Tutorial 8

Notes on spectroscopy
1H NMR
Chemical shifts you should memorize:

N.B. Phenolic OH appears at 8-10 ppm

Definitions and concepts you should understand:

• NMR active nuclei (1H, 13C …..etc)

• NMR inactive nuclei (2D, 12C, 14N, …etc)
• NMR chart details (X-axis, Y-axis, Upfield, downfield, chemical shift units, TMS, shielded
and desheilded peaks, integration….etc) ?
• NMR experiment solvents?
• Which protons are D2O exchangeable?
• How can you identify the multiplicity of each proton?
 IR

IR absorption frequences you should memorize:

N.B. For carbonyl compounds you should know that the carbonyl group absorption band is
generally between 1680-1850 cm-1 (i.e. approximately within this range.)

Definitions and concepts you should understand:

• IR helps in identification of functional groups.
• IR concept (quantized bond vibrations).
• IR chart details (X-axis, Y-axis, IR range, what is meant be absorption band ….etc) ?
• H-bond effect on OH absorption band.
• How can you differentiate between primary and secondary amines ?
• How can you differentiate between OH of alcohol and OH of carboxylic acid.
 Mass Spectrometry

Data you should memorize:

Atomic mass:
H=1
C=12
N=14
O=16
Cl=35 (isotope= 37)
Br=79 (isotope=81)

Isotopic abundance:

Definitions and concepts you should understand:

• Mass spectrometry helps in identification of molecular weight of compounds.
• Mass spectrometry concept (ionization & fragmentation of molecules then detection of
positive species).
• The chart details (X-axis, Y-axis, Base peak, molecular ion peak, M++2 in isotopes like
chlorinated and brominated compounds ….etc) ?
• General rules for cleavage (tropylium ion m/z=91, phenyl m/z=77)
 Questions & answers on Spectroscopy

1. What is the structure of the compound that gives the following IR and NMR spectra ?

a doublet 6H

b singlet 1H

c multiplet 1H

Answer is B
2. To check that a secondary alcohol has been completely oxidized to a ketone, the IR spectrum of
the ketone product shows……….. .
a) absorption bands at 3300cm-1 and 1650cm-1.
b) no absorption around 3300cm-1.
c) no absorption around 1650cm-1.
d) no absorptions at 3500cm-1 and 1650cm-1.

3. Which of the following compounds best corresponds to the IR spectrum shown below?

Answer is C.

4. Calculate the m/z value of the molecular ion peak of the above mentioned compound.

Answer:
C6H12O= (12x6)+(1x12)+(1x16)= 100

6. Which of the compounds given below has the following 1H-NMR data:
Chemical shift: 1.3 (t, 3H); 2.8 (s, 1H), 4.3 (q, 2H)

a) CH3CH2COC=CH2
b) CH3CH2OOCC≡CH
c) CH3CH2CH2Br
d) CH3OCH3.
7. Which of the following statements regarding 1H-NMR spectroscopy is wrong?
a) NMR signals towards the left of the spectral chart correspond to larger
chemical shifts.
b) Chemical shifts are larger when shielding effects are greater
c) Chemical shifts are larger when deshielding effects are greater.
d) A hydrogen signal splits into n+1 peaks when the number of equivalent hydrogen atoms on
adjacent atom(s) is n.

8. Why does the O-H absorption of CH3OH appear as a broad band in the infrared ?
a) Rotational energy levels broaden the absorption.
b) Hyperconjugation resonance broadens the absorption.
c) Resonance broadens the absorption.
d) Hydrogen bonding broadens the absorption.

9. Which one of the following information cannot be obtained from an infrared spectrum ?
a) The molecular mass.
b) The presence of C=O bonds.
c) The presence of O-H bonds.
d) The presence of N-H bonds.

10. What is the compound that corresponds to the following mass spectrum?

a) Toluene.
b) Ethylbenzene.
c) Tert butyl benzene.
d) Propylbenzene.
N.B. The any alkyl benzene can show tropylium ion (m/z=91) which is the base peak in most cases. So all
the choices may be correct. However, the molecular ion peak here is 106 so it is ethylbenzene only which
has this mass. In this case, you should ccalculate the mass of ech choice and find the one which fits the
correct choice.
 11. Which of hydrogen(s) a-d in the given aldehyde gives a multiplet peak in 1H -NMR spectrum?

a) Hydrogens (a).
b) Hydrogen (b).
c) Hydrogens (c).
d) Hydrogen (d).

12. Which of the following statements about tetramethylsilane is incorrect?

a) It produces a single peak at ∂=10 ppm.
b) It is inert.
c) It is sovent.
d) It is used to provide a reference against which other peaks are measured.

13. Predict the 1H-NMR and Mass Spectra of the following compounds.

1
H-NMR Spectroscopy

2.05 ppm (s, 6H, 2CH3)

1.5 ppm (d, 3H, CH3)
3 ppm (q, 1H, CH)
7 ppm (s, 5H, C6H5)

Mass Spectrometry
 Case study

Nifedipine is a drug used for hypertension treatment. As pharmacist, you are requested to confirm its
structure using different spectroscopic techniques.
Answer the following questions:

14. The IR spectrum of nifedipine shows a band at 1690 cm -1 due to the

vibration of…….. group.
a) CH
b) NH.
c) NO2.
d) Carbonyl.

15. The IR spectrum of nifedipine shows a band at 3200 cm-1 due to the vibration of…….. group.
a) C=C
b) NH.
c) NO2.
d) Carbonyl.

16. The 1H NMR spectrum of nifedipine shows the ester methyl protons……..
a) upfield.
b) downfiled.

17. The chemical shift of the aromatic protons in nifedipine 1H NMR spectrum is approximately
at……..ppm.
a) 1-3.
b) 4-6.
c) 6-8.
d) 9-11.

18. The ester methyl protons in nifedipine 1H NMR spectrum appear as……...peak(s).
a) singlet.
b) doublet.
c) triplet.
d) multiplet.

19. An impurity of nifedipine with hydrolyzed ester (see the structure) shows 1H NMR spectrum
with a carboxylic acid proton at chemical shit equals ……...
a) 11.
b) 6.
c) 4.
d) 2.
20. An impurity of nifedipine with ethyl ester (see the structure) shows 1H NMR spectrum with the
ethyl group peak(s) as …….
a) doublet.
b) triplet.
c) quartet
d) (b) and (c).

Given the following mass spectrum of nifedipine, answer questions 21-25

21. The peak corresponding to the molecular mass of nifedipine is called….….

a) the molecular ion peak.
b) the molecular anion peak.
c) the radical peak.
d) None of the above.

22. The peak corresponding to the molecular mass of nifedipine is ……

a) Peak A.
b) Peak B.
c) Peak C.
d) None of the above.

23. The base peak is ……

a) Peak A.
b) Peak B.
c) Peak C.
d) None of the above.
24. The X-axis refers to ……
a) m.
b) m/z.
c) z.
d) m/d.

25. The Y-axis refers to ……

a) relative mass.
b) relative weight.
c) relative abundance.
d) (a) and (b).