Академический Документы
Профессиональный Документы
Культура Документы
OH
+
OH
..
..
OH
O
H
OH
O
O
OH2
OH
OH
OH
H
O
Radical reactions
CH3CH2 +
Cl
Cl
CH3CH2Cl + Cl
Pericyclic reactions
This reaction occurs as a result of a cyclic reorganization of electrons
OH
Cycloaddition reactions
new bond
+
new bond
Sigmatropic reactions
H3C
H3C
CH2
H3C
H3C
Electrocyclic reaction
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Electrocyclic Reactions
These reactions are defined as involving the cyclization of an n pi-electron
system to an (n-2)pi + 2sigma-electron system or the reverse process.
(n-2)e
(n-2)e
disrotatory
ring closure
-system
disrotatory
B
-system
-system
conrotatory
conrotatory
ring closure
CO2Me
CO2Me
Conrotatory
H
CO2Me
example:
H
CO2Me
H
H
Elcetrocyclic reactions
CH3
CH3
CH3
tion
a
t
o
r
con
H
CH3
H
CH3
disrota
tion
H
CH3
HH
CH3
CH3
H
rota
n
o
c
tion
H
H
CH3
CH3
CH3
disrota
tion
H
CH3
H
F bond length
1.42 A0
H bond length
0.74 A0
F bond strength
38 Kcal/mol
H bond strength
104 Kcal/mol
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.
HOMO
HOMO
Thermally allowed,
Thermally forbidden,
photochemically forbidden photochemically allowed
4q
Conrotatory
Disrotatory
4q+2
Disrotatory
Conrotatory
q = integer
CH3 disro
H H
CH3
on
tati
h
conrot
ation
CH3
CH3
CH3
CH3
CH3
H
CH3
H
tion
a
t
o
disr
CH3
CH3
con
rot
atio
n
CH3
CH3
HOMO
LUMO
*
H
CH3
CH3
H
H
H
H
CH3
CH3
Q. Show that the cyclobutane below open by two alternative conrotarory procsses.
What is the product in each instance? Do you expect them to be formed in equal
amounts?
CH3
H
H
CH3
H3C
CH3
CH3
CH3
CH3
CH3
an electrocyclic reaction
CH3
CH3
CH3
h
HO
HO
provitamin D3
7-dehydro cholesterol
H3C
CH3
CH2
vitamin D3
CH3
CH3
Cycloaddition reactions
H3C
H3C
CH3
O
O
O
CH3
a [4+2]
cycloaddition reaction
(Diels-Alder reaction)
heat
O
UV light
a [2+2]
cycloaddition reaction
CHO
diene
dienophile
adduct
+
NO2
diene
dienophile
NO2
adduct
Captan
(an industrial application of Diels-Alder reaction)
O
NH3
O
Cl
NH
CCl3
S
Captan
(agricultural fungicide)
CCl3
O
O
H
O
'endo' adduct