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.
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:
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.
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.