Topic 8: Introduction to Organic Chemistry

1. Formulae: Empirical, Molecular, Structural (condensed, displayed/full

structural, skeletal), Stereochemical
2. Aliphatic compounds: compounds with open chains of carbon atoms,
may be branched or unbranched, may contain single, double or triple bonds
or combinations of these
3. Alicyclic compounds: compounds with closed rings of Carbon atoms
4. Aromatic compounds: compounds containing at least one aromatic
system such as a benzene ring
Hierarchy of
suffix naming
Highest priority

Functional
Prefix
Group
name
Carboxylic acid

Suffix
name
-oic acid

Ester

-oate

Acid halide

-oyl halide

Amide

-amide

Nitrile

Cyano-

-nitrile

Aldehyde

Formyl-

-al

Ketone

Oxo-

-one

Alcohol
Amine

HydroxylAmino

-ol
-amine

Alkene

-ene

Structure
O
R - C - OH
O
R C OR
O
RCX
H
RN
H
RCN
O
RCH
O
R C R
ROH
O
RCN
R
H
R C = C R

Lowest priority
5. Addition: reaction between 2 molecules to form a single molecule. An
unsaturated functional group is usually involved
6. Substitution: when one atom or group of atoms is substituted by another.
There are always at least 2 product
7. Elimination: formation of an unsaturated compound with the elimination
of a small molecule
8. Oxidation: a reaction in which at least one oxygen atom is added to the
molecule or hydrogen atoms removed from the molecule
9. Reduction: a reaction in which oxygen atoms are removed from the
molecule or hydrogen atoms are added to the molecule

10. Condensation: the expulsion of a small molecule when 2 molecules

come together to form a bigger molecule
11. Hydrolysis: a reaction in which a molecule is split into 2 by the action of
water, often catalysed by dilute acids/alkalis
12. Homolysis: aka homolytic fission, involves splitting of a single bond
resulting in equal sharing of the bonding electrons to each resultant particle
results in the formation of radicals
13. Heterolysis: aka heterolytic fission, involves splitting of a bond resulting
in unequal sharing of the bonding electrons to each resultant fragment
results in the formation of ions
14. Electrophile: electron-deficient/electron-seeking reagents that can
develop an electron deficient centre
15. Nucleophile: electron-rich/nucleus-seeking reagents
16. Reaction Intermediates: species that are formed in one of the steps of
the reaction mechanism and are consumed in later steps
17. Free radicals: electrically neutral atom/groups of atoms that has an
unpaired electron
18. Carbocation (Carbonium ion): a species that contains a Carbon atom
bearing a positive charge strong electrophile
19. Carbanion: a species that contains a Carbon atom bearing a negative
charge strong nucleophile
20. Isomers: structures having the same molecular formula but having
different arrangements of the atoms
21. Structural isomerism: substances with the same molecular formula but
different structural formula functional group/positional/chain
22. Stereoisomerism: substances with the same attachment of atoms to
each other, but different spatial arrangement geometric/optical
23. Optical activity: ability of a compound to rotate the plane of polarised
light
Topic 9: Alkanes
Mechanism of Free Radical Substitution
Stage 1: Initiation
Cl Cl

UV

2Cl

Stage 2: Propagation
Cl

+ CH4

HCl +

CH3

CH3 + Cl2

Stage 3: Termination
Cl + Cl
Cl
+
CH3 +

Cl2
CH3
CH3

CH3Cl
CH3 CH3

CH3Cl + Cl

24. Equation of Combustion: CxHy + (x +

y
4 )O2

xCO2 +

y
2 H2O
25. Cracking: a process in which C C bonds in long-chain alkane molecules
are broken to produce smaller molecules of alkanes and alkenes
26. Thermal cracking:
a. Criterion: heat with steam at 800oC, moderate pressure, in absence
of air
b. Proceeds by free radical mechanism
c. Very little rearrangement of the chains
27. Catalytic cracking:
a. Criterion: 500oC, slight pressure, passed over Al2O3 & SiO2
b. involves formation of carbocations which can undergo internal
rearrangement before forming the final products
28. Catalytic Reforming: chanese straight-chain alkanes into branchedchain alkanes and cyclic hydrocarbons without the loss of any carbon
atoms, but often with the loss of hydrogen atoms
Topic 10: Alkenes
1. Alkenes: unsaturated hydrocarbons that contain at least one carbon-carbon
double bond
Mechanism of Electrophilic Addition
Stage 1: Rate-determining step
H

H
C=C
H
H

H Br
+

H H
HCC+ +
H H

Br

Stage 2: Fast Step

H H
H C C + Br
H
H

H Br
HCCH
H H

* In an electrophlic addition to an alkene, the electrophile adds in such

a way so as to generate the most stable carbocation intermediate
2. Markovnikovs Rule: in the addition of HX to an alkene, the H atom adds
to the C atom of the double bond that already has the greater number of H
atoms directly attached
Mechanism of Electrophilic Addition of Halogens
Stage 1: Rate determining step

H
C=C
H
H

Br Br
+

HH
HCCH
Br+

Br

Stage 2: Fast Step

HH
HCCH
Br+

Br

HCCH
Br Br

Criterion: absence of light, liquid Br, room temperature

3. Hydration:
a.
Industrial Conditions: Phosphoric acid H3PO4 catalyst, 300oC,
70 atm
b. Lab Conditions: conc. H2SO4, room temperature, warm with water
c.
Alkene -> Alcohol
4. Hydrogenation:
a.
Conditions: Hydrogen gas, Ni/Pd/Pt catalyst, high
temperature, high pressure
b.
Alkene -> Alkane
5. Mild Oxidation:
a. Conditions: KMnO4, NaOH, cold
b. Observations: purple KMnO4 is decolourised and a brown precipitate
of MnO2 is formed
c. Alkene -> Alcohol
6. Oxidative Cleavage
a. Conditions: conc. KMnO4, dilute H2SO4, heat
b. Observations: purple KMnO4 is decolourised
c. Alkanes with terminal double bonds (=CH2) would, upon oxidation,
evolve CO2 and H2O
Topic 11: Arenes
1. Huckels Rule: estimates whether a planar ring will exhibit aromatic
properties
a. 4n + 2 electrons in the delocalised p-orbital cloud
b. Planar and cyclic
c. Every atom in the circle is able to participate in delocalising the
electron cloud by having a p-orbital or an unshared pair of
electrons
2. Order of precedence as principal functional group: -CO2H > -OH >
-CH3 > -halogen > -NO2

Mechani
sm
Nitration

Condition
s&
Reagents
Conc.
HNO3,
conc.
H2SO4,
heat at
55oC

Reactions of Benzene
Observatio Note
Stages
ns
Yellow oil
(nitrobenzene)
formed

Above
100oC,
further
nitration
will occur
to give
1,3,5nitrobenze
ne

1: Generation of electrophile
HNO3 + 2H2SO4
NO2+ + 2HSO4+ H3O+
2: Attack by electrophile to form
carbocation intermediate (slow
step)
H NO2
+
+ NO2
(carbocation)
3: Extraction of proton by base
HSO4- to restore stable delocalised
system and regeneration of
catalyst
O2N H
NO2
+ HSO4-

Halogenati Br2(l),
on
anhydrous
FeBr3/AlBr3
as
catalyst,
warm

FriedalCrafts

CH3Cl/AlC
l3 as

Decolourisa
-tion of
reddishbrown Br2(l),
formation
of dense
white
fumes of
HBr, chlorobenzene
formed

Methylbenzene is

Lewis
acid
catalysts
are
required
to
generate
the
strong
electrophi
le Br+

Not
feasible

H2SO4
1: Generation of electrophile
FeBr3 + Br2
FeBr4- + Br+
2: Attack by electrophile to form
carbocation intermediate (slow
step)
H Br
+
+ Br
(carbocation)
3: Extraction of proton by base
HSO4- to restore stable delocalised
system and regeneration of
catalyst
Br H
Br
+ FeBr4+
FeBr3 + HBr
1: Generation of electrophile
CH3Cl + AlCl3
CH3+ + AlCl4-

alkylation
(not in
syllabus)

catalyst,
warm

formed

for longer
alkyl
substitue
nt due to
occurrenc
e of 1,2hydride
shift that
results in
a more
stable
carbocati
on

2: Electrophilic attack to form

carbocation
H CH3
+
+ CH3
(carbocation)
3: Extraction of proton by AlCl4- to
restore stable delocalised system
and regenerate catalyst
H3C H
CH3
+ AlCl4AlCl3 + HCl

3. Activating groups: Electron-donating substituent that increases the

electron density of the benzene ring, thereby increasing the reactivity of the
benzene ring
4. Deactivating groups: Electron-withdrawing substituent that decrease the
electron density of the benzene ring, thereby decreasing the reactivity of
the benzene ring
5. Through the sigma bond Inductive effect
Present when there is a difference in electronegativity between the bonding
atoms
6. Through the pi bond Resonance effect
Present when there is overlapping of p-orbitals
Substituen
t

Inductiv
e effect

Alkyl groups
eg. CH3

Electrondonating

Resonan Overall
ce effect effect on
reactivity
Activating

Effect on position of
incoming
electrophile attack
2, 4-directing

Polar OH,
Electron- Electron-NH2,
withdrawi donating
-OCH3
ng
Halogens
Electron- Electron- Deactivating
2, 4-directing
Cl,
withdrawi donating
-Br
ng
Contain polar
Electron3- directing
multiple
withdrawi
bonds
ng
eg. CHO,
-NO2
7. Activating groups and halogens are 2, 4-directing

8. Deactivating groups are 3-directing

Reaction Condition
s&
Reagents
Ring
Conc.
reaction: HNO3,
Nitration
conc.
H2SO4,
heat at
30oC

Observati
ons

Note

Stages

2nitromethyl
benzene
and 4nitromethyl
benzene
are major
products

Above
30oC,
disubstituti
on is
possible
and 2, 4dinitromet
hyl
benzene is
produced
Further
heating to
110oC
leads to
formation
of 2, 4, 6trini
tromethylb
en zene
(TNT)

1: Generation of electrophile
HNO3 + 2H2SO4
NO2+ + 2HSO4+ H3O+
2: Attack by electrophile to form
carbocation intermediate (slow
step)
CH3
CH3
+
H
+ NO2
NO2
(carbocation)
CH3
+ NO2+

CH3

(carbocation)
H NO2
3: Extraction of proton by base
HSO4- to restore stable delocalised
system and regeneration of
catalyst
CH3 H
CH3
NO2
NO2
+ HSO4
+ H2SO4
CH3

CH3
+ HSO4-

+ H2SO4

Ring
reaction:
Halogenati
on

Br2(l),
anhydrous
FeBr3/AlBr3
as
catalyst,
absence of
light, room
temperatu
re

Decolouris
a-tion of
reddishbrown Br2(l),
formation
of dense
white
fumes of
HBr

O2N H
Lewis acid
CH3
catalysts
CH3
are
+ Br2
+HBr
required
to
generate
the strong
electrophi
le Br+

NO2
CH3
Br +

Br

Sidechain
reaction:
Free
radical
Substituti
on

Cl2(g), UV
light or
heat

Greenishyellow Cl2
decolouris
es slowly

Sidechain
reaction:
Oxidation

KMnO4,
dilute
H2SO4,
heat

Purple
KMnO4 is
decolouris
ed and
white
precipitate
of benzoic
acid is
formed

More than
one
+ HCl
chlorine
atom can
be
incorporat
e if
excess Cl2
is used
Benzoic
acid is
always
formed
regardles
s of the
length of
the alkyl
side chain

CH3

CH2Cl

CH2CH2CH3 + 5[O]
COOH + CH3COOH +H2O

CH2CH3 + 6[O]
COOH + CO2 + 2H2O
CH3
CHCH3 + 9[O]
COOH + 2CO2 + 3H2O