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Jack Wood
1.1 Introduction to Aromatic Chemistry
Arenes
Benzene
- Benzene is the starting material for the synthesis of many other aromatic
materials.
- Benzene is classified as a carcinogen, linked to causing cancer.
- Benzene is a colourless liquid, with a sweet odour and it is highly
flammable.
- Natural sources of benzene include Volcanoes and Forest Fires.
- Benzene is a component of crude oil, petrol and cigarette smoke.
1.2 The Structure of Benzene
- It fails to explain the properties of benzene fully, even though It fitted the
molecular C6H6.
- He suggested that benzene had two forms, differing only by the positions
of the double bonds.
- He suggested that they were in such equilibrium that an approaching
bromine molecule could not be attracted to a double bond before the
structure changed. Hence Bromine could not react with the double
bonds.
Hydrogenation of Benzene
- The Kekule structure of Benzene contained three C=C bonds, the name
for the proposed structure was cyclohexa-1,3,5-triene.
- When an alkene reacts with hydrogen, the energy change is called the
enthalpy change of hydrogenation.
- When one C=C bond reacts with hydrogen, the enthalpy change of
hydrogenation is -120kJ mol-1.
- When it reacts with three C=C bonds, the enthalpy change of
hydrogenation is expected to be -360kJmol-1, three times that of
cyclohexane.
- The actual structure of Benzene has much less energy than the proposed
Kekule structure.
- The energy is known as the delocalisation energy, or resonance energy,
of Benzene.
- This evidence suggests that the real structure of Benzene is more stable
than a structure containing C=C bonds. It helps to explain why it is less
reactive than alkenes.
- Benzene is a cyclic hydrocarbon with six carbon atoms and six hydrogen
atoms. The six carbon atoms are arranged in a planar hexagonal ring.
Each carbon atom is bonded to two other carbon atoms and one
hydrogen atom.
- The shape around each carbon atom is a bond angle of 120 degrees.
- Each carbon atoms has four outer shell electrons. The three bonds in this
plane are called sigma bonds. This leaves a fourth outer shell electron in
a 2p orbital above and below the plane of carbon atoms.
- The electron in a p-orbital of a carbon atom overlaps with the electrons in
the p-orbitals of the carbon atoms on the other side.
- The overlap produces a system of Pi Bonds which spread over all six
carbon atoms.
1.4 Benzene and its Reactions
Reactivity
- In Benzene the region of high electron density above and below the plane
of carbon atoms attracts electrophiles.
- Benzene takes part in substitution reactions instead of addition reactions.
Nitration of Methylbenzene
Halogenation of Benzene
- Benzene does not react with halogens on its own, but it does with a
halogen carrier such as, FeCl3, FeBr3, AlCl3 and AlBr3. Iron metal can be
used as it reacts with any halogen present to form the required Iron(III)
Halide.
- This is an Electrophilic substitution reaction in which one of the hydrogen
atoms is replaced by a halogen atom.
- Benzene reacts with bromine in the same way that it reacts with chlorine.
This time the halogen carrier catalyst needed is AlBr3, FeBr3 or Fe. The
organic product is Bromobenzene, a compound used in the production of
pharmaceuticals.
Nitration
- The electrophile is the nitryl cation or nitronium ion and has the formula
NO2+
- The equation: HNO3 + H2SO4 NO2+ + HSO4- + H2O
- The NO2+ electrophile then reacts with benzene. The mechanism shown
in book.
- Finally the H+ reacts with the HSO4- from the first step to reform H2SO4
so the sulphuric acid is acting as a catalyst.
- H+ + HSO40 H2SO4
Halogenation
- Benzene is too stable to react with Bromine on its own, Br2, however it
does react in the presence of a carrier such as FeBr3. The halogen carrier
generates the Bromonium ion, Br+, which is a more powerful electrophile
than Br2.
- Equation: Br2 + FeBr3 Br+ + FeBr4-
- Finally the H+ reacts with FeBr4- from the first step to form the other
product of the overall reaction, HBr, and to reform FeBr3. So the Iron (III)
bromide is acting as a catalyst.
-
1.17 Amines
- A primary amine is one with only one carbon chain attached to the
nitrogen.
- Four carbons in the alkyl chain, given the name butyl.
- A secondary amine is one with two carbon chains attached to the
nitrogen.
- In Fig 5. Contains three carbons in longest chain, so it is –Propyl.
- Suffix added is –amine.
- Shorter alkyl chain has one carbon attached to Nitrogen so it is N-methyl
- So the compound is N-methylpropylamine.
Basicity in amines
Diazotisation
Coupling