Unit 4 A2 Organic Chemistry

Page 1
MINI MOCK ORGANIC CHEMISTRY including STRUCTURE DETERMINATION A2: Units 4.4-4.11

Q1. (a) Write an equation for the formation of methyl propanoate, CH3CH2COOCH3, from methanol and propanoic acid. (1)
(b) Name and outline a mechanism for the reaction between methanol and propanoyl chloride to form methyl
propanoate.(5)
(c) Propanoic anhydride could be used instead of propanoyl chloride in the preparation of methyl propanoate from
methanol. Draw the structure of propanoic anhydride(1)
(d) (i) Give one advantage of the use of propanoyl chloride instead of propanoic acid in the laboratory
preparation of methyl propanoate from methanol.
(ii) Give one advantage of the use of propanoic anhydride instead of propanoyl chloride in the industrial
manufacture of methyl propanoate from methanol. (2)
(e) An ester contains a benzene ring. The mass spectrum of this ester shows a molecular ion peak at m/z = 136.
(i) Deduce the molecular formula of this ester.
(ii) Draw two possible structures for this ester. (3)(Total 12 marks)

Q2. (a) P, Q and R have the molecular formula C6H12
All three are branched-chain molecules and none is cyclic.
P can represent a pair of optical isomers.
Q can represent a pair of geometrical isomers.
R can represent another pair of geometrical isomers different from Q.
Draw one possible structure for one of the isomers of each of P, Q and R. (3)
(b) Butanone reacts with reagent S to form compound T which exists as a racemic mixture. Dehydration of T forms
U, C5H7N, which can represent a pair of geometrical isomers.
(i) State the meaning of the term racemic mixture and suggest why such a mixture is formed in this reaction.
(ii) Identify reagent S, and draw a structural formula for each of T and U. (6)(Total 9 marks)
Q3. (a) The reaction of but-1-ene with chlorine produces 1,2-dichlorobutane, C4H8Cl2
(i) Given that chlorine exists as a mixture of two isotopes,
35
Cl and
37
Cl, predict the number of molecular ion
peaks and their m/z values in the mass spectrum of C4H8Cl2
(ii) The mass spectrum of 1,2-dichlorobutane contains peaks at m/z = 77 and 79. Draw the structure of the
fragment ion which produces the peak at m/z = 77 and write an equation showing its formation from the
molecular ion.(6)
(b) The reaction of but-2-ene with hydrogen chloride forms a racemic mixture of the stereoisomers of
2-chlorobutane.
(i) Name the type of stereoisomerism shown by 2-chlorobutane and give the meaning of the term racemic
mixture. State how separate samples of the stereoisomers could be distinguished.
(ii) By considering the shape of the reactive intermediate involved in the mechanism of this reaction, explain
how a racemic mixture of the two stereoisomers of 2-chlorobutane is formed.(7)
(c) The reaction of but-2-ene with chlorine produces 2,3-dichlorobutane, C4H8Cl2
(i) State the number of peaks, their integration ratio and any splitting of peaks in the proton n.m.r. spectrum
of 2,3-dichlorobutane.
(ii) Compound S, an isomer of C4H8Cl2, produces a proton n.m.r. spectrum which consists only of a singlet, a
triplet and a quartet with an integration ratio of 3:3:2 respectively.
Compound T, also an isomer of C4H8Cl2, produces a proton n.m.r. spectrum which consists only of two
singlets with an integration ratio of 3:1. Draw the structures of S and of T.
(6)
(Total 19 marks)

Unit 4 A2 Organic Chemistry
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Q4. Haloalkanes are useful compounds in synthesis.Consider the three reactions of the haloalkane A shown below.
(a) (i) Draw a
branched-chain isomer of A that
exists as optical isomers.(1)



(ii) Name the
type of mechanism in Reaction
1.(1)



(iii) Give the full
IUPAC name of compound B. (1)


(b) The infrared spectra shown below are those of the four compounds, A, B, C and D.
Using Table 1 on the Data Sheet, write the correct letter in the box next to each spectrum.
(i)


(ii)





(iii)


Unit 4 A2 Organic Chemistry
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(iv)


(4)

(c) Draw the repeating unit of the polymer formed by B and name the type of polymerisation involved.
Draw the Repeating unit and name the type of polymerisation...(2)
(d) (i) Outline a mechanism for Reaction 3.(4)
(ii) State the conditions used in Reaction 3 to form the maximum amount of the primary amine, D. (1)
(iii) Draw the structure of the secondary amine formed as a by-product in Reaction 3 (1)
(e) D is a primary amine which has three peaks in its
13
C n.m.r. spectrum.
(i) An isomer of D is also a primary amine and also has three peaks in its
13
C n.m.r. spectrum. Draw the
structure of this isomer of D.(1)
(ii) Another isomer of D is a tertiary amine. Its
1
H n.m.r. spectrum has three peaks. One of the peaks is a
doublet. Draw the structure of this isomer of D. (1) (Total 17 marks)
Q5. (a) (i) Write an equation for the reduction of pentan-2-one by aqueous NaBH4 to form pentan-2-ol.
Use [H] to represent the reductant.
(ii) Name and outline a mechanism for this reduction.
(iii) State why the pentan-2-ol produced in this reaction is not optically active. (7)

(b) Predict the m/z values of the two most abundant fragments in the mass spectrum of pentan-2-one.
Fragment 1 .................................................Fragment 2 (2)(Total 9 marks)

Q6.Lactic acid, CH3CH(OH)COOH, is formed in the human body during metabolism and exercise. This acid is also
formed by the fermentation of carbohydrates such as sucrose, C12H22O11.
(a) (i) Give the IUPAC name for lactic acid. (1)
(ii) Write an equation for the formation of lactic acid from sucrose and water. (1)
(b) A molecule of lactic acid contains an asymmetric carbon atom.
The lactic acid in the body occurs as a single enantiomer.
A racemic mixture (racemate) of lactic acid can be formed in the following two-stage synthesis.

(i) Name and outline a mechanism for Stage 1.(5)
Unit 4 A2 Organic Chemistry
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(ii) Give the meaning of the term racemic mixture (racemate). (1)
(iii) Explain how you could distinguish between a racemic mixture (racemate) of lactic acid and one of the
enantiomers of lactic acid. (2)
(c) A mixture of lactic acid and its salt sodium lactate is used as an acidity regulator in some foods. An acidity
regulator makes sure that there is little variation in the pH of food.
(i) Write an equation for the reaction of lactic acid with sodium hydroxide. (1)
(ii) The acid dissociation constant Ka for lactic acid has the value 1.38 10
4
mol dm
3
at 298 K.
Calculate the pH of an equimolar solution of lactic acid and sodium lactate. (2)
(iii) Suggest an alternative name for the term acidity regulator. Explain how a mixture of lactic acid and sodium
lactate can act as a regulator when natural processes increase the acidity in some foods. (3)
(d)

PLA is the condensation polymer formed from lactic acid, and used to make disposable plastic cups.

The polymer is described as 100% biodegradable and 100% compostable.Compostable material breaks
down slowly in contact with the moist air in a garden bin. This produces compost that can be used to improve
soil.The manufacturers stress that PLA cups differ from traditional plastic cups that are neither
biodegradable nor compostable.
(i) Draw a section of PLA that shows two repeating units.(2)
(ii) Name the type of condensation polymer in PLA. (1)
(iii) An intermediate in the production of PLA is a cyclic compound (C6H8O4) that is formed from two PLA
molecules.Draw the structure of this cyclic compound.(1)
(iv) Traditional non-biodegradable plastic cups can be made from poly(phenylethene), commonly known as
polystyrene.Draw the repeating unit of poly(phenylethene).(1)
(v) The manufacturers of PLA claim that the material will break down to compost in just 12 weeks.
Suggest one reason why PLA in landfill may take longer than 12 weeks to break down. (1)(Total 22
marks)
Q7. (a) Outline a mechanism for the reaction of CH3CH2CH2CHO with HCN and name the product. (5)
(b) Outline a mechanism for the reaction of CH3OH with CH3CH2COCl and name the organic product. (5)
(c) An equation for the formation of phenylethanone is shown below. In this reaction a reactive intermediate is
formed from ethanoyl chloride. This intermediate then reacts with benzene.

(i) Give the formula of the reactive intermediate.
(ii) Outline a mechanism for the reaction of this intermediate with benzene to form phenylethanone.(4)
(Total 14 marks)
Q8. (a) Name and outline a mechanism for the reaction between propanoyl chloride,
CH3CH2COCl, and methylamine, CH3NH2 . Draw the structure of the organic product.(6)
(b) Benzene reacts with propanoyl chloride in the presence of aluminium chloride. Write equations to show the role
of aluminium chloride as a catalyst in this reaction. Outline a mechanism for this reaction of benzene.(5)
(c) Write an equation for the reaction of propanoyl chloride with water. An excess of water is added to 1.48 g of
propanoyl chloride. Aqueous sodium hydroxide is then added from a burette to the resulting solution.
Calculate the volume of 0.42 mol dm
3
aqueous sodium hydroxide needed to react exactly with the mixture
formed.(5)(Total 16 marks)
Unit 4 A2 Organic Chemistry
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Q9.This question is about acylium ions, [RCO]
+
(a) The acylium ion is formed in a mass spectrometer by fragmentation of the molecular ion of
methyl ethanoate.
Write an equation for this fragmentation.Include in your answer a displayed formula for the radical formed. (2)
(b) The acylium ion can also be formed from ethanoyl chloride. The ion reacts with benzene to
form C6H5COCH3
(i) Write an equation to show the formation of this acylium ion by the reaction of ethanoyl chloride with one
other substance. (2)
(ii) Name and outline a mechanism for the reaction of benzene with this acylium ion.(4)
(iii) Ethanoic anhydride also reacts with benzene to form C6H5COCH3 Write an equation for this reaction. (1)
(Total 9 marks)
Q10. Two reactions of benzene are shown below.
(a) Name X and give the reagent and catalyst required for Reaction 1.
Write an equation for the formation of the
reactive intermediate involved in this
reaction.
Name and outline a mechanism for the
reaction of this reactive intermediate with
benzene to form X. (8)
(b) (i) Deduce the structure of
Y and give the organic reagent needed for
Reaction 2.
(ii) Give the reagent(s)
needed for Reaction 3. (3)
(Total 11 marks)


Q11. The following reaction scheme
shows the formation of two amines, K and L, from methylbenzene.
(a) (i) Give the reagents needed to carry out Step 1.
Write an equation for the formation from these reagents of
the inorganic species which reacts with methylbenzene.
Reagents Equation
(ii) Name and outline a mechanism for
the reaction between this inorganic species
and methylbenzene. (7)
(b) Give a suitable reagent or combination of reagents
for Step 2. (1)

(c) (i) Give the reagent for Step 4 and state a condition
to ensure that the primary amine is the major product.
Reagent .. Condition
(ii) Name and outline a mechanism for
Step 4. (7)
(d) Explain why amine K is a weaker base than
ammonia. (2)
(e) Draw the structure of the organic compound formed when a large excess of bromomethane reacts with amine
L.(1)
(f) Draw the structure of the organic compound formed when ethanoyl chloride reacts with amine L in an addition
elimination reaction.(1)(Total 19 marks)
Unit 4 A2 Organic Chemistry
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Q12. Propanoyl chloride can be used, together with a catalyst, in Step 1 of the synthesis of
1-phenylpropene from benzene via compounds P and Q as shown below.

(a) The mechanism of Step 1 is an electrophilic substitution. Write an equation to show the formation of the
electrophile from propanoyl chloride. Outline the mechanism of the reaction of this electrophile with benzene in
Step 1.(5)
(b) The mass spectrum of P contains a molecular ion peak at m/z = 134 and major fragmentation peaks at m/z = 105
and 77. Identify the species responsible for the peak at m/z = 105 and also that responsible for the peak at m/z
= 77. Write an equation for the formation, from the molecular ion, of the species responsible for the peak at m/z
= 105.(4)
(c) NaBH4 can be used in the reaction in Step 2. Name the mechanism involved in this reaction. Molecules of Q
show optical isomerism but the sample of Q formed in Step 2 is optically inactive. State, in terms of their
structure, why molecules of Q show optical isomerism. Explain, by reference to the mechanism, why the sample
of Q obtained in Step 2 is not optically active.(7)
(d) Identify a suitable reagent for the reaction in Step 3. Name the type of stereoisomerism shown by the product of
this reaction. State what is required in the structure of molecules to allow them to show this type of
stereoisomerism. (4)(Total 20 marks)
Q13. Ethylbenzene is made by the reaction shown below.
(a) Identify two other substances required as catalysts
in this preparation. (2)
(b) Write an equation for the reaction of these
two substances with ethene to form the reactive
intermediate involved in the formation of ethylbenzene. (1)
(c) Name and outline a mechanism for the reaction between this reactive intermediate and benzene.(4)
(d) Draw the structure of the product formed in a similar reaction between benzene and cyclohexene.(1)
(e) Ethylbenzene is used to make phenylethene which can be polymerised to form poly(phenylethene). Name this
type of polymerisation and draw the structure of the repeating unit in the polymer.Type of polymerisation
........................................Repeating unit (2)(Total 10 marks)
Q14.This question is about the primary amine CH3CH2CH2NH2
(a) The amine CH3CH2CH2NH2 reacts with CH3COCl Name and outline a mechanism for this reaction.Give the
IUPAC name of the organic product. (6)
(b) Isomers of CH3CH2CH2NH2 include another primary amine, a secondary amine and a tertiary amine.
(i) Draw the structures of these three isomers.Label each structure as primary, secondary or tertiary.(3)
(ii) Use Table 1 on the Data Sheet to explain how you could use infrared spectra in the range outside the
fingerprint region to distinguish between the secondary amine and the tertiary amine. (2)
(c) The amine CH3CH2CH2NH2 can be prepared by two different routes.
Route A is a two-stage process and starts from CH3CH2Br.
Route B is a one-stage process and starts from CH3CH2CH2Br.
(i) Identify the intermediate compound in Route A.Give the reagents and conditions for both stages in Route
A and the single stage in Route B.(7)
(ii) Give one disadvantage of Route A and one disadvantage of Route B. (2)(Total 20 marks)

Unit 4 A2 Organic Chemistry
Page 7
Q15. The amide or peptide link is found in synthetic polyamides and also in naturally
occurring proteins.
(a) (i) Draw the repeating unit of the polyamide formed by the reaction of propanedioic acid with
hexane-1,6-diamine.(2)
(ii) In terms of the intermolecular forces between the polymer chains, explain why polyamides can be made
into fibres suitable for use in sewing and weaving, whereas polyalkenes usually produce fibres that are
too weak for this purpose. (3)
(b) (i) Name and outline a mechanism for the reaction of CH3CH2COCl with CH3NH2 (5)
(ii) Give the name of the product containing an amide linkage that is formed in the reaction in part (b) (i). (1)
(c) The dipeptide shown below is formed from two different amino acids.
Draw the structure of the alternative dipeptide that could be formed by these two
amino acids. (1)


(d) The amino acids serine and aspartic acid are shown below.
(i) Give the IUPAC name of serine. (1)
(ii) Draw the structure of the species formed when aspartic acid
reacts with aqueous sodium hydroxide.(1)


(iii) Draw the structure of the species formed when serine reacts with
dilute hydrochloric acid (1)

(iv) Draw the structure of the species formed when serine reacts with an excess of bromomethane.(1) (Total 16 marks)

Q16. The compound (CH3CH2)2NH can be made from ethene in a three-step synthesis as shown below.

(a) Name the compound (CH3CH2)2NH (1)
(b) Identify compounds F and G. (2)
(c) For the reactions in Steps 1, 2 and 3, give a reagent or reagents name the mechanism.
Balanced equations and mechanisms using curly arrows are not required. (6)
(d) Identify one organic impurity in the product of Step 3 and give a reason for its formation. (2)(Total 11 marks)
Q17. (a) Name and outline a mechanism for the reaction of CH3CH2NH2 with CH3CH2COCl. Name the amide formed. (6)
(b) Haloalkanes such as CH3Cl are used in organic synthesis. Outline a three-step synthesis of CH3CH2NH2 starting
from methane. Your first step should involve the formation of CH3Cl . In your answer, identify the product of the
second step and give the reagents and conditions for each step.Equations and mechanisms are not required.
(6) (Total 12 marks)
Q18.Alanine and aspartic acid are naturally occurring amino acids.
(a) Draw the structure of the zwitterion formed by alanine.(1)
(b) Draw the structure of the compound formed when
alanine reacts with methanol in the presence of a small amount of
concentrated sulfuric acid (1)
(c) Draw the structure of the species formed by aspartic
acid at high pH. (1)
(d) Draw the structure of a dipeptide formed by two aspartic acid molecules.(1)(Total 4 marks)
Unit 4 A2 Organic Chemistry
Page 8


Q19.(a) The tripeptide shown is formed from the amino acids alanine, threonine and lysine.
(i) Draw a separate circle around each of the asymmetric carbon atoms in
the tripeptide.(1)
(ii) Draw the zwitterion of alanine.(1)
(iii) Give the IUPAC name of threonine. (1)
(iv) Draw the species formed by lysine at low pH.(1)

Q19(b) The repeating unit shown represents a polyester.
(i) Name this type of polymer. (1)


(ii) Give the IUPAC name for the alcohol used to prepare this polyester. (1)
(c) The repeating unit shown represents a polyalkene co-polymer. This co-polymer is made from two different alkene
monomers.
(i) Name the type of polymerisation occurring in the formation of this co-polymer. (1)
(ii) Draw the structure of each alkene monomer: Alkene monomer 1 ; Alkene
monomer 2 (2)
(d) One of the three compounds shown in parts (a), (b) and (c) cannot be broken down
by hydrolysis.Write the letter (a), (b) or (c) to identify this compound and explain why hydrolysis of this compound does
not occur. Compound ...................................Explanation (2)(Total 11 marks)
Q20.A possible synthesis of the amino acid X is shown below.
(a) Name and outline a
mechanism for Step 1. (5)
(b) Give the IUPAC
name of the product of Step 2. (1)
(c) For Step 3, give the
reagent, give a necessary
condition and name the
mechanism. (3)
(d) At room temperature,
the amino acid X exists as a solid.
(i) Draw the
structure of the species present in
the solid amino acid.(1)

(ii) With reference to your answer to part (d)(i), explain why the melting point of the amino acid X is higher than the melting point of
CH3CH2CH(OH)COOH. (2)
(e) There are many structural isomers of X, CH3CH2CH(NH2)COOH.
(i) Draw a structural isomer of X that is an ethyl ester (1)
(ii) Draw a structural isomer of X that is an amide and also a tertiary alcohol.(1)
(iii) Draw a structural isomer of X that has an unbranched carbon chain and can be polymerised to form a polyamide.(1)
(f) Draw the structure of the tertiary amine formed when X reacts with bromomethane.(1) (Total 16 marks)
Unit 4 A2 Organic Chemistry
Page 9
Q21. Fibres are made from natural and from synthetic polymers. Both types of polymer have advantages and
disadvantages.
(a) Consider the following amino acid.
(i) Draw the structure of the amino acid species present in a solution at pH 12.
(ii) Use your understanding of amino acid chemistry to deduce the structure of the dipeptide formed
from two molecules of this amino acid and illustrate your answer with a sketch showing the structure of
the dipeptide.
(iii) Protein chains are often arranged in the shape of a helix. Name the type of interaction that is
responsible for holding the protein chain in this shape (3)
(b) Alkenes are the building blocks of synthetic addition polymers.
Consider the hydrocarbon G, (CH3)2C=CHCH3, which can be polymerised.
(i) Draw the repeating unit of the polymer.
(ii) Draw the structure of an isomer of G which shows E-Z isomerism.
(iii) Draw the structure of an isomer of G which does not react with bromine water.(3)
(c) Draw the repeating unit of the polymer formed by the reaction between butanedioic acid and hexane-1,6-diamine.(2)

(d) Two plastic objects were manufactured, one from the polyalkene represented by the repeating unit in part (b)(i) and the other
from the polyamide represented by the repeating unit in part (c).After use it was suggested that both objects be disposed of as landfill.
(i) Describe an experiment in which you could compare the biodegradability of these two objects. (3)
(ii) Describe an advantage or a disadvantage of a different method of disposal of such objects compared with landfill.. (3)
(Total 14 marks)
Q22.Common substances used in everyday life often contain organic compounds.
(a) State an everyday use for each of the following compounds.
(i) CH3(CH2)17COO

Na
+
(1)
(ii) CH3(CH2)19COOCH3 (1)
(iii) [C16H33N(CH3)3]
+
Br

(1)

(b) The following structures are the repeating units of two different condensation polymers.For each example, name
the type of condensation polymer. Give a common name for a polymer of this type.
(i) Type of condensation polymer Common name (2)





(ii) Type of condensation polymer Common name (2)



(iii) Explain why the polymer in part (b)(ii) has a higher melting point than the polymer in part (b)(i). (2)(Total 9 marks)







Unit 4 A2 Organic Chemistry
Page 10
Q23. (a) The repeating units of two polymers, P and Q, are shown below.




(i) Draw the structure of the monomer used to form polymer P. Name the type of polymerisation involved.
Structure of monomer Type of polymerisation .......................................................................
(ii) Draw the structures of two compounds which react together to form polymer Q. Name these two compounds and name
the type of polymerisation involved.
Structure of compound 1Name of compound 1 .........................................................................
Structure of compound 2Name of compound 2 ........................................................................
Type of polymerisation .......................................................................
(iii) Identify a compound which, in aqueous solution, will break down polymer Q but not polymer P. (8)

(b) Draw the structures of the two dipeptides which can form when one of the amino acids shown below reacts with the other.

Structure 1 Structure 2 (2)
(c) Propylamine, CH3CH2CH2NH2, can be formed either by nucleophilic substitution or by reduction.
(i) Draw the structure of a compound which can undergo nucleophilic substitution to form propylamine.
(ii) Draw the structure of the nitrile which can be reduced to form propylamine.
(iii) State and explain which of the two routes to propylamine, by nucleophilic substitution or by reduction, gives the less
pure product. Draw the structure of a compound formed as an impurity.
Route giving the less pure product ...................................Explanation Structure of an impurity (5)(Total 15 marks)
Q24. (a) Synthetic polyamides are produced by the reaction of dicarboxylic acids with compounds such as
H2N(CH2)6NH2
(i) Name the compound H2N(CH2)6NH2
(ii) Give the repeating unit in the polyamide nylon 6,6. (2)
(b) Synthetic polyamides have structures similar to those found in proteins.
(i) Draw the structure of 2-aminopropanoic acid.
(ii) Draw the organic product formed by the condensation of two molecules of 2-aminopropanoic acid.(2)
(c) Compounds like H2N(CH2)6NH2 are also used to make ionic compounds such as X, shown below.
(i) X belongs to the same type of compound as (CH3)4N
+
Br

Name this type of compound.
(ii) State a reagent which could produce X from H2N(CH2)6NH2
and give a necessary condition to ensure that X is the major
product. Reagent Condition
(iii) Name the mechanism involved in this reaction to form X. (4)
(Total 8 marks)





Unit 4 A2 Organic Chemistry
Page 11
Q25. (a) Name compound Y, HOCH2CH2COOH (1)
(b) Under suitable conditions, molecules of Y can react with each other to form a polymer.
(i) Draw a section of the polymer showing two repeating units.(1)
(ii) Name the type of polymerisation involved. (1)
(c) When Y is heated, an elimination reaction occurs in which one molecule of Y loses one molecule of water. The organic product
formed by this reaction has an absorption at 1637 cm
1
in its infrared spectrum.
(i) Identify the bond that causes the absorption at 1637 cm
1
in its infrared spectrum. (1)
(ii) Write the displayed formula for the organic product of this elimination reaction.(1)
(iii) The organic product from part (ii) can also be polymerised. Draw the repeating unit of the polymer formed from this organic
product.(1)
(d) At room temperature, 2-aminobutanoic acid exists as a solid.Draw the structure of the species present in the solid form.(1)
(e) The amino acid, glutamic acid, is shown below.
Draw the structure of the organic species formed when glutamic acid reacts with
each of the following.
(i) an excess of sodium hydroxide(1)
(ii) an excess of methanol in the presence of concentrated sulfuric acid(1)
(iii) ethanoyl chloride(1)

(f) A tripeptide was heated with hydrochloric acid and a mixture of amino acids was formed. This mixture was separated by
column chromatography.Outline briefly why chromatography is able to separate a mixture of compounds.Practical details are
not required. (3) (Total 13 marks)
Q26.Describe how you could distinguish between the compounds in the following pairs using one simple test-tube reaction
ineach case. For each pair, identify a reagent and state what you would observe when both compounds are tested
separately with this reagent.
(a) Reagent; Observation with R & S (3)

(b) Reagent; Observation with T & U (3)
(c.) Reagent; Observation with V with W(3) (Total 9 marks)








Q27. Use the data given on the back of the Periodic Table (PT) to help you answer this question.
Compounds A to G are all isomers with the molecular formula C6H12O2

(a) Isomer A, C6H12O2, is a neutral compound and is formed by the reaction between compounds X and Y in the presence of a
small amount of concentrated sulphuric acid.. X and Y can both be formed from propanal by different redox reactions. X has an
absorption in its infra-red spectrum at 1750 cm
1
.Deduce the structural formulae of A, X and Y. Give suitable reagents, in each case,
for the formation of X and Y from propanal and state the role of concentrated sulphuric acid in the formation of A.(7)
(b) Isomers B, C, D and E all react with aqueous sodium carbonate to produce carbon dioxide.. Deduce the structural
formulae of the three isomers that contain an asymmetric carbon atom.The fourth isomer has only three singlet peaks in its
proton n.m.r. spectrum. Deduce the structural formula of this isomer and label it E.(4)
(c) Isomer F, C6H12O2, has the structural formula shown below, on which some of the protons have been labelled.
A proton n.m.r. spectrum is obtained for F. Using Table 1 at the back of the
Periodic Table (PT), predict a value of for the protons labelled a and also for
those labelled b. State and account for the splitting patterns of the peaks
assigned to the protons a and b.(6)

(d) Isomer G, C6H12O2, contains six carbon atoms in a ring. It has an absorption in its infra-red spectrum at 3270 cm
1
and shows
only three different proton environments in its proton n.m.r. spectrum. Deduce a structural formula for G.(2)(Total 19 marks)







Unit 4 A2 Organic Chemistry
Page 12
Q28. The conversion of compound A into compound B can be achieved in two steps as shown below.
The intermediate compound, X, has an
absorption at 1650 cm
1
in its infra-red
spectrum.
(a) Identify compound X. Explain your
answer.(2)
(b) For each step in this conversion, give the reagents and essential conditions required and outline a mechanism.(11)
(c) Show how the number of peaks in their proton n.m.r. spectra would enable you to distinguish between compounds A
and B.(2)(Total 15 marks)
Q29. A possible synthesis of 1,4-diaminobenzene is shown below.
(a) Identify a suitable reagent or combination of
reagents for Step 1. Name and outline a mechanism for the
reaction.(6)

(b) Identify a suitable reagent or combination of reagents for
Step 2. Name and outline a mechanism for the reaction.(6)

(c) Identify a suitable reagent or combination of reagents for
Step 4. Draw the repeating unit of the polymer formed by reaction
of 1,4-diaminobenzene with pentanedioic acid.
(3)(Total 15 marks)






Q30.N.m.r. spectroscopy can be used to study the structures of organic compounds.
(a) Compound J was studied using
1
H n.m.r. spectroscopy.
(i) Identify a solvent in which J can be dissolved before obtaining its
1
H n.m.r.
spectrum.(1)
(ii) Give the number of peaks in the
1
H n.m.r. spectrum of J. (1)
(iii) Give the splitting pattern of the protons labelled a. (1)
(iv) Give the IUPAC name of J. (1)


(b) Compound K was studied using
13
C n.m.r. spectroscopy.
(i) Give the number of peaks in the
13
C n.m.r. spectrum of K. (1)

(ii) Use Table 3 on the Data Sheet to suggest a value of the peak for the carbon
labelled b. (1)
(iii) Give the IUPAC name of K. (1)(Total 7 marks)



Q31.This question concerns isomers of C6H12O2 and how they can be distinguished using n.m.r. spectroscopy.
(a) The non-toxic, inert substance TMS is used as a standard in recording both
1
H and
13
C n.m.r. spectra.
(i) Give two other reasons why TMS is used as a standard in recording n.m.r. spectra. (2)
(ii) Give the structural formula of TMS.(1)




Unit 4 A2 Organic Chemistry
Page 13
Q31(b) The proton n.m.r. spectrum of compound P (C6H12O2) is represented in Figure 1.
The integration trace gave information about the five peaks as shown in


(i) Use Table 2 on the Data Sheet, Figure 1 and Figure 2 to deduce the
structural fragment that leads to the peak at 2.2.
(ii) Use Table 2 on the Data Sheet, Figure 1 and Figure 2 to deduce the
structural fragment that leads to the peaks at 3.5 and 1.2. (1)
(iii) Use Table 2 on the Data Sheet, Figure 1 and Figure 2 to deduce the
structural fragment that leads to the peaks at 3.8 and 2.6.(1)
(iv) Deduce the structure of P. (1)

(c) These questions are about different isomers of P (C6H12O2).
(i) Draw the structures of the two esters that both have only two peaks in their proton n.m.r. spectra. These peaks both have
an integration ratio of 3:1.. Ester 1 Ester 2 (2)
(ii) Draw the structure of an optically active carboxylic acid with five peaks in its
13
C n.m.r. spectrum.(1)
(iii) Draw the structure of a cyclic compound that
has only two peaks in its
13
C n.m.r. spectrum and
has no absorption for C = O in its infrared
spectrum.(1)(Total 11 marks)


Q32. Spectral data for use in this question
are provided below the Periodic Table (first item on
the database).
Compound Q has the molecular formula C4H8O2
(a) The infra-red spectrum of Q is shown below.
Identify the type of bond causing the absorption
labelled R and that causing the absorption labelled
S. (2)

(b) Q does not react with Tollens reagent or
Fehlings solution. Identify a functional group which
would react with these reagents and therefore
cannot be present in Q.(1)

(c) Proton n.m.r. spectra are recorded using a solution of a substance to which tetramethylsilane (TMS) has been added.
(i) Give two reasons why TMS is a suitable standard.
(ii) Give an example of a solvent which is suitable for use in recording an n.m.r. spectrum. Give a reason for your choice (4)
(d) The proton n.m.r. spectrum of Q shows 4 peaks.The table below gives values for each of these peaks together with
their splitting patterns and integration values. What can be deduced about the structure of Q from the presence of the following
in its n.m.r. spectrum?
(i) The singlet peak at =
2.20
(ii) The singlet peak at =
3.40
(iii) Two triplet peaks (3)

(e) Using your answers to parts (a), (b) and (d), deduce the structure of compound Q.(1)(Total 11 marks)

/ ppm 3.8 3.5 2.6 2.2 1.2
Integration ratio 2 2 2 3 3
/ppm 2.20 2.69 3.40 3.84
litting pattern singlet triplet singlet triplet
Integration value 3 2 1 2
Unit 4 A2 Organic Chemistry
Page 14
Q33. Three sections of the proton n.m.r. spectrum of CH3CHClCOOH are shown below.
(a) Name the compound CH3CHClCOOH
(1)
(b) Explain the splitting patterns in the peaks
at 1.72 and 4.44 (2)
(c) Predict the splitting pattern that would be
seen in the proton n.m.r. spectrum of the
isomeric compound ClCH2CH2COOH (1)
(d) The amino acid alanine is formed by the
reaction of CH3CHClCOOH with an excess of
ammonia. The mechanism is nucleophilic
substitution. Outline this mechanism, showing
clearly the structure of alanine.(5)




(e) The amino acid lysine has the structure. Draw structures to show the product formed in each case when lysine reacts
with
(i) an excess of aqueous HCl,
(ii) an excess of aqueous NaOH,
iii) another molecule of lysine.( 3)
(Total 12 marks)


Unit 4 A2 Organic Chemistry
Page 15
Q34. The proton n.m.r. spectrum of compound X is shown below.
Compound X, C7H12O3, contains
both a ketone and an ester
functional group.
The measured integration trace for
the peaks in the n.m.r. spectrum of
X gives the ratio shown in the table
below.

Refer to the spectrum, the
information given above and the
data below the Periodic Table
provided to answer the following
questions.
(a) How many different types of
proton are present in compound X?
(1)
(b) What is the whole-number
ratio of each type of proton in
compound X? (1)
(c) Draw the part of the structure
of X which can be deduced from the
presence of the peak at 2.20. (1)





(d) The peaks at 4.13 and 1.26 arise from the presence of an alkyl group. Identify the group and explain the
splitting pattern.(3)
(e) Draw the part of the structure of X which can be deduced from the splitting of the peaks at 2.76 and 2.57. (1)
(f) Deduce the structure of compound X. (2)(Total 9 marks)
Q35. Compounds C (first compound) and D (second compound), shown below, are isomers of C5H10O
(a) Name compound C. (1)
(b) Use Table 2 on the Data Sheet to help you to answer this
question.
(i) Suggest the wavenumber of an absorption which is present in
the infra-red spectrum of C but not in that of D.
(ii) Suggest the wavenumber of an absorption which is present in the infra-red spectrum of D but not in that of C. (2)
(c) Deduce the number of peaks in the proton n.m.r. spectrum of C. (1)
(d) Identify a reagent that you could use to distinguish between C and D. For each of C and D, state what you would
observe when the compound is treated with this reagent. (3)
(e) Compound E, CH3CH2CH2CH2CHO, is also an isomer of C5H10O. Identify a reagent which will react with E but not with
C or D. State what you would observe when E is treated with this reagent. (2)(Total 9 marks)



Chemical shift, /ppm 4.13 2.76 2.57 2.20 1.26
Integration ratio 0.8 0.8 0.8 1.2 1.2