Haloalkanes

a Write an equation for the preparation of

product A from 1-chlorobutane and name
I Name each of the following haloalkanes
product A. ( 1 mark)
H H H H H
I I I I I
c1-c-c-c-c-c-H
b The formation of product A is an example
of a hydrolysis reaction.
I HI HI HI HI
H
Name the type of mechanism for the
hydrolysis of haloalkanes. (1 mark)

I H3
I I
c State and explain the effect on the rate

H-C-C-C-C-H
I of hydrolysis of replacing 1-chlorobutane
with 1-bromobutane. (1 mark)

I
H
I
Br
I
H
I
H
d Methoxybutane can be made from
1-chlorobtitane and sodium methoxide.
The methoxide ion acts as a nucleophile.

I
I I I
H-C-C-C-C-CI
H3 Suggest a mechanism for this reaction.
(3 marks)

I
H
I
1-1
I
H
I
Cl
4 Haloalkane, H, has a relative molecular mass
of 127 and has the following composition by
mass:
H Ci-13 H H H 1-1
I I I I I I
1-1-c-c-c-c-c-c-H
C, 37.8 %; H, 6.3%; Cl, 55.9%.
a Deduce the empirical formula and
I CHI 3 ClI ClI 1-1I HI
H b
molecular formula of H. (3 marks)
Compound H reacts with an excess of
(4 marks) aqueous sodium hydroxide under reflux
to form compound J.
2 Nucleophilic substitution takes place when a
bromoalkane is hydrolysed by heating with What is the molecular formula of J.
an alkali in aqueous solution. (1 mark)

a Explain the term nucleophilic c Write an equation for the formation of J

substitution. (2 marks) from H. ( J mark)
b Write an equation for the reaction of 5 In the stratosphere, nitrogen monoxide, NO,
2-bromopropane with a hydroxide ion in is linked with ozone depletion.
aqueous solution. ( I mark) Complete the equations below that describe
c Outline the mechanism for this reaction. how NO contributes to ozone depletion.
(3 marks) Step I: NO + 0 3 - ........... + ...........
d State and explain what would happen
to the rate of the hydrolysis reaction
if 2-bromopropane was replaced with
Step 2: N0 2 + ...........
Overall: ........... + .......... . -
- NO + .......... .
20 2
(3 marks)
2-iodopropane. (1 mark)
OCR F322 June 2012 Q4(d)
3 Haloalkanes are useful synthetic reagents for
the preparation of many important chemicals. 6 A student carried out an investigation
Some reactions of 1-chlorobutane is shown to compare the rates of hydrolysis of
below: 1-iodopropane and 1-bromopropane.
The student heated hot aqueous sodium
CH3CH2CH2CH2CI CH3CH2CH2CH20H

l
hydroxide with each haloalkane and
product A
Cll,O"Na' found that 1-iodopropane was hydrolysed
faster. The equation for the reaction with
1-iodopropane is shown below.
CH3CH2CH2CH20CH3
methoxybutane CH 3 CH 2 CH 2 I + OH- - CH 3 CH 2 CH 2 0H + 1-
 a Outline the mechanism for this
( i) (i) lodoethane is reacted with ammonia.
hydrolysis of 1-iodopropane. Write an equation for this reaction.
Show curly arrows and relevant ( l mark)
dipoles. (3 marks) (ii) The first tep in the mechanism f the
(ii) State the name of this type of reaction between CH 3 CH 2 CH 2 Br and
mechanism. ( 1 mark) NH 3 is shown below.
b Explain why 1-iodopropane is hydrolysed H H
faster than 1-bromopropane. (1 mark) I + I
CH3CH 2 -C-Br -CH 3CH 2 -C-NH 3 + ....... ,
OCR F322 June 2009 Q6 I
H
I
H
7 Haloalkanes are polar molecules and react
with nucleophiles. Complete the mechanism. Include relevant
dipoles, lone pairs, curly arrows and the
a The displayed formula of chlorornethane missing product. (3 marks)
is hown below. Label the dipole on the
C-Cl bond. b A student investigates the rate of
hydrolysis of six haloalkanes. The student
mixes 5 cm 3 of ethanol with five drops of
H-C-CI haloalkane. This mixture is warmed to
50 °c in a water bath. The student adds
( / mark) 5 crn 3 of aqueous silver nitrate, also heated
b Chloromethane is hydrolysed by a to 50 °c, to the haloalkane. The time taken
solution of sodium hydroxide as sh wn in for a precipitate to form is recorded in the
the equation below. results table. The student repeats the whole

-
experiment at 60 °C instead of 50 °C.
CR�c1 + oH- _, CH 3 0H + c1-
(i) State the solvent in which the sodium
'
Time taken for a precipitate to
hydroxide is dissolved. (l mark) Haloalkane form Is
(ii) State and explain the role of the
hydroxide ion, OH-, in this reaction. CHlHzCHzCHzCI 243 121
(I mark)
CH 3 CHzCHzCH 2 Br 121 53
(iii) Show, with the aid of curly arrows,
the mechanism of this hydrolysis. CHlHzCHzCHz' 40 19
(3 marks) CHlHzCHBrCH 3 89 42
(iv) What would happen to the rate of (CH )zCHCH Br 110 55
3 2
hydrolysis if chloromethane were (CH
3 )3 CBr 44 21
replaced by iodomethane? Explain
your answer. ( l mark) Describe and explain the factors that affect
8 This question is about halogenated the rate of hydrolysis of haloalkanes. Include
hydrocarbons. ideas about
a Haloalkanes undergo nucleophilic • the halogen in the haloalkanes
substitution reactions with ammonia • the groups attached to the carbon of
to form amines. Amines contain the the carbon-halogen bond (the type of
-NH 2 functional group. For example, haloalkane)
1-bromopropane reacts with ammonia to
form propylamine, CH 3 CH 2 CH 2 NH 2 . � the temperature of the hydrolysis.
In your answer you should link the evidence
CH 3 CH 2 CH 2 Br + 2NH 3 _, CH 3 CH 2 CH 2 NH 2
with your explanation. ( 7 marks)
+ NH 4 Br
OCR F322 Jan 1 I Q5