MUHIMBILI UNIVERSITY COLLEGE OF HEALTH SCIENCES

SCHOOL OF PHARMACY
SEMESTER SIX CA TEST – JUNE 2006
MEDICINAL CHEMISTRY -SPECTROSCOPY
DATE: Tuesday, 16 April 2024TIME 10:00-12.30 am

Answer all questions in the answer sheets provided. Any answer made on this question paper shall
not be marked.
SECTION A ATTEMPT ALL QUESTION
MULTIPLE CHOICE QUESTIONS (1 points each)

A suitably calculated mark shall be deducted for a Guesswork leading to incorrect responses.

1. Which of the following absorption bands can be used to distinguish between CH3-
C(=O)-CH3 and CH3-C(=O)-H?
a. 3300 cm-1
b. 2950 cm-1
c. 1380 cm-1
d. 1700 cm-1
e. 2700 cm-1
The most significant difference between the IR spectrum of a ketone and aldehyde is the
aldehyde C–H stretch at 2700 cm-1.
2. In which order are the various parts of a mass spectrometer found?
a. sample - ionization chamber - collector - magnet - recorder
b. ionization chamber - sample - collector - magnet - recorder
c. ionization chamber - sample - magnet - collector - recorder
d. sample - ionization chamber - magnet - collector -recorder
e. ionization chamber - magnet - sample - collector – recorder
3. Which of the following solvents is the best to use when taking an IR spectrum
a. methanol
b. benzene
c. CCl4
d. TMS
e. ethanol
4. What does IR spectroscopy allow us to determine?
a. the molecular weight of a compound
b. the kinds of bonds in a compound
c. the molecular formula of a compound
d. the number of carbons in a compound
e. the carbon–hydrogen framework of a compound
5. Which of the following is not true about electromagnetic radiation?
a. Energy is directly proportional to wavenumber.
b. Energy is directly proportional to the velocity of light.
c. Frequency is directly proportional to wavenumber.
d. Frequency is directly proportional to wavelength.
e. Energy is inversely proportional to wavelength.
6. Which of the following C–H bonds exhibits a stretch at the greatest wavenumber?

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 a. C–H of a methyl group
b. C–H of a benzene ring
c. C(=O)-H
d. C=C-H
e. CC-H
7. Which of the following compounds has a vibration that is infrared inactive?
a. a: carbon monoxide
b. b: ethyne
c. c: ethene
d. d: carbon dioxide
e. b, c, and d
Symmetrical molecules will have infrared inactive vibrations
8. Which alkene is formed from a McLafferty rearrangement of methyl pentyl ketone?
a. propene
b. methylpropene
c. 2-butene
d. 1-butene
e. ethane
9. Which of the following will exhibit no IR absorption band between 1780–1650 cm-1 or
between 3400–3100 cm-1?
a. a: an ether
b. b: an aldehyde
c. c: an amide
d. d: a terminal alkyne
e. a and c
10. Which of the following is not a true statement?
a. Electromagnetic energy with wavenumber 100 cm-1 is higher in energy than
electromagnetic energy with wavenumber 1000 cm-1.
b. The functional group region is higher in energy than the fingerprint region.
c. Rock, scissor, wag, and twist are types of bending vibrations.
d. It requires more energy to stretch a bond than to bend it.
e. High frequencies, large wavenumbers, and short wavelengths are associated
with high energy.
11. Which of the following is the base peak in the mass spectrum of 2-bromo-2-
methylpropane?
a. 57
b. 43
c. 136
d. 138
e. 15
12. What part of an IR spectrum is called the functional group region?
a. 4000–3000 cm-1
b. 4000–2000 cm-1
c. 4000–1000 cm-1
d. 3000–1000 cm-1
e. 2000–400 cm-1
13. How can the mass spectrum of a hydrocarbon exhibit an M + 2 peak?
a. from 13C and 2H
b. from 13C and 1H

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 c. from 2H
d. from 12C and 2H
e. from 13C
In a hydrocarbon, the only heavy isotopes are 13C and 2H. Since each only contributes
one additional mass unit, two are needed to get M + 2.
14. What determines the intensity of an IR absorption?
a. the change in shape during vibration
b. the change in bond length during vibration
c. the change in dipole moment during vibration
d. the change in polarizability during vibration
e. the molecular weight of the bonding atoms
15. Which of the following is not true about the M + 1 peak?
a. a: It is one unit higher than the molecular ion peak.
b. b: It is one unit higher than the base peak.
c. c: It is one unit higher than the parent peak.
d. d: It is one unit higher than the most intense peak.
e. b and d
Parent peak is the same as molecular ion.
16. Which two peaks will tell you whether an unknown compound contains bromine?
a. M – 2 and M
b. M – 1 and M
c. M – 2 and M + 2
d. M and M + 2
e. M and M + 1
17. Which of the following is a true statement?
a. Stretching vibrations occur at longer wavelengths than bending vibrations.
b. Stretching vibrations occur at higher frequencies than bending vibrations.
c. Stretching vibrations occur at larger wavenumbers than bending vibrations.
d. a and b
e. b and c
18. Which of the following shows the correct relative positions of bonds in terms of
decreasing wavenumber?
a. CC > O–H > C=C > C=O
b. O–H > C=C > CC > C=O
c. O–H > C=O > CC > C=C
d. O–H > CC > C=O > C=C
e. CC > C=C > O–H > C=O
19. Which of the following absorption bands can be used to distinguish between
CH3CH2C(=O)-NH-CH3 and CH3C(=O)-N(CH3)2?
a. ~3400 cm-1
b. ~2950 cm-1
c. ~1450 cm-1
d. ~1700 cm-1
e. ~3100 cm-1
20. Which of the following compounds will show the following m/z values in its mass
spectrum? 41, 43, 57, 87, 101, 116
a. butyl propyl ether
b. CH3-C(=O)-CH2CH3
c. 1-bromopropane
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 d. CH3CH2OH
e. 2-chloropropane
21. Which of the following is not a true statement?
a. The intensitity of an absorption band depends on the size of the dipole moment
change associated with the vibration.
b. The more polar the bond the less IR radiation it will absorb.
c. The intensity of an absorption band depends on the number of bonds
responsible for the absorption.
d. It takes more energy to stretch a bond than to bend it.
e. For a vibration to cause absorption of IR radiation, the dipole moment of the
molecule must change when the vibration occurs.
22. Which of the following is not a true statement?
a. If "a" is more shielded than "b," "a" will appear farther upfield than "b."
b. Downfield is to the left in an 1H NMR spectrum.
c. Signals occurring at low frequencies will have small chemical shift values.
d. If "a" is less shielded than "b," "a" will require a greater frequency than "b."
e. The chemical shift of hydrogen will vary with the operating frequency of the
NMR spectrometer.
23. What is the ratio of peak intensities in a clean triplet?
a. 3:1:3
b. 1:2:1
c. 2:1:2
d. 1:1:1
e. 1:3:1
24. What major piece(s) of information can be obtained from 1H NMR?
a. Magnetic moment, Chemical environment, Type of protons present,
Connectivity, Integration
b. Magnetic moment, Chemical environment, Precession frequency, Type of
protons present, Connectivity, Integration
c. Connectivity, Integration, Chemical environment, and Type of protons present,
d. Chemical environment, Precession frequency, Type of protons present,
Connectivity, to a lesser extent the Magnetic moment
e. To a greater extent Chemical environment, Magnetic moment, Precession
frequency, Type of protons present and Integration
25. Why to alkenes protons appear downfield in a 1H spectrum?
a. The double bond in an alkene is stronger.
b. Due to the anisotropic field on the  electrons in the double bond.
c. The carbons involved in the double bond of an alkene are sp2 hybridized.
d. Due to the possible spin states of an alkene.
e. b and c
f. all of the above reasons contributes high delta values observed
26. Straight chain methyl protons are generally observed as a …
a. doublet.
b. singlet.
c. triplet.
d. not observed in a simple 1H spectrum
27. A small, broad singlet is observed at 4.8 ppm, the compound is most likely classified
as …
a. a carboxcylic acid or aldehyde.

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 b. an amine or alcohol.
c. an ether.
d. an alcohol or an hemi acetal
e. an amine or an acetal
28. Do diastereotopic groups give rise to the same chemical shifts in 1H NMR?
a. Yes and no it all depend on the types of isomers isolated.
b. Yes,diastereotopic groups are always equivalent.
c. Yes, because they are enantiomers.
d. No, because they produce enantiomers.
e. No, because diastereotopic groups are not equivalent groups.
29. How does the energy difference in NMR compare with the energy difference of
molecules at room temperature?
a. There is no difference in energy, thus making signals much easier to obtain.
b. The applied magnetic field creates an energy difference, promoting more nuclei
to the –1/2 spin state.
c. The energy difference is small and is not a factor in NMR.
d. The applied magnetic field creates an energy difference, promoting more nuclei
to the +1/2 spin state.
e. None of above
f. All of the above
30. What would the 1H NMR spectrum of 1,3-cyclohexadiene look like?
a. 3 signals: a doublet and two triplets
b. 3 signals: a singlet, a multiplet, and a doublet
c. 3 signals: a triplet, a multiplet, and a doublet
d. 3 signals: a triplet, a multiplet, and a doublet of doublets
e. 3 signals: two doublets and a multiplet
The molecule has a mirror plane of symmetry. The methylene would be a doublet. One vinyl
proton would be a doublet and the middle one would be a multiplet.
31. Which of the following is not a true statement?
a. Diethyl ketone shows two signals in its 1H NMR spectrum.
b. Deshielded protons are located farther downfield in an NMR spectrum.
c. A C-2 hydrogen of 1-chlorobutane shows a signal farther downfield than a
signal for a C-1 hydrogen.
d. Dimethyl ketone shows two signals in its 13C NMR spectrum.
e. Protons that are deshielded require a higher frequency to sense the effective
magnetic field.
The two methyl groups are equivalent. The carbonyl carbon is the second signal.
32. Which of the following describes the 1H NMR spectrum of CH3CH2-CH(=O)?
a. two doublets and a triplet
b. a singlet, a doublet, and a quartet
c. a singlet, a triplet, and a doublet of doublets
d. a singlet, a triplet, and a quartet
e. two triplets and a multiplet
The methyl and aldehyde C–H are triplets, while the methylene would be a multiplet
33. Which of the following is true?
a. a: More shielded protons require a lower frequency to come into resonance.
b. b: Protons in electron-rich environments are less shielded.
c. c: B(effective) = B(applied) – B(local)
d. d: Electron-withdrawing groups shield neighboring atoms.

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 e. a and c
34. Which set of protons in 1-bromo-5-fluoropentane has the smallest value for its
chemical shift?
a. It is the protons on C-1.
b. It is the protons on C-3.
c. It is the protons on C-4.
d. It is the protons on C-5.
e. It is the protons on C-2.
The protons furthest from the electronegative elements will have the smallest chemical shift.
35. What would the 1H NMR spectrum of nitrobenzene, C6H5-NO2, look like?
a. It would have 2 signals: a doublet and a triplet.
b. It would have 3 signals: a doublet and 2 triplets.
c. It would have 3 signals: a doublet, a doublet of doublets, and a triplet.
d. It would have 3 signals: 2 doublets and a triplet.
e. It would have 1 unsplit signal.
The ortho protons would give a doublet, the meta would be a doublet of doublets, and the
para would be a triplet.
36. How many signals would you expect to see in the 1H NMR spectrum of trans-1,2-
dichlorocyclopropane?
a. 1
b. 2
c. 3
d. 4
e. 5
The molecule has a rotation axis, so both methine protons are equivalent, as are both
methylene protons.
37. Which of the hydrogens in CH3OCH2-C6H5-CH3 would show the signal with the
lowest value for its chemical shift? (Consider the special case that the two substituents
on the benzene ring are at the 1- and 4-positions.)
a. the hydrogens of the methyl group bonded to the oxygen
b. the hydrogens of the methyl group bonded to the benzene ring
c. the hydrogens on the benzene ring adjacent to the ether group
d. the hydrogens of the methylene group
e. the hydrogens on the benzene ring adjacent to the methyl group
The oxygen will have a stronger deshielding effect than the benzene ring.
38. Identify the compound with molecular formula C9H12 that has a triplet at 1.21 ppm
(3H), a singlet at 2.30 ppm (3H), a quartet at 2.60 ppm (2H), and a singlet at 7.04 ppm
(4H).
a. 1,3,5-trimethylbenzene
b. propylbenzene
c. 1-ethyl-4-methylbenzene
d. 1,2,4-trimethylbenzene
e. isopropylbenzene
39. In an FT-IR spectrum, how can you tell the difference between an aldehyde and a
ketone when both are carbonyl containing compounds?
a. One requires more than one spectroscopic technique to be able to distinguish
them
b. The aldehyde C=O stretch will absorb at a much lower frequency that the
ketone C=O stretch.

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 c. The aldehyde has a characteristic weak doublet in the C-H stretching region.
d. The ketone C=O stretch is always less intense than the aldehyde C=O stretch.
e. The ketone group has two characteristic C=O stretching bands.
f. All of the above
40. Compared to a carbon–carbon double bond, a carbon–carbon triple bond
a. is shorter, stronger, and stretches at a greater wavenumber.
b. is longer, stronger, and stretches at a greater wavenumber.
c. stretches at the same wavenumber since the same atoms are involved.
d. is shorter, weaker, and stretches at a greater wavenumber.
e. is shorter, stronger, and stretches at a lower wavenumber.
41. Which of the following compounds will have its carbon–oxygen double bond stretch
at the lowest wavenumber?
a. CH3-C(=O)-CH2OCH3
b. CH3-C(=O)-CH3
c. CH3-C(=O)-OCH3
d. CH3-C(=O)-H
e. H-C(=O)-H
42. Which part of the IR spectrum is called the "fingerprint region"?
a. 3000–2000 cm-1
b. 3000–1000 cm-1
c. 2000–1000 cm-1
d. 2000–600 cm-1
e. 1000–600 cm-1
43. Which of the following absorption bands could be used to distinguish between 2-
hexanone and cyclohexanone?
a. 1700 cm-1
b. 2700 cm-1
c. 1380 cm-1
d. 1450 cm-1
e. 2950 cm-1
44. At what wavenumber will the carbon–hydrogen bond formed by hydrogen attached
to an sp2 carbon show a stretching vibration?
a. ~2100 cm-1
b. ~3300 cm-1
c. ~3600 cm-1
d. ~3050 cm-1
e. ~2950 cm-1
45. Which of the following is not a true statement?
a. The intensity of an absorption band depends on the number of bonds
responsible for the absorption.
b. It takes more energy to stretch a bond than to bend it.
c. The more polar the bond the less IR radiation it will absorb.
d. The intensity of an absorption band depends on the size of the dipole moment
change associated with the vibration.
e. For a vibration to cause absorption of IR radiation, the dipole moment of the
molecule must change when the vibration occurs.
46. Which of the following bonds will show an absorption band at the greatest
wavenumber?
a. N–H

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 b. C=O
c. C=C
d. C–O
e. C–H
47. What types of absorptions are helpful in determining the type of substitution on an
aromatic compound and what range are these found in?
a. Fundamental; 1000-1300 cm-1
b. Fermi resonance; 2800-3500 cm-1
c. Overtones; 1650-2000 cm-1 and 690-880 cm-1
d. C=C stretching; 1400-1700 cm-1
e. Both a and d
f. All of the above
48. Which of the following statements describes alpha-cleavage?
a. It is homolysis of a C–C bond that is one sigma bond removed from the carbon
that is attached the radical cation.
b. It is homolysis of a C–C bond that is bonded to the carbon that is attached to
the radical cation.
c. It is heterolysis of a C–C bond that is one sigma bond removed from the carbon
that is attached the radical cation.
d. It is the removal of a hydrogen atom bonded to an alpha-carbon.
e. It is heterolysis of a C–C bond that is bonded to the carbon that is attached to
the radical cation.
49. In what region of the IR spectrum would you find an absorption band that would
distinguish between CH3-C(=O)-OCH2CH3 and CH3-C(=O)-CH2CH3?
a. 2900 cm-1
b. 3300–3100 cm-1
c. 1250–1050 cm-1
d. 1600–1500 cm-1
e. 1420–1380 cm-1
50. How can one differentiate between a N-H stretch and an O-H stretch in an IR
spectrum?
a. The N-H signal is less intense and narrow while the O-H signal is very intense
and broad.
b. The O-H signal is less intense and narrow while the N-H signal is very intense
and broad.
c. The N-H signal is at a much lower frequency than the O-H signal.
d. Unable to differentiate between the two.
e. Practically it does not bring sense to use IR data as differential
51. The mass spectrum of diisobutyl ether will have peaks at what m/z value?
a. 130 and 102
b. 130 and 101
c. 130 and 45
d. 130 and 57
e. 130 and 115
52. Which of the following will show an absorption band at the greatest wavenumber?
a. C=O
b. C–N
c. C=C
d. C–O

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 e. CC
53. Which of the following ketones can undergo a McLafferty rearrangement?
a. CH3-C(=O)-CH3
b. CH3CH2-C(=O)-CH2CH3
c. CH3CH2CH2-C(=O)-CH2CH3
d. CH3CH2-C(=O)-CH3
54. What is a molecular ion?
a. It is a compound that has gained an electron.
b. It is a compound that has gained a pair of electrons.
c. It is a compound that has an unpaired electron and a negative charge.
d. It is a compound that has lost an electron.
e. It is a compound that has lost a pair of electrons.
55. Which of the following sets of absorption bands would you expect to see in the IR
spectrum of C6H5-C(=O)-CH3?
a. ~1700 cm-1, ~1600 cm-1, ~1500 cm-1
b. ~2100cm-1, ~1600 cm-1, ~1500 cm-1
c. ~3300 cm-1, ~2700 cm-1, ~1200 cm-1
d. ~3100 cm-1, ~1600 cm-1, ~1100 cm-1
e. ~1700 cm-1, ~1600 cm-1, ~1000 cm-1
56. Which of the following is a true statement?
a. Shorter wavelengths and smaller wavenumbers are associated with higher
energy.
b. Longer wavelengths and higher frequencies are associated with higher energy.
c. Longer wavelengths and lower frequencies are associated with lower energy.
d. Smaller wavenumbers and higher frequencies are associated with lower
energy.
e. Larger wavenumbers and lower frequencies are associated with higher energy.
57. What is the effect of hydrogen bonding on the position and shape of an O–H stretch?
a. It is shifted to higher wavenumbers and remains sharp.
b. It is shifted to higher wavenumbers and broadens.
c. It is shifted to lower wavenumbers and broadens.
d. It stays at the same wavenumber and broadens.
e. It is shifted to lower wavenumbers and remains sharp
58. Which of the following is not a true statement?
a. A C=O stretch occurs at a greater wavenumber than a C–O stretch.
b. A C=C-H stretch occurs at a greater wavenumber than a CC-H stretch.
c. A C=N stretch occurs at a greater wavenumber than a C–N stretch.
d. A C=O stretch occurs at a greater wavenumber than a C=C stretch.
e. A C–H stretch occurs at a greater wavenumber than a C–H bend.
59. In what region of the 1H NMR spectrum would you find the signal for the acidic
hydrogen of a carboxylic acid?
a. 0–2.5 ppm
b. 2.5–5 ppm
c. 5–7.5 ppm
d. 7.5–10 ppm
e. 10–12 ppm
60. What is the multiplicity of the methylene hydrogens of a carbon that is attached to a
methyl group and to a methoxy group?
a. Quartet

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 b. doublet
c. quintet
d. singlet
e. triplet

61. Which signal of C6H5-C(=O)-CH(CH3)2 has the greatest integrated signal area?
a. It is the aromatic protons that are a singlet.
b. It is the methine signal that is a septet
c. It is the methylene signal that is a multiplet.
d. It is the methyl signal that is a triplet.
e. It is the methyl signal that is a doublet.
62. How many signals would you expect to see in the 1H NMR spectrum of 1-
bromopropane and 2-bromopropane?
a. 1-Bromopropane has 3 and 2-bromopropane has 3.
b. 1-Bromopropane has 4 and 2-bromopropane has 4.
c. 1-Bromopropane has 2 and 2-bromopropane has 3.
d. 1-Bromopropane has 3 and 2-bromopropane has 2.
e. 1-Bromopropane has 3 and 2-bromopropane has 4.
63. Which of the following compounds is frequently used as an internal reference in 1H
NMR spectroscopy?
a. DMF
b. TMS
c. DMSO
d. DMS
e. TNS
64. In what region of the 1H NMR spectrum would you expect to find signals that are due
to methyl groups?
a. 0–2 ppm
b. 2–4 ppm
c. 4–6 ppm
d. 6–8 ppm
e. 8–10 ppm
65. Identify the compound with molecular formula C4H8Br2 whose 1H NMR spectrum
consists of 2 singlets, one at 1.97 ppm and one at 3.89 ppm.
a. 1,2-dibromobutane
b. 1,1-dibromo-2-methylpropane
c. 1,4-dibromobutane
d. 1,3-dibromo-2-methylpropane
e. 1,2-dibromo-2-methylpropane
66. The chemical shift is calculated using which of the following equations?
a. δ = operating frequency of the spectrometer (MHz)/distance downfield from
TMS (Hz)
b. δ = distance upfield from TMS (Hz)/operating frequency of the spectrometer
(MHz)
c. δ = distance downfield from TMS (Hz)/operating frequency of the
spectrometer (MHz)
d. δ = distance downfield from TMS(Hz)/magnet strength of the spectrometer
e. δ = distance downfield from TMS (Hz) X operating frequency of the
spectrometer (MHz)

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 67. Which of the following cannot be determined using the Beer-Lambert law?
a. the absorbance of the sample
b. the concentration of the sample
c. the length of the light path through the sample
d. the molecular formula of the sample
e. the molar absorptivity of the sample
68. Which of the following compounds has the UV spectrum with the greatest lambda
max?
a. 1-heptene
b. 1,5-heptadiene
c. 1,3-heptadiene
d. 1,3,6-heptatriene
e. 1,3,5-heptatriene

SECTION C Answer all questions from this section.

69.
a. State Beer-Lambert law (1 marks)
b. The linearity of the Beer-Lambert law is limited by chemical and instrumental
factors explain. (5 marks)
c. Define the following terminologies: chromophore, auxochrome, bathochromic
shift, hypochromic effect (4 marks)
d. List applications of Mass Spectrometry (5 marks)

e. Giving examples, differentiate between hard and soft ionization techniques in

70.
a. The spectrum of a newly discovered drug XXX yet to be given a name is shown
below (appendix A), assign the different -values for each of the different
protons.( 8 marks)

(c) (d)
H H (e)
(a) (b) H (f)
CH3 CH2 O N CH3
C

H H O
(c) (d)
b. Acetonitrile (CH3CN) has resonance at 1.97  while methyl chloride (CH3Cl)
has resonance at 3.05 , even though the dipole moment of acetonitrile is 3.92 D

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 while that that of methyl chloride is 1.85 D. The larger dipole moment suggests
that the electronegativity of this group is larger than that of chlorine atom.
Explain why the methyl hydrogens on acetonitrile are actually more shielded
than those in methyl chloride in contrast to expected results based on
electronegativity. (5 marks)
c. In a high throughput combinatorial chemistry many compounds of diverse
chemical structures and properties can be synthesized. Pesambili et al in an
attempt to synthesized a new Anti retrovirus agent the actually isolated an
intermediate compound and called it ‘PESAVIR’. In order to further this
attempt structural elucidation was important. The UV of this compound shows
only end absorption; The IR spectrum was determined on a neat liquid sample.
The H-NMR spectrum shows overlapping absorption for two similar groups
centering on 1.2 . The spectra are summarized on appendix II. Using this
spectral information deduce the structure of PESAVIR. (12 marks)

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