ORGANIC REACTION MECHANISMS

AS
Bond fission
Free radical substitution Eletrophilic addition

A2
Addition Elimination Electrophilic substitution
Nitration Bromination Friedel-Crafts

Bromination of alkene
Hydration of alkene Addition polymerisation Elimination

Acylation Nucleophilic addition

Formation of polypeptides

Nucleophilic substitution
Formation of polyamides Dehydration Formation of polyesters Esterification Alkaline hydrolysis
Paul TC-2007

BOND FISSION
(Breaking of the bond)
HOMOLYTIC FISSION
Br Br Homolytic fission

Curly arrow

2x

Br

One electron moving

A pair of electrons moving

Free radicals (= an unpaired electron) Reaction of ALKANES = Free radical substitution Br2 2 Br. HETEROLYTIC FISSION + Br Br Heterolytic fission Br -

Br

Electrophile Nucleophile (= electron pair acceptor) (= electron pair donor)

Reaction of ALKENES = Electrophilic addition Br2 Br +. + Br Paul TC-2007

FREE RADICAL SUBSTITUTION MECHANISM

Initiation
Br Br 2 Br

Initiation Br2 2 Br
H
H C

Propagation
H

Propagation +
H Br

H+

Br

CH4 + Br CH3+ HBr

H H H C

H H Br Br H C Br

Br

CH3+ Br2 CH3Br + Br

Major organic product

Termination
H C H

Br

Br
H

Br H C

Br

Termination 2 Br Br2
Least favourable

H H H C

H Br

2 CH3 H3C-CH3
Possible

Br

H3C + Br CH3Br
H

MostPaul TC-2007 favourable

BROMINATION OF ALKENE

Br
-

Br
H3C
+

Nucleophile

H3C

:Br C H
H

H3C C H3C H
+

Br C

2-methylpropene

H3C H H3C
H C

Br Br

Carbocation

C
H

(Electrophile)

1,2-dibromo-2-methylpropane

Paul TC-2007

HYDRATION OF ALKENE MECHANISM

H3C
H3C C C

2-methylpropene

2-methylpropan-1-ol

H3C

H3C C H
C

H O

H+

H+
H3C H
O

H3C
C H

H3C H H

H3C C C O
+

C+

H
Paul TC-2007

ADDITION POLYMERISATION MECHANISM

Monomer

Cl Cl

H H Cl
+

H
=

Cl
+

H
=

Chloroethene

= C=C

C H H

C H

C H

H H

H HH

Trigonal planar 120o Cl H Cl Polychloroethene

Cl H

Cl H
or

C H

C H

C H

C H

C H

C H

C H

C H
n

Repeat unit

Repeat unit

= Any 2 consecutive C along the C chain

Dimer Trimer

Paul TC-2007

NUCLEOPHILIC SUBSTITUTION MECHANISM

R - X + :Nu-

R - Nu + :X-

H
OH - +

H C
+ +

Cl

HO

Cl -

H H

ELECTRON CLOUD from the nucleophile SHIFTS toward +C atom, and a DATIVE COVALENT BOND starts to form. As this happens, the C X bond is WEAKENS and eventually BREAKS HETEROLITICALLY.

Paul TC-2007

H
OH H H

Cl

ELIMINATION MECHANISM

C H

H
H2O
+

Cl

C H

H H C C
+

Cl -

H TC-2007 Paul

H+

DEHYDRATION

H C C

H C C

H
H+ +

H C C
H
+

Paul TC-2007

HO C R
O + H
+ Protonation

HO C
R H R O
+ +

H O HO
C
Nucleophilic attack

O
Proton transfer

ESTERIFICATION MECHANISM

R HO

H
O
+

O R

+ H+
R

H
O

H
Water elimination

Proton elimination

O R

C+ R

+ H2O
Paul TC-2007

ADDITION-ELIMINATION MECHANISM (NUCLEOPHILIC SUBSTITUTION)

H

H
+ + C

Cl-

+
HO

Nucleophilic addition

Cl

+
-

O-

OH

Nucleophilic substitution

Elimination

H C Cl
+

+
OHPaul TC-2007

ALKALINE HYDROLYSIS MECHANISM

Nucleophilic attack

R OHR O C O

HO
R

C O

O- Na+

Break down of the tetrahedral intermediate

R R
R OH Na+ O-

C C O
R O- Na+ H

Proton transfer

Paul TC-2007

NITRATION

Formation of the electrophile: NO2+

HNO3 + H2SO4 H2NO3+ HNO3 + H2SO4 H2NO3+ + HSO4H2 O + NO2+ H2O + NO2+ + HSO4nitronium ion

Electrophilic substitution:
H
+

NO2

NO2

NO2

+ H+

HSO4-

Regeneration of the catalyst: H+ + HSO4-

H2SO4

Overall equation: C6H6 + HNO3

H2SO4 cat. 50oC

C6H5NO2 + H2O

Paul TC-2007

BROMINATION

Formation of the electrophile: Br+

Br2 + FeBr3 Br+ + FeBr4H Br Br

Electrophilic substitution:
H
+

Br

+ H+

FeBr4-

Regeneration of the catalyst:

H+ + FeBr4FeCl3 cat.

FeBr3 +HBr
C6H5Br + HBr

Overall equation:

C6H6 + Br2

Paul TC-2007

FRIEDEL-CRAFT MECHANISM

Formation of the electrophile: CH3+

CH3Cl + FeCl3 CH3+ + FeCl4H CH3 CH3

Electrophilic substitution:
H
+

CH3

+ H+

FeCl4-

Regeneration of the catalyst: H+ + FeCl4-

FeCl3 + HCl
C6H5CH3 + HCl

Overall equation:

C6H6 + CH3Cl

FeCl3 cat.

Paul TC-2007

ACYLATION MECHANISM

Formation of the electrophile: CH3CO+

CH3COCl + FeCl3 CH3CO+ + FeCl4H COCH3 COCH3

Electrophilic substitution:
H
+

COCH3

+ H+

FeCl4-

Regeneration of the catalyst: H+ + FeCl4-

FeCl3 + HCl

Overall equation:
C6H6 + CH3COCl
FeCl3 cat.

C6H5COCH3 + HCl
Paul TC-2007

NUCLEOPHILIC ADDITION MECHANISM

H
+ -

bond weakens and breaks heterolytically

NC - +
Dative covalent bond formation

C H

O H NC
oxoanion

bond weakens and breaks heterolytically

CN

C H

O-

Dative covalent bond formation

H NC
2-hydroxynitrile

C
+

O +
-

H CN

This reaction is useful because the chain is extended by 1 carbon. TC-2007 Paul

H N H

H C R
Monomer 2-amino acid

FORMATION OF POLYPEPTIDES O H H O H
C OH + H N C R C OH ` + H N

H C R C

OH

Peptide link (amide)

Peptide link (amide)

H N

H C

O C N

H C

O C

N H

C R

+ 2 H2O

H
Trimer

R
Repeat unit (aminoacid residue)

OH

H N H C R

O C
n
Paul TC-2007

DIBASIC ACID and DIAMINE to form POLYAMIDES

H
N (CH2)n N H H

O
C (CH2)n C OH

H N (CH2)n N

O
C (CH2)n C OH

+
H OH

+
H

+
H OH

Repeat unit
H N (CH2)n N H

Repeat unit
O O N (CH2)n N OHH

O
C (CH2)n C

O +3 H2O OH

C (CH2)n C

H Peptide link 2 monomers (amide)

Peptide link (amide)

H Peptide link (amide)

Repeat unit
O O

N (CH2)n N H H

C (CH2)n C
Paul TC-2007

REACTION OF DIBASIC ACID and DIOL to form POLYESTERS

O O O O

HO C (CH2)n C OH + H O (CH2)n O H+ HO C (CH2)n C OH+ H O (CH2)n

O
HO C (CH2)n

O O C Ester link (CH2)n O H + 3 H2O

C O (CH2)n O H C (CH2)n Ester Ester link link Repeat unit (2 monomers)

O O (CH2)n O H C (CH2)n
Repeat unit (2 monomers)

O
C

Paul TC-2007