PROBLEM SET 3a

Lectures 1/21 & 1/26 Klein Chapters 15 and 16

Spectroscopy Practice

Provide a structure that best corresponds to the spectroscopic data provided (see the subsequent pages for
spectra). Match the 1H and 13C NMR signals to each proton and carbon of your solution. The spectra used for
this problem set are reproduced from the Aldrich spectral database.

Suggested way to solve spectroscopy problems where you are asked to identify the unknown compound:

(a) Determine the chemical formula:

e.g. for LRMS 273 Elemental analysis C, 65.91%, H, 7.01% N 15.37%; O, 11.71%
determine the number of atoms by:
percentage of atom x MW (LRMS)
# of atom =
atomic weight of atom
For carbon:
0.6591 x 273
# of C = = 14.98
12.011 (round up to 15)
Solve for the remaining atoms the same way to obtain:

H = 19, N = 3, O = 2
so, Chemical Formula = C15H19N3O2

(b) Next, determine the degrees of unsaturation:

2 x # of C + 2 + # of N – # of halides – X of H
HDI =
2
(c) Use IR and NMR to identify functional groups (arenes, olefins, acetylenes, nitriles, azides, allenes, amides,
esters, aldehydes, ketones, hydroxyls, amines, etc.)

(d) Interpret 1H NMR (1. kinds of distinct H’s; how many H’s does each peak represent; 3. splitting—what is
adjacent to the H?)

(e) Interpret 13C NMR (1. number of distinct C’s’ 2. kind of C’s.)

(f) Assemble fragments into possible molecules

(g) Eliminate possibilities by re-checking the spectral data against your potential solutions.
a. LRMS: 164; Elemental analysis: C, 73.15%; H, 7.37%; O, 19.49%
(see the next 2 pages for IR, 1H and 13C)
 MICRONS
2.5 3 3.5 4 4.5 5 5.5 6 7 8 9 10 11 12 13 15 20 25 30 45 100
100 0.0
90 % .05
T
80 R A 0.1
70 A B
N S 0.2
60 S O
M R
50 I B
0.3

40 T A 0.4
T N
30 0.5
A C
N E 0.6
20 0.7
C 0.8
10 E 1.0
0 2.0

I
N
T
E
N
S
I
T
Y

4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200 100
WAVENUMBERS NICOLET RAMAN 950
 CDCl3 QE-300
240 220 200 180 160 140 120 100 80 60 40 20 0

12 11 10 9 8 7 6 5 4 3 2 1 0
2H 2H 2H 3H 3H
b. LRMS: 131; Elemental analysis: C, 82.41%; H, 6.92%; N, 10.68%
(see the next 2 pages for IR, 1H and 13C)
 MICRONS NICOLET 20SX FT-IR
2.5 2.6 2.7 2.8 2.9 3 3.5 4 4.5 5 5.5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 21 22
100 0.0

90 .05

80 0.1

70
%
T
0.2
R A
60 A B
N S
S O
M R
50 0.3
I B
T A
T N
A C
40 0.4
N E
C
E
0.5
30
0.6

20 0.7

0.8
0.9
10 1.0

0 2.0
4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 450
WAVENUMBERS
 CDCl3 QE-300
240 220 200 180 160 140 120 100 80 60 40 20 0

12 11 10 9 8 7 6 5 4 3 2 1 0

5H 2H 2H
c. LRMS: 86; Elemental analysis: 69.72%; H, 11.70%; O, 18.58%
(see the next 2 pages for IR, 1H and 13C)
 MICRONS
2.5 3 3.5 4 4.5 5 5.5 6 7 8 9 10 11 12 13 15 20 25 30 45 100
100 0.0
90 % .05
T
80 R A 0.1
70 A B
N S 0.2
60 S O
M R
50 I B
0.3

40 T A 0.4
T N
30 0.5
A C
N E 0.6
20 0.7
C 0.8
10 E 1.0
0 2.0

I
N
T
E
N
S
I
T
Y

4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200 100
WAVENUMBERS NICOLET RAMAN 950
 CDCl3 QE-300
240 220 200 180 160 140 120 100 80 60 40 20 0

12 11 10 9 8 7 6 5 4 3 2 1 0

1H 2H 2H 2H 3H
d LRMS: 199; Elemental analysis: C, 54.30%; H, 5.57%; Br, 40.14%
(see next 2 pages for IR, 1H and 13C)
 MICRONS NICOLET 20SX FT-IR
2.5 2.6 2.7 2.8 2.9 3 3.5 4 4.5 5 5.5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 21 22
100 0.0

90 .05

80 0.1

70
%
T
0.2
R A
60 A B
N S
S O
M R
50 0.3
I B
T A
T N
A C
40 0.4
N E
C
E
0.5
30
0.6

20 0.7

0.8
0.9
10 1.0

0 2.0
4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 450
WAVENUMBERS
 CDCl3 QE-300
240 220 200 180 160 140 120 100 80 60 40 20 0

12 11 10 9 8 7 6 5 4 3 2 1 0
5H 1H 1H1H 3H
2. Predict the products of the following reactions. Then use the 1H and 13C NMR spectra
to determine if the observed product was the expected product. List the specific
resonances of the spectra that support your conclusion. If the spectra do not match the
expected product, suggest an alternative explanation for the identity of the isolated
compound. The spectra for this problem were taken by members of the Anderson
research group at UIC.

a.

O
Cl
OH Cl
O
Me
DMSO, NEt 3
Ph
 1.56
1.55
4.78
4.77
4.76
4.74
7.43
7.43
7.43
7.42
7.31
7.31
7.30
7.30
1.92
2.85

0.93

3.00
11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5
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 131.68
128.39
128.30
122.62

90.99

84.03

76.80

58.87

24.40
58.79
77.31
77.06
230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10
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b.

OH
Br
NaH, THF
c.

O (i) MeMgCl, Et2O

(ii) H3O+
H
(iii) PCC, CH2Cl2
d.

O
Cl
Me Cl
OH O
DMSO, NEt 3
Me
 9.86

2.31
7.40

7.17
1.00

2.00

0.99

6.00
11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5
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 192.56

138.66
136.60
136.10

127.47

20.95
77.51
77.25
77.00
230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10
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e.

O (i) n-BuLi, THF

Ph (ii) H3O+
 Btz' z -.---_
zBZ' ( ----'

90t't
BOt'h \
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7 .ffi$"

q
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59S'9-_-\:
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{ s.'ret ffi
(r
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CO
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3. Match the following structure to the following 1H and 13C NMR spectra. These spectra do not
contain CDCl3 resonances. Only the resonances corresponding to the compounds are present.
The spectra for this problem are reproduced from the National Institute of Advanced Industrial
Science and Technology, http://riodb01.ibase.aist.go.jp/sdbs/ on Feb. 18, 2011.

a.

cumene

b.

Ph Me

c.

OH

d.
O
Me

Me carvone

e.
O

MeO anisaldehyde

f.
N

H2N
i.

integration: 7.45 ppm = 2H (doublet), 7.24 ppm = 3H (multiplet), 2.1 ppm = 3H (singlet)
ii.

integration: 9.97 ppm = 1H (singlet), 7.89 ppm = 2H (doublet), 7.01 ppm = 2H (doublet), 3.88
ppm = 3H (singlet)
iii.

integration: 7.42 ppm = 2H (doublet), 6.76 ppm = 2H (doublet), 4.32 ppm = 2H (broad singlet)
iv.

integration: 7.44-7.21 ppm = 4H (multiplet), 2.88 ppm = 1H (heptet), 1.35 ppm = 6H (doublet)
v.

integration: 6.77 ppm = 1H (singlet), 4.82 ppm = 2H (doublet), 2.77-2.51 ppm = 2H (multiplet),
2.49-2.29 ppm = 2H (multiplet), 1.82 ppm = 3H (singlet), 1.78 ppm = 3H (singlet)
vi.

integration: 12.02 ppm = 1H (broad singlet), 8.12 ppm = 2H (doublet), 7.77-7.34 ppm = 3H
(multiplet)
4. The following IR spectra match compounds a-f in problem 3. Identify the key characteristics
of these spectra that identify the functional groups present in compounds a-f. The spectra for
this problem are reproduced from the National Institute of Advanced Industrial Science and
Technology, http://riodb01.ibase.aist.go.jp/sdbs/ on Feb. 18, 2011.

a. cumene
b. 1-phenyl-1-propyne
c. benzoic acid
d. carvone
e. p-anisaldehyde
f. p-amino benzonitrile