Arenes - reactions and chemical tests

Electrophilic substitution Benzene A planar molecule with the carbon atoms arranged in a hexagonal ring Sigma bonds (single covalent bonds) are formed in between sp2 orbitals of each carbon atom with two other carbon atoms and a hydrogen atom. The p orbital of each carbon atom makes side-on overlap with the p orbitals of the two adjacent carbon atoms on either side. Thus 6 pi electrons are free to move throughout the pi orbitals and are said to be delocalized in the hexagonal ring. This delocalization of electrons is known as aromaticity, and gives benzene great stability.

Nitration of benzene General equation

Products Reagent Conditions

Reaction type

Mechanism

Nitrobenzene and water Concentrated HNO3 and concentrated H2SO4 (catalyst) Reflux at 50 - 60 (prevents further substitution at the benzene ring) Electrophilic substitution 1. Formation of electrophile (NO2+, nitronium ion): in the presence of concentrated H2SO4, which is a stronger acid, concentrated HNO3 acts as a base and becomes protonated, eventually forming NO2+. 2. Attack of electrophile, NO2+, on the benzene ring to form a carbocation intermediate. The delocalized electron cloud is disrupted as two electrons are used to form a new bond with the NO2+ ion. 3. Loss of proton to regain aromaticity and regeneration of the catalyst, H2SO4. (Conc. H2SO4 is important as concentrated nitric acid contains only very small amounts of NO2+, so will not have any effect on benzene in the absence of conc. Sulfuric acid)

Equations

Arenes - reactions and chemical tests

Halogenation of benzene General equation

Products Reagent Conditions

Reaction type

Mechanism

Halogenoarene (aryl halide) and HX X2 in AlX3 or Fe or FeX3 as catalyst, for the corresponding X = Cl or Br. Also known as Lewis acid or Friedel-Craft catalysts Room temperature Electrophilic substitution 1. Formation of electrophile (Cl+, chlorine cation) a. Chlorine molecule approaches the benzene ring b. The delocalized electrons in the ring repel electrons in the Cl-Cl bond, thus giving the chlorine molecule small dipole charges at its two ends. c. The + end of the chlorine molecule acts as the electrophile. This happens in the presence of aluminium chlorine, which increases the amount of polarization in the chlorine molecule 2. Attack of electrophile, Cl+, on the benzene ring to form a carbocation intermediate. The delocalized electron cloud is disrupted. 3. Loss of proton from the carbocation intermediate to form a stable monosubstituted chlorobenzene (delocalized pi electron system resumes). Catalyst AlCl3 is regenerated.

Equations

Halogenation of methylbenzene General equation

Products Reagent Conditions

Reaction type

2-halogenomethylbenzene, 4-halogenomethylbenzene, HX X2 in AlX3 or Fe or FeX3 as catalyst, for the corresponding X = Cl or Br. Room temperature in the absence of UV light (to prevent FRS) Electrophilic substitution

Arenes - reactions and chemical tests

Nitration of methylbenzene General equation

Products Reagent Conditions

Reaction type

Mechanism

2-nitromethylbenzene (ortho), 4-nitromethylbenzene (para), water Concentrated HNO3 and concentrated H2SO4 (catalyst) Reflux at 30 (methyl group activates the ring and makes the ring more susceptible to electrophilic substitution) Electrophilic substitution 1. Formation of electrophile (NO2+, nitronium ion): in the presence of concentrated H2SO4, which is a stronger acid, concentrated HNO3 acts as a base and becomes protonated, eventually forming NO2+. 2. Attack of electrophile, NO2+, on the benzene ring to form a carbocation intermediate. The delocalized electron cloud is disrupted as two electrons are used to form a new bond with the NO2+ ion. 3. Loss of proton to regain aromaticity and regeneration of the catalyst, H2SO4. With each nitro group introduced, the benzene ring is further deactivated. Subsequent nitration will require more vigorous conditions.

Equations

Further substitution

Arenes - reactions and chemical tests

Side chain reactions (reactions on the methyl substituent) Halogenation of benzene General equation

Products Reagent Conditions

Reaction type

Mechanism

X2 Ultraviolet light Free radical substitution 1. Initiation 2. Propagation 3. Termination

Equations

Arenes - reactions and chemical tests

Side-chain reactions (chemical tests) Side-chain oxidation General equation

Products Reagent Conditions

Reaction type

Description

Benzoic acid (in acidic medium)/benzoate ion (basic medium) KMnO4 in dilute H2SO4 or acidified KMnO4 Reflux/heat Oxidation Aqueous KMnO4 in acidic medium oxidises the methyl group in methybenzene to a carboxyl group (-COOH). Benzoic acid is formed (white insoluble solid) KMnO4 in basic medium benzoate ion is produced instead KMnO4 in acidic medium will not react with benzene in this way chemical test to distinguish between benzene and methylbenzene The entire alkyl side chain will be oxidized to the carboxyl (-COOH) group. The other carbon atoms will be lost as carbon dioxide. For oxidation, the carbon directly bonded to the benzene ring must have at least 1 H attached to it 1,1-dimethylethylbenzene is resistant to oxidation. Acidic aqueous K2Cr2O7 is not strong enough to oxidize alkyl side chains on benzene no reaction occurs with acidified aqueous K2Cr2O7 The purple acidic aqueous potassium manganate (VII) is decolourised. White precipitate of benzoic acid is formed. Effervescence is seen if ethybenzene and alkylbenzenes with longer alkyl side chains are oxidized.

Observations