JS Organic Practical Course

Additional NMR spectra to aid structural determination

Three types of data are supplied :
-2D homonuclear corelation spectra (HH COSY)
-2D heteronuclear corelation spectra (CH COSY)
-1D Nuclear Overhauser spectra (NOE)
Data is supplied for experiments :
-2 (Benzoin), 3b (1,4-Diphenyl-1,3- butadiene)
-5 (2,6-Dimethyl-3-heptan-5-one)
-6a (1-Phenylbutane-1,4-diol)
-6b (-Phenyl--butyrolactone)
-7 (cis-Caran-trans-4-ol)

Additional NMR analysis

connections through bonds and space
Correlation Spectra (COSY) through bond connections
HH COSY - connections of proton spins through bonds
CH COSY- direct link of carbon to proton(s)
Long range CH COSY

Connections through space

Nuclear Overhauser (NOE) experiments
1D : Difference NOE, DPFGSE-NOE
2D : NOESY, ROESY

How to read a COSY

HH COSY
diagonal is the 1D spectrum
off diagonal signal(s) display the connections of the spins
true signal must have mirror image across the diagonal
CH COSY
signals are the direct correlation between the C and H
Long range CH COSY
often can correlate several protons to a carbon
(or vice versa - whichever is most appropriate )
e.g. links carbon signals with NO protons directly attached

2 CH COSY Benzoin
Direct correlation of

1H

hydrogen to carbon resonances

axis

(pp

(pp

80.0

126

128

90.0
130

100
132

110

134

(ppm)

8.00

7.80

7.60

120

7.40

Expansion of aromartic region

130

13C

axis
(ppm)

8.0

7.2

6.4

5.6

4.8

3B CH COSY (E,E)-1,4-Diphenyl-1,3-butadiene
(pp

Direct correlation of
hydrogen to carbon resonances

126

128

3'
4'

2' 1' 1
2
5'

130

4
132

6'
134
(ppm)

7.40

7.20

7.00

6.80

6.60

3B HH COSY (E,E)-1,4-Diphenyl-1,3-butadiene
(pp

6.40

6.60

(pp

6.80

7.00

6.40

7.20

7.40

6.60

7.60
7.60

(ppm)

7.40

7.20

7.00

6.80

6.60

Diagonal contains the 1D spectrum

6.80

Connections between atoms are

symmetrical about the diagonal

7.00

Generally, the higher the contour

the stronger the connection

3'
4'

2' 1' 1
2
5'

6'

7.20

7.40

4
7.60
(ppm)

7.60

7.40

7.20

7.00

6.80

6.60

5 HH COSY 2,6-Dimethyl-5-hydroxyheptan-3-one
O
3
2
1

OH

1H

5
4

(ppm)

6
7

1.6

(ppm)

2.4

1.2

1.6

3.2

2.0

1H
2.4

(ppm)
(ppm)

2.8

2.4

2.0

1.6

1.2

0.8

4.0

3.2

2.4

1.6

0.8

5 CH COSY 2,6-Dimethyl-5-hydroxyheptan-3-one
(ppm)

16

O
3

OH
24

32

7
40

(ppm)

48

17.2

17.6

56

18.0

18.4

64

18.8

(ppm)

1.12

1.08

1.04

1.00

0.96

0.92

0.88

72

Methyl region

(ppm)

13C

3.6

3.2

2.8

2.4

2.0

1.6

1.2

1H

5 CH COSY 2,6-Dimethyl-5-hydroxy-heptan-3-one
Expansion of the 2.40-2.75ppm region
(ppm)

40.0

2.54ppm
40.8

CH

41.6

2.45ppm
2.56ppm

42.4

43.2

-CH244.0

Spin-Spin Coupling information

from the CH2 (Hz)
(ppm)

2.72

44.8

2.64

2.56

2.48

2.40

5 Long Range CH COSY 2,6-Dimethyl-5-hydroxyheptan-3-one

(ppm)

Notice CH correlations to :
- a longer range
i.e. two or more bonds
for a CH correlation

40

80

- a carbonyl resonance
i.e. a quaternary peak

120

- a hydroxyl peak

160

200

Keto Carbon 216 ppm

(ppm)

3.6

3.2

2.8

2.4

2.0

1.6

1.2

6A CH COSY of 1-Phenyl-1,4-butanediol
1H
(ppm)

HO

13C

OH

40

1
o,m 1H signals
overlap

60

4
(ppm)

80

122.0

124.0

126.0

100
128.0

130.0

(ppm)

7.40

7.36

7.32

7.28

7.24

120

(ppm)

8.00

7.00

6.00

5.00

4.00

3.00

2.00

1.00

6A HH COSY of 1-Phenyl-1,4-butanediol
(ppm)

1.6

HO

2
1

2.4

3
4

OH

3.2

4.0

4.8

5.6

6.4

7.2

(ppm)

7.2

6.4

5.6

4.8

4.0

3.2

2.4

1.6

6B CH COSY -Phenyl--butyrolactone
(pp

(pp
24

28

40
32

60

36
(ppm)

2.80

2.60

2.40

3
2

1 H

2.20

2.00

1.80

80

2
(pp

4 O

100

122

124

126

120

128

4
5

130

(ppm)

(ppm)

8.00

7.00

7.68

7.60

7.52

6.00

7.44

7.36

7.28

5.00

7.20

7.12

4.00

3.00

140
2.00

CH3

7 CH COSY cis-caran-trans-4-ol

H
OH
H

(ppm)

16

CH3

CH3

20

H
(ppm)

24

16

28

24

32
32

40

36

(ppm)

2.00

1.80

1.60

1.40

1.20

1.00

0.80

48
(ppm)

16

56

Me

20

Me

64

24

28

Me

72
32

(ppm) 3.2
(ppm)

2.0

1.6

1.2

0.8

2.8

2.4

2.0

1.6

1.2

0.8

7 HH COSY cis-caran-trans-4-ol
(pp

CH3

0.8

OH
H

H
CH3

1.2

1.6

CH3

2.0

2.4

2.8

3.2
(ppm)

3.2

2.8

2.4

2.0

1.6

1.2

0.8

7 HH COSY cis-caran-trans-4-ol
H

CH3

OH

(pp

0.8

CH3

CH3

1.2

1.6
(pp

2.0

0.8

2.4

1.2

2.8

1.6

3.2
2.0

2.4

2.8

3.2
(ppm)

3.2

2.8

2.4

2.0

1.6

1.2

0.8

(ppm)

3.2

2.8

2.4

2.0

1.6

1.2

0.8

More complex NMR experiments to detemine the

configuration of the cis-Caran-trans-ol
Long range CH COSY
used to find correlations to proton(s) other than those directly attached to a carbon
used to establish links to hydroxy groups and quaternary carbon peaks

Nuclear Overhauser Effect (NOE)

This will etablish interactions of the spins through SPACE
Difference NOE experiment irradiate a specific proton and observe any changes
(a normal spectrum is subtracted from the irradiated spectrum to give the DIFFERENCE spectrum

expect to differentiate between the two methyl peaks on the cyclopropyl ring
one should be lying in the same plane as the two cis protons on the ring

7 Long range CH COSY cis-Caran-trans-ol

2'

CH3 H
H
H
H
8

CH3

3
4
7

1
6

OH

(ppm)

OH
H
H
H

16
24

CH3

32

40
48
56
64

Solvent DMSO-d6

72
(ppm)

4.0

3.2

2.4

1.6

0.8

7 Difference NOE NMR cis-Caran-trans-4-ol

Normal Spectrum

3.0

2.8

2.6

2.4

2.2

2.0

1.8

1.6

1.4

Difference Spectrum

Methyl at 0.93 ppm

irradiated

3.0

2.0

2.8

2.6

2.4

2.2

1.8

1.6

1.4

1.2

1.0

Positive NOE

1.2

1.0

Methyl at 0.89 ppm

irradiated

3.0

2.8

2.6

2.4

2.2

2.0

1.8
(ppm)

1.6

1.4

0.8

1.2

0.8

No NOE

1.0

0.8