Main classes of organic reactions

Main organic reactions are:

(i) addition reaction, (ii) elimination reaction and (iii) substitution
reaction.
All of these reactions may take place in either (i) polar mechanism,
or through (ii) free radical mechanism.
Polar reactions may be electrophilic or nucleophilic.
 Types of Steps in Reaction Mechanisms
• Bond formation or breakage can be symmetrical or unsymetrical
• Symmetrical- homolytic
• Unsymmetrical- heterolytic
 Free Radical Reactions
• Not as common as polar reactions
• Radicals react to complete electron octet of valence shell
• A radical can break a bond in another molecule and abstract a partner with an
electron, giving substitution in the original molecule
• A radical can add to an alkene to give a new radical, causing an addition
reaction
 Steps in Radical Substitution
• Three types of steps
• Initiation – homolytic formation of two reactive species with unpaired electrons
• Example – formation of Cl atoms form Cl2 and light

• Propagation – reaction with molecule to generate radical

• Example - reaction of chlorine atom with methane to give HCl and CH 3.

• Termination – combination of two radicals to form a stable product:

CH . + CH .  CH CH
 Polar Reactions
• Molecules can contain local unsymmetrical electron distributions due to differences in
electronegativities
• This causes a partial negative charge on an atom and a compensating partial positive
charge on an adjacent atom
• The more electronegative atom has the greater electron density
• Elements such as O, F, N, Cl more electronegative than carbon
 Nucleophilic Substitution Reaction

Reaction

Reaction

•Rearrangement reactions – a molecule undergoes changes in

the way its atoms are connected
Nucleophilic addition reactions:

Electrophilic addition reactions:

Addition reactions – two molecules combine
• Addition of Cl2 and Br2
carried out with either the pure reagents or in an inert solvent such as CH 2Cl2
Br Br
CH3 CH= CHCH3 + Br2 CH3 CH-CHCH3
CH2 Cl2
2-Butene 2,3-Dibromobutane

• addition of bromine or chlorine to a cycloalkene gives a trans-dihalocycloalkane

Br Br
+ Br2 +
CH2 Cl2
Br Br
Cyclohexene
trans-1,2-Dibromocyclohexane
(a racemic mixture)

• addition occurs with anti stereoselectivity; halogen atoms add from the opposite face
of the double bond
CH3 CH3 Br2 CH3 CH3 CH3 CH3
H H H H
H H Br Br Br Br
S S R R
racemic mixture

CH3 CH3 Br CH3 CH3

H Br2 H
H H H
H CH3 Br CH3 Br Br
S R
meso
Racemic mixture
Addition of HX :
Carried out with pure reagents or in a polar solvent such as acetic acid
Addition is regioselective
Br H H Br
CH3 CH=CH2 + HBr CH3 CH-CH2 + CH3 CH-CH2
Propene 2-Bromopropane 1-Bromopropane
(not observed)
slow, rate
  determining
H
CH3 CH=CHCH3 + H Br CH3 CH-CHCH3 + Br
sec-Butyl cation
(a 2° carbocation
intermediate)
Br
+ CH3 CHCH2 CH3 fast
Br CH3 CHCH2 CH3
Bromide ion sec-Butyl cation 2-Bromobutane
(a nucleophile) (an electrophile)

Markovnikov’s rule: in the addition of HX, H2O, or ROH to an

alkene, H adds to the carbon of the double bond having the greater
number of hydrogens
On similar reduction other hydrocarbons are produced.
CH2= CH2 +H2 Ethane
CH3 CH= CH2 +H2 Propane
CH3 CH= CH CH3 +H2 Butane
• Addition of H2O
• addition of water is called hydration
• acid-catalyzed hydration of an alkene is regioselective; hydrogen adds preferentially
to the less substituted carbon of the double bond
• HOH adds in accordance with Markovnikov’s rule
OH H
H2 S O4
CH3 CH=CH2 + H2 O CH3 CH-CH2
Propene 2-Propanol
CH3 CH3
H2 S O4
CH3 C= CH2 + H2 O CH3 C-CH2
HO H
2-Methylpropene 2-Methyl-2-propanol
-Elimination: removal of atoms or groups of atoms from adjacent carbons to form a
carbon-carbon double bond
– a type of b-elimination called dehydrohalogenation (the elimination of HX)
• Saytzeff rule: the major product of a elimination is the more stable (the more highly
substituted) alkene
Br -
CH3 CH2 O Na
+
+
CH3 CH2 OH
2-Bromo-2- 2-Methyl-2-butene 2-Methyl-1-
methylbutane (major product) butene

Br CH3 O- Na+
+
CH3 OH
1-Bromo-1-methyl- 1-Methyl- Methylene-
cyclopentane cyclopentene cyclopentane
(major product)
• Substitution reactions – parts from two molecules exchange

Free Radical Substitution Reaction

Electrophilic Substitution Reaction

 Nucleophilic reactions: nucleophilic substitution (SN)

Nucleophilic substitution: -> reagent is nucleophil

-> nucleophil replaces leaving group
-> competing reaction (elimination + rearrangements)
leaving
group
nucleophilic
substitution
C Nu +
-
Nu -
+ C X X
Nucleophile

• in the following general reaction, substitution takes place on an sp3 hybridized (tetrahedral)
carbon

tert-butyl bromide tert-butyl alcohol

 Nucleophilic Substitution

• Some nucleophilic substitution reactions

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

-
HO CH3 -OH An alcohol
-
RO CH3 -OR An ether
-
HS CH3 -S H A thiol (a mercaptan)
-
RS CH3 -S R 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

21
 SN1 reaction: unimolecular nucleophilic substitution
SN1 is illustrated by the solvolysis of tert-butyl bromide
Step 1: ionization of the C-X bond gives a carbocation intermediate

Step 2: reaction of the carbocation (an electrophile) with aq. NaOH (a

nucleophile) gives an alcohol
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 3: proton transfer completes the reaction

H3 C H3 C CH3 H
CH3 H
+ fast +
C O + O C O + H O
H3 C H3 C
H CH3
H3 C H3 C CH3

C6 H5 C6 H5 C6 H5 C6 H5
-
-Cl CH3 OH
C Cl C+ + CH3 O C + C OCH3
-H H
H H H

Cl Cl Cl
Cl (S)-Enantiomer (R)-Enantiomer
(R)-Enantiomer Planar carbocation
(achiral)
A racemic mixture
SN1
An energy diagram for an SN1 reaction

24
 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

• An energy diagram for an SN 2 reaction

• there is one transition state and no reactive intermediate