© The Hong Kong Polytechnic University

The Hong Kong Polytechnic University

Department of Applied Biology and Chemical Technology

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Course : B.Sc.(Hons.) in Chemical Technology

Higher Diploma in Chemical Technology

Year : 2 Subject: Organic Chemistry I

Class : 12447 Subject Code: ABCT2742

12352

Session : 2015 – 2016 , Semester 2

Date : 3 May 2016

Time Allowed: 3 hours Time: 08:45 – 11:45

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This question paper has SIX pages. (including this page)

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Instructions to Candidates :

There are TWELVE questions in TWO Sections. Answer all the questions in BOTH Sections.

Use separate answer scripts for Section A (GREEN) and Section B (WHITE)
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DO NOT TURN OVER THIS PAGE UNTIL YOU ARE TOLD TO DO SO.

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Section A (Questions 1 – 5): Answer ALL questions (40%)

Write your answers for Section A in the GREEN answer book
1. Below is the structure of a caffeine molecule. What is/are the hybridization state(s) of these four
“nitrogen” atoms?

(4 marks)
2. (a) Show the dipole moment of sodium phenoxide.

(b) Identify the strongest Brönsted acid and Brönsted base in the following reaction. What is the
difference in definition between Brönsted acid and Lewis acid?

(8 marks)

3. Sketch the 1H NMR and 13C NMR (1H-decoupled) spectra of the following compound.

(8 marks)

4. The following 1H NMR spectrum was obtained from an aromatic carbonyl compound with a
formula of C8H8O. Suggest a possible molecular structure of the compound. Explain your answer.

(10 marks)

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5. Based on the following spectroscopic data, determine the structure of the halogenated aromatic
compound with proper explanations.

MS data: M+ = 232
1
H NMR spectrum

13
C NMR spectrum

(10 marks)

-End of Section A-

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Section B (Questions 6 – 12): Answer ALL questions (60%)

Write your answers for Section B in the WHITE answer book

6. Allylic C-H bromination 3-methylcyclohexene occurred when treating with N-

bromosuccimide in the presence of peroxide. Monosubstituted allyl bromides were obtained as
a mixture of two regioisomers 6.1 and 6.2 in 89% overall yield.

(a) As the bromination proceeded by a free radical mechanism, what is the structure of the major
carboradical formed in this reaction? Justify your answer with a potential energy diagram.

(5 marks)

(b) With reference to your answer in part (a), give the structures of the regioisomeric bromides.
Which regiosiomer would be the major product?

Explain your rationale using a potential energy diagram associated with the C-Br bond formation.

(5 marks)

7. For the reaction of methyl chloride with NaBr in acetone, discuss briefly how each of the
following would affect the rate of reaction [illustrate your answers with potential energy
diagrams where applicable]:

(a)   Doubling [methyl chloride]

(b)  Changing the methyl chloride to tert-butyl chloride

(c)   Changing the leaving group from Cl- to OTs- (OTs = p-toleuensulfonate)

(10 marks)

8. The following reactions do not proceed as given in (a) – (e).

In each case, suggest the structure(s) of the major product(s). Explain briefly your answers.

(a) CH 3 CH 3
CH 3
KOEt OEt
Br
ethanol, heat

(b) Me Me
OH HCl Cl
* * * *
CaCl2 (excess)

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(c) Br 2 Br Br

MeOH

(d) O
H 3O+
OH
MeO 2C MeMgBr MeO 2C
H (excess) Me

(12 marks)

9. The following isomeric bromides 9.1 and 9.2 would undergo nucleophilic substitution with NaSPh
by SN2 mechanism.

(a) Give the structures of the reaction products.

(b) For reactants 9.1 and 9.2, which one has higher potential energy? Repeat the same analysis for
the reaction products.
(c) Suggest with explanation which bromide (9.1 or 9.2) would react faster. Propose the transition
state structures and map these structures to a potential energy diagram.

Br
PhSNa

OMe 9.1

Br
PhSNa

OMe 9.2

(8 marks)

10. Compound 10.1 undergoes acid-catalyzed hydration in sulphuric acid to form alcohols.
Rationalize the observed results on the relative reactivity of a series of substituted alkenes.

OH
H 2SO 4 H 2O
cold
Z
10.1 Z

relative rates with changing Z

-OCH 3 (4980) >> -CH3 (16.4) > -H (1.0) >> -CF3 (1.13 X 10 -3)

(8 marks)

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11. Propose a stepwise mechanism for the following cyclization reaction.

H2SO4

(5 marks)

12. Outline the efficient syntheses in (a) and (b). Suggest how the desired compounds can be
synthesized using the given starting materials and any necessary inorganic reagents and organic
reagents with no more than three carbons.

(a) CH 3
steps H 3C
CHO
O

(b) steps

steps

Et

(7 marks)

-End of Section B-

-END OF PAPER-