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Reactions of 2-bromo-4-phenylcyclohexanols with base and silver oxide
C6H5 Br O
O
OH
C6H5 C6H5
Ag2O H
or OH- Ag2O Ag2O
or OH- Or OH-
OH
OH H
Stable not
C6H5 suitable for -HBr
OH
C6H5 Br C6H5
Br
Br
Ag2O
C6H5 Br OH
CHO
Ag2O induces –Br-
C6H5
C6H5
Br
OH- O
C6H5
OH
CHO
:OH
..
OH NaNO2, HCl NaNO2, HCl N2
N2
OH
OH
NH2 NH2
OH
OH
H
:OH
.. NH2 NH2
OH NaNO2, HCl NaNO2, HCl
N2
N2
O
O
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25-04-2020
Pericyclic Reactions
Three Classes of Organic Reactions
Polar reactions Y + R X R Y + X
R = aliphatic as well as aromatic
O OH
OH2
H+ OH
OH OH
..
.. O OH O OH
OH OH H
O H
O
O O
Radical reactions
CH3CH2 + Cl Cl CH3CH2Cl + Cl
Pericyclic reactions
This reaction occurs as a result of a cyclic reorganization of electrons
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Three most common types of pericyclic reactions
Elcetrocyclic reactions
new bond
Cycloaddition reactions new bond
Diels-Alder reaction
+
Sigmatropic reactions new bond
H3 C H3 C
new bond is formed
bond broken at the end of
bond is broken in the the -system
middle of the system
CH 2
H3C H H 3C H
Certain common features of pericyclic reactions
•They are all concerted reactions, electron reorganization takes place in
single step. Therefore, there is one TS and no intermediates
• As the reactions are concerted, they are highly stereospecific
• The reactions are generally not effected by catalysts or by a change in
solvent
Product configuration depends on
•Configuration of the reactant
•The number of double bonds in the reactant
•Whether the reaction is photochemical or thermal
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Some pericyclic reactions are induced thermally or photochemically
[4+2]-cycloaddition (Diels-Alder reaction)
X X
h
No reaction +
Y Y
[2+2]-cycloaddition
Ph Ph Ph Ph
h +
No reaction
Ph Ph
Ph Ph
Some pericyclic reactions are induced thermally and photochemically
Electrocyclic reaction
Me h Me Me
Me Me Me
Me
Me h Me
Me Me
Me
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Conservation of Orbital Symmetry Theory
R. B. Woodward and Roald Hoffmann (1965)
In phase orbitals overlap during the course of a pericyclic reaction
Based on Frontier Molecular orbital theory (1954, Fukui)
(HOMO, LUMO)
•The occupied orbitals of different molecules repel each other.
•Positive charges of one molecule attract the negative charges of the other.
•The occupied orbitals of one molecule and the unoccupied orbitals of the
other (especially the HOMO and LUMO) interact with each other causing
attraction.
Molecular orbital symmetry controls
•Weather or not compound undergoes a reaction under particular conditions
•What product will be formed
A molecular orbital description (ethene)
(zero probability of finding electrons)
•Overlap of in-phase p orbitals gives a bonding molecular orbital that is lower in energy
than the p atomic orbitals.
•Overlap of out-of-phase p atomic orbitals gives an antibonding molecular orbital that is
higher in energy than the p atomic orbitals.
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1,3-butadiene
Asymmetric
Nodes are more than no. of
bonding interactions
Symmetric
Asymmetric
bonding interactions are more
than no. of nodes
Symmetric
Four p atomic orbitals overlap to give the four molecular orbitals
1,3,5-hexatriene
Six p atomic orbitals overlap to give the six molecular orbitals
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Suprafacial and Antrafacial
Suprafacial
Four and six membered
rings must form through
Suprafacial
Antrafacial
Woodward-Hoffmann Rules for Cycloaddition Reactions
Even implies 4n electrons
Odd implies 4n+2 electrons
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Cycloaddition reactions
H3C CH3 a [4+2]
H3 C CH3
+
cycloaddition reaction
(Diels-Alder reaction)
O O O
O
O O
O O
heat
a [2+2]
+ O O cycloaddition reaction
UV light
O
O
Cycloaddition reactions
• Why does maleic anhydride react easily with butadiene,
but not at all with ethylene?
O
O
+ O O
O
O
O
O
+ O O
O O
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HOMO of one reactant should react with LUMO of the other reactant
Thermal Photo chemical
HOMO Excited state HOMO
LUMO LUMO
LUMO HOMO
HOMO LUMO
Q. Classify the following as [m+n] cycloaddition reactions
CH3
* +
CH3
O O
* +
CH2 OCH3 OCH3
* +
CH2
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25-04-2020
General description of Diels-Alder reaction
CHO CHO
diene dienophile adduct
+
NO2
diene dienophile NO2
adduct
Dienes permanently in s-cis conformation undergo Diels-Alder reactions with ease
Dienes permanently in s-trans conformation cannot undergo Diels-Alder reaction
Q. Which of the following do not respond to the Diels-Alder reaction as a diene?
Q. Arrange the following dienes according to their reactivity towards Diels-
Alder reaction
But
But
But
&
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Q. Following compounds are synthesized by Diels-Alder reaction, find
out suitable dienes and dienophiles for their synthesis.
O
Me O
O H
CO2Me
CN
CN O
CO2Me
H MeO
Captan
(an industrial application of Diels-Alder reaction)
O O O
H H
NH3
+ O O NH
H H
O O O O
H
Cl CCl3
S
N S CCl3
H
O
Captan
(agricultural fungicide)
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The endo rule for Diels-Alder reaction
O O
H
+ O O
H
O O
O
H
H O
O
H O
O
H
O 'exo' adduct (not formed)
'endo' adduct (formed)
H
+ H
'endo' adduct
Diels-Alder reaction : endo rule
endo
HOMO relationship
Primary bonding
between two alkenes
interactions leading
to new σ bonds
LUMO
Secondary bonding
Interactions leading to
endo product
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25-04-2020
Reaction of cyclopentadiene with maleic anhydride
HOMO
O
O O LUMO
primary bonding interaction
secondary bonding interaction
Cl Cl
Cl Cl
Cl Cl
O
Cl Cl
Cl Cl
Cl D ie ldrin Cl
A ld erin
In 1 95 0's tw o v ery effe ctive p es tic ide s
Cl Cl
Cl
Cl
O
Cl Cl O
O
flame retardent
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