Organic Chemistry

(12)2, 4
Chlorogenic acid occurs naturally in coffee and an edible species of bamboo.
O H
O
OH
O H
O
OH
O
OH
OH

The chlorogenic acid molecule contains a saturated ring, an aromatic ring and an alkene
group.
a) [6]
i. Identify as fully as you can the other functional groups present in chlorogenic
acid.

ii. How many chiral carbon atoms are there in a molecule of chlorogenic acid?

b) When chlorogenic acid is reacted under suitable conditions with NaOH(aq), followed
by acidification, two crystalline solids may be obtained, one non-aromatic and one
aromatic.
Draw the displayed formula of each of these compounds. [2]

c) Draw the structural formula of the compound formed when the aromatic compound
R you have drawn in part (b) is added to an excess of Br
2
dissolved in an organic
solvent. [2]

d) When the aromatic compound R is reacted with an excess of NaHCO
3
(aq),
compound S is formed which has the molecular formula C
9
H
7
O
4
Na. [3]
i. Suggest the structural formula of S.

ii. Suggest why this product contains only one Na atom/ion although the
NaHCO
3
is in excess.

(12)2, 5
Lactic acid (2-hydroxypropanoic acid), CH
3
CH(OH)CO
2
H, is present in milk.
Lactic acid can also be produced in the laboratory from ethanol, CH
3
CHO, by the following
reactions.
Step 1 Step 2
CH
3
CHO CH
3
CH(OH)CN CH
3
CH(OH)CO
2
H

a) [5]
i. Name the reagent and conditions used and the type of reaction that occurs in
step 1.

ii. Describe the mechanism of this reaction. In your answer you should show all
charges and lone pairs and show the movement of electrons by curly arrows.
Lactic acid present in milk rotates the plane of polarised light.
Lactic acid produced in a laboratory by the reactions above does not rotate the plane of
polarised light.
b) [4]
i. What feature of the lactic acid present in milk causes the rotation of the plane
of polarised light?

ii. Suggest, in terms of the mechanism of step 1 in the above reaction scheme,
and the shape of the CH
3
CHO molecule, why synthetic lactic acid does not
rotate the plane of polarised light.
The effect of plane polarised light on tartaric acid (2,3-dihydroxybutanedioic acid),
HO
2
CCH(OH)CH(OH)CO
2
H was investigated by Loius Pasteur.
C
CO
2
H
OH H
C H OH
CO
2
H

Pasteur identified three different types of tartaric acid molecule.
Molecule A rotated plane polarised light to the right
Molecule B rotated plane polarised light to the left
Molecule C had no effect on plane polarised light
c) Suggest an explanation for these observations. [3]
(12)3, 4
d) Ionic charges are important in determining the 3-dimensional structure of the
haemoglobin molecule. The four protein chains of deoxyhaemoglobin are held in
position by 8 ionic salt links. Some of these interactions are between the C-terminal
end of one chain and the N-terminal end of another chain, whereas other interactions
are between aspartic acid residues on one chain and arginine residues on another
chain. [5]
i. Using the tetrapeptide whose structure is given below, and taking account of
the ionic forms that the amino acid residues exist in at pH7, draw the
structures of two of these tetrapeptide chains to illustrate both of the ionic
interactions mentioned above.

C CH
2
N H
2
O
NH CH C
O
(H
2
C)
3
NH
C NH
N H
2
NH CH C
O
C H
2
C
OH
NH
O
CH
2
C OH
O




ii. Describe two further ways, other than ionic linkages, by which the tertiary
structures of proteins can be stabilised.


Glycine Arginine Aspartic Glycine
acid
e) The antibiotic valinomycin acts by allowing the uncontrolled movement of ions
across cell membranes. Valinomcin is a cyclic compound containing six amino acid
and six hydroxyacid residues. [3]

i. Apart from the peptide group, what other fuctional group is present in the
valinomycin molecule?
When treated with a peptide enzyme, the peptide bonds in the ring of valinomycin are
hydrolysed. Only two products are formed.
ii. Draw the structural formulae of the two compounds produced.

(12)3, 5
Malic acid occurs in green apples and grapes. It is often added to beverages and
confectionery to confer a sour taste.
O
O H
OH
O
OH

a) Suggest the reagents and conditions you would use in a three-step synthesis of malic
acid from bromoethanal, identifying the intermediates G and H. [5]
Br
O
step 1 step 2 step 3
G H malic acid

b) Malic acid can be dehydrated to give a mixture of two isomeric alkenedioic acids with
the molecular formula C
4
H
4
O
4
. [6]

i. Draw the structures of the isomers, and state the type of isomerism they show.

ii. Suggest reagents and conditions for the dehydration reaction.

iii. The pK
a
values of the two acidic groups in one isomer, J, are 3.0 and 4.4,
whereas in the other isomer, K, they are 1.9 and 6.2.

Use the pK
a
values to suggest which isomer, J or K, produces the more stable
mono-anion on treatment with 1mol of NaOH? Explain your answer.

iv. Draw the displayed formula of the mono-anion produced in (iii), and use your
formula to suggest an explanation for why it is more stable than the mono-
anion of the other isomer.
Gently heating the anhydrous crystals of one of the isomers J or K produces a neutral
compound L, C
4
H
2
O
3
, which does not react with sodium metal or give a precipitate with
2,4-dinitrophenylhydrazine.
Compound L reacts with ammonia to give a compound M, C
4
H
5
NO
3
, which gives a salt on
reaction with NaOH but not with HCl. Compound M decolourises Br
2
(aq).
c) Suggest structures for compounds L and M, and identify which isomer, J or K,
produces L. Write equations for all reactions, and explain the observations. [6]

When malic acid is heated with acidified K
2
Cr
2
O
7
, compound N is formed. Heating N in an
inert solvent for several hours produces P, C
3
H
4
O
3
and a gas Q. Both N and P react with
2,4-dinitrophenylhydrazine. Compound P also gives a yellow precipitate with aqueous
alkaline iodine.
d) Suggest structures for N and P, and use the information given to suggest the identity
of gas Q. [3]

(11)2, 5
Compound K has the molecular formula C
4
H
8
O
2
.
K decolourises aqueous bromine.
When 0.10mol of K is reacted with an excess of sodium metal, 2.4dm
3
of hydrogen are
formed, measured at room temperature and pressure.
a) Use all of the above information to determine the identity and number of each of the
functional groups present in compound K.
For each functional group you identity, explain how you came to your decision. [5]

i. Reaction with aqueous bromine.

ii. Reaction with sodium metal.

b) Draw the displayed formulae of all the possible stereoisomers of K which have the
following features

They have molecular formula C
4
H
8
O
2
and give the reactions stated earlier.
No oxygen atom is attached to any carbon atom which is involved in a double
bond.
No carbon atom has more than one oxygen atom joined to it.
For each structure you draw, state the type of stereoisomerism it shows and give one
further piece of relevant information about it.
You are not required to label functional groups. [7]

(11)2, 6
Compound W has the molecular formula C
7
H
7
OCl. It is an aromatic compound which
contains two functional groups.
Data about the reactions of W are given in the table.
reaction reagent result
1 AgNO
3
(aq), warm
White solid formed which is soluble in an excess of
NH
3
(aq)
2 Br
2
(aq) in an excess White solid formed which has M
r
= 379.2
3
MnO
4
-
/OH
-
heat under
reflux then acidify
MnO
4
-
is decolourised;
One organic product formed with M
r
= 138
4 Na
Colourless gas evolved;
White solid formed which is soluble in H
2
O
5
NaOH(aq) at room
temperature
Colourless solution formed

In this question, when identifying functional groups, your answers should be unambiguous.
a) [5]
i. What is the white solid that is formed in reaction 1?

ii. Name the functional group that reaction 1 shows to be present in W.

iii. Based only on reaction 4, give the names of two different functional groups
that could be present in W.

iv. Which of the functional groups you have named in (iii) is confirmed by
reaction 5? Explain your answer.

b) Deduce the molecular formula of the organic product formed in reaction 3. [1]

c) [6]
i. Deduce the molecular formula of the white solid formed in reaction 2.

ii. What type of reaction takes place in reaction 2?

iii. Explain clearly how the formation of this compound shows that compound W
is an aromatic compound rather than an aliphatic compound.

iv. Name the functional group present in W that is confirmed by reaction 2.

v. Which other reaction confirms that W is aromatic? Explain your answer.

d) You now have enough information to determine the structural formula of W. [4]

i. Draw the fully displayed structure of W.

ii. Explain clearly why you have placed each of the two functional groups in
their particular positions.

(11)3, 2
c) Heating malonic acid (HO
2
CCH
2
CO
2
H) with P
4
O
10
at 140C produces an easily-
liquefied gas F which has a boiling point of 7C and has the molecular formula C
3
O
2
.
[4]
i. Suggest a structure for F and describe its shape.

ii. The addition of water to F re-forms malonic acid. Suggest the product of the
reaction of F with each of the following.
NH
3
(g)
HCl(g)

d) Suggest synthetic routes to the following dicarboxylic acids starting from
1,2-dibromoethane. [4]
BrCH
2
CH
2
Br
HO
2
C-CO
2
H
HO
2
C-CH
2
CH
2
-CO
2
H


(10)2, 5
Animal skin and bone contains the protein collagen.
Gelatin, which is used in the food and pharmaceutical industries, is another protein which
may be obtained from collagen.
The structure of a portion of the gelatin molecule is shown below. This portion contains a
number of amino acids and imino acids. The latter are related to amino acids but contain
the >NH group instead of the NH
2
group. In this question we will refer to both sorts of acid
as amino acid.
NH CH C H
3
CH
3
C
O
NH CH C
H
O
N
C
O
NH CH
C H
2
C
CH
2
CH
2
NH
C
NH
2
NH
O
NH CH
H
C
O
NH CH
CH
2
CH
2
C
OH
O
C
O
N
OH
C
O
NH CH C
O
H
N
C
O
CH
3

Gelatin is prepared by the denaturation of collagen.
a) [2]
i. What is meant by the term denaturation?

ii. Suggest a brief outline of one method by which collagen may be denatured to
produce gelatin.

b) How many different amino acid residues are present in this portion of the gelatin
molecule? [1]

c) Two of these amino acid residues are present more than once in this portion. [5]

i. Draw a displayed formula for each of these amino acids.

ii. One of the amino acid residues present in this portion of the gelatin molecule
contains more than one chiral atom.
Draw the displayed formula of this amino acid and indicate each chrial atom
with an asterisk (*).


Skin is a very tough, flexible and waterproof substance which is easily pierced by sharp
objects.
Kevlar

is an aromatic polyamide which is used in stab-proof vests and also in high quality
bicycle tyres.
C C C H
3
O
O
N
H
N
H
H
n

Proteins and Kevlar

may be hydrolysed in a similar manner.

d) [5]
i. How could proteins by hydrolysed in the laboratory to form a mixture of their
constituent amino acids?

ii. What compounds will be produced when Kevlar

is hydrolysed?
Give their structural formulae.

iii. Proteins and Kevlar

are polyamides.
What is the essential difference between their monomers?
Sutures are the stiches that surgeons use to hold skin, internal organs, blood vessels and other
tissues of the human body together after they have been severed by injury or surgery.
Soluble stiches which are used within the body may be made by reacting together glycolic
acid, HOCH
2
CO
2
H, and lactic acid, CH
3
CH(OH)CO
2
H.
e) When one molecule of glycolic acid reacts with one molecule of lactic acid, it is
possible to form two esters with different structural formulae.

Draw the structural formula of each of these esters. [2]
In the material used for soluble stiches, many molecules of each acid have been reacted to
form a long chain polyester molecule which contains many ester groups.
This polyester material may be used in surgery to sew up wounds inside the body.
Over a period of time the polyester undergoes a chemical reaction and breaks up to re-form
the two individual hydroxyacids.
f) [2]
i. Suggest what type of chemical reaction causes the polyester material to break
up over a period of time.

ii. Suggest why the products of this reaction are soluble in water.

(10)3, 1
a) [5]
i. Explain what is meant by the term entropy of a chemical system.

ii. Describe and explain how the entropy of each of the following systems will
change during the stated process. Assume the pressure of each system remains
at 1atm throughout.
1mol of Cl
2
(g) at 298K is added to 1mol of N
2
(g) at 298K.
1mol of Cl
2
(g) at 298K is heated to 373K.
1mol of Cl
2
(g) at 298K is reacted with iodine according to the
following equation.

()

()

()
1mol of Cl
2
(g) at 1000K is photolysed according to the following
equation.

()

b) [2]
i. Describe how the reaction of hydrogen with chlorine differs from that of
hydrogen with bromine.

ii. How would you expect the reaction of hydrogen with fluorine to differ from
that of hydrogen with chlorine?

c) Chloroalkanes and bromoalkanes can be made by the reaction of the corresponding
halogen with alkanes, for example: [6]

i. State the conditions needed for this reaction.

ii. Name and describe the mechanism of this reaction.

iii. Suggest why it is not possible to make iodoalkanes by this method.


d) Suggest a structural formula for each of the compounds A D in the following
schemes. [4]
CH
3
C H
3
CH
3
Cl
2 NaOH in ethanol
heat
CH
2
C H
3
CH
3
+
CH
3
C H
3
CH
3
A
C
6
H
13
Cl
mixture of these two compounds formed
CH
3
C H
3
CH
3
Cl
2 NaOH in ethanol
heat
B
C
10
H
18
Cl
2
CH
3
C H
3
CH
2
C
C
7
H
12
Br
2
(in an inert solvent) D
C
7
H
12
Br
2
NaOH in ethanol
heat
CH
3


e) Chlorofluoralkanes, CFCs, were once used as refrigerant fluids and aerosol
propellants. In many applications they have now been replaced by alkanes. This is
because CFCs contribute to the destruction of the ozone layer. [3]

i. Suggest one reason why CFCs were originally used for these purposes.

ii. Explain how CFCs destroy the ozone layer.

iii. Suggest one potential hazard of using alkanes instead of CFCs.

(10)3, 2
The soy bean, Glycine max, is a legume native to East Asia. It was first cultivated in China
over 5000 years ago.
The beans have many culinary uses, including soy oil, soy sauce, soy milk, dofu and TVP
(textured vegetable protein made from soy flour).
a) Soy sauce is produced by the fermentation of soy beans by the mould Aspergillus
oryzae. The distinctive salty taste of the sauce is due to salts of glutamic acid formed
during fermentation. [6]
HO
2
C
CO
2
H
N H
2


i. Explain what is meant by the term pK
a
as applied to a weak acid HA.

There are three pK
a
values associated with glutamic acid: 2.1, 4.1 and 9.5.

ii. Make use of these pK
a
values to suggest the major species present in solutions
of glutamic acid with the following pH values.
pH 1
pH 3
pH 7
pH 11

b) Dofu is made by coagulating soy milk and then pressing the curds between fine cloth
to extrude most of the moisture. Coagulating agents that have been used include
certain salts, acids or enzymes. Coagulation is due to the denaturation of the proteins
in the soy milk.

[You may find that including suitable sketches or diagrams will help you in your
answers to parts (i), (ii) and (iii).] [8]

i. What aspect of a proteins structure is altered during coagulation, and why
does this occur?
The calcium salts CaSO
4
and CaCl
2
are often used to produce dofu.
ii. Suggest how Ca
2+
(aq) ions can interact with a protein to bring about
denaturation.

iii. Suggest how a weak acid might interact with a protein to bring about
denaturation.

The addition of glucono-delta-lactone, GDL, to soy milk produces a soft form of dofu due to
a gradual acidification of the mixture. In aqueous solution the following equilibrium is slowly
set up.
O
O H
O H
OH
OH
O
+
O H
2
OH
O H
O H
OH
OH
CO
2
H

When 1.00g of GDL (M
r
= 178) was dissolved in 50.0cm
3
water and the solution allowed to
reach equilibrium, the concentration of gluconic acid was found to be 0.0670moldm
-3
.
iv. Write an expression for K
c
for the equilibrium above, and use the data given to
calculate its value. You can assume that [H
2
O] = 55.5moldm
-3
throughout.

c) Soy beans, and especially the dofu made from them, are a good source of dietary
isoflavenoids, which are claimed to help in the prevention of some cancers. The major
isoflavenoid in soy is diadzein. [6]

O O H
O
OH


i. Draw the structural formula of the compound formed when diadzein reacts
with an excess of Br
2
(aq).

When diadzein is treated with H
2
and Ni, compound F, C
15
H
14
O
4
, is formed. One
mole of compound F reacts with three moles of sodium metal. F also dissolves in
NaOH(aq). F reacts with acidified K
2
Cr
2
O
7
to give compound G, C
15
H
12
O
4
, which
gives an orange precipitate with 2,4-dinitrophenylhydrazine reagent.

ii. Suggest a structural formula for F and for G, identifying any chiral carbon
atoms. Explain the reactions which occur.


(10)3, 3
The direct oxidation of alcohols in a fuel cell represents potentially the most efficient method
of obtaining useful energy from a renewable fuel.
c) [3]
i. Use suitable bond energy values from the Data Booklet to calculate H for the
combustion of one mole of ethanol according to

. Use a value of 805kJmol

-1
for the bond energy of each C=O
bond in CO
2
.

ii. Suggest a reason for the difference between your calculated value and that
given as -1367kJmol
-1
.

d) Alcohol J, C
x
H
y
OH, is a volatile fungal metabolite whose presence when detected in
air can indicate hidden fungal attack on the timbers of a house.
When 0.10cm
3
of liquid J was dissolved in an inert solvent and an excess of sodium
metal added, 10.9cm
3
of gas (measured at 298K) was produced.
When 0.10cm
3
of liquid J was combusted in an excess of oxygen in an enclosed
vessel, the volume of gas (measured at 298K) was reduced by 54.4cm
3
. The addition
of an excess of NaOH(aq) caused a further reduction in gas volume of 109cm
3

(measured at 298K). [8]

i. Use these data to calculate values for x and y in the molecular formula
C
x
H
y
OH for J.
Alcohol J reacts with acidified K
2
Cr
2
O
7
, and can be dehydrated to alkene K. On
treating K with an excess of hot acidified concentrated KMnO
4
, an equimolar mixture
of ethanoic acid and propanone is produced.
ii. Use this information to deduce the structural formulae for J and K, explaining
your reasoning.

iii. Suggest suitable reagents and conditions for the conversion of J and K.

iv. Explain whether K can show geometrical isomerism.

(10)3, 4g
Oxidation is an important reaction in organic chemistry. Both aldehydes and carboxylic acids
can be prepared by the oxidation of alcohols with acidified K
2
Cr
2
O
7
. [5]
i. Describe how you could ensure that only either the aldehyde or the carboxylic acid is
produced during the oxidation process.

ii. Compounds L and M, both C
9
H
10
, and compound N, C
9
H
12
O, are all oxidised by hot
concentrated alkaline KMnO
4
, followed by acidification, to give
benzene-1,2-dicarboxylic acid, P.

CO
2
H
CO
2
H


Compound L reacts with Br
2
(aq), but compound M does not.
Compound N reacts with alkaline aqueous iodine.
Suggest structures for compounds L, M and N.