Radical Allylic Halogenation!

high concentration!
low temperature
+ Cl2
CCl4

Cl
Cl

NBS generates low concentrations of Br2 and HBr!

NBS scavenges HBr to rapidly produce Br2!
Br2 production sustains chain reaction!
Large amounts of HBr results in addition across alkene!
O

low concentration!

+ Cl2

high temperature

N Br

O
hv or ROOR

Cl

CCl4

N H

O
NBS: N-bromosuccinimide!
NCS: N-chlorosuccinimide!

Initiation!
Propagation!

Br +

Br
N

O + H Br

H
N

O + Br Br

Termination (recombination of radicals in propagation)!

203 222B2 2016

Rev07.2016

Problem
1
!
26
!

!Page!
!585!
!619!

Allylic and Benzylic Halogenation!

Facile substitution due to the incipient radical stability!

+ X2
H H

+ HX

or

H H
H

X2

or

+ HX

Stability!
>~!

>

R3C

R3C H

>

R2HC

R2HC H

>

RH2C

R
RH
2HC
2C! H

>

H3C

H3C H

>

bond dissociation energy (kJ/mol)!

203 222B2 2016
Rev07.2016

Allylic Position!

Molecular orbitals are linear combinations of the constituting atomic orbitals (LCAO-MO)!
Node: site of no electron density (nodal plane)!

Number of nodal planes , energy of molecular orbital !

Conjugated unsaturated system: systems with p orbital on atom adjacent to a double bond!
Allylic system!

n!

n!

Delocalized electrons: electrons that are not confined to one atom or bond but shared by multiple atoms
and bonds!
Delocalization increase, number of resonance structure increase, stability increase!
Carbocation stability!

203 222B2 2016

Rev07.2016

Problem
2

!Page!
!587!

Delocalization and Resonance!

Delocalized electrons: electrons that are not confined to one atom or bond.!

Resonance forms are only for representation purposes, NOT the true structure!

Electrons that are shared by multiple atoms and bonds!

Electron delocalization stabilizes a molecule/ion.!
All atoms part of the delocalized system lie in the same plane (coplanar)!
Each resonance structure is a proper Lewis structure (octet rule)!
Each resonance structure has the same number of unpaired electron (there are exceptions)!
Full headed arrows represent movement of electron pairs!
Fishhook half arrows represent movement of single electrons!

The true structure is the resonance hybrid, a hybrid of all possible resonance forms!
The true structure energy is lower than each resonance structure!
resonance!
Different resonance forms are NOT in equilibrium!

equilibrium!

Difference between resonance forms is the placement of the and non-bonding valence electrons. Atoms are at the
same place, and the connection between atoms are the same!
Only electrons move (different resonance structures differ only in electron distribution)!

203 222B2 2016

Rev07.2016

O
Problem
3
5

!Page!
!590!
!591!

Resonance!

More stable resonance forms contribute more to the true structure!

Incomplete octet (duet) is bad!

Neutral form more stable than charge separated form!
More covalent bonds, more stable!
Negative charge on more electronegative atom, more stable!
Positive charge on less electronegative atom, more stable!

The more resonance structures, the more stable.!

203 222B2 2016

Rev07.2016

Problem
4

!Page!
!591!

Hyperconjugation!

Hyperconjugation: electron delocalization (via orbital overlap) from a filled bonding orbital to an adjacent
unfilled orbital!

Interaction between system with substituents!

Conformation (p163)!

Carbocation stability (p256)!

Alkene stability (p295)!

203 222B2 2016

Rev07.2016

Polyunsaturated Hydrocarbons!

Alkadiene: hydrocarbon containing 2 double bonds!

Alkatriene: hydrocarbon containing 3 double bonds!
Alkadiyne: hydrocarbon containing 2 triple bonds!
Alkenyne: hydrocarbon containing 1 double and 1 triple bond!
Cumulated alkenes: 1 carbon in two carbon-carbon double bonds (cumulenes)!
Conjugated alkenes: alternating double/triple and single bonds!
Isolated alkenes: one or more saturated carbon (sp3) between double bonds!
H

H
C

Lowest!
Unoccupied!
Molecular!
Orbital!
Highest!
Occupied!
Molecular!
Orbital!

203 222B2 2016

Rev07.2016

Problem
19

!Page!
!618!

Ultraviolet-Visible Spectroscopy (UV-vis)!

c = !
: frequency (Hz)!
: wavelength (m, 10-6 m; nm, 10-9 m)!
c: speed of light 2.99792458x108 m/sec!

E = h!
: frequency (Hz)!
h: Planks constant 6.63x10-34 Jsec!
E: energy (J)!

Absorption of UV-vis light (electromagnetic radiation/photons) corresponds to the excitation of electrons

from lower electronic energy levels to higher ones!
UV-vis spectrum = electronic absorption spectrum!

A = lc = log (Ireference/Isample)!
I: intensity of light!
c: concentration (M, mol/L)!
l: pathlength (cm)!
: molar absorptivity or extinction coefficient (AUM-1cm-1)!
A: absorbance!

-* alkenes: isolate, max<200 nm; conjugated max>200 nm!

Conjugation increase, max increase!

203 222B2 2016

Rev07.2016

Stability of Dienes!

Conjugated dienes more stable than non-conjugated dienes (isolated dienes are more stable
than cumulated dienes).!
More substituted dienes are more stable than less substituted dienes.!
Measured by heat of hydrogenation.!

Hhydrogenation (kJ/mol)!
+
H

H2

H
C

+ 2H2

+ 2H2

+ 2H2

+ 2H2

203 222B2 2016

Rev07.2016

Pt/C

Pt/C

Pt/C

Pt/C

Pt/C

Problem
23

!Page!
!619!

Conjugated Dienes
1,2- vs 1,4-Addition of Halides!

1,2-addition (direct addition) versus 1,4-addition (conjugate addition)!

Anti attack!
Cl
+ Cl2

203 222B2 2016

Rev07.2016

Cl

Cl
+ Cl

+ Cl

Cl

10

1,2- versus 1,4-Addition!

1,2-addition (direct addition) versus 1,4-addition (conjugate addition)!

Kinetic control: conditions that favor kinetic product!

Product favored at low temperatures, usually shorter reaction time!

Usually less stable product, but forms faster!

Thermodynamic control: conditions that favor thermodynamic product!

Product favored at high temperatures, usually longer reaction time!

Usually more stable product, but forms slower!

H Br

Br
H

203 222B2 2016

Rev07.2016

Br

Problem
9
10
20,25,29

11

!Page!
!605!
!607!
!619!

Diels-Alder Reaction!

Pericyclic reaction: concerted cyclic shift of electrons on the perimeter.!

Otto Diels and Kurt Alder (1950 Nobel Prize)!

[4+2] Cycloaddition reaction: form cyclic product with 4 electrons from the diene and 2 electrons from
the dienophile.!

Negative entropy!
Enthalpically favored: break two bonds, form two bonds!

HOMO (highest occupied molecular orbital) of diene and LUMO (lowest unoccupied molecular orbital) of
the dienophile react.!
s-cis conformation for the diene is necessary (s-trans, no reaction)!

203 222B2 2016

Rev07.2016

Problem
38
42

12

!Page!
!620!
!621!

Electron Donating/Withdrawing!

Inductive effect: through bond polarization, withdrawal or donation of electron density through bond due
to electronegativity!

Withdrawing!

Donating!

Resonance effect: through resonance contributions (lone pair), withdrawal or donation of electron density
through bond due to overlap of a p orbital on the substituent with a p orbital on the aromatic ring!

Withdrawing!

Donating!

203 222B2 2016

Rev07.2016

13

Electron Donating/Withdrawing!
Strongly Donating!

Moderately Donating!

Weakly Donating!

Strongly Withdrawing!

Moderately Withdrawing!

Weakly Withdrawing!

203 222B2 2016

Rev07.2016

14

Stereospecificity of Diels-Alder!

Reaction is stereospecific!
O
O

O
O

+
R

203 222B2 2016

Rev07.2016

15

Endo Configuration of Diels-Alder!

Endo configuration is favored if dienophile has substituents with electrons.!

p orbitals of dienophile substituent interact with p orbitals of diene.!

R
+

O
+

O
Problem
40
45

203 222B2 2016

Rev07.2016

16

!Page!
!621!
!622!

Regiochemistry of Diels-Alder!

Frontier molecular orbital considerations for unsymmetrical combinations!

OCH3

O
H

Normal electron demand Diels-Alder reactions!

EDG
EWG

EDG
+

EWG

Inverse electron demand Diels-Alder reactions !

EWG
EDG
+

EWG
+
EDG

203 222B2 2016

Rev07.2016

17

Diels-Alder: Reactivity!

Reactivity: cyclic dienes are more reactive than acyclic ones (forces s-cis) !

OCH3
O

203 222B2 2016

Rev07.2016

18

Stereochemistry of Diels-Alder!

Endo configuration is favored if dienophile has substituents with electrons.!

Frontier molecular orbital considerations for unsymmetrical combinations!
A

A B
B
C

B A

C D

D C

E
F
H
G

+
D C

A
B
C

G
E

G
H
F
E

F/H endo!

A B

A B

A B

D C

bottom!
C D

F
E
G
H

top!
D C
B A

E
F
H
G

bottom!
C D

G
H
F
E

H
G
E
F

top!
D C
B A

bottom!
C D

G
H
F
E

E/G endo!

top!

203 222B2 2016

Rev07.2016

A B

F/H endo!

B A
E
G
H

E
F
H
G

A
B
C

F
H

E/G endo!

D C

A
B
C

E
G

A B

A
B
C
D

H
G
E
F
Problem
!Page!
14-17
!616!
39
!620!
43,44
!621!
49
!622!
Comprehensive!
28,30
!619!
33
!620!

19