Test 3/Organic Chemistry/A2

1. Benzenecarboxylic acid (benzoic acid) and phenylmethanol (benzyl alcohol) are compounds
which occur naturally and have a wide range of uses. For example, benzenecarboxylic acid is
used as a food preservative and phenylmethanol is used as a solvent.

A laboratory sequence for the preparation of these two compounds is shown below.

(a) In the first step of the synthesis, benzene reacts with hydrogen chloride and carbon
monoxide in the presence of aluminium chloride in an electrophilic substitution called the
Gattermann-Koch reaction. The hydrogen chloride and carbon monoxide together behave
as if they form the unstable species methanoyl chloride (HCOCl).
(i) Give the mechanism for step 1, including the formation of the electrophile.

3

(ii) Identify the reagents and essential conditions used in the remaining steps of the
sequence. You may assume that the correct reaction temperatures are being used.

Step 2…………………………………………………………………………………...

Step 3………………………………………………………………………………. 2

 Test 3/Organic Chemistry/A2

(b) Phenol reacts faster than phenylmethanol in electrophilic substitution reactions. Suggest
why this is so.

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

......................................................................................................................................... 2

(c) Tranexamic acid is an amino acid. It is a white crystalline solid which melts at 300 °C. It
is used to reduce bleeding during surgery and dental procedures and is especially useful
where patients suffer from deficiencies in blood-clotting factors. The structure of
tranexamic acid can be drawn as shown below.

As the name suggests, tranexamic acid is the trans form of a compound that forms
geometric (or cis-trans) isomers.
(i) Suggest how tranexamic acid can form geometric isomers although it does not have a
C=C double bond.

…………………………………………………………………………………..............

…………………………………………………………………………………....... 1

(ii) Complete the diagram to show the structure of the cis isomer.

1
 Test 3/Organic Chemistry/A2

(iii) Explain why tranexamic acid melts at 300 °C while the alkane, undecane
(C11H24) which has almost the same number of electrons, melts at −26 °C.

…………………………………………………………………………………..............

…………………………………………………………………………………....... 2

Total: 11

2. (a) It is suggested that the structure of tiglic acid is either that of A or B.

(i) The mass spectrum of tiglic acid shows two prominent peaks at mass/charge ratios 45
and 55. Write the formulae of the fragments giving rise to each of these peaks.

m/z = 45………………………………………………………………………………...

m/z = 55…………………………………………………………………………….. 2

(ii) Does this data from the mass spectrum alone enable you to decide which of A or B is
the structure of tiglic acid? Explain your answer.

…………………………………………………………………………………..............

…………………………………………………………………………………....... 2

(b) The position of a C=C double bond in a molecule can be determined by ozonolysis.
The compound is reacted with ozone and then dilute acid, two carbonyl compounds being
produced as shown below.

Ozonolysis of tiglic acid gives two carbonyl compounds, C and D.

 Test 3/Organic Chemistry/A2

Compound C gives a silver mirror with Tollens’ reagent and gives iodoform with iodine
in alkali.
Compound D does not give a silver mirror with Tollens’ reagent, but does give iodoform
with iodine in alkali.

(i) From the results of the experiments, give the structural formulae of C and D and state
which of the structures A or B could represent tiglic acid.

3
(c) The first steps in the preparation of an azo dye from benzene are shown below.

(i) Phenylamine is converted into the benzenediazonium cation using sodium nitrite and
hydrochloric acid at a temperature between 0 °C and 10 °C. Explain why the
temperature must not be lower or higher than these limits if a good yield is to be
obtained.

…………………………………………………………………………………..............

………………………………………………………………………………….........2
 Test 3/Organic Chemistry/A2

(ii) Suggest how you could convert a sample of the benzenediazonium cation into an azo
dye. Give the name of the other compound you would use and the skeletal formula of
the azo dye you would obtain.

3

(d) Imipramine has been prescribed as an antidepressant. The structure of imipramine is

shown below.

The medicine is usually supplied as a salt. The salt is formed when one mole of
imipramine reacts with one mole of hydrochloric acid.
(i) Suggest why the nitrogen atom labelled b is more likely to be protonated than the
nitrogen atom labelled a when the salt is formed.

…………………………………………………………………………………………..

…………………………………………………………………………………………..

……………………………………………………………………………………….2

Total: 14
 Test 3/Organic Chemistry/A2

3. Nutrasweet is the trade name of the simple dipeptide, aspartame, consisting of asp-phe. It is
used as a sweetener in fruit drinks and yoghurts. It is 200 times as sweet as cane sugar
(sucrose) and is useful for slimmers.

(a) (i) Draw the structural formula of aspartame.

[1]
(ii) Name the group which is present in the dipeptide but not in the amino acids.

……………………………………………………………………………………... 1

(b) What sort of R group interactions are likely with each of the amino acids

(i) asp………………………………………………………………………………………

(ii) phe………………………………………………………………………………….. [2]

(c) Suggest why aspartame cannot be used in baked foods, such as cakes. Illustrate any
chemical change by a simple reaction.

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

...........................................................................................................................................2
(d) write equations for the reaction of aspartic acid with NaOH.

……………………………………………………………………………………..…... 1

(e) write equations for the reaction of aspartic acid with CH3CH2Cl.

…………………………………………………………………………………..……... 1
[Total: 8]
 Test 3/Organic Chemistry/A2

4. PLA is a biodegrable polymer made from corn starch. The structure of part of a PLA chain is
shown below.

(a) On the structure of PLA above, circle the repeating unit. 1
(b) Draw the structural formula of the monomer A, that could be used to form PLA. Water
would also be produced in this reaction.

1
(c) In practice, monomer A cannot be used directly to form PLA because the water produced
in the process reacts with the polymer.
Instead, corn starch is processed to form compound B. A bond in B is then broken and
the molecules join together to form PLA.

(ii) On the structure of B above, indicate with an arrow a bond that would be broken in
this process.
1
(iii) Explain why the process for producing PLA from B is more successful than the
one starting with A.
………………………………………………………………………………………
………………………………………………………………………………………
 Test 3/Organic Chemistry/A2

…………………………………………………………………………………. 2

(d) Molecules of compound B are chiral. This means that PLA can exist in two different
forms. Two particular chiral forms of PLA can be blended together to produce a more
crystalline material than normal PLA.
(i) Give the meaning of the term crystallinity when it is used to discuss the properties of
polymer.
………………………….………………………………………………………………
……………………….…………………………………………..………………….1
(e) PLA has some similar uses to poly(ethene). In addition to its biodegradability, suggest
one reason why PLA is considered to be a ‘greener’ product than poly(ethene).

………………………………………………………………………………………….. 1
[Total: 7]