Chapter 10: Conjugation in Alkadienes and Allylic Systems
Conjugation: a series of overlapping p-orbitals
10.1: The Allyl Group - allylic position is the next to a double
bond
vinyl hydrogen
vinyl carbon H allylic hydrogen
(sp2 hybridized) C
C
C
H
allylic carbon
OH Cl
allyl alcohol allyl chloride
10.2: Allylic Carbocations - carbocation with a vinyl group
as a substituent (next to a double bond)
C
C C
220
Allyl carbocations are stabilized by resonance
C C
C C C C
C C !+ C !+
C C !+ C C !+
C C
Recall from Chapter 1.8:
The atoms must remain fixed in all resonance forms. Resonance
forms differ only by the placement of electrons
No one resonance form is entirely accurate. The actual structure
is a hybrid of all the resonance forms. Resonance forms do not
necessarily contribute equally to the resonance hybrid.
221
1
10.3: SN1 Reactions of Allylic Halides - allylic halides and
sulfonates are more reactive toward than simple alkyl halides
toward nucleophilic substitution by the SN1 mechanism
H H H H
CH3 H
H C H
C
C
C
CH3 H C CH3 H C C C CH3
C C CH3 C C
H Cl H CH3 H CH3 Cl CH3
over 100x more Resonance stabilized
reactive than carbocation intermediate
(H3C)C-Cl
H H
CH3 H
H C
C C CH3 H C C C CH3
H OH OH CH3
85 : 15
222
10.4: SN2 Reactions of Allylic Halides - allylic halides and
sulfonates are more reactive toward than simple alkyl halides
toward nucleophilic substitution by the SN2 mechanism
H H ~ 80x more
H C Cl SN2
C C
H
C
C
C
Nu reactive than
H H H H H H Cl-CH2CH2CH2CH3
223
2
10.5: Allylic Free Radicals
1/2 • C 1/2 •
C • C
C C
•
C C
C C
1 1/2 bonds
Map of the electron density
due to the unpaired electron
(the “spin”)
224
Free Radical Stabilities are Related to Bond-Dissociation Energies
410 kJ/mol •
CH3CH3 CH—
CH—H CH3CH2 CH2 + H•
397 kJ/mol •
(CH3)2CH—
CH—H (CH3)2CH + H•
380 kJ/mol •
(CH3)3C—H (CH3)3C + H•
368 kJ/mol •
H2C CHCH2—H H2C CHCH2 + H•
C—H bond is weaker in propene because the resulting allyl
radical is more stable than the alkyl radicals. 225
3
10.6: Allylic Halogenation - Allylic halogenation of an alkene
takes place through a free radical mechanism.
Br O
NBS, h!
N Br
CCl4
O
N-bromosuccinimide
(NBS)
226
Limitation: Allylic halogenation is only useful when all of the
allylic hydrogens are equivalent and the resonance forms of
allylic radical are equivalent.
NBS, h!
• •
Br +
Br
10.7: Allylic Anions
C C C
C C C C
!- C C !-
227
4
pKa ~ 60 _
CH3CH3 CH—
CH—H CH3CH2 CH2 + H+
_
pKa ~ 43
H2C CHCH2—H H2C CHCH2 + H+
10.8: Classes of Dienes
Diene: molecule with two double bonds
C-C
single bond
C C C
C=C
Alkene Diene double bonds Cumulated
Diene
Conjugate Diene (allene)
Conjugated diene: alternating double and single bonds 228
10.9: Relative Stabilities of Dienes
Recall from Chapter 6 that heats of hydrogenation (ΔH°H2) was
used to measure the relative stability of isomeric alkenes
Figure 10.4 (p. 396) ΔH°H2
H2, Catalyst
-126 KJ/mol
H2, Catalyst -252 KJ/mol
(2 x 126 = 252)
H2, Catalyst
-111 KJ/mol
(126 - 111 = 15)
H2, Catalyst
-226 KJ/mol
the double bonds of conjugated dienes are more stable than
isolated double bonds.
229
5
10.10: Bonding in Conjugated Dienes
When the carbons of a conjugate diene all lie in the same plane,
the π-molecular orbitals overlap.
• •
The four π-electrons of a conjugated diene • •
are delocalized over the four p-orbitals
_ • •• _
+
•
+
Bond lengths in pm
H3C CH3 H2C CH2 H2C CH CH3 H2C CH CH CH2 H2C CH CH CH2
153 133 151 146 134
230
There are three conformations of butadiene.
The (lower case) s prefix designates a conformation around
single (σ) bond. H H
H C H C
C H C H 180° rotation of
H
C
C
H H
C
C
H the central σ-bond
H H
s-trans s-cis
The perpendicular conformation is
16 KJ/mol higher in energy than the
90° rotation of the s-cis
Energy
central σ-bond
The s-cis conformation is 12 KJ/mol
s-cis higher in energy than the s-trans
231
s-trans
6
O
H
n
Vitamin A (retinal) poly-acetylene Arene
β-carotene
lycopene
alkenes conjugated to carbonyls
O
O
H
acrolein cyclohexenone
(!,"-unsaturated aldehyde, enal) (!,"-unsaturated ketone, enone)
alkenes conjugated to non-bonding pairs of electrons
O
R
O
N 232
10.11: Bonding in Allenes (please read)
sp hybridized
C C C
sp2 hybridized
10.12: Preparation of Dienes
Preparation of conjugated dienes (1,3-dienes) from alkenes:
allylic bromination followed by dehydrohalogenation
Br
NBS, h! (CH3)3CO - K+
CCl4
233
7
10.13: Addition of Hydrogen Halides to Conjugated Dienes
Isolated dienes: double bonds react independently.
Conjugated dienes: the π-bonds of a conjugated diene react as
a single unit.
Electrophilic Addition to Conjugated Alkenes: The addition of
HX to butadiene. Recall that the addition of HX to alkenes
follows Markovnikov’s Rule
H-X
X
X The observed product is
H3C
CH3
+ derived from the most stable
H
H3C carbocation intermediate
not observed
The addition of HX to a conjugated diene occurs to give a
resonance stabilized allyl carbocation
234
H H
H Br
Br Br
H Br
H
The distribution Br
of products is 1,2-addition 1,4-addition
(direct addition) (conjugate addition)
dependent upon
temperature 25 °C 44% 56%
-80 °C 81% 19%
At low temperature the reaction is under kinetic control, the
major product is the one that forms fastest.
The reaction is under thermodynamic control at higher
temperature, the major product is the most stable.
235
8
Figure 10.8
ΔG°act (1,2-addition) < ΔG°act (1,4-addition)
The 1,2-addition product is formed faster
than the 1,4-addition products. Kinetics
(rate) favors 1,2-addition
ΔG° (1,4-addition) > ΔG° (1,2-addition)
The 1,4-addition product is more stable
than the 1,2-adition products. Thermo-
dynamics favors 1,4-addition
236
10.14: Halogen Addition to Dienes
Electrophilc additions of other electrophile to dienes give
similar results
Br2 Br
+ Br
Br Br
37 % 63 %
1,4-addition
1,2-addition
Br2 Br
+ + Br
Br Br Br
Br
3% 21 % 76 %
1,2-addition 1,2-addition 1,4-addition
237
9
10.16: The π Molecular Orbitals of Ethylene and 1,3-Butadiene
π-MO’s of ethylene (from Chapter 2)
!-antibonding MO Lowest Unoccupied
ψ2 Molecular Orbital (LUMO)
!-bonding MO Highest Occupied
Molecular Orbital (HOMO)
ψ1
238
π-molecular orbitals of butadiene
3 Nodes
0 bonding interactions
3 antibonding interactions
ANTIBONDING MO
2 Nodes
1 bonding interactions
2 antibonding interactions
ANTIBONDING MO
1 Nodes
2 bonding interactions
1 antibonding interactions
BONDING MO
0 Nodes
3 bonding interactions
0 antibonding interactions
BONDING MO
ψ2 is the Highest Occupied Molecular Orbital (HOMO)
ψ3 is the Lowest Unoccupied Molecular Orbital (LUMO) 239
10
Molecular orbitals of conjugated polyenes
Antibonding
Energy
Bonding
H2C CH2
180 nm 217 nm 258 nm 290 nm
380 nm 400 nm 450 nm 500 nm 550 nm 600 nm 700 nm 780 nm 240
violet-indigo blue green yellow orange red
10.15: The Diels-Alder Reaction (a very important reaction) -
Reaction between a conjugated diene and an alkene (dienophile)
to give a cyclohexene.
‡
Diene Dienophile transition cyclohexene
state
Mechanism:
concerted - reaction (bond breaking and bond forming) takes
place in a single step.
Cycloaddition - non-cyclic reactant react to form a cyclic product
Pericyclic - cyclic “aromatic-like” transition state
‡
=
Diels-Alder Benzene
Transition State 241
11
The Diels-Alder reaction is favored by electron withdrawing
groups on the dienophile and electron donating groups on the
diene.
H H O O O
H R OR
H H
ethylene
(unreactive) conjugated carbonyls (aldehydes, ketones and esters)
O O
N CO2R
C
O
O O
Good dienophiles
The diene must adopt an s-cis conformation to be reactive:
s-trans s-cis
(unreactive conformation) (reactive conformation) very unreactive very reactive
diene diene
242
Stereochemistry of the Diels-Alder Reaction:
The stereochemistry of the alkene reactants (dienophile) is
preserved in the product.
O H O
H
!
+ O O
H
H
O O
O O
H
H !
+ CH3 CH3
H3C H H
CH3
O O
H
H !
+ CH3 CH3
H CH3 CH3
H
243
12
10.17: A π Molecular Orbital Analysis of the Diels-Alder
Reaction
HOMO ψ2 of butadiene
diene
ψ2 of ethylene
LUMO
dienophile
The orbitals between the diene and dienophile involved in
bond formation are in phase - symmetry allowed.
HOMO
CH2 CH2 orbitals are
CH2 CH2 out of phase
LUMO
Symmetry forbidden
244
13