AROMATICITY AND THE HUCKEL RULE Minimum requirements for aromaticity: 1. Huckel’s rule must be followed, i.e.

the number of π electrons = 4n + 2 where n is a whole number (n=0, 1, 2….). 2. There must be a cyclic, planar array of π electrons. Note: - Examples may include bo th neutral molecules and molecular ions. If an ion confor ms to the minimum requirements for aromaticity, expect that it is stable enough to be easily prepared. - A heteroatom may utilize sp2-hybridized orbitals for bonding in apparent nonconformance to the rules of thumb for determining hybridization state if doing so will result in aromatic stability. Examples: n = 0:
vs. 2 π e-s over 3 p orbitals n=0; aromatic not aromatic; 3rd carbon does not contribute to the π system

n = 1:

not aromatic; not complete cyclic π array

4n + 2 = 4 π electrons n = 1/2 not aromatic

4n + 2 = 6 π electrons n=1 aromatic

N

O

N N

N

N N

pyrrole

furan

imidazole

pyridine

pyrimidine

6 π electrons delocalized over 5 p orbitals; aromatic

6 π electrons delocalized over 6 p orbitals; aromatic

cycloheptatriene not aromatic

8 π electrons delocalized tropylium cation aromatic over 7 p orbitals; not aromatic 6 π electrons delocalized over 7 p orbitals; aromatic

2 NOMENCLATURE OF BENZENOID COMPOUNDS
I. Monosubstituted Compounds - may be named as derivatives of benzene. Examples include:

NO2

Cl

Br

nitrobenzene

chlorobenzene

bromobenzene

-special names also accepted by IUPAC for some compounds, such as:

CH3

CH3 CH CH3

NH2

OH

toluene cumene

aniline

phenol

OCH3

COOH

SO3H

O C H

anisole

benzoic acid

benzenesulfonic acid

benzaldehyde

CN

O C CH3

CH CH2

benzonitrile acetophenone styrene

II. Disubstituted Compounds: - these are named as derivatives of benzene or the monosubstituted compounds with special names. Three positional isomers are possible, as shown below. These isomers have special designations, which appear as a hyphenated italicized prefix in the IUPAC name of the compound.

Y Z

Cl Cl

CH3 NO2

1,2-disubstituted ortho (o)

o-dichlorobenzene

o-nitrotoluene

3

Y

Br

Cl

Z
1,3-disubstituted meta (m)

Br
m-dibromobenzene

OH
m-chlorophenol

Y

NO2

NO2

Z
1,4-disubstituted para (p)

F
p-fluoronitrobenzene

NH2
p-nitroaniline

III. More Highly Substituted Compounds For compounds having greater than two substituents, use numbers to indicate positions of substituents. The carbon bearing the substituent that corresponds to a special name is always assigned the number 1, otherwise the carbons bearing substituents are numbered so that alphabetical ordering is observed.

CH3 O2N NO2

OH O2N NO2

OH OCH3

NO2
2,4,6-trinitrotoluene

NO2
2,4,6-trinitrophenol

CHO
4-hydroxy-3methoxybenzaldehyde

4 ELECTROPHILIC AROMATIC SUBSTITUTION General equation:
H + Y-Z Y + HZ

where YZ is the electrophilic reagent and Y + is the electrophile. General mechanism:
H (1) + Y+ ADDITION + Y + Y H H + H Y

the benzenonium cation; a resonance stabilized reaction intermediate

+ (2)

H Y + Z ELIMINATION

Y + HZ

KINDS OF EAS REACTIONS (summary) A. Nitration
OH + HNO3 H2SO4 + N O

Electrophile: nitronium ion +NO2

B. Sulfonation
O H fuming H2SO4 S O H O

Electrophile: sulfur trioxide SO3

C. Aromatic halogenation
H X2 FeX3 X = Cl or Br X

Electrophile: halonium ion X+

D. Friedel Crafts Alkylation
H RCl AlCl3 R

Electrophile: carbocation R+

E. Friedel Crafts Acylation
O H R C AlCl3 Cl O C
R

Electrophile: acylium ion R-C+=O

5
ELECTROPHILIC AROMATIC SUBSTITUTION OF SUBSTITUTED BENZENES Benzene is nitrated by a mixture of concentrated nitric acid and sulfuric acid at around 80 °C.
HNO3 , H2 SO4 80 °C NO2

Further nitration of benzene is considerably more difficult. temperature are required.
NO2 NO2 fuming HNO3 , H2 SO4 , 100 °C NO2 meta 93.2 % ortho 6.4 % NO2 +

Strong acid and higher
NO2 NO2 +

NO2 para 0.3 %

On the other and, toluene undergoes nitration more rapidly than benzene. In this case, the predominant products are the ortho and para isomers.
CH3 CH3 HNO3 , H2 SO4 30 °C CH3 + NO2 NO2 ortho 62 % para 33 % NO2 meta 5% + CH3

As shown by the above examples, when an electrophilic reagent attacks an aromatic ring, the group already attached to the ring determines how readily the attack occurs (i.e. reactivity of the ring) and where it occurs (i.e., orientation). CLASSIFICATION OF SUBSTITUENT GROUPS Nearly all groups fall into one of two classes, activating and ortho, para – directing, or deactivating and meta – directing. The halogens are in a class by themselves, being deactivating but ortho, para – directing.

6

CLASSIFICATION OF SUBSTITUENT GROUPS

Activating; directors

ortho,

para Deactivating: directors
O N O

meta Deactivating; directors -F

ortho,

para

Strongly activating O H NHR,

-Cl -Br -I

NH2, NR2

CH3 N CH3 CH3

Moderately activating O R O NH C CH3
O C

C

N O

OH

C

OR

SO3H

Weakly activating

O C H

O C R

R

THEORY OF REACTIVITY AND ORIENTATION

Reactivity in electrophilic aromatic substitution depends upon the tendency of a substituent group to release or withdraw electrons. The substituent group may exert this effect either by resonance or induction. A group that releases electrons activates the ring. Although it activates all positions of the benzene ring, it activates the ortho and para positions much more than it does the meta position. Because of this, activating groups are also ortho- and para-directors. For example, aniline is highly activated towards electrophilic aromatic substitution and undergoes EAS reactions much faster than ordinary benzene. The reaction products are essentially ortho- and para-substituted. Draw the resonance structures of aniline to account for this behavior.

7

NH2

A

B

C

D

E

resonance structures of aniline A group that withdraws electrons deactivates the ring. Although it deactivates all positions of the benzene ring, the ortho and para positions are especially deactivated. Thus, the electron withdrawing group is also meta-directing because the meta position is least deactivated towards EAS. Draw the resonance structures of benzaldehyde to illustrate this.
O C H

A

B C D resonance structures of benzaldehyde

E

ORIENTATION OF SUBSTITUTION IN DISUBSTITUTED BENZENES The presence of two substituents on a ring makes the problem of orientation more complicated but certain definite predictions can usually be made. The two may be located so that the directive influence of one reinforces the other. This is clearly seen for compounds I, II, and III. The orientation of further substitution is clearly indicated by arrows.
O CH3 SO3H NC NHCCH3

NO2 NO2 I II III

When the directive effect of one group opposes that of the other, it may be difficult to predict the major product. In some cases, complicated mixtures of several products may be obtained. However, the following generalizations may be made: 1. Strongly activating groups generally win out over the deactivating or weakly activating groups. The sequence of directing power is as follows:

8

O NH2, OH > OR, NH C CH3 > , R > meta directors

2.

There is often little substitution at the position between two groups that are meta to each other.

Exercises: I. Predict the major product(s) of each of the following reactions:
OCH3 HNO3, H2SO4

1.

H 3C

O

2.

H 3C

NHCCH3 Br2, FeBr3

O Br2, FeBr3

3.
OCH3

H

Cl HNO3, H2SO4

4.
CH3

Cl HNO3, H2SO4

5.

Br

9 II. Supply the missing reagents and intermediate products in each of the following two-step conversions.
NO2

1.
Br

CH3

SO3H

2.

COOH

3.
NO2

SO3H

4.
Cl

10 ARENES
includes alkylbenzenes, alkenylbenzenes, alkynylbenzenes

REACTIONS: A. Free radical halogenation of alkylbenzenes – the preferred site is the sp3-carbon right next to the benzene ring, also known as the benzylic carbon. Cl
benzylic CH2CH3 CHCH3 Cl2 hν 56 % CHCH3 Br exclusive product reactive intermediate: the resonance-stabilized benzylic free radical 44 % CH2CH2Cl

Br2 hν

-

the 1° and 2° benzylic halides produced from this reaction are very reactive to both SN1 reactions because of the resonance-stabilization of the benzylic carbocation and S N2 reactions because of low steric congestion around the electron deficient carbon. Tertiary benzylic halides undergo SN1 reactions only.
1°benzylic CH2Cl aq NaOH SN1 or SN2 benzyl chloride benzyl alcohol CH2OH

11
B. Reactions of Alkenylbenzenes/Alkynylbenzenes 1. Hydrogenation – occurs rapidly in the side chain using ordinary catalysts.
H2, Pd/C

x's H2 high T & P Rh cat.

2. Electrophilic addition - examples: a.
Br HBr Recall: Markownikoff's Rule

reactive intermediate: the resonance-stabilized benzylic carbocation

b.
C C CH3 aq H2SO4 HgSO4 O C CH2 CH3

1-phenylpropyne

phenyl ethyl ketone the Markownikoff product

C. Oxidation of the Side Chain of Arenes – occurs only if benzylic H is present.

O CHR2 aq KMnO4, heat C OH

12 CHEMISTRY 40 Problem Set – Aromatic Compounds
I. Indicate whether each of the following compounds or ions is aromatic or not: + a. c.

.. O ..

b.

d.

2.

Write the structures of the products formed from the reaction of the following reagents with (i) benzene, (ii) ethylbenzene and (iii) benzoic acid. If no reaction occurs, write NR. a. b. c. d. e. fuming sulfuric acid cold, dilute KmnO4 CH3 COCl, AlCl3 hot KMnO4 Br2/CCl 4, light f. g. h. i. CH3Cl, AlCl3 H2O, H+ HNO3, H2SO 4 Cl2, FeCl3

3.

Predict the major product(s) that will be obtained upon monobromination of each of the following compounds. Indicate whether the reaction will be faster or slower than the bromination of benzene. a. nitrobenzene b. benzaldehyde c. aniline

4.

Arrange the following compounds in the order of increasing reactivity towards ring nitration. a. benzene, iodobenzene, aniline, toluene b. O
C H OCH3 Cl CH3

5.

Suggest a scheme for the preparation of each of the following compounds from benzene. a. p-bromobenzenesulfonic acid b. 2,5-dichloronitrobenzene c. p-chlorobenzoic acid d. o-nitrotoluene e. benzyl alcohol f. styrene

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