184 + ORGANIC SPECTROSCOPY

( = CH-) signal was 22 mm. Let us calculate the % of keto and enol forms in
the sample.
The methylene group of the keto form - 2H 10 mm ==
The methine group of the enol form == 1H =22 mm
Therefore, 2H == 44 mm

% of the keto form = 44 10

+ 10 x 100 = 18.5%

44
% of the enol form= 44 + 10 x 100 = 81.5%

Quantitative analysis of the mixtures like ethanol-water; acetic acid-water

etc. has already been discussed in Section 5 .16. PMR spectroscopy has also been
used for the quantitative analysis of the mixtures of diastereomers as weil as for
determining the enantiomeric excess (ee), i.e. optical purity.

5.20 Continuous Wave (CW) and Fourier Transform (FT)

NMR Spectroscopy
The common method for obtaining NMR spectra is to irradiate the sample with
a constant radio frequency while changing (sweeping) the applied magnetic
field (field sweep). Altematively, NMR ë é É Å ú ç ã É í É ê ë =operate at a constant magnetic
field while the radio frequency is varied (frequency sweep). Both the methods
give the same NMR spectrum. This commonly used technique is called continuous
wave (CW) NMR spectroscopy.
In a recent method for obtaining NMR spectra, the sample is irradiated with
an intense pulse of allradio frequencies in the desired range (e.g. covering all 1H
frequencies) at once while keeping the magnetic field constant. All the nuclei
under study absorb at their individual frequencies and are flipped to their higher
energy spin states. This results in an interferogram (calledfree induction decay,
FID or time-domain spectrum) which cannot be interpreted directly. The time-
domain spectrum is converted into ordinary frequency-domain spectrum (showing
the intensity of absorption against frequency) by performing a mathematical
operation known as Fourier transformation. This technique is called pulsed-
Fourier transform nuclear magnetic resonance (FT-NMR) spectroscopy. It gives
good spectra even with very small quantities of samples (less than a milligram).
The principal advantage ofFT-NMR spectroscopy is a great increase in sensitivity
per unit time of experiment. It is the increase in sensitivity brought about by the
introduction ofFT-NMR spectroscopy which has allowed the routine observation
of 13C NMR spectra.

5.21 Some Solved Problems

Problem 1. Give the relative positions of the PMR signals and their multiplicity
in each of the following compounds:
(i) CH 3CH2COCH3 (ii) CH 3CH 2CHO
(iii) CH 3CH 200CCH 2CH 2COOCH 2CH3 (iv) (CH 3hCHCOOH
 Proton Nuclear Magnetic Resonance (PMR) Spectroscopy + 185
Solution
a b c
(i) CH3CH2COCH3
On moving downfield, the sequence of signals is protons a, then c and b.
Multiplicity of signals: Protons a (triplet), b (quartet) and c (singlet).
a b c
(ii) CH3CH2CHO
On moving downfield, the sequence of signals is proton a, then b and c.
Multiplicity of signals: Protons a (triplet), b (multiplet) consisting of
eight lines [(3 + 1) (1 + 1) = 8] and c (triplet).
a b c c b a
(iii) CH3CH200CCH2CH2COOCH2CH3
On moving downfield, the sequence of signals is protons a, then c and
b.
Multiplicity of signals: Protons a (triplet), b (quartet) and c (singlet).
b
H3C"'- b c
(iv) a /CHCOOH
H3C
Multiplicity of signals: Protons a (doublet), b {septet) and c (singlet).

Problem 2. Comment on the nurober of signals and their splitting, if any, in the
PMR spectra of the following compounds:

(iii) Cl--@-CocH,
Solution

(il ] J Å ú OÅ ç Å ú O J J ] =
ú = ú =
a a

In certain cases, environments of chemically nonequivalent protons arenot

different enough for the signals tobe noticeably separated, and in such cases we
may see fewer signals than we predict. For example, in some (but not all)
186 + ORGANIC SPECTROSCOPY
aromatic compounds the ortho, meta and para protons have nearly the same
chemical shifts, and hence for NMR purposes they are nearly equivalent, i.e.
exhibit only one signal (singlet). This is the situation in the present case. Thus,
all the five phenyl protons a are nearly equivalent and appear as a singlet. This
compound shows two singlets-one due to the phenyl proton a and the other due
to the methylene proton b.

-@- /
d
CH3
(ii) CH3 CH""' d
CH3
'----v-----'
b
This compound contains four kinds of protons, hence will exhibit four PMR
signals. Proton a, a singlet; proton b, a singlet; protons c, a septet because it has
six neighboring protons (6 + 1 = 7); protons d have one neighboring proton, hence
will appear as a doublet (1 + 1 = 2).
a b
H H

(iii) ci*cocH,
ú
H H =
In this compound, protons b which are ortho to the carbonyl group will have
quite different chemical shift compared to protons a which are ortho to the
chloro group. Thus, this compound has three kinds of protons and will exhibit
three signals. Protons a have one neighboring proton, hence will appear as a
doublet (1 + 1 = 2). Similarly, protons b will also appear as a doublet. The
methyl proton c has no neighboring proton, hence will appear as a singlet.
Problem 3. In an organic compound, three kinds of protons appear at 60, 100
and 180 Hz when the spectrum is recorded at 60 MHz NMR spectrometer. What
will be their relative positions (in Hz) when 90 MHz spectrometer is used?
Solution. The chemical shift in Hz is directly proportional to the strength of the
applied magnetic field (and, therefore, to the applied frequency). Thus

60
(i) 60 x90=90Hz

(ii) l: X 90 =150Hz

(iii) l:g X 90 =270Hz

Problem 4. Propose the structure for the compounds that fit the following
1H NMR data:
 Proton Nuclear Magnetic Resonance (PMR) Spectroscopy + 187
(i) CsHwO
8 0.95, 6H, doublet
8 2.10, 3H, singlet
8 2.43, lH, multiplet
(ii) C4H 7Br0
8 2.11, 3H, singlet
8 3.52, 2H, triplet, J = 6 Hz
8 4.40, 2H, triplet, J = 6 Hz
Solution (i) The compound with molecular formula C5H 100 shows a doublet
due to six protons. This indicates that these six protons are equivalent and the
carbons bearing them are attached to a -CH- group, i.e. the molecule has
I
(CH 3)zCH- group; the -CH- proton appears as a multiplet (septet). One
I
singlet due to three protons indicates that the compound contains a methyl group
which has no proton on the atom to which it is attached. Thus, the structure for
the compound which fits the above data is
H3C"
CHCOCH3
H3C/
(ii) The compound C4H7Br0 shows two triplets with the same coupling constant
(J =6Hz) showing that it contains two nonequivalent adjacent methylene groups
coupled with each other (-CH2-CH2- ) . The presence of a three proton singlet
indicates the presence of a methyl group which has no proton on the atom to
which it is attached. Thus, the structure for the compound is
BrCH2CH 2COCH3
Problem 5. Acompound C6H 100 2 shows a significantiR bond at 1770 cm- 1, and
three 1H NMR signals at -r 5.8, 7.5 and 9.1 with relative intensity 1 : 1 : 3,
respectively. Deduce the structure of the compound.
Solution. The presence of an IR bond at 1770 cm- 1 indicates that the compound
is a Iactone (cyclic ester). It shows three 1H NMR signals. Hence, there are three
kinds of protons in the compound. Since the total number of protons is 10 and
the intensity ratio is 1 : 1 : 3, the number of each kind of protons is 2, 2 and 6,
i.e. the compound has two nonequivalent CH 2 and two equivalent CH 3 groups.
Thus, the structure of the compound is

Problem 6. Draw the structure of a compound with each of the following molecular
formulae that will show only one PMR signal:
188 + ORGANIC SPECTROSCOPY
(i) C3H6Clz (iv) CsHw
Solution

(i) (ii)

(iv)

0
Problem 7. An organic coropound has roolecular formula C3H7Br. lts PMR
spectruro is shown in Fig. 5.28. Deduce the structure of the coropound.

v- lr
--'

{
TMS

ú=
8 7 6 5 4 3 2 0 8
Fig. 5.28

Solution. The PMR spectruro of the coropound shows three signals, viz. two
triplets and one sextet, hence it contains three kinds of protons. On rooving
upfield the successive heights of the integration curves at the signals are
8 roro, 8 roro and 12 roro, i.e. the ratio of the nurober of each kind of protons is
1 : 1 : 1.5. Since the roolecular formula of the coropound is C3H 7Br, the nurober
of each kind of protons is 2H, 2H and 3H. This indicates that the coropound has
a b c
CH3CH 2CH2- group and thus, its structure is CH3CHzCHzBr.
The proton a appear as an upfield triplet, while protons c as a downfield
triplet. The protons b appear as a sextet. However, the protons b roight be
expected to exhibit twelve Iines, i.e. (3 + I) (2 + 1) = 12 because they are
coupled with two equivalent groups of three protons a and two protons c. In
practice, lab is approxiroately equal to lbc and therefore overlapping of Iines
occurs as shown in Fig. 5.28 and thus, a sextet is observed. Since lab = lbco we
can say that the b protons have five equivalent neighboring protons, hence
appear as a sextet, i.e. 5 + 1 = 6. Thus, the structure of the given coropound is:
CH 3CH 2CH 2Br
Problem 8. The PMR spectruro of an organic coropound C8H9Br shows a quartet
at 5.5 8, a doubletat 2.0 8 and an unsyroroetrical roultiplet at -7.4 8 in the
intensity ratio 1: 3: 5, respectively. Deduce the structure of the coropound.
 Proton Nuclear Magnetic Resonance (PMR) Spectroscopy + 189
Solution. The molecular formula of the compound is C8H9Br and the intensity
ratio of different kinds of protons present is 1 : 3 : 5. Therefore, the nurober of
each kind of protons will be 1H, 3H and 5H. The presence of an unsymmetrical
multipletat -7.4 Ö due to 5H shows the presence of a phenyl group (C 6H5- ) ,
and the presence of a quartet due to 1H and a doublet due to 3H indicates the
presence of -TH-CH 3 group. Thus, the structure of the given compound is

C 6 H 5 -C H-CH 3
úê=
Problem 9. Using PMR spectroscopy, how will you distinguish the following pairs?
(i) 1,2-dimethoxyethane and 1,1-dimethoxylethane
(ii) cis-1-chloropropene and trans-1-chloropropene
(iii) Acetone and methyl acetate.
a b b d
Solution (i) 1,2-dimethoxyethane (CH30CH2CH20CH3) will exhibit two
a b c
singlets due to protons a and b, while 1,1-dimethoxyethane (CH30hCHCH3
will exhibit one singlet due to proton a, one quartet due to proton b and one
doublet due to protons c.
(ii) cis-1-chloropropene and trans-1-chloropropene can be distinguished on the
basis oftheir coupling constants. The cisisomer will have lower coupling constant
(leis= 6-12Hz) than the Irans isomer (J1rans = 12-18Hz).

(iii) Both the methyl group in acetone (CH3COCH3) are equivalent, hence it will
show only one singlet. In methyl acetate (CH3COOCH3) the two methyl groups
are nonequivalent, hence it will show two singlets.
Problem 10. An organic compound having molecular formula C5H 11 Cl gave the
following 1H NMR data:
ö 1.0 (t, 3H), 1.5 (s, 6H) and 1.8 (q, 3H)
Deduce the structure of compound.
Solution. The 1H NMR spectrum of the compound exhibits a three proton triplet
and a two proton quartet which indicate the presence of the CH3CH2- group.
The appearance of a six proton singlet shows the presence of two equivalent
CH3- groups which must be attached to a carbon containing no hydrogen.
Thus, the structure of the compound having molecular formula C5H 11 Cl is

Problem 11. Fig. 5.29 shows the PMR spectrum of a compound having molecular
formula C8H 100. Deduce the structure of the compound.
Solution. The PMR spectrum of the compound shows four signals, viz. two
singlets, one doublet and one quartet. Hence, it contains four kinds of protons.
190 + ORGANIC SPECTROSCOPY

I 00 MHz proton NMR spectrum

CDCl3 solution

TMS
...
- ú = ....r
Exchange
withD20
l
10 9 8 7 6 5 4 3 2 0 8
Fig. 5.29

On rooving upfield, the successive heights of the integration curves at the signals
are 15 roro, 3 roro, 3 roro, and 9 roro, i.e. the ratio of the nurober of each kind of
protons is 5 : 1 : 1 : 3. Since the roolecular forroula of the coropound is C 8H 100,
the nurober of each kind of protons is 5H, 1H, 1H and 3H.
The appearance of a five proton singlet at -7.2 8 indicates the presence of a
phenyl (C 6H5- ) group. The presence of a three proton doublet and one proton
quartet shows the presence of a CH 3CH group. The proton (1H) causing a singlet
is exchangeable with D2 0 which shows the presence of a hydroxyl group. Thus,
the structure of the coropound consistent with the above observations is

PROBLEMS

1. For which of the following isotopes NMR spectroscopy is possible and why?
12C, I4N, zH, 35Cl, 32S, I6o and 3Ip

2. Discuss the process of absorption of energy during the nuclear magnetic transitions.
3. Predict the number of signals and their relative intensities in the low resolution
PMR spectra of the following compounds:
(a) Toluene (b) Propanal (d) Propionamide
4. What is chemical shift? Giving examples, discuss the factors which affect the
magnitude of the chemical shift.
5. Explain spin-spin coupling and splitting of signals with examples.
6. Predict the number of signals and their multiplicity in the PMR spectra of the
following compounds:

(a) CH 3CH 20 0 C - @ - - COOCH 2 CH 3

 Proton Nuclear Magnetic Resonance (PMR) Spectroscopy • 191

(b) C) (c) 0
1\
\_/
0 (d) c1-@-c1

7. Write notes on:

(a) Shielding and deshielding (b) Relaxation processes (c) Coupling constant
8. (a) Why are the NMR absorption positions expressed relative to a reference
compound?
(b) Why is TMS a good reference compound in NMR spectroscopy?
9. In PMR spectroscopy, what information can be obtained from the following:
(a) Number of signals (b) Chemical shifts (c) Areas under peaks
(d) Splitting of signals (e) Coupling constants
10. In an AX spectrum, the four lines were observed at 8 5.8, 5.7, 1.1 and 1.0
(measured from TMS with an instrument operating at 100 MHz). What are the
chemical shift positions (in 8) of the A and X nuclei, and the coupling constant
(in Hz) between them?
11. Give a structure consistent with each of the following sets of NMR data:
(a) C3H5Cl 3 : 8 2.20 singlet, 3H; 8 4.02, singlet 2H
(b) C 10H 14 : 8 1.30, singlet, 9H; 87.28, singlet 5H
(c) C 10H 14 : 8 0.88, doublet, 6H; 8 1.86, multiplet, lH; 8 2.45; doublet, 2H;
8 7.12, singlet, 5H.
12. Predict the number of signals and their relative intensities in the PMR spectra of
the following isomers:
(a) Acetone and propanal
(b) Ethylbenzene and p-xylene
(c) 2-pentanone and 3-pentanone
13. What is the cause of different chemical shifts for various hydrogens in NMR
spectroscopy? Why are chemical shifts generally expressed in 8 or r values
instead of in cps?
14. A compound C 10H 13Cl gave the following NMR data:
8 1.57, singlet, 6H; 8 3.07, singlet, 2H; 8 7.27, singlet, 5H
Deduce the structure of compound.
15. Write explanatory notes on :
(a) Shi ft reagents
(b) Spin-spin decoupling
(c) Nuclear Overhauser Effect (NOE)
16. Using PMR spectroscopy, how will you distinguish the following pairs:
(i) Maleie acid and fumaric acid
(ii) 1-chloropropane and 2-chloropropane
(iii) Intermolecular hydrogen bonding and intramolecular hydrogen bonding
17. Explain the following:
(a) Acetylenic protons absorb at higher field than olefinic protons.
192 + ORGANIC SPECTROSCOPY
(b) The hydroxylic proton of ethanol does not split the PMR signal of its
methylene protons in the presence of a trace of acid.
(c) No signal for deuterium is observed in the PMR spectrum of a compound,
e.g. CD 3CH 2CH 3 •
18. An organic compound has molecular formula C3H6Br2 . Its PMR spectrum is
given in Fig. P5.1. Interpret the spectrum and assign the structure to the compound.

II
_r TMS

- l
8 7 6 5 4 3 2 0 8
Fig. P5.1

19. Discuss the characteristic features of the first order PMR spectra. How can the
more complex (second order) PMR spectra be simplified for obtaining more
information?
20. Write notes on:
(a) Chemical and magnetic equivalence of protons.
(b) Factors affecting coupling constants.
21. The following 1H NMR absorptions were recorded and are listed in Hz from
TMS standard. Convert the absorption values into 8 units.
(i) 451 Hz at 60 MHz spectrometer
(ii) 430 Hz at 90 MHz spectrometer
(iii) 543 Hz at 100 MHz spectrometer
22. A compound has molecular formula C3H80. Its IR spectrum shows, a strong
absorptionband at 3380 cm-1 with no other characteristic band. The PMR spectrum
of the compound displayed signals 8 1.2 (d, 6H), 3.8 (s, 1H) and 4.9 (s, lH).
Deduce the structure of this compound.
23. (a) Give an account of vicinal and geminal couplings in PMR spectroscopy.
(b) Write a note on chemical exchange and spin-spin decoupling.
24. Using PMR spectroscopy, how will you distinguish the following isomeric
compounds:
(i) 1,4-dioxane and 1,3-dioxane
(ii) t-butyl bromide and 1-bromo-2-methyl propane
(iii) 1-butyne and 2-butyne
25. Propose a structure consistent with the 1H NMR data of each of the following
compounds:
(a) C4H 100: 8 1.28 (s, 9H), 1.35 (s, lH)
(b) C4H 100 2 : 8 3.25 (s, 6H), 3.45 (s, 4H)
(c) C 10H 13 CI: 81.57 (s, 6H), 3.07 (s, 2H), 7.27(s, 5H)
 Proton Nuclear Magnetic Resonance (PMR) Spectroscopy + 193
26. If the observed chemical shift of a proton is 315 Hz form TMS at a 90 MHz NMR
spectrometer, what is the chemical shift in terms of 8? Express it in -rvalue also.
27. The PMR spectrum of a compound C 8H 10 is given in Fig. P5.2. Analyse the
spectrum and assign the structure to the compound.

_,...-
TMS

8 7
Ä.

6
.l
5 4
--1L
3 2
11 0 ö
Fig. P5.2

28. A compound containing C, H, 0 and Cl shows a strong IR absorption band near

1710 cm- 1 and a broad band near 2800 cm- 1• Its PMR spectrum displays two
triplets at 8 2.8 and 3.8 and a singletat about 812 in the intensity ratio 2 : 2 : I,
respectively. Deduce the structure of the compound.
29. A pale yellow organic compound with molecular forrnula CJI5N03 exhibited an
unsymmetrical multiplet in the region 1.8-2.9 't' (4H) and a singletat 0.1 't' (IH)
in its NMR spectrum. Deduce the structure of the compound.
30. (a) How is PMR spectroscopy useful in the detection of aromaticity?
(b) Discuss the use of deuterium exchange and deuterium labelling in PMR
spectroscopy.
31. Fig. P5.3 shows PMR spectrum of a compound C8H 100. Interpret the spectrum
and assign the structure to the compound.

100 MHz PMR spectrurn

CDCI 3 solution

TMS

10 9 8 7 6 5 4 3 2

Fig. P5.3

32. Cyclohexane gives only one PMR signal (singlet) at the room temperature,
whereas at -l00°C it gives two sharp singlets. Explain this observation.
(Hint: At room temperature the interconversions of the two equivalent chair
conforrnations is so fast that the PMR spectrometer sees protons in their average
194 + ORGAN/C SPECTROSCOPY
environment and records them as a singlet. At -100°C the time between inter-
conversions is long enough for the spectrometer to record the PMR of the molecu1e
as one conformation or the other, and thus one singlet for the six axial and the
other for the six equatorial protons are observed.)

References

I. A. Ault and G.O. Dudey, An Introduction to Nuclear Magnetic Spectroscopy,

Holden-Day, San Francisco, 1978.
2. A.E. Derome, Modem NMR Techniques for Chemistry Research, Pergamon,
Oxford, 1987.
3. D. Neuhaus and M. Williamson, The Nuclear Overhauser Effect in Structural and
Conformational Analysis, VCH Publishers Inc., New York, 1989.
4. D.H. Williams and I. Fleming, Spectroscopic Methods in Organic Chemistry,
McGraw-Hill, New York, 1966.
5. E.D. Becker, High Resolution NMR, Academic Press, New York, 1969.
6. F.A. Bovey, NMR Spectrometry, Academic Press, New York, 1969.
7. H. Booth, Telrahedran Letters, 1965, 411.
8. J.D. Roberts, Nuclear Magnetic Resonance Applications to Organic Chemistry,
McGraw-Hill, New York, 1959.
9. J.D. Roberts, An lntroduction to the Analysis of Spin-Spin Splitting in High-
Resolution Nuclear Magnetic Resonance Spectra, McGraw-Hill, New York, 1962.
10. J.R. Dyer, Applications of Absorption Spectroscopy of Organic Compounds,
Prentice-Hall, Englewood Cliffs, N.J., 1965.
11. K. Nakanishi, V. Woods and L.H. Durham, A G!lide Book to the Interpretation of
NMR Spectra, Holden-Day, San Francisco, 1967.
12. L.M. Jackman and S. Sternhell, Applications of NMR Spectroscopy in Organic
Chemistry, 2nd Ed., Pergamon, New York, 1969.
13. R.H., Jr., Bible, Interpretation of NMR Spectra, Plenum Press, New York, 1965.
14. R.J. Abraham, J. Fisher and P. Loftus, Introduction to NMR Spectroscopy, 2nd
Ed., Wiley, London-New York, 1989.
15. R.M. Silverstein, G.C. Bassler and T.C. Morrill, Spectrometric ldentification of
Organic Compounds, 5th Ed., Wiley, London-New York, 1991.
16. S. Sternhell and J.R. Kaiman, Organic Structures from Spectra, Wiley, Chichester-
New York, 1986.
17. T.C. Parrar and E.D. Becker, Pulse and Fourier Transform NMR, Academic
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18. W.W. Paudler, Nucler Magnetic Resonance, Wiley, New York, 1987.