5.

3 ARENES: BENZENE
Syllabus specification Arenes: benzene

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a. use thermochemical, x-ray diffraction and infrared data as evidence for the structure and stability of the benzene ring. Students may represent the structure of benzene as

or as appropriate in equations and mechanisms b. describe the following reactions of benzene, limited to: i) combustion to form a smoky flame. treatment with: ii) bromine. iii) concentrated nitric and sulfuric acids. iv) fuming sulfuric acid. v) halogenoalkanes and acyl chlorides with aluminium chloride as catalyst (Friedel-Crafts reaction). vi) addition reactions with hydrogen. c. describe the mechanism of the electrophilic substitution reactions of benzene in halogenation, nitration and Friedel-Crafts reactions including the formation of the electrophile. d. carry out the reactions in 5.4.1b where appropriate (using methylbenzene or methoxybenzene). e. carry out the reaction of phenol with bromine water and dilute nitric acid and use these results to illustrate the activation of the benzene ring.

Introduction:
Arenes are hydrocarbons with a ring or rings of carbon atoms in which there are delocalised electrons. Benzene, the simplest arene with a molecular formula C6H6, is an important and useful chemical which is obtained by the catalytic reforming of fractions from crude oil. Arenes are sometimes called aromatic compounds.

Study of the structure of benzene is an another example that shows how scientific models develop in response to new evidence. This links to further investigations of the models that chemists use to describe the mechanisms of organic reactions.

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General properties of benzene
It is a Colourless liquid with a characteristic odour. Boils at 80oC and freezes at 6oC. Immiscible with water but soluble in organic solvent. Gives smoky luminous sooty flame on burning.

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Structure of benzene:
Benzene, C6H6, is a cyclic compound that has six carbon atoms in a hexagonal ring. Several structures for benzene have been proposed. Early theories suggested that there were alternative single and double bonds between the carbon atoms (fig 5.3.1), but this did not fit with later experimental evidence. It was shown that all the carbon-carbon bonds are the same length and that the molecule is planar.

Fig. 5.3.1 Simplified structure of benzene

Two modern theories are used to explain the structure. The Kekule version assumes that benzene is a resonance hybrid between the two structures as given below. This model can be used to explain many chemical properties and reaction of benzene.

Fig 5.3.2 The displayed formula of kekules benzene ring structure The other theory assumes that each sp2 hybridized carbon atom is joined by a - (sigma) bond to each of its two neighbours, and by a third - sigma bond to s-orbital of hydrogen atom forming a hexagonal planar ring. The fourth bonding electron is in p-orbital(called as non-hybrid porbital) in the right angle to the planar of - (sigma) bonds. This p-orbital overlap side way, and the six p-orbitals overlap above and below the plane of the ring of carbon atoms. This produces a delocalised -(pi)bonding system of electrons, as in:

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Fig. 5.3.3 The delocalisation of the electrons in the -bonds of the symmetrical six-membered ring structure of benzene

Evidences for structure and extra stability of benzene

(i) Thermochemical evidence: via enthalpy of hydrogenation. Benzene is more stable than cyclohexatriene, which is the theoretical compound with three single and three localised double carbon-carbon bonds. The amount by which it is stabilised can be calculated from the enthalpies of hydrogenation. For example, the enthalpy of hydrogenation of one mole cyclohexene is -120 kJ. H = -120 kJ mol1

H2(g) Cyclohexane

Cyclohexene

Therefore , H for the addition to three localised double bonds in cyclohexatriene would be 3 x (-120) = -360 kJ mol1. However for benzene:

+ 3H2(g) Benzene cyclohexane

H = -208kJ mol1

Thus,152 kJ less energy is given out because of benzenes unique structure. This is called the delocalisation stabilisation energy or resonance energy and can be shown in an enthalpy-level diagram. VIHS/DEPARTMENT OF CHEMISTRY Page 3

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Cyclohexatriene Enthalpy kJmol-1 H = -360 kJ mol-1 H = -152 kJ (resonance energy)

Benzene H = -208 kJ mol-1 Cyclohexane, C6H12

Fig.5.3.4 Enthalpy-level diagram for the hydrogenation of benzene and cyclohexatriene. Thermo-chemical evidence: via bond enthalpies The amount by which benzene is stabilised can also be calculated from average bond enthalpies. The enthalpy of formation of gaseous benzene is +83 kJ mol -1. The value for the theoretical molecule cyclohexatriene can be found using the Hesss law cycle below: 6C(s) + 3H2(g) Hf C6H6(g)

Step 1 Step 2 6C(g) + 3H2(g)

Step 3

6C(g) + 6H(g)

Step 1 equals 6 x enthalpy of atomisation of carbon(Hatm[C(s)]) = 6 x (+715) = +4290 kJ Step 2 equals 3 x HH bond enthalpy = 3 x (+436) = + 1308kJ Step 3 equals enthalpy change of bonds made, which is calculated as below Three CC = 3 x (-348) = -1044 kJ Three C=C = 3 X (-612) = -1836 kJ Six CH = 6 x (-412) Total = -2472 kJ = - 5362 kJ

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Hence the Hf of cyclohexatriene = Hstep 1 + Hstep 2 + Hstep 3 = +4290 + 1308 +(-5352) = +246 kJ mol-1.

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The actual enthalpy of formation of gaseous benzene is +83 kJ mol-1. The value calculated above is 163 kJ more and approximately equals the resonance energy of benzene. Hence, the structure with the delocalised electron system is energetically more stable.

X-ray diffraction evidence

X-ray diffraction shows the position of the centre of atoms. If the diffraction pattern of benzene is analysed, it clearly shows that all the bond lengths between the carbon atoms are the same. Which is not the same in the case of cyclohexene. Table 1. comparison of bond length in benzene and cyclohexene. Bond All the six carbon-carbon bonds in benzene Carbon-carbon single bond in cyclohexene Carbon-carbon double bond in cyclohexene 0.134 0.154 Bond length/nm 0.140

0.140 nm

Electrons are equally distributed over six carbon atoms due to delocalisation of the pi- bonding electron system. If benzene has cyclohexatriene structure, equal distribution of electrons cannot be seen on the carbon ring. Thus, benzene is thermodynamically more stable due to its delocalized pibonding system.

Fig.5.3.5 Electron density map of benzene.

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Infra red evidence:

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Comparison of the infrared spectrum of aromatic compounds with those of aliphatic compounds containing a C=C group showed slight differences. The C H stretching vibration in benzene is at 3036cm-1 and the C=C stretching is at 1479cm-1, whereas the equivalent vibrations in an aliphatic compound such as cyclohexene are at 3023 and 1438cm-1.

Fig. 5.3.6 IR spectra for (a) cyclohexzene and (b) benzene.

Naming benzene derivatives.

The derivatives of benzene are named either as substituted products of benzene or as compounds containing the phenyl group, C6H5. The names and structures of some derivatives of benzene are given below.

Systematic name Chlorobenzene Nitrobenzene Methylbenzene Phenol Phenylamine Phenylethanone Phenylmethanol

Substituent group Chloro, -Cl Nitro, -NO2 Methyl,-CH3 Hydroxyl, -OH Amine, -NH2 Ethanone,-COCH3 Methanol,-CH2OH

Structure C6H5-Cl C6H5-NO2 C6H5-CH3 C6H5-OH C6H5-NH2 C6H5-COCH3 C6H5-CH2OH

When more than one hydrogen atom is substituted, numbers are used to indicate the positions of substituent on the benzene ring. The ring is usually numbered clockwise and the numbers used are the lowest ones possible. In some cases, the ring is numbered anticlockwise to get the lowest possible numbers.

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are assumed to occupy the 1 position.

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In phenyl compounds, such as phenol and phenylamine, the OH and NH2, groups

Fig. 5.3.7 Naming substituted benzene compounds.

Reactions of benzene
(i) combustion: Benzene burns in a limited amount of air with a smoky flame. Combustion is incomplete and particles of carbon are formed. The complete combustion of benzene requires large volume of oxygen.

2C6H6(l) + 15O2(g) (ii) Addition:

12CO2(g) + 6H2O(l)

The double bond in benzene is not as susceptible to addition as is the double bond in alkenes. However, it does react with hydrogen in the presence of a hot nickel catalyst to form cyclohexane.

+ 3H2 Benzene Reagents: Hydrogen gas. Conditions: In the presence of Raney nickel(finely divided with a very large surface area and very high catalytic activity)catalyst at high temperature(about 150 oC). Reaction type: Electrophilic addition. cyclohexane

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Electrophilic substitution:
(iv) Halogenation Dry benzene reacts with chlorine gas in the presence of iron (or a catalyst of

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anhydrous iron(III) chloride). Steamy fumes of hydrogen chloride are given off and chlorobenzene(C6H5Cl) is formed. Cl + Cl2(g) chlorobenzene + HCl(g)

Benzene Reagents: Chlorine gas.

Conditions: Room temperature and pressure, in the presence of anhydrous FeCl 3. Reaction type: Electrophilic substitution. Mechanism: Heterolytic electrophilic substitution.

The mechanism for this reaction is as follows. Step 1: The catalyst, anhydrous iron(III) chloride , is made by the reaction of iron with chlorine Fe + 1 Cl2 FeCl3

This reacts with more chlorine, forming the electrophile Cl+ Cl+ + [FeCl4]

Cl2 + FeCl3

electrophile Step 2: The Cl+ attacks the -electrons in the benzene ring, forming an intermediate with a positive charge. Finally, the [FeCl4] ion removes an H+ ion from benzene, producing chlorobenzene(C6H5Cl) and reforming the catalyst(FeCl3)

H+ + [FeCl4]

HCl + FeCl3

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Note: The addition of Cl+ to benzene is similar to the first step of the addition of chlorine to ethene. The difference arises at the next step. The benzene intermediate loses an H+, thus regaining the stability of the delocalised system, whereas the intermediate with ethene adds Clion. A catalyst must be present for the addition of Cl+ to benzene, because the activation energy of the first step is higher than that for the addition to ethene.

Reaction with nitric acid: Nitration.

When benzene is warmed with a mixture of concentrated nitric and sulfuric acid, a nitro-group(NO2) replaces a hydrogen atom in the benzene ring. Nitrobenzene and water are produced.

Conc.H2SO4 + HNO3(conc.) Benzene 50oC

NO2 + H 2O

nitrobenzene

Reagents: A mixture of Conc.H2SO4 and Conc.HNO3(nitrating mixture) Conditions: Warm under reflux at 50oC. Reaction Type: Electrophilic substitution. Mechanism: Heterolytic electrophilic substitution.

The mechanism for this reaction is as follows. Step 1:The sulfuric acid reacts with the nitric acid to form the electrophile NO2+. The temperature must not go above 50 oC or some dinitrobenzene(C6H4(NO2)2) is formed. 2H2SO4 + Acid HNO3 base 2HSO4 + H3O+ + NO2+ electrophile

Step 2: The NO2+ attacks the -electrons in the benzene ring, forming an intermediate with a positive charge. Finally, the HSO4 ion removes an H+ ion from benzene, producing nitrobenzene(C6H5NO2) and reforming the catalyst(H2SO4).

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HSO4 + Role of H2SO4

H+

H2SO4

Acts as a catalyst, as it increases the rate of reaction and remains chemically unchanged as it is being regenerated at the end of the reaction. Acts as an acid(proton donor), as it donates protons in the reaction.

Role of HNO3 It generates nitronium ion,NO2+, which acts as an electrophile in the mechanism. It acts as a base by accepting protons.

Exercise
(01) Benzene prefers to undergo substitution reaction rather than addition reactions. Explain.

(02) In the nitration of benzene sulphuric acid acts as an acid whereas nitric acid acts as a base. Show by an equation how this is so.

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(03) Why Raney nickel is used in the manufacture of cyclohexane from benzene?

(04) Explain why smoky flame are seen during the combustion of benzene.

(05) Write an equation for the bromination of benzene. By using appropriate arrow draw the mechanism of this reaction.

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Reaction with fuming sulphuric acid: Sulfonation.
When benzene is warmed with fuming sulfuric acid, benzenesulfonic acid is

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produced. Fuming sulphuric acid is a solution of sulphur trioxide in sulphuric acid. The electrophile is the SO3 molecule. SO3H + SO3 Benzene Reagents: fuming sulphuric acid Conditions: Heat under reflux Reaction Type: Electrophilic substitution. Mechanism: Heterolytic electrophilic substitution. benzenesulfonic acid

The mechanism for this reaction is as follows.

Step 1

Step 2

This reaction is important in the manufacture of detergents, where a substituted benzene ring is sulfonated and the final product is neutralised.

Friedel-Crafts reaction: (i) Reaction with halogenoalaknes

In the presence of an anhydrous aluminium chloride catalyst, alkyl group(eg C 2H5) can be substituted into the ring.

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ethylbenzene and hydrogen chloride. C2H5 + C2H5 Cl benzene Reagents: Halogenoalkanes ethylbenzene + HCl

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For example, In the reaction between benzene and chloroethane, the products are

Conditions: Heat under reflux at 50oC, in the presence of anhydrous AlCl3 as a catalyst. Reaction Type: Electrophilic substitution. Mechanism: Heterolytic electrophilic substitution.

Note:The reaction mixture must be dry.

The mechanism for this reaction is as follows. Step 1: The electrophile, +CH2CH3, is produced by the reaction of the catalyst with the halogenoalkane:
+

CH3CH2Cl + Chloroethane

AlCl3

CH2CH3 + [AlCl4]

electrophile

Step 2: The positive carbon atom attacks the system in the benzene ring: Step 3: The intermediate loses a H+ ion so as to regain the stability of the benzene ring.

Finally, the catalyst is regenerated by the reaction: H+ + [AlCl4]

HCl

+ AlCl3.

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In this reaction, a catalyst is used to increase the positive nature of the electrophile and make it better at attacking benzene rings. AlCl3 acts as a Lewis Acid and helps break the CCl bond.

Friedel-Crafts reaction: (ii) Reaction with acyl(acid) chlorides.

In the presence of an anhydrous aluminium chloride catalyst, benzene reacts with acylchlorides to form ketones.

For example, In the reaction between benzene and ethanoyl chloride, the products are phenylethanone and hydrogen chloride.

COCH3 + CH3COCl Benzene Reagents: Acyl(acid) chlorides Conditions: Heat under reflux at 50oC, in the presence of anhydrous AlCl3 as a catalyst. Reaction Type: Electrophilic substitution. Mechanism: Heterolytic electrophilic substitution. phenylethanone + HCl

The mechanism for this reaction is as follows. Step 1: The electrophile, CH3C+O is produced by the reaction of the acylchloride with the catalyst: CH3C+O + [AlCl4] electrophile

CH3COCl

AlCl3

ethanoyl chloride

Step 2: The positive carbon atom attacks the -system in the benzene ring. Step 3: The intermediate loses a H+ ion so as to regain the stability of the benzene ring.

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Finally, the catalyst is regenerated by the reaction: H+ + [AlCl4]

HCl + AlCl3.

Phenol
Phenol(C6H5OH) contains an OH group on a benzene ring. A lone pair of electron on the oxygen atom becomes part of the delocalised -system and makes phenol much more susceptible to attack by electrophiles.

simple structure of phenol.

Fig. 5.3.8 Orbital structure of phenol.

Properties of phenol.
Phenol is less acidic than carboxylic acid but more acidic than alcohol(-COOH > phenol > -OH). Therefore it can easily loses a proton and form stable phenoxide ion. H+(aq)

C6H5OH(aq)

C6H5O(aq) Phenoxide ion

It is a solid at room temperature.

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It is more reactive than benzene. It can be used as antiseptic compounds.

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It is partially soluble in water due to the formation of hydrogen bond with water.

Reactions of phenol.
(i) Reaction with aqueous sodium hydroxide. Phenol reacts with sodium hydroxide to form a salt - sodium phenoxide. it is ionic and water soluble C6H5O Na+(aq) + H2O(l)

C6H5OH(aq) + NaOH(aq)

This reaction is an evidence for the acidic character of phenol. (ii) Reaction with sodium metal. Phenol reacts with sodium to form an ionic salt - sodium phenoxide and hydrogen. This reaction is similar to that with aliphatic alcohols such as ethanol 2C6H5O Na+(s)

2C6H5OH(s)

2Na(s)

H2(g)

(iii) Reaction with carbonates and hydrogen carbonates. Phenol does not react with carbonates and hydrogen carbonates as is is weakly acidic.

(iv) Electrophilic substitution:

The OH group in phenol is electron releasing therefore it increases the electron density of the delocalised system which makes substitution much easier compared to benzene as a p orbital on the oxygen overlaps with the p orbitals in benzene

Fig. 5.3.9 p-orbitals in the system.

The p orbital on the Oxygen overlaps with the p orbitals in the ring.

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takes place at the 2,4 and 6 positions.

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The electron density is greatest at the 2,4 and 6 positions which results in the substitution

2 6 6 6 6 4 6 Reaction with aqueous bromine. The electron rich ring in phenol is attacked by bromine water, in an electrophilic substitution reaction. The brown bromine water is decolorised and a white precipitate of 2,4,6tribromophenol and a solution of hydrogen bromide are formed. No catalyst is needed.

Phenol

2,4,6-tribromophenol (white precipitate)

Reagents : Conditions:

Aqueous bromine Room temperature and pressure.

Reaction type: Electrophilic substitution Observation: Orange colour decolourises/ formation of white ppt./ misty fumes.

Reaction with nitric acid:

The ring is sufficiently activated for nitration to take place with dilute nitric acid. At room temperature, the organic product is a mixture of 2-nitrophenol and 4-nitrophenol.

OH

OH NO2 + HNO3(aq) +

OH

H 2O

NO2 Phenol 2-nitrophenol 4-nitrophenol

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Reagents : Conditions: Dilute nitric acid Room temperature and pressure.

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Reaction type: Electrophilic substitution

If the mixture is heated 2,4 and 2,6 dinitrophenol are formed as well. If concentrated nitic acid is used, 2,4,6-trinitrophenol is the product.

Checklist
After studying this topic, you should be able to: Define electrophile. Estimate resonance energy of benzene from hydrogenation and bond enthalpy data. Write equations and state conditions for the reactions of benzene and phenol with bromine and nitric acid and benzene with sulphuric acid and the friedel- crafts reactions. Draw mechanisms for the halogenations, nitration and friedel- crafts reactions of benzene. Explain why the ring in methylbenzene is slightly activated and that in phenol very activated.

Practice questions
(01) Explain why phenol can be nitrated under much milder conditions than those required to nitrate benzene. ................................................................................................................................................... ................................................................................................................................................... ................................................................................................................................................... .................................................................................................................................................. (02) In the reaction shown below, the aromatic compound 1,4-dimethylbenzene reacts with 2-bromobutane. The reaction is catalysed by aluminium chloride, AlCl3, which dissolves in the reaction mixture.

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(a) (i) Name the type of reaction and the mechanism. ...................................................................................................................................................

(ii) Write the equation to show how the attacking species forms and give the mechanism for the reaction. Equation:

Mechanism:

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(03) Some reactions of benzene are shown below.

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(a) (i) Write the equation to show how the catalyst, AlCl3, reacts with reagent A to form the species which attacks the benzene ring.

(ii) Draw the structure of the intermediate ion formed when the species in (ii) attacks the benzene ring.

(b) The methylbenzene formed in reaction 1 generally reacts in a similar way to benzene but faster, as the ring is said to be activated. (i) Explain how the presence of a methyl group activates the benzene ring. ................................................................................................................................................... ...................................................................................................................................................

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................................................................................................................................................... ................................................................................................................................................... (ii) Use your answer to (i) to explain why methylbenzene reacts faster. ................................................................................................................................................... ................................................................................................................................................... ................................................................................................................................................... ................................................................................................................................................... (c) (i) Draw the structural formula of compound X, formed in reaction 2.

(ii) The organic product of reaction 2 is also formed when the same reactants, but with an aluminium catalyst, are heated using microwave radiation. Suggest two reasons why this technique may be considered greener. ................................................................................................................................................... ................................................................................................................................................... ................................................................................................................................................... ................................................................................................................................................... ................................................................................................................................................... (d) Name reagent B needed for reaction 3.

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(04) Explain, in terms of the bonding in the benzene ring, why the enthalpy of hydrogenation is less exothermic than would be expected from a molecule with three double bonds. ................................................................................................................................................... ................................................................................................................................................... ................................................................................................................................................... ................................................................................................................................................... ................................................................................................................................................... (05)(i) Explain why phenol, C6H5OH, and methoxybenzene, C6H5OCH3, are much more reactive than benzene with bromine. ................................................................................................................................................... ................................................................................................................................................... ................................................................................................................................................... ................................................................................................................................................... ................................................................................................................................................... .................................................................................................................................................. ................................................................................................................................................... ................................................................................................................................................... ................................................................................................................................................... (ii) Write the equation for the reaction between phenol and bromine water. State symbols are not required.

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