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2D NMR Course 2015 Final Assignment
Due date Wed 9 Jan 2016
Either: hand to Marcel Jaspars OR email to [email protected] requesting an acknowledgement.
The 1H, 13C, DEPT-135, HSQC, COSY, HMBC and selective 1D TOCSYs for Erythromycin are provided as a MestreNova file and as a series of PDF pages.
Note:
1.) The 13C NMR spectrum shows an additional quaternary carbon at 221.05 ppm 2.) The HMBC shows an additional series of correlations from δC 221.05 ppm to δH 3.82; 3.08;
2.68; 1.92; 1.71; 1.14 ppm 3.) The sample has been contaminated with plasticiser. The 1H and 13C NMR reference data is
provided at the end of this PDF.
O
O O
O
O
OH
O
HO
OH
OH
O
OH
O
N
O
O
O
O
Erythromycin
14
8
12
14
15
1617
18
19
20
1'2'
3'
4'5'
6'
7'
7'
1''
2'' 3''4''
5''6''
7''
8''
Plasticiser
Question:
Using the NMR data please assign all the 1H and 13C NMR data to the structure of Erythromycin.
Your answer should contain:
1.) A data table containing atom number as above; δC/ppm; C/CH/CH2/CH3; δH/ppm; mult; J/Hz; COSY correlations; HMBC correlations
2.) Structures of erythromycin annotated with: a. 1H NMR assignments b. 13C NMR assignments c. COSY correlations d. HMBC correlations
O
O O
O
O
OH
O
HO
OH
OH
O
OH
O
N
14
8
12
14
15
1617
18
19
20
1'2'
3'
4'5'
6'
7'
7'
1''
2'' 3''4''
5''6''
7''
8''
0.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.0f1 (ppm)
-20
0
20
40
60
80
100
120
140
160
180
200
220
240
erythromycin_1Herythromycin_CDCl3
2.77
27.1
1
1.43
3.93
1.68
3.55
4.04
9.46
1.65
1.48
1.44
1.42
2.43
2.09
3.50
1.46
1.13
1.04
2.43
1.84
0.99
1.00
2.62.72.82.93.03.13.23.33.43.53.63.73.83.94.04.14.24.34.44.54.64.74.84.95.0f1 (ppm)
-10
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180erythromycin_1Herythromycin_CDCl3
1.48
1.44
1.42
2.43
2.09
3.50
1.46
1.13
1.04
2.43
1.84
0.99
1.00
0.80.91.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.5f1 (ppm)
-20
-10
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210erythromycin_1Herythromycin_CDCl3
2.77
27.1
1
1.43
3.93
1.68
3.55
4.04
9.46
1.65
102030405060708090100110120130140150160170f1 (ppm)
-2000
0
2000
4000
6000
8000
10000
12000
14000
16000
18000
20000
22000
24000
26000
28000
30000erythromycin_13Cerythromycin_13C
9.26
10.5
510
.79
12.1
314
.22
16.0
816
.31
18.4
118
.77
21.2
321
.50
21.6
127
.07
28.8
735
.09
37.9
938
.63
39.5
240
.37
45.0
045
.27
49.6
1
61.7
365
.65
65.7
069
.01
71.0
272
.74
74.7
975
.11
76.8
4 CD
Cl3
76.9
977
.16
CDCl
377
.36
77.4
8 CD
Cl3
78.1
180
.08
83.6
8
96.4
4
103.
30
128.
9613
1.05
132.
36
167.
75
175.
89
6065707580859095100105110115120125130135140145150155160165170175f1 (ppm)
-2000
-1000
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
11000
12000
13000
14000
15000
16000
17000
18000
19000
20000
21000
22000
23000erythromycin_13Cerythromycin_13C
61.7
3
65.6
565
.70
69.0
171
.02
72.7
474
.79
75.1
176
.84
CDCl
376
.99
77.1
6 CD
Cl3
77.3
677
.48
CDCl
378
.11
80.0
883
.68
96.4
4
103.
30
128.
9613
1.05
132.
36
167.
75
175.
89
810121416182022242628303234363840424446485052f1 (ppm)
-2000
-1000
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
11000
12000
13000
14000
15000
16000
17000
18000
19000
20000
21000
22000
23000
24000
25000erythromycin_13Cerythromycin_13C 9.
26
10.5
510
.79
12.1
3
14.2
2
16.0
816
.31
18.4
118
.77
21.2
321
.50
21.6
1
27.0
7
28.8
7
35.0
9
37.9
938
.63
39.5
240
.37
45.0
045
.27
49.6
1
101520253035404550556065707580859095100105110115120125130f1 (ppm)
1
2
erythromycin_dept13513C OBSERVE
2
erythromycin_13Cerythromycin_13C 1
65707580859095100105110115120125130f1 (ppm)
1
2
erythromycin_dept13513C OBSERVE
2
erythromycin_13Cerythromycin_13C 1
810121416182022242628303234363840424446485052f1 (ppm)
1
2
erythromycin_dept13513C OBSERVE
2
erythromycin_13Cerythromycin_13C 1
0.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.0f2 (ppm)
10
20
30
40
50
60
70
80
90
100
f1 (
ppm
)
erythromycin_hsqcerythromycin_CDCl3
2.22.32.42.52.62.72.82.93.03.13.23.33.43.53.63.73.83.94.04.14.24.34.44.54.64.74.84.95.05.1f2 (ppm)
60
65
70
75
80
85
90
95
100
105
f1 (
ppm
)
erythromycin_hsqcerythromycin_CDCl3
0.80.91.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.62.72.82.93.03.13.23.33.4f2 (ppm)
10
15
20
25
30
35
40
45
50
f1 (
ppm
)
erythromycin_hsqcerythromycin_CDCl3
0.800.850.900.951.001.051.101.151.201.251.301.351.401.451.50f2 (ppm)
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
f1 (
ppm
)
erythromycin_hsqcerythromycin_CDCl3
0.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.0f2 (ppm)
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
f1 (
ppm
)
erythromycin_cosyerythromycin_CDCl3
2.32.42.52.62.72.82.93.03.13.23.33.43.53.63.73.83.94.04.14.24.34.44.54.64.74.84.95.05.1f2 (ppm)
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
3.0
3.2
f1 (
ppm
)
erythromycin_cosyerythromycin_CDCl3
0.80.91.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.62.72.82.93.03.13.2f2 (ppm)
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
3.0
3.2
f1 (
ppm
)
erythromycin_cosyerythromycin_CDCl3
1.01.52.02.53.03.54.04.55.05.56.06.57.07.5f2 (ppm)
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
f1 (
ppm
)
erythromycin_hmbcerythromycin_CDCl3
1.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.2f2 (ppm)
166
167
168
169
170
171
172
173
174
175
176
177
178
f1 (
ppm
)
erythromycin_hmbcerythromycin_CDCl3
0.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.2f2 (ppm)
10
20
30
40
50
60
70
80
90
100
110
f1 (
ppm
)
erythromycin_hmbcerythromycin_CDCl3
1.01.52.02.53.03.54.04.55.0f2 (ppm)
60
65
70
75
80
85
90
95
100
105
110
f1 (
ppm
)
erythromycin_hmbcerythromycin_CDCl3
0.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.2f2 (ppm)
10
15
20
25
30
35
40
45
50
f1 (
ppm
)
erythromycin_hmbcerythromycin_CDCl3
0.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.2f1 (ppm)
1
2
3
4
5
6
7
8
9
10
erythromycin_seltocsy_5ppmerythromycin_CDCl3 10
erythromycin_seltocsy_5ppmerythromycin_CDCl3 9
erythromycin_seltocsy_5ppmerythromycin_CDCl3 8
erythromycin_seltocsy_5ppmerythromycin_CDCl3 7
erythromycin_seltocsy_5ppmerythromycin_CDCl3 6
erythromycin_seltocsy_5ppmerythromycin_CDCl3 5
erythromycin_seltocsy_5ppmerythromycin_CDCl3 4
erythromycin_seltocsy_5ppmerythromycin_CDCl3 3
erythromycin_seltocsy_5ppmerythromycin_CDCl3 2
erythromycin_seltocsy_5ppmerythromycin_CDCl3 1
0.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.0f1 (ppm)
1
2
3
4
5
6
7
8
9
10
11TOCSY 4.8 ppm
0.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.8f1 (ppm)
1
2
3
4
5
6
7
8
9
10
11TOCSY 4.35 ppm
0.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.4f1 (ppm)
1
2
3
4
5
6
7
8
9
10
11TOCSY 4.30 ppm
Extremely Challenging Polyfunctionalized Compounds 569
Problem 12.41
Exact MS ((+)-CI) = 391.2848
UV �max = 243 nm (� = 13,000)
278 nm (� = 1100)
319 nm (� = 50)
Hint: can be obtained from plastic
tubing 3800 3400 3000 2600 2200
WAVENUMBERS cm–1
1800 1400 1000 600
100
80
60
40
20
0
FT-IR
(NEAT)
100
5771
83
113
149
167
279
391EIMS70 eV80
60
40
40 60 80 100 120 140 160 180 200 220
m/z
240 260 280 300 320 340 360 380 400
20
0
2030405060708090100110120130140150160170 ppm
10
.46
13
.55
22
.53
23
.32
28
.48
29
.94
38
.30
67
.40
12
8.2
91
30
.38
13
2.0
6
16
7.0
5
13C NMR
62.8 MHz
CDCl3
CDCl3
s s
d d t
t t t q qt d
1.52.02.53.03.54.04.55.05.56.06.57.07.5 ppm
6.6
8.6
1.1
2.3
1.1
1.0
7.57.67.7 ppm
7.5
20
9
7.5
27
57
.53
23
7.5
38
9
7.7
03
4
7.7
10
1
7.7
14
87
.72
15
4.204.25 ppm
4.1
94
14
.20
64
4.2
16
04
.22
83
4.2
33
44
.24
48
4.2
55
2
1.01.11.21.31.41.51.61.7 ppm
0.9
04
30
.91
63
0.9
31
30
.94
62
1.3
26
31
.32
95
1.4
20
91
.43
41
1.6
83
11
.69
54
1.7
07
7
1H NMR
500 MHz
CDCl3
12-Crews-Chap12.indd 56912-Crews-Chap12.indd 569 8/25/2009 7:53:51 PM8/25/2009 7:53:51 PM
OUP � UNCORRECTED PROOF
