AROMATIC HYDROCARBONS Definition: compounds with spicy or sweet smelling odors derived fromplants Recent: benzene and derivatives

of benzene; compounds that exhibit the properties of benzene

Facts about Benzene 1. Planar cyclic compound of alternating double bonds with planes of pi es above and below the plane of the ring. Any pair of adjacent p orbitals is capable of lateral overlap to form a pi bond. 3 double bonds can be formed from overlap of p orbitals of

II

III

C1 &C2/C3 & C4/ C5 & C6

C2&C3/C4&C5/C6&C1

pi es are shared by all the 6 carbons

hybrid

Which of these structures (I,II) is benzene ? Neither. The true structure of benzene is a hybrid of I and II(not a mixture of I & II). In the hybrid the pi es are delocalized all over the ring. Terminologies: Delocalization is used whenever pi es simultaneously form a bond between and more than a single pair of atoms. Resonance- phenomenon of delocalization of es Resonance hybrid- single specie that combines the characteristics of two or more structures that only differ in their electronic arrangements. Contributing Species- individual structures that have no real existence 2. All C=C bonds arenof equal length, 1.39 A (intermediate bond; shorter than that of C-C single bond, 1.53 A; longer than that of C = C double bond, 1.34 A) 3. Reacts by SUBSTITUTION instead of ADDITION (typical of alkenes with = bonds). Because of the delocalization the degree of stability is so great that the pi bonds will normally resist breaking. Substitution reaction leaves the pi e cloud around the ring intact.(ring structure must be intact) 4. Acts as if saturated, does not decolorize KMnO4, does not react with Br2 in the cold or in the absence of sunlight and catalyst.

Aromatic Character: Aromaticity is associated with several structural requirements 1. Compounds must be cyclic structure with alternating single and double bonds 2. Compounds must be planar. so that pi es can delocalize 3. Compounds must have number of pi es that shows Huckels Rule : 4n + 2 = Pi es Where n= 0,1,2 . (positive integer) Examples:

Nomenclature of Aromatic Compounds A. Monosubstituted Benzene Give the name of the group and add the word benzene. No need to use a locating number for the group because all 6 positions of benzene are equivalent.

CH3 CCH3 Br NO2 bromo benzene CH3CH2

Some monosubstituted benzene occur so frequently , so they are considered as parent compounds and given common names (that should be memorized)

CH3

Cl

CH3

OH

COOH

CH=CH2

tolune

phenol

benzoic acid CHO

styrene

NH2 aniline benzaldehyde

SO3H

benzene sulfonic acid

Sometimes it is convenient to name the benzene ring as a group.

CH2 phenyl benzyl

CH3CHCH2CH3

CH2CH2OH

2-phenyl butane

2-phenyl ethanol

biphenyl

CH2Cl

CH2 O C=O CH3 benzyl acetate

benzyl chloride

B. Disubstituted Benzene 1. Indicate the relative positions of the groups using a) Prefixes (for common names; same groups) Ortho (o) groups are on adjacent Cs Meta (m) groups areseparated by 1 C Para (p) groups are on opposite Cs b) Numbers (for IUPAC names )
Br Br Br Br

Br O di bromo benzene m dibromo benzene

Br p dibromo benzene

2. When the 2 groups are different, list in alphabetical order

Cl

CH2 CH3 1-chloro 2 ethyl benzene

3. If one of the groups is part of a parent compound , the disubstituted benzene is named as a derivative of the parent compound.
OH Cl 2-chloro phenol NO2

CH3

COOH

4-nitro toluene

Br

3-bromo benzoic acid

NH2 OH 4-amino phenol or 4-hydroxy aniline

4. Certain disubstituted benzene are referred to by their common names

CH3 CH3

CH3 CH3

CH3 o-xylene m-xylene

CH3 p-xylene

C. Polysubstituted Benzene: Groups are indicated with numbers 1. Groups are the same-numbering starts around the ring so as to have lowest locating numbers to the groups.
Br Br Br 1,2,3 tribromo benzene Br Br Br 1,2,4,tribromo benzene

2. Groups are different , list alphabetically and the one last named is understood to be in position number 1.

NO2

Cl 3-chloro-5 fluoro nitrobenzene ( not 3-fluoro-5chloro nitrobenzene)

3. If one of the groups is part of the parent compound, the carbon that bears the functional group of the parent compound is carbon 1.
OH Br NO2 2,6 dibromo phenol NO2 CH3 NO2 2.4,6 trinitro toluene

Br

D. Polynuclear Aromatic HC-benzene rings fused together to form polynuclear aromatic HCs
8 7 6 5 4 1 2 3 naphthalene 7 6 5 10 4 8 9 1 2 3

anthracene

phenanthrene

pyrene

Sources of Aromatic Compounds Major Sources Coal Tar main source until 1940 (as demand increases shifted to petroleum industry) Petroleum-alkanes and cycloalkanes >>> benzene and alkyl benzene by catalytic dehydrogenation Preparation of Some Aromatic HC A. Benzene=Dehydrogenation of cyclohexane (cycloalkane) using a catalyst
+ 3 H2

B. Toluene= Dehydrogenation of methy cyclohexane or n-pentane

CH 3 - H2 or CH 3 CH2 CH 2 CH 2CH 2 CH 2 CH 3 cat. CH 3 + 3 H2

C. Xylene
CH3 - H2 CH3 cat. CH3 CH3 +
3 H2

Benzene, toluene, xylene are the basic raw materials from which other Aromatic HCs are obtained by the reactions of Aromatic HCs Reactions of Aromatic HCs General Considerations: 1. Aromatic ring with its delocalized pi es is an e rich system, thus susceptible to E+ (electrophile) attack

2. Aromatic ring with its pi es delocalized is extremely stable , so highly reactive E+ is required. This E+ is to be generated by an acid catalyst (e pair acceptor) 3. Aromatic ring must be preserved Role of the Acid Catalyst : To generate the strong E+
Br Br FeBr3 acid e'pair acceptor
+

Br

+ FeBr4

base e'pair donor CH3Cl

FeCl3

CH3

FeCl4

HONO2 + HOSO3H

R C=O Cl SO3

AlCl3

+ HOSO3 H + HOSO3 H

HOSO3 H

General Mechanism: 1. E+ approaches the pi e cloud of the ring and forms a bond to carbon creating a carbocation
E E

II I III The structure of the carbocation can be approximated by the 3 resonance structures . In the carbocation the charge spreads over the 5 carbons although more so on the carbons that are o and p to the position attacked by the E+

2. To retain aromaticity the carbocation does not combine with the Nu-. The removal of the proton by the Nu- in the reaction mixture allows the es from the C-H bond to go back into the ring thus restoring the aromatic system.
E H Nu
-

E + HN u

Overall Result: Substitution of the E+ for a H : Electrophillic Aromatic Substitution A. Halogenation

H + Br2 FeBr3 Br + HBr

B. Alkylation
H + CH3 CH2 Cl FeCl3 CH2 CH3 + HCl

C. Acylation
H CH + 3C=O Cl FeCl3 C=O CH3 + HCl

D. Nitration
H + HONO2 HOSO3H NO2 + H2 O

E. Sulfonation
H + OR H + HOSO3H HOSO3H SO 3H + SO 3 HOSO3H SO 3H

H2 O

F. Side chain Reactions of Aromatic Compounds 1. Halogenation of an Alkyl Side Chain if under uv. :SFR
CHCH3 CH2 CH3 Cl2
2o

CHCH3 Cl +

HCl

uv CH2 CH2
1o

2. Oxidation of an Alkyl Side Chain -R into COOH group by treatment of hot KMnO4 regardless of length of the R
CH3 COOH

hot KMnO4

C CH 3 CH3 CH3

hot KMnO4

COOH

COOH hot KMnO4 HOOC

CH3

DISUBSTITUTED BENZENES: Monosubstituted benzenes are capable of undergoing further substitution, When a second group G, is introduced into the monosubstituted benzene, 3 possible isomeric compounds can be formed. They are:
Y G ortho Y G G meta para Y

The orientation of the second incoming group G , depends upon the nature of the original/initial group. That is the original group affects the ring in 2 ways: 1. It directs a second group to an ortho or para positions or to a meta position Ortho or para when it allows e delocalization to go into the ring: E delocalization towards the ring tends to increase e density at the ortho and Para positions of the ring making the ring susceptible to the E+ attack. Meta when it allows edelocalization away from the ring: E delocalization away from the ring, decreases edensity of the ortho and para positions of the ring without affecting the meta position. The meta position is still with an appreciable amount of edensity thereby still making it susceptible to the E+ attack. 2. It can activate or deactivate the ring towards Substitution.

Groups that release es toward the ring more effectively than the H they will replace will activate the ring towards E+ substitution . Such group will cause the reaction to go faster than with benzene. Groups that withdraw es away from ring more effectively than the H they will replace, will deactivate the ring towards E+ substitution. Such group will cause the reaction to go slower than with benzene.

ORTHO/PARA DIRECTORS(there is at least a lone pair on the atom that is directly attached to the ring) OH OR NH2 NHR NR2

ORTHO/PARA DIRECTORS

C6H5 CH3 R

F Cl Br I

STRONGLY ACIVATING

MODERATELY ACTIVATING

DEACTIVATING

META DIRECTORS(there is at least a positive charge or partial positive on the atom that is directly attached to the ring) NO2 SO3H COOH COOR CHO COR CN STRONGLY DEACTIVATING

Excersises: 1. Name each of the ff:

F F Cl CH=CH2 NO2 OH CH3

Cl CH3C CH2CH3

CH

CH2CH3 CH2Cl NO2

2. Draw the structure of each of the compound named a. 2-phenyl pentane b. M-chloro benzaldehyde c. M-nitrobenzoic acid d. P-nitro ethyl benzene e. O-ethyl aniline 3. Draw the structures of the reactant and the product for the transformation shown here and supply the necessary reagents A through F 1. 2. 3.
benzene
toluene
toluene

A
C
E

toluene

B
D

benzyl chloride
p-chloro benzoic acid
4-bromo-2- nitro toluene

p-chloro toluene
o-nitro toluene F

II. Complete the following reactions. When a mixture of ortho and para isomers is expected , show both isomers.
+ CH3CHCl CH3
NO 2 + Br2

AlCl3

1.

F eB r3

2.
OCH3 + Cl2 FeCl3

3.
C=O CH 3 + HNO3 H2 SO4

4.
NO2 CH3 + Br2 uv

5.

CH 3 + KMnO4

6.

O2N

CH3 CHCH3

Cl2

uv

7.