Problem Set 1 - NMR Spectra

Reich
Two Isomers of C4H8O2 Chem 345

Problem R-16A: C4H8O2

300 MHz 1H NMR Spectrum in CDCl3
IHD = 1
Source: Aldrich Spectral Viewer/Reich
3

O
Hz
O 30 20 10 0
CH2 CH3
X
CH3
3

Observed protons are circled

protons causing splitting are underlined
2
O CH2 CH3

quartet

4.2 4.1 2.05 2.00 1.30 1.25

10 9 8 7 6 5 4 3 2 1 0
ppm

Problem R-16B: C4H8O2

300 MHz 1H NMR Spectrum in CDCl3 IHD = 1
Source: Aldrich Spectral Viewer/Reich
3

O
CH2 CH3
O
3
O CH3

X
Hz CH2 CH3
30 20 10 0

1.20 1.15 1.10

2

3.70 3.65 2.4 2.3

10 9 8 7 6 5 4 3 2 1
ppm
 Two Isomers of C4H8O2

Problem R-16C: C4H8O2 IHD = 1

300 MHz 1H NMR Spectrum in CDCl3
CH2 CH2 CH3
Source: Aldrich Spectral Viewer/Reich CH2 CH3
O

H O
Hz
30 20 10 0

O
3.00

H
1.8 1.7 1.6

2.11 2.06

8.1 8.0
CH2 CH2 O

1.00 0.95
1.01

4.15 4.10

10 9 8 7 6 5 4 3 2 1 0
ppm

Problem R-16D: C4H8O2 IHD = 1

100 MHz 1H NMR Spectrum
Source: Reich
1.17

O
1.00
0.94
OH

CH2 CH2 CH3 CH2 CH3

CH2 CH2

0.32

1.0
OH 2.4 2.3 1.7 1.6

12 11 10 9 8 7 6 5 4 3 2 1 0
ppm
Problem R-18L C4H9Br Hz
30 20 10 0
300 MHz 1H NMR spectrum in CDCl3
Source: Aldrich Spectra Viewer/Reich IHD = 0 CH2 CH3

Br CH2 CH2 CH2 CH2 CH2 CH3

pentet sextet

1.95 1.90 1.85 1.80 1.75 1.70 1.65 1.60 1.55 1.50 1.45 1.40 1.35

X CH2 CH3
1.00 0.95 0.90
2.20

1.42

1.00

3.45 3.40 3.35

10 9 8 7 6 5 4 3 2 1 0
34.8
33.6

21.3

13.2

Problem R-18L: C4H9Br

75 MHz 13C NMR spectrum
Solv: CDCl3
Source: ASV/Reich
CDCl3

200 180 160 140 120 100 80 60 40 20 0

ppm
 Problem R-7N C8H10O US
300 MHz 1H NMR spectrum in CDCl3 IHD = 4
Source: Aldrich Spectra Viewer 33-09
CH2 CH3

7.3 7.2 7.1 7.0 6.9 6.8

O CH2 CH3

R 5

2
1.4

4.0 3.9

9 8 7 6 5 4 3 2 1 0
ppm
Infrared Spectrum:
129.5

120.6

114.6

63.3

14.9

Problem R-7N: C8H10O

75 MHz 13C NMR spectrum
Solv: CDCl3
Source: ASV/Reich

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
ppm
 Problem R-7R: C5H9BrO2
300 MHz 1H NMR spectrum in CDCl3 IHD = 1
Source: Aldrich Spectra Viewer 33-09

X
X CH2 CH2 CH2 CH2 CH2 CH3

Hz
30 20 10 0

3.6 3.5 3.4 3.3 3.2 3.1 3.0 2.9

1.43
O 3
2 2 2
Br O 1.05
1.00 1.00
1.3
O CH2 CH3

4.2

10 9 8 7 6 5 4 3 2 1 0
Infrared Spectrum: ppm

100

80
Percent Transmittance

60

40

20

4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200
Change of scale cm-1
at 2000 cm-1
170.4

61.0

37.8

25.9

14.2

Problem R-7R: C5H9BrO2

75 MHz 13C NMR spectrum
Solv: CDCl3
Source: ASV/Reich
CDCl3

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
ppm
 Problem R-7P C9H10O
300 MHz 1H NMR spectrum in CDCl3
Source: Aldrich Spectra Viewer 33-09 IHD = 5 US

R = electron withdrawing group

Hz
R 30 20 10 0
CH2 CH3

8.0 7.9 7.8 7.7 7.6 7.5 7.4

2.32

O
2
5 X 1.54

CH2 CH3

1.00

3.1 3.0 3.0 1.25 1.20

10
Infrared Spectrum: 9 8 7 6 5 4 3 2 1 0
ppm
200.6

136.9
132.8
128.5
127.9

31.8

8.2

Problem R-7P C9H10O

75 MHz 13C NMR spectrum
1
Solv: CDCl3 4
Source: ASV/Reich 4

O
CDCl3

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
ppm
Problem R-7M: C11H14O
300 MHz 1H NMR IHD = 5
Solv: CDCl3
Source: A. Fiedler/Reich Hz
30 20 10 0
O
nonet

Ph CH2 CH (CH3)2
R = electron withdrawing group
CH (CH3)2
R

X
CH2 CH
6.14

7.95 7.90 7.60 7.55 7.50 7.45 7.40 7.35 2.40 2.35 2.30 2.25 2.20
ppm ppm ppm

2.98

2.00
2.03

1.01
1.00
ppm

2.85 2.80
ppm

8 7 6 5 4 3 2 1 0
ppm

Problem R-7M C11H14O

75 MHz 13C NMR spectrum
Solv: CDCl3
Source: ASV/Reich
199.9

137.3
132.7
128.5
128.0

47.4

25.1
22.8

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
ppm
 Problem R-7K C5H9ClO2 IHD = 1
250 MHz 1H NMR spectrum in CDCl3 Hz
Source: Adam Fiedler/Reich 30 20 10 0
O
O
Cl
3.26
O O 3.13

Cl
CH2 CH3
Correct structure
This is a reasonable alternative CH CH3
structure - also fits the 1H NMR
2.16
data

X = O, Cl X CH2 CH3

X CH CH3 1.00

4.45 4.40 4.35 4.30 4.25 4.20 4.15 1.35 1.30 1.25
ppm 1.70 1.65 ppm
ppm

8 7 6 5 4 3 2 1 0
ppm
Infrared Spectrum:
100

80
Percent Transmittance

60

40

20

4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200
Change of scale cm-1
at 2000 cm-1

Problem R-7K: C5H9ClO2

170.1

62.0

52.6

21.5

14.0

75 MHz 13C NMR spectrum

Solv: CDCl3
Source: ASV/Reich
CDCl3

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
ppm
 Problem R-7O C5H8
300 MHz 1H NMR spectrum in CDCl3 CH2 CH3
Source: Aldrich Spectra Viewer 33-09 Hz
40 20 0

triplet of doublets (td)

H CH2 CH2 H CH2 CH2 CH2 CH3

1
3
2
2

2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9

H IHD = 2

There is a long-range coupling

(over 4 bonds) between the
alkyne proton and the CH2 group

10 9 8 7 6 5 4 3 2 1 0
ppm

Problem R-7O: C5H8

75 MHz 13C NMR spectrum
Solv: CDCl3 H
Source: ASV/Reich C

H
C

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
ppm
Problem R-18C C10H12O IHD = 5
300 MHz 1H NMR spectrum in CDCl3
CH2 CH3
Source: Aldrich Spectra Viewer/Reich CH2 CH3
quartet

O Hz
30 20 10 0
Ph

2.50 2.45 2.40

2.51
CH2
3
R 5 1.05 1.00 0.95

2 1.52
2

1.02
1.00

7.35 7.30 7.25 7.20 7.15

3.70 3.65 3.60

10 9 8 7 6 5 4 3 2 1 0
208.8

134.4
129.3
128.6
126.8

49.8

35.1

7.8

Problem R-18C: C10H12O

75 MHz 13C NMR spectrum CDCl3
Source: ASV/Reich

O
CDCl3

220 200 180 160 140 120 100 80 60 40 20 0

ppm
 Reich
Chem 345

Problem R-18R: C5H10O2 IHD = 1 CH2 CH2 CH3 CH2 CH3

300 MHz 1H NMR Spectrum in CDCl3
Source: Aldrich Spectral Viewer/Reich

O
Hz
30 20 10 0
Propyl acetate O CH2 CH2 1.70 1.65 1.60

CH3
1.49 1.57

1.09
1.00

3
1.00 0.95 0.90
2 2
3
4.05 4.00 2.05 2.00

10 9 8 7 6 5 4 3 2 1 0
ppm

Problem R-18S: C5H10O2 IHD = 1 CH2 CH2 CH3

300 MHz 1H NMR Spectrum in CDCl3
Source: Aldrich Spectral Viewer/Reich
CH2 CH3
O CH3
O
CH2 CH2
O
methyl butyrate Hz
30 20 10 0

1.00
1.7 1.6
0.96

0.64 0.66

3
2 2 0.95 0.90
3.70 3.65 2.35 2.30 2.25 3

10 9 8 7 6 5 4 3 2 1 0
ppm