REACTIONS OF BENZENE

Benzene is odourless and immiscible with water. Its molecular formula is CH. Its a colourless liquid that boils at 80C and freezes at 6C. It is non-polar. ll the bond an les in a molecule of benzene is A C-C single bond in cyclohexane ring has a bond length of 0.154nm. A C-C double bond in cyclohexane ring has a bond length of 0.133nm. A C-C bond in benzene ring has a bond length of 0.139nm.

Arrangement of electrons in benzene

Each carbon atom forms a single sigma bond with each of the two carbon atoms joined to it. This forms the skeleton of the ring giving it a planar hexagonal ring. Each carbon atom has one p orbital containing a single electron, and it is the lobes of these p orbitals that fuse to form a single ring of charge above and another ring below the sigmabonded skeleton. With these extended pi-bonds the electrons are free to move around the entire ring these electrons are described as being delocalised. It is the delocalisation that causes all the C-C bonds in benzene to be identical, which also makes the benzene molecule to stable.

Addition reactions of benzene with:

Hydrogen Benzene is mixed with hydrogen in the presence of Raney Nickel Catalyst (finely divided with a very large surface area and very high catalytic activity) at a temperature of 150C. It undergoes addition reaction to form cyclohexane. This formation is important in the production of nylon. Halogens Benzene undergoes addition reaction with Bromine rapidly in presence of UV light to form 1,2,3,4,5,6hexabromocyclohexane. This is a free-radical reaction due to the rapid reaction and requirement of light to overcome activation energy. The corresponding 1,2,3,4,5,6-hexaclorocyclohexane is an insecticide.

Substitution reactions of benzene with:

Fuming Sulfuric Acid Fuming sulfuric acid reacts with benzene to produce benzenesulfonic acid. This reaction is called sulphonation and it takes place in room temperature. It involves hazardous chemicals to its rarely performed in school laboratories.

Fumin sulfuric acid is conc. Sulfuric acid that contains additional sulfur trioxide, with which benzene reacts more readily because sulfur trioxide is an effective electrophile. Halogens In dark, benzene doesnt react with bromine unless there is a catalyst of iron(III) bromide or iron filin s present this catalyst is called a halogen carrier. The three are refluxed together and bromobenzene is formed.

Iron can be used instead of iron(III) bromide because iron reacts with some of the bromine present to form iron(III) bromide: 2Fe(s) + 3Br(l) FeBr(s) The iron(III) bromide polarises the bromine molecule, forming a complex: BrBr + FeBr BrBr.FeBr This acts as an electrophile, forming first a weak pi complex and then the more stable sigma complex: The proton is then lost and this reacts to regenerate the iron(III) bromide complex.

Nitration of benzene Benzene does not react with conc. Nitric acid. However it does react with a mixture of conc. Nitric acid and conc. sulfuric acid this is called nitrating mixture. The product is nitrobenzene, providing that the temperature is kept below 55C

The round-bottomed reaction flask with the nitrating mixture is held in a beaker of cold water by a clamp. The reaction flask has a tap funnel containing benzene. The benzene is slowly added dropwise to the mixture in the flask. The acids react and give out heat, as does the addition of benzene to the nitrating mixture this is why the cold water and slow addition are needed. If the temperature rises above 55C, multiple substitution occurs and 1,3dinitrobenzene is formed resulting in a mixture of products:

Nitrobenzene is toxic, flammable, pale yellow, liquid aromatic compound with an odour of bitter almonds. pproximately 95% of nitrobenzene is used in the production of phenylamine (CHNH), which is used to make diazonium dyes.

Alkylation of benzene This reaction involves substituting an alkyl group into a benzene ring. It involves refluxing benzene with a halogenoalkane in the presence of a halogen carrier catalyst, such as aluminium chloride.

The aluminium chloride polarises the halogenoalkane molecule, promoting the formation of an electrophilic alkyl cation. This is attracted to the benzene ring, ,forming first a pi complex and then a sigma complex. This breaks down to form the alkylbenzene product.

Acylation of benzene When benzene is refluxed with an acyl chloride the product is a ketone. For example:

The product can easily be reduced to form a secondary alcohol.

Both alkylation and acylation are types of Friedel-Crafts reaction.

The effect of substituent groups on reactions of the benzene ring:

Some functional groups donate electron density to the ring, causing electrophilic substitutions to occur faster than they would in benzene itself. Some functional groups withdraw electron density from the ring, causing electrophilic substitutions to occur more slowly than they would in benzene itself.

REACTIONS OF PHENOL
These substitution reactions occur much more readily with phenol than with benzene. This is because the OH group on the benzene ring, the presence of which directs the incoming groups of the substitution reaction to particular positions around the ring.

Substitution reactions in phenol with:

Bromine water When bromine is added to a solution of phenol in water, multi-electrophilic substitutions takes place immediately without heating or introducing a halogen carrier. The bromine water is decolorised. The product is a white precipitate of 2,4,6-tribromophenol which smells of antiseptic:

The corresponding chlorine compound produced by reacting chlorine water and phenol is trichlorophenol, which is widely used as an antiseptic in solution. Dilute nitric acid When dilute nitric acid is added to a solution of phenol, a white precipitate of 2,4,6-trinitrophenol is formed. This is also a multi-electrophilic substitution reaction. Compared to benzene, phenol does not need a sulfuric acid to assist nitration and the nitric acid is dilute. This compound is sometimes also known as picric acid. Again, the effect of the OH group in activating the benzene ring can be seen and the substitutions happen in the 2, 4 and 6 positions of the ring:

The reason electrophilic substitution reactions occur easily with phenol is because the OH group of a phenol has an oxygen atom with two pairs of non-bonding electrons. One pair is drawn into the delocalised pi electron system. The benzene ring is now better at attracting electrophiles, so reactions occur more easily. The 2, 4 and 6 positions are particularly susceptible to attack.