ORGANIC CHEMISTRY

Dr Nam T. S. Phan
Faculty of Chemical Engineering
HCMC University of Technology
Office: room 211, B2 Building
Phone: 8647256 ext. 5681
Email: ptsnam@hcmut.edu.vn
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 Chapter 3: COMMON REACTION
MECHANISMS
Reaction mechanism: the description of the
step-by-step process by which reactants
are changed / converted into products

Nucleophilic substitution Nucleophilic addition

Electrophilic substitution Electrophilic addition

Elimination
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 NUCLEOPHILIC SUBSTITUTION
REACTIONS (SN)
• A nucleophile: an electron-rich species that can
form a covalent bond by donating 2 electrons to a
positive center
• A nucleophile is any negative / neutral molecule
that has 1 unshared electron pair
• Substitution reaction: chemical reaction in which
1 atom / group replaces another atom / group in the
structure of a molecule
• In a nucleophilic substitution reaction, a
nucleophile attacks / bonds with the positive center
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BIMOLECULAR NUCLEOPHILIC
SUBSTITUTION REACTION (SN2)

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 Stereochemistry of SN2 reactions

• The nucleophile attacks from the back side / the side

directly opposite the leaving group
• This attacks causes an inversion of configuration
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UNIMOLECULAR NUCLEOPHILIC
SUBSTITUTION REACTION (SN1)

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Note: slow step is rate-determining step 10
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Stereochemistry of SN1 reactions

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However, few SN1 reactions occur with
complete racemization

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Factors affecting the rates of
SN1 & SN2

1. The structure of the substrate

2. The concentration & reactivity of

the nucleophile

3. The reaction solvent

4. The nature of the leaving group

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 Affects of substrate structure

Steric
hindrance
Steric effect in the SN2 reaction
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Affects of nucleophile concentration
& strength
1) Neither the concentration nor the
structure of the nucleophile affects the
rates of SN1 reactions since the
nucleophile does not participate in the
rate-determining step

2) The rates of SN2 reactions depend on

both the concentration and the structure
of the nucleophile
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Nucleophiles that have the same attacking atom:
nucleophilicity roughly parallels basicity:

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ROH, HOH

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 Affects of solvents on SN2
• In polar aprotic solvent, nuceophilicity parallels basicity
Polar aprotic solvents solvate cation but not anions

Rates of SN2 reactions are generally increased in

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polar aprotic solvent
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 Affects of solvents on SN1
Polar protic solvents solvate cation & anions effectively

Rates of SN1 reactions are generally increased in

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polar protic solvent
 Affects of leaving group
The best leaving groups are those that become the most
stable ions after they depart

The best leaving groups are weak bases

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SN1 vs SN2

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 ELIMINATION REACTIONS

In an elimination reaction:
+ Groups / atoms are eliminated from a reactant
+ A double bond is formed between the 2 carbons
from which atoms are eliminated
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 BIMOLECULAR ELMINATION (E2)

Strong base 29
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 Stereochemistry of E2 reactions

• Anti-elimination is highly favored in an E2

reaction
2 groups / atoms are removed from opposite
sides of C-C bond

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Regioselectivity of E2 reactions

Zaitsev’s rule for an E2 reaction:

more substituted alkene is
normally obtained

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 Keep in mind that the major product of an E2
reaction is always the more stable alkene (not
always the more substituted alkene)

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In some E2 reactions, the less stable alkene is the
major product due to steric effects
Zaitsev’s product

Hofmann’s product
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UNIMOLECULAR ELMINATION (E1)

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Weak base

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Rearrangements in E1 & SN1

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 Stereochemistry of E1 reactions
The carbocation formed in the 1st step is planar,
so both syn & anti-elimination can occur

The major product is the

more stable alkene
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SN vs E

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 ELETROPHILIC ADDITION
REACTIONS (AE)
• Electrophilic: electron-seeking / loving
• Most electrophiles:
+ Are positively charged
+ Have an atom which carries a partial positive
charge
+ Have an atom which does not have an octet
of electrons
An electrophilic addition reaction is an addition
reaction where carbon-carbon double bonds or
triple bonds are attacked by an electrophile 44
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•Not a
carbocation,
but a cyclic
halonium
ion
• More
stable than
carbocation

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As the cyclic halonium cation is formed in the
1st step, it can react with whatever nucleophile
presence in the reaction mixture

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Stereochemistry of AE reactions

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Markovnikov’s rule

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Carbocation rearrangement in AE

More stable

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More stable

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 Relative reactivities of alkenes in AE

O2N H HOOC H Cl H H3C H

< < <
H H H H H H H H

H3C CH3 H3C CH3 H3C CH3

< < <
H H H CH3 H3C CH3

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 NUCLEOPHILIC ADDITION
REACTIONS (AN)
The carbonyl group is polar because the oxygen, being
more electronegative, has greater share of double-bond
electrons

The partial positive

carbon can be attacked
by nucleophiles

The addition of nucleophiles to the carbon

atom of the carbonyl group in nucleophilic
addition reactions 54
 Reaction mechanism

Rate-determining step
Positive A nucleophile
center

slow

fast 55
 Relative reactivities in AN

O O O
NO2 CH2 C > Cl CH2 C > CH3 C
H H H

> H3C C CH3 > H3C C OR > H3C C NH2

o o o

> H3C C O- Eletronic & steric effetcs

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o
ELECTROPHILIC SUBSTITUTION
REACTIONS (SE)
In an electrophilic substitution reaction, an
electrophile substitutes for a hydrogen of an
aromatic compound

Although benzene has 3 double bonds, the overall

reaction is electrophilic substitution rather than
electrophilic addition 57
 Reaction mechanism
Rate-determining step

An electrophile

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Nonaromatic, not stable, not formed

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 +I,
+C, - I,
Relative reactivity -C,
+H

Electron-donating Eelectron-withdrawing

Activating Deactivating

ortho/para-directing meta-direcring
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