CHAPTER 3

AN OVERVIEW OF
COMMON MECHANISMS

LECTURER: PHAN THỊ HOÀNG ANH

I. KINDS OF ORGANIC REACTIONS
Based on the structure change of the reactant molecules

 Substitution reactions (S)

 Elimination reactions (E)

 Addition reactions (A)

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 Rearrangement reactions

Rearrangement can accompany many of the reactions such as

substitution, addition, and elimination reactions.

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Based on the way bond forming and breaking
Bond-breaking reaction → homolysis, heterolysis
Symmetrical bond-
breaking → radical

Unsymmetrical bond-
breaking → polar

Bond-forming reaction → homogenic, heterogenic

Symmetrical bond-
forming → radical

Unsymmetrical bond-
forming → polar 4
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 Unimolecular reaction: one molecule is involved in the rate-determining step

 Bimolecular reaction: two molecules are involved in the rate-determining step

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 Radical reactions
Chemical reactions that involve free-radicals

Radical substitution reaction

Radical addition reaction

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Radical substitution of alkane

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 Polar reactions
 Polar reactions occur because of the electrical attraction between
positively polarized (Electrophile) and negatively polarized
(Nucleophile) centers on functional groups in molecules.

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 Nucleophile, electrophile
 Nucleophile (Greek - nucleus loving) : characterized by its ability to react
with a positive charge or partial positive charge
 Nucleophilic center: capable of donating a pair of electrons - may be
atoms possessing a localized lone pair, s bond, p bond.
 Nucleophiles can be either neutral or negatively charged

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 Electrophile (Geek - electron loving): characterized by its ability to react
with a negative charge or partial negative charge.
 Electrophilic center: an electron-deficient atom with an empty
atomic orbital or a low-energy antibonding orbital, can form a bond by
accepting a pair of electrons from a nucleophile.
 Electrophiles can be either neutral or positively charged

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 Electrons move from a Nucleophile to an Electrophile

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 Formal charge
 Formal charge is the charge assigned to individual atoms in a Lewis
structure.
 Formal charges provide a method for keeping track of electrons, but
they may or may not correspond to real charges.

O: FC = 6 – (1 e bonding +
6e non bonding) = -1

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CH4 C : FC = 4 – 4e bonding = 0
H: FC = 1 – 1e bonding = 0

NH4
N: FC = 5 – 4e bonding = +1

NH3-BH3

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Common bonding patterns in organic compounds and ions

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D.1.13. Determine formal charge in following structures

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 L. 1.6

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Curved arrow in polar reaction mechanisms
1. Curly arrow represents the actual movement of a pair of electrons
from an Nucleophile (Nu:)to an Electrophile (E).

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2. Charge is conserved in each step of a reaction

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M1
3. The octet rule must be followed.
→ no second-row atom can be left with ten electrons (or four for
hydrogen).
→ If an electron pair moves to an atom that already has an octet (or
two for hydrogen), another electron pair must simultaneously move
from that atom to maintain the octet.

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M1
Mc.6.22. Add curved arrows to the following polar reactions to indicate the
flow of electrons in each:

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Mc.6.23. Follow the flow of electrons indicated by the curved arrows in each of the
following polar reactions, and predict the products that result:

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Mc. 6.39. Identify the bonds broken and formed in each step of the reaction, and
draw curved arrows to represent the flow of electrons in each step

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Mc.6.41. Predict the product(s) of each of the following biological reactions by
interpreting the flow of electrons as indicated by the curved arrows

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SOME COMMON REACTION MECHANISMS

Nucleophilic Substitution SN

Substitution Electrophilic Substitution SE

Radical Substitution SR

Electrophilic addition AE
Addition
Nucleophilic addition AN

Elimination 34
Nuclephilic substitution SN
 The characteristic reaction of alkyl halides

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Electrophilic substitution SE
 The characteristic reaction of aromatic compounds

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Radical substitution SR
 The characteristic reaction of alkanes

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Electrophilic addition AE
 The characteristic reaction of unsaturated hydrocarbons (alkenes,
alkynes, alkadienes)

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Nucleophilic addition AN
 The characteristic reaction of carbonyl compounds

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 Elimination reactions (E)
 The characteristic reaction of alkyl halides to prepare alkenes

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