CHAPTER 1

..Organic Reactions and Their

Mechanism

Organic Reactions and their Mechanisms

A reaction mechanism is a detailed description of the bonding changes as
a reaction proceeds. The reaction mechanism also includes the many
important principles of organic chemistry. A plausible reaction
mechanism must be consistent with the principles of organic chemistry.

Bond Making and Bond Breaking Processes:

Heterolysis and Homolysis
A covalent bond may break by either of two different processes:
heterolysis or homolysis.

Heterolysis (Gr: hetero- "different" + lysis-"cleavage")

A:B

+
A + B

Double-barbed arrow
is used to show movement
of an electron pair.

ions

Homolysis (Gr: homo-"the same" + lysis)

A:B

A. + B .
radicals

Single-barbed arrow
is used to show movement
of a single electron.

Bond Heterolysis
Bond heterolysis typically is found with polar covalent bonds where
the intrinsic electronegativities promote polarization of the bonding
electrons.
Electrophile(cations)

A:B

+
A + B
Nucleophile(anions)

polar covalent bond

Assisted Bond Heterolysis

Bond heterolysis may be assisted by a second molecule or chemical
species that can either donate or accept an electron pair..

A:B

A:B

D+

+ A:B

A : B + D+

C:A + B

C donates an electron
pair in forming bond to A
as B departs as anion.

A+ + B : D D+ accepts an electron pair

as it bonds to B releasing A+.

HomolysisCleavage
refertobreakingcovalentbondbetweensame/diffatomswith
smallelectronegativitydifference
formfreeradical, Cl,H,CH3
endothermicabsorbenergytobreakdownthecovalentbond
providedbysunlight(UVlight)/high
temperature

Example

OrganicReagents

Divideinto3group:

Electrophile
Nucleophile
Freeradical

Electrophile
means

Areagentwhichcanacceptanelectronpairinarxn

or
Amolecule/ionwhichiselectrondeficient(lowedensity)and
attacktheelectronrichspecies(highedensity)
arepositivechargedspecies

Nucleophile
means

Areagentwhichdonateanelectronpairinarxn

or
Amolecule/ionwhichiselectronrichandattacktheelectron
deficientcentre
arenegativelychargedoraneutralmoleculehavingan
atomwithalonepairofelectrons

Examples:
Nucleophile

Electrophile

a)OH ,CN ,Cl ,Br ,I

a)H+andother+veions

b)Doubleandtriplebond
ofalkeneandalkynes

b)Halogenandhalogenacids

c)Compoundcontainingan
atomwithlonepair

c)H2SO4,HNO3,HNO2

d)R2O:,:NH3,R3N:,etc

d)NO2,AlCl3,BF2,etc

e)Lewisbase

e)Oxidisingagent(Cl2,Br2)

Molecules/atomswhichcontainunpairedelectronwhichare
neutralandreactive

FreeRadical

Example:H,CH3andCl

Resultofhomolyticcleavagein
acovalentbond

Four General Categories of Organic Reactions

Organic reactions tend to fall into four categories:
substitutions, additions, eliminations, rearrangements.
Substitutions
In a substitution reaction, one atom or group replaces another in a
structure. This type of reaction is commonly observed in saturated
hydrocarbons and aromatics.
Nucleophilicsubstitution

+ Na+ -OH

R-X
an alkyl halide

Ar-H
an aromatic

+ Br2

H2O

Fe

R-OH + Na+ X-

Ar-Br + HBr

The mechanisms of the above two substitution reactions are

completely different.

Electrophilic
substitution

Additions
means

Areactioninwhichatomsorgroupsareaddedtothe
reactant.

Addition reactions are found in organic compounds with multiple bonds:

alkenes, alkynes, carbonyl-containing compounds. In this reaction, thecomponent of the multiple bond is lost as new bonds are formed to the
carbon (or other atomic) centers .

H
C

+ Br2
H

Br Br
Bromine adds to the alkene (ethene).

Eliminations
means

Arxnthatinvolvestheremovalofatomsormoleculesfrom
thereactant

These reactions are the reverse of addition reactions. In an elimination

reaction, a molecule loses atoms or groups from adjoining carbon (or
other atomic) centers, forming a multiple bond.

Br

H
C

H + KOH
H

+ K+ Br- + H2O

C
H

The above reaction is a dehydrohalogenation, loss of HBr, of an alkyl

halide to form an alkene.

Rearrangements

In rearrangement reactions, there is a reorganization of

the atoms or groups in a structure.

H+

In the presence of acid, the alkene on the left rearranges to the alkene
on the right.

means

Areactioninwhichinvolvesthemigrationofanatomsor
groupsfromsitetoanotherwithinthesamemolecule

Reaction Mechanisms and Chemical Intermediates

Reaction mechanisms are detailed descriptions of changes at the
molecular level as reactants become products. Often the reactions
involve a sequence of steps with one or more chemical species
called intermediates that are formed and consumed.

Chemical intermediates typically are not stable structures that can be

put in a bottle. Many exist for very short times (10-6 - 10-9 seconds).

Check this out!!!

1) CH3 CH2 Cl + OH2)

3)

4)

CH3CH3 + Cl2

uv

CH3 CH2 OH

Cl-

CH3CH2Cl + HCl
Cl

Cl 2

AlCl 3

CH3 CH = CH2 + Br2

CCl4

CH3CH(Br)CH2(Br)

H
5)

CH3 C = O + HCN

CH3 C - OH
CN

H
6)

CH3 CH2OH

7)

(CH3)2C = CH2 +

8)

CN- + CH3Br

9)

(CH3)2CHCl + NaOH

CH2 = CH2 + H2O

Br2

(CH3)2CBrCH2Br

CH3CN + Br-

(CH3)2CHOH + NaCl