BENZENE AND IT’S DERIVATIVES

 Benzene and all substances with structures and chemical properties that
resemble benzene are classified as aromatic compounds.

It has 6 carbons with

3 double bonds

 Benzene and its derivatives undergo a type of reaction called electrophilic

aromatic substitution, in which a ring hydrogen is substituted by another group.

NAMING SUBSTITUTED BENZENE COMPOUNDS

 A substituted benzene is derived by replacing one or more hydrogen atoms of
benzene by another atom or group of atoms.

Br – Bromo I – Iodo - COOH – Carboxylic Acid

F – Fluoro NH2 – Amino - CHO – Aldehyde
Cl – Chloro NO2 - Nitro - OH - Alcohol

 Example:

MONOSUBSTITUTED BENZENES
  Some monosubstituted benzenes are named by adding the name of the
substituent group as a prefix to the word benzene.
 Monosubstituted benzene has the formula C6H5G, where G is the group
replacing a hydrogen atom.
CH2CH3 Br

O2N Cl

nitrobenzene ethylbenzene chlorobenzene bromobenzene

 Certain monosubstituted benzenes have special names.

Phenyl Group

 The C6H5- group is known as the phenyl group, and the name phenyl is
used to name compounds that cannot easily be named as benzene
derivatives.
1 CH3
2 H2
CH 3 4 5 C
CHCH2CH3

Cl

3-chloro-2-phenylpentane diphenylmethane

Disubstituted Benzenes
 The prefixes ortho-, meta-, and para- (abbreviated o-, m-, and p-) are used to
name disubstituted benzenes.

ortho ortho

meta meta

para
Dichlorobenzenes, C6H4Cl2

 The three isomers of dichlorobenzene have different physical properties.

meta-dichlorobenzene
Cl Cl Cl

Cl

Cl
ortho-dichlorobenzene
Cl
para-dichlorobenzene
Disubstituted Benzenes

 When the two substituents are different and neither is part of a compound
with a special name, the names of the two substituents are given in
alphabetical order, followed by the word benzene.
Cl CH2CH3

Br

ortho-bromochlorobenzene
NO2
para-ethylnitrobenzene
 Dimethyl Benzenes

 The dimethylbenzenes have the special name xylene.

CH3 CH3 CH3

H3C

H3C
DISTANCE: 1 & 2 ortho-xylene meta-xylene
CH3
DISTANCE: 1 & 3 DISTANCE: 1 & 4
para-xylene
Disubstituted Benzenes

 When one of the substituents corresponds to a monosubstituted benzene

that has a special name, the disubstituted compound is named as a
derivative of that parent compound.
CH3
NO2 NH3

HO

Br
ortho-nitrophenol meta-bromoaniline NO2
para-nitrotoluene
Polysubstituted Benzenes

 When there are more than two substituents on a benzene ring, the carbon
atoms in the ring are numbered starting at one of the substituted groups.
 Numbering must be done in the direction that gives the lowest possible
numbers to the substituent groups.
CH3 OH

O2N 1 NO2 1 Cl
6 2 6 2

5 3 5 3
4 Br
4
NO2 5-bromo-2-chlorophenol
2,4,6-trinitrotoluene (TNT)
ALCOHOLS, ETHERS AND THIOLS

ALCOHOLS
 Alcohols are classified as primary (1°), secondary (2°), or tertiary (3°) depending
on whether the carbon atom to which the –OH group is attached is directly
bonded to one, two, or three other carbon atoms respectively.

H C C

C C OH C C OH C C OH

H H C
primary (1o) o
secondary (2 )
alcohol alcohol tertiary (3o)
alcohol
 Polyhydroxy alcohols and polyols are general terms for alcohols that have more
than one –OH group per molecule.
 Polyhydroxy compounds are very important molecules in living cells, as they
include the carbohydrate class of biochemicals.

Structural Representations of Alcohols

 An alcohol such as 2-butanol can be written in a single-line formula by enclosing
the –OH group in parentheses and placing it after the carbon to which it is
bonded.

OH
CH3CH2CHCH3 CH3CH2CH(OH)CH3
Application to Biochemistry
IUPAC Rules for Naming Alcohols
1. Select the longest continuous chain of carbon atoms containing the –OH group.
2. Number the carbon atoms in this chain so that the one bearing the -OH group
has the lowest possible number.
3. Form the parent alcohol name by replacing the final –e of the corresponding
alkane by –ol. When isomers are possible, locate the position of the –OH group
by placing the number (hyphenated) of the carbon atom to which the –OH is
bonded immediately before the parent alcohol name.
4. Name each alkyl side chain (or other group), and designate its position by
number.
Example: CH3CH2CH2CH2OH = 1-butanol

Nomenclature of Alcohols

Physical Properties of Alcohols

 The physical properties of alcohols are related to those of both water and alkane
hydrocarbons.
 An alcohol molecule is made up of a waterlike hydroxyl group joined to a
hydrocarbonlike alkyl group.

O O
H H R H
water alcohol
Boiling Points of Alcohols
 Alcohols have relatively high boiling points.
 The boiling points of the normal alcohols increase in a regular fashion with
increasing number of carbon atoms.
 Branched-chain alcohols have lower boiling points than corresponding straight-
chain alcohols.
 Alcohols containing up to three carbon atoms are infinitely soluble in water.
 The –OH group on the alcohol molecule is responsible for both the water
solubility and relatively high boiling points of the low-molar-mass alcohols.

Hydrogen Bonding in Alcohols

Glucose is one of the most important carbohydrates in biochemistry. It has six

carbons and five alcohol groups (molar mass = 180.2 g). How would you predict
the water solubility of glucose to differ from that of 1-hexanol?
ETHERS

 Ethers have the formula R-O-R

◦ R can be aliphatic or aromatic

 Ethers are slightly polar due to the polar C=O bond
 Ethers are organic compounds in which two saturated carbon atoms are bound
through a single oxygen atom.

Common Names of Ethers

 Individual ethers may be known by several names.
 Common names for ethers consist of the names of the two groups attached to
the O listed in alphabetical order (or size) and followed by ‘ether’

 Example:

CH3 CH3CH2
CH3 CH O CH3 O

Isopropyl methyl ether Ethyl phenyl ether

H3C O CH3 H3C O CH2CH3

ether ether
methyl methyl methyl ethyl
dimethyl ether ethyl methyl ether
IUPAC Nomenclature of Ethers
 The IUPAC names for ethers are based on the alkane name of the longest chain
attached to the oxygen which is the parent name
 The shorter chain is named as an alkoxy substituent
◦ Alkane with the -ane replaced by -oxy (to obtain the alkoxy group name)
◦ Name as alkoxy name then the parent chain. Number the alkoxy
substituent to indicate where it attaches to the parent alkane.
◦ e.g., CH3CH2O = ethoxy
 CH3CH2CH2CH2CH2-O-CH3 = 1-methoxypentane

Properties of Ethers
 Ethers are somewhat more polar than alkanes, but are much less polar than
alcohols.
 Ethers – especially diethyl ether – are exceptionally good solvents for organic
compounds.

H SO3H

O O

H H
hydrogen
bond
O O
H3C CH2CH3 H3C CH2CH3

ether-water ether-acid
Formation of Peroxides from Ethers
 Ethers react with O2 to form hydroperoxides and peroxides (unstable compounds
which can explode)

◦ R – O – O – H = hydroperoxide
◦ R – O – O – R = peroxide

Example:

O
+ O2 O
H3CH2C CH2CH3
H3CH2C CHCH3

O-O-H
diethyl ether hydroperoxide

THIOLS
 Organic compounds that contain the R - SH group are known as thiols or
mercaptans.
 Similar in structure to alcohols with S replacing O
 Name is based on longest alkane chain with the suffix –thiol position indicated by
number
 Example:
Properties of Thiols
1. Foul odors.
 Thiols, as many other sulfur-containing compounds can have nauseating
aromas
 Defensive spray of North American striped skunk
 Onions and garlic

2. Oxidation to disulfides: [O]

Disulfides have the formula R-S-S-R 2 RSH  R-S-S-R

thiol disulfide
 R may be aliphatic or aromatic

Naming Thiols