Aromatic Hydrocarbons

Timberlake LecturePLUS 1999

Aromatic Compounds and Benzene

Aromatic compounds contain benzene. Benzene, C6H6 , is represented as a six carbon ring with 3 double bonds. Two possible can be drawn to show benzene in this form. H H
H H
Timberlake LecturePLUS 1999

H H H

H H
2

H H

Benzene Structure
The structures for benzene can also be written as a single structure where the alternating double bonds are written as a circle within the ring.
Benzene structure

Timberlake LecturePLUS 1999

Aromatic Compounds in Nature and Health

Many aromatic compounds are common in nature and in medicine.
COOH COOCH3 CHO CH3 CH3CHCH2 OCH3 OH Aspirin Vanillin Ibuprofen CH3 CHCOOH

Timberlake LecturePLUS 1999

Naming Aromatic Compounds

Aromatic compounds are named with benzene as the parent chain. One side group is named in front of the name benzene.
CH3 Cl

methylbenzene (toluene)
Timberlake LecturePLUS 1999

chlorobenzene
5

Monosubstituted Benzenes

are named using benzene as the parent name preceded by the substituent name (as a prefix; all one word):

NO2

CH2CH3

fluorobenzene

nitrobenzene

ethylbenzene

Alkyl-substituted Benzenes

Alkyl substituted benzenes are named according to the length of the carbon chain of the alkyl group. With six carbons or fewer in the alkyl chain, they are named as alkylbenzene. e.g., propylbenzene:

CH2CH2CH3

Alkyl-substituted Benzenes

With more than six carbons in the alkyl chain, they are named as a phenylalkane, where the benzene ring is named as a substituent (phenyl) on the alkane chain e.g., 4-phenylnonane
CH2CH2CH3 CHCH2CH2CH2CH2CH3 =

CH 3CH 2CH 2

CHCH 2CH 2CH 2CH 2CH 3

CH3CH2CH2CHCH2CH2CH2CH2CH3

4-phenylnonane
8

Common Names of Subs. Benzenes

There are a number of nonsystematic (common) names commonly used for certain monosubstituted benzenes These common names should be memorized. These common names are used as base names when naming di- or trisubstituted aromatic compounds derived from them.

Common Names of Subs. Benzenes

Do you still remember ? Toluene (an alkybenzene) Aniline (amine) Phenol (an alcohol)

benzoic acid

Cumene (an alkylbenzene)

Styrene (an alkylene Benzene) benzaldehyde

benzonitrile Acetophenone (a keton)

Anisole (an eter)

10

Common Names of Subs. Benzenes

CH3 OH NH2

OCH3

H C

CH2 O C

O C

O C

OH
CH3 CHCH3

CH3

C N

11

Common Names of Subs. Benzenes

CH3 OH NH2

toluene OCH3

phenol

H C CH2

aniline

O C H

anisole

O C OH

styrene

O C CH3

benzaldehyde C N

benzoic acid

CH3 CHCH3

acetophenone

benzonitrile

cumene
12

13

Disubstituted Benzenes
ortho= o= 1,2-disubstituted (two groups on adjacent carbons on the F ring)
F

o-difluorobenzene or 1, 2-difluorobenzene
14

Disubstituted Benzenes
meta= m= 1,3-disubstituted (two groups having one unsubstituted carbon between them)
Br Br

m-dibromobenzene or 1, 3-dibromobenzene

15

Disubstituted Benzenes
para- = p= 1,4-disubstituted (two groups on opposite sides of the ring)
Cl Cl p-dichlorobenzene or 1, 4-dichlorobenzene

16

Disubstituted Benzenes

When one of the substituents changes the base name, o-, m-, and p- can be used to indicate the position of the other substituent.

Br

OH

3 2

2Cl

1
NH2

p-bromoaniline or 4-bromoaniline

o-chlorophenol or 2-chlorophenol
17

The Phenyl Group

When a benzene ring is a substituent, the term phenyl is used (for C6H5 ) You may also see Ph or f in place of C6H5 Benzyl refers to C6H5CH2

18

Disubstituted Benzenes

Relative positions on a benzene ring

ortho- (o) on adjacent carbons (1,2) meta- (m) separated by one carbon (1,3) para- (p) separated by two carbons (1,4)

Describes reaction patterns (occurs at the para position)

19

Common Names of Disubs. Benzenes

There are a few nonsystematic (common) names for disubstituted benzenes that you should be familiar with:
CH3 CH3 CH3 m-xylene CH3 OH CH3 OH m-cresol p-cresol OH
20

CH3 CH3 CH3 p-xylene

o-xylene CH3

o-cresol

Polysubstituted Benzenes
The ring is numbered in a direction to encounter the next substituent with the lowest number. The substitutents are listed in alphabetical order when writing the name. Common names of the monosubstituted benzenes are used as parent names for polysubstituted aromatics.

21

Polysubstituted Benzenes

Polysubstituted benzenes are named by numbering the position of each substituent on the ring (with more than two substituents, numbering must be used rather than o, m-, and p-.) The numbering is carried out to give the substituents the lowest possible numbers. Carbon #1 is always a carbon bearing a substituent. For rings with common names, the carbon bearing the substituent responsible for the common name is always carbon #1.
22

Benzenes With More Than Two Substituents

23

Polysubstituted Benzenes
Br OH

2
Br

Cl

1
NO2

2CH2CH3

3 4

4-bromo-2-ethyl-1-nitrobenzene

5-bromo-2-chlorophenol

24

Polysubstituted Benzenes
Br

3
O2N

1 CH3 6
Cl O2N

Br

1 2 CH2CH3 3
Cl

2-bromo-6-chloro-4-nitrotoluene

1-bromo-3-chloro-2-ethyl-5-nitrobenzene

25

Polycyclic Aromatic Hydrocarbons (PAH)

naphthalene

anthracene phenanthrene

pyrene

benzo [a] pyrene

26

Aromatic Hydrocarbons

From high temperature distillation of coal tar

27

Problem

28