14.

Conjugated Compounds
and Ultraviolet Spectroscopy
共軛化合物和紫外線光譜

Based on McMurry’s Organic Chemistry, 9th edition

Conjugated and Nonconjugated Dienes
 Compounds can have more than one double or triple
bond
 If they are separated by only one single bond they
are conjugated 共軛 and their orbitals interact
 The conjugated diene 共軛二烯 1,3-butadiene has
properties that are very different from those of the
nonconjugated diene, 1,5-pentadiene

1,3- 丁二烯
2
 Why this Chapter?
 Conjugated compounds are common in nature
 Extended conjugation leads to absorption of visible
light, producing color
 Conjugated hydrocarbon with many double bonds are
polyenes (lycopene is responsible for red color in
tomatoes)
 Examine properties of conjugated molecules and
reasons for the properties

Lycopene 茄紅素 A conjugated polyene

3
 14.1 Stability of Conjugated Dienes:
Molecular Orbital Theory

 Conjugated dienes 共軛二烯 are typically formed

by elimination of HX from an allylic halide

4
 Stability of Conjugated Dienes
 Significant properties of conjugated dienes
 Possess a shorter central single bond

 Conjugated dienes are more stable than

nonconjugated indicated by heats of hydrogenation
Heats of Hydrogenation for Some Alkenes
and Dienes
Stability of Conjugated Dienes: Valence Bond Theory
 According to the valence bond theory, orbital
hybridization is the reason behind the stability of
conjugated dienes
 Central C–C single bond is caused by σ overlap of sp2
orbitals and is shorter and stronger than sp3
 sp2 orbitals possess 33% s character and sp3 orbitals possess
25% s character

H2C C C CH2 H2C C C CH2 H2C C C CH2

H H H H H H
 Stability of Conjugated Dienes: Molecular
Orbital Theory
 Interaction between the  orbitals of a conjugated
diene causes an increased stability
 According to the molecular orbital theory, two 
molecular orbitals result when a  bond is formed by
the combination of two p orbitals
 One  molecular orbital possesses lesser energy than
the starting p orbitals causing it to be bonding
 The other  molecular orbital possesses a higher energy
than the starting p orbitals and has a node between
nuclei, causing it to be antibonding
Molecular orbital of nonconjugated dienes

Two isolated C=C

Stability of Conjugated Dienes: Molecular Orbital
Theory

 Conjugated Dienes generate four  molecular

orbitals:
 2 bonding molecular orbitals and 2 antibonding
molecular
 The 4  electrons occupy two bonding molecular
orbitals and lower energy than in isolated C=C

10
Molecular orbital of conjugated dienes
Two conjugated C=C
MO Energy Diagram

• The average
energy of electrons is
lower in the
conjugated
compound.
•This lower energy (E)

is the resonance
stabilization of the
E conjugated diene

12
 Stability of Conjugated Dienes: Molecular Orbital
Theory
 In addition, The bonding -orbitals are made from 4 p
orbitals that provide greater delocalization ( 非定域 ) and
lower energy than in isolated C=C
 we say electrons in 1,3-butadiene are delocalized over
the  bond system
 Delocalization leads to stabilization

H2C C C CH2 H2 C C C CH2 H2C C C CH2

H H H H H H

C H C H
HC C H
H H

conjugation: 2p orbital overlap 13

14.2 Electrophilic Additions to Conjugated Dienes:
Allylic Carbocations
 Review: addition of electrophile to C=C
 Markovnikov regiochemistry via more stable carbocation

15
1,2- and 1,4-Addition to Conjugated Dienes
 Conjugated dienes undergo electrophilic reactions to produce a
mixture of products
 1,2- and 1,4-Addition product
 1,4-addition products are formed due to the intermediate action of
allylic carbocations
 For conjugated dienes, the intermediate is a resonance
stabilized allylic cation 烯丙基陽離子 .
 Nucleophile adds to either carbon 2 or 4, both of which have the

delocalized positive charge.

 1,2- and 1,4-Addition
共軛雙烯的親電子加成反應得到 1,2- 和 1,4- 加成產物，中間體涉及一穩定
的 allylic cation

16
 1,2- and 1,4-Addition to Conjugated Dienes

1 2 3 4
1,2- and 1,4-Addition to Conjugated Dienes

0o C
 Electrophilic Additions to Conjugated Dienes:
Allylic Carbocations
 Addition of H+ leads to delocalized allylic carbocation
Mechanism
Step 1:
delocalized allylic cation
2 4
1 1

primary allylic
1,2-addition intermediate 1,4-addition intermediate
0o C

19
 Products of Addition to Delocalized Carbocation
 The reaction between Br– the allylic cation occurs either at C1 or C3 as
both carbons share the positive charge

The transition states for the two possible products are not equal in energy

Step 2:
1 2 1
4

20
 Addition of HBr
delocalized allylic cation
H H +
H H H H
H
H2C C C CH2 H3C C C CH2 H3C C C CH2
+ +
2 allylic carbocation 1 allylic carbocation
more stable
_ _
Br Br

H H H H
H3C C C CH2 H3C C C CH2
Br Br
1,2-addition product 1,4-addition product
more stable

21
14.3 Kinetic vs. Thermodynamic Control of
Reactions
 Thermodynamic Control 熱力學控制 : At completion, all
reactions are at equilibrium and the relative concentrations are
controlled by the differences in free energies of reactants and
products
( 熱力學控制 , 平衡控制 )
平衡時，利用産物的相對穩定度，來控制的主産物和副産物的比例。
 Kinetic Control 動力學控制 : If a reaction is irreversible or if a
reaction is far from equilibrium, then the relative concentrations of
products depends on how fast each forms, which is controlled by
the relative free energies of the transition states leading to each
( 動力學控制 , 反應速度控制 )
非平衡時，利用過渡狀態相對能量大小或者反應速率的相對快慢，
來控制的主産物和副産物的比例。

22
Kinetic versus Thermodynamic Control of
Reactions
 Consider a reaction with B and C as products

B forms faster than C

 ΔGǂB < ΔGǂC
C is more stable than B
 ΔG˚C > Δ G˚B
動力學控制 不可逆反應
AB

熱力學控制 可逆反應
AC
Energy Diagram for Competing Reactions
動力學控制
AB

熱力學控制 AC
 Kinetic versus Thermodynamic
Control of Reactions
 Reactions under kinetic control 動力學控制
 Product of an irreversible reaction depends
only on relative rates and not on stability
 B is the major product
 Reactions under thermodynamic control 熱力學控制
 Product of a readily reversible reaction
depends only on stability and not on relative
rates
 C is the major product
Kinetic and Thermodynamic Control of
Reactions
 Addition to a conjugated diene at or below
room temperature normally leads to a mixture
of products in which the 1,2 adduct
predominates over the 1,4 adduct
 At higher temperature, product ratio changes
and 1,4 adduct predominates

26
 1,2- and 1,4-Addition
 Applying the principles of kinetic control and
thermodynamic control to the electrophilic addition
reactions of conjugated dienes
 Kinetic control ( 動力學控制 , 反應速度控制 ) :
 in addition of HBr to a conjugated diene, 1,2-
addition occurs faster than 1,4-addition

+ +
CH2 = CH-CH-CH3 CH2 -CH=CH-CH3
a 2° allylic carbocation a 1° allylic carbocation
(greater contribution) (lesser contribution)
1,2-addition intermediate 1,4-addition intermediate

more faster 27
1,2- and 1,4-Addition
 Thermodynamic control ( 熱力學控制 ; 平衡控
制 ): in addition of HBr to a butadiene, the
1,4-addition product is more stable than the
1,2-addition product
Br CH3 H
CH3 CHCH= CH2 + C C
H CH2 Br
3 - bromo-1-butene
(less stable alkene) 4- bromo-2-butene
(more stable alkene)
1,2-product 1,4-product
more stable
 Kinetic Control at 0°C
 At 0°C, transition state for the 1,2-addition has a lower
Ea because it is a more stable allylic secondary
carbocation.
 The 1,2-addition will be the faster addition at any
temperature.
 The nucleophilic attack of the bromide on the allylic
carbocation is irreversible at this low temperature.
 The product that forms faster predominates (kinetic
product).
 Because the kinetics of the reaction determines the
product, the reaction is said to be under kinetic control.

29
 Thermodynamic Control at 40°C
 The 1,2-addition is still the faster addition, but at
40°C, the bromide attack is reversible.
 The 1,2-product ionizes back to the allylic cation.
 An equilibrium is established at 40 °C, which
favors the most stable product: more stable
alkene
 The 1,4-addition is the most stable product
(thermodynamic product) because it has a more
substituted double bond.
 Because the thermodynamics of the reaction
determines the product, the reaction is said to be
under thermodynamic control.

30
Kinetic vs. Thermodynamic Control
Kinetic control Thermodynamic
at 0C Control at 40C

Major product
at 40C

Major product
at 0C
Kinetic product Thermodynamic
product
•低溫不可逆反應動力學控制。高溫可逆反應熱力學控制。

•低溫時： 1 ， 2- 加成產物易生成（活化能較低），是由反應速度決定的產物

（動力學控制）。 1 ， 4- 加成不易進行（活化能較高）。
高溫時： 1 ， 4- 加成為主要產物（為較穩定產物，達到平衡時比例高） ，是 31

由穩定性決定的產物（熱力學控制）
Kinetic vs. Thermodynamic Control
14.4 The Diels-Alder Cycloaddition Reaction
 Cycloaddition reaction 環加成反應 in which conjugated dienes
undergo an addition reaction with alkenes to yield substituted six-
membered cyclohexene 環己烯 products
 The formation of the ring involves no intermediate (concerted
formation of two bonds 一步的協同反應 )
( 協同反應 : 反應一步完成，不經歷中間體，只經歷一個過渡狀態 )

• The reaction is very useful to create cyclic molecules

• Nobel prize, 1950

反應特點：
産物為六元碳環結構

立體特異性反應

 位置特異性反應

環加成反應，獲得環狀化合物的方法 33
The Diels-Alder Cycloaddition Reaction
 The Diels-Adler reaction is a pericyclic reactions
 Pericyclic reactions 周環反應 are single-step
reactions that redistribution of bonding electrons
through a cyclic transition state 六環過渡狀態
Mechanism of the Diels–Alder cycloaddition reaction

 The reaction occurs in a single step through a cyclic

transition state 環狀過渡狀態 in which the two new
carbon–carbon bonds form simultaneously.
(concerted reaction 協同反應 )

H W H
C  C W
C C H
H H
H
diene dienophile cyclohexene
Nucleophile Electrophile

35
 Orbital Overlap of the Diels–Alder
Reaction - Concerted Mechanism

2 1 2 1
2 1

3 3
3 4
4

36
Mechanism of Diels-Alder Reactions
環己烯

二烯 親二烯劑
Nucleophile Electrophile
環己二烯
 Orbital Overlap of the Diels–Alder
Reaction - Concerted Mechanism

2 1 2 1
2 1

3 3
3 4
4

38
 14.5 Characteristics of the Diels-Alder Reaction
• The Denophile (diene lover) 親二烯劑
• The alkene possesses an electron-withdrawing substituent,
such as C=O or CN, the Diels-Adler reaction takes place
at a high speed
• Alkynes can also be dienophiles

Electrophile

順丁烯二酸酐 苯醌
39
 Denophile
Electrostatic potential maps of ethylene, propenal, and
propenenitrile show that electron-withdrawing groups
make the double-bond carbons less negative

reactive
unreactive reactive
dienophile
dienophile dienophile
Stereochemical Requirements
Diels-Alder 反應為立體特異性的反應
 syn stereochemistry 同邊立體化學
- the configuration of the dienophile is retained
: syn stereochemistry.
 endo rule 內向型法則

 s-cis conformation

- Diene must be in s-cis conformation.

Stereospecificity of the Diels-Alder Reaction
 The Diels-Adler reaction is stereospecific 立體特異性
 Forms a single product stereoisomer
 Retains the stereochemistry of the dienophile

Z- dienophile
 cis product

E- dienophile
 trans product
 Endo and Exo isomer
 Endo-exo isomer is a special type of isomer with a
substituents on a bridged bicyclic 橋鍵聯雙環烷 system.
 endo 內向型 : for the isomer with the substituent located

closest, or "syn" (cis) to the longest bridge (2-C bridges)

 exo 外向型 : for the isomer with the substituent located

closest to the shortest bridge (1-C bridges) or “anti" to

the longest bridge
Stereochemistry of the Diels-Alder Reaction
 The orientation of the diene and dienophile partners favors
the formation of the endo product instead of the exo product
 Diels-Adler reactions yield endo products because the
reactants are positioned directly above one another
 Increased overlap of diene and dienophile orbitals

順丁烯二酸酐
44
 Endo Rule
 The p orbitals of the electron-withdrawing groups on the
dienophile have a secondary overlap with the p orbitals of
C2 and C3 in the diene.
 Secondary overlap( 次級軌道作用 ) stabilizes the transition
state, and it favors products having the electron-
withdrawing groups in endo positions ( 內向型位置 )
 Conformations of Dienes in the Diels-Alder
Reaction
 Dienes can undergo a Diels-Adler reaction only if
they adopt an s-cis conformation
 s-cis :“s” stands for “single bond”
 Carbons 1 and 4 are close enough to react through
cyclic transition, unlike the s-trans conformation

less stable more stable

只有 s-cis 1,3-Butadiene 参
與 Diels-Alder reaction
 The conformation of the diene must be s-cis
• Dienes that are unable to adopt a s-cis
conformation do not undergo Diels-Adler reactions

• 1,3-cyclopentadiene : Fixed s-cis diene, highly reactive

in Diels-Adler reactions
 Regiospecificity 位置特異性 補充

 Para/Ortho rule 對位 / 鄰位法則 : The 6-membered ring

product of the Diels-Alder reaction will have electron-
donating (diene) and electron-withdrawing groups
(dienophile) at 1,2 or 1,4 position but not 1,3 position.

H H D
D
C 1,4 position
C para
W W
H
H H
not
C D W
1,2 position
C
W W ortho
H
D D
48

位置特異性 : 鄰位或對位產物為主要產物
補充

49
 補充

OCH3 OCH3
O O

H H
50
14.6 Diene Polymers: Natural and Synthetic
Rubbers
 Conjugated dienes can be polymerized
 The initiator for the reaction can be a radical, or an
acid
 Polymerization: 1,4 addition of growing chain to
conjugated diene monomer

51
 Natural Rubber
 A material from latex 膠乳 , in plant sap 植物汁液
 In rubber repeating unit has 5 carbons and Z stereochemistry of all C=C
 Gutta-Percha 馬來樹膠 is natural material with E in all C=C
 Looks as if it is the head-to-tail polymer of isoprene 異戊二烯 (2-methyl-
1,3-butadiene)

異戊二烯

52
 Synthetic Rubber
 Diene polymerization is used in the commercial
production of rubber
 Polymerization of chloroprene yields neoprene
 Expensive synthetic rubber with good weather 風化
resistance

2- 氯丁二烯
 Vulcanization 硫化 , 硬化
 Natural and synthetic rubbers are too soft to be used in products
 Vulcanization involves heating rubber with sulfur which causes the
rubber to harden
 Sulfur forms bridges between hydrocarbon chains (cross-links)
 Elasticity of rubber is due to the irregular structure of polymer
chains caused by the double bonds
 Double bonds cause polymers to bend

54
 14.7 UV Spectroscopy

UV Spectroscopy specifically used to determine the molecular
structure of conjugated compounds
 Not used as widely as mass spectrometry, infrared
spectroscopy, or nuclear magnetic resonance
 Examines the nature of conjugated  electron system

 Conjugated compounds can absorb light in the ultraviolet region

(200-400 nm) of the spectrum
 200-400 nm photons excite electrons from a  bonding orbital to
a * antibonding orbital.

Mass spectrometry Molecular size and formula

Infrared spectrometry Functional groups
NMR spectrometry Carbon-hydrogen framework
UV spectrometry Nature of conjugated  electron system
55
 UV Spectroscopy
 Ultraviolet region of electromagnetic spectrum
 Short-wavelength of the visible region to the long-
wavelength end of the X-ray region
 The region from 2 x 10-7m to 4 x 10-7m (200 to 400 nm) is most
useful in organic chemistry
 200-400 nm photons excite electrons from a  bonding
orbital to a * antibonding orbital.

56
 Principle of UV Spectroscopy

 Organic molecules absorb enough energy from UV

radiation to cause an electron shift from a lower-
energy orbital to a higher-energy orbital
 UV irradiation causes a  electron to shift from

the highest occupied molecular orbital

(HOMO) to the lowest unoccupied molecular
orbital (LUMO)
 Termed pi to pi star ( to *) excitation
 Ultraviolet Excitation of 1,3-Butadiene
 Example: 1,4-butadiene has four  molecular orbitals
with the lowest two occupied
 Electronic transition is from HOMO to LUMO at 217
nm (peak is broad because of combination with
stretching, bending)

基態 激發態

58
Ultraviolet Excitation of 1,3-Butadiene and
Ethylene
   * for ethylene and butadiene

59
 Recording an Ultraviolet Spectrum
 A sample is irradiated with UV light whose
wavelength alternates continuously
 Energy is absorbed when the wavelength matches
the energy required to cause electron displacement
 Absorbed energy is detected and displayed on a chart
that plots wavelength versus absorbance (A)

I0
A  log
I
 Quantitative Use of UV Spectra
 Ultraviolet Spectrum: A plot of absorbance (A) versus
wavelength ()
I0
A  log
I
A: absorbance
I0: intensity of the incident light
I: intensity of the light transmitted through sample

 Absorbance, A, follows Beer’s Law:

A = cl
 : Molar absorptivity 莫耳吸收係數 (extinction coefficient)
c: Concentration in mol/L
l: Sample pathlength in cm
 To determine the concentration of the sample when A, ɛ,
and l are known A
c
 .l
61
14.8 Interpreting UV Spectra: The Effect of
Conjugation
 Wavelength of UV radiation that causes  to * excitation in a
conjugated molecule ultimately depends on the nature of the
conjugated system
 Degree of conjugation has a significant influence on the
wavelength of UV absorption
 Energy difference between HOMO and LUMO ( * ) is

inversely proportional to the degree of conjugation

 max: wavelength where UV absorbance for a compound is greatest
 max increases as conjugation increases (lower energy)
 1,3-butadiene: 217 nm, 1,3,5-hexatriene: 258 nm
 Substituents on  system increase max

63
Ultraviolet Absorptions of Some Conjugated
Molecules
Sample UV Absorptions

65
14.9 Conjugation, Color and the Chemistry of
Vision
 Visible region is about 400 to 800 nm
 Extended conjugation systems of some compounds cause
their UV absorptions to extend into the visible region
 The key substance for vision, -Carotene  胡蘿蔔素 , 11
double bonds in conjugation, max = 455 nm

視網醛 66
Ultraviolet Spectrum of β-carotene
 Conjugation, Color and the Chemistry of Vision
 Human vision is possible through the light-sensitive
receptor in the eye, Rhodopsin 視紫質 .
 Rhodopsin is responsible for absorbing light in eye
and triggering nerves to send signal to brain

視紫質 opsin 視蛋白

68
Summary

 Conjugated diene comprises alternating double

and single bonds
 Conjugated dienes are more stable than
nonconjugated dienes
 The formation of 1,4-addition products are
exclusive to reactions with conjugated dienes
 In a reaction involving formation of 1,2 NS 1,4-
addition products, kinetic control is believed to
cause the 1,2 adduct and thermodynamic
control is believed to cause the 1,4 adduct
Summary

 Diels-Adler cycloaddition is another reaction

unique to conjugated dienes
 Reaction is stereospecific
 Ultraviolet spectroscopy is specifically used in
the determination of conjugated π-electron
systems
 Upon UV irradiation, energy is absorbed that
causes the π electron to shift from the highest
occupied molecular orbital (HOMO) to the
lowest unoccupied molecular orbital (LUMO)