5.4.
1 – Organic Chemistry – Arenes
Arenes or aromatic compounds includes a ring of six carbon atoms with delocalised bonding.
Simplest arene is benzene, with molecular formula C6H6
Six C atoms in a hexagonal ring, one H atom bonded to each C atom
Each C atom is bonded to two other C atoms and one H atom by single covalent σ-bonds
High electron density, does not typically react by addition but by electrophilic substitution
One delocalized electron on each C atom in a p orbital
Six p electrons are delocalised in a π-system above and below the plane of carbon
atoms
Kekulé suggested the following structure, which is now evidenced to be false:
Evidence for the structure and stability of the benzene ring:
Thermochemical
Hydrogenation of cyclohexene, with 1 double
bond, has ΔH = -120 kJmol-1
Suggests reaction with benzene, with 3
double bonds, would give ΔH = -360
kJmol-1
However, measured value for hydrogenation of
benzene is actually ΔH = -208 kJmol-1
Shows that benzene is more stable than a structure with 3 C=C bonds due to the
delocalised π-system
X-ray diffraction
X-ray diffraction provides information about bond lengths
C-C in cyclohexane has length 0.154nm, C=C in cyclohexane has length
0.133nm
Expected benzene to be a distorted hexagon
However, benzene is a flat, regular hexagon
Unused 2p orbital on each of six
carbons can overlap sideways in both
directions, resulting in a delocalised
π-electron cloud
C–C bonds in benzene are all equal
length, between a single and a double bond
Infra-red spectroscopy
IR spectrum of a compound containing a double bond shows an absorption
between 1610 and 1680 cm-1
However, this absorption is absent in benzene compounds
Reactions of benzene
Arenes mainly undergo electrophilic substitution reactions, due to its high electron density.
However, benzene requires much more forcing conditions to make it react than ethene
Does not decolorize bromine water
Will not react with hydrogen at an appreciable rate under conditions at which
ethene reacts
Benzene will not react with oxidising agents like alkaline KMnO4
Lower density than ethene, benzene requires stronger electrophiles
Once electrophile has been added to the ring, the subsequent step is likely to be loss
of a proton
Stable delocalised π-system is regained
1. Combustion
Completely combusts in excess oxygen
Low carbon to hydrogen ratio, combusts with a very sooty/smoky flame
2. Bromine
React with halogens in the presence of a halogen carrier catalyst AlCl3
3. Nitration
React with concentrated nitric acid in the presence of concentrated sulphuric
acid (catalyst)
Carried out at room temperature
4. Sulphonation
React with concentrated fuming sulphuric acid to form sulphonic acids
Heat under reflux for several hours
5. Freidel-Crafts Alkylation
Reaction with a halogenoalkane in the presence of halogen carrier catalyst AlCl3
Important in organic synthesis, C-C bond forming reaction
Heat under reflux for several hours
6. Freidel-Crafts Acylation
Reaction with an acyl chloride in the presence of halogen carrier catalyst AlCl3
Important in organic synthesis, C-C bond forming reaction
7. Addition with Hydrogen
Addition of hydrogen in the presence of finely divided Nickel catalyst to form
cyclohexane
Requires more extreme conditions than alkene, 200°C and 10 atm
Phenols are arenes with an -OH group directly attached to the benzene ring.
White crystalline solid which is sparingly soluble in water at room temperature
The benzene ring helps to stabilise a negative charge on the phenoxide ion,
C6H5O–, and this makes phenol acidic
Substituted phenols are used as antiseptics and disinfectants
Reaction of phenols:
1. Bromine – electrophilic substitution
Activating hydroxyl group in phenol can donate electrons to the delocalised π-
system
Helps to stabilise the intermediates of electrophilic substitution
Increases electron density, makes phenol much more reactive than
benzene
React immediately with bromine water
Decolorizing it and forming a white precipitate of 2,4,6-tribromophenol
2. Nitration
Nitrated with dilute nitric acid at room temperature
5.4.2 – Organic Chemistry – Amines, amides, amino acids and proteins
Amines are organic derivates of ammonia containing the functional group NH2
Primary amines have one alkyl group attached to the nitrogen eg. RNH2, secondary has
two eg. R2NH, tertiary has three, R3N
Properties of amines:
Characteristic fishy smell
Small amines can form hydrogen bonds with water and can dissolve readily in water
When dissolved in water, like ammonia, they form an alkaline solution.
The bigger the amine, the greater the London forces between the amines, so
less soluble
Preparation of amines:
Aliphatic amines are produced by heating a halogenoalkane
In a sealed tube with excess ethanolic ammonia
Aromatic amines are produced by the reduction of a nitrobenzene
Add concentrated hydrochloric acid to a mixture of nitrobenzene and tin
Heat the mixture under reflux
Reactions of primary amines:
1. Acids
Primary aliphatic amines act as Bronsted-Lowry Bases, and react with acids to
form salts
Lone pair of electrons on the nitrogen is readily available for forming a
dative covalent bond with a H+ and so accepting a proton
Amines are bases than ammonia
Alkyl groups are electron-releasing and push electrons towards the
nitrogen atom
Secondary amines are stronger bases than primary amines
More alkyl groups that are substituted onto the N atom in place of H
atoms
2. Halogenoalkanes
Lone pair on the nitrogen will attack areas of positive charge
Amines are nucleophiles are and will attack the δ+ carbon in
halogenoalkanes
Primary amines react with halogenoalkanes to form secondary amines, then
tertiary amines
3. Acid chlorides
React with acid chlorides to form acid amides
4. Complex ions
Lone pair of electrons on the nitrogen enable amines to act as ligands
o Forms dative covalent bonds into transition metal ions to form coloured
complex ions
eg. reaction with hydrated copper(II) ion
5. Formation of azo dyes
Nitrobenzene is heated under reflux with tin in concentrated HCl as a reducing
agent
