Physic Organic Chemistry

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Reage on
Reacti s
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Mech
 4
Presented by
• Khairunnisah “084”
• Sherli Hermanita “026”

Group
• Fahri Ihsan “007”
• Dian Degusty “040”
Reaction Mechanisms
Reaction Mechanism – is an overall description of how
a reaction occurs.
This basically describes in detail exactly what takes
place at each stage of a chemical transformation
ALL CHEMICAL REACTIONS INVOLVE BOND-
BREAKING AND BOND-MAKING.
Reaction mechanisms
Reaction mechanisms
There are two of reaction pathway:

Polar reaction
Free radical reaction
Polar reaction

Polar reactions involve a species with an even number

of electrons and thus have only electrons pairs in their
orbitals. This is where the electrons are taken by the
most electronegative atom in a bond.

In polar reaction have:

Electrophile
Nucleophile
Polar reaction : Electrophile

A molecule or ion that accepts a pair of electrons to

make a new covalent bond is called an electrophile
(from the Greek for "electron loving").
 Wants to pair up with a negative charge.

Typical of electrophile
Polar reaction : Nucleophile

A molecule or ion that donates a pair of electrons to

form a new covalent bond is called a nucleophile
(from the Greek for "nucleus loving"). 
Wants a to pair up with a positive charge.
Type of nucleophile
Polar reaction

Electrons always flow from nucleophile to

electrophile:

Example:

In this reaction, chloride ion is the leaving group.

Leaving group
Example of polar reaction
 In this polar reaction, know as an electrophilic addition
reaction the strong nucleophile the ethylene reacts with
the proton of hydrogen bromide (electrophile) to yield
bromoethane.
Process polar reaction mechanisms
Rule 1 – Electrons move from a nucleophilic source to an electrophilic
sink.

Rule 2 – The nucleophilie can be either negatively charged or neutral.

Rule 3 – The electrophile can be either positively charged or neutral.

Rule 4 – The octet must be followed.

Nucleophilic mechanism
(SN1 and SN2)
Chemists propose two limiting mechanisms for nucleophilic displacement
 a fundamental difference between them is the timing of bond breaking and
bond forming steps

At one extreme, the two processes take place simultaneously; designated S N2

 S = substitution
 N = nucleophilic
 2 = bimolecular (two species are involved in the rate-determining step)
 rate = k[haloalkane][nucleophile]

In the other limiting mechanism, bond breaking between carbon and the leaving
group is entirely completed before bond forming with the nucleophile begins.
This mechanism is designated SN1 where
– S = substitution
– N = nucleophilic
– 1 = unimolecular (only one species is involved in the rate-determining step)
– rate = k[haloalkane]
Nucleophilic reactions: nucleophilic substitution (SN)

Nucleophilic substitution:
 -> reagent is nucleophil

 -> nucleophil replaces leaving group

 -> competing reaction (elimination + rearrangements)

leaving
group
nucleophilic
substitution
Nu + -
C X C Nu + X-
Nucleophile
Nucleophilic subtitution
Some nucleophilic substitution reactions

- -
Reaction: Nu + CH3 X CH3 Nu + X

HO - CH3 -OH An alcohol

-
RO CH3 -OR An ether
-
HS CH3 -SH A thiol (a mercaptan)
-
RS CH3 -SR A sulfide (a thioether)
-
I CH3 -I An alkyl iodide
+
NH3 CH3 -NH3 An alkylammonium ion
+
HOH CH3 -O-H An alcohol (after proton transfer)
H
SN1 reaction: unimolecular nucleophilic substitution

tert-butyl bromide
 SN1 is illustrated by the solvolysis of
 Step 1: ionization of the C-X bond gives a carbocation intermediate

H3 C slow, rate CH3

determining
C Br C+ + Br
H3 C
H3 C H 3 C CH3
A carbocation intermediate;
carbon is trigonal planar
  Step 2: reaction of the carbocation (an electrophile) with methanol
(a nucleophile) gives an oxonium ion
CH3 H3 C CH3 H3 C CH3
fast
CH3 O + C+ + OCH3 O C + C O
CH3 H3 C
H H H H3 C H
H3 C CH3 CH3

 Step
H3 C 3: proton transfer completes the reaction
H3 C CH3
CH3 H H
+ + fast +
C O O C O + H O
H3 C H3 C
H CH3
H3 C H3 C CH3
SN1
An energy diagram for an SN1 reaction
SN2 reaction: bimolecular nucleophilic substitution

 both reactants are involved in the transition state of the

rate-determining step
 the nucleophile attacks the reactive center from the side
opposite the leaving group

H
H - - H
HO + C Br -
HO C Br HO C + Br
H
H H
HH H

Transition state with

simultaneous bond breaking
and bond forming
SN2
An energy diagram for an SN 2 reaction
 there is one transition state and no reactive intermediate
Effect of substituents on SN
reactions
 SN1 reactions
 governed by electronic factors, namely the relative stabilities
of carbocation intermediates
 relative rates: 3° > 2° > 1° > methyl

 SN2 reactions
 governed by steric factors, namely the relative ease of
approach of the nucleophile to the site of reaction
 relative rates: methyl > 1° > 2° > 3°
nucleophilicity

Effectiveness Nucleophile
Br-, I -
good CH3 S- , RS-
HO-, CH3 O-, RO-
O O
CH3 CO-, RCO-
moderate
CH3 SH, RSH, R2 S
NH3 , RNH2 , R2 NH, R3 N
H2 O
CH3 OH, ROH
poor O O
CH3 COH, RCOH
Free radical

 A radical (also called a free radical) is described as a neutral

chemical species that contains an odd number of electrons
and thus has a single unpaired electrons in its orbital.
Radical reactions can involve:
 Bond forming and bond breaking
 Substitution
 Insertion
 Addition
 Elimination
 Rearrangement
 Single electron transfer (SET)
Type of Reactions
Addition Reactions
Addition Reactions – are when two reactants add
together to form a single product with no atoms “left
over”.

Example:

H Br
+ H Br H H
H H
Ethylene Bromoethane
Elimination Reactions
Elimination Reactions – are when a single reactant
breaks down to form two products. This is the
opposite of an addition reaction.

Example:

H OH Acid Catalyst + H OH
H H
H H
Ethylene
Substitution Reactions
Substitution Reactions – occurs when two
reactants exchange parts to give two new
products.

Example:

H H
Light
H C H + Cl Cl H C Cl + H Cl
H H
Rearrangement Reactions
Rearrangement Reactions – occurs when a single
reactant undergoes a reorganization of bonds and
atoms to yield an isomeric product.

Example:

H3CH2C H Acid Catalyst H3C H

H H H CH3

1-Butene 2-Butene
Pericyclic reaction
Pericyclic reaction: a reaction that takes place in a
single step, without intermediates, and involves a
cyclic redistribution of bonding electrons. There three
classes of pericyclic reactions:
1. Cycloaddition: two molecules combine to form a
ring.
2. Electrocyclic: one molecule, an intramolecular
cyclization.
3. Sigmatropic: an intramolecular rearrangement.
Oxidation and reduction reaction
Oxidation is the loss of electrons or an increase in
oxidation state by a molecule, atom, or ion.
Reduction is the gain of electrons or a decrease in
oxidation state by a molecule, atom, or ion.
 Kind of free radical reaction

Initiation – The symmetrical breaking of a bond

into 2 free radicals.

Cl Cl Cl + Cl
• Propagation – The reaction of a free radical with
normal atoms to create new free radicals.
Cl + H-CH3 Cl H + CH3
• Termination – The reaction of two free radical to
create a normal bond again.
Cl + Cl Cl Cl
Finished…
Bye..