Queen Mary

UNIVERSITY OF LONDON
COURSE UNIT EXAMINATION

CHE102B Fundamentals of Organic Chemistry (Semester B)

Main Examination Period 2018

Question 1
MULTIPLE CHOICE QUESTIONS

Instructions

1 For each question, 1 – 25, there are five possible answers (A) to (E), only ONE of
which is correct.

2 You must indicate your response to each question on the MULTIPLE CHOICE
EXAMINATION ANSWER SHEET in the way described on that sheet. Instructions are
at the top of the sheet. Take time to read the instructions carefully.

3. Each question is worth ONE mark.

4. Negative marking does not apply in this examination paper.

5. Enter on the Multiple Choice examination answer sheet

(a) the date

(b) your surname (please PRINT)
(c) your first name(s)
(d) your candidate number (listen for verbal instructions)
(e) the test number (which is 226)
(f) the College number (which is 13)

For (d), (e) and (f) please mark the appropriate boxes too.

THIS BOOKLET MUST NOT BE REMOVED FROM THE EXAMINATION ROOM

Ó Queen Mary University of London 2018

Page 2 CHE102B (2018)

MULTIPLE CHOICE QUESTIONS

1. What is the hybridization and geometry of the carbon atoms involved in an alkyne triple bond?

A) sp3, trigonal planar

B) sp2, trigonal planar
C) sp3, tetrahedral
D) sp, linear
E) sp, trigonal planar

2. Which of the following base(s) could be used to quantitatively deprotonate alkyne 1?

A) Imidazole or K2CO3
B) n-BuLi and PhLi
C) n-BuLi, PhLi and LDA
D) n-BuLi, PhLi, LDA and K2CO3
E) Any of them would work

3. What is the major product of the following transformation?

A) 1
B) 2
C) 3
D) 2 and 4
E) 4

4. Which of these compounds have conjugated systems?

A) All of them
B) 1, 2, 3, 4
C) 1, 2, 4
D) 1, 2, 3
E) 2, 3, 4
CHE102B (2018) Page 3

5. Which of these molecules are aromatic?

A) All of them
B) 1, 2 and 3
C) 1 and 2
D) 1, 2 and 5
E) 1, 2, 3 and 5

6. Arrange the following compounds in order of decreasing acidity (i.e. most acidic first, least acidic last).

A) 3, 1, 2, 4
B) 3, 2, 1, 4
C) 2, 4, 1, 3
D) 4, 2, 1, 3
E) 2, 3, 4, 1

7. Arrange the following carbocations in order of decreasing acidity (i.e. most acidic first, least acidic last).

A) 4, 1, 3, 2
B) 2, 3, 1, 4
C) 3, 2, 1, 4
D) 2, 1, 3, 4
E) 4, 2, 1, 3

8. For the following compounds, the relative rate of reactivity with the same electrophilic species E+ is in the
order:

A) 1>2>3>4
B) 2>4>3>1
C) 2>3>1>4
D) 1 > 4 > 3 >2
E) 4>2>3>1
Page 4 CHE102B (2018)

9. Which is the major product of the following transformation?

10. Which is the major product of the following transformation?

11. Which of the structures A-E is NOT a correct representation of the Wheland intermediate of the nitration
of anisole?
CHE102B (2018) Page 5

12. Which is the major product of the following reaction?

13. Which is the major product of the following reaction?

14. Identify the main product of the following reaction:

15. The following tetrahedral intermediate is unstable and will quickly undergo elimination. Identify which
product will be formed.
Page 6 CHE102B (2018)

16. For the following step in the a-bromination of an enolate, which is the correct curved arrow mechanism?

17. Which of the following reagents are reducing agents?

A) 1, 2 and 3
B) 2, 3 and 5
C) 1, 4 and 5
D) 2 and 3
E) 4 and 5

18. Which of the following statements is true for the reaction between pentan-2-one and ethylamine in the
presence of acid?

A) The reaction will lead to the formation of an enamine.

B) The reaction will lead to the formation of an amine.
C) The reaction will lead to the formation of an amide.
D) The reaction will lead to the formation of an oxime.
E) The reaction will lead to the formation of an imine.

19. What will be the first step in the mechanism of the following reaction?

20. Which term describes the relationship between propanone and propen-2-ol?
A) Tautomers
B) Enantiomers
C) Resonance structures
D) Conformational isomers
E) Stereoisomers
CHE102B (2018) Page 7

21. Which of the following statements is true?

A) 1 and 2 are both oxidations

B) 1 and 2 are both reductions
C) 1 is an oxidation and 2 is a reduction
D) 1 is a reduction and 2 is an oxidation
E) 1 and 2 are neither oxidation nor reduction

22. Which of the following compounds cannot be used to form an imine by reaction with a carbonyl
compound?

23. Which of the following compounds has a hemiacetal functionality?

24. Put the following compounds in order according to how readily LiAlH4 reacts with the carbonyl group
(most reactive first, least reactive last).

A) 1, 2, 3, 5, 4
B) 4, 1, 3, 5, 2
C) 1, 3, 4, 5, 2
D) 4, 5, 3, 2, 1
E) 1, 2, 5, 3, 4

25. Identify the main product of the following reaction:

______________________________________________________________________

End of Multiple Choice Questions

Main Examination Period 2018

CHE102B Fundamentals of Organic Chemistry (Semester B) Duration: 2 hours

YOU ARE NOT PERMITTED TO START READING THIS QUESTION PAPER UNTIL
INSTRUCTED TO DO SO BY AN INVIGILATOR.

Answer ALL the questions in Section A and ONE question from Section B.

The total of marks available on the paper is 80, with Section A worth 50 marks and Section B worth
30 marks.
A marking scheme is provided for your guidance. A data booklet is also provided, which may contain
data and formulae relevant to the questions on this examination paper.
Approved molecular models are permitted in this examination. All molecular model sets must be
disassembled at the start of the examination.
If you answer more questions than specified, only the first answers (up to the specified number)
will be marked. Cross out any answers that you do not wish to be marked.

Calculators are permitted in this examination. Please state on your answer book the name and type
of machine used.

Complete all rough workings in the answer book and cross through any work that is not to be assessed.

Possession of unauthorised material at any time when under examination conditions is an assessment
offence and can lead to expulsion from QMUL. Check now to ensure you do not have any notes,
mobile phones, smartwatches or unauthorised electronic devices on your person. If you do, raise your
hand and give them to an invigilator immediately.

It is also an offence to have any writing of any kind on your person, including on your body. If you
are found to have hidden unauthorised material elsewhere, including toilets and cloakrooms it will be
treated as being found in your possession. Unauthorised material found on your mobile phone or other
electronic device will be considered the same as being in possession of paper notes. A mobile phone
that causes a disruption in the exam is also an assessment offence.

EXAM PAPERS MUST NOT BE REMOVED FROM THE EXAM ROOM

Examiners: Dr X Cambeiro and Dr N Lebrasseur

© Queen Mary University of London, 2018

Page 2 CHE102B (2018)

SECTION A

Question 1

Answer all the multiple-choice questions in the supplementary book using the multiple-choice
examination answer sheet provided. [25 marks]

Question 2

Answer all parts

(a) Secondary amines react with ketones under anhydrous acidic conditions to give enamines.

O H
R2 R3
+ N A + H2O
H

(i) Propose a structure for enamine A. [1 mark]

(ii) Define the terms nucleophile and electrophile. [1 mark]

(iii) State which compound acts as a nucleophile in this reaction; in your answer you should
clearly identify the nucleophilic centre. [1 mark]

(iv) State which compound acts as an electrophile in this reaction; in your answer you should
clearly identify the electrophilic centre. [1 mark]

(v) Explain why this reaction is carried out under acidic conditions. [3 marks]

(vi) Propose a curved arrow mechanism to account for the formation of A. [5 marks]

(b) The following synthetic sequence shows the reaction of fluorobenzene with concentrated HNO3
and H2SO4 to give a mixture of isomers B and C. After separation of the mixture, further reactions
on purified C provide isomeric compounds D and E.

(i) Identify compounds B, C, D and E. [4 marks]

Question 2 continued overleaf

CHE102B (2018) Page 3

(ii) Provide a curved arrow mechanism explaining the formation of C. You do NOT need to show
in detail the formation of NO2+. [3 marks]
(iii) Provide a curved arrow mechanism for the transformation of C into D. [2 marks]

(iv) Provide a curved arrow mechanism for the transformation of 1 into E. You do NOT need to
show in detail the formation of NO+. [4 marks]

SECTION B

Question 3

Answer all parts

(a) Consider the following reaction.

(i) Identify the major product(s) of this reaction. [2 marks]

(ii) Provide a curved arrow mechanism to explain the reaction. [3 marks]

(iii) Draw an energy profile diagram for the reaction. Clearly label all the intermediates and
transition states. Indicate which is the rate-determining step. [3 marks]

(iv) Justify the regioselectivity of the reaction. For this, draw the different resonance structures of
the three isomeric Wheland intermediates (ortho, meta and para) and mark clearly any
factors affecting their relative stabilities. Why is this a valid analysis? [7 marks]

(b) Formaldehyde (CH2O) is a gas under normal conditions but is well known in aqueous solutions
as its hydrate form, formalin (CH2(OH)2).

(i) Propose a curved arrow mechanism to account for the formation of formalin. [4 marks]

(ii) Attempt to isolate formalin leads to its decomposition back to formaldehyde and water. On
the other hand, in the case of trichloroacetaldehyde (CCl3CHO) the hydrate is stable with
respect to dehydration. Propose an explanation for this observation. [4 marks]

(c) Consider the following reaction.

(i) Propose a structure for compounds F and G. [1 mark]

Question 3 continued overleaf

(ii) Under which reaction conditions should this reaction be carried out? Justify your answer.
Page 4 CHE102B (2018)

[2 marks]
(iii) Propose a curved arrow mechanism to account for the formation of 2. [4 marks]

Question 4

Answer all parts

(a) Compounds 3 and 4 below can be prepared from benzene by very similar routes, differing only
in the order of the steps. Propose a synthesis for each of them. Justify your choice regarding the
order of the steps and discuss any selectivity issues you expect. Curved arrow mechanisms are
not required. You may use any of the suggested reagents below, or choose your own.[10 marks]

(b) Identify the product H of the following reaction and provide a curved arrow mechanism to explain
its formation. [5 marks]

(c) With reference to the following reaction scheme:

(i) Suggest suitable reagent(s) for carrying out step a. [2 marks]

(ii) Propose a curved arrow mechanism for step a. [3 marks]

(iii) Name the functional group(s) present in compound 6. [2 marks]

(iv) Identify compound I, propose a curved arrow mechanism to account for its formation and
discuss any selectivity issues in this step. [8 marks]

End of Paper