1.

(a)

2-aminobutane, CH3CH2CH(NH2)CH3, is a chiral molecule that can be optically active. It

can be made from CH3CH2CH(CONH2)CH3.
(i)

What is a chiral molecule?

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

(ii)

How is optical activity detected experimentally?

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

(b)

State the reagents and conditions necessary to convert CH3CH2CH(CONH2)CH3

to 2-aminobutane.
...............................................................................................................................
...............................................................................................................................
(3)

(c)

(i)

CH3CH2CH(CONH2)CH3, D, can be made from 2-bromobutane in four steps

shown below.

CH 3 CH 2 CHBrCH 3

Mg

Grignard A

i) CO 2
ii) HCl(aq)

B
PCL 5

CONH 2
CH 3 CH 2

CH 3

H
D

NT Exampro

Give the structural formulae of the three intermediate compounds A, B and C.

A

(3)

(ii)

Grignard reagents are often made in a solvent of dry ethoxyethane. Why must the
ethoxyethane be dry?
......................................................................................................................
(1)

(iii)

Give the reagents and conditions for the conversion of C to D.

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

(d)

Butanone can be made from 2-bromobutane by a synthetic route involving two steps, the
first using aqueous sodium hydroxide and the second potassium dichromate(VI) solution
acidified with dilute sulphuric acid.
(i)

Give the structural formula of the intermediate compound in this synthetic route.

(1)

NT Exampro

(ii)

Butanone reacts with 2,4-dinitrophenylhydrazine solution but not with Fehlings

solution. Why is this?
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)

(iii)

Butanone also reacts with iodine in sodium hydroxide solution. What structural
feature of butanone is shown by this reaction?

(1)

(iv)

Give the structural formulae of both the organic products from the reaction in (iii).

(2)
(Total 17 marks)

2.

(a)

Three isomers A, B and B have the molecular formula C4H8O.

All three compounds give an orange precipitate with 2,4-dinitrophenylhydrazine reagent.
B and C also give a silver mirror when warmed with ammoniacal silver nitrate solution.
Write the structural formulae of A, B and C .
Substance A

NT Exampro

Substance B

Substance C

(3)

(b)

Substance A reacts with the Grignard reagent, C2H5MgBr

(i)

Give the equation for the preparation of this Grignard reagent.

..
(1)

(ii)

State the conditions for this preparation.

..
..
(2)

(iii)

Write the structural formula of the product obtained when this Grignard reagent
reacts with substance A.

(1)

NT Exampro

(c)

C2H5MgBr reacts with carbon dioxide to form the acid C2H5COOH. This acid can be
converted to propanamide in a two step process.

step 1
C2H5COOH

step 2
C2H5COCl

C2H5CONH2

State the reagent required for each step.

Step 1 .
Step 2 .
(2)

(d)

C2H5MgBr also reacts with ethanal to form substance D, which exists as a pair of optical
isomers.
(i)

Draw the structural formulae of these two isomers and use them to explain why
these isomers exist.

(4)

(ii)

What is the difference in property between these isomers?

..
(1)

(e)

(i)

Write down the name and the structural formula of the organic compound formed
when substance D is heated under reflux with a solution of potassium
dichromate(VI) in dilute sulphuric acid.
Name ..
Structural formula.

(2)

(ii)

State the colour of the solution remaining after this reaction.

..
(1)
(Total 17 marks)

3.

(a)

NT Exampro

What is meant by a chiral compound?

5

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

(b)

Substitution reactions of halogenoalkanes can proceed via an SN1 or SN2 mechanism.

In the case of SN1, a chiral halogenoalkane does not give a chiral product.
(i)

Give the equation for the reaction between 2-bromobutane and aqueous hydroxide
ions, using structural formulae.

(ii)

Give the mechanism for this SN1 reaction.

(iii)

Explain why the product is not chiral.

..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(8)

(c)

In an experiment designed to find the mechanism of the reaction between a

halogenoalkane, RX, and hydroxide ions, the following data were obtained at
constant temperature.

(i)

NT Exampro

Initial concentration of
RX/mol dm3

Initial concentration of
OH /mol dm3

Initial rate
/mol dm 3 s1

0.01

0.04

8 10 6

0.01

0.02

4 10 6

0.005

0.04

4 10 6

Deduce the order with respect to RX and OH and hence write the rate equation for
the reaction.

(ii)

Calculate a value for the rate constant for the reaction.

(4)

(d)

How does the rate of nucleophilic substitution of halogenoalkanes, RX, change with the
halogen in the compound? Give reasons for your answer.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(3)
(Total 16 marks)

4.

Three compounds A, B and C have the molecular formula C4H8O. All three compounds give a
yellow precipitate with 2,4-dinitrophenylhydrazine reagent, B and C also give a silver mirror
with ammoniacal silver nitrate solution and a red precipitate with Fehlings solutions.
(a)

Suggest possible identities for the compounds A, B and C by completing the table below.

Structural formula

Name

(6)

NT Exampro

(b)

The reduction of A gives D, C4H10O.

(i)

D exists as a pair of optical isomers. Draw a structural formula for D and use it to
explain why these isomers exist.

..........................................................................................................................
..........................................................................................................................
(ii)

What is the difference in property between the isomers?

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

(iii)

What class of compound is D?

..........................................................................................................................
(6)

(c)

What class of compound is produced when B and C are reduced?

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

(d)

Write down the name of the organic compound formed when substance B is heated with
acidified sodium dichromate(VI), and state the colour of the remaining solution.
Name:

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

Colour:

..................................................................................................................
(2)
(Total 15 marks)

5.

(a)

State the reagent(s) used for the conversion of ethanol to

(i)

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

(ii)

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

NT Exampro

(b)

Suggest a series of reactions by which ethanol can be converted to 2-hydroxypropanoic

acid, CH3CH(OH)COOH. For each reaction specify the reagents and conditions
necessary.

(6)

(c)

Explain whether a solution of 2-hydroxypropanoic acid, made in this way, would have
any effect on a beam of plane polarised monochromatic light.
...................................................................................................................................
...................................................................................................................................
(2)

(d)

2-hydroxypropanoic acid reacts with lithium tetrahydridoaluminate (III)(lithium

aluminium hydride).
State the conditions necessary for this reaction and give the structural formula of the
organic product.
Conditions ................................................................................................................
...................................................................................................................................
Structural formula

(2)
(Total 12 marks)

NT Exampro

6.

(a)

Outline the reaction of propanone with the following reagents. Give the equation for the
reaction, the conditions, and the name of the organic product.
(i)

Hydrogen cyanide
Equation:

Conditions:

Name of product:

(3)

(ii)

Sodium tetrahydridoborate(III) (sodium borohydride)

Equation (you may represent NaBH4 as [H]):

Conditions:

Name of product: ..

(3)

(b)

(i)

Give the mechanism for the reaction in (a)(i).

(3)

(ii)

What type of mechanism is this?

(1)

(iii)

What feature of the carbonyl group makes this type of mechanism possible?
Explain how this feature arises.

(2)

NT Exampro

10

(iv)

Explain briefly, by reference to its structure, why ethene would not react with HCN
in a similar way.

(1)
(Total 13 marks)

7.

(a)

State the reagents and the conditions required for:

(i)

the elimination of HBr from 2-bromopropane;

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

(ii)

the reduction of butanoic acid to butan-1ol;

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

(iii)

the conversion of animal fat into soap.

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

(b)

Give the functional group identified by a positive test with each of the following reagents.
2,4 dinitrophenylhydrazine reagent: ..........................................................................
Ammoniacal silver nitrate: .........................................................................................
Phosphorus pentachloride: .........................................................................................
Bromine water: ...........................................................................................................
(4)

(c)

Three compounds P,Q and R all have the same molecular formula C4H8O.
When 2,4-dinitrophenylhydrazine reagent was added to each, P gave a precipitate.
When ammoniacal silver nitrate was warmed with each, P gave a silver mirror.
When phosphorus pentachloride, PCl5, was added to dry samples of each, Q and R gave
off steamy fumes.
When bromine water was shaken with each, Q and R turned it colourless.
(i)
Draw two possible structural formulae for P.

NT Exampro

11

(2)

(ii)

Q is chiral and can be oxidised to a ketone. Draw the structures to show the two
optical isomers of Q.

(2)

(iii)

R can be oxidised to an acid S which has geometric isomers. Draw the formula of
the two geometric isomers of the acid S.

(2)
(Total 17 marks)

8.

Citral is a colourless natural product, which gives lemons their characteristic flavour and smell.
Its structural formula is:

CH 3
CH 3
(a)

(i)

CH CH 2

CH 3
CH 2

CH CHO

How would you show that citral has a carbonyl group, C==O?
Reagent ......
Observation ....
(2)

(ii)

How would you show that citral is an aldehyde?

Reagent ......
Observation ....
(2)

NT Exampro

12

(b)

Citral has geometric isomers. Draw them and explain why they are not easily
interconvertable.
Structures:

Reason
..
(3)

(c)

Bromine, dissolved in tetrachloromethane, was added slowly to a solution of citral.

(i)

Describe what you would observe when this was done.

....
....
(1)

(ii)

Draw the structural formula of the product of this reaction when excess bromine
is added.

(1)

(iii)

This product is chiral. Mark all the atoms which cause chirality with a on the
structural formula that you have given in (ii) above.
(2)

NT Exampro

13

(d)

Citral can be reduced to an alcohol

(i)

State a reagent and the conditions that could be used for this reaction.
Reagent ......
Conditions ..
(2)

(ii)

How would you test the product to show that it has an OH group?
Reagent ......
Observation ....
(2)

(e)

Citral can be oxidised to an acid C9H15COOH (Mr = 168) which ionises in water
C9H15COOH + H2O H3O+ + C9H15COO
4.62 g of this acid was dissolved in water to give a solution of volume 250 cm3.
This solution had a pH of 2.91.
(i)

Write the expression for Ka for this acid.

(1)

(ii)

Calculate the concentration of the acid in mol dm3.

(1)

(iii)

Calculate the value of Ka of the acid.

(3)
(Total 20 marks)

9.

Propenal, CH2=CHCHO, is one of the materials that gives crispy bacon its sharp odour. In the
following question assume that the carboncarbon double bond and the aldehyde group in
propenal behave independently.

NT Exampro

14

(a)

Give the structural formulae of the compounds formed when propenal reacts with:
(i)

hydrogen bromide;
(2)

(ii)

hydrogen cyanide;
(1)

(iii)

2,4-dinitrophenylhydrazine.
(2)

(b)

(i)

Give the mechanism for the reaction between hydrogen cyanide and the aldehyde
group. You may represent the aldehyde group as

R
C

H
(3)

(ii)

The reaction in (i) occurs best in slightly acidic conditions. It is slower if the pH is
high or low. Suggest reasons why this is so.
High pH .

Low pH ..
.
(3)

(c)

Explain why lithium tetrahydridoaluminate(III) (lithium aluminium hydride), LiAlH4,

reacts only with the >C=O bond and not with the >C=C< bond, even though these bonds
have the same electronic structure.
..
..
..
(2)

(d)

Suggest reactions, giving equations and conditions, which would convert propenal into a
compound which would react with iodine in the presence of sodium hydroxide solution.
(4)
(Total 17 marks)

NT Exampro

15