"You cannot reason a person out of a position he did not reason himself into in the first place.

" Jonathan Swift

H N

H N

Br

O Indigo (Blue in Blue Jeans)

N H

Chapter 16

Br

O Tyrian Purple (Mollusks)

N H

Conjugated double bonds

Lycopene (red dye in tomatoes, berries)
2,6,10,14,19,23,27,31-Octamethyl-dotriaconta-2,6,8,10,12,14,16,18,20,22,24,26,30-tridecaene
H 3C

HO2C CO2H
H 3C

CH3

CH3 H 3C N Fe N N CH3
O R

N Mg N H 3C MeO O

N N CH3

O O

H 3C Heme

Chlorophyll

Conjugated Alkenes
Conjugated
CO2H

5.5 kJ/mole more stable than linolenic acid (below

Red Shift in electronic spectra More stable than corresponding non-conjugated molec sp2-sp2 s bonds are shorter and stronger than sp3-sp2 b

Not Conjugated
H H H H CO2H

Linolenic Acid

Identifying Conjugated Organics

O 1,4-cyc lohex adiene benzene 1-propenylbenzene

1,3-cyc lohex adiene

3-methy lenec yclohexene

cy clohexa-2,5-dienone

1,4-pentadiene

1,3-butadiene

1,3-pentadiene

cy clopentadiene

allylbenzene or 3-phenylpropene or 3-propeny l benzene

1,2-diphenylethane

1,2-diphenylethyne

trans-1,2-diphenylethene

trans-azobenzene

Conjugated C=C Bonds and Electronic Spectra

Conjugated Alkenes
HO2C CO2H

Crocetin (from Saffron; 422 nm)

O H N

O Indigo Blue (605 nm)

N H

Lycopene (505 nm)

H 3C CH3

620 nm 640 nm 600 nm

680 nm 720 nm 400 nm 420 nm 580 nm 560 nm 530 nm

H 3C N Mg N H 3C MeO O R O

N N CH3

O O

500 nm 430 nm 465nm

Chlorophyll a (675 nm)

Structure Determination in Conjugated Systems: UV Spectroscopy

The electrons in the highest occupied molecular orbital (HOMO) undergo a transition to the lowest unoccupied molecular orbital (LUMO)

Conjugated Alkenes
620 nm 640 nm 600 nm
680 nm 720 nm 400 nm 420 nm 430 nm 465nm 580 nm 560 nm 530 nm 500 nm
3 275 nm

# Do uble Bonds
1

max
177 nm

224 nm

310 nm

342 nm

380 nm

11

455 nm

Butadiene: Molecular Orbitals

1,3-Butadie ne
4

Ethyle ne

4 p-orbitals
215 nm 185 nm

H H H H
2

30 kJ/mole

H H

H H H H
1

Conjugated C=C Bonds and Electronic Spectra

620 nm 640 nm 600 nm 680 nm 580 nm 560 nm 530 nm

720 nm 400 nm
420 nm

500 nm 430 nm 465nm

Conjugation, Color and the Chemistry of Vision

b-Carotene is converted to Vitamin A, which is converted to 11-cis-retinal:

Conjugation, Color and the Chemistry of Vision

11-cis-retinal is converted to rhodopsin in the rod cells of the retina. Visual pigments are responsible for absorbing light in eye and triggering nerves to send signal to brain

SUNSCREENS
O OH H2N 4-Aminobenzoic acid PABA
1-(4-Methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione Avobenzone O O O

HO

O O N 2-ethylhexyl 2-cyano-3,3diphenyl-2-propenoate Octocrylene

N N N HO N N N

2,2_-methanediylbis[6-(2H-benzotriazol-2-yl)-4(2,4,4-trimethylpentan-2-yl)phenol] Bisoctrizole

Special Properties of Conjugated Dienes

Length of the central single bond is shorter than nonconjugated similar molecule Comparison of 1,3-Butadiene and Butane with C-13 NMR
148 pm H2C=CH-CH=CH2 1,3-Butadiene Shorter Bond 153 pm CH3-CH2-CH2-CH3 Butane

Why more stable (thermodynamics) than nonconjugated?

Isolated Conjugated 4

LUMO

LUMO 3

HOMO HOMO

p-p overlap is better than hyperconjugation

More reactive (kinetics) than non-conjugated

Isolated Conjugated

LUMO

LUMO 3

LUMO is lower more electrophilic

HOMO HOMO

HOMO is higher more nucleophilic

Faster reactions, less G for reactions (start lower)

Br H HBr H Br

Br H Br HBr Ea HBr H

Ea Br H Br H

Isolated

Conjugated

LUMO

LUMO 3

HOMO HOMO

Substracts Double bond character to C2-C3

Adds Double bond character to C2-C3

30 kJ/mole barrier to rotation

Diene Preparation
Based Induced Elimination of HX

Br

NBS CCl4

+K -OC(CH ) 3 3

HOC(CH3)3
3Bromocyclohexene 1,3Cyclohexadiene

Cyclohexene

Electrophilic Additions to Conjugated Dienes: Allylic Carbocations

Electrophilic addition to 1,3-Butadiene yields a mixture of two products: 1,2 addition 1,4 addition

Non-conjugated alkene addition reactions

CH3 H3C C CH2
2Methylpropene

HCl Ether

H3C C CH3 CH3

Tertiary Carbocation

Cl H3C C CH3 CH3

2-Chloro-2methylpropane

H2C C C C CH2 H H2 H

HCl Ether

Cl

Cl

H3C C C C CH3 H H2 H

 At room temperature, electrophilic addition to a conjugated diene leads to a product mixture where the 1,2 adduct predominates over the 1,4 adduct. At high temperatures, the product ratio changes and the 1,4 adduct predominates
Br
H2C C C CH2 H H

HBr

H2C C C CH3 H H
1,2 adduct

H3C C C C Br H H H2
1,4 adduct 29% 85%

At 0oC: At 40oC:

71% 15%

Reacting Butadiene with Electrophiles

H H Cl H H H H H ClCl Cl

Anti-Bonding

Non-Bonding

or

1/2

1/2

Bonding 1

Allyl Cations

Allylic and Benzylic Cations

H Cl HCl Ether H H

H Br HBr H minor major H H Br

Diene polymerizations

Vulcanization:

Diels-Alder Reaction
O RT O O Electron rich diene Electron poor alkene O O O

Net: 2 Pi bonds converted to sigma bonds in cycloaddition reaction yielding a six-membered ring

Diels-Alder Reaction
Dienes
R3SiO OMe

Dienophiles

O N R O O

O OMe

O OMe

CN NC

CN

O O Me O Me O CO2Me MeO O OMe

Diels-Alder Reaction:Diene Reactivity

Diels-Alder Possible NO Diels-Alder

s-cis "cis-like" arrangement about the middle carbon-carbon single bond

H H H H H H H H

s-tr ans "trans-like" arrangement about the middle carbon-carbon single bond

Generally more reacti than acyclic dienes

H H

H H No Reaction

s-trans

s-cis

Sterically driven to s-trans conf ormation

Locked in s-trans conformation

Diels-Alder Reaction
TWO MODES OF APPROACH H H O O O O H O H O H O H O

ONLY SYN ADDITION O O O H H O H O O H H O

O H O

No way of telling which approach is used with this syste

Diels-Alder Reaction
Meso TWO MODES OF A PPROA CH H H O 200 C O O O EXO H O (R) H O (R) (S) H O (S) H O (S) (S) H O (R) (R) H O O

O O O H H ENDO Room Temperature O O H (R) H O (R) (S) H O

(S) (R) H O O (S) H O (R)

O H O (S)

ONLY SYN ADDITION BUT ONLY THE ENDO (Bottom) DIASTEREOMER FORMS AT ROOM TEMP (KINETIC PRODUCT)

Meso

Diels-Alder Reaction
H H O O EXO

O O O H ENDO H
O

Higher temperature is required to reach product for exo path

O O O O G H O Ea H O

O O O H O G O H O Ea

Stability of exo product is greater

H O 200 C O H O ENDO

H O O H O EXO

Running reaction at room temp gives kinetic product (endo)

Running reaction at higher temp gives thermodynamic product (ex

Diels-Alder Reactions
O O OMe H H OMe H H CO2Me H

CN

CN

CN CN NC CN H

Me3SiO Me OMe O

Me3SiO

H 1) Heat 2) Aqueous acid

MeO Me O

Me O

Diels Alder in Synthesis

Look for cyclohexene = product of DA

O O O

O H O

Steroid Synthesis
The key DielsAlder reactions used to prepare the C ring of estrone and the B ring of cortisone are as follows:

38

Diels-Alder Reactions
RT 190 C
Me CO2Me

Me Me

Me

CO2Me

Me Me

Me CO2Me MeO2C Me

Me

CO2Me CO2Me

Me

Me

CO2Me

Me

CO2Me CO2Me

Me

MeO2C

Me

Diels-Alder Reactions
O H O H

O O NC CN

CN H H CN

O O Si O Me Me O O O O N O O Si Me Me O O N O > 90 C Me Me Si O N O O Me Si O Me O

Room Temperature

O N O O

Glassy Polymer

Viscous Liquid

Diels-Alder Reactions
O N N N R O

H N N H

O N R O

Diels-Alder Reactions
O 155 C Benzene H HO

O O -CO O

Diels-Alder Poly mer O

NMR of Dienes
5.80 2.15 2.15 5.80 5.90 5.90

4 PPM
124.7 22.1 22.1 124.7 125.8 125.8

120

100

80 PPM

60

40

20

NMR of Dienes
6.03 5.61

H
2.05

H
2.05

H
5.61

H
6.03

4 PPM

19.3

130.3 126.9

126.9 19.3

130.3

140

120

100

80 PPM

60

40

20

Need to know
Diene nomenclature Recognize conjugated versus non-conjugated systems Know reaction and mechanism: -addition of Br2 or Cl2 to dienes -addition of HCl or HBr to dienes -Diels Alder cycloaddition (exo and endo) Understand kinetic versus thermodynamics products for diene reactions and Diels Alder cycloaddition reactions Be able to synthesize dienes from alkanes through bromination and elimination reactions. Extra special: predict regiochemistry of Diels Alder cycloadditions
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