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Chemistry H2 9746
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Revision Exercise 21: Structural Elucidation

1 Compound A has the molecular formula C8H10. When A is treated with chlorine in the
presence of ultraviolet light, compound B having the molecular formula C8H9Cl is formed.

A also reacts with chlorine under a different condition to produce compound E which is
isomeric with B. When B is heated with aqueous NaOH, compound C with molecular
formula C8H10O is formed. However, when E is subjected to heating with aqueous NaOH,
no new compound is formed.

When C is heated with acidified potassium manganate (VII), compound D is formed, which
gives an orange precipitate when heated with 2,4-dinitrophenylhydrazine. When E is
heated with acidified potassium manganate (VII), effervescence is observed and compound
F with molecular formula C7H5O2Cl is formed.

Deduce the structural formulae of compounds A to F, explaining your reasoning.

2 A certain organic solvent was distilled to produce a single compound A. When A was
reacted with 2,4-dinitrophenylhydrazine, an orange precipitate was produced. With
aqueous alkaline iodine, A gave a pale yellow precipitate. A did not react with either hot
acidified potassium dichromate (VI) nor with aqueous bromine. Reduction of A with LiAlH4
in dry ether yielded an equimolar mixture of two isomers, B and C, with the molecular
formula C8H16O.

Suggest the structural formulae of A, B and C, explaining the reactions involved.

3 Alcohol A has the molecular formula C6H14O. Reaction of A with acidified potassium
manganate (VII) produces compound B. B forms a yellow precipitate when warmed with
aqueous alkaline iodine. Heating A with concentrated H2SO4 at 170oC produces C, C6H12.
Vigorous oxidation of C with hot concentrated acidified potassium manganate (VII) forms 3-
methylbutanoic acid as one of the products.

Deduce the structural formulae of compounds A to C, explaining your reasoning.

4 Compound A, C6H7ON, is sparingly soluble in water but dissolves in hydrochloric acid. It

also dissolves in aqueous NaOH but not in aqueous Na2CO3.

On reaction with 1 mol ethanoyl chloride, A forms compound B, C8H9O2N. B is no longer

soluble in hydrochloric acid but is still soluble in aqueous NaOH. On reacting B with
aqueous bromine, compound C with molecular formula C8H6O2NBr3 is formed.

When A is treated with 2 mol ethanoyl chloride, compound D with molecular formula
C10H11O3N is formed. D is neither soluble in hydrochloric acid nor in aqueous NaOH.

Deduce the structural formulae of compounds A to D, explaining your reasoning.

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5 A neutral compound A has the molecular formula, C14H18O3NBr. When A is refluxed with
aqueous NaOH, three compounds B, C and D are obtained.

Upon analysis, B is found to be a straight-chain molecular with molecular formula C3H9N.

When B is treated with excess chloroethane, E is formed. E has a relative molecular mass
of 179.5 and gives a white precipitate immediately when treated with aqueous silver nitrate.

C has the molecular formula C3H5O3Na. Upon acidification, it yields F. F is also obtained
when A is refluxed with dilute H2SO4. It was found that 2 mol of aqueous NaOH is required
for complete neutralisation of 1 mol of F.

D (C8H7O3Na), upon addition of acidified potassium dichromate(VI) and heating with

immediate distillation, yields G. Treating G with 2,4-dinitrophenylhydrazine gives an orange
precipitate with the following structure:

H O 2N
N
NH NO2

HOOC

Deduce the structural formulae of compounds A to G, explaining your reasoning.

6 P, C10H16O, is an insect sex attractant. When P is gently oxidised with warm acidified
potassium dichromate (VI) it gives Q, C10H14O, which gives an orange precipitate with 2,4-
dinitrophenylhydrazine reagent, but does not give an orange precipitate with Fehling’s
reagent.

Treatment of Q with cold dilute acidified potassium manganate (VII) gives R, C10H20O7, but
Q with hot concentrated acidified potassium manganate (VII) gives S, T and carbon dioxide
in the ratio 1:1:2.

S, C3H6O, gives a yellow precipitate with alkaline aqueous iodine.

T can be synthesised from the following reaction sequence.

HCN H+/K2Cr2O7 boiling

CH2(CHO)2 → U → V → T, C5H4O6
NaCN (aq) warm H2SO4 (aq)

Identify compounds S, T, U and V. Suggest a possible structure for Q and thus for R and P.
Explain your reasoning.

7 An optically active compound F, C9H12O, reacts with acidified K2Cr2O7 to give G,

C9H10O. F reacts with iodine in aqueous sodium hydroxide to give a yellow precipitate and
the sodium salt of the acid H, C8H8O2. H is oxidised by acidified KMnO4 to form I, C8H6O4.

Suggest the structures of F, G, H and I, giving relevant equations to explain your

reasoning.
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8 J, C9H11I, on boiling with aqueous potassium hydroxide gave a compound K, C9H12O. With
acidified sodium dichromate(VI), compound K yielded L, C9H10O. With hot acidified
potassium manganate(VII), compound K yielded M, C7H6O2. K when warmed with
potassium hydroxide and iodine is able to produce yellow precipitate.

Suggest the structures of J, K, L and M, giving relevant equations to explain your

reasoning.

9 Compound C, C6H10O, is an insect pheromone. C reacts with Fehling’s solution,

decolourises Br2(aq) and gives an orange precipitate with 2,4-dinitrophenylhydrazine
reagent. Treatment of C with H2 over a nickel catalyst produces D, C6H14O, which reacts
with hot acidified K2Cr2O7 to give E, C6H12O2. Neither D nor E reacts with 2,4-
dinitrophenylhydrazine, but both react with sodium metal.

Compound E can be obtained from 3-bromopentane by the following route.

ethanolic KCN H3O+

Br F E
heat heat

Identify the lettered compounds D to F, explaining your reasoning and suggest a possible
structure for C.

10 The molecules of compound K, C7H15Br, are chiral. On treatment with NaOH(aq), K

produces alcohol L, C7H15OH, which does not react with hot acidified Na2Cr2O7(aq).
Treating compound K with ethanolic NaOH produces a mixture of four different isomeric
alkenes with the formula C7H14, only two of which are cis-trans isomers of each other.

Suggest the structural formulae of compound K and the four alkenes.

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