9

Spectroscopic Solutions of
Structural Problems

9.1 Introduction
Various spectroscopic methods described in this book provide sufficient information
for the structure determination of organic compounds. A general approach to
solving structural problems by a combination of spectroscopic methods is given
as follows:
1. Molecular formula and molecular weight of a compound is known from its
eiemental analysis and mass spectrum. The molecular formula gives an idea
about the number and kinds of possible functional groups.
2. Index of hydrogen deficiency is determined from the molecular formula that
gives the sum of multiple bonds and rings in the compound (Section 8.8(i)).
It helps in limiting the possibilities of structures for further consideration.
3. The UV spectrum gives indication about the presence (or absence) of a
conjugated system, an aromatic ring, a carbonyl group (aldehydic or ketonic)
etc.
4. The IR spectrum shows the presence (or absence) of certain functional
groups, e.g. carbonyl groups, hydroxyl groups, -NH- etc., and C == C and
C=C bonds.
5. The PMR spectrum reveals the envtronment of hydrogen atoms in the
molecule. It gives the number and kinds of protons present in the molecule.
Spin-spin splitting teils about the neighboring protons. In brief, we should
examine the PMR spectrum for the presence of -CH 3 , CH 3CH 2- ,
-CH 2-CH 2 , (CH 3)zCH-, -CH=CH-, -C==CH etc. groups;
aromatic protons, and protons on heteroatoms, i.e. exchangeable protons.
Thus, the PMR spectrum Ieads to some extent to the molecular skeleton.
6. The CMR spectrum gives the number of kinds of carbons, and the number
of methine carbons, methylene carbons, methyl carbons, and carbons having
no hydrogen. Thus, the CMR suggests the carbon skeleton of the molecule.
7. The mass spectrum, in addition to molecular weight, shows the presence of
certain structural units, and the fragmentation pattern indicates their points
of attachment in the molecule.

L. D. S. Yadav, Organic Spectroscopy

© Springer Science+Business Media Dordrecht 2005
296 + ORGANIC SPECTROSCOPY
The following solved problems demonstrate the use of various spectral data
in structure determination.

9.2 Some Solved Problems

Problem 1. An organic compound with molecular formula C6H 120 2 gave the
following spectral data:

UV: Arnax 283 nm, Emax 27 (hexane).

IR: Significant absorption bands at 1705, 2900 and 3450 cm- 1.
1H NMR: ö 1.3 (six proton singlet), 2.2 (three proton singlet) and 3.8 (one

proton singlet, exchangeable with D20).

13C NMR (Off-resonance decoupled) : Two singlets, one triplet and two quartets,

one of the singlets is at ö 210 and the other at ö 70.

Mass: Prominentpeaks at mlz 116, 58 and 43.
Deduce the structure of the compound and explain the spectral data.

Solution. The index of hydrogen deficiency (Section 8.8(i)) calculated for the
given molecular formula C6H 120 2 = x- f + f - 1 = 6- 1{ + 1 = 1.
UV: The compound shows Amax 283 nm with Emax 27 which indicates the
presence of an aldehydic or a ketonic ) C = 0 group. This band is
due to forbidden transition n ~ tr* of the) C = 0 group.
IR: Absorption bands at 1705, 2900 and 3450 cm- 1 may be assigned to
ketonic )C=O, alkyl and hydroxyl groups, respectively.
1H NMR: The compound shows four signals indicating the presence of four
kinds of protons. The six proton singletat ö 1.3 indicates the presence
of two equivalent -CH3 groups with no neighboring proton. The
three proton singlet at ö 2.2 shows the presence of another methyl
group with no adjacent proton. The one proton singlet at 3.8
(exchangeable with D20) shows that the proton is attached to a
heteroatom, in this case to oxygen, i.e. the compound contains an
-OH group.
13C NMR (Off-resonance decoupled): The presence of two singlets shows the

presence of two nonequivalent carbons having no hydrogen, one of

these may be the carbonyl carbon (Ö 210) and the other the carbon
containing the -OH groups. One triplet shows the presence of a
-CH2- group, and two quartets indicate the presence of two
nonequivalent -CH3 groups.
Mass: The peak at mlz 116 is due to molecular ion as indicated by the given
molecular formula (C6H 120 2). The presence of a peak at mlz 43 is
+
due to CH3 C==O. The formation of a fragment ion peak of even
mass nurober from the even mass numbered molecular ion shows
that the fragmentation has occurred through a rearrangement involving
the cleave of two bonds.
From the above explained spectral data, the deduced structure of the compound is
 Spectroscopic Salutions of Structural Problems + 297

The calculated index of hydrogen deficiency also corresponds to this structure.

The presence of peaks at mlz 116, 58 and 43 in the mass spectrum of the
compound is explained by the formation of corresponding ions as follows:

mlz 116 (M*)

-(CH 3) 2 COHCH 2 +
_ _....::!.....:.:;_____ ____:~ CH 3 C = 0
mlz 43

McLafferty rearrangement

Problem 2. An organic compound C8H 140 4 gave the following spectral data:
UV: No significant absorption above 210 nm.
IR: Significant absorption bands at 1735 and 2950 cm- 1•
1H NMR: 8 1.2 (six proton triplet, J = 7 Hz), 2.6 (four proton singlet) and 4.2
(four proton quartet, J = 7 Hz).
13C NMR (Off-resonance): One singlet, two triplets, and one quartet. The singlet

isat8175.
Mass: Prominent peaks at m/z 174 (W), 129 and 101.
Deduce the structure of the compound and explain the spectral data.
Solution
UV: The absence of absorptionband above 210 nm indicates the absence
of conjugation, aldehydic and ketonic carbonyl groups and an aromatic
ring.
IR: Absorptionbands at 1735 and 2950 cm- 1 indicate the presence of an
ester and alkyl groups, respectively.
1H NMR: The presence of a six proton triplet at 81.2 and a four proton quartet

at 8 4.2 (both having J =7Hz) indicates the presence oftwo equivalent

298 + ORGANIC SPECTROSCOPY
CH3CH 2- groups. The four proton singlet at 8 2.6 may be due to a
-CH2-CH2- group with equivalent protons. Thus, the compound
contains two equivalent CH3CH 2- groups and one -CH2-CH2-
group.
13C NMR (Off-resonance): One singlet at 8 175 may be due to the carbonyl

carbon of the ester group. Two triplets and one quartet indicate that
there are two kinds of -CH2- groups and one kind of CH 3-
group.
Mass: The molecular ion (~) peak at mlz 174 corresponds to the molecular
formula C 8H 140 4 of the compound.
On the basis ofthe spectral data, as explained above, and the given molecular
formula, the deduced structure of the compound is
CH 2COOCH 2CH3
I
CH 2COOCH 2CH3
The index of hydrogen deficiency calculated for C 8H 140 4 = 8- 124 + 1 = 2 is
also in agreement with this structure because it has two double bonds.
The fotmation of ions corresponding to the peaks at m/z 174 (M+), 129 and
101 is as follows:

t
0 0
II II
CH 2-C-OCH 2CH3 CH 2-c-OCHzCH3
I e
-2e I
CH 2-C-OCHzCH3 CH 2-c-OCHzCH3
II II
0 0
r-------------- mlz 174 (Ar)

LCH,CH,o
+
j-cH,cH,oc~ö
CH 2-C=O
I
CH 2-c-cHzCH3 +
II CHz
0 I
m/z 129 CHz-C-O-cH2CH3
II
0
m/z 101

Problem 3. A compound containing C, H, 0 and ahalogen shows molecular ion

peak at mle 1081110 in the intensity ratio 3 : 1. The IR spectrum shows a very
broad band in the range of 2500-3300 cm- 1 and centering around 2900 cm- 1, and
a strong intensity band at 1705 cm- 1• In the 1H NMR spectrum of the compound,
two triplets at 8 2.8 and 3.8 and a singlet at 8 12 are found in the intensity ratio
2 : 2: 1. One of the 13C NMR peaks (proton-noise decoupled) is a low intensity
 Spectroscopic Salutions of Structural Problems + 299
peak at 8 170. Deduce the structure of the compound and explain the spectral
data.
Solution. The compound shows molecular ion peak at m/e 108/110, i.e. the W
peak at m/e 108 and M + 2 peak at m/e 110 in the intensity ratio 3 : 1. This clearly
indicates that the compound contains a chlorine atom. The presence of a broad
IR band in the range 2500-3300 cm- 1 indicates the presence of an -OH group,
and the strong band at 1705 cm- 1 may be due to carboxylic carbonyl group, i.e.
the compound contains a -COOH group. The presence of two PMR triplets at
8 2.8 and 3.8 show the presence of two adjacent and nonequivalent -CH2-
groups, i.e. -CH2-CH2- group, and the presence of a very low field singlet
at 8 12 indicates the presence of a carboxylic proton. These are found in the
intensity ratio 2 : 2 : 1. The presence of a low intensity peak at 8 170 in the 13C
NMR (proton-noise decoupled) spectrum supports the presence of the carbonyl
group of the carboxylic acid.
Thus, the compound under investigation contains -Cl, -CH2-CH2- and
-COOH groups, and its structure is
Cl-CH2-CH2-COOH
This structure is strictly in accordance with the given spectral data as explained
above.
Problem 4. A compound with molecular weight 130 gave a negative iodoform
test.lt absorbs at 292 nm, Emax 16 in the UV spectrum. It shows significant bands
at 3042,2941,2862,2740, 1722, 1605, 1575 and 1462 cm- 1 in its IR spectrum.
In the PMR spectrum, three signals are present at r 2.73 (multiplet), 7.2 (doublet)
and 0.22 (triplet) in the intensity ratio 5 : 2 : 1, respectively. Determine the
structural formula of the compound.
Solution. The UV absorption at 292 nm, Ernax 16 is characteristic of an aldehydic
or ketonic carbonyl group arising from n ~ n* forbidden transition. The IR
absorption band at 1722 cm- 1 also supports the presence of the carbonyl group.
This is an aldehydic carbonyl group because the compound shows characteristic
C-H stretching absorption of -CHO group at 2862 and 2740 cm- 1. The
absorptions at 3042 and 2941 cm- 1 are due to =C-H saturated (or aromatic
C-H) and C-H stretching, respectively. The absorptions at 1605, 1575 and
1462 cm- 1 are due to aromatic ring C-C Stretching.
The PMR spectrum shows a multipletat r2.73 which indicates the presence
of an aromatic ring; a doublet and a low field triplet are present at r 7.2 and 0.22,
respectively, showing the presence of -CH2CHO group. The signals are in the
intensity ratio 5 : 2 : 1, respectively.
The above discussion and the molecular weight ( 130) of the compound suggest
that its structure is

~CH,CHO

Problem 5. An organic compound with molecular formula C6H 100 2 furnished

the following spectral data:
300 + ORGANIC SPECTROSCOPY
UV: No significant absorption above 210 nm.
IR: Significant absorption bands at 1760 and 2950 cm- 1•
PMR: 8 1.5 (3H, d), 2.2 (6H, s) and 6.8(1H, q)
13 C NMR (Off-resonance decoupled): One singlet at 8 165, one doublet and
two quartets.
MS: Prominentpeaks at mle 146, 87 and 43.

Deduce the structure of the compound and explain the spectral data.

Solution
UV: No absorption above 210 nm indicates the absence of conjugation,
aldehydic and ketonic )c=O group, and aromatic ring.
IR: Absorptionbands at 1760 and 2950 cm- 1 are due to Stretching of an
ester )c=O and an alkyl C-H band, respectively.
PMR: The presence of a 3H doubletat 81.5 and 1H quartetat 8 6.8 indicate
the presence of a CH3CH ( group. The 6H singlet at 8 2.2 indicates
the presence of two equivalent CH3- groups with no neighboring
protons. The remaining two carbon and four oxygen atoms constitute
two -COO- groups.
13 C NMR (Off-resonance decoupled): The singletat 8165 is due to ester carbonyl

carbon. One doublet is due to the methine <)CH-) carbon and

two quartets are due to two kinds of -CH 3 carbons.
MS: The peak at mle 146 is due to molecular ion as shown by the molecular
+
formula. The peak at mle 43 is due to CH 3 C- 0.
From the above discussion it is clear that the compound contains one CH3CH(.
two CH 3- and two -COO- groups. Thus, the structure of the compound is

This structure of the compound is strictly in accordance with the spectral data
as explained above and the molecular formula.
 Spectroscopic Salutions of Structural Problems + 301
The peaks at m!e 146, 87 and 43 in the MS are

+
CH3CH=OCOCH3
mle87

Problem 6. An organic compound with molecular mass gave the following

spectral data:
UV: No significant absorptionband above 200 nm.
IR: Significant absorption bands at 2940, 2270 and 1460 cm- 1.
PMR: 2.72 (septet, J = 6.7 cps) and 1.33 (doublet, J = 6.7 cps) in the
intensity ratio 1 : 6.
Deduce the structure of the compound and explain the spectral data.
Solution. The IR absorption bands at 2270, 2940 and 1460 are due to C=N,
C-H and C-C Stretching, respectively.
Two PMR signals, a septet and a doublet with the same values of coupling
constant suggest the presence of (CH 3)zCH- groups. This corresponds to 43
mass units. The remaining 69 - 43 = 26 mass units are due to C=N group as
also indicated by the IR spectrum. Thus, the compound contains (CH 3)zCH-
and C;;;;;;N structural units, and its structure is

Problem 7. An organic compound containing C, H and 0 gave the following

spectral data:
Mass: Molecular ion (M+) peak at mfz 158.
UV: Amax 225 nm, Emax 50 (hexane).
IR: Significant absorption bands at 1757, 1828 and 2857-3077 cm- 1.
1H NMR: 8 2.70 (septet, J = 6.7 Hz) and 1.20 (doublet, J = 6.7 Hz) in the
intensity ratio 1 : 6, respectively.
13 C NMR (Off-resonance decoupled): One singlet, one doublet and one quartet.
302 + ORGANIC SPECTROSCOPY
The singlet is at about 8 170.
Deduce the structure of the compound and explain the spectral data.
Solution
Mass: The molecular ion (W) peak at mlz 158 shows that the molecular
mass of the compound is 158.
UV: A..nax 225 nm with 8max 50 indicates a carboxylic, ester or anhydride
)e=o group.
IR: Bands at 1757 and 1828 cm- 1 are the characteristic of anhydride
(-C0-0-CO-) grouping. The absorption at 2857-3077 cm- 1 is
due to alkyl e-H Stretching.
1H NMR: A septet and a doublet with the same coupling constant (J = 6.7 Hz)

show the presence of (eH 3h eH- group.

Be NMR (Off-resonance decoupled): One singlet at 8 170 may be due to
carbonyl group of the an hydride function: the doublet and quartet
~
indicate the presence of eH- and eH3- groups.
/
Thus, the spectral data as explained above, indicate the presence of (eH3heH-
and -C0-0-eO- groups whhich amounts to 115 mass units. The remaining
158 - 115 = 43 mass units may be another (eH3h eH- group. Hence, the
structure of the compounds is

Problem 8. Explain the following spectral data systematically and deduce the
structure of an organic molecule containing e, H and 0:
UV: Amax 278 and 319 nm.
IR: Significant absorption bands at 3070-3010, 2970-2860, 1685, 1605,
1580 and 1450 cm- 1 •
PMR: 82.1 (3H, s) and 7.5 (5H, m).
Be NMR: 8 198 and 137 (two singlets), 134, 129 and 128 (three doublets) and
26 (one quartet).
MS: mle 120 (W), 105, 77, 51 and 43.
Solution
UV: Amax 278 and 319 indicate the presence of a carbonyl (an aldehyde
or a ketone) group and an aromatic ring.
IR: Absorption bandsat3070-3010and2970-2860cm-1 areduetothe aro-
matic and alkyl e-H Stretch, respectively. The band at 1685 cm- 1
may be due to the aromatic ketonic )e=O group. The absorption bands
at 1605, 1580 and 1450 cm- 1 are characteristic of an aromatic ring.
PMR: The presence of a five protonmultipletat 8 7.5 indicates the presence
 Spectroscopic Solutions of Structural Problems + 303
of a phenyl group and the singletat o2.1 shows the presence of a
eH3- group.
Be NMR: The presence of two singlets, three doublets and one quartet indicates
the presence of six kinds of carbons including two kinds of )eH - and
o
one eH3- groups. The singlet appearing at 198 (low field) is due
to the ketonic groups.
MS: Ar at m I e 120 shows that the molecular mass of the compound is 120.
The above discussion clearly shows that the compound contains e 6H5- , )e=O
(keto) and eH3- structural units which amount to 120 mass units, i.e. the
molecular mass of the compound. Thus, the structure of the compound is
0
II
©Jc-eH3

The peaks at m/e 105, 77, 51 and 43 are explained by the following fragmentation
modes:
Problem 9. Explain the following spectral data given by an organic compound

©Jc-<:H, +
0
II
-CH3
©J~
e-o
@+ -C:!Hz
~
mle l20(M+) mle 105 mle17 mle5l

1-C6Hs
eH3ü=O+ mle 43
e 9H 100 2 and deduce the structure of the compound.
UV: Arnax 257 nm, Ernax 194.
IR: Significant absorption bands at 3040, 2950, 1740, 1480, 1440 and
1220, 700 and 750 cm- 1•
PMR: o
1.96 (3H, s), 5.00 (2H, s) and 7.22 (5H, s).
Be NMR (Off-resonance): Two singlets, one triplet, one quartet and three
o
doublets. One of the singlets is at 171 and the other is at 136. o
MS: Prominentpeaks at mle 150 (W), 108, 91, 79, 78 and 77.
Solution
UV: Amax 257 nm, Ernax 194 indicate the presence of an aromatic ring.
IR: Absorption bands at 3040, 1480, 1440, 700 and 750 indicate the
presence of a monosubstituted benzene ring. The presence of a band
at 1740 tagether with another band at 1220 cm- 1 is characteristic of
304 • ORGANIC SPECTROSCOPY

an acetate. The band at 2950 cm- 1 is due to alkyl C-H stretching.

PMR: The presence of five proton singlet at 87.22 is due to aromatic
protons. The singlet nature of this peak shows that the compound is
a monosubstituted benzene derivative and the substituent has nearly
the same electronegativity as the ring carbon. A three proton singlet
at 8 1.96 indicates the presence of a CH 3- group on a carbonyl
carbon. The other singlet (2H, 8 5.00) shows the presence of a CH 2
group and its chemical shift is in accordance with its attachment to
a benzene ring on one side and oxygen atom on the other.
13C NMR (Off-resonance): The quartet and triplet indicate the presence of a
CH 3- and a -CH2- group, respectively. The three doublets are
due to three kinds of =CH- groups of the benzene ring. One
singlet at 8 136 is the ring carbon containing a substituent and the
other singlet at 8 171 is due to the ester carbonyl carbon.
MS: The peak at m/e 150 is due to the molecular ion and at m/e 91 is
characteristic of benzyl (or tropylium) ion. The peaks at m/e 79, 78
and 77 are additional proof for the benzene ring while the peak at
+
mle 43 is due to CH 3 C=O.

Thus, following is the structure of compound consistent with its given molecular
formula and spectral data
The following fragmentation modes explain the formation of fragment ions

corresponding to the observed peaks in the mass spectrum of the compound:

+
CHz
~ -CH 3COO'
~ 4
ß-cleavage
mle91

! l-H·
(r;'y'OH
@mle91
0mle 107

mle77 mle79 mle78

 Spectroscopic Salutions of Structural Problems + 305
Problem 10. A hydrocarbon containing 85.7% C and 14.3% H is transparent
above 210 nm in UV spectrum. lt shows IR absorption bands at 3020, 1675 and
965 cm- 1. lts PMR spectrum reveals a doublet at -r 8.40 and a quartet at -r 4.45
in the integral area ratio 3 : 1, respectively. Determine the structural formula of
the compound.
Solution. From the given C and H percentage, the empirical formula of the
compound comes to be C4H8 .
The UV spectrum is transparent above 210 nm. This indicates the absence of
conjugation, carbonyl group and aromatic ring.
Since aromatic ring is absent, IR absorption at 3020 is due to =C-H Stretching
and that at 1675 due to C=C stretching.
In the PMR spectrum, the doublet and quartet may be due to CH3-CH=
group.
Since the empirical formula (C 4 H8) is just double of it, the probable structure
of the compound is CH 3 -CH=CH-CH 3 . The presence of an IR band at
965 cm- 1 is

Problem 11. Rationalizing the following spectral data, deduce the structure of a
compound with molecular formula C3H7NO:
UV: Amax 238 nm, Ernax 10500.
IR: Significant absorptions at 3428, 2941-2857, 1681 and 1452 cm- 1.
1H NMR: 8 1.9 (3H, s), 2.7 (3H, s) and 8.13 (lH, s).
13C NMR (Off-resonance decoupled): Two quartets and one singlet. The singlet
is at 8 176.
Solution
UV: The absorption at 238 nm, Emax 10500 is characteristic of conjugation.
IR: The bands at 2941-2857 and 3428 cm- 1 are due to C-H and N-H
stretching, respectively. The band at 1681 cm- 1 is caused by stretching
of C=O group which is in conjugation with the lone pair of electrons
of nitrogen atom.
1H NMR: Two singlets, each due to three protons, indicate the presence of two
methyl groups, one of which (at 8 2.7) may be due to a methyl group
attached to nitrogen atom. The low field one proton singlet is due to
-NH-.
13 C NMR (Off-resonance decoupled): Two quartets confirm the presence of
two methyl groups, and the singlet at 8 176 indicates an amino
C=O group.
306 + ORGANIC SPECTROSCOPY
Thus, the structure of the compound is
0
II
H3C-C-NH-CH3

Problem 12. An organic compound C9H 12 gave the following spectral data:
UV: Amax268 nm, Ernax 480.
IR: Singificant absorption bands at 3065-2910, 1608 and 1473 cm- 1.
PMR: 8 2.26 (9H, s) and 6.79 (3H, s).
13C NMR (Off-resonance decoupled): One quartet, one doublet and one singlet.

Explaining the spectral data, derive the structure of the compound.

Solution
UV: Amax 268, Emax 480 indicate the presence of an aromatic ring.
IR: Absorption band at 3065-2910 cm- 1 may be due to aromatic and
saturated C-H stretching. The bands at 1608 and 1473 cm- 1 are due
to C=C and C-C stretching.
o
PMR: The singletat 6. 79 indicates the presence of three aromatic protons,
and the singlet at o2.26 is due to nine alkyl protons. Thus, there is
a benzene ring containing three methyl groups.
13C NMR (Off-resonance decoupled): One quartet is due to methyl group, one

doublet due to =CH of aromatic ring and the singlet is due to the
ring carbons to which the methyl group is attached.

Thus, the structure of the compound which fits the given spectral data is
Problem 13. An organic compound with molecular mass 100 gave the following
spectral data:
UV: Amax 274 nm, Ernax 2050.
IR: Significant absorption bands at 3030, 2940, 1725, 1605, 1505, 1060
and 830 cm- 1.
PMR: 82.35 (3H, s), 3.82 (3H, s) and 7.20-7.85 (unsymmetrical pattem, 4H).
Rationalizing the spectral data, deduce the structure of the compound.
Solution
UV: Amax 274 nm, fmax 2050 indicates the presence of conjugation or
aromatic ring.
IR: Band at 3030 and 2940 cm- 1 are due to =CH and alkyl C-H
stretching, respectively. The band at 1725 cm- 1 may be due to C=O
stretching of an ester group. This is supported by the presence of
 Spectroscopic Salutions of Structural Problems + 307
another band at 1060 cm- 1 due to C-0 Stretching. The presence of
absorption bands at 1605 and 1505 cm- 1 indicate the presence of an
aromatic ring.
PMR: The presence of a four proton signal with unsymmetrical pattern at
8 7.20-7.85 indicates the presence of a disubstituted benzene ring.
Singlets at 8 2.35 and 3.82 (3H each) show the presence of two
methyl groups.
Thus, there are two methyl groups, one disubstituted benzene ring and an ester
group in the molecule. The IR band at 830 cm- 1 is characteristic of para-disubstituted
benzene ring. This suggests that the following is the structure of the compound:

Problems 14. Explain the spectral data and deduce the structure ofthe compound
from its UV, IR, PMR, CMR and mass spectra given in Fig. 9.1 (a-e).
o..J ~

0.3 -

.-€""'
u 0.6
UV spectrum no significant
-

0 absorption above 210 nm

"'
,L:l
<(
0.9 -

1.2 -

1.5 - 1 -
200 250 300 350
..l.(nm)
(a)

IR spectrum
(liquid film)

1735

4000 3000 2000 1600 1200 800

v(nm- 1)
(b)
308 + ORGANIC SPECTROSCOPY
100 MHzproton NMR spectrum
CDCI3 solution

~ ,-
6H

---
4H
4H
- ~
1=7 Hz
1=7 Hz
[ 1

10 9 8 7 6 5 4 3 2 0
8 (ppm)
(c)

20 MHz carbon-13
NMR spectrum

l
CDC13 solution

1 j I

LL
Off-resonance decoupled

Proton decoupledl j.
220 200 180 160 140 120 100 80 60 40 20 0 8 (ppm)
(d)

90 101 Mass spectrum

101

10

20 40
Jl II

60
I
80
l Mt 174 C8H140 4

100 120 140 160 180 200 220 240 260 280 300 320 340
mle
(e)
Fig. 9.1

Solution
UV: No significant absorption above 210 nm indicates the absence of
conjugation, aldehydic or ketonic carbonyl group and an aromatic
ring.
IR: The presence of a significant band at 1735 cm- 1 indicates the presence
of an ester group.
1H NMR: The presence of a triplet (6H) at 01.2 and a quartet (4H) at 84.2 both
 Spectroscopic Solutions of Structural Problems + 309
having the same value of the coupling constant (J = 7 Hz) indicates
the presence of two equivalent CH 3CH 2- groups. The four proton
singlet at 8 2.6 may be due to -CH2CH2- group with equivalent
protons. Thus, the compound contains two equivalent CH3CH2-
groups and one -CH2-CH2- group.
13C NMR (Proton decoupled): The presence of four signals shows the presence
of four kinds of carbon atoms in the compound.
13c NMR (Off-resonance decoupled): One singlet at 8 175 may be due to the
carbonyl carbon of the ester group. Two triplets and one quartet
indicate the presence of two kinds of -CH2- and one kind of
-CH3 groups.
Mass: The molecular ion (Mt) peak at mlz 174 corresponds to the molecular
formula C8H 140 4 of the compound.
On the basis of the spectral data explained above and the given molecular
formula, the deduced structure of the compound is

CH 2 COOCH 2 CH3
I
CH 2 COOCH 2 CH3
The formation of ions corresponding to the indicated peaks in the MS at
mlz 174 (~). 129 and 101 is

+
6
II
e
H 2C-c-OCH2CH3
-2e I
H 2C-C-0CH 2CH3
II
0
. - - - - - - - - - - - - mlz 174 (Mt)

1-cH,CH,Ü j-CH,CH,<X>Ö

+
H 2C-C=O+ CHz
I I
H 2C-c-CH2CH3 HzC-c-OCHzCH3
II II
0 0
m/z 129 mlz 101

PROBLEMS

1. An organic compound with molecular formula C 6H 120 3 gave the following spectral
data:
UY: il.,nax 283 nm, e,nax 27 (hexane).
IR: Significant absorption bands at 1715 and 2900 cm- 1.
310 + ORGANIC SPECTROSCOPY
PMR: 8 2.2 (three proton singlet), 2.6 (two proton doublet, J = 7 Hz), 3.4
(six proton singlet) and 4.8 (one proton triplet, J = 7 Hz).
13C NMR (Off-resonance decoupled): One singlet, one doublet, one triplet and
two quartets. The singlet is at 8 205.
Mass: Prominentpeaks at mlz 132, 101, 75 and 43.
Deduce the structure of the compound and explain the spectral data.
2. A compound with the molecular weight 116 gave the following spectral
information:
UV: Amax 283, Ernax 22.
IR: A very broad band in the region 2500-3000 cm- 1 and a strong band at
1715 cm- 1.
PMR: 8 2.12 (3H, s), 2.60 (2H, t), 2.25(2H, t) and 11.1 (lH, s).
Deduce the structure of the compound and explain the spectral data.
3. A compound with molecular formula C6 H 120 gave the following spectral data:
UV: Aruax 280 nm, Ernax 25.
IR: Significant bands at 1715 and 2900 cm- 1.
1H NMR: Two singlets at 8 1.0 and 2.0 in the intensity ratio 3: 1.

Explaining the spectral data, deduce the structure of the compound.

4. A compound with molecular formula C5H7N0 2 gave the following spectral data:
UV: No significant absorption above 210 nm.
IR:Significant bands at 1745, 2270 and 2950 cm- 1•
PMR: 8 1.3 (3H, t), 3.5 (2H, s) and 4.3 (2H, q).
13C NMR (Proton-noise decoupled): Two singlets, two triplets and one quartet.
One of the singlets appear at 8 165.
MS: Prominentpeaks at mle 113, 86, 68 and 40.
Rationalizing the spectral data, deduce the structural formula of the compound.
5. An organic compound with molecular mass 160 show UV absorption at 212 nm,
Ern.,. 60. Its IR spectrum reveals bands at 2940-2860, 1740, 1460, 1260 and
1050 cm- 1• In the PMR spectrum of the compound, three signals are observed:
8 1.3 (triplet, J = 7.2 cps), 2.5 (singlet) and 4.2 (quartet, J = 7.2 cps) in the
intensity ratio 3 : 1 : 2, respectively.
Deduce the structure of the compound and explain the spectral data.
6. An organic compound with molecular mass 150 gave the following spectral data:
UV: Arnax 205, Ernax 75.
IR: Significant absorption bands at 3460,3035,2650,1720 and 1265 cm- 1.
PMR: 8 3.6 (singlet), 4.5 (singlet) and 11.0 (singlet) in the intensity ratio
I : 1 : 1.
Explaining the spectral data, determine the structure of the compound.
7. An organic compound with molecular weight 54 is transparent to UV spectrum
above 200 nm. In the IR spectrum, it shows bands at 3290, 2128 and 620 cm- 1•
In its 1H NMR spectrum, the following three signals are observed: 81.2 (triple,
J = 7.1 cps), 1.5 (quartet, J = 7.1 cps) and 2.4 (singlet) in the intensity ratio
3 : 2 : 1, respectively.
Derive the structure of the compound consistent with the given data.
8. An organic compound C3H60 absorbs at 176 nm, Ernax 15000. It shows IR bands
at 3520, 1650 and 1280 cm- 1• In its PMR spectrum four signals·are observed at
 Spectroscopic Solutions of Structural Problems + 311
8 5.2 (double doublet), 5.7 (multiplet-complicated), 3.8 (singlet) and 2.I (doublet)
in the intensity ratio 2 : 1: I : 2, respectively.
Derive the structural formula of the compound and write its name.
9. An organic compound with molecular weight 58 is transparent above 200 nm in
its UV spectrum. lt shows absorption bands at 2940-2860 and I460 cm- 1 in its IR
spectrum. The PMR spectrum of the compound exhibits signals at 8 4.75
(t, J= 7.I cps) and 2.75 (quintet, J= 7.I cps) in the intensity ratio 2: I. Derive
the structure of the compound.
10. A hydrocarbon with molecular formula C5H8 exists in two isomeric forms. One
of the isomers gives the following spectral data:
IR: Significant absorption bands at 3320 and 2130 cm- 1.
13C NMR (Off-resonance): 8 83 (one singlet), 67 (one doublet), 20-30 (two triplets)
and I5 (one quartet).
Explaining the spectral data, derive the structure of the compound and give the
possible structure of its other isomer also.
11. An organic compound containing C, H and 0 gave the following spectral data:
UV: Ärnax 220 nm, Emax I800 (EtOH).
IR: Significant absorption bands at 3075, 2975, I745, I605, I500 and
I450 cm- 1•
PMR: 82.02 (singlet), 2.93 (triplet, J =7Hz), 4.30 (triplet, J =7Hz) and 7.30
(singlet) in the intensity ratio 3 : 2 : 2 : 5, respectively.
Mass: Prominentpeaks at mlz I64 (M'"), 9I,60, 73 and 43.
Explaining the spectral data, derive the structural formula of the compound.
12. An organic compound C6 H 140 gave the following spectral data:
UV: No significant absorption above 210 nm.
IR: Significant bands at 2850-2960 and I080 cm- 1•
PMR: 8 l.l (doublet) and 3.6 (septet) in the ratio 6 : I.
MS: Prominentpeaks at mlz 102, 87, 59, 45, and 43.
Deduce the structure of the compound and, explain the spectra data.
13. An organic compound with molecular mass I 52 shows UV absorption at 223 nm,
Emax IOO.It shows bands at 2900-3I25, 2690, 2600, l7I5 and 1440 cm- 1 in its IR
spectrum. In 1H NMR spectrum the following signals were observed: 8 1.83 (d,
J = 7.2 cps), 4.52 (q, J = 7.2 cps) and 11.93 (s) in the intensity ralio 3 : 1 : 1. The
mass spectrum of the compound shows molecular ion peak at mlz 152 and
another peak of equal intensity at mlz 154.
Explaining the spectral data, deduce the structure of the compound.
14. An organic compound with molecular weight 130 shows IR absorption bands at
2860-3080, 1825, 1755 and 1455 cm- 1. In PMR spectrum, it shows two signals:
one triplet (J = 7.1 cps) and one quartet (J = 7.1 cps) at 81.3 and 2.2, respectively
in the intensity ratio 3 : 2. 13C NMR (proton-noise decoupled) reveals three
signals.
Explain the spectral data and deduce the structure of the compound.
15. An organic compound C4H9NO gave the following spectral data:
UV: A.nax 220 nm, Emax 63.
IR: Significant bands at 3500, 3400, 1682 and 1610 cm- 1•
1H NMR: 8 1.0 (doublet), 2.1 (septet) and 8.08 (singlet) in the intensity ratio

6: 1 : 2.
312 + ORGANIC SPECTROSCOPY
Rationalizing the spectral data, derive the structural formula of the compound.
16. An organic compound with molecular mass 71 is transparent in the UV spectrum.
In IR spectrum, it shows bands at 2860-2940, 2250 and 1460 cm- 1. lts PMR
spectrum shows two singlets at 8 4.22 and 3.49 in the intensity ratio 2 : 3.
Deduce the structure of the compound and explain the spectral data.
17. Rationalizing the spectral data, derive the structure of an organic compound with
molecular mass 72:
UV: Absorption at 274 nm, Emax 17.
IR: Significant absorption bands at 2860-2940, 1715 and 1460 cm-•.
1H NMR: 8 2.48 (q, J = 7.2 cps), 2.12 (s) and 1.07 (t, J = 7.3 cps) in the intensity

ratio 2 : 3 : 3.
18. An organic compound C6H 120 2 is transparent above 210 nm in its UV spectrum.
lt shows IR absorption bands at 2925, 1745 and 1455 cm-•. Its PMR spectrum
reveals two singlets at 8 1.97 and 1.45 in the intensity ratio 1 : 3. Derive the
structure of the compound and explain the spectral data.
19. An organic compound containing C, H and 0 is not acidic in nature but can be
easily oxidized to a crystalline compound (m.p. 122°C). lt gives the following
spectral data:

UV: A..nax 255 nm, Emax 202.

IR: Significant absorption bands at 3400, 3065, 2290, 1500 and 1455 cm-•.
1H NMR: 83.90 (singlet), 4.60 (singlet) and 7.26 (singlet) in the intensity ratio
1 : 2 : 5, respectively.
13C NMR (proton-noise decoupled): Shows five signals.
MS: Prominent peaks at 108 (M+), 107, 105, 79, 77 and 51.
Explaining the given data, deduce the structure of the compound.
20. Explaining the spectral data, deduce the structure of the compound from its UV,
IR, 1H NMR, 13C NMR and mass spectra given in Fig. P9.1 (a-e).
21. Explain the spectral data and deduce the structure of the compound from its UV,

j
6
~ 0.9
UV spectrum
33.3 mg/10 ml EtOH
1.2
I cmcell

250 300 350

A.(nm)
(a)
 Spectroscopic Salutions of Structural Problems + 313

IR spectrum
(liquid film)

1705

4000 3000 2000 1600 1200 800

v (cm-1)
(b)

I 00 MHz proton
NMR spectrum
CDCI 3 solution

_/

l_ l

10 9 8 7 6 5 4 3 2 0
(c) 8 (ppm)

20 MHz carbon-13
NMR spectrum

1.
CDC1 3 solution

1 J,l

.lll
Off-resonance decoupled

Proton decoupled

...-l ,.. .
220 200 180 160 140 120 100 80 60 40 20 0 8 (ppm)
(d)

90 43 Mass spectrum

... 70
""'Po
".rJ:Q 50
29
'-
0 30 MT72
;;!< 57
10 l
20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340
mle
(e)
Fig. P9.1
314 + ORGANIC SPECTROSCOPY
IR, 1H NMR, 13 C NMR and mass spectra given in Fig. P9.2 (a-e).

0.3

0
u 0.6
c

~"' 0.9
UV spectrum
1l 0.491 mg/10 ml EtOH
< 0.2 cm cell

1.2

1.5
200 250 300 350
..1.(nm)
(a)

IR spectrum
(nujol mull)

1720

4000 3000 2000 1600 1200 800

v(cm- 1)
(b)

I 00 MHz proton NMR spectrum

CDC13 solution

r-

{
>--

- --~
l
10 9 8 7 6 5 4 3 2 I 0
8 (ppm)
(c)
 Spectroscopic Salutions of Structural Problems + 315
20 MHz carbon-13

L
NMR spectrum
CDCI 3 solution
l lt ,tJ,

l
Off-resonance decoupled "

Proton decoupled A

220 200 180 160 140 120 100 80 60 40 20 0 ö (ppm)

(d)

90 177 Mass spectrum

170 149

J 50
166
'Cl 30 194

tT l
~ Mt
10
~ Jl ~ I I 222 C12Ht4Ü4

20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340
mle
(e)
Fig. P9.2