KRA343 Structure and Materials (2020)

NMR Spectroscopy – James Horne

Assignment

This assignment is due at 17:00, Friday 22/05/20 – please scan and upload
your annotated spectra and written/typed analysis of the data to MyLo.

You may choose to collaborate (with appropriate social distancing measures)

with your peers in groups of two to three and hand in a single report for each
group or you may work individually. Group members will receive the same
marks. Working together can be helpful for learning for many people so I am
happy to encourage this but it is OK if you wish to do it alone.
Please note this is a relatively complicated example that is designed to give
you maximum opportunity to engage with data and analysis. Performing this
task will be the single most useful thing you can do to prepare you for
examinations. Please feel free to engage with me while you are working
through it. I’m happy to help answer your queries so you can get on top of the
data.
Please submit these pages for assessment with any additional annotations on
spectra also included.

Name(s): …………Akashkumar B Patel……………………………………………….

……………………Student Id- 513001……………………….…………………………

……………………Date-22/05/2020………..……………………………………………
………………………………………………………………………………………………

KRA343 NMR Spectroscopy assignment 2020 – James Horne 1

The following spectra are of the same compound, molecular formula
C28H35NO5 with approximately 15 mg dissolved in 0.6 mL CDCl3. The
spectra were recorded at 600 MHz for 1H and 150 MHz for 13C. The following
spectra with appropriate expansions are provided:

 1
H (1D); peaks are labelled in ppm
 COSY45
 1
H-decoupled 13C (1D); peaks are labelled in ppm
 HSQCme
 HMBC

The structure of the compound is as follows:

C28H35NO5

Please note there is a double bond missing in the third ring of

the embedded structures in the spectra shown below.

KRA343 NMR Spectroscopy assignment 2020 – James Horne 2

 1. Using the molecular formula provided, determine the number of
degrees of unsaturation (double bond equivalents) - this is a highly
relevant and important step when dealing with an unknown structure.
[1 mark]

2. Mark the 2D spectra to indicate whether they are COSY, HSQCme or

HMBC spectra [3 marks]

3. Using whichever spectra are required, determine the number of each

type of carbon atom indicate which spectra and data you used to
determine this [4 marks]

Number of CH3
Number of CH2
Number of CH
Number of C

4. How do the data support the determination of the supplied structure of

this compound? Show, in a logical manner, the steps you have taken.
Indicate, where necessary, any annotations on the spectra themselves
that you wish to be assessed. Include all relevant information from the
data or from your calculations, not just for the one piece of information
you used to justify the structure. Be aware that there may not always
be sufficient information to arrive at a complete structural solution in
practice. In such cases be sure to indicate the limitations of the data.
In brief, give me as much as you can find in the data! [30 marks]

5. Report your list of assignments for the structure in standard journal

reporting format – please annotate the atoms in the supplied structure
so I may understand your assignments [10 marks]

KRA343 NMR Spectroscopy assignment 2020 – James Horne 3

KRA343 NMR Spectroscopy assignment 2020 – James Horne 4
 J
J
3
H -
P
C H
O
1 .9989 C
H D
1 .0091 H3 HC -
3
C N 3
-
1 .8910 O 7
O 8
O 3
O 0
H 1
/
U
s
e
6 r
s
/

0 .9796
0.9846

1.0259
4
1.0183
1.0000
1.0095

0.9436

1.0036

5.9157
2
1 .0295

8.7207

3 .1120
3 .8284
[p 3 .0832
p
m
]
0 2 4 6 8 10 [rel]
KR
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[rel]
43
N
M
R N O
O
Sp

10
H3C OH
ect
ro
H3 C CH O
sc H3C O
op 3

8
y
as
sig
n

6
m
en
t
20

4
20
–
Ja
m

2
0
1 .00911.9989

0.9846
1.8910

0.9796
7.5 7.0 6.5 6.0 5.5 5.0 [ pp m ]

6
 J
J
1.0259 3
H -
4. P
C H
0 O
1.0183 C
H D
H3 HC -
3
C N 3
-
1 .0000 O 7
O 8
O 3
O 0
3. 1 .0095
H 1
5 /
U
s
e
r
s
/

3. 0 .9436
0

1.0036

2.
5

5.9157

2.
0
1.0295

8.7207
1.
5

3.0832

1.
0 3.1120
3 .8284

[p
p
m
]
0 2 4 6 8 10 [rel]
 J
J
3
H -
P
C H
O
C
H D
H3 HC -
3
C N 3
-
7. O 7
6 O 8
O 3
O 0
H 1
/
U
s
e
r
7. 7.4935 s
5 1.9989 /
7.4905
7.4811
7.4704
7.4678
7.4246
7.4228
1.0091 7.4208
7. 7.4132
4 7.4103
7.3978

7.
3

7.
2
1.8910 7.1763
7.1642

7.
1

[p
p
m
]
0 2 4 6 8 10 [rel]
 J
J
5. 3
H -
P
8 C H
O
C
H D
H3 HC -
3
C N 3
-
O 7
O 8
O 3
O 0
5. H 1
7 /
U
s
e
r
s
/

5. 5.5921
6 5.5881
0.9796
5.5847
5.5814
5.5774

5.
5

5.4364
5.4300
5.4253
0.9846 5.4213
5. 5.4181
4 5.4148
5.4109
5.4061
5.3997

5.
3

5.
2
[p
p
m
]
- 0.0 0.5 1.0 1.5 [rel]
 J
J
3
H -
P
C H
O
4.
C
H D
H3 HC -
2 3
C N 3
-
O 7
O 8
O 3
O 0
H 1
/
4.0955 U
4. s
1 4.0855 e
4.0815 r
1.0259 4.0755 s
4.0717 /
4.0657
4.0617
4.0517
4.
0

3.9538
3.9443
3.9370
1.0183 3.9341
3.9275
3. 3.9248
9 3.9173
3.9078

3.
8

3.7330
1.0000
3.7266
3.7189
3.
3.7125
7

[p
p
m
]
- 0.0 0.5 1.0 1.5 [rel]
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[rel]
43
N
M

3.0520
3.5199

3.0422
R N O

3.0380
O
Sp

3.0281
3.5065
H3C OH
ect
ro
H3 C CH O

1.5
sc H3C O
op 3

y
as
sig
n

1.0
m
en
t
20
20

0.5
–
Ja
m

- 0.0
0.9436
1.0095

3.6 3.5 3.4 3.3 3.2 3.1 3.0 [ pp m ]

11
 0.9436 J
J
3
H -
P
C H
O
C
H D
H3 HC -
3
C N 3
-
O 7
2. O 8
9 O 3
O 0
H 1
/
U
s
e
r
s
2. /
8
2.7688
2.7616
1.0036 2.7526
2.7459
2.7395
2.7331
2. 2.7236
7 2.7164

2.
6

2.
5

2.
4

[p
p
m
]
- 0.0 0.5 1.0 1.5 [rel]
 J
J
3
H -
P
C H
O
C
H D
H3 HC -
3
C N 3
-
2. O 7
3 O 8
O 3
O 0
H 1
/
U
s
e
r
2. s
2 2.1890
/
2.1876
2.1848
5.9157 2.1627
2.1597
2.1503
2.1413
2.1381
2.
2.1218
1
2.1156

2.
0

1.9427
1.9402
1.9312
1.0295 1.9285
1.9223
1.
1.9197
9
1.9107
1.9082

1.
8

[p
p
m 8.7207
]
- 0 1 2 3 4 [rel]
 J
J
3
H -
P
C H
O
C
H D
1. H3 HC -
3
7 C N 3
-
O 7
O 8
O 1.6643
3
O1. 6482 0
H1.6414 1
/
U
s
1. e
6 r
1.5870
s
/
8.7207 1.5557

1.5352

1.
5 1.5151
1.4973
1.4943

1.4597
1.4533
1.4383
1. 1.4319
4

1.
3

1.
2
3.0832 1.1844

[p
p
m
]
- 0 1 2 3 4 [rel]
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[rel]
43
N
M

1.1844

0.9583

0.8990
R N O
O
Sp

10
H3C OH
ect
ro
H3 C CH O
sc H3C O
op 3

8
y
as
sig
n

6
m
en
t
20

4
20
–
Ja
m

2
0
8.7207

3.0832

3.1120

3.8284
1.3 1.2 1.1 1.0 0.9 0.8 [ pp m ]

15
 J
J
177.8048 -
177.3457 P
H
D
170.6157 -
3
1
1
/
U
15 s
0 e
r
s
140.4449 /
h
j
131.5761 h
129.3521
129.0255
126.8730
123.9788

10
0

72.3810

62.5556

50 51.8292
43.5617
43.5267
43.3850
41.0527
39.4472
37.4992
35.6033
33.5784
33.3497
26.4215
26.3524
[p 22.4951
p 21.2879
m 18.9487
]
- 0.0 0.5 1.0 1.5 2.0 2.5 [rel]
 J
J
18 -
0 P
H
177.8048 D
177.3457 -
3
1
1
/
U
17 170.6157 s
0 e
r
s
/
h
j
h

16
0

15
0

14 140.4449
0

131.5761
13 129.3521
0 129.0255
126.8730

123.9788

12
0
[p
p
m
]
- 0.0 0.5 1.0 1.5 2.0 2.5 3.0 [rel]
 J
J
-
72.3810 P
H
D
70
-
3
-
1
/
U
s
e
62.5556 r
s
60 /
h
j
h

51.8292
50

43.5617
43.5267
43.3850
41.0527
40 39.4472

37.4992

35.6033
33.5784
33.3497

30

26.4215
26.3524

22.4951
21.2879
20
18.9487
[p
p
m
]
- 0.0 0.5 1.0 1.5 2.0 [rel]
 F2 [ppm]
2
3
4
5
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6
1
33
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KRA343 NMR Spectroscopy assignment 2020 – James Horne 19

 F2 [ppm]
2
3
4
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1

5
33
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KRA343 NMR Spectroscopy assignment 2020 – James Horne 20

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N
M
R

F1 [ppm]
Sp
ect
ro
sc
op

7.1
y
as
sig
n

7.2
m
en
t

7.3
20
20
–
Ja

7.4
m

7.5
7.6
7.5 7.4 7.3 7.2 7.1 F2 [ppm]

21
 F2 [ppm]
2
3
4
5
/Users/hjhorne/nmr

6
1
32

7
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KRA343 NMR Spectroscopy assignment 2020 – James Horne 22

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N
M
R

F1 [ppm]
Sp
ect
ro
sc
op
y

30
as
sig
n
m
en

40
t
20
20
–

50
Ja
m

60
4.0 3.5 3.0 2.5 2.0 1.5 F2 [ppm]

23
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N
M
R

80 F1 [ppm]
Sp
ect
ro
sc
op
y
as

90
sig
n
m

100
en
t
20

110
20
–
Ja

120
m

130
7.5 7.0 6.5 6.0 5.5 F2 [ppm]

24
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N
M

122 F1 [ppm]
R
Sp
ect
ro
sc
op
y
as

124
sig
n
m

126
en
t
20

128
20
–
Ja
m

130
132
7.5 7.4 7.3 7.2 F2 [ppm]

25
 F2 [ppm]
2
3
4
5
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6
1
34
JJ-PHD-3-78

KRA343 NMR Spectroscopy assignment 2020 – James Horne 26

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N
M

130F1 [ppm]
R
Sp
ect
ro
sc
op
y
as
sig

140
n
m
en

150
t
20
20
–

160
Ja
m

170
180
7.0 6.5 6.0 5.5 F2 [ppm]

27
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N
M
R

F1 [ppm]
Sp
ect
ro
sc
op

130
y
as
sig

140
n
m
en

150
t
20
20
–

160
Ja
m

170
180
4.0 3.5 3.0 2.5 2.0 1.5 F2 [ppm]

28
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N
M
R

F1 [ppm]
Sp
ect
ro
sc
op

30
y
as
sig
n

40
m
en
t
20

50
20
–
Ja

60
m

70
7.0 6.5 6.0 5.5 5.0 F2 [ppm]

29
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N
M
R

F1 [ppm]
Sp
ect
ro
sc
op

30
y
as
sig
n

40
m
en
t

50
20
20
–
Ja

60
m

70
80
4.0 3.5 3.0 2.5 2.0 1.5 F2 [ppm]

30