Chapter 21, Benzene and and the Concept of Aromaticity

21-1

Benzene - Kekul
In

1872, August Kekul proposed the following structure for benzene.

H H C C H C C H C C H H H H C C H C C H C C H H

This

structure, however, did not account for the unusual chemical reactivity of benzene.

21-2

Benzene - Resonance
We

often represent benzene as a hybrid of two equivalent Kekul structures.

Each makes an equal contribution to the hybrid and thus the C-C bonds are neither double nor single, but something in between.

Ben zene as a hybrid of tw o equ ivalen t contributin g s tru ctures

21-3

Benzene - Resonance Model

The

concepts of hybridization of atomic orbitals and the theory of resonance, developed in the 1930s, provided the first adequate description of benzenes structure.
The carbon skeleton is a planar regular hexagon. All C-C-C and H-C-C bond angles 120.
H 120 H 2 2 sp -sp 120 C C 120 H C C H C C 109 pm sp2 -1 s H H 139 pm

21-4

The Pi System of Benzene

(a) The carbon framework with the six 2p orbitals. (b) Overlap of the parallel 2p orbitals forms one torus above the plane of the ring and another below it this orbital represents the lowest-lying pi-bonding molecular orbital.

21-5

Benzene-Molecular Orbital Model

The

molecular orbital representation of the pi bonding in benzene.

21-6

Orbitals of the pi System of Benzene

Number of nodal surfaces 3

0
21-7

Benzene - Resonance
Resonance

energy: The difference in energy between a resonance hybrid in which the electrons are delocalized and the most stable one of its hypothetical contributing structures in which electrons are localized on particular atoms and in particular bonds.
One way to estimate the resonance energy of benzene is to compare the heats of hydrogenation of benzene and cyclohexene.
21-8

Benzene- Resonance Energy

Experimental data Model

21-9

Concept of Aromaticity
The

underlying criteria for aromaticity were recognized in the early 1930s by Erich Hckel, based on molecular orbital (MO) calculations. To be aromatic, a compound must
Be cyclic. Have one p orbital on each atom of the ring. Be planar or nearly planar so that there is continuous or nearly continuous overlap of all p orbitals of the ring. Have a closed loop of (4n + 2) pi electrons in the cyclic arrangement of p orbitals.
21-10

Frost Circles
Frost

circle: A graphic method for determining the relative order of pi MOs in planar, fully conjugated monocyclic compounds.
Inscribe in a circle a polygon of the same number of sides as the ring to be examined such that one of the vertices of the polygon is at the bottom of the circle. The relative energies of the MOs in the ring are given by where the vertices of the polygon touch the circle.

Those

MOs

Below the horizontal line through the center of the ring are bonding MOs. on the horizontal line are nonbonding MOs. above the horizontal line are antibonding MOs.
21-11

Frost Circles
Frost circles describing the MOs for monocyclic, planar, fully conjugated four-, five-, and six-membered rings.

21-12

Relationship of hexa-1,3,5-triene to benzene

How does the linear triene relate to benzene?

21-13

Relationship of hexa-1,3,5-triene to benzene

Relationship of hexa-1,3,5-triene to benzene

Look at orbitals 2 and 3.

p3 p2 Bonding, stabilizing

Curve around

Antibonding, destabilizing

Aromatic Hydrocarbons
Annulene:

A cyclic hydrocarbon with a continuous alternation of single and double bonds.

[14]Annulene is aromatic according to Hckels criteria. n=3
H H H H H HH HH H H H H

H [14]Ann ulene (aromatic)

21-16

Aromatic Hydrocarbons
[18]Annulene is also aromatic.
H H H H H H H H H H H H H H [18]A nnu lene (aromatic) H H H H

n=4

21-17

Aromatic Hydrocarbons
According to Hckels criteria, [10]annulene should be aromatic; it has been found, however, that it is not. Nonbonded interactions between the two hydrogens that point inward toward the center of the ring force the ring into a nonplanar conformation in which overlap of the ten 2p orbitals is no longer continuous.

[10]A nnu lene

21-18

Aromatic Hydrocarbons
What is remarkable relative to [10]annulene is that if the two hydrogens facing inward toward the center of the ring are replaced by a methylene (CH2) group, the ring is able to assume a conformation close enough to planar that it becomes aromatic.
CH2 Bridged [10]ann ulen e

21-19

Antiaromatic Hydrocarbons
Antiaromatic

hydrocarbon: A monocyclic, planar, fully conjugated hydrocarbon with 4n pi electrons (4, 8, 12, 16, 20...).
An antiaromatic hydrocarbon is especially unstable relative to an open-chain fully conjugated hydrocarbon of the same number of carbon atoms.

Cyclobutadiene

is antiaromatic.

In the ground-state electron configuration of this molecule, two electrons fill the p1 bonding MO. The remaining two electrons lie in the p2 and p3 nonbonding MOs.

21-20

Cyclobutadiene
The ground state of planar cyclobutadiene has two unpaired electrons, which make it highly unstable and reactive.

21-21

Cyclooctatetraene
Cyclooctatetraene, with 8 pi electrons is not aromatic; it shows reactions typical of alkenes. X-ray studies show that the most stable conformation is a nonplanar tub conformation. Although overlap of 2p orbitals occurs to form pi bonds, there is only minimal overlap between sets of 2p orbitals because they are not parallel.

view ed from above

view ed throu gh an edge

21-22

Cyclooctatetraene
MO

energy diagram for a planar conformation of cyclooctatetraene.

21-23

Heterocyclic Aromatics
Heterocyclic

compound: A compound that contains more than one kind of atom in a ring.
In organic chemistry, the term refers to a ring with one or more atoms that differ from carbon.

Pyridine

and pyrimidine are heterocyclic analogs of benzene; each is aromatic.

4 3 2 1 5 3 4 5 6

N
2 1

Pyridine

Pyrimidine
21-24

Pyridine
The nitrogen atom of pyridine is sp2 hybridized. The unshared pair of electrons lies in an sp2 hybrid orbital and is not a part of the six pi electrons of the aromatic system (the aromatic sextet). Resonance energy of pyridine is134 kJ (32 kcal)/mol.
21-25

Furan and Pyrrole

The oxygen atom of furan is sp2 hybridized. one unshared pairs of electrons on oxygen lies in an unhybridized 2p orbital and is a part of the aromatic sextet. The other unshared pair lies in an sp2 hybrid orbital and is not a part of the aromatic system. The resonance energy of furan is 67 kJ (16 kcal)/mol.

21-26

Other Heterocyclics
HO N H CH2 CH2 NH 2

N H

Indole

Serotonin (a neurotransmitter)
O CH3 N N

N N

N N H

H3 C O

N N CH3

Purine

Caffeine

21-27

Aromatic Hydrocarbon Ions

Any

neutral, monocyclic, unsaturated hydrocarbon with an odd number of carbons must have at least one CH2 group and, therefore, cannot be aromatic.
CH2 Cyclopropene CH2 Cyclopentadiene CH2 Cycloheptatriene

Cyclopropene, for example, has the correct number of pi electrons to be aromatic, 4(0) + 2 = 2, but does not have a closed loop of 2p orbitals.

21-28

Cyclopropenyl Cation
If, however, the CH2 group of cyclopropene is transformed into a CH+ group in which carbon is sp2 hybridized and has a vacant 2p orbital, the overlap of orbitals is continuous and the cation is aromatic.
H + H H + H H H + H

H H Cycloprop enyl cation represented as a h yb rid of three equ ivalen t contributin g s tru ctures

21-29

Cyclopropenyl Cation
When 3-chlorocyclopropene is treated with SbCl5, it forms a stable salt.
H

+
Cl

Sb Cl 5

H Sb Cl 6

3-Chlorocyclopropene

Antimony(V) chloride (a Lewis acid)

Cyclopropenyl hexachloroantimonate

This chemical behavior is to be contrasted with that of 5-chloro-1,3-cyclopentadiene, which cannot be made to form a stable salt.

21-30

Cyclopentadienyl Cation
H + A gBF4 Cl 5-Chloro-1,3cyclopentadiene + H BF4
-

+ Ag Cl

Cyclope ntadienyl te trafluoroborate

If planar cyclopentadienyl cation were to exist, it would have 4 pi electrons and be antiaromatic. Note that we can draw five equivalent contributing structures for the cyclopentadienyl cation. Yet this cation is not aromatic because it has only 4 pi electrons.

21-31

Cyclopentadienyl Anion, C5H5 To

convert cyclopentadiene to an aromatic ion, it is necessary to convert the CH2 group to a CH group in which carbon becomes sp2 hybridized and has 2 electrons in its unhybridized 2p orbital.

H H

H H

H H
:

H H

H H

H th e origin of th e 6 pi electrons in the cyclopen tadienyl anion

H H Cyclopentad ienyl anion (aromatic)

n=1
21-32

Cyclopentadienyl Anion, C5H5 As seen in the Frost circle, the six pi electrons of cyclopentadienyl anion occupy the p1, p2, and p3 molecular orbitals, all of which are bonding.

21-33

Cyclopentadienyl Anion, C5H5 The

pKa of cyclopentadiene is 16.

In aqueous NaOH, it is in equilibrium with its sodium salt. H

H

CH2 + NaOH
H

:
H

H Na+ + H2 O

p K a 16.0

p K a 15.7

It is converted completely to its anion by very strong bases such as NaNH2 , NaH, and LDA.

21-34

Cycloheptatrienyl Cation, C7H7+

Cycloheptatriene

forms an aromatic cation by conversion of its CH2 group to a CH+ group with its sp2 carbon having a vacant 2p orbital.
H H + H H H H H H + H H H

H H H Cyclohep tatrien yl cation (Tropylium ion ) (aromatic)

21-35

Nomenclature
Monosubstituted

alkylbenzenes are named as derivatives of benzene.

Many common names are retained.

Toluene
OH

Eth ylbe nzene

N H2 CHO

Cumene
COOH

Styrene
OCH3

Phenol

Aniline

Benzaldehyde

Benzoic acid

Anisole

21-36

Nomenclature
Benzyl

and phenyl groups

CH3 CH2

Benzene

Phenyl group, PhO H 3 CO

Toluene
O

Benzyl group, Bn-

Ph 1-Phenyl-1-pentanon e 4-(3-Me thoxyphenyl)2-butanone (Z)-2-Phen yl2-bute ne

21-37

Disubstituted Benzenes
Locate

two groups by numbers or by the locators ortho (1,2-), meta (1,3-), and para (1,4-).
Where one group imparts a special name, name the compound as a derivative of that molecule.
CH3 NH2 COOH NO2 Cl CH3

CH3 Br 4-Bromotolu ene 3-Chloroan iline 2-N itrobenzoic acid m -Xylene (p -Bromotoluen e) (m -Chloroan iline) (o -N itrob enzoic acid )

21-38

Disubstituted Benzenes
Where neither group imparts a special name, locate the groups and list them in alphabetical order.
CH2 CH3
4 3 2 2

NO2
1

Br

Cl 1-Chloro-4-ethylben zene (p -Ch loroethylbenzen e)

1-Bromo-2-nitrob enzene (o -Bromon itroben zene)

21-39

Polysubstituted Derivatives
If one group imparts a special name, name the molecule as a derivative of that compound. If no group imparts a special name, list them in alphabetical order, giving them the lowest set of numbers.
CH3
1 2

OH N O2 Br
6 1 2

N O2 Br
4 2

Br

Cl 4-Ch loro-2-nitrotoluen e

Br 2,4,6-Tribromophen ol

CH2 CH3 2-Bromo-1-ethyl-4nitrobenze ne

21-40

Phenols
The

functional group of a phenol is an -OH group bonded to a benzene ring.

OH OH OH OH CH3 Phenol 3-Methylphenol (m -Cres ol) OH 1,2-Be nzenediol 1,4-Be nzenediol (Catech ol) (Hydroqu inone ) OH

21-41

Acidity of Phenols
Phenols

are significantly more acidic than alcohols.

OH + H2 O O- + H3 O+
+ CH3 CH2 O + H3 O

pK a = 9.95 pK a = 15.9

CH3 CH2 OH + H2 O

21-43

Acidity of Phenols
Separation

of waterinsoluble phenols from water-insoluble alcohols.

21-44

Acidity of Phenols (Resonance)

The greater acidity of phenols compared with alcohols is due to the greater stability of the phenoxide ion relative to an alkoxide ion.
O O H O O O H

These 2 Kekul s tru ctures are equivalent

H These th ree con trib utin g s tru ctures delocalize th e negative charge on to carb on atoms of th e rin g

21-45

Phenol Subsitituents (Inductive Effect)

Alkyl

and halogen substituents effect acidities by inductive effects:

Alkyl groups are electron-releasing. Halogens are electron-withdrawing.
OH OH OH OH OH

CH3 Phen ol pK a 9.95 m- Cres ol p Ka 10.01 CH3 p- Cres ol pK a 10.17

Cl Cl m-Chlorop henol p-Chororophen ol pK a 8.85 p Ka 9.18

21-46

Phenol Subsitituents(Resonance, Inductiion)

Nitro groups increase the acidity of phenols by both an electron-withdrawing inductive effect and a resonance effect. OH OH OH

NO2
Phe no l p K a 9.95

NO2

m- N itrop h e n ol p- N itrop h e n ol p K a 8.28 p K a 7.15

21-47

Acidity of Phenols
Part of the acid-strengthening effect of -NO2 is due to its electron-withdrawing inductive effect. In addition, -NO2 substituents in the ortho and para positions help to delocalize the negative charge.
O O

delocalization of negative charge onto oxygen further increas es the resonance stabilization of phenoxide ion
O

N+ O O O

N+

21-48

Synthesis: Alkyl-Aryl Ethers

Alkyl-aryl

ethers can be prepared by the Williamson ether synthesis:

but only using phenoxide salts and haloalkanes. haloarenes cannot be used because they are unreactive to SN2 reactions.
X + RO - N a+ no reaction

21-51

Synthesis: Alkyl-Aryl Ethers

OH + CH2 = CHCH2 Cl Phenol 3-Ch loropropene (Allyl chloride) N aOH, H2 O, CH2 Cl 2

OCH2 CH= CH2 Phenyl 2-prope nyl ether (Allyl phenyl ether)

O OH + CH3 OSOCH3 Phenol O D imethyl su lfate

N aOH, H2 O, CH2 Cl 2

OCH3 + N a2 SO 4 Methyl phenyl e ther (Anisole)

21-52

Synthesis: Kolbe Carboxylation

Phenoxide

ions react with carbon dioxide to give a carboxylate salt.

OH NaOH H2 O O Na
+

CO2 H2 O Sodiu m phen oxid e

OH O + CO Na

HCl H2 O

OH O COH

Phenol

Sodium salicylate

S alicylic acid

21-53

Mechanism: Kolbe Carboxylation

The mechanism begins by nucleophilic addition of the phenoxide ion to a carbonyl group of CO2.
O O O O C O

+ Sodium phenoxide

C O

keto-enol tautomerism (2)

OH

O C O

(1)

A cyclohexadienone intermediate

Salicylate anion

Go back to aromatic structure

21-54

Synthesis: Quinones
Because

of the presence of the electron-donating -OH group, phenols are susceptible to oxidation by a variety of strong oxidizing agents.
OH H2 Cr O 4 O

Phenol

O 1,4-Be nzoqu inon e (p- Quin one)

21-55

Quinones
OH OH K2 Cr2 O7 H2 SO4 1,2-Benzen ediol (Catechol) OH K2 Cr2 O7 H2 SO4 OH 1,4-Ben zenediol (Hydroquin on e) O 1,4-Benzoquin on e (p-Qu inone) 1,2-Benzoquin on e (o-Qu inone) O O O

21-56

Quinones
Readily

reduced to hydroquinones.

O Na2 S2 O4 , H2 O (reduction ) O 1,4-Benzoqu inone (p-Qu inone)

OH

OH 1,4-Benzen ediol (Hydroq uinone)

21-57

Coenzyme Q
Coenzyme
O MeO reduction MeO O Coenzyme Q (oxid ized form) n H oxidation MeO OH Coenzyme Q (redu ced form) n H MeO

Q is a carrier of electrons in the respiratory chain.

OH

21-58

Benzylic Oxidation
Benzene

is unaffected by strong oxidizing agents such as H2CrO4 and KMnO4

Halogen and nitro substituents are also unaffected by these reagents. An alkyl group with at least one hydrogen on its benzylic carbon is oxidized to a carboxyl group.
CH3 O2 N Cl H2 Cr O4 O2 N COOH Cl

2-Chloro-4-nitrotoluene

2-Chloro-4-nitrobenzoic acid

21-60

Benzylic Oxidation
If there is more than one alkyl group on the benzene ring, each is oxidized to a -COOH group.
H3 C CH3 K2 Cr 2 O 7 H2 SO 4 O HOC O COH

1,4-Dime thylbenzene ( p- xylene)

1,4-Be nzenedicarboxylic acid (terephthalic acid)

21-61

Benzylic Chlorination
Chlorination

and bromination occur by a radical chain mechanism.

CH3
+ Cl 2

heat or light

CH2 Cl
+ HCl

Toluene

Benzyl chloride
Br NBS ( PhCO2 ) 2 , CCl4

Ethylbenzene

1-Bromo-1-phenylethane (racemic)

21-62

Mechanism: Benzylic Reactions

Benzylic

radicals (and cations also) are easily formed because of the resonance stabilization of these intermediates.
The benzyl radical is a hybrid of five contributing structures.
C C

21-63

Benzylic Halogenation
Benzylic bromination is highly regioselective.
Br NBS (PhCO2 ) 2 , CCl4 Eth ylb enzene 1-Bromo-1-phen yleth ane (the only product formed )

Benzylic chlorination is less regioselective.

Cl + Cl2 Eth ylb enzene heat or ligh t 1-Chloro-1p henylethan e (90%) Cl + 1-Ch loro-2ph enylethan e (10%)
21-64

Hydrogenolysis
Hydrogenolysis:

Cleavage of a single bond by H2

Benzylic ethers are unique in that they are cleaved under conditions of catalytic hydrogenation.
this bond is cleaved O Benzyl butyl ether + H2 Pd/ C Me OH + 1-Butanol Toluene

21-65

Synthesis, Protecting Group: Benzyl Ethers

The

value of benzyl ethers is as protecting groups for the OH groups of alcohols and phenols.
To carry out hydroboration/oxidation of this alkene, the phenolic -OH must first be protected; it is acidic enough to react with BH3 and destroy the reagent.
1 . ClCH2 Ph 2 . BH3 THF O Ph 3 . H2 O2 / NaOH Et 3 N

OH 2-(2-Propen yl)p henol (2-A llylp henol)

OH O Ph

H2 Pd/ C

OH

OH 2-(3-Hyd roxyprop yl)p henol 21-66