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An arena is an aromatic hydrocarbon containing a benzene ring.

Benzene is the simplest arene and substituted arenes have alkyl groups attached to the benzene ring. Physical properties of benzene A colorless liquid (b.p. 80 C, m.p. 5.5 C) with a characteristic aromatic smell. It is immiscible with water, forming the upper of two layers, but is soluble in organic solvents. Burns with a sooty flame due to high carbon content. Stability of benzene Two structures are used to represent benzene: the Kekule structure developed between 1865-1872 the modern delocalised structure developed in the 1930s

Delocalised structure of benzene The delocalised structure of benzene shows a benzene molecule as a hybrid state between Kekules two structures with no separate single and double bonds. In this hybrid state: Each carbon atom contributes one electron from its p-orbital to form bonds. The -bonds are spread or delocalised over the whole ring. The delocalised structure of a benzene molecule is shown as a hexagon to represent the carbon skeleton and a circle to represent the six delocalised electrons. In the delocalised struture of benzene, each bond is identical with the electrons delocalised over the ring of the six carbon atoms. Experiments show that the C-C bond length is 0.139 nm, between the bond lengths for single and double carbon-carbon bonds. The delocalisation of -electrons also accounts for the fact that benzene undergoes electrophilic substitution reactions.

Chemical Properties The reactins of benzene are different from those of alkanes. Alkenes react with bromine in the dark at room temperature. Using the same conditions with benzene, there is no reaction. Similarly they resist oxidation by potassium manganate (VII) and potassium dichromate (VI). The stability of the delocalised system resists addition, which would disrupt this stability.

Electrophlic substituition The availability of -electrons in benzene serves as a source of electrons (i.e. a nucleophilic reagent), and its reactions are characteriszed by electrophilic substitution in the ring.

1. Nitration A nitrating mixture containing equal quantities of concentrated nitric (V) acid and sulphuric acid is added to the benzene. The mixture is then refluxed on a water bath maintained at 45-55 oC. Nitrobenzene, a pale yellow liquid is formed.

Considerable heat is evolved during the reaction. The ideal is to keep the temperature of 45-55 oC when the nitration is as rapid as possible. At higher temperatures, 1,3-dinitrobenzene and 1,3,5-trinitrobenzene are formed.

The role of concentrated sulphuric acid is to generate the nitronium ion, NO2+ as the electrophile. To do this, sulphuric acid protonates nitric acid. Loss of water from protonated nitric acid forms the NO2+ ion, the electrophile necessary for the nitration.

Mechanism for electrophilic substitution In this step, nitric acid accepts a proton from the stronger acid, sulphuric acid. The protonated nitric acid then loses water to form the NO2+ ion.

The NO2+ then reacts with benzene to form an unstable intermediate.

Nitrobenzene is formed when a base such as the HSO4- ion or H2O in the reaction mixture removes a proton from the intermediate

2. Halogenation The Lewis acid most commonly ued for chlorination and bromination reactions are FeCl3, FeBr3 and AlCl3. 3. Friedel-Crafts Reaction (A) Friedel-Crafts alkylation

Mechansim Using a halogenoalkane, RCl, in the preence of AlCl3 as a Lewis acid, a carbocation is generated. This carbocation acts as a powerful electrophile which reacts with benzene.

(B) Friedel-Crafts acylation The group is called an acyl group. Two common acyl groups are ethanoyl (acetyl) group and the benzoyl group. An acylium ion is the electrophile required for this reaction. The acylium ion is then able to react with benzene ring, introducing an acyl group onto the ring. The mixture of benzene (excess), acyl chloride (or acetic anhydride), an anhydrous AlCl3 catalyst is refluxed on a water bath at 80 oC.

4. Sulphonation

(B) Addition reactions of benzene Althought benzene is clearly an unsaturated compound, it undergoes few addition reactions as addition results in the destruction of the stable delocalised system. Howefver, in the presence of UV light or, with transition metal catalysts at high temperatures, it is possible to break the delocalisation in the bezene ring to give an addition product.

1. Hydrogenation of benzene Cyclohexane is formed if a mixture of benzene vapour and hydrogen is passed over a nickel catalyst at 180 oC.

2. Addition of chlorine to benzene If chlorine is bubbled through refluxing benzene in the presence of ultraviolet light or sunlight without a catalyst, an addition reaction occurs with chlorine to give 1,2,3,4,5,6-hexachlorocyclohexane. No intermediate compounds are formed.

Methylbenzene (Toulene) Physical properties A colorless liquid with a smell resembling that of benzene. It has a higher boiling point. Its freezing point (-93 oC) is considerably lower than that of benzene (5.5 oC), even though its relative molecular mass is higher. Benzene can be arranged closely as its planar structure has more symmetry. Hence the attractive forces between the benzene molecules are stronger. It is immiscible with water but mixes with ethanol and ethoxyethane in all proportions.

Uses of methylbenzene Methylbenzene is used as a solvent because it is less toxic than benzene. Source of the explosive trinitrotoluene (TNT), and as an additive in petrol.

Chemical properties (A) Reactions involving the methyl group or side chain Oxdiation Oxidising agent:- acidified potassium manganate (VII) / hot chromic acid/ acidified sodium dichromate (VI)/ dilute HNO3 Condition:- reflux

1. Note: Any alkyl radical attached to the nucleus is converted to a carboxyl group by the above oxidising agents, the remainedr of the hydrocarbon chain being oxidised to carbon dioxide and water.

2. Side chain oxidiation is not restrictedd to alkyl groups. Alkenyl groups are oxidised in the same way.

3. If a milder oxidising agent is used ( MnO2 or CrO2Cl2), toluene is only oxidised as far as benzaldehydes.

4. When methylbenzene is refluxed with alkaline potassium manganate (VII) the product is a carboxylate salt of benzoic acid. Acidification with dilute HCl produces benzoic acid.

Halogenation 1. When chlorine is bubbled through boiling methylbenzene in strong sunlight or ultraviolet light, substitution occurs in the side chain via free radical substitution.

2. Hydrolysis takes place when the above products are boiled with aqueous sodium hydroxide.

(B) Reactions involving the benzene ring Methylbenzene is more reactive than benzene towards the electrophilic reagents, which substitute in the benzene ring. This is because the saturated methyl group, which is electron-donating, activates ther ing with regard to electrophilic attack in the ortho and para positions, giving rise to the 1,2-isomer and 1,4-isomer respectively. A small amount of the 1,3-isomer (meta position) is also produced. Milder conditions are employed than in the reactions of benzene. 1. Halogenation

2. Other ring-subsitution reactions Nitration, sulphonation, and Friedel-Crafts Alkylation and Acylation of the ring .

3. Addition reactions-hydrogenation

Effects of substituent group on further substitution In electrophilic aromatic substitution of a monosubstituted benzene, three products are possible: the new group may become oriented ortho, meta, or para to existing group. Compound Methylbezene Main products obtained on further substitution Rate of nitration of the compound compared with the nitration of benzene

Phenylamine

Nitrobenzene

The electron density distribution in a benzene ring is greatly affected when a hydrogen atom is substituted by som eother atom or group, -G -G (electron donating group) Electron density in the ring increases Electron substitution will be easier than with benzene The ring is activated -G (electron withdrawing group) Electron density in the ring decreases Electron substitution will be more difficult than with benzene The ring is deactivated

The donation or withdrawal of electrons come about through an inductive or resonance effect.

Resonance electron donation and withdrawal If a substituent has a lone pair on the atom that is directly attached to the benzene ring, the lone pair can be delocalised into the ring; these substituents are said to donate electrons by resonance. Substituents such as NH2, -OH, -OR, and Cl donate electrons by resonance. These substituents also withdraw electrons inductively because the atom attached to the benzene ring is more electronegative than H. If a substituent is attached to the benzene ring by an atom that is doubly or triply bonded to a more electronegative atom, the electrons of the ring can be delocalised onto the substituent; these substituent are said to withdraw electrons by resonance. Substituents such as C=O, C=N and NO2 withdraw

electrons by resonance. These substituents also withdraw electrons inductively because the atom attached to the benzene ring has a full or partial positive charge and therefore is more electronegative than H.

Inductive electron donation and withdrawal If a substituent that is bonded to a benzene ring is less electron withdrawing than H, the electrons in the bond that attaches the hydrogen to the ring. Such a substituent donates electrons inductively compared with H. Donation of electrons through a bond is called inductive electron donation. Alkyl substituents (such as CH3) donate electrons inductively compared with H. If a substituent is more electron withdrawing than H, it will withdraw the electrons away from the benzene ring more strongly than will H. Withdrawal of electrons through a bond is called inductive electron withdrawal. NH3+ group is a substituent that withdraws electrons inductively because it is more electronegative than -H.

Saturated groups are predominantly ortho/para-directing; and unsaturated groups are predominantly meta-directing. o-p-directing groups Activating Deactivating -CH3 (-R) -F -OH -Cl -O-Br -NH2 -I -Ar (-C6H5) m-directing groups Deactivating -NO2 -SO3H -CHO -COOH -CN -N+H3

1. Give one simple chemical test to distinguish between cyclohexene and benzene. State clearly how each compound behaves in the test and write balanced equations for the reaction involved. 2. Concentrated sulphuric acid is used in the nitration of benzene to give nitrobenzene. Write a balanced equation for the nitration of benzene. Explain the role of sulphuric acid and give a brief description of the mechanism for the nitration. 3. State and explain what would happen in the following experiment: A few iron filings are added to benzene containing a little bromine. 4. Suggest a possible identity of compound D, explaining your reasoning and giving equations where appropriate: D contains 66.4% carbon, 5.5% of hydrogen and 28.1% of chlorine, by mass. When D is heated under reflux with aqueous sodium hydroxide, it is converted to a compound with the molecular formula C7H8O. 5. Methylbenzene can be used as an additive in unleaded petrol. Some chemical transformations of methylbenzene are given below.

(a) Suggest reagents and conditions for each of the reactions I, II and III. Describe as fully as you can the type of the reaction undergone in each case. (b) There are two other positonal isomers of A. Draw their structural formulae, and sugegst which one is more likely to be formed along with A in reaction III. (c) Give an outline of the mechanism of reaction II. 6. (a) When chlorine is pased through boiling toluene in the presence of light and the absence of a catalyst, substitution of chlorine into the methyl group occurs. (i) Draw the structural formula of one of the organic products in this reaction. (ii) By making appropriate equations, suggest a mechanism for this reaciton. (b) When chlorine reacts with methylbenzene in the presence of catalyst (iron fillings), substitution of chlorine into the aromatic nucleus occurs. (i) Draw full structural formulae for two organic products of this reaction. (ii) Suggest reasons for the difference between this reaction and that described in (a). 7. (a) An experiment was carried out by bubbling chlorine gas into methylbenzene in the presence of sunlight but in the absecne of a catalyst. (i) Draw the structural formulae and give the IUPAC names for two of the compounds formed in the reaction. (ii) Write the mechanism for the reaction. (b) With the aid of equations, explain why benzene tends to undergo substitution reactions with chlorine whereas cyclohexene undergoes addition reactions with chlorine. 8.