen  number of hyperconjugating structure  stability
1 1
  Polarity  dipole moment 
Heat of hydrogenation bond length  a 
General Organic Chemistry 5

Problem : The correct order for the stability among following compound in solution phase is:
H3C H3C
CH3CH2 CH3CH2CH2 CH CH2 H3C C CH2
H3C H3C
(II) (II) (III) (IV)

(a) I > II > III > IV (b) I > III > IV > II (c) IV > III > II > I (d) IV > III > I > II
Soln. Number of  hydrogen  stability..
Thus,
(I) (II) (III) (IV)
H3C H3C
CH3CH2 CH3CH2CH2 CH CH2 H3C C CH2
H3C H3C
Number of  hydrogen 3 2 1 0
Stability, I > II > III > IV
Hence, option (a) is correct.
Types of hyperconjugation:
(i) Positive-Hyperconjugation (Separation of positive charge moiety)
Example: (For the stabilization of electron deficient species)
H3C CH2 CH2
 
H3C CH2 R3Si

H
filled + H+ filled + R3Si
 H H H  H H H
C C C C C C C C
H  H  
H H H H H H
H H

Vacant
p-orbital
(ii) Negative-Hyperconjugation (separation of negative charge moiety)
(For the stabilization of electron rich species)
X
(X) is high electronegative (usually F)


filled orbital (Lone-pair or anion) anti to each other

Example :

F F–
 H H H
FH2C CH2
C C C C
H
H H H
H

C–F(*) C
Note: CF3 group attached to carbanion/aromatic ring shows negative-hyperconjugation.