Benzene and Its Derivatives

Aromatic Hydrocarbon
- very "aromatic," hence the name.

- benzene the most common. Toxic, industrially important.

- hybrid ring structure, since 3 double bonds not always in

the same location. so, C-6 H-6 formula.

- Nomenclature involves both the use of benzene suffix as

well as common names.

- important application: Fused Aromatics and Carcinogens,

such as Benzo-a-pyrene and smoke
 Kekules Structure of Benzene

 (A)The bonds in C6H6 are

something between single
and double, which gives it
different chemical
properties than double-
bonded hydrocarbons.
(B) The six-sided symbol
with a circle represents the
benzene ring. Organic
compounds based on the
benzene ring are called
aromatic hydrocarbons
because of their aromatic
character.
Benzene
 Benzene
Benzene is one of the most fascinating molecules. The structure of
this molecule eluded chemists until 1865 when Friedrich August
Kekul proposed that it consisted of a hexagonal ring with a
carbon atom at each vertex.

Benzene is both toxic and carcinogenic. In fact, it might be

considered "the mother of all carcinogens," as a large number of
carcinogens have structures that include benzene rings.

I recall my Organic Chemistry professor joking about how he used

to "practically bathe in benzene up to the elbows" when he would
use it in his research (presumably before it was identified as a
carcinogen). He predicted that this would probably lead to his
demise. He was right--he died due to leukemia several years ago.
 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 H H

H H H H

H H
 Aromatic Compounds
and the Structure of Benzene

In the early days the word aromatics was used to

described many fragrant molecules isolated from
natural sources.
Today the term aromatic is used to describe
benzene like molecules.
Benzene is a flat, symmetrical molecule with the
molecular formula C6H6.
It has alternating three carbon-carbon double and
three single bonds.
 Benzenes relatively lack of chemical
reactivity is due to its structure.
There are two possible structures with
alternating double and single bonds.
 Benzene can only be explained by assuming that the
actual structure of benzene is an average of the
above two possible equivalent structures-known as
resonance.

Simple aromatic compounds like benzene are non-

polar, insoluble in water, volatile, and flammable.

Unlike alkenes, several aromatic hydrocarbons are

toxic. Benzene itself is implicated as a cancer
causing chemical.
 Aromatic Compounds in Nature and
Health
Many aromatic compounds are common in nature and
in medicine.
CHO
COOH
COOCH3 CH3 CH3
CH3CHCH2 CHCOOH
OCH3

OH

Aspirin Vanillin Ibuprofen

 Naming Aromatic Compounds
Aromatic compounds are named with benzene as the parent
chain.
One side group is named in front of the name benzene.
- No number is needed for mono-substituted benzene since all
the ring positions are identical.

CH3 Cl

methylbenzene chlorobenzene
(toluene)
 Naming Aromatic Compounds

When two groups are attached to benzene, the ring is

numbered to give the lower numbers to the side groups.
The prefixes ortho (1,2), meta (1,3-) and para (1,4-) are
also used.
Cl
CH3 Cl
CH3

Cl CH3

1,2-dimethylbenzene 1,3-dichlorobenzene 1-chloro-4-methylbenzene

(ortho-dimethylbenzene) (meta-dichlorobenzene) (para-chloromethylbenzene)
 Some Common Names

Some substituted benzene rings also use a common name.

Then naming with additional more side groups uses the
ortho-, meta-, para- system.
CH3 CH3 OH

Cl
Toluene meta-chlorotoluene phenol
(Methylbenzene) (meta-chloromethylbenzene) (hydroxybenzene)
 Many substituted aromatic compounds have
common names in addition to their systematic
names.
 Learning Check
Select the names for each structure:
Cl
a. Chlorocyclohexane
b. Chlorobenzene
c. 1-chlorobenzene
CH 3
a. Meta-xylene
b. Meta-dimethylbenzene
c. 1,3-dimethylbenzene
CH 3
 Learning Check

Write the structural formulas for each of the following:

A. 1,3-dichlorobenzene

B. Ortho-chlorotoluene
 New Attached Groups
Phenyl
4-phenyl-1-butene

Benzyl

Benzyl alcohol

Nitro -NO2
Refer to your chart for order
of priority! 2,4,6-trinitrotoluene
 DDT and Benzene website
DDT the first of the chlorinated organic insecticides, was originally prepared in 1873, but it was not until
1939 that Paul Muller of Geigy Pharmaceutical in Switzerland discovered the effectiveness of DDT as an
insecticide he was awarded the Nobel Prize in medicine and physiology in 1948 for this discovery).
The use of DDT increased enormously on a worldwide basis after World War II, primarily because of its
effectiveness against the mosquito that spreads malaria and lice that carry typhus. The World Health

Organization estimates that during the period of its use approximately 25 million lives were saved.
DDT seemed to be the ideal insecticideit is cheap and of relatively low toxicity to mammals (oral LD50 is
300 to 500 mg/kg). However, problems related to extensive use of DDT began to appear in the late 1940s.
Many species of insects developed resistance to DDT, and DDT was also discovered to have a high toxicity
toward fish.
The chemical stability of DDT and its fat solubility compounded the problem. DDT is not metabolized very
rapidly by animals; instead, it is deposited and stored in the fatty tissues. The biological half-life of DDT is
about eight years; that is, it takes about eight years for an animal to metabolize half of the amount it
assimilates. If ingestion continues at a steady rate, DDT builds up within the animal over time.
The use of DDT was banned in the United States in 1973, although it is still in use in some other parts of the
world. The buildup of DDT in natural waters is a reverisble process: the EPA reported a 90% reduction of
DDT in Lake Michigan fish by 1978 as a result of the ban
Estrogen and aromatics
 Estrogen and Chemicals
Too Much Estrogen...

Excessive levels of estrogen can also increase the risk of breast cancer. The
female hormone signals cells to proliferate, which is necessary and normal
during conception and fetal attachment to the womb. At other times, however,
estrogen may tell normal cells to grow uncontrollably.

Twenty years ago, nutrition educator Carlton Fredericks, Ph.D., noted that
some women produced five more estrogen than did other women, increasing
their risk of breast cancer. Other women may increase their risk through
estrogen-replacement therapy.

But several years ago, researchers stumbled across something completely

unexpected: many common pesticides and plastics contain chemicals that
mimic estrogen in the body. These estrogenic chemicals, called xenoestrogens,
end up in the food and can greatly increase the risk of breast cancer. Four
years ago, Mary Wolff, Ph.D., of the Mt. Sinai School of Medicine in New
York City, found that high levels of estrogen-mimicking pesticides increased
breast cancer risk in women by four times.
 Estrogen continued
Because hormones are so powerful, only small quantities can do a lot of
damage. In one experiment, researchers found that 2 to 5 parts per billion of
bisphenol-A (BPA), one type of xenoestrogen, are enough to trigger
hormonal changes.

Combinations of pesticides magnify the risk, and such combinations are

common in foods and the environment. Last year, John McLachan, Ph.D., an
expert on pesticides and hormones at Tulane University, New Orleans,
reported in the journal Science that combinations of just two estrogen-like
pesticides were 1,000 times more potent than they were by themselves. What
happens when you mix together dozens of common estrogen-mimicking
chemicals? It's anyone's guess - but it doesn't bode well.

According to Malins, these xenoestrogens, along with the estrogen a woman

normally produces, could add to the free radical burden on breast cancer
cells. Additional free radicals, he pointed out, might also be generated when
the body breaks down estrogens and xenoestrogens. All these free radicals
would greatly increase a person's "oxidative stress" - and the need for
compensatory antioxidant vitamins.
 The connection between:
Hormones in the Human Body and Organic Aromatics