Question/Answer Booklet CHEM CHEM110

CHEM 110
THE UNIVERSITY OF AUCKLAND

FIRST SEMESTER, 2017

Campus: City

CHEMISTRY

Chemistry of the Living World

(Time allowed: THREE hours)

OFFICE USE ONLY
1
NOTE: (9 marks)
2
Answer ALL questions.
(11 marks)
This booklet is both the examination paper and the answer book. 3
Answers to questions are to be written in the spaces provided with each (13 marks)
question, and pages 1 to 14 must be handed in at the end of the 4
examination. (10 marks)
A spectroscopy data sheet and a useful equations sheet are attached at 5
the back of the booklet. Tear these off for use during the examination. (13 marks)
6
Be sure to PRINT your name and ID number legibly below and
(8 marks)
print your ID number only at the top of EACH page.
7
(12 marks)
8
(12 marks)
9
(12 marks)

ID: ____________________________ TOTAL

(100 marks)

SURNAME: _____________________________

FIRST NAME: ___________________________

_______________________________________

Page 1 of 16
Question/Answer Booklet CHEM 110

ID:______________________________________
QUESTION 1 (9 marks)
(a) (9 marks) Each of parts (i) – (xii) is worth ½ mark, (xiii) – (xv) are worth 1 mark each.
The compounds in the grid below may be used in more than one answer.
For parts (i) – (xiii) give in the box to the right the letter of one compound which:
A B C D E F

G H I J K L
COCH3

(i) is an ester. (vii) can exist as E/Z isomers.

(ii) is a 2o alcohol. (viii) can react with 2 equivalents of

LiAlH4 (followed by H3O+) to
give a primary alcohol.

(iii) is a 1o alkyl halide. (ix) can undergo nucleophilic acyl

substitution.

(iv) is an alkyne (x) will absorb UV light of the

longest wavelength.

(v) contains a stereocentre (xi) has 4 signals at > 100 ppm in its
1
H decoupled 13C NRM spectrum.

(vi) is least polar. (xii) contains a cyclohexane ring

(xiii) can react with CH3MgBr followed by H3O+ to give a racemic product.

(xiv) give two compounds from the grid that can undergo BOTH substitution
and elimination reactions.

(xv) give two compounds from the grid that have no sp3 hybridised carbons.

Page 2 of 16
Question/Answer Booklet CHEM 110

ID:______________________________________
QUESTION 2 (11 marks)
Questions (a)-(h) refer to compound M.
(a) (i) (½ mark) Circle the amide functional group in M.

(ii) (½ mark) and classify the amide as 1o / 2o / 3o

(circle one)

(b) (1½ marks) Name the three other oxygen-containing functional groups in in M.

(c) (½ mark) How many sp2 carbons are present in M? ___________

(d) (1 mark) Complete the molecular formula for compound M: C____H27NO____

(e) (1½ mark) By inspection, compound M has _________ DBEs (double bond equivalents).
Justify your answer.

(f) (2 marks) One of the stereocentres on M has been marked with an asterisk (*)
Rank and label, from highest (1) to lowest (4), the groups attached to this
stereocentre.

One the basis of YOUR assignment, the stereocentre is R/S

(Circle as appropriate.)
(g) (1 mark) Label all of the remaining stereogenic centres in M on the structure above.

(h) Compound M can be prepared as a single enantiomer by treating compound

N with NaOH. NaBr is the inorganic by-product of this reaction.
(i) (½ mark) This reaction is an example of:
addition / elimination / substitution
(Circle as appropriate.)
(ii) (1 mark) Complete the structure of compound N, right.

(iii) (1 mark) Explain how compound M and compound N could be distinguished by:
(a) Mass spectrometry

(b) IR spectroscopy

Page 3 of 16
Question/Answer Booklet CHEM 110

ID:______________________________________
QUESTION 3 (13 marks)
(a) Hydroboration-oxidation of alkenes results in the formation of alcohols, with the anti-Markovnikoff
product as the major product. The first step of this reaction is addition of BH3 (from B2H6) to the
alkene in a concerted mechanism.

+ enantiomer
BH 2
H BH2

(i) (1 mark) Label the electrophile and nucleophile in the reaction above.

(ii) (1 mark) Use curly arrows to complete the mechanism of this step on the scheme above.

(iii) (1 mark) With reference to your mechanism, explain why only the trans product is observed.

(iv) (1½ marks) Complete the structure (right) of the second enantiomer produced
in this step, and explain why both enantiomers are observed.

Overall, this reaction gives two regioisomeric alcohol products, with B as the major product.

(v) (1½ marks) How many signals would be expected for the
1
H decoupled 13C NMR spectrum of compound C? ___________
Justify your answer by appropriate labelling on the structure of C above.

(vi) (1 mark) Comparing the 1H NMR spectra of compounds A, B and C:

Compound A / B / C will have a signal at 3.5 ppm. This signal will be split into ________ lines.
(circle as appropriate)

Office use only

P4

/7
Page 4 of 16
Question/Answer Booklet CHEM 110

ID:______________________________________
QUESTION 3 cont.

Alkynes can also undergo addition reactions with a single equivalent of BH3, following the same
mechanism seen for alkenes.
(vii) (1½ marks) Draw the product of the following reaction, clearly indicating stereochemistry
where applicable.

(b) (i) (2½ marks) Use curly arrows to complete the following mechanism:
+ H 2O
H+
HO OH HO OH 2 HO H O

O H+

(ii) (½ mark) In this mechanism H+ is acting as a ________________

(iii) (1½ marks) Give the systematic name for compound D, produced in the reaction above.

Office use only

P4 P5 Q3

/7 /6 /13

Page 5 of 16
Question/Answer Booklet CHEM 110

ID:______________________________________
QUESTION 4 (10 marks)
(a) (2 marks) Circle the appropriate classifications for each of the substituents with respect to
electrophilic aromatic substitution.

CH3 ortho/para or meta directing activating or deactivating

CN ortho/para or meta directing activating or deactivating

(b) (i) (2½ marks) Complete the reaction scheme below showing the preparation of compounds E and
F from benzene by completing the missing structures and reagents in the boxes provided.

NH2
CH3 HNO3 CH3 CH3
H2SO4
Step 2
+ E

(ii) (1 mark) Give the structure of the second

aromatic product of step 2 in the box
provided (right). O

HN
CH3

(iii) (2½ marks) Compound E can also be converted to the homologue G. Complete the reaction
scheme below by filling in the missing structures and reagents in the boxes provided.

(iv) (2 marks) Rank compounds E, F and G from most to least basic.

Justify your choice.

Page 6 of 16
Question/Answer Booklet CHEM 110

ID:______________________________________
QUESTION 5 (13 marks)
On the reaction scheme below:
(a) (½ mark) Circle the appropriate classification for compound Q.
(b) (1 mark) Give the systematic name for compound R.
(c) (6 marks) In the boxes on the reaction arrows give the ‘reagents’ required.
(d) (5½ marks) Draw, in the boxes provided, the structures of compounds used/formed.

major minor

conc.
H2SO4
Mg, 1.
Cl ether

OH
2. H3O+
Q
1o / 2o / 3o

1. O O
2. H3O+
OH H SOCl2
OH

excess
CH3OH/H+
CN

NCH3

H O
1.
R OH 2.
OEt

1. LiAlH4
2. H3O+ Br2
FeBr3
name:______________________

Page 7 of 16
Question/Answer Booklet CHEM 110

ID:______________________________________
QUESTION 6 (8 marks)
(a) Compound S has molecular formula C11H16O. Compound S has no absorptions in the IR spectrum
between 3700-3200 cm-1.
(i) (1 mark) Calculate the double bond equivalents present in S. ________________
Show working:

(ii) (1 mark) There are 8 signals in the proton decoupled 13C NMR spectrum of compound S.
What does this indicate?

(iii) The 1H NMR compound S is shown below along with some tabulated data for the 5 signals
(working from right to left).

Signal: Signal: Signal: lines

position area observed
1.1 6H 2 lines
2H 3 lines
2H 3 lines
1H 7 lines
5H 1 line

(iv) (1 mark) Complete the signal position

column for the remaining 4 signals.

(v) (5 marks) Determine the structure of compound S.

Show how all the spectroscopic information given fits your answer.

Compound S

Page 8 of 16
Question/Answer Booklet CHEM 110

ID:______________________________________
QUESTION 7 (12 marks)

(a) The chemical structures of L-alanine (Ala) and

L-serine (Ser) are shown right.

(i) (1½ marks) Complete the structure of the Ala – Ser dipeptide on the structure below.

O H
C C
C N
H
H

(ii) (½ mark) The type of protein secondary structure that aligns in a cylindrical
shape is called a(n) ___________________.

(b) The pKa values for alanine are as follows pKa1 = 2.35 and pKa2 = 9.87.

(i) (½ mark) pKa1 is the pKa of the -CO2H / -NH3+ / -NH2 functional group.
(circle as appropriate)

(ii) (1 mark) Draw the zwitterionic form of alanine in the box

provided.

(iii) (1 mark) In what pH range will the zwitterion be the MAJOR

species?

(c) Radical oxidation can cause significant damage to proteins.

(i) (½ mark) Define the term ‘radical’ in the context of chemistry.

(ii) (1 mark) What is the key property of radical reactions that allows radicals to cause extensive
biological damage, even at very low concentration?

Office use only

P9

/6
Page 9 of 16
Question/Answer Booklet CHEM 110

ID:______________________________________
QUESTION 7 Cont.
(d) The Fischer projections of three hexoses, A, B and C are shown below.
CHO CHO CHO
H OH HO H HO H
H OH H OH HO H
HO H H OH H OH
HO H H OH H OH
CH2 OH CH2 OH CH2 OH

D E F

(i) (½ mark) What is the relationship between sugars D and E? ____________________.

(ii) (½ mark) What is the relationship between sugars D and F? ____________________.

(iii) (½ mark) Which sugar(s) are in the D-configuration? _________________________.

(iv) (2 marks) Complete the Haworth projection for sugar F, right.

(v) (1 mark) This Haworth projection shows the ______ anomer.

Justify your choice.
O OH

(e) Two reactions of glucose are shown below.

(1½ marks) In which reaction(s) is the sugar acting as the nucleophile?

Justify your choice.

Office use only

P9 P10 Q7

/6 /6 /12
Page 10 of 16
Question/Answer Booklet CHEM 110

ID:______________________________________
QUESTION 8 (12 marks)
(a) A proposed mechanism for the reaction of a primary alcohol with SOCl2 is shown below.

(i) (1 mark) Write the equation for the overall reaction.

(ii) (1½ marks) Circle any reactive intermediates in the mechanism above.

(iii) (1 mark) This reaction is proceeding via an SN1 / SN2 / E1 / E2 mechanism.

Circle one
Justify your choice with reference to the mechanism above.

(vi) (2 marks) The rate law for this reaction is rate = k[ROH][SOCl2]. Show how this can be derived
from the mechanism above.

(v) (1½ marks) One set of experimental rate data for this reaction is given below. Calculate the rate
constant (k) for this reaction.
[ROH] [SOCl2] Rate
-1 -1
0.0171 mol L 0.0244 mol L 1.22 x 10-4 mol L-1 s-1

Office use only

P11
Page 11 of 16 /7
Question/Answer Booklet CHEM 110

ID:______________________________________
QUESTION 8 (continued)
(b) The elimination of many pharmaceutical compounds from the bloodstream follows first order
kinetics. The rate constant for the elimination of ibuprofen at 37 oC is 9.67 x 10-5 s-1.

(i) (2 marks) The initial concentration of ibuprofen in a patients’ blood plasma was measured to be
1.21 x10-4 mol L-1. What will the concentration be after 3 hours?

The rate at which a drug is eliminated is often given in terms of the drug’s half-life, instead of as a rate
constant. Salbutamol (Ventolin) has a half-life of 96 minutes.

(ii) (1 mark) How long will it take for the blood concentration of salbutamol to drop to 0.125 x its
original level?

(iii) (½ mark) For a first order reaction, the rate of reaction:

increases / stays the same / decreases over time.
(circle as appropriate)

(iv) (½ mark) For a first order reaction, the half-life of the reaction:
increases / stays the same / decreases over time.
(circle as appropriate)

(c) (1 mark) Suggest one way you could increase the rate of a reaction that:

(i) Involves a change to the rate constant (k) for the reaction.

(ii) Does NOT involve a change to the rate constant (k) for the reaction.

Office use only

P11 P12 Q8

Page 12 of 16 /7 /5 /12
Question/Answer Booklet CHEM 110

ID:______________________________________
QUESTION 9 (12 marks)
(a) 25 mL of an unknown acid is titrated against 0.012 mol L-1 NaOH. The resulting titration curve is shown
below.

(i) (½ mark) What volume of NaOH was

required to reach the equivalence point? ______mL

(ii) (1½ marks) What is the concentration of the original acid

solution?

(iii) (½ mark) Indicate the buffer region on the graph, right.

(iv) (1 mark) What is the pKa of the unknown acid? ________

Justify your answer.

(v) (1 mark) Give two pieces of information from the titration curve that tell you the unknown acid
is a weak acid.

The table below gives data for three common indicators.

Indicator pKin Acid form Base form

methyl red 5.0 red yellow
thymol blue 8.9 yellow blue
Alizarin 11.7 red purple

(vi) (1 mark) Which indicator is most suitable for the titration described above?
Justify your choice.

(vii) (½ mark) What colour will this indicator be at the start of the titration? ___________

Office use only

P13

/6
Page 13 of 16
Question/Answer Booklet CHEM 110

ID:______________________________________
QUESTION 9 (cont.)
(b) Sodium hypobromate (NaBrO) is the salt of a weak acid (HBrO, pKa = 8.70).

(i) (1 mark) Give the chemical equation for sodium hypobromate dissolving in water.

(ii) (1 mark) Identify two conjugate acid/base pairs in your reaction above.

_______________________ and ____________________

(iii) (3 marks) Calculate the pH of a 0.015 mol L-1 solution of sodium hypobromate.
Clearly state any assumptions that you make.

(iv) (1 mark) Hypochlorous acid has a pKa of 7.46. Is sodium hypochlorate more or less basic than
sodium hypobromate?
Justify your choice?

Office use only

P13 P14 Q9

/6 /6 /12
ATTACHMENT FOLLOWS
Page 14 of 16
Question/Answer Booklet CHEM CHEM110
ATTACHMENT

CHEM 110 SPECTROSCOPY DATA SHEET

IMPORTANT INFRARED ABSORPTION REGIONS
(STRETCHING FREQUENCIES)
Bond Present   (cm1)
OH (alcohol, phenol) 3700 – 3200
(carboxylic acid) 3600 – 2500 (broad)
NH 3500 – 3100
CH 3100 – 2800
C=O 1850 – 1600
C=C (aliphatic) 1680 – 1600
(aromatic) 1620 – 1550
CO 1250 – 1050 (less definitive)

1
H NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY (1H NMR)
Approximate Chemical Shifts () of Hydrogens in Organic Compounds
Hydrogens (H) in various 
chemical environments (ppm downfield from TMS)
(CH3)4Si (TMS) 0
R2CHCR 1.0 (approx.)

R2CHCZ* 1.0 - 2.0

Hydrogens bonded
to sp3 carbon R2CHC=C 1.6 - 1.9

R2CHC=O 2.0 - 2.5

R2CHAr 2.5 - 3.5

R2CHX** 2.0 - 3.7
R2CHO 3.3 - 4.5

HC=C 4.5 - 7.0

Hydrogens bonded
HAr 6.5 - 8.0
to sp2 carbon
HCR 9.5 - 10.0
O
HOR 3.0 - 6.0 (variable)
Hydrogen bonded HOCR 10.5 - 12.0
to oxygen
O

Notes: **X = Cl, Br, I or the N of an amine *Z = O, C=O, or X (as defined above)
R = H or alkyl group

Page 15 of 16
Question/Answer Booklet CHEM CHEM110
ATTACHMENT
Useful Equations and Constants

A = εlc
DBE = ½(2n4 + n3 – n1 + 2)
1 1

pH = -log10[H3O+]
2
/

1
Kw = [H3O+] x [OH-] = 1 x 10-14 /

1 1
ln

Page 16 of 16