Professional Documents
Culture Documents
TIME: 3 HOURS
INSTRUCTOR: Dr Reg Mitchell
IN THIS EXAM THERE SHOULD BE 26 PAGES (check this)
(includes THIS COVER SHEET) + A BLUE SIGNATURE SHEET
[NOTE PAGES ARE PRINTED BOTH SIDES]
YOU ALSO SHOULD HAVE
A GREEN COMPUTER SHEET
A YELLOW ANSWER SHEET PACK (2 sheets, 4 sides)
A PINK DATA SHEET PACK (3 sheets, 6 sides)
Report to the invigilator if any of these are missing now
ANSWER QUESTIONS 1-54 [1.5 marks each] ON THE GREEN COMPUTER SHEET
WITH A PENCIL = 81 marks;
ANSWERS THAT REQUIRE YOU TO DRAW A STRUCTURE, GIVE A FORMULA,
ETC, HAVE LETTERS AS QUESTION #’S. ANSWER THESE ON THE YELLOW
SHEETS PROVIDED. USE A PEN OR PENCIL, BUT MAKE SURE YOUR ANSWER IS
READABLE = 80 marks. Total Marks = 161; Total minutes = 180!
Q1
Q2
Q3
Q4
| | | | | | | | | |
34 30 26 22 18 17 16 9 8 7 00's cm-1
CHEM 213 2006 Final Exam Page 3
C N COCl NH2
CHO
CHO
Scale | | | | | |
1700 1220 1050 860 770 690 cm-1
In its mass spectrum, A showed an M+ at 142 and an M+2 peak at 144 in a 3:1 ratio. As
well an 8% (M+1) peak at 143 was seen. High resolution MS indicated only one oxygen
atom to be present in a molecule of A. Fragment peaks were seen at m/z 15, 31 and 35.
Determine the molecular formula for A and write it on the yellow answer sheet [2 marks]
Determine the structure of A and draw it on the yellow answer sheet -show all H’s [5
marks]
CHEM 213 2006 Final Exam Page 4
OH
OH
O
HO
Testosterone Estradiol
The structures of the principal male and female sex hormones, testosterone and estradiol
are shown above.
Using the wavelength choices (nm)
(a) 315-325 (b) 270-280 (c) 250-260 (d) 210-215 (e) 200-205 (f) 180-190
and ε choices
(a) 10,000 (b) 1000 (c) 100 (d) 30 (e) 1
12 How would you expect the spectrum of estradiol to change on addition of NaOH
CHEM 213 2006 Final Exam Page 5
Compound B, the smelly component emitted by pulp mills, showed M+ at m/z 62 and also
peaks at 63 and 64 in a 100:2.2:4.4 ratio. Fragment peaks were seen at m/z 15, 32 and 47.
Determine the structure of compound B and write in the space provided on the yellow
answer sheet. [3 marks]
19 What would you see in the 13C NMR spectrum (not decoupled) of compound B [no
spin active nuclei is present other than those you are familiar with]
(a) s (b) d (c) t (d) q (e) 5 (f) 6 (g) 7 (h) dq (i) d7 (j) tq
CHO CHO
1 2
Cl CH3 Cl
CH3
D D D
D
H Cl H
Cl H CH3
H H
Cl H Cl H
CH3 H
CHO CHO
3 4
CH3 Cl CH3
Cl
D D D
D
H Cl H
Cl H CH3
H CHO
Cl H Cl H
CH3 H
CHO H
5 6
Cl CH3 Cl
CH3
D D D
D
H Cl H
Cl CH3 CH3
H CHO
Cl Cl H
H CHO H
H H
8
7
CHEM 213 2006 Final Exam Page 8
#H’s 1 1 1 1 1 3 3
approx δ 10 5 3 2 1
(scale distorted)
CHEM 213 2006 Final Exam Page 9
COSY SPECTRUM OF C
#H’s 1 1 1 1 1 3 3
approx δ 10 5 3 2 1
(scale distorted)
CH3 O OCH 3
Ha H
Hb
23 What will be the spin system for the aromatic protons at 60 MHz
24 What will be the spin system for the aromatic protons at 600 MHz
CHEM 213 2006 Final Exam Page 11
25 At what frequency (Hz) would you expect to find the O-H stretch
(a) 4.7 x 108 (b) 5 x 108 (c) 5.3 x 108 (d) 5.3 x 109 (e) 4.7 x 1011
(f) 1 x 1014 (g) 7.5 x 1014 (h) 1 x 1015 (i) 7 x 1015 (j) 3 x 1018
Using:
(a) 0 (b) 1 (c) 2 (d) 3 (e) 4 (f) 7 (g) 17 (h) 18 (i) 21 (j) 24
Then using
(a) s (b) d (c) t (d) q (e) ddd (f) dt (g) dq (h) 5 lines (i) 6 lines (j) 7 lines
29 How will the 31P NMR (see data sheet) spectrum appear at low temperature
30 How will the 1H NMR spectrum appear at room temperature
31 How will the 1H NMR spectrum appear at low temperature
The transition from v=0, J=3 to v=1, J=2 of one of the fundamental vibrations of CO2 in its
ir spectrum is found at 2338 cm-1, while the transition from v=0, J=1 to v=1, J=2 is found at
2358 cm-1
36 What is the energy for the v=1, J=0 level for this vibration (kJ mole-1)
(a) 0.14 (b) 0.28 (c) 4.2 (d) 14 (e) 28
(f) 42 (g) 55 (h) 56 (i) 68 (j) 70
37 In nature, CO2 exists as 12CO2, CO2 and 14CO2. What will be the order for ν0.
13
12
(a) C < 13C < 14C (b) 13C < 14C < 12C (c) 14C < 13C < 12C (d) 14C < 12C < 13C
(e) 12C < 14C < 13C (f) 13C < 12C < 14C
39 If the spin quantum number for D is 1, how will the 13C NMR spectrum of DCCl3
appear
(a) 1:2:1 triplet (b) 1:1:1 triplet (c) 1:3:3:1 quartet (d) 1:1:1:1 quartet
(e) 1:4:1 triplet (f) 1:1 doublet (g) 1:3:1 triplet (h) 3:1 doublet
(i) 1:3 doublet (j) singlet
40 At UVIC, we use the 360MHz proton magnet to observe deuterium spectra. What
frequency (MHz) will the probe operate at to observe 2D (pink data sheet)
(a) 300 (b) 120 (c) 100 (d) 278 (e) 66.7
(f) 1080 (g) 53 (h) 27 (i) 11 (j) 9
CHEM 213 2006 Final Exam Page 14
Y
CH3 O CH2 Cl
Pt
Cl H
89
Y has a spin of 1/2 and is 100% abundant.
Assume 1JPt,H = 600 Hz, 2JPt,Y = 100 Hz, 2JPt,H = 60 Hz, 2JY,H = 50 Hz, 3JY,H = 15 Hz,
4
JPt,H = 3 Hz and all 5JX,Z are zero. Assume normal H-H couplings.
using:
(a) t8 (b) 8 (c) dt (d) q (e) td7 (f) dt8 (g) dtd7 (h) dtq (i)ddt (j) tq
43 How will the 1H spectrum of the Pt-H appear for a molecule that only contains 195Pt
44 How will the 89Y spectrum appear for a molecule that does not contain 195Pt
45 How will the 89Y spectrum appear for a molecule that only contains 195Pt
46 What will be the width (Hz) of the 195Pt spectrum (i.e. distance in Hz between far left
hand and far right hand lines)
(a) 2118 (b) 820 (c) 1280 (d) 2460 (e) 920
(f) 960 (g) 1059 (h) 1080 (i) 609 (j) 618
CHEM 213 2006 Final Exam Page 15
47 For the compound F3C-PtHCl2, if 1JPt,H = 600 Hz, 2JPt,F =100Hz and 3JH,F = 16 Hz,
and if the proton spectrum shows the most upfield line is 2324 Hz shielded from
TMS, what is the chemical shift of this H. The spectrum was run at 400 MHz
(a) -5.00 (b) -4.00 (c) +5.00 (d) +4.00 (e) -5.81
(f) +5.81 (g) -4.20 (h) +4.20 (i) -5.20 (j) +5.20
48 How many Hz separate the tallest peaks in the natural abundance proton spectrum
of this compound
(a) 8 (b) 16 (c) 32 (d) 48 (e) 50 (f) 100 (g) 300 (h) 600
49 What is the spin system of this compound with a spin active platinum
(a) AB3X (b) ABB’B”X (c) AM3X (d)AMM’M”X
(e) AX3 (f) AXX’X” (g)ABCMX
For the fluorines of the compound referred to in Q47, what would be the intensities of the
lines in the real fluorine spectrum of an actual natural abundance sample - write your
answer using the format 1:1:2:1etc on the yellow answer sheet [3 marks]
50 If one had a spectrometer which could measure 13C, 19F, 195Pt and 1H on the same
probe using the same magnetic field strength, in which order would the nuclei
appear to resonate as the frequency of the probe was increased
COMPOUND E, C4H5BrO2
The IR spectrum:
| | |
3400 2400 1690 cm-1
13
C NMR:
170s 137s 131t 39t
CHEM 213 2006 Final Exam Page 17
1
H NMR Spectrum
Write your proton integration values on the yellow answer sheet in the place provided
in the form a:b:c:d [2 marks]
Draw your structure for compound E on the yellow answer sheet in the place provided
[8 marks]
CHEM 213 2006 Final Exam Page 18
Compound F, C9H9Br
IR:
13
C NMR spectrum: 136s 134d 129d 128d 127d 126d 36t
1
H NMR Spectrum [300MHz]
Integrations 5 :1:1 : 2
Multiplicity m d dt d
* = overlapping dt
Draw your structure for compound F on the yellow answer sheet in the place provided
[8 marks]
CHEM 213 2006 Final Exam Page 19
Compound G, C4H11O3P
Phosphorus is pentavalent in this compound.
13
C NMR Spectrum: 62td 16qd
13
C{31P} NMR Spectrum: 62t 16q
IR Spectrum:
| | |
2400 ~1300 ~1000 cm-1
Ignore the small bands at 3400 cm-1, and (for now) the band at 2400 cm-1.
Consider what the oxygens must be.
1
H NMR Spectrum [300MHz]:
<----------------------->
Integrations: 1 : 4 : 6
Multiplicity d ~qd t
CHEM 213 2006 Final Exam Page 20
Draw your structure for compound G on the yellow answer sheet in the place provided
[10 marks]
Also draw on the yellow answer sheet in the place provided, the vibration you think is
responsible for the 2400cm-1 peak in the IR spectrum [1 mark]
CHEM 213 2006 Final Exam Page 21
COMPOUND H, C10H14O
The IR spectrum :
|
3400 cm-1
Integrations: 1 :1:1 : 1 : 1: : 3 : 6
Multiplicities d d s s 7 s d
The peak at δ 4.8 exchanges with D2O. Only the * 6.5 singlet is significantly shielded.
CHEM 213 2006 Final Exam Page 22
From the above data, you should be able to get two isomers as possible structures.
Draw both of these isomers now on the yellow answer sheet. [12 marks].
When you have finished the exam, come back and using the data below, refine your answer
to a single isomer which you should then circle [5 marks].
Part of the HMQC (J=10 Hz) [Longe range Hetcor] spectrum of compound H
δ 4.8 3.2 2.2 1.2
Now circle the correct isomer for compound H on the yellow answer sheet in the space
provided. [ 5 marks]
CHEM 213 2006 Final Exam Page 24
COMPOUND I gave a high resolution mass spectrum molecular weight of 181.073, which
indicated one of the following formulae
C H N O
6 13 - 6
7 9 4 2
9 11 1 3
12 9 2 -
Determine the molecular formula for compound I and enter it on the yellow answer sheet
in the space provided. [1 mark]
Integrations 1 : 1 : 3 : 3:3
CHEM 213 2006 Final Exam Page 25
Using the observed chemical shifts, you should be able to determine a structure for
compound I.
You can confirm it with the HMQC spectra below:
Protons
carbons
Protons
carbons
Determine the structure of compound I and draw it on the yellow answer sheet
[12 marks]
CHEM 213 2006 Final Exam Page 26
-END-
FINAL EXAMINATION, DECEMBER 2006 YELLOW ANSWER SHEETS
CHEMISTRY 213 - F01 PRACTICAL SPECTROSCOPY
LAST NAME:
REGISTRATION NUMBER:
{Page 15} Relative intensities of the fluorine lines for compound of question 47 [3 marks] =
[format required = 1:b:c: etc] =
{Page 20} STRUCTURE FOR COMPOUND G (show all H’s) [10 marks]
{Page 20} What vibration is responsible for the 2400 cm-1 peak [ 1 mark]
{Page 22} TWO ISOMERS FOR COMPOUND H (show all H’s) [12 marks]
{Page 25} STRUCTURE FOR COMPOUND I (show all H’s) [12 marks]
PINK DATA SHEETS FOR USE IN CHEM 213
EJ = h2J(J+1)/8π2I
ν = (1/2π)(k/μ)1/2
ν = (γ/2π)Bo
NU/NL = e-x where x = ΔE/RT
I = m1m2r2/(m1+m2)
1 13 2 11 19 31 195 29
NUCLEUS H C D B F P Pt Si
MAGNETOGYRIC RATIO (() 27 7 4 9 25 11 6 5
I (spin quantum number) 1/2 1/2 1 3/2 1/2 1/2 1/2 1/2
% ABUNDANCE 100 1 0.02 80 100 100 34 5
Isotopic masses:
( M + 1) % = 11
. x + 0.016 y + 0.38 z
. x) 2
(11 + (0.016 y ) 2 + (0.38 z) 2
( M + 2) % = + 0.2 w
200
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