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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.
O OH
CH3 CH3 CH3 O OH
electrophilic substitution Cl Cl
oxidation
Cl2, AlCl3, rt OR
A OR
KMnO4/H+ reflux
E Cl
free radical substitution Cl F
Cl2, uv light
Cl CH3 HO CH3
O CH3
B C D
Since A has C:H ratio close to 1, there is likely to be a benzene ring. A undergoes
free radical substitution with Cl2 in uv light to form B (monosubstitution). A reacts
with Cl2 via electrophilic substitution to form E.
distillation.
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.
A
CH3
HO OH
C* C*
CH3 H3C
H H
B mirror line C
A is a carbonyl compound (either aldehyde or ketone) due to positive condensation
reaction with 2,4 DNPH. Indeed, A is a methyl ketone as further affirmed by positive
tri-iodoform test (oxidative cleavage) to form CHI3 as the pale yellow precipitate.
Since A did not react with hot acidified K2Cr2O7, it does not contain primary nor
secondary alcohol groups and hence cannot be oxidised. Since A did not react with
Br2(aq), it does not contain phenol (no electrophilic substitution), phenylamine (no
electrophilic substitution) nor C=C (no electrophilic addition).
Reduction of A with LiAlH4 in dry ether reduced the ketone functional group to a
corresponding secondary alcohol B and C. Since an equimolar mixture of isomers
are obtained, it is likely that B and C are enantiomers of each other and hence
contain a chiral carbon.
However, due to C:H ratio of 1:2 but A is not an alkene, a cyclic structure must be
present. Hence, to fulfil structures of A, B and C, a cyclohexane ring must be
present.
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.
3
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.
CH3 CH3
CH3
NH2 HN O HN O
HN O
Br Br
O
OH OH O CH3
OH
Br
C D
A B
Since A has a C:H ratio of close to 1, a benzene ring is likely to be present. As A is
sparingly soluble in water but dissolves in HCl (acid-base neutralisation), an amine
(more specifically phenylamine) group is present. Since it also dissolves in
NaOH(aq) (acid-base neutralisation), a phenol group is present but not a –COOH
group.
When A is treated with 2 mol CH3COCl, 1 ester group and 1 amide group are now
formed via nucleophilic substitution since the resultant compound D is neither
soluble in HCl nor NaOH(aq).
5 A neutral compound A has the molecular formula, C14H18O3NBr. When A is refluxed with
4
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.
H O 2N
N
NH NO2
HOOC
D is also a carboxylate salt and is oxidised to the aldehyde G (due to heating with
immediate distillation with K2Cr2O7). G undergoes condensation reaction with 2,4-
DNPH to give the formula shown above.
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.
Identify compounds S, T, U and V. Suggest a possible structure for Q and thus for R and P.
Explain your reasoning.
Q reacts with cold dilute KMnO4 and undergoes oxidation and diol formation
indicated by 6 –OH groups increase and hence 3 C=C bonds are present. Strong
oxidation (oxidative cleavage) of Q with hot concentrated acidified KMnO4 gives S, T
and CO2 in 1:1:2 ratio, indicating presence of 2 terminal alkene groups.
S is a methyl ketone or contains –CH(CH3)(OH) group but is the former due to the
molecular formula; S is propanone.
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.
Identify the lettered compounds D to F, explaining your reasoning and suggest a possible
structure for C.
D E F
H
H3C CH3
H2C CH3
CHO
CHO
C
H3C H
CH3
OHC
When A is heated under reflux with ethanol and concentrated sulphuric acid it gives C,
C22H36O2. A solution of C shaken with finely divided palladium under an atmosphere of
hydrogen gives D, C22H44O2.
Treatment of C with hot concentrated acidified potassium manganate (VII) breaks it down
into three products, CH3(CH2)4CO2H, HO2C(CH2)3CO2C2H5 and E, C3H4O4, in the ratio of
1:1:3 respectively.
H H H H
O
H3C
C
H H H H O
CH3
H H H H
O
H3C A
H H H H OH
H H H H
H3C
B
H H H H OH
H H H H
O
H3C
D
H H H H O
CH3
O O
E
HO OH
When A is heated under reflux with ethanol and concentrated H 2SO4, it undergoes
esterification to give C, further supporting that it is a monocarboxylic acid since
there is an increment of 2 C atoms in C. As C undergoes reduction by H 2/Pd to give D
which has 8 H atoms more, there are 4 C=C bonds in C.
C is then strongly oxidised (oxidative cleavage) to give the three products, of which
E is a dicarboxylic acid and hence has to appear within the long chain alkene since it
is cleaved at both ends to give rise to a dicarboxylic acid. Hence, the sequence is
one of the other two products followed by 3 E then the last product.
Note: ester group in the second product is not hydrolysed probably due to
complications involved should there be subsequent hydrolysis giving rise to more
products and hence confusion, but there should be hydrolysis owing to acid and
heat being present.
9
And should there be an extension, let E be HCOOH / H2C2O4 (and may well be
oxidised directly to CO2, tricking one into thinking that there is a terminal alkene) –
note that 2 acids can be further oxidised – methanoic acid and ethanedioic acid to
CO2 and H2O, and CO2 respectively
End of Paper