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112

CHAPTER 2

INFRARED SPECTROMETRY

Problem 2.3 Spectrum A

Problem 2.3 Spectrum B

Problem 2.3 Spectrum C

Problem 2.3

Problems 2.3 and 2.4

Problem 2.3 Spectrum D

Problem 2.4 Spectrum E

Problem 2.4 Spectrum F

PROBLEMS

113

114

CHAPTER 2

INFRARED SPECTROMETRY

Problem 2.4 Spectrum G

Problem 2.4 Spectrum H

Problem 2.4 Spectrum I

Problem 2.4

Problem 2.5

Problem 2.5 Spectrum J

Problem 2.5 Spectrum K

Problem 2.5 Spectrum L

PROBLEMS

115

116

CHAPTER 2

INFRARED SPECTROMETRY

Problem 2.5 Spectrum M

Problem 2.6 Spectrum N

Problem 2.6 Spectrum O

Problems 2.5 and 2.6

Problem 2.6

Problem 2.6 Spectrum P

Problem 2.6 Spectrum Q

Problem 2.6 Spectrum R

PROBLEMS

117

118

CHAPTER 2

INFRARED SPECTROMETRY

Problem 2.7 Spectrum S

Problem 2.8 Spectrum T

Problems 2.7 and 2.8

Chapter 8 Additional Problems 1

MASS

45

CI Reagent gas methane


169

100

89

50

IR

139
137

107

100
50

100

m/z

195
197

75

171

63

50

170

180

190

200

50

4.6

4.4

4.2

2000
Wavenumber (cm-1)

4.0

3.8

3.6

663

4.8

1126

1
NMR 300 MHz
HHNMR

1304

3000

1458

4000

2877

3440

%Transmittance

100

1000

3.4

3.2

3.0

2.8

ppm

45

ppm

1313
C/DEPT

C/DEPT NMR 75.5 MHz

75

70

65

60

55

50

Chapter 8 Additional Problems 2

% of Base Peak

MASS

97

100 41
50

100

81

70

55

113

83
51

98 111

65

50

50

141

110

100

m/z

CI Reagent gas methane

120

153

130 m/z
140

150

1712

2870

80

4000

3000

2000
Wavenumber (cm-1)

11
H

HNMR
NMR600
300MHz
MHz

1880

1103
1149

1458

90

2931
2954

%Transmittance

IR 100

1870

13
13C/DEPT

Hz 1800

1790

Hz 680

Hz

670

120

100

440

1000

430

420

410

400

390

Hz

ppm

MHz
C/DEPT NMR
NMR150.9
75.5 MHz

180

160

140

80

60

40

20 ppm

Chapter 8 Additional Problems 3A

MASS
% of Base Peak

92

120

100
50

152

65

53

50

60

70

80

90

IR

m/z

100

110

120

130

140

150

50

10.5
13

10.0

9.5

9.0

2000
Wavenumber (cm-1)

4460

8.5

8.0

1000

Hz 4200

4180 Hz

4120

7.5

6.5

5.5

7.0

702
760

4680 Hz

4700

1092
1215
1304

H NMR 600 MHz

1442

3000

1616
1678

4000

2954

3190

%Transmittance

100

6.0

Hz

5.0

4.5

ppm

C/DEPT NMR 600 MHz

170

160

150

140

130

120

110

100

90

80

70

60

50 ppm

Chapter 8 Additional Problems 3B


ppm 11

F1

10

4 ppm

10

10

F2

HMQC 600 MHz

ppm

F1

60

60

80

80

100

100

120

120

140

140

160

160

11

10

F2

COSY 600 MHz

4 ppm

Chapter 8 Additional Problems 4A

% of Base Peak

MASS

100
50

55

IR

149

77

65

50

60

70

103

91

80

90

121

100
m/z

110

120

131

130

140

150

160

50

2000
Wavenumber (cm-1)

791
856

1034
1153
1265

3000

1427
1512
1597

2850
2935
3016

3514

%Transmittance

100

4000
1

164

1000

H NMR 600 MHz

4140

4120

7.0
13

Hz

6.5

3820

6.0

3800 Hz

5.5

3660

5.0

1140

Hz

4.5

4.0

3.5

3.0

1120

2.5

2.0

Hz

ppm

C/DEPT NMR 150.9 MHz

140

130

120

110

100

90

80

70

60

50

40

30

20 ppm

Chapter 8 Additional Problems 4B


ppm 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0

F1

6
ppm

F2

HMQC 600 MHz

ppm
20

20

40

40

60

60

F1 80

80

100

100

120

120

140

140
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0

F2

COSY 600 MHz

ppm

Chapter 8 Additional Problems 4C

HMQC 600 MHz

ppm

7.0

6.5

6.0

ppm 4.0 3.9

ppm

1.9 1.8

ppm

7.0

6.5

6.0

ppm 4.0 3.9

ppm

1.9 1.8

ppm

20
30
40
50
ppm
105
110

F1
115
120
125
130
135
140
145
150

F2

Chapter 8 Additional Problems 5A

% of Base Peak

MASS

41

55

70
83

100

97
111

50

125

50

IR

168

140

100
m/z

150

50
910

1466

3000

1643

2854
2924

3078

%Transmittance

100

4000
1

2000
Wavenumber (cm-1)

1000

H NMR 300 MHz

1760

6.0

1740

5.5

Hz

Hz

1500

5.0

4.5

620

4.0

600 Hz

3.5

280

3.0

260 Hz

2.5

2.0

1.5

ppm

13
13

C/DEPT
NMR
75.5 MHz
C
NMR 75.5
MHz

29.8

140

130

120

110

100

29.6

90

29.4

80

29.2

70

ppm

29.0

60

50

40

30

20 ppm

Chapter 8 Additional Problems 5B

ppm 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0

ppm

COSY 300 MHz

F1

F2

HETCO 300 MHz

ppm
1

F1

140

120

100

80

F2

60

40

20

ppm

Chapter 8 Additional Problems 6A

% of Base Peak

MASS

10

93

68

100

136
79
77

53

50

40

50

60

70

121

107

80

IR

m/z

90

100

110

120

130

140

100

887

1442

%Transmittance

795

1373

2924

1643

3078

4000

3000

2000
Wavenumber (cm-1)

1000

H NMR 600 MHz

1050

1300

5.5
13

5.0

4.5

1000

950

1250

900

1200

4.0

3.5

Hz

850

1150

Hz

1100

3.0

2.5

2.0

ppm

30

20 ppm

C/DEPT NMR 150.9 MHz

150

140

130

120

110

100

90

80

31.0

30.5 ppm

70

60

50

40

Chapter 8 Additional Problems 6B


ppm

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

11

1.5 ppm

COSY 600 MHz

1.5

2.0

2.0

ppm

2.5

2.5
1.6

3.0

3.0

1.8

F1 3.5

3.5

2.0

4.0

4.0

2.2

4.5

2.2

2.0

1.8

ppm

1.6

4.5

5.0

5.0

5.5

5.5

F2

HMQC 600 MHz

ppm
20

20

40

40

ppm
20

60

60
25

F1 80

80
30

100

100
35

120

120
40

140

140
45
2.2

5.5

5.0

4.5

2.0

4.0

1.8

3.5

F2

ppm

1.6

3.0

2.5

2.0

1.5 ppm

Chapter 8 Additional Problems 6C

12

HMBC 600 MHz

ppm

5.6

5.4

5.2

5.0

4.8

ppm

2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4

ppm

5.6

5.4

5.2

5.0

4.8

ppm

2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4

ppm

20

25

30

35

40

F1
ppm
110
115
120
125
130
135
140
145
150

F2

Chapter 8 Additional Problems 7A

MASS

13

% of Base Peak

81
67

100

152

109

41
53

50

50

IR

137

123

60

70

80

90

m/z

100

110

120

130

140

150

100

50

H NMR 600 MHz

1134
1211
1288
1373
1450

3000

1612
1682

2870
2924

4000

2000
Wavenumber (cm-1)

1000

2.7 2.6 2.5 2.4 2.3 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

ppm

13
13

C/DEPT
MHz
C/DEPT NMR
NMR 150.9
600 MHz

200

180

160

140

120

100

80

60

40

ppm

Chapter 8 Additional Problems 7B


ppm 3.0

F1

2.8

2.6

2.4

2.2

2.0

1.8

1.6

1.4

1.2

1.0

14
ppm

1.0

1.0

1.2

1.2

1.4

1.4

1.6

1.6

1.8

1.8

2.0

2.0

2.2

2.2

2.4

2.4

2.6

2.6

2.8

2.8

F2

HMQC 600 MHz

ppm

20

20

25

25

30

30

F1 35

35

40

40

45

45

50

50

3.0

2.8

2.6

2.4

2.2

COSY 600 MHz

2.0

F2

1.8

1.6

1.4

1.2

1.0

ppm

Chapter 8 Additional Problems 7C

15

HMBC 600 MHz

ppm 2.8

2.6

2.4

2.2

2.0

1.8

1.6

1.4

1.2

1.0

0.8

ppm

2.6

2.4

2.2

2.0

1.8

1.6

1.4

1.2

1.0

0.8

ppm

21
22
23
24
25
26

F1

27
28
29
30
31
32
33
ppm
50
52
ppm
150

200
2.8

F2

Chapter 8 Additional Problems 8A

16

MASS
% of Base Peak

109

100
124

50

43

40

53
81

50

60

70

80
m/z

IR

90

100

110

120

50

6.5

6.0

Hz

3670

5.5

2000
Wavenumber (cm-1)

3660

5.0

Hz

1420

4.5

802

7.0

4220

1026

4230

1296

H NMR 600 MHz

1520

3000

1674

4000

2924

3124

%Transmittance

100

1000

1410

4.0

Hz

3.5

3.0

2.5

ppm

1313

C/DEPTNMR
NMR
150.9
C/DEPT
600
MHzMHz

180 170 160 150 140 130 120 110 100

90

80

70

60

50

40

30

ppm

Chapter 8 Additional Problems 8B


ppm 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0

17
ppm

COSY 600 MHz

F1

F2

HMQC 600 MHz

ppm

20

20

40

40

60

60

F1 80

80

100

100

120

120

140

140

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0

F2

ppm

Chapter 8 Additional Problems 8C

18

HMBC 600 MHz

ppm

7.2 7.0 6.8 6.6 6.4 6.2

2.4

2.3

ppm

20

20

30

30

40

40

50

50

60

60

70

70

80

80

90

90

100

100

110

110

120

120

130

130

140

140

150

150

160

160

170

170

180

180

F1

7.2 7.0 6.8 6.6 6.4 6.2

ppm

F2

2.4

2.3

ppm

Chapter 8 Additional Problems 9A

% of Base Peak

MASS

19

121

100

198

50

65

77

105

93

50

100

150

m/z

IR

200

90
80
70

7.8

7.7

7.6

7.5

7.4

7.3

7.2

7.1

7.0

702

7.9

2000
Wavenumber (cm-1)

1149

H NMR 600 MHz

1281

3000

1442

4000

1597
1635

3286

%Transmittance

100

1000

6.9

6.8

6.7

6.6

ppm

13
13

C/DEPT
MHz
C/DEPTNMR
NMR600
150.9
MHz

130

129

ppm

195 190 185 180 175 170 165 160 155 150 145 140 135 130 125 120

ppm

Chapter 8 Additional Problems 9B


ppm 8.0

F1

7.8

7.6

7.4

7.2

7.0

6.8

6.6

20
ppm

6.6

6.6

6.8

6.8

7.0

7.0

7.2

7.2

7.4

7.4

7.6

7.6

7.8

7.8

F2

HMQC 600 MHz

ppm

115

115

120

120

F1 125

125

130

130

135

135

140

140
ppm

8.0

7.8

7.6

7.4

7.2

F2

COSY 600 MHz

7.0

6.8

6.6

Chapter 8 Additional Problems 9C

21

HMBC 600 MHz

ppm 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5

ppm

115

120
ppm
128

130

132

F1

134

136

138

ppm

180

200
8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5

F2

ppm

Chapter 8 Additional Problems 10A

% of Base Peak

MASS

22

43
97

100
50

55

40

50

140

69

60

79

70

80

IR

m/z

90

100

110

120

130

140

50

2700

4.4

4.2

4.0

3.8

3.6

2680 Hz

3.4

3.2

2540

3.0

764

H NMR 600 MHz

2000
Wavenumber (cm-1)

1072

3000

1358

4000

1682
1720

2854
2924

%Transmittance

100

1000

2520 Hz

2.8

2.6

2.4

2.2

2.0

1.8

ppm

1313

C/DEPTNMR
NMR
150.9
C/DEPT
600
MHzMHz

200

180

160

140

120

100

80

60

40

ppm

Chapter 8 Additional Problems 10B


ppm 4.5

4.0

3.5

3.0

2.5

2.0

2.0

23

ppm

COSY 600 MHz

2.0
ppm 2.1

2.5

2.0

1.9

1.8

1.7

ppm

2.5

1.7
1.8

F1 3.0

3.0

1.9

3.5

3.5

2.0

4.0

4.0

4.5

4.5

F2

HMQC 600 MHz

ppm
20
30

20

ppm
18

30

20

40

F1

40

22

50

24

50

60

26

60

70

28
2.2

2.0

70

ppm

1.8

80

80

90

90

4.5

4.0

3.5

3.0

F2

2.5

2.0

ppm

Chapter 8 Additional Problems 10C

24

HMBC 600 MHz

ppm

4.5

4.0

3.5

3.0

2.5

2.0

ppm

4.5

4.0

3.5

3.0

2.5

2.0

ppm

20
25

ppm

90
100

F1
110
120
130
140
150
ppm

210

215

F2

Chapter 8 Additional Problems 11A

25

83

IR

100

125

166
169

50
50

150

m/z

90
80

2000
Wavenumber (cm-1)

949

1188

H NMR 600 MHz

1404

3000

1705
1728

2962

3178

%Transmittance

100

4000
1

114

98

100

184

x 20

69
71

43

% of Base Peak

MASS

1000

x64
13 12 11 10 9 ppm

2.9 2.8 2.7 2.6 2.5 2.4 2.3 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
13

ppm

C/DEPT NMR 150.9 MHz

30.2
30.2

200

180

160

140

30.1

ppm

30.1 ppm

120

100

80

60

40

20

ppm

Chapter 8 Additional Problems 11B


ppm 3.0

F1

2.8

2.6

2.4

2.2

2.0

1.8

1.6 1.4

1.2

1.0

26
ppm

1.0

1.0

1.2

1.2

1.4

1.4

1.6

1.6

1.8

1.8

2.0

2.0

2.2

2.2

2.4

2.4

2.6

2.6

2.8

2.8

F2

HMQC 600 MHz

ppm
15

15

20

20

25

25

30

30

F1 35

35

40

40

ppm

45

45

50

30.0

55

30.5

50
55
ppm

2.4 2.2 2.0 1.8 1.6 1.4 1.2

3.0

2.8

2.6

2.4

2.2

2.0

F2

COSY 600 MHz

1.8

1.6 1.4

1.2

1.0

ppm

Chapter 8 Additional Problems 11C

27

HMBC 600 MHz

ppm 3.2

3.0

2.8

2.6

2.4

2.2

3.0

2.8

2.6

2.4

2.2

2.0

1.8

1.6

1.4

1.2

1.0

0.8

ppm

2.0

1.8

1.6

1.4

1.2

1.0

0.8

ppm

20

25

30

35

F1
40

45

50

55

ppm
180
190
200
210
3.2

F2

Chapter 8 Additional Problems 12A

% of Base Peak

MASS

28
121

93

100

136
79
77

50

105

65

53

50

60

70

80

90
m/z

IR

100

110

120

130

140

825

980

1.8

5.5
13

1134

3000

H NMR 600 MHz

1.9

1373
1450

2924

4000
1

2870

2993

%Transmittance

100

1.7

5.0

1.6

1.5

4.5

1.4

4.0

2000
Wavenumber (cm-1)

1.3

1.2

3.5

1.1

1.0

3.0

1000

0.9

2.5

ppm

2.0

1.5

ppm

30

20 ppm

C/DEPT NMR 150.9 MHz

130

120

110

100

90

80

70

60

50

40

Chapter 8 Additional Problems 12B


ppm 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0
1

29

ppm
1

ppm 2.0 1.8 1.6 1.4 1.2 1.0 0.8 ppm

1.0

F1 3

1.5

F2

HMQC 600 MHz

ppm
20

20

ppm
15

40

40
20

60

F1 80

COSY 600 MHz

60

25

80

30
2.5

2.0

1.5

1.0

ppm

100

100

120

120

6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0

F2

ppm

Chapter 8 Additional Problems 12C

30

HMBC 600 MHz

ppm

5.7 5.6

ppm

2.0

1.8

1.6

1.4

1.2

1.0

0.8

ppm

ppm

2.0

1.8

1.6

1.4

1.2

1.0

0.8

ppm

16

18

20

22

24

F1
26

28

30

ppm
120

130

140
7

F2