Organic Chemistry

Nomenclature
 Vocabulary
• Functional group
• Cyclic, heterocyclic
• Isomer, stereoisomer, enantiomer
• Racemate, racemic
• Polarised
 Learning Objectives
• understand and be able to work with IUPAC
nomenclature extended to more complex compounds
including cyclic, aromatic and heterocyclic compounds
• be able to draw and build structures which show
geometrical (E-Z) and optical isomerism
• know that optical isomers will rotate the plane of
polarised light
• understand the effects of chemical reactions on
stereoisomers, including racemisation
• appreciate that stereoisomers may have different
effects on living systems
Cyclic compounds
 NAMING AROMATIC COMPOUNDS

CH3 Cl NO2 COOH

methylbenzene chlorobenzene nitrobenzene benzenecarboxylic acid

(toluene) (benzoic acid)

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 NAMING AROMATIC COMPOUNDS
CH3 CH3

1,3-dimethylbenzene
(m-xylene)

CH3 4-methyl-1-chlorobenzene
Cl

COOH COOH
OH

O2N NO2
2-hydroxybenzenecarboxylic
3,5-dinitrobenzenecarboxylic
acid
acid

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 NAMING AROMATIC COMPOUNDS
NH2 CH3 CH2 CH2 CH3

phenylamine
(aniline)

2-phenylbutane

O CH3
CH CH2 C

phenylethene phenylethanone

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 NAMING AROMATIC COMPOUNDS
O

C O O
O CH3 C CH3

phenylethanoate methyl benzenecarboxylate

(methyl benzoate)

NH C CH3

N-phenylethanamide

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Heterocyclic compounds
 Stereoisomerism
• Geometric isomerism
• Optical isomerism
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GEOMETRIC ISOMERISM

CH3 H
X
C C

H CH3
CANNOT ROTATE AROUND C=C

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 GEOMETRIC ISOMERISM

CH3 H CH3 CH3

C C C C

H CH3 H H
(E) but-2-ene (Z) but-2-ene

E entgegen (opposite) Z zusammen (together)

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 GEOMETRIC ISOMERISM
PRIORITY: H < CH3 < CH2CH3

Look at atomic numbers of atoms attached to C=C (or

subsequent atoms if the same).

Highest values opposite = E

Highest values together = Z

9 F CH3 6
12 1 H CH2CH3 12,
6, 612

C C C C
6
12 CH3 Br 35 12
6 CH3 CH3 12
6

E 2-bromo-3-fluorobut-2-ene E 3-methylpent-2-ene
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 GEOMETRIC ISOMERISM

CH3 H CH3 CH3

C C C C

H CH3 H H
trans but-2-ene cis but-2-ene
(E) but-2-ene (Z) but-2-ene

BOTH C ATOMS OF C=C MUST HAVE

TWO DIFFERENT GROUPS

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 TASK
CH3 H

C C NO

CH3 H
methylpropene

H H H Cl

C C C C YES

Z E
CH3 Cl CH3 H
1-chloropropene

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 TASK
CH3 CH2 CH3

C C NO

CH3 H
2-methylpent-2-ene

H CH2 CH2 CH3

C C NO

H CH2 CH3
2-ethylpent-1-ene

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 TASK
CH3 CH3 H CH3

C C C C YES
E Z
H CH2 CH3 CH3 CH2 CH3

3-methylpent-2-ene

H H

C C NO

H CH2 CH3
but-1-ene

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 TASK
CH3 CH3 CH3 CH2 CH3
C C C C YES

CH3 CH2 Z CH2 CH3 CH3 CH2 E CH3

3,4-dimethylhex-3-ene

CH3 CH3 CH3 Cl

YES
C C C C
Z E
Br Cl Br CH3
2-bromo-3-chlorobut-2-ene
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• All molecules have a mirror image – but
for most molecules it is the same
molecule.

H H

C C
H H
H H
F F
fluoromethane
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• For some molecules the mirror image is a
different molecule
(the mirror image is non-superimposable).

OH OH

C C
COOH HOOC
H H3C H
CH3
(-) lactic acid (+) lactic acid
in sour milk in muscles

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• Left and right hands are an example of
non-superimposable mirror images.
• This usually happens when a molecule contains a C
atom with four different groups attached (chiral /
asymmetric C).
• Such molecules are said to be chiral or optically active.

a a

C C
d d
b c c b

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Chirality
• The optical isomers are called enantiomers.
• These are distinguished by +/-, D/L or more correctly R/S.
• A 50/50 mixture of the two enantiomers is called a racemic
mixture or a racemate.

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TASK Some of the following molecules
are optically active.
For each one, click its name below and decide whether it is optically active or not.
Click again to see if you are correct.

a) propan-2-ol e) butanone

b) 2-chlorobutane f) 2-methylbutanoic acid

c) 1-chlorobutane g) butan-2-ol

d) 3-methylhexane h) 1-chloro-3-methylpentane

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propan-2-ol CH3 CH CH3

OH

NOT OPTICALLY ACTIVE

Click here to go back to the optical isomerism task

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2-chlorobutane CH3 CH CH2 CH3

Cl
CH2CH3 CH2CH3

C C
CH3 H3C
H H
Cl Cl
OPTICALLY ACTIVE
Click here to go back to the optical isomerism task

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1-chlorobutane CH2 CH2 CH2 CH3

Cl

NOT OPTICALLY ACTIVE

Click here to go back to the optical isomerism task

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3-methylhexane CH3 CH2 CH CH2 CH2 CH3
CH3

CH2CH2CH3 CH2CH2CH3

C C
CH3 CH3
H H
CH2CH3 CH3CH2

OPTICALLY ACTIVE

Click here to go back to the optical isomerism task

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butanone O

CH3 C CH2 CH3

NOT OPTICALLY ACTIVE

Click here to go back to the optical isomerism task

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propan-2-ol CH3 CH CH3

OH

NOT OPTICALLY ACTIVE

Click here to go back to the optical isomerism task

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2-methylbutanoic acid CH3 O

CH3 CH2 CH C OH

CH2CH3 CH2CH3

C C
H H
CH3 CH3
COOH HOOC

OPTICALLY ACTIVE
Click here to go back to the optical isomerism task

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butan-2-ol OH

CH3 CH2 CH CH3

CH2CH3 CH2CH3

C C
H H
CH3 CH3
OH HO

OPTICALLY ACTIVE

Click here to go back to the optical isomerism task

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1-chloro-3-methylpentane CH3 Cl

CH3 CH2 CH CH2 CH2

CH2CH3 CH2CH3

C C
H H
CH3 CH3
CH2CH2Cl CH2ClCH2

OPTICALLY ACTIVE

Click here to go back to the optical isomerism task

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• Molecules that are optical isomers are
called enantiomers.
• Enantiomers have identical chemical and
physical properties, except:
• Their effect on plane polarised light;
• Their reaction with other chiral molecules

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• Light is a form of electromagnetic
radiation.
 • The wave vibrations are perpendicular to
the direction of travel of the wave.

normal light plane-polarised light plane-polarised light after

(waves vibrate in all directions) (vibrates in only one direction) clockwise rotation

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 • Optical isomers rotate the plane of plane
polarised light.

(-)-enantiomer (+)-enantiomer (±)-racemate

(anticlockwise rotation) (clockwise rotation) (no overall effect)

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POLARIMETERS
can be used to analyse the effect optical
isomers have on plane polarised light:
• Chiral molecules often react differently
with other chiral molecules.
• This is like the idea that a right hand does
not fit a left handed glove – the molecule
must be the correct shape to fit the
molecule it is reacting with.
• Many natural molecules are chiral and
most natural reactions are affected by
optical isomerism.
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• For example, most amino acids (and so
proteins) are chiral, along with many other
molecules.

• In nature, only one optical isomer occurs

(e.g. all natural amino acids are rotate
polarised light to the left).

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• Many drugs are optically active, with one
enantiomer only having the beneficial
effect.
• In the case of some drugs, the other
enantiomer can even be harmful, e.g.
thalidomide.

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• In the 1960’s thalidomide was given to
pregnant women to reduce the effects of
morning sickness.
• This led to many disabilities in babies and
early deaths in many cases.

The photographs are both from ‘Molecule of the Month’ at Bristol University:
http://www.chm.bris.ac.uk/motm/thalidomide/start.html
O NH O O NH O
O O

H2C C C H2C
CH2 N N CH2
H H

O O

S thalidomide (effective drug) R thalidomide (dangerous drug)

The body racemises each enantiomer,

so even pure S is dangerous as it
converts to R in the body.

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• Thalidomide was banned worldwide
when the effects were discovered.
• However, it is starting to be used again to
treat leprosy and HIV.
• Its use is restricted though and patients
have to have a pregnancy test first
(women!) and use two forms of
contraception (if sexually active).

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 CH3 CH3

O O

H C CH2 H2C C H

H3C CH3

S carvone (caraway seed) R carvone (spearmint)

Caraway Seed has a warm, pungent, slightly

bitter flavour with aniseed overtones.
 CH3 CH3

CH2 C H H C CH2

CH3 H3C

S limonene (lemons) R limonene (oranges)

 Effects of chirality
• Flavour: the artificial sweetener aspartame has two
enantiomers. L-aspartame tastes sweet whereas D-
aspartame is tasteless.
• Odor: R-(–)-carvone smells like spearmint whereas S-
(+)-carvone smells like caraway.
• Drug effectiveness: the antidepressant drug
Citalopram is sold as a racemic mixture. However,
studies have shown that only one of the enantiomers is
responsible for the drug's beneficial effects.
• Drug safety: D-penicillamine is used for treatment
whereas L-penicillamine is toxic.