Conjugated Unsaturated

Systems
Introduction
❖ A conjugated system involves at
least one atom with a p orbital
adjacent to at least one p bond
● e.g.

conjugated allylic allylic allylic

diene radical cation anion
O

enone enyne
 1,3-Dienes such as 1,3-butadiene contain two carbon-carbon double
bonds joined by a single s bond

When p orbitals overlap, the electron density in each of the

p bonds is spread out over a larger volume, thus lowering the
energy of the molecule and making it more stable
 Allylic Substitution and the
Allyl Radical
vinylic X
carbons Electrophilic
X2 addition
(sp2)
low temp
CCl4 X

X2
+ H X
allylic high temp
carbon (and low conc. X Radical
(sp3) of X2) reaction
C-H bond is weaker in propene because the resulting allyl radical
is more stable than alkyl radicals
 Allylic Chlorination
(High Temperature)]

Radical reaction
o
400 C
+ Cl2 Cl + H Cl
gas phase
❖ Radical Reaction Mechanism
● a.Chain initiation

Cl Cl 2 Cl

● b.Chain propagation
H + Cl + H Cl

(allylic radical)
❖ Radical Reaction Mechanism
● b. Chain propagation
+ Cl Cl Cl + Cl

● c. Chain termination

+ Cl Cl
 Radical Reaction

H + H

o -1
DH = 369 kJmol

H + H

DHo = 465 kJmol-1

Radical Reaction Mechanism
Eact
H + X + HX
(low)

Eact
X + H + HX
(high)

Relative stability
allylic > 3o > 2o > 1o > vinylic
of radicals:
 Allylic Bromination with N-Bromo-
succinimide (Low Concentration of Br2)
❖ NBS is a solid and nearly insoluble in CCl4
● Low concentration of Br•
Br
H + O N O h or ROOR
(NBS) heat, CCl4

H
Br + O N
O
A reagent that is frequently used in ALLYLIC BROMINATIONS in the
laboratory is N-bromobutanimide (N-bromosuccinimide, NBS) suspended
in tetrachloromethane. This species is nearly insoluble in CCl4 and is a
steady source of very small amounts of bromine formed by reaction with
trace impurities of HBr

Mechanism:
❖ Examples : Allyllic bromination
Br

NBS
ROOR, CCl4
heat

NBS
ROOR, CCl4 Br
heat
The Stability of the Allyl Radical
Molecular Orbital Description of
the Allyl Radical
Ch. 13 - 17
Resonance Description of the
Allyl Radical

2 2
1 3 1 3

3
3
2 2
1
1
The Allyl Cation
❖ Relative order of Carbocation
stability
> >

(3o allylic) (3o) (allylic)

> > >

(2o) (1o) (vinylic)
Resonance Theory Revisited
Rules for Writing Resonance Structures
❖ Resonance structures exist only on paper.
Although they have no real existence of their
own, resonance structures are useful because
they allow us to describe molecules, radicals,
and ions for which a single Lewis structure is
inadequate
❖ We connect these structures by double-
headed arrows (), and we say that the
hybrid of all of them represents the real
molecule, radical, or ion
❖ In writing resonance structures, we
are only allowed to move electrons

resonance structures

H
H

not resonance structures

❖ All of the structures must be proper
Lewis structures

:O: O

X 10 electrons!

not a proper
Lewis structure
❖ All resonance structures must have
the same number of unpaired
electrons

X
❖ All atoms that are part of the
delocalized p-electron system must
lie in a plane or be nearly planar

no
delocalization
delocalization
of p-electrons
of p-electrons
❖ The energy of the actual molecule is
lower than the energy that might be
estimated for any contributing
structure

❖ Equivalent resonance structto the

hybrid, and a system descriures
make equal contributions bed by
them has a large resonance
stabilization
❖ The more stable a structure is (when
taken by itself), the greater is its
contribution to the hybrid

(3o allylic cation) (2o allylic cation)

greater contribution
 Estimating the Relative Stability
of Resonance Structures
❖ The more covalent bonds a
structure has, the more stable it is

(more stable) (less stable)

O O

(more stable) (less stable)

❖ Structures in which all of the atoms
have a complete valence shell of
electrons (i.e., the noble gas
structure) are especially stable and
make large contributions to the
hybrid
O O

this carbon has this carbon has

6 electrons 8 electrons
❖ Charge separation decreases
stability

OMe OMe

(more stable) (less stable)

Alkadienes and Polyunsaturated
Hydrocarbons

❖ Alkadienes (“Dienes”)
2 4
1
3 2 3
1,3-Butadiene
1 4

2 4 6 6 5
1 1,3-Cyclohexadiene
3 5
(2E,4E)-2,4-Hexadiene
❖ Alkatrienes (“Trienes”)
2 4 6 8

1 3 5 7

(2E,4E,6E)-Octa-2,4,6-triene
❖ Alkadiynes (“Diynes”)
1 2 3 4 5 6

2,4-Hexadiynes

❖ Alkenynes (“Enynes”)
6 5 6 7
4 1 3 5 8

2 2 4
3

Hex-1-en-5-yne (2E)-Oct-2-en-6-yne
Heks-1-en-5-una Okt-2-en-6-una
❖ Cumulenes
enantiomers

H H H H
C C C C C C
H H H H
(Allene)
(a 1,2-diene)
❖ Conjugated dienes

❖ Isolated double bonds

1,3-Butadiene: Electron
Delocalization
Bond Lengths of 1,3-Butadiene
1.47 Å
2 4

1 3

1.34 Å
sp3 sp sp3
sp2 sp3

1.54 Å 1.50 Å 1.46 Å

Conformations of 1,3-Butadiene
trans
single single
bond bond

cis
(s-cis) (s-trans)

H H

(less stable)
Molecular Orbitals of 1,3-Butadiene
Electrophilic Attack on Conjugated
Dienes: 1,4 Addition
2 4
H Cl
1 3 25oC

Cl
H + H
Cl
(78%) (22%)
(1,2-Addition) (1,4-Addition)
 H
Mechanism
X
❖

Cl H + H
(a)
Cl
H 1,2-addition product

(a)
(a) + +
Cl
H H
(b) (b)
(b)
H
Cl 1,4-addition product
Kinetic Control versus Thermodynamic
Control of a Chemical Reaction
Br
-80oC
+
Br
(80%) (20%)
+ At low temperature the major product is
formed by 1,2-addition.
HBr Br
+
40oC Br
(20%) (80%)
At higher temperature the major product
is formed by 1,4-addition.
 Br 40 oC, HBr

Br
1,2-Addition 1,4-Addition
product product

Kinetic product Thermodynamic

product
 The Diels–Alder Reaction:
A 1,4-Cycloaddition Reaction
of Dienes
In 1928 two German chemists, Otto Diels and Kurt Alder,
developed a 1,4-cycloaddition reaction of dienes ➔
one of such great versatility and synthetic utility that Diels
and Alder were awarded the Nobel Prize in Chemistry in 1950

[4p+2p]
+ [4+2]
cycloaddition

(diene) (dienophile) (adduct)

Diels–Alder reaction is one between a conjugated diene
(a 4p-electron system) and a compound containing a double
bond (a 2p-electron system) called a dienophile
 O O
❖ e.g.
benzene
+ O O
o
100 C

O O
1,3-Butadiene Maleic Adduct
(diene) anhydride (100%)
(dienophile)

The Diels–Alder reaction

➔ a pericyclic reaction:
concerted reactions that
take place in one step
through a cyclic transition
state in which symmetry
characteristics of
molecular orbitals control
the course of the reaction
All Diels-Alder reactions have the following
features in common:

[1] They are initiated by heat; that is, the Diels-

Alder reaction is a thermal reaction.
[2] They form new six-membered rings.
[3] Three p bonds break, and two new C - C a bonds
and one new C - C p bond form.
[4] They are concerted; that is, all old bonds are
broken and all new bonds are formed in
a single step.
11A. Factors Favoring the Diels–Alder
Reaction
Type A EDG EDG
EWG EWG
+

Type B EWG EWG

+
EDG EDG

- Type A and Type B are normal Diels-

Alder reactions
EWG =CHO, COR, CO2H, CO2R, CN, Ar, CO-O-CO,
or halogen
❖ Relative rate
O

30oC
Diene + O D.A. cycloadduct

O
❖ Relative rate

20oC
+ Dienophile D.A. cycloadduct
❖ Steric effects
11B. Stereochemistry of the
Diels–Alder Reaction
1. The Diels–Alder reaction is
stereospecific: The reaction is a syn
addition, and the configuration of the
dienophile is retained in the product
2. The diene, of necessity, reacts in
the s-cis rather than in the s-trans
conformation

O O
+
R
X R

Highly strained
 ❖ e.g.
COOMe COOMe
heat
+

(diene locked
in s-cis
conformation)
COOMe
heat
+ No Reaction

(diene locked
in s-trans
conformation)
❖ Cyclic dienes in which the double bonds are held
in the s-cis conformation are usually highly
reactive in the Diels–Alder reaction
❖ Relative rate
O

30oC
Diene + O D.A. cycloadduct

O
3. The Diels–Alder reaction occurs
primarily in an endo rather than an exo
fashion when the reaction is kinetically
controlled H H

longest bridge R is exo

R

H H H
EXO ➔the electron-withdrawing group of the
dienophile is aligned away from the p electrons
of the diene in the transition state
H
ENDO ➔ dienophile reacts such that the p
R R is endo electron orbitals of its electron withdrawing
group align under (or above) the p electron
electron orbitals of the diene,
❖ Alder-Endo Rule
● If a dienophile contains activating
groups with p bonds they will
prefer an ENDO orientation in
the transition state

ENDO ➔ dienophile reacts such that the p electron

orbitals of its electron withdrawing group align under (or
above) the p electron electron orbitals of the diene,
❖ e.g. Alder-Endo Rule
Alder-Endo Rule

Ch. 13 - 59
Ch. 13 - 63
❖ Stereospecific reaction

(i) X X
+
X X

X X
+
X X
❖ Stereospecific reaction
(ii) Y Y

Y Y
Y Y

+
Y

Y
❖ Examples
(A) Me Me
NC CN CN
D.A. CN
+
CN
NC CN CN

(B) Me Me Me
NC CN CN
D.A. CN
Me +
CN
NC CN CN
❖ Diene A reacts 103 times faster than
diene B even though diene B has two
electron-donating methyl groups

Me Me

Me Me
H

(s-c i s ) (s-t r ans )

❖ Examples
• Rate of Diene
(C) O O
H C > Diene D
(27 times), but
D.A. Diene D >>
+ O O
Diene E

O H O • In Diene C,
(D) O H O group →
electron
D.A. donating group
+ O O → increase
rate
O H O • In Diene E,
(E) O
2 tBu group →
D.A. steric effect,
+ O No Reaction cannot adopt
s-cis
conformation
O
Ch. 13 - 69