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2244A

Semester 1, 2011

Page 1 of 27

CONFIDENTIAL
THE UNIVERSITY OF SYDNEY
Faculties of Science, Engineering and Arts
TABLE NO.......................................................................................
CANDIDATE'S SURNAME ...........................................................
OTHER NAMES .............................................................................
SID NUMBER..................................................................................

CHEM2401/CHEM2911/CHEM2915 MOLECULAR REACTIVITY & SPECTROSCOPY


________________________________________________________________________________
Time allowed: 3 hours

SEMESTER 1 2011
Instructions to Candidates

All questions are to be attempted.


All information the candidate wishes to present for examination is to be written in the spaces provided.
The space provided is an indication of the length of response required. However, additional space has
been provided on pages 12, 18 and 27.
Only University-approved non-programmable calculators can be used in the examinations. Students
are warned, however, that credit may not be given, even for a correct answer, where there is
insufficient evidence of working required to obtain the solution.
Required data as well as a Periodic Table are printed on a separate data sheet.

This examination paper consists of 27 pages.


Please check that this booklet is complete and affirm this by signing below.
I have checked this booklet and affirm that it is complete.
SIGNATURE .........................................................
If you have an incomplete booklet, obtain a replacement from the Examination Supervisor immediately.
THIS EXAMINATION BOOKLET IS NOT TO BE TAKEN FROM THE EXAMINATION ROOM.

________________________________________________________________________________
FOR OFFICIAL USE ONLY
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Max Score
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Total Mark

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180

Mark

/180

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Question 1

Semester 1, 2011

Page 2 of 27

5 Marks

Show your understanding of the use of curly arrow notation by drawing the structures for all
products in the following reactions.

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Question 2

Semester 1, 2011

Page 3 of 27

10 marks

Provide curly arrows to show electron movement in the following reactions. Note that non-bonding
electron pairs are not shown, and you should add them to the starting materials where appropriate.

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Question 3

Semester 1, 2011

Page 4 of 27

5 marks

The diketone dimedone shown below undergoes acid catalysed tautomerisation to give the
corresponding enol. Complete the scheme using curly arrow notation. Note that non-bonding
electron pairs are not shown, and you should add them where appropriate.

Question 4

4 marks

a) In the boxes provided, rank the following bases from best (1) to worst (4) base for
performing an E2 reaction.

b) In the boxes provided, rank the following species from best (1) to worst (4) nucleophile for
performing an SN2 reaction.

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Question 5

Semester 1, 2011

Page 5 of 27

14 marks

Under certain reaction conditions, organic compounds can predictably undergo substitution
reactions (via SN1 or SN2 mechanisms) and/or elimination reactions (via E1, E2 or E1CB
mechanisms). Illustrate your understanding of these pathways in the following examples by:
i) indicating the reaction mechanism(s) favoured by the particular type of: leaving group,
substrate, nucleophile/base and solvent employed
ii) predicting the major pathway(s) that will occur under these conditions and
iii) providing the structure(s) of the major product(s) of the reaction

a)

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b)

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Semester 1, 2011

Question 6

Page 7 of 27

5 marks

The mechanism of the peroxide mediated epoxidation of cyclohexenone is shown below.

Given that:
a. The overall reaction is endothermic.
b. The Hammond postulate predicts that the structure of the first transition state will
most closely resemble the intermediate.
c. The second step of the reaction is the rate determining step.
i)

Sketch a reaction profile that accurately represents the reaction, and

ii) Label each transition state, intermediate, and indicate the activation energy for the rate
determining step.

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Semester 1, 2011

Question 7

Page 8 of 27

5 marks

The reaction below shows equilibration between two conformational isomers of cyclohexane
(R = H).

(a) In the boxes provided, identify each conformer as either chair or boat.
(b) Draw the hydrogen atoms Ha and Hb onto the right hand structure. Take care with your
bond angles.
(c) How many signals would you expect in the 1H NMR spectrum of cyclohexane (R = H)?
Explain your answer.

(d) What effect does changing R from H to methyl (Me) to tert-butyl (tBu) have on the
position of the equilibrium? Why?

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Question 8

Semester 1, 2011

Page 9 of 27

5 marks

The amino acid L-phenylalanine is shown below

a) Assuming replacement by deuterium (D), which of Hc and Hd is the pro-S hydrogen? Which
is the pro-R? Show your working.
(2 marks)

b) The 1H NMR signals due to Hc and Hd are shown below. Draw a Newman projection
showing the arrangement of atoms around the C2C3 bond in phenylalanine, and use it to
explain why these protons do not give rise to a simple two-hydrogen doublet.
(3 marks)

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Semester 1, 2011

Question 9

Page 10 of 27

6 marks

For each of the following pericyclic reactions, add curly arrows to complete a mechanism, and
classify the reaction as either a sigmatropic rearrangement, an electrocyclisation, or a cycloaddition/
cycloreversion.
(a)

Reaction type:
(b)

Reaction type:
(c)

Reaction type:

Question 10 4 marks
Draw structures for the products of the following Diels-Alder reactions. Indicate the relative
stereochemistry where appropriate.
(a)

(b)

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Question 11 6 marks
a) Propose a mechanism to explain the formation of 1-methylcyclohexane (the major product)
in this reaction. Make sure to indicate the initiation and propagation stages of your
mechanism.
(5 marks)

b) In the above reaction, 1-methylcyclohexane is formed in preference to cycloheptane


(9:1 product ratio). Why?
(1 mark)

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Semester 1, 2011

Page 12 of 27

This page is left blank for additional space (if required).


If you need more space for an answer, use this page. Ensure that any answers are clearly labeled
with the page number from which they have been continued.
_______________________________________________________________________________

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Semester 1, 2011

Question 12

Page 13 of 27

10 marks

Complete the following table to show the major organic products formed.

REACTANT

REAGENT(S)/CONDITIONS

Na+ OCH3, MeOH

(i)

(ii)
KMnO4 (excess) / H2O
95 C

(iii)
O

H2, PdC

NO2

(iv)
Br

SO3 / conc. H2SO4

(v)

O
OCH3

i)

Cl

AlCl3 (1 equiv.)
ii) H3O

MAJOR ORGANIC PRODUCT(S)

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Question 13

Semester 1, 2011

Page 14 of 27

11 marks

Suggest appropriate reagents and conditions for the following conversions (more than one step is
required in each case). Assume that any mixtures of ortho- and para- substituted compounds can
be separated. Draw the structures of intermediate compounds.
(7 marks)

(4 marks)

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Semester 1, 2011

Question 14

Page 15 of 27

8 marks

Complete the following equations by drawing stick diagrams of the organic products, and name the
functional group formed in each case.

N
H

+ H2O

PhSO3H (catalyst)

f unctional group?

NH2

+ H2O
PhSO3H (catalyst)

f unctional group?

CH2OH
O
PhSO3H (catalyst)
f unctional group?

NCH3
1. NaBH4
2. H3O
f unctional group?

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Semester 1, 2011

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Question 15 14 marks
Using curly arrows, provide a detailed mechanism for each of the following reactions.

a)

(6 marks)

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Semester 1, 2011

Page 17 of 27
(8 marks)

b)

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Semester 1, 2011

Page 18 of 27

This page is left blank for additional space (if required).


If you need more space for an answer, use this page. Ensure that any answers are clearly labeled
with the page number from which they have been continued.
_______________________________________________________________________________

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Question 16

Semester 1, 2011

Page 19 of 27

20 marks

The energy levels of the orbitals of a polyene such as hexatriene, pictured below, can be
approximated to those of a particle in a one-dimensional box whose length is equal to the sum of the
bonds in the conjugated system.

a)

Draw the first three wavefunctions for hexatriene, showing the position of any nodes relative
to the position of the carbon atoms in the molecule.
(3 marks)

b)

Use de Broglies equation, p = mv =h/, to show that the separation between adjacent energy
levels for a particle inside a one-dimensional box of length L and infinitely high sides is given
by:

h 2 2 n 1
8 mL 2
(5 marks)

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c) If each C-C bond is 0.139 nm in length, what is the length of the box for hexatriene?
(2 marks)

d)

Calculate the energy (in J) required to excite an electron from the highest occupied to the
lowest unoccupied orbital in hexatriene using the particle in a box model.
(4 marks)

e) Predict what will happen to the energy of the equivalent transition as the length of the polyene
increases.
(3 marks)

f) Explain why the energy levels for the electrons in a molecule such as hexatriene are observed to
be quantized whereas the energy levels for macroscopic objects are not
(3 marks)

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Semester 1, 2011

Question 17

Page 21 of 27

24 marks

The infrared spectrum of CH4(g) contains a single strong band in the C-H stretching region, at 3020
cm-1. The Raman spectrum shows a band at 2914 cm-1.

(a)

Sketch the form of the vibrational modes which correspond to these bands and explain their
infrared and Raman activity.
(5 marks)

(b)

Explain why there is only one band in the C-H region of the infrared spectrum, even though
there are four C-H bonds in methane.
(3 marks)

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(c)

Semester 1, 2011

Page 22 of 27

Predict the wavenumber for the band in the infrared spectrum of deuterated methane, CD4
(4 marks)

(d)

The infrared spectrum of methane also contains weak bands at 6006 and 9047 cm-1. Explain
the origin of these bands and hence calculate (in cm-1) the harmonic frequency, e, the
anharmonicity constant, exe, and an estimate of the bond dissociation, D0.
(8 marks)

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(e)

Would you expect the experimental value for D0 to be larger, smaller or the same as the value
you calculated above?
(2 marks)

(f)

The upper atmosphere of Neptune contains 1% methane which is responsible for the blue
colour of the planet. Explain the molecular origin of this colour.
(2 marks)

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Question 18

Semester 1, 2011

Page 24 of 27

24 marks

Hexa-peri-benzocoronene (HBC) is a large polycyclic aromatic hydrocarbon molecule with formula


C42H18. It is used in molecular solar cells and is a proposed component of interstellar material.
(a)

Draw a Jablonski diagram, indicating the processes which account for the spectra labelled A
and B in the figure below.

40

(8 marks)

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(b)

Semester 1, 2011

Page 25 of 27

Where is the absorption maximum of the So S1 transition? Explain.


(4 marks)

(c)

Add state(s) to your Jablonski diagram in (a) to explain the appearance of the spectrum
labelled C.
(4 marks)

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(d)

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The molecular orbitals of HBC can be deduced by interacting seven aromatic rings linked by
"single" bonds. The HOMOs of HBC may be described by (in-phase) benzene HOMOs on
each of these rings. Indicate on the two HBC structures, by using shaded and unshaded lobes,
the HOMOs of HBC.
(8 marks)

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Semester 1, 2011

Page 27 of 27

This page is left blank for additional space (if required).


If you need more space for an answer, use this page. Ensure that any answers are clearly labeled
with the page number from which they have been continued.
_______________________________________________________________________________