1.	Adrenalin is a hormone which raises blood pressure, increases the depth of breathing and delays fatigue in muscles, thus allowing people to show great strength under stress.
	Benzedrine is a pharmaceutical which stimulates the central nervous system in a similar manner to adrenalin.

(a)	(i)	On the structure for benzedrine mark with a (*) any asymmetric carbon atom that causes chirality.
(1)
 
(ii)	Suggest why adrenalin is more soluble in water than is benzedrine.
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(2)
 
(b)	Give the structural formulae of the organic products obtained when benzedrine reacts with:
(i)	an aqueous acid such as dilute hydrochloric acid;

(1)
 
(ii)	ethanoyl chloride in the absence of a catalyst;

(1)
 
(iii)	excess ethanoyl chloride in the presence of the catalyst anhydrous aluminium chloride.

(2)

(d)	It is possible to eliminate a molecule of water from adrenalin which for the purpose of this question may be represented as R–CH(OH)–CH2–NH–CH3.  Draw the structural formulae of the two stereoisomers produced.

(2)
 
(e)	The mass spectra of both benzedrine and adrenalin have a peak at a mass/charge ratio of 44.  Draw the structure of the species which give these peaks.
(i)	in benzedrine;

(1)
 
(ii)	in adrenalin.

(1)
(Total 11 marks)

2.	(a)	Define:
(i)	the standard enthalpy of formation of benzene, C6H6(l);
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(2)
 
(ii)	the standard enthalpy of combustion of benzene, C6H6(l).
......................................................................................................................
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(2)

(b)	Calculate the standard enthalpy of formation of benzene, C6H6(l), using the following enthalpy of combustion data:
Substance	DH/kJ mol–1	
C6H6(l)	–3273	
H2(g)	–286	
C(s)	–394	

(3)
 
(c)	If the standard enthalpy of formation is calculated from average bond enthalpy data assuming that benzene has three C==C and three C––C bonds, its value is found to be +215 kJ mol–1.
Explain, with reference to the structure and stability of benzene, why this value differs from that calculated in (b). Use an enthalpy level diagram to illustrate your answer.

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(4)
 
(d)	Benzene reacts with bromine when gently warmed in the presence of a catalyst of anhydrous iron(III) bromide.
(i)	The reaction is first order with respect to benzene and first order with respect to bromine.  Write the rate equation for the reaction.
......................................................................................................................
(1)
 
(ii)	The mechanism of this reaction involves an attack by Br+ followed by loss of H+.

	Deuterium, symbol D, is an isotope of hydrogen, and the C––D bond is slightly stronger than the C––H bond.  If step 2 were the rate-determining (slower) step, suggest how the rate of this reaction would alter if deuterated benzene, C6D6, were used instead of ordinary benzene, C6H6, and explain your answer.
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(2)
(Total 14 marks)

3.	(a)	Benzene, C6H6, reacts with ethanoyl chloride, CH3COCl, to give a compound of molecular formula C8H8O.
(i)	Identify another substance that must be present for this reaction to occur and state the function of this substance in this reaction.
………………...……………….………………….…………………………..
………………...……………….………………….…………………………..
(2)
 
(ii)	Give the mechanism for this reaction.

(4)
 
(b)	Phenol, C6H5OH, reacts differently from benzene with ethanoyl chloride. State the type of reaction that would occur between phenol and ethanoyl chloride and give the structure of the organic product.
	Type of reaction ..……………………………………………………………………
	Structure of the organic product

(2)
 
(c)	A benzene ring containing two hydroxy groups, C6H4(OH)2, can exist as a range of isomers.
(i)	Draw the structure of each isomer.

(2)

(ii)	A polymer can be formed by reacting one of these isomers with the di-acyl chloride, ClCOCH2COCl.
	Draw a diagram indicating clearly the structure of such a polymer.

(2)
 
(d)	The compound 4-hydroxyazobenzene

	can be obtained from phenylamine and phenol in two steps.  Identify the intermediate formed and give the reagents and conditions for each step.
…………..…………...……………….………………….…………………………..
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(4)
(Total 16 marks)

4.	This question is about the reactions of methoxybenzene, which are summarised in the following diagram.

(a)	Draw the fully displayed formula for methoxybenzene.

(1)
 
(b)	Three of the reactions in the diagram are electrophilic substitution reactions.
	Explain what is meant by the term electrophilic substitution.
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 (2)

(c)	Draw the structural formula for 2-nitromethoxybenzene formed when methoxybenzene reacts with nitric acid.

(1)
 
(d)	Give the molecular formulae of two of the products, A and B, formed when methoxybenzene reacts with bromine in an inert solvent.
A

B

(2)
 
(e)	(i)	Suggest the name for the organic product, C, formed when methoxybenzene reacts with concentrated sulphuric acid.
............................................................................................................................
(1)
(ii)	Suggest ONE use for the class of chemicals to which C belongs.
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(1)
 
(f)	(i)	Name reactant D and catalyst E needed to make methoxycyclohexane from methoxybenzene.
D ........................................................................................................................
E ........................................................................................................................
(2)

(ii)	This reaction is not a substitution reaction.
	Give TWO alternative names which do describe this type of reaction.
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(2)
 
(g)	Many arenes like methoxybenzene are made from benzene.
(i)	What is the natural resource from which benzene is produced?
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(1)
(ii)	Suggest why methoxybenzene rather than benzene is used in schools and colleges.
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(1)
(Total 14 marks)

5.	(a)	The enthalpy of hydrogenation of cyclohexene is –120 kJ mol–1.

(i)	Predict the value of DH for the reaction:

.....................................................................................................................................
(1)

(ii)	Suggest the value of DH for the hydrogenation of the hypothetical molecule
1,3,5-cyclohexatriene:

.....................................................................................................................................
(1)
 
(iii)	The enthalpy of hydrogenation of benzene is –208 kJ mol–1. Explain in terms of the structure and bonding in benzene why this value is different from your answer to (a)(ii).
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(3)
 
(b)	Benzene, C6H6, reacts with bromine to form bromobenzene, C6H5Br, and hydrogen bromide.
(i)	Give the formula of the catalyst that is needed for the reaction.
.....................................................................................................................................
(1)

(ii)	Give the mechanism for the reaction, making clear the role of the catalyst.

(4)
 
(iii)	State the type of mechanism that is commonly found with reactions of benzene and its derivatives.
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(1)
(Total 11 marks)

6.	This question is about the reactions of benzene and some related compounds.

(a)	(i)	Name the reagent and conditions for Reaction 1.
Reagent ..................................................................................................................
Conditions...............................................................................................................
(2)
(ii)	Give the formula of the attacking species in this reaction.
...............................................................................
(1)
 
(b)	(i)	Give the structural formula of the organic compound A formed in Reaction 2.

(1)

(ii)	State the type of reaction and its mechanism in Reaction 2.
Type .......................................................................................................................
Mechanism ............................................................................................................
(2)
 
(iii)	Phenol, C6H5OH, will react with bromine in a similar way to benzene, but no catalyst is needed. Explain why phenol will react readily with bromine without a catalyst.
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(2)
 
(c)	(i)	Give the name of product B.
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(1)
 
(ii)	Explain how aluminium chloride acts as a catalyst in Reaction 3. You may find it helpful to use an equation in your answer.
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(2)

(d)	(i)	What condition is needed for chlorine to react with benzene in Reaction 4?
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(1)
(ii)	Give the systematic name of the product of Reaction 4.
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(1)
(Total 13 marks)

7.	(a)	Give the structural formula of the organic product when phenol is reacted with:
(i)	sodium hydroxide solution

(1)
 
(ii)	aqueous bromine

(1)

(iii)	ethanoyl chloride.

(1)
 
(b)	An azo dye can be made from benzenediazonium chloride.
(i)	State the reagents and conditions needed to make benzenediazonium chloride from phenylamine.
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(3)

(ii)	Write an equation, using structural formulae, to show the reaction between benzenediazonium ions and phenol to give the azo dye.

(2)
 
(iii)	What condition is required for the reaction in (ii) above?
............................................................................................................................
(1)
(Total 9 marks)

8.	The reaction sequence below shows a method that could be used to convert benzene into benzoic acid.

(a)	(i)	Name the reagent and catalyst that could be used to convert benzene into A in Step 1.
Reagent ......................................... Catalyst ..........................................................
(2)
 
(ii)	Name the type of reaction in Step 1 and its mechanism.
	Type ............................................... Mechanism ...................................................
(2)
 
(iii)	Write an equation to show how the catalyst interacts with the reagent in Step 1 and explain how this helps the reaction to take place.
Equation

Explanation ............................................................................................................
...............................................................................................................................
...............................................................................................................................
(2)
 
(b)	(i)	B has several isomers. Draw the structural formula of ONE of these isomers, and give its systematic name.
Structural formula

	Name ......................................................................................................................
(2)

(ii)	Name the reagent and catalyst you would use to try to make your isomer from A.
Reagent .......................................... Catalyst ..........................................................
(2)
 
(c)	(i)	Name the type and mechanism of the reaction in Step 3.
Type ............................................... Mechanism ....................................................
(2)
(ii)	By considering halogenoalkane B, suggest whether the reaction in Step 3 is first or second order. Justify your answer. Draw formulae to show the mechanism that you suggest.
................................................................................................................................

(2)
 
(d)	What type of reaction is Step 4?
.......................................................................................................................................
(1)

(e)	Suggest TWO reactions in which you would observe the same results when carried out with either compound C or benzoic acid. Describe what you would see in each of the two reactions.
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(4)
(Total 19 marks)

9.	(a)	Equations for the hydrogenation of three compounds are given below, together with the corresponding enthalpy changes.

	Explain, in terms of the bonding in benzene, why the enthalpy change of hydrogenation of benzene is not –360 kJ mol–1.
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(3)

(b)	Benzene can be converted into phenylamine, C6H5NH2, in two stages. Give the reagents needed for each step and identify the intermediate compound formed.
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(4)
 
(c)	Benzene, C6H6, reacts with bromoethane, CH3CH2Br, in the presence of a catalyst, to form ethylbenzene, C6H5CH2CH3, and hydrogen bromide.
(i)	Give the formula of a catalyst for this reaction.
...........................................................................................................................
(1)

(ii)	Give the mechanism for the reaction between benzene and bromoethane, including the formation of the species that reacts with the benzene molecule.

(4)
 
(iii)	Name the type of mechanism involved in this reaction.
...........................................................................................................................
(1)
(Total 13 marks)

10.	This question is about the arene, naphthalene. The structure of naphthalene can be shown as

(a)	What is the molecular formula of naphthalene?
.....................................................................................................................................
(1)

(b)	The enthalpy change, ΔH, for the addition of hydrogen to cyclohexene to form cyclohexane is –120 kJ mol–1.

(i)	Calculate the enthalpy change of the hydrogenation reaction shown below.

ΔH = ...................... kJ mol–1
(1)
 
(ii)	Experimental work shows that ΔH for the hydrogenation of naphthalene is actually –333 kJ mol–1. What does this suggest about the stability and structure of naphthalene?
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(2)
 
(iii)	Would you expect naphthalene to decolorise bromine solution? Justify your answer.
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(1)

(c)	The Friedel-Crafts reaction enables an alkyl group to be attached to an arene ring.
(i)	Suggest the reagent and catalyst you would need to make  from naphthalene.
Reagent ..............................................................................
Catalyst ..............................................................................
(2)
 
(ii)	Name the type of reaction and its mechanism.
...........................................................................................................................
(2)
(Total 9 marks)

11.	Toluene is the non-systematic name of an arene widely used in industry. Its formula is C6H5CH3. Some of its reactions are summarised in the following diagram.

(a)	(i)	Give the systematic name of toluene.
...........................................................................................................................
(1)
 
(ii)	Draw a possible structural formula for compound A.

(1)

(b)	(i)	Name the TWO reagents needed for Reaction 2.
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(2)
 
(ii)	Give the formula of the attacking species in Reaction 2.
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(1)
 
(c)	(i)	Give the reaction type and mechanism in Reaction 3.
	Reaction Type
...........................................................................................................................
	Mechanism
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(2)
 
(ii)	Suggest why Reactions 1, 2 and 3 all take place under milder conditions than similar reactions involving benzene.
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(2)
 
(d)	What type of reaction does toluene undergo in Reaction 4?
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(1)

(e)	Name the TWO reagents needed for Reaction 5.
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(2)
(Total 12 marks)

12.	The reaction scheme below shows a synthesis of the antiseptic, Dettol, from benzene.

	Study this reaction scheme carefully before answering any of the questions below.
 
(a)	(i)	Give the structural formula of A.

(1)
 
(ii)	Name reagent W.
...........................................................................................................................
(1)
 
(iii)	State the type of reaction and the mechanism for the conversion of benzene into A.
...........................................................................................................................
(1)
 
(iv)	Give the formula of the species which attacks benzene to form A.
...........................................................................................................................
(1)
 
(b)	(i)	Suggest the structural formula of B. You may find it helpful to study the formula for Dettol, as well as your answer to (a)(i), when answering this question.

(1)
 
(ii)	Give the formulae for reagent X and catalyst Y.
Reagent X ........................................... Catalyst Y ...........................................
(2)
 
(iii)	What gaseous inorganic compound will also be produced during the formation of B?
...........................................................................................................................
(1)
 
(c)	(i)	Give the systematic name for Dettol.
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(1)

(ii)	Suggest why Dettol does not mix well with water.
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(1)
(Total 10 marks)

13.	An important industrial compound, S, has the formula

(a)	(i)	Name the reagents and give the conditions where necessary for the two steps needed to make
	
Step 1 Reagent ..................................................................................................
Conditions .................................................................................................
Step 2 Reagent ..................................................................................................
(3)
 
(ii)	Name the type of reaction in each step.
Step 1 ................................................................................................................
Step 2 ................................................................................................................
(2)

(b)	(i)	What is the specific name given to the reaction when an alkyl group is introduced into the benzene ring by electrophilic substitution?
...........................................................................................................................
(1)
(ii)	Give the molecular formula of the reagent and of the catalyst needed to make 
Reagent .............................................................................................................
Catalyst .............................................................................................................
(2)
(Total 8 marks)

14.	The drug ibuprofen can be synthesised from benzene by the route shown below.

(a)	Name the type and mechanism of the reaction in Step A, and suggest a suitable reagent and catalyst.
Type and mechanism ..................................................................................................
Name of the reagent for Step A ..................................................................................
Catalyst .......................................................................................................................
(3)

(b)	Step C is a reduction.
	Give ONE reason why lithium tetrahydridoaluminate, LiAlH4, is preferred to hydrogen as a reducing agent in this reaction.
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(2)
 
(c)	A sample of the final product was analysed by combustion. 1.00 g was burnt in oxygen. It produced 2.78 g carbon dioxide and 0.786 g water.
	State the molecular formula of ibuprofen and show that these results are consistent with it.

(4)
 
(d)	Ibuprofen can be analysed by instrumental methods. The infrared spectra of ibuprofen and two other drugs, aspirin and paracetamol, not necessarily in that order, are shown opposite.

(i)	Explain, referring to the structure of each molecule, why infrared spectroscopy is not a good technique to distinguish aspirin from ibuprofen.
...........................................................................................................................
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(1)

(ii)	Deduce which of X, Y or Z is the infrared spectrum of paracetamol, giving a piece of evidence from the spectrum you select.

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(1)
 
(iii)	Ibuprofen and aspirin can be distinguished using their mass spectra.
	A line at mass/charge ratio 57 occurs only in the mass spectrum of ibuprofen.
Give the formula of the ion which produces this line.
...........................................................................................................................
	Suggest the mass/charge ratio of one line which occurs in the mass spectrum of aspirin but not ibuprofen, and the formula of the species which produces it.
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(3)
(Total 14 marks)