EXTRA QUESTIONS FOR 2.

8 HALOALKANES

1. Methylbenzene is converted into (chloromethyl)benzene in a free radical substitution

reaction.

C6H5CH3 + Cl2 → C6H5CH2Cl + HCl

(i) Write an equation for the initiation step.

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

(ii) Write equations for the two propagation steps.

(2)

(iii) Give the formula of another possible organic product of the reaction.

...........................................................................................................................
(1)
(Total 4 marks)

2. The reaction of bromine with ethane is similar to that of chlorine with ethane. Three steps in the
bromination of ethane are shown below.

Step 1 Br2 2Br•

Step 2 Br• + CH3CH3 CH3CH2• + HBr

˙

Step 3 CH3CH2• + Br2 CH3CH2Br + Br•

(a) (i) Name this type of mechanism.

...........................................................................................................................

(ii) Suggest an essential condition for this reaction.

...........................................................................................................................

(iii) Steps 2 and 3 are of the same type. Name this type of step.

...........................................................................................................................

(iv) In this mechanism, another type of step occurs in which free-radicals combine.
Name this type of step. Write an equation to illustrate this step.

Type of step .......................................................................................................

Equation.............................................................................................................
(5)

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 (b) Further substitution in the reaction of bromine with ethane produces a mixture of liquid
organic compounds.

(i) Name a technique which could be used to separate the different compounds in this
mixture.

...........................................................................................................................

(ii) Write an equation for the reaction between bromine and ethane which produces
hexabromoethane, C2Br6, by this substitution reaction.

...........................................................................................................................
(2)
(Total 7 marks)

3. (a) Dichloromethane, CH2Cl2, is one of the products formed when chloromethane, CH3Cll,
reacts with chlorine.

(i) Name the type of mechanism involved in this reaction and write an equation for each
of the steps named below.

Name of type of mechanism ...............................................................................

Initiation step

............................................................................................................................

First propagation step

............................................................................................................................

Second propagation step

............................................................................................................................

(ii) Write an overall equation for the formation of dichloromethane from chloromethane.

...........................................................................................................................
(5)

(b) A compound contains 10.1% carbon and 89.9% chlorine by mass. Calculate the molecular
formula of this compound, given that its relative molecular mass (Mr) is 237.0

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................

.....................................................................................................................................
(3)

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 (c) Suggest the formulae of two bromine-containing organic compounds formed when
dibromomethane, CH2Br2, reacts with bromine.

Compound 1 ...............................................................................................................

Compound 2 ...............................................................................................................
(2)
(Total 10 marks)

4. (a) When 3-bromo-2,3-dimethylpentane, (CH3)2CHCBr(CH3)CH2CH3, reacts with aqueous

potassium hydroxide, an alcohol is formed.

(i) Name the type of reaction taking place and give the role of the reagent.

Type of reaction ...............................................................................................

Role of reagent .................................................................................................

(ii) Outline a mechanism for the reaction, showing clearly the structure of the alcohol
formed.

(5)

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 (b) When 3-bromo-2,3-dimethylpentane reacts with ethanolic potassium hydroxide, three
structurally isomeric alkenes are formed.

(i) Name the type of reaction taking place and give the role of the reagent.

Type of reaction ...............................................................................................

Role of reagent .................................................................................................

(ii) One of the reaction products is 2,3-dimethylpent-2-ene.

Give the structure of this alkene and outline a mechanism for its formation.

Structure of alkene

Mechanism

(iii) Give the structures and names of the other two alkenes which are also formed.

Structure of second alkene

Name .................................................................................................................

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 Structure of third alkene

Name .................................................................................................................
(10)
(Total 15 marks)

5. Bromoethane, CH3CH2Br, reacts with sodium hydroxide in an elimination reaction to form

ethene.

(i) Outline a mechanism for this elimination reaction.

(ii) Suggest one reason why this method for making ethene is not used in industry.

...........................................................................................................................

...........................................................................................................................
(4)
(Total 4 marks)

6. Consider the following scheme of reactions.

Reaction 1 Reaction 2
H 2 C=CH 2 CH 3 CH 2 Br CH 3 CH2 CN
ethene HBr bromoethane P

Reaction 3 Reaction 5

C 2 H 4O CH 3 CH 2 NH 2
epoxyethane Q

Reaction 4

HOCH 2 CH 2 OH
ethane-1,2-diol

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 In Reactions 2 and 5, bromoethane undergoes nucleophilic substitution.

(i) Identify a reagent for Reaction 2. Name the organic product, P.

Reagent for Reaction 2 .....................................................................................

Name of product P .........................................................................................

(ii) Identify a reagent for Reaction 5. Name the organic product, Q.

Reagent for Reaction 5 ..................................................................................

Name of product Q .........................................................................................

(iii) Outline a mechanism for Reaction 5.

(8)
(Total 8 marks)

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7. (a) Draw the structure of 2-bromo-3-methylbutane.

(1)

(b) (i) Draw the structure of methylbut-2-ene.

(ii) Methylbut-2-ene is formed when 2-bromo-3-methylbutane is treated with ethanolic

potassium hydroxide. Name and outline the mechanism for this reaction.

Name of mechanism .........................................................................................

Mechanism

(5)

(c) Name the isomer of methylbut-2-ene which is also formed when 2-bromo-3-methylbutane
is treated with ethanolic potassium hydroxide.

.....................................................................................................................................
(1)
(Total 7 marks)

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8. When 2-chloropropane reacts with sodium hydroxide, two different reactions occur.
Each reaction produces a different organic product.

Reaction 1 CH 3 C CH 3 + NaOH CH3 CH CH3 + NaCl

Cl OH
Reaction 2 CH 3 C CH 3 + NaOH CH3 CH CH2 + NaCl + H2 O

Cl

(i) Outline a mechanism for Reaction 1 and state the role of the hydroxide ion in this
reaction.

Mechanism

Role of the hydroxide ion .................................................................................

(ii) Outline a mechanism for Reaction 2 and state the role of the hydroxide ion in this
reaction.

Mechanism

Role of the hydroxide ion .................................................................................

(7)
(Total 7 marks)

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9. (a) A substitution reaction occurs when 2-bromopropane reacts with aqueous sodium
hydroxide.

(i) Draw the structure of the organic product of this reaction and give its name.

Structure

Name ...........................................................................................................

(ii) Name and outline the mechanism for this reaction.

Name of mechanism ......................................................................................

Mechanism

(5)

(b) Under different conditions, 2-bromopropane reacts with sodium hydroxide to produce
propene.

(i) Name the mechanism for this reaction.

......................................................................................................................

(ii) State the role of sodium hydroxide in this reaction.

......................................................................................................................
(2)
(Total 7 marks)

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10. Consider the following reaction scheme.

Reaction 1
CH 3 CH = CH 2 CH 3 CHBrCH3 + CH 3 CH 2 CH 2 Br
propene 2-bromopropane 1-bromopropane
(a minor product)

Reaction 2 Reaction 3

CH3 CH(OH)CH 3
propan-2-ol

(a) Give a suitable reagent and state the essential conditions required for Reaction 3.

Reagent ...………………………………….…………………………………….…..

Conditions ..…………………..……………………………………………………..
(2)

(b) The reagent used for Reaction 3 can also be used to convert 2-bromopropane into propene.
State the different conditions needed for this reaction.

.....................………………………………………………………………………….
(1)
(Total 3 marks)

11. Compound X, (CH3)2CHCN, can be formed from a haloalkane, C3H7Br.

(i) Name compound X.

...........................................................................................................................

(ii) Give the reagent and conditions necessary to form X from C3H7Br.

Reagent..............................................................................................................

Conditions..........................................................................................................

(iii) Name and outline the mechanism for this reaction, showing clearly the structure of
C3H7Br.

Name of mechanism..........................................................................................

Mechanism

(7)
(Total 7 marks)

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12. (a) The equation below shows the reaction of 2-bromopropane with an excess of ammonia.

CH3CHBrCH3 + 2NH3 → CH3CH(NH2)CH3 + NH4Br

Name and outline the mechanism involved.

Name of mechanism ...............................................................................................

Mechanism

(5)

(b) When 2-bromopropane is heated with ethanolic potassium hydroxide, an elimination

reaction occurs. State the role of potassium hydroxide and outline a mechanism for this
reaction.

Role of potassium hydroxide ...................................................................................

Mechanism

(5)
(Total 10 marks)

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13. Classify the following reaction.

C3H7Br + KOH → C3H6 + KBr + H2O

...............................................................................................................................
(1)
(Total 1 mark)

14. (i) Give the structural formula and name of the organic product of the reaction between
CH3CH2CH2CH2Br and potassium cyanide.

Structural formula.............................................................................................

Name.................................................................................................................

(ii) Name and outline the mechanism involved in this reaction.

Name.................................................................................................................

Mechanism

(iii) Suggest why CH3CH2CH2CH2F reacts less rapidly than CH3CH2CH2CH2Br with
potassium cyanide.

...........................................................................................................................

...........................................................................................................................
(6)
(Total 6 marks)

15. (a) Name and outline a mechanism for the reaction of 2-bromo-2-methylpropane with
ethanolic potassium hydroxide to form the alkene 2-methylpropene, (CH3)2C=CH2

Name of mechanism ..................................................................................................

Mechanism

(4)

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 (b) When 2-bromo-2-methylpropane reacts with aqueous potassium hydroxide,
2-methylpropan-2-ol is formed as shown by the following equation.

CH3 CH 3

H3C C CH 3 + KOH H3C C CH 3 + KBr

Br OH

State the role of the hydroxide ions in this reaction.

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

(c) Write an equation for the reaction that occurs when CH3CH2CH2CH2Br reacts with an
excess of ammonia. Name the organic product of this reaction.

Equation ......................................................................................................................

Name of product ..........................................................................................................

(3)
(Total 8 marks)

16. Alkenes can be made in the laboratory from halogenoalkanes by heating them with a
suitable reagent. By a similar method, cyclohexene can be prepared from
bromocyclohexane.

(i) Suggest the name of a suitable reagent and state an essential condition, other than
heat, for this reaction, starting from bromocyclohexane.

Reagent .............................................................................................................

Condition ..........................................................................................................
(2)

(ii) Using graphical formulae, write an equation for this reaction.

(2)

(iii) Give the name of this type of reaction.

...........................................................................................................................
(1)
(Total 5 marks)

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17. (a) (i) Write an equation for the reaction between 1-bromopropane and potassium cyanide.

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

(ii) Give the name of the type of mechanism involved in the reaction in (b)(i).

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

(b) Give the formula of the attacking species in (b) and state what feature of its structure is
responsible for its role.

Formula ..........................................................................................................

Structural feature ............................................................................................

(2)
(Total 4 marks)

18. Consider the following reaction in which an alkene is formed from a haloalkane.

heat
CH 3 CHBrCH 2 CH 3 + KOH → CH 3 CH = CHCH 3 + KBr + H 2 O
ethanol solvent but −2 − ene

(a) Name the haloalkane used in this reaction.

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

(b) Name and outline a mechanism for this reaction.

Name of mechanism ....................................................................................................

Mechanism

(4)
(Total 5 marks)

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19. (a) The reaction of chloromethane with chlorine to form trichloromethane is a free radical
substitution involving several propagation steps.

(i) Write an overall equation for this reaction.

............................................................................................................................

(ii) What is meant by the term propagation step?

............................................................................................................................

............................................................................................................................

(iii) Write an equation for a propagation step in which chloromethane reacts.

............................................................................................................................

(iv) Write an equation for a propagation step in which trichloromethane is formed.

............................................................................................................................
(4)

(b) Write an equation and outline a mechanism for the reaction of chloromethane with an
excess of ammonia.

Equation .....................................................................................................................

Mechanism

(5)
(Total 9 marks)

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20. When a mixture of chlorine with an excess of methane is irradiated with ultraviolet light, a
reaction occurs with chloromethane as the main organic product.

Write an equation and a mechanism for the formation of chloromethane.

(5)
(Total 5marks)

21. Ethene can be converted into a variety of useful products as illustrated below.

CH 3 CH 2 OH
ethanol

Reaction 1
acid catalyst

H 2 C CH 2
ethene

Reaction 2 Reaction 3
Ag catalyst HBr

O
H 2C CH 2 CH 3 CH 2 Br
epoxyethane bromoethane

Reaction 4 Reaction 5

OH OH CH 3 CH 2 NH 2
ethylamine
H 2 C CH 2
compound X

(b) Give a reagent for reaction 5.

(1)
(Total 1 mark)

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22. Consider the following scheme of reactions for making ethane-1,2-diol from ethene by two
different routes.

Reaction 2
BrCH 2 CH 2 Br HOCH 2 CH 2 Br
X Y
Reaction 1 Reaction 3
Br 2 NaOH(aq)

H 2 C CH 2 HOCH 2 CH 2 OH
ethene ethane-1,2-diol

Reaction 4 H 2O Reaction 5
O
H 2C CH 2
Z

Name and outline a mechanism for Reaction 3. Explain why compound Y is susceptible
to attack by hydroxide ions.
(4)
(Total 4 marks)

23. Ethene is an important starting point for the manufacture of plastics and pharmaceutical
chemicals. Most of the ethene used by industry is produced by the thermal cracking of ethane
obtained from North Sea gas (Reaction 1). It is also possible to make ethene either from
chloroethane (Reaction 2) or from ethanol (Reaction 3).

CH 3 CH 2 Cl
chloroethane

Reaction 2

Reaction 1 Reaction 3
CH 3 CH 3 H 2 C CH 2 CH 3 CH 2 OH
ethane ethene ethanol

(a) Give essential conditions and reagents for Reaction 2.

(2)

(b) Name and outline a mechanism for Reaction 2. Suggest a reason why chloroethane is not
chosen by industry as a starting material to make ethene commercially.
(5)
(Total 7 marks)

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24. Reaction of 2-bromobutane with potassium hydroxide can produce two types of product
depending on the solvent used. In aqueous solution, the formation of an alcohol, E, is more likely
but in ethanolic solution the formation of alkenes is more likely.

(a) For each type of product, name the type of reaction occurring and state the role of the
potassium hydroxide.
(4)

(b) Name alcohol E and draw its structural formula. By reference to the structure of the
halogenoalkane, explain why the initial step in the mechanism of the reaction producing the
alcohol occurs.
(5)
(Total 9 marks)

25. The structural formulae of compounds A, B, C and D, which are the four structural isomers
of molecular formula C4H9Cl, are given below.

CH3CH2CH2CH2Cl CH3CH(Cl)CH2CH3 (CH3)2CHCH2Cl (CH3)2C(Cl)CH3

A B C D

(i) Give the name of compound D.

(1)

(ii) When refluxed with an alcoholic solution of KOH, compound B undergoes an

elimination reaction. Two structurally isomeric products are formed. Draw the
graphical formulae of these two structural isomers.
(2)

(iii) Draw the graphical formula for the product of the reaction between compound C and
NaOH(aq). Give an outline of the mechanism involved in this reaction.
(4)
(Total 7 marks)

26. In aqueous ethanolic alkali, 2-bromo-2-methylbutane undergoes either substitution or

elimination reactions to produce an alcohol or a mixture of two alkenes, respectively. Give
the structures and names of these three compounds. Account for the formation of the
various products by reference to the mechanisms of the reactions involved.
(14)
(Total 14 marks)

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