12.

5 REACTION IN ORGANIC COMPOUNDS

C H E M I S T RY U N I T
SK027
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12.5 REACTION IN ORGANIC COMPOUNDS

OBJECTIVES:
1.Explain covalent bond cleavage:
• homolytic cleavage to produce free radicals
• Heterolytic cleavage to produce carbocation and
anion
2. State the relative stabilities of 1o,2o,3o
• Carbocations/Carboniums
• Free radicals
• Carbanions
Explain the inductive effect of alkyl group towards
the stability of carbocations and carbanions.
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12.5 REACTION IN ORGANIC COMPOUNDS

OBJECTIVES:

3. Define electrophile and nucleophile

i. types of electrophiles: Lewis acids, cations
and electron deficient sites in organic compounds
ii. types of nucleophiles: Lewis base,anions and
electron rich sites in organic compounds

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12.5 REACTION IN ORGANIC COMPOUNDS

COVALENT BOND CLEAVAGE / FISSION

• All chemical reactions involved bond-breaking
and bond-forming .
• Reactions occur at the active site/functional
group.
• Reactive intermediate occurs in the course of
reaction
• Types of covalent bond cleavage:
a. Homolytic cleavage
b. Heterolytic cleavage

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12.5 REACTION IN ORGANIC COMPOUNDS

HOMOLYTIC CLEAVAGE
• ..is a bond fission in which the two shared
electrons of the covalent bond are split equally
between the two atoms.
• Occurs in a non-polar bond involving two atoms
of similar electronegativity.
• Free radicals (atoms/group of atoms contains
an unpaired valence electron) are formed.
Example:
uv
Cl Cl Cl + Cl
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12.5 REACTION IN ORGANIC COMPOUNDS

HETEROLYTIC CLEAVAGE
• .. Is the bond-breakage in which both electrons
remain on one of the atoms.
• Occurs in a polar bond involving two atoms of
different electronegativities.
• Cation and anion are formed.
Example: C Br C + Br

Carbocation / carbonium

C E C + E
Carbanion
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12.5 REACTION IN ORGANIC COMPOUNDS

R
CH3 < R CH2 < R CH <
R C
R R
R
CH 3 < R CH 2 < R CH < R C
R R

Methyl < 1° < 2° < 3°

• The stability of carbocation & free radical increases with
the number of alkyl groups present.
• The alkyl groups are electron-releasing, thus help to
stabilize the +ve charge on the carbocation / free radical.
• This is called the inductive effect
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12.5 REACTION IN ORGANIC COMPOUNDS

Relative Stabilities of intermediates

- R
- - -
CH 3 > R CH 2 > R CH > R C
R R

Methyl > 1° > 2° > 3°

• The alkyl group decreases the stability of a carbanion
• The greater the number of alkyl group, the less stable
is the carbanion
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12.5 REACTION IN ORGANIC COMPOUNDS

Reagents and sites of organic reactions

a) Electrophile
• ..is an electron-deficient species which capable of
accepting electron pairs.
• it attacks electron-rich areas of organic molecules.
• can be either neutral or positively charged.
Type Example
Cations NO2+, H3O+
Lewis acid AlCl3, BF3
Carbocation C+
Oxidising agents Br2, Cl2
Site of low e density δ+ δ- δ+ δ- δ+ δ-
C=O C–X C – OH
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12.5 REACTION IN ORGANIC COMPOUNDS

Reagents and sites of organic reactions

b) Nucleophile
• ..is an electron-rich species which is capable of donating
electron pairs.
• it attacks low electron density areas of organic molecules.
• can be either neutral or negatively charged.
Type Example
Anions OH-, RO-, Cl-, CN-
Lewis base NH3, H2O, H2S
Carbanion C-
Site of high e density Benzene
C=C C C
ring
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12.5 REACTION IN ORGANIC COMPOUNDS

Exercises: 1. The bond dissociation energies for homolytic

cleavage are as below,
Bond Bond dissociation
energies (kJmol-1)
CH3 H 435
CH3CH2 H 410
C6H5CH2 H 356
(CH3)2C H 397
(CH3)3C H 381
What is homolytic cleavage, write the free radicals that are
formed due to the homolytic cleavage and rank them
increasing order of stability.
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12.5 REACTION IN ORGANIC COMPOUNDS

Exercises: 2. a) Classify the following species as free

radical, carbonium ion, carbanion,
electrophile or nucleophile.
i) (CH3)2CH-
ii) CH3CH2•
iii) CH3O-
iv) NO2+
v) (CH3)3C+

b) Ethane reacts with bromine according to the equation

CH3CH3 + Br2 → CH3CH2Br + HBr
i) Classify this reaction
ii) Write the structural formula of the organic species
formed when CH3CH3 undergoes homolytic fission.
iii) Write the structural formulae of the species formed
when CH3CH2Br undergoes heterolytic fission.
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12.5 REACTION IN ORGANIC COMPOUNDS

Exercises:
3. (a) Explain how free radicals are formed. Write an
equation for the bromine-bromine bond cleavage
in the bromination of methane. State the type of
bond cleavage.
(b) Which of the following species is likely to be an
electrophile, and which a nucleophile ?
CH3OCH2CH3, AlCl3, CH3OH, NH3,

C6H5N2+, (CH3)CH2+ ,OH- ,

CH3CH=CH2,