A10084W1
FIRST PUBLIC EXAMINATION
Preliminary Examination in Chemistry
SUBJECT 2: ORGANIC CHEMISTRY
Trinity Term 2015
Tuesday, 9 June − 9.30 a.m. − 12.30 p.m.
Time allowed 3 hours
CANDIDATES SHOULD ANSWER FIVE QUESTIONS, AT LEAST ONE OF
WHICH MUST BE CHOSEN FROM SECTION B
The numbers in square brackets [x] indicate marks that the examiners normally expect to
assign to each part of the question.
Use a separate booklet for each question.
The following abbreviations may be used:
Me = CH3; Et = C2H5; tBu = Me3C; Ph = C6H5; Ac = COCH3; D = Deuterium;
Ts = p-MeC6H4SO2; DMF = HCONMe2; equiv. = equivalent(s) ; aq. = aqueous.
Assume reactions are carried out at ambient temperature and are worked up with a proton
source unless otherwise indicated.
In section A, all formulae depicting chiral molecules refer to racemic mixtures unless a
single enantiomer is explicitly specified.
In section B, all formulae depicting chiral molecules refer to a single enantiomer unless
otherwise stated.
Wavy lines indicate undefined stereochemistry.
DO NOT TURN OVER THE FIRST PAGE UNTIL INSTRUCTED TO DO SO.
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SECTION A
1. Answer ALL Parts I, II and III.
Part I.
For each of the following pairs explain, with reasoning, which is the stronger acid.[4 × 2]
(a) Cl 3CCO2H CH 3CO2H
(b)
(c)
O O
(d) CO2Et NO 2
Me Me
Part II.
For each of the following pairs explain, with reasoning, which is the stronger base.[4 × 2]
(a) MeNH 2 MeCN
(b) Me Me Ph Ph
O O
O NH
(c)
H 2N NH 2 H 2N NH 2
NMe 2 N
(d)
Part III.
Explain, with the aid of mechanisms, the chemistry in steps (i), (ii) and (iii) below. [4]
(i) Ac2O (1 equiv.), K 2CO3
HO
NHAc
HO
NH 2 (ii) Ac2O (1 equiv.), HCl (iii) K 2CO3
AcO + −
NH 3 Cl
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2. Answer BOTH Parts I and II.
Part I.
Give mechanisms for three of the following reactions. [3 × 4]
O O
(a) NaOEt
EtO CO2Et
OEt then AcOH
O
(b) O
catalytic KCN, EtOH
O
O O
O OH
catalytic H + O
(c)
HO OH
MeO OMe O
(d) O OH
NaBH 4, EtOH
Part II.
Explain, with the aid of mechanisms, the chemistry in the following sequence. [8]
O O O
1. NaOEt, then Br CO2Et
OH
Me OEt Me
2. NaOH, then H +, then heat
O
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3. Answer ALL Parts I, II and III.
Part I.
Using the Cahn-Ingold-Prelog rules, assign stereochemical descriptors to the deuterated
bromoalkene enantiomer shown below. [4]
D H
Me
Me
Br
Part II.
Draw all the stereoisomers of each of the following compounds and indicate if they are
related as enantiomers or diastereomers. [4 × 2]
CH2(CHBrCl) 2 MeCH CHCH CHMe
Me
Me Me S
Et O
Part III.
For the following three-step sequence, use mechanistic reasoning to determine the
stereochemistry of the final product. [8]
HO H 1. TsCl, HO H
N
Me Et 2. NaOAc, DMF Me Et
single enantiomer 3. KOH, H 2O
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4. Predict, with mechanistic reasoning, the major product in five of the following
reactions. [5 × 4]
(a) Br 2
(b) OsO4, H 2O
CHBr 3, KOtBu
(c)
1. MeCO 3H
(d)
2. LiAlD 4
HBr,
trace (PhCO 2)2
(e)
UV light
BuLi (2 equiv.)
(f) Cl
then AcOH
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5. Answer ALL Parts I, II and III.
Part I.
Explain the relative rates of nucleophilic substitution by sodium iodide (NaI) in acetone
(Me2C=O) at 60 °C for the substrates shown below. [4]
O
Cl Cl Cl
Ph
relative rate: 0 (no reaction) 1 100000
Part II.
Rationalise the following three sets of observations with the aid of mechanisms.
[3 × 4]
OH
(a)
Br
HBr (aq.)
or Br +
80%
OH 20%
(b) H13 C6 C6H13 H13 C6
H 2O
Br HO H 83% + H OH 17%
H EtOH
Me Me Me
single enantiomer single enantiomer single enantiomer
(c) MeS Me MeS Me MeS Me
NaCN H AgCN
H H
H DMF H DMF H
Me CN Me Br Me NC
Part III.
Predict, using mechanistic reasoning, the outcome of the following reaction. [4]
Me
Ph KOtBu
Ph
Br
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6. Answer ALL Parts I, II and III.
Part I.
Suggest a mechanism for the reaction shown below. [4]
NO 2 NO 2
Br 2, FeBr 3
Br
Part II.
Rationalise the following observations with the aid of mechanisms. [8]
Cl Cl Cl
HNO 3 NO 2
70% + 30%
50 °C
NO 2
BUT Cl Cl Cl
H 2SO 4 SO 3H
99% + 1%
50 °C
SO 3H
Part III.
Propose reagents for two of the following synthetic transformations; more than one
step may be necessary in each case. Mechanisms are not required. [2 × 4]
NO 2 (b) Cl EtS O
(a) F
Me
Cl Cl
OH OH
(c)
Me HO 2C CO2H
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7. Answer BOTH Parts I and II.
Part I.
Suggest reagents for eight of the transformations in the following scheme; more than one
step may be necessary in each case. Mechanisms are not required. [8 × 2]
O O OAc
(ix) (x) Me
Br
Ph NMe 2 Ph OH Ph Me Ph Me
Ph Me
(ii) (iii) (iv)
O O
(i) (v)
Ph Me
Ph Ph Ph Me
(viii) (vii) (vi)
O
O O HN Ph
Ph
Ph Me Br
Ph Me
Part II.
Rationalise the following observations with the aid of mechanisms, indicating why A is
not obtained in the second reaction. [4]
O EtMgBr HO
Et
Ph Cl Ph Et
A
BUT
O O
OMe EtMgBr
Ph N Ph Et
Me
END OF SECTION A
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SECTION B
8. Answer ALL Parts I, II and III.
Part I.
Glutamic acid is shown below in non-ionic form, and has the following pKa values: 2.10,
4.07 and 9.47.
NH 2
HO OH
O O
Glutamic acid
(i) Assign, with justifications, the pKa values to the functional groups in glutamic acid.[4]
(ii) Calculate the isoelectric point for glutamic acid, and give an explanation for your
deduction. [4]
Part II.
Describe, with the aid of mechanisms, how a chemical method can be used to determine
the N-terminal amino acid residue of a peptide. Your answer should indicate why the
chemistry involved is selective for the N-terminal residue. [4]
Part III.
Show mechanisms for the formation of both A and B, and draw all the stereoisomers of B
that could be formed. [8]
H
O Ph N O
1. NH 4Cl, NaCN MeOH, HCl, then NaOMe
A
Ph H 2. HCl, H 2O O N Ph
H
B
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9. Answer BOTH Parts I and II.
Part I.
The four bases and the sugar shown below are all precursors of DNA.
NH 2 O NH 2 O
Me HO 5!
N N NH N NH O
N
CHOH
N N N N NH 2 N O N O 3!
H H H H OH
Adenine (A) Guanine (G) Cytosine (C) Thymine (T) 2!-Deoxyribose
(a) Draw the structure of the dinucleotide 5ʹ′-AC-3ʹ′. [6]
(b) Draw the structure of the duplex resulting from the dinucleotide 5ʹ′-AC-3ʹ′ pairing with
its complementary sequence. [6]
Part II.
Answer two of the following. [2 × 4]
(a) Why does the backbone of RNA undergo base-catalysed hydrolysis more easily than
DNA?
(b) Why is thymine used as a base in DNA, but uracil takes its place in RNA?
NH
N O
H
Uracil (U)
(c) In the flow of information between DNA, RNA and protein, what do the terms
translation, codon and anti-codon refer to?
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