-
Chem 4010/5326: Organic Spectroscopic Analysis Fall 2015 Problem
Set 4 In addition to the problems assigned on the class schedule,
do the following: (1) Determine the structure of the compound using
the spectral information provided and assign as many 1H and 13C
resonances as possible. (a)
OH
10
8,9
8,9
76
43
1
25
42404260 Hz
1.52.02.53.03.54.04.55.05.56.06.57.0 ppm
1501401301201101009080706050400
50
100
65 77
91 115
135
150
% o
f Bas
e Pe
ak
m/z
4000 3000 2000 1000Wavenumber (cm-1)
50
100
% T
rans
mitt
ance
590
810
945
1088115312271458151615811620
28702962
3464
IR
MASS
1H NMR 600 MHz
19001920 Hz
27802800 Hz39403960 Hz40404060 Hz
740760 Hz13601380 Hz
3 4 6 OH 7 10 8,9
CHH3C
CH3 OH
CH3
H
H
H
12
3
45
6
Thymol
97
8
10
Problem 7.3A
44913_07_p341-380 11/30/04 1:20 PM Page 350
42404260 Hz
1.52.02.53.03.54.04.55.05.56.06.57.0 ppm
1501401301201101009080706050400
50
100
65 77
91 115
135
150
% o
f Bas
e Pe
ak
m/z
4000 3000 2000 1000Wavenumber (cm-1)
50
100
% T
rans
mitt
ance
590
810
945
1088115312271458151615811620
28702962
3464
IR
MASS
1H NMR 600 MHz
19001920 Hz
27802800 Hz39403960 Hz40404060 Hz
740760 Hz13601380 Hz
3 4 6 OH 7 10 8,9
CHH3C
CH3 OH
CH3
H
H
H
12
3
45
6
Thymol
97
8
10
Problem 7.3A
44913_07_p341-380 11/30/04 1:20 PM Page 350
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(b) Note: It may be difficult to completely assign all
protons/carbons with the data given.
Problem 7.3B
2030405060708090100110120130140150 ppm
13C/DEPT NMR 150.9 MHz
ppm
1.52.02.53.03.54.04.55.05.56.06.57.07.5 ppm
2
3
4
5
6
7
1 5 2 3 4 6 7
DQFCOSY 600 MHz
CHH3C
CH3 OH
CH3
H
H
H
12
3
45
6
Thymol
97
8
10
346
OH
7
10
8,9
CDCl3 10
8,9
F2
F1
44913_07_p341-380 11/30/04 1:20 PM Page 351
OH
H
1
2
34
5
6
7
89
10 11
31503200 Hz
1.01.52.02.53.03.54.04.55.05.5 ppm
IR
MASS
1H NMR 600 MHz
% o
f Bas
e Pe
ak
m/z15010050
50
100
41 5567
79
91110
122135
149
164
4000 3000 2000 1000Wavenumber (cm-1)
50
100
%T
rans
mitt
ance
7561072
13421442
16511697
28772962
O
CH3
CH2CH2
CH3
HH
cis-jasmone
17001750 Hz
1250 Hz 550600 Hz
14001450 Hz
Problem 7.5A
44913_07_p341-380 11/30/04 1:21 PM Page 363
-
31503200 Hz
1.01.52.02.53.03.54.04.55.05.5 ppm
IR
MASS
1H NMR 600 MHz
% o
f Bas
e Pe
ak
m/z15010050
50
100
41 5567
79
91110
122135
149
164
4000 3000 2000 1000Wavenumber (cm-1)
50
100
%T
rans
mitt
ance
7561072
13421442
16511697
28772962
O
CH3
CH2CH2
CH3
HH
cis-jasmone
17001750 Hz
1250 Hz 550600 Hz
14001450 Hz
Problem 7.5A
44913_07_p341-380 11/30/04 1:21 PM Page 363
406080100120140160180200 ppm
13C/DEPT NMR 150.9 MHz
CDCl3
ppm
1.01.52.02.53.03.54.04.55.05.56.0 ppm
1
2
3
4
5
6
DQFCOSY 600 MHz
F1
F2
O
CH3
CH2CH2
CH3
HH
cis-jasmone
Problem 7.5B
44913_07_p341-380 11/30/04 1:21 PM Page 364
1 3 2 9 8 5 4 7,10,6,11
8 9 6 11 10 7 4,5
-
(c)
O
O
12
3
4
5
6 8
7
43004350 Hz
1.52.02.53.03.54.04.55.05.56.06.57.0 ppm
IR
MASS
1H NMR 600 MHz
2500 Hz
3450 Hz36503700 Hz
750 Hz1100 Hz
3 4,5 67 8
H3C
HC
CH
HC
CH
OCH2
CH3
O
1
23
45
6
7
8
Ethyl sorbate
2
% o
f Bas
e Pe
ak
m/z140130120110100908070605040
50
100
140125
111
97
95
67
41
4000 3000 2000 1000Wavenumber (cm-1)
50
100
% T
rans
mitt
ance
29812912
171616471620
132712461142
999
868
Problem 7.2A
44913_07_p341-380 11/30/04 1:20 PM Page 346
43004350 Hz
1.52.02.53.03.54.04.55.05.56.06.57.0 ppm
IR
MASS
1H NMR 600 MHz
2500 Hz
3450 Hz36503700 Hz
750 Hz1100 Hz
3 4,5 67 8
H3C
HC
CH
HC
CH
OCH2
CH3
O
1
23
45
6
7
8
Ethyl sorbate
2
% o
f Bas
e Pe
ak
m/z140130120110100908070605040
50
100
140125
111
97
95
67
41
4000 3000 2000 1000Wavenumber (cm-1)
50
100
% T
rans
mitt
ance
29812912
171616471620
132712461142
999
868
Problem 7.2A
44913_07_p341-380 11/30/04 1:20 PM Page 346
-
Problem 7.2B
30405060708090100110120130140150160170 ppm
13C/DEPT NMR 150.9 MHz
1 5 23 4 67
CDCl3
8
6.056.106.15 ppm
36203640366036803700 Hz
H3C CH CH CH CH C
O
OC2H5
irr irr
H3C CH CH CH CH C
O
OC2H5
irr
H3C CH CH CH CH C
O
OC2H5
irr
1H Homodecoupled 600 MHz
1H NMR 600 MHz
H3C
HC
CH
HC
CH
OCH2
CH3
O
1
23
45
6
7
8
Ethyl sorbate
44913_07_p341-380 11/30/04 1:20 PM Page 347
Problem 7.2B
30405060708090100110120130140150160170 ppm
13C/DEPT NMR 150.9 MHz
1 5 23 4 67
CDCl3
8
6.056.106.15 ppm
36203640366036803700 Hz
H3C CH CH CH CH C
O
OC2H5
irr irr
H3C CH CH CH CH C
O
OC2H5
irr
H3C CH CH CH CH C
O
OC2H5
irr
1H Homodecoupled 600 MHz
1H NMR 600 MHz
H3C
HC
CH
HC
CH
OCH2
CH3
O
1
23
45
6
7
8
Ethyl sorbate
44913_07_p341-380 11/30/04 1:20 PM Page 347
-
(d)
O
S1
2
34
5 6
Problem 8.5
2.53.03.54.04.55.05.56.06.57.07.5 ppm
405060708090100110120130140150160170180190 ppm
13C/DEPT
1H NMR
MASS
IR
21202140 Hz22802300 Hz
% o
f Bas
e Pe
ak
m/z130120110100908070605040
50
100
3943
49 5783
111
126
4000 3000 2000 1000Wavenumber (cm-1)
50
100
%T
rans
mitt
ance
3089
1662
1415
1273
1061933856
725
590
13C/DEPT NMR 75.5 MHz
1H NMR 300 MHz
m/z %M 126 (M) 100.0 127 (M+1) 8.2 128 (M+2) 4.9
44913_08_p381-425 11/23/04 3:29 PM Page 386
Problem 8.5
2.53.03.54.04.55.05.56.06.57.07.5 ppm
405060708090100110120130140150160170180190 ppm
13C/DEPT
1H NMR
MASS
IR
21202140 Hz22802300 Hz
% o
f Bas
e Pe
ak
m/z130120110100908070605040
50
100
3943
49 5783
111
126
4000 3000 2000 1000Wavenumber (cm-1)
50
100
%T
rans
mitt
ance
3089
1662
1415
1273
1061933856
725
590
13C/DEPT NMR 75.5 MHz
1H NMR 300 MHz
m/z %M 126 (M) 100.0 127 (M+1) 8.2 128 (M+2) 4.9
44913_08_p381-425 11/23/04 3:29 PM Page 386
Problem 8.5
2.53.03.54.04.55.05.56.06.57.07.5 ppm
405060708090100110120130140150160170180190 ppm
13C/DEPT
1H NMR
MASS
IR
21202140 Hz22802300 Hz
% o
f Bas
e Pe
ak
m/z130120110100908070605040
50
100
3943
49 5783
111
126
4000 3000 2000 1000Wavenumber (cm-1)
50
100
%T
rans
mitt
ance
3089
1662
1415
1273
1061933856
725
590
13C/DEPT NMR 75.5 MHz
1H NMR 300 MHz
m/z %M 126 (M) 100.0 127 (M+1) 8.2 128 (M+2) 4.9
44913_08_p381-425 11/23/04 3:29 PM Page 386
6 4 3 5
6 1 2
5,3,4
-
Simpson problems 6.3: By removing one of the methylene groups
from the CH2–CH2 bridge “pulls” HB up. This impacts the dihedral
angle between the HB atom and the HE and HX atoms.
HE
HXHB
HE
HXHB
HB
HX
HE
HBHX
HE
θ1
θ2
θ1 = θ1
θ1
θ2
θ1 < θ1
