15.

Benzene and
Aromaticity
苯與芳香性

Based on McMurry’s Organic Chemistry, 9th edition

Aromatic Compounds 芳香族化合物
 Aromatic was used to described some fragrant
compounds in early 19th century
 Current: distinguished from aliphatic 脂肪族
unsaturated compounds by chemical behavior
(aromatic unsaturated compounds that undergo
substitution rather than addition)
Why this Chapter?

 Reactivity of substituted aromatic compounds

is tied to their structure

 Aromatic compounds provide a sensitive

probe for studying relationship between
structure and reactivity

3
15.1 Sources and Names of Aromatic
Hydrocarbons
 Coal 煤渣 and petroleum 石油 are the major sources of simple
aromatic compounds
 Petroleum primarily comprises alkenes and few aromatic compounds

苯 甲苯 二甲苯 茚

萘 蒽 菲
聯苯 4
 Naming Aromatic Compounds
 Aromatic compounds possess the largest number of
nonsystematic names, of which some are allowed by the IUPAC
 Many common names (toluene 甲苯 = methylbenzene; aniline
苯胺 = aminobenzene

甲苯 苯甲醛

酚 苯甲酸

苯胺 二甲苯

苯乙烯

苯乙酮
Naming Aromatic Compounds
 Monosubstituted benzenes have systematic names
with –benzene being the parent name
 C6H5Br = bromobenzene
 C6H5NO2 = nitrobenzene
 C H CH CH CH
6 5 2 2 3 = propylbenzene

6
 The Phenyl Group
 Arenes 芳烴 are alkyl-substituted benzenes
 Based on the size of the alkyl substituents, they are
termed alkyl-substituted benzene or phenyl-substituted
alkane

The term phenyl 苯基 (Ph or Φ) is used when a
benzene ring is a substituent in the –C6H5
 The term benzyl 甲苯基 is used for the C6H5CH2– group

CH2Cl benzyl
chloride
7
 Disubstituted Benzenes
 Relative positions on a benzene ring
 ortho- (o) 鄰位 on adjacent carbons (1,2)

 meta- (m) 間位 separated by one carbon (1,3)

 para- (p) 對位 separated by two carbons (1,4)

 Describes reaction patterns (“occurs at the para position”)

8
Naming Benzenes With More Than Two Substituents
 Numbers with the lowest possible values are chosen
 List substituents alphabetically with hyphenated numbers
 Common names, such as “toluene” can serve as root name (as in
TNT)

當苯環上連有多個官能團時，以優先的官能團為主體，從該官能團
開始編號，其他的為取代基
9
 15.2 Structure and Stability of Benzene
 The reactivity of benzene is much lesser than that of alkenes
 Benzene reacts slowly with Br2 to give bromobenzene (where Br
replaces H)
 Substitution reaction rather than addition reaction that is common
to alkenes, suggesting that in benzene there is a higher barrier

10
Heats of Hydrogenation as Indicators of Stability
• Benzene has about 150 kJ/mol (36 Kcal/mol) more
“stability” than an isolated set of three double bonds
• Unusual Stability of Benzene
 150 kJ/mol (36 Kcal/mol)  Resonance energy
 Unusual Structure of Benzene
 All its C-C bonds are the same length: 139 pm —
between single (154 pm) and double (134 pm) bonds
 Electron density in all six C-C bonds is identical
 Structure is planar, hexagonal
 C–C–C bond angles 120°

12
 Unusual Structure of Benzene
 Each C is sp2 and has a p orbital perpendicular to the
plane of the six-membered ring
 Defining three localized  bonds in which a given p
orbital overlaps only one neighboring p orbital
 All  electrons move freely in the entire ring due to
equal overlap of all p orbitals
 Resonance of benzene is another factor that influences
its rate of reactivity
 Benzene’s Resonance Structure
 Each sp2 hybridized C in the ring has an unhybridized p orbital
perpendicular to the ring which overlaps around the ring.
 Aromatic compound : a cyclic compound containing conjugated
double bonds and having an unusually large resonance energy.

p orbital overlaps induce a ring current

14
 Unusual Reactions of Benzene
 Alkene + dilute,cold KMnO4 or OsO4 diol (addition)
Benzene + KMnO4 or OsO4  no reaction.
 Alkene + Br2/CCl4  dibromide (addition)
Benzene + Br2/CCl4  no reaction.
 With FeCl3 catalyst, Br2 reacts with benzene to form
bromobenzene + HBr
(substitution!). Double bonds remain.
Br Br
Br2, FeBr3

CCl4
Br

is not formed 15
Valence Bond Theory Description of Benzene
Valence Bond Theory
 The two benzene resonance forms can be

represented by a single structure with a circle in the

center to indicate the equivalence of the carbon–
carbon bonds
 The ring does not indicate the number of  electrons in

the ring but is a reminder of the delocalized structure

價鍵理論缺點 :
苯為穩定，而環丁二烯為不穩定，無法以共振結構解釋 16
Molecular Orbital Description of Benzene
 The 6 p-orbitals combine to give
 Three bonding orbitals with 6  electrons,

 Three antibonding with no electrons

leading to 150 kJ/mol (36 Kcal/mol) stabilization of energy

 Orbitals with the same energy are degenerate

分子軌道理論解釋 :
分子中六個 P 軌道通過線性組合，生成六個 π 分子軌道，其中三個鍵結軌道，三
個反鍵結軌道。在基態時，苯分子的六個 π 電子填入三個鍵結軌道中，其能量比
原子軌道低，所以體系能量較低，使苯分子趨於穩定。 17
Molecular Orbital Description of Cyclobutadiene
 Following Hund’s rule, two electrons are in 補充
separate orbitals.
 This diradical would be very reactive.

bonding
分子軌道理論解釋 :
分子中四個 P 軌道通過線性組合，生成四個 π 分子軌道，其中一個鍵結軌
，
二個非鍵結軌道，一個反鍵結軌道。在基態時，環丁二烯分子的二個 π 電
填
入一個鍵結軌道中，另外二個 π 電子分別填入二個非鍵結軌道中，形成二 18
 15.3 Aromaticity 芳香性 and the Hückel
4n+2 Rule
Benene and aromatic compounds 芳香性化合物 :
 Cyclic and conjugated

 Each atom in the ring must have an unhybridized p

orbital
 Planar hexagon: bond angles are 120°, carbon–carbon

bond lengths 139 pm

 Unusually stable - heat of hydrogenation 150 kJ/mol (36

Kcal/mol) less negative than a cyclic triene

 Undergoes substitution rather than electrophilic addition

 Resonance hybrid with structure between two line-bond

structures

19
 Hückel’s 4n+2 Rule 胡克耳規則
 Aromatic ( 芳香性 ): the compound has a
continuous ring of overlapping p orbitals (planar
conformation) and has 4N + 2  electrons.
 Antiaromatic ( 反芳香性 ) : the compound has a
continuous ring of overlapping p orbitals (planar
conformation and has 4N  electrons.

有 4n + 2 個電子，均在同一個平面的環烯具有 " 芳香性 "

有 4n 個電子，均在同一個平面的環烯具有 " 反芳香性 "

20
 Aromaticity and the 4n + 2 Rule
Aromatic requirements
 Huckel’s rule 胡克耳規則 , based on calculations – a
planar cyclic molecule with alternating double and single
bonds has aromatic stability if it has 4n+ 2  electrons
(n is 0,1,2,3,4)
 For n=1: 4n+2 = 6; benzene is stable and the electrons
are delocalized

Aromatic( 芳香性 ) 判斷： 4n+2  電子，環狀共軛結構，平面結構

21
 Anti- and Not aromatic
 Antiaromatic ( 反芳香性 ) compounds are cyclic ( 環狀
), conjugated, with overlapping p orbitals around
the ring, but the energy of the compound is greater
than its open-chain ( 開鏈 ) counterpart.
 Not aromatic ( 非芳香性 ) compounds do not have a
continuous ring of overlapping p orbitals and may
be not planar.

similar CH3

stability CH3

less stable more stable (nonaromatic)

(antiaromatic) 22
Compounds With 4n  Electrons Are Antiaromatic
 Antiaromatic : Planar, cyclic molecules with 4 n 
electrons are much less stable than expected
(destabilization)
 Cyclobutadiene has 4  electrons and antiaromatic.
 It is highly reactive and so unstable

 it dimerizes by a self-Diels-Alder reaction at low

temperature

23
 Compounds With 4n  Electrons Are Antiaromatic :
May be Not Aromatic
 Cyclooctatetraene has 8  electrons and not aromatic.
 it’s not planar, so it’s not aromatic.
 The  electrons localized into four double bonds rather
than delocalized around the ring. The molecule is tub
shape.

It is reacting with Br2, KMnO4, and HCl as if it were
four alkenes

not planar
not aromatic
24
[N]Annulenes
環烯

[4] antiaromatic [6] aromatic [8] nonaromatic

cis
trans
cis

10 all cis H H two trans naphthalene

[10] nonaromatic(not planar) [10] nonaromatic(not planar) [10] aromatic (planar)

12 16 20

[12] nonaromatic [16]nonaromatic [20] nonaromatic

cis
cis
H
14 18 H

cis
trans trans
cis
[14] aromatic(planar) [18] aromatic (planar) [14] nonaromatic (not planar)
25
 Aromatic Stability and the Molecular Orbital
Theory
 Aromatic compounds have (4N + 2) electrons and the orbitals are filled.
 Antiaromatic compounds have only 4N electrons and have unpaired electrons in two degenerate orbitals

26
Why 4n +2? Molecular Orbital Description
 When electrons fill the various molecular orbitals, it
takes two electrons (one pair) to fill the lowest-lying
orbital and four electrons (two pairs) to fill each of n
succeeding energy levels
 This is a total of 4n + 2
Energy levels of the six benzene π molecular orbitals

27
 15.4 Aromatic Ions
 The 4n + 2 rule applies to ions as well as neutral species
 Both the cyclopentadienyl anion 環戊二烯陰離子 and the
cycloheptatrienyl cation 環庚三烯陽離子 are aromatic
 The key feature of both is that they contain 6  electrons in a ring of
continuous p orbitals

28
 Aromatic Ions
 When one hydrogen is removed from the saturated
CH2 in an aromatic ion, rehybridization of the carbon
from sp3 to sp2 would result in a fully conjugated
product with a p orbital on every product
 Methods to remove the hydrogen molecule
 Removing the hydrogen with both electrons (H:–) from
the C–H bond results in a carbocation
 Removing the hydrogen with one electron (H·) from the
C–H bond results in a carbon radical
 Removing the hydrogen without any electrons (H+) from
the C–H bond results in a carbanion
Cyclopentadienyl Anion and
Cycloheptatrienyl Cation
 Aromaticity of the Cyclopentadienyl Anion
 1,3-Cyclopentadiene contains conjugated double bonds joined
by a CH2 that blocks delocalization
 Removal of H+ at the CH2 produces a aromatic cyclic 6-electron
cyclopentadienyl anion, which is stable
 Removal of H- or H• generate antiaromatic 4 electron
cyclopentadienyl cation and an not aromatic cyclopentadienyl 5
electron radical.

not aromatic

antiaromatic not aromatic aromatic 31

Aromaticity of Cyclopentadienyl Anion
 Disadvantages of the four--electron cyclopentadienyl
cation and the five--cyclopentadienyl radical
 Highly reactive
 Difficult to prepare
 Not stable enough for aromatic systems
 Advantages of using the six--electron
cyclopentadienyl anion
 Easily prepared
 Extremely stable for aromatic systems
 pKa =16
Aromaticity of the Cyclopentadienyl Anion
1,3-Cyclopentadiene is Relatively acidic (pKa = 16)
because the anion is stable

sp3 →
sp2 + p

33
Why 4n +2? Molecular Orbital Description
Energy levels of the five cyclopentadienyl molecular orbitals

34
With conjugated systems such as
cyclopendadienyl cation and anion, the resonance
approach is a poor predictor of stability. The
Huckel rule, based on molecular orbital theory, is
a much better predictor of stability for these
aromatic and antiaromatic systems

35
 Aromaticity of Cycloheptatrienyl cation
 Cycloheptatriene has 3 conjugated double bonds joined by a CH2
 Removal of “H-” leaves the Cycloheptatrienyl cation
 The cation has 6 electrons and is aromatic

36
Which of the following is an
aromatic compound?

Non-aromatic Aromatic
There is an sp3 carbon in All carbons are sp2
the ring, delocalization will hybridized and it obeys
not be complete. Huckel’s rule.

37
15.5 Aromatic Heterocycles: Pyridine and Pyrrole

 Heterocycles 雜環化合物 : Cyclic compound

contain elements other than carbon in a
ring, such as N,S,O
 Aromatic heterocycles 芳香性雜環化合物 :
Aromatic compounds can have elements
other than carbon in the ring

38
 Pyridine
 Pyridine 吡啶 is a six-membered heterocycle with a nitrogen atom in its
ring
  electron structure resembles benzene
(6  electrons)
 The nitrogen lone pair electrons are not part of the aromatic system (sp2,
perpendicular orbital)
 Pyridine is a weak base compared to normal amines but protonation
does not affect aromaticity

39
 Pyridine and Pyrimidine
 The  structure of pyridine 吡啶 is quite similar to
that of benzene
 All five sp2-hybridized carbon possess a p orbital
perpendicular with one to the plane of the ring
 Each p orbital comprises one  electron
 The nitrogen atom is also sp2-hybridized and
possesses one electron in a p orbital
 Pyrimidine 嘧啶 comprises two nitrogen atoms in a
six-membered, unsaturated ring
 The sp2-hybridized nitrogen atoms share an electron
each to the aromatic  system
Pyridine

41
 Pyridine
 Aromatic six-membered heterocyclic
 Pyridine has a resonance energy of 27 kcal/mol,
For N:
2
1. Planar 1. this sp hybrid orbital is
2. Cyclic, p orbital perpendicular to the six
on each atom of 2p orbitals of the pi system
the ring
3. 6  electron
• aromatic
N
• resonance energy
= 27 kcal/mol
2. this pair of electrons
is not a part of the
aromatic sextet
, not  electron
3. Weak basicity
pKb= 8.8
 Pyrrole
 Pyrrole 吡咯 is a five-membered heterocycle with one nitrogen
  electron system similar to that of cyclopentadienyl anion
 Four sp2-hybridized carbons with 4 p orbitals perpendicular to the ring and 4
p electrons
 Nitrogen atom is sp2-hybridized, and lone pair of electrons occupies a p
orbital (6  electrons)
 Since lone pair electrons are in the aromatic ring, protonation destroys
aromaticity, making pyrrole nonbasic
 Imidazole 嘧唑 is a five-membered heterocycle with two nitrogen

43
 Pyrrole

nonbasic
N

basic N

nonbasic
N

44
 Pyrrole 吡咯
• Aromatic five-membered heterocyclic
• Resonance energy= 22 Kcal/mol

• the pyrrole nitrogen

atom is sp2 hybridized
with a lone pair of
electrons in the p
orbital. This p orbital
overlaps with the p
orbitals of the carbon
atoms to form a
lone pair e- on N
continuous ring.
involve in the ring
,  electron 45
 Pyrrole
 Pyrrole is aromatic because the lone pair on nitrogen is
delocalized. it has six pi electrons
 N-protonated pyrrole is nonaromatic because the nitrogen is sp3

nonbasic nitrogen

46
 Imidazole 嘧唑 補充

this pair of electrons

this pair of is a part of the
electrons aromatic sextet
is not a part ,  electron
of aromatic
, not  electron N N H

basic non basic

H
N
- pKa = 6.10
Amino acid CH2 CHCO 2
N+ +
Histidine NH
H 3
47
 How Do We Know That Cyclopentadiene’s
Lone-Pair Electrons Are π Electrons?
補充
• If a lone pair can be used to form a π bond in a resonance
contributor, the lone-pair electrons are π electrons.
Resonance Contributors of Pyrrole and Furan
補充
• If a lone pair can be used to form a π bond in a resonance
contributor, the lone-pair electrons are π electrons.
Rings of Pyrimidine and Imidazole
 Pyrimidine 嘧啶 and imidazole 嘧唑 rings are
important in biological chemistry
 Pyrimidine is the parent ring system present
in cytosine, thymine, and uracil
 Histidine contains an aromatic imidazole ring
15.6 Polycyclic Aromatic Compounds
 Polycyclic aromatic compounds 多環芳香族化合物 : two or more
benzene-like rings fuse together.
 Many are carcinogenic 致癌性 .
 Compounds from fused benzene or aromatic heterocycle rings are aromatic
 Fused rings 駢環 :Two rings are joined together and share two adjacent carbons

萘 蒽 苯駢芘
resonance energy resonance energy
= 60 Kcal/mol =84 Kcal/mol 51
Naphthalene Orbitals
 Three resonance forms and delocalized electrons

 Naphthalene and other polycyclic aromatic

hydrocarbons possess certain chemical properties
that correspond to aromaticity
 Heat of hydrogenation in naphthalene is
approximately 250 kJ/mol
 Aromaticity of Naphthalene
 Naphthalene possesses a cyclic, conjugated
electron system
 p orbital overlap is present along the ten-carbon
periphery of the molecule and across the central bond
 Aromaticity is due to the  electron delocalization caused
by the presence of ten  electrons (Hückel number)
 Reactivity of Polynuclear Hydrocarbons
As the number of aromatic rings increases, the
resonance energy per ring decreases, so larger
polycyclic aromatic compounds will add Br2.
H 9 Br

resonance energy
= 36 X 2 Kcal/mol
H 10 Br
Expeiment 13.3
O O O
O

heat
O

anthracene O
maleic anhydride
54
 補充
食品安全標準
2019.01.01 食品藥物管理署實施
「食品中污染物質及毒素衛生標準」

 增列 食品污染物 「苯駢芘」 (benzopyrene)

• 一種多環芳香烴類，也被列為致癌物，食品在乾燥、燒
烤或煙燻等高溫加工過程，可能產生這類物質。
• 新法針對燒烤或煙燻肉類、醃漬的水產品、乾燥水果、
食用油脂、嬰兒食品及膳食補充品（如蜂王乳）等訂定
不同限量。
 DNA Mutations 基因突變 補充

Benzo[a]pyrene, one of the most thoroughly studied

carcinogens 致癌物 , is formed whenever organic compounds
undergo incomplete combustion

DNA alkylation
by arene oxide
cause errors in
reading of genetic
code
carcinogen

56
DNAmRNA  PROTEIN
 Heterocyclic Analogs of Naphthelene
 Quinolone, isoquinolone, and purine have pyridine-
like nitrogens that share one  electron
 Indole and purine have pyrrole-like nitrogens that
share two  electrons
15.8 Spectroscopy of Aromatic Compounds
 Infrared Spectroscopy
 C–H stretching absorption is seen at 3030 cm–1
 A series of peaks are present between 1450 and
1600 cm–1
 Caused by the complex molecular motions of the ring
 Ultraviolet Spectroscopy
 Presence of a
conjugated  system
makes ultraviolet
spectroscopy possible
 Intense absorption
occurs near 205 nm
 Less intense absorption
occurs between 255 nm
and 275 nm

benzenoid band (B band):

芳香族化合物的
特徵吸收帶。是苯環振動及 π→π* 重疊引起的。
在 255 ～ 275nm 之間出現精細結構吸收，又稱苯
的多重吸收
Nuclear Magnetic Resonance Spectroscopy

 The aromatic ring shields hydrogens

 Absorption occurs between 6.5 and 8.5 δ
 The ring current is responsible for the difference
in chemical shift between aromatic and vinylic
protons
 Ring current is the magnetic field caused by the
circulation of delocalized  electrons when the
aromatic ring is perpendicular to a strong
magnetic field
 The effective magnetic field is greater than the
applied field
 NMR : Ring Currents
 Aromatic ring oriented perpendicular to a strong magnetic field,
delocalized  electrons producing a small local magnetic field
 Opposes applied field in middle of ring but reinforces applied

field outside of ring

pi 電子產生誘導磁場。環外氫，氫位於誘導磁力線上的方向，與外磁場方向一致
時 ，產生加成作用，共振所須外加磁場減小 去遮蔽效應，低磁場區， 值大
。

61
1 H NMR of Aromatic Compounds

環內氫，位於誘導磁力線上的方向與外磁場方向相反時 ，產生抵消作用，共振所須外加
磁場增大 ， 遮蔽效應，高磁場區， 值小。
 1
H NMR spectrum of p-bromotoluene
• Aromatic protons appear as two doublets at 7.04 and 7.37 δ
• Benzylic methyl protons appear as a sharp singlet at 2.26 δ

C7H7Br

p-bromotoluene
13
C NMR of Aromatic Compounds
 Carbons in aromatic ring absorb at  110 to 140
 Shift is distinct from alkane carbons but in same
range as alkene carbons

64
13
C NMR of Aromatic Compounds
 Three Isomers of Dichlorobenzene
 The mode of substitution influences the
formation of two, three, or four resonances in
the proton-decoupled 13C NMR spectrum
The Proton-Decoupled 13C NMR Spectra of
the Three Isomers of Dichlorobenzene
Summary

 The term aromatic refers to the class of

compounds that are structurally similar to
benzene
 Apart from IUPAC terms, disubstituted benzenes
are also called ortho, meta, or para derivatives
 The C6H5 unit is called a phenyl group
 The C6H5CH2 unit is called a benzyl group
 The Hückel rule states that in order to be
aromatic, a molecule must possess 4n + 2 
electrons, where InI = 0,1,2,3, and so on
Summary

 Planar, cyclic, conjugated molecules with

other numbers of  electrons are antiaromatic
 Pyridine and pyrimidine are six-membered,
nitrogen containing, aromatic heterocycles