ch05

Answers for Student Exercises 5.1 1

3.5 3.0 2.5 2.0 1.5 1.0 0.5ppm ppm

3.5

3.0

2.5

2.0

1.5

1.0

0.5

3.5

3.0

2.5

2.0

1.5

1.0

0.5

ppm

1.01.21.41.61.82.02.22.42.62.83.0 ppm

45

40

35

30

25

20

15

10

5

45

40

35

30

25

20

15

10

5

F2

F2

F1

F1

COSY

HMQC

1

2

3

4

Br

(a) 1-bromobutane

12

34

Group # H C1 3.40 33.52 1.85 36.13 1.20 22.14 0.85 13.5

(a)


F2

F2

1 2 3 4ppm

1.01.21.41.61.82.02.22.42.62.83.0 ppm50

45

40

35

30

25

20

15

10

5

F1

HMBC

12

3

4

Hz

45 40 35 30 25 20 15 10 5 ppm

-3000

-2000

-1000

3000

2000

1000

0

-3000

-2000

-1000

3000

2000

1000

0

12 3 4

CenterFrequency

INADEQUATE

F1

Br

(a) 1-bromobutane

12

34

Group # H C1 3.40 33.52 1.85 36.13 1.20 22.14 0.85 13.5

(a)


1.52.02.53.03.54.04.55.05.56.0ppm ppm

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

ppm

1.52.02.53.03.54.04.55.05.56.0 ppm

20

40

60

80

100

120

20

40

60

80

100

120

F2

F2

F1

F1

COSY

HMQC

1

23

4 O1

23

4

5 6

7O

8 9

(b) (cyclohex-2-enyl)methyl acetate

Group # H C1 2.80 36.02 5.59 131.53 5.59 125.54 1.96 29.85 1.65 27.06 1.80 33.47 4.05 67.58 NA 170.59 2.10 20.7

7

56

9

23

7

14

5

6

7

9

(b)


F2

F2

123

4ppm

1.52.02.53.03.54.04.55.05.56.0 ppm

40

60

80

100

120

140

160

180

F1

HMBC

Hz

20406080100120140160180 ppm

-10000

-5000

10000

5000

0

-10000

-5000

10000

5000

0

12 4CenterFrequency

INADEQUATE

F1

O

1

23

4

5 6

7O

8 9

(b) (cyclohex-2-enyl)methyl acetate

Group # H C1 2.80 36.02 5.59 131.53 5.59 125.54 1.96 29.85 1.65 27.06 1.80 33.47 4.05 67.58 NA 170.59 2.10 20.7

567 9

12

34 56

79

8

98 7 6 53

(b)


7 6 5 4 3 2 1ppm ppm

6

5

4

3

2

1

6

5

4

3

2

1

ppm

7 6 5 4 3 2 1 ppm

140

120

100

80

60

40

20

140

120

100

80

60

40

20

F2

F2

F1

F1

COSY

HMQC

4

10

5

2

3

10

4

8

F2

F2

F1

F1

COSY

HMQC

2

3

8

6

9

56

9

OH

O

12

3

45

6

78

9

10

Group # H C1 NA 143.22 6.68 150.03 2.05 28.34 2.05 30.75 5.68 122.16 6.22 131.17 NA 206.78 2.65 45.59 3.20 60.510 1.05 8.9OH 0.5-4 NA

OH

(c)


F2

F2

7

2 34

ppm

7 6 5 4 3 2 1 ppm

200

180

160

140

120

100

80

60

40

20

F1

HMBC

Hz

200 180 160 140 120 100 80 60 40 20 Hz

-10000

-5000

15000

10000

5000

0

-10000

-5000

15000

10000

5000

0

12 4CenterFrequency

INADEQUATE

F1

56 109

12

345

610

98

9 87 6 5 3

OH

O

12

3

45

6

78

9

10

Group # H C10 1.05 8.93 2.05 28.34 2.05 30.78 2.65 45.59 3.20 60.55 5.68 122.16 6.22 131.11 NA 143.22 6.68 150.07 NA 206.7

OH 0.5-4 NA

8

10

(c)


2.5 2.0 1.5 1.0 0.5ppm ppm

2.5

2.0

1.5

1.0

0.5

2.5

2.0

1.5

1.0

0.5

ppm

2.5 2.0 1.5 1.0 0.5 ppm

80

70

60

50

40

30

20

10

80

70

60

50

40

30

20

10

F2

F2

F1

F1

COSY

HMQC

4

5

34

1

3

5

Group # H C1 1.80 67.62 NA 84.63 2.20 25.04 1.50 21.25 0.85 12.5

H13 2

45

1

(d)


F2

F2

2

3 4ppm

2.5 2.0 1.5 1.0 0.5 ppm90

80

70

60

50

40

30

20

10

F1

HMBC

Hz

90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 Hz

-4000

-2000

6000

4000

2000

0

-4000

-2000

6000

4000

2000

0

1 2 4CenterFrequency

INADEQUATE

F1

51

53

Group # H C1 1.80 67.62 NA 84.63 2.20 25.04 1.50 21.25 0.85 12.5

H13 2

45

1

34

5

(d)


1.01.52.02.53.03.54.04.55.05.56.06.57.0ppm ppm

1

2

3

4

5

6

1

2

3

4

5

6

ppm

1.01.52.02.53.03.54.04.55.05.56.06.57.0 ppm

140

120

100

80

60

40

20

140

120

100

80

60

40

20

F2

F2

F1

F1

COSY

HMQC

4

5

34

1

3

5 1

Group # H C1 1.86 28.82 NA 196.93 6.09 137.64 6.82 142.15 2.05 23.46 1.00 13.9

O

1 34

52 6

6

6

(e)


F2

F2

2

34ppm

1.52.02.53.03.54.04.55.05.56.06.57.0 ppm200

180

160

140

120

100

80

60

40

20

F1

HMBC

Hz

200 180 160 140 120 100 80 60 40 20 Hz

-10000

-5000

15000

10000

5000

0

-10000

-5000

15000

10000

5000

0

12 4CenterFrequency

INADEQUATE

F1

5 1

53

1

34

5

Group # H C1 1.86 28.82 NA 196.93 6.09 137.64 6.82 142.15 2.05 23.46 1.00 13.9

O

1 34

52 6

6

6

6

(e)


1.01.52.02.53.03.54.04.55.05.56.06.57.0ppm ppm

1

2

3

4

5

6

1

2

3

4

5

6

ppm

1.01.52.02.53.03.54.04.55.05.56.06.57.0 ppm

140

120

100

80

60

40

20

140

120

100

80

60

40

20

F2

F2

F1

F1

COSY

HMQC

4

5

3

4

1

3

5

1

2

2

O1 23

45

Group # H C1 3.20 55.82 6.14 143.53 4.63 102.04 2.05 23.15 1.00 13.6

(f)


F2

F2

2

3 4ppm

1.52.02.53.03.54.04.55.05.56.06.57.0 ppm

140

120

100

80

60

40

20

F1

HMBC

Hz

150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 Hz

-5000

10000

5000

0

-5000

10000

5000

0

12 4CenterFrequency

INADEQUATE

F1

51

53

1

3

4

5

2

O1 23

45

Group # H C1 3.20 55.82 6.14 143.53 4.63 102.04 2.05 23.15 1.00 13.6

(f)


1.01.52.02.53.03.54.04.55.05.56.06.57.0ppm ppm

1

2

3

4

5

6

1

2

3

4

5

6

ppm

1.01.52.02.53.03.54.04.55.05.56.06.57.0 ppm

140

120

100

80

60

40

20

140

120

100

80

60

40

20

F2

F2

F1

F1

COSY

HMQC

4

5

3

4

1

3

5

1

NH

O

O1

2 34

5

Group # H C1 2.95 28.42 NA 157.83 4.10 63.04 1.60 20.75 0.85 13.0

NH 4.5-7.5 NA

NH

(g)


F2

F2

2

3 4ppm

1.52.02.53.03.54.04.55.05.56.06.57.0 ppm

140

120

100

80

60

40

20

F1

HMBC

Hz

140 120 100 80 60 40 20 Hz

-10000

-5000

10000

5000

0

-10000

-5000

10000

5000

0

12 4CenterFrequency

INADEQUATE

F1

51

53

1

3

4

5

NH

O

O1

2 34

5

Group # H C1 2.95 28.42 NA 157.83 4.10 63.04 1.60 20.75 0.85 13.0

NH 4.5-7.5 NA

(g)


1.01.52.02.53.03.54.04.55.05.56.0ppm ppm

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

ppm

1.01.52.02.53.03.54.04.55.05.56.0 ppm

120

100

80

60

40

20

120

100

80

60

40

20

F2

F2

F1

F1

COSY

HMQC

3

2

1

3

1

2

O O1

2 3

Group # H C1 1.20 11.62 3.40 61.03 4.95 113.3

(h)


F2

F2

2

3 2ppm

1.52.02.53.03.54.04.55.05.56.0 ppm

120

100

80

60

40

20

F1

HMBC

Hz

120 110 100 90 80 70 60 50 40 30 20 10 Hz

-8000

-6000

-4000

-2000

8000

6000

4000

2000

0

-8000

-6000

-4000

-2000

8000

6000

4000

2000

0

12

CenterFrequency

INADEQUATE

F1

1

3

1

3

O O1

2 3

Group # H C1 1.20 11.62 3.40 61.03 4.95 113.3

(h)


0.60.81.01.21.41.61.82.0ppm ppm

0.6

0.8

1.0

1.2

1.4

1.6

1.8

0.6

0.8

1.0

1.2

1.4

1.6

1.8

ppm

0.60.81.01.21.41.61.82.0 ppm80

70

60

50

40

30

20

10

80

70

60

50

40

30

20

10

F2

F2

F1

F1

COSY

HMQC

3

5

1

3

1

5 HO

1

23

45

6

Group # H C1 1.20 29.82 NA 68.33 1.50 46.74 1.20 15.15 0.85 14.16 1.20 29.8

OH 0.5-4.0 NA

64

OH

6

4

(i)


F2

F2

2

3 5ppm

0.81.01.21.41.61.82.0 ppm

70

60

50

40

30

20

10

F1

HMBC

Hz

75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 Hz

-4000

-2000

6000

4000

2000

0

-4000

-2000

6000

4000

2000

0

1,62CenterFrequency

INADEQUATE

F1

1

3

1

3

HO

1

23

45

6

Group # H C1 1.20 29.82 NA 68.33 1.50 46.74 1.20 15.15 0.85 14.16 1.20 29.8

OH 0.5-4.0 NA

46

45

6

4 5

(i)


1.21.41.61.82.02.22.42.62.83.0ppm ppm

1.2

1.4

1.6

1.8

2.0

2.2

2.4

2.6

2.8

1.2

1.4

1.6

1.8

2.0

2.2

2.4

2.6

2.8

ppm

1.21.41.61.82.02.22.42.62.83.0 ppm

15

20

25

30

35

40

15

20

25

30

35

40

F2

F2

F1

F1

COSY

HMQC

3

1

3

1

2

SS

1 23

Group # H C1 2.10 17.52 2.60 33.53 1.60 29.6

2

(j)


F2

F2

2

3ppm

1.41.61.82.02.22.42.62.83.0 ppm

15

20

25

30

35

40

F1

HMBC

Hz

121416182022242628303234363840 Hz

-1500

-1000

-500

2000

1500

1000

500

0

-1500

-1000

-500

2000

1500

1000

500

0

2CenterFrequency

INADEQUATE

F1

1

3

1

3

SS

1 23

Group # H C1 2.10 17.52 2.60 33.53 1.60 29.6

2

1

3 to 3'

(j)


2.53.03.54.04.55.05.56.06.57.07.58.0ppm ppm

3

4

5

6

7

3

4

5

6

7

ppm

1.21.41.61.82.02.22.42.62.83.0 ppm

40

60

80

100

120

40

60

80

100

120

F2

F2

F1

F1

COSY

HMQC

3

3

2

2

Group # H C1 NA 130.62 7.80 127.23 7.25 129.24 NA 141.25 NA 171.06 2.95 38.57 2.95 38.58 2.25 21.3

N

O

1

2

3

4

5

6

78

6,7

8

6,7

8

(k)


F2

F2

2

3ppm

3.03.54.04.55.05.56.06.57.07.58.0 ppm

40

60

80

100

120

140

160

F1

HMBC

Hz

20406080100120140160 Hz

-10000

-5000

10000

5000

0

-10000

-5000

10000

5000

0

2CenterFrequency

INADEQUATE

F1

3

13

2

1

Group # H C1 NA 130.62 7.80 127.23 7.25 129.24 NA 141.25 NA 171.06 2.95 38.57 2.95 38.58 2.25 21.3

N

O

1

2

3

4

5

6

78

67

8

4

5

6 7

8

5 67

84

(k)


2.53.03.54.04.55.05.56.06.57.07.58.0ppm ppm

3

4

5

6

7

3

4

5

6

7

ppm

1.21.41.61.82.02.22.42.62.83.0 ppm

40

60

80

100

120

40

60

80

100

120

F2

F2

F1

F1

COSY

HMQC

3

3

8

O

OH

1

2

34

5

6

78

Group # H C1 NA 123.62 NA 154.73 6.85 115.44 7.05 132.95 7.25 120.86 7.70 129.77 NA 197.68 2.40 26.3

OH 5.5-12.5 NA45

6

6

5

4

(l)


F2

F2

2

3ppm

3.03.54.04.55.05.56.06.57.07.58.0 ppm

40

60

80

100

120

140

160

180

F1

HMBC

Hz

406080100120140160180 Hz

-10000

-5000

10000

5000

0

-10000

-5000

10000

5000

0

2CenterFrequency

INADEQUATE

F1

3

13

1

6 8

4

56

7

8

567 84

O

OH

1

2

34

5

6

78

Group # H C1 NA 123.62 NA 154.73 6.85 115.44 7.05 132.95 7.25 120.86 7.70 129.77 NA 197.68 2.40 26.3

OH 5.5-12.5 NA

45

(l)


567891011ppm ppm

5

6

7

8

9

10

5

6

7

8

9

10

ppm

567891011 ppm

60

80

100

120

140

160

180

200

60

80

100

120

140

160

180

200

F2

F2

F1

F1

COSY

HMQC

1

1

2

2

ClH

O

12

Group # H C1 4.95 59.52 9.80 199.7

(m)


F2

F2

2

ppm

567891011 ppm

60

80

100

120

140

160

180

200

F1

HMBC

Hz

6080100120140160180200 Hz

-10000

-5000

10000

5000

0

-10000

-5000

10000

5000

0

2CenterFrequency

INADEQUATE

F1

1

1

2

1

ClH

O

12

Group # H C1 4.95 59.52 9.80 199.7

(m)


4.55.05.56.06.57.07.58.0ppm ppm

4.5

5.0

5.5

6.0

6.5

7.0

7.5

4.5

5.0

5.5

6.0

6.5

7.0

7.5

ppm

4.55.05.56.06.57.07.58.0 ppm

130

140

150

160

170

180

190

200

130

140

150

160

170

180

190

200

F2

F2

F1

F1

COSY

HMQC

1

2

2

HH

H

F1trans

2

1cis

Group # H C1cis 4.85 132.2

1trans 4.23 132.22 6.79 191.2

1cis

1trans

(n)


F2

F2

2

ppm

4.55.05.56.06.57.0 ppm

130

140

150

160

170

180

190

F1

HMBC

Hz

130140150160170180190 Hz

-4000

-2000

6000

4000

2000

0

-4000

-2000

6000

4000

2000

0

2CenterFrequency

INADEQUATE

F1

1

2

1

HH

H

F1trans

2

1cis

Group # H C1cis 4.85 132.2

1trans 4.23 132.22 6.79 191.2

1cis 1trans

(n)


1.52.02.53.03.54.04.55.05.56.0ppm ppm

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

ppm

1.52.02.53.03.54.04.55.05.56.0 ppm

40

60

80

100

120

140

160

40

60

80

100

120

140

160

F2

F2

F1

F1

COSY

HMQC

4

6

O O1

2

34

5

6

2'3'

Group # H C1 4.95 77.9

2,2' 1.60 32.93,3' 1.44 23.94 1.44 26.95 NA 168.06 2.00 20.8

33'22'

1

1

6

22'

33'4

(o)


F2

F2

2

ppm

2.02.53.03.54.04.55.05.56.0 ppm

40

60

80

100

120

140

160

F1

HMBC

Hz

20406080100120140160 Hz

-10000

-5000

10000

5000

0

-10000

-5000

10000

5000

0

2CenterFrequency

INADEQUATE

F1

3

1

3

1

6

4

5

6

5 64

4

Group # H C1 4.95 77.9

2,2' 1.60 32.93,3' 1.44 23.94 1.44 26.95 NA 168.06 2.00 20.8

O O1

2

34

5

6

2'3'

22'33'

1

(o)

Answers for Student Exercises 5.2

31

ppm

7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

78

4 5 5' 2OH

3 3'

CH3 1

F2

F1

CH2=

g= geminalv= vicinallr= long range

g

g

g

lr

v

v

v

vv

v

v

v

lr

v

v

H3C CH3

CH2

CH2HO

H 54

3

2

1

8

76


32

Carbon 13 Signals

1 2 3 4 5 6 7 8 CH3 CH2= 1H 1 Bonded

2 Bonded S 3 Bonded I 4 Bonded g 5 Bonded n 6 l 7 Bonded a 8 Bonded l CH3 Bonded s CH2= Bonded

H3C CH3

CH2

CH2HO

H 54

3

2

1

8

76


1.01.11.21.31.41.51.61.71.81.92.02.12.22.3 ppm

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

1H NMR 600 MHz

13C/DEPT 600 MHz

1300 Hz

580600620 Hz820840860 Hz10001050 Hz

1250 Hz 1150 Hz

O

123 4

5

6

2-methylcyclopentanone

6

6

2

4

5 3

1

6

2

4 5 3

4 3

5


1.01.21.41.61.82.02.22.4ppm ppm

1.0

1.2

1.4

1.6

1.8

2.0

2.2

1.0

1.2

1.4

1.6

1.8

2.0

2.2

ppm

1.01.21.41.61.82.02.22.4 ppm

15

20

25

30

35

40

45

15

20

25

30

35

40

45

F2

F2

F1

F1

HMQC 600 MHz

COSY 600 MHz

3 6

2 4 5 3 4

6

2

4

5

3

6

2

4

5

3

O

123 4

5

6

2-methylcyclopentanone

5

3

4

5


2.02.53.03.54.04.55.05.56.06.57.07.58.0 ppm

406080100120140160180200 ppm

1H NMR 600 MHz

13C/DEPT 600 MHz

47504800 Hz

15001550 Hz

44004450 Hz 43004350 Hz

17001750 Hz 12001250 Hz

O

1 2

3

45

6

7

8

910

1

7 6 2 4

5

3 8 9

10

7 6

2 4

3

8 9

7 6

2 4 3

8 9


2345678ppm ppm

2

3

4

5

6

7

8

2

3

4

5

6

7

8

ppm

23456789 ppm

40

60

80

100

120

140

40

60

80

100

120

140

F2

F2

F1

F1

HMQC 600 MHz

COSY 600 MHz

ppm

7.27.47.67.88.08.2 ppm

125

130

135

7.07.58.0ppm ppm

7.0

7.5

8.0

O

1 2

3

45

6

7

8

910

7

6

2

4 3

8

9

7

6

2 4

3

8

9


2.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0 ppm

30405060708090100110120130140150160 ppm

51905200 Hz

1H NMR 600 MHz

13C/DEPT 600 MHz

25802590 Hz43604370 Hz

49004910 Hz

780790 Hz

54705480 Hz

N

O

O

CH2CH3

ethyl nicotinate

1

2

3

4

5

6 78

1

7

4

5 3

8

1 7

6 2

4 5

3

8

1

7

4 5 3

8

13C/DEPT NMR 150.9 MHz


23456789ppm ppm

2

3

4

5

6

7

8

9

2

3

4

5

6

7

8

9

ppm

23456789 ppm

20

40

60

80

100

120

140

160

20

40

60

80

100

120

140

160

F2

F2

F1

F1

HMQC 600 MHz

COSY 600 MHz

N

O

O

CH2CH3

ethyl nicotinate

1

2

3

4

5

6 78

1

7

6

2 4

5

3

8

1

7

4

5

3

8

1 7

4 5 3

8


Hz

20406080100120140160 ppm

-25000

-20000

-15000

-10000

-5000

25000

20000

15000

10000

5000

0

-25000

-20000

-15000

-10000

-5000

25000

20000

15000

10000

5000

0

Hz

125130135140145150155160165 ppm

12000

13000

14000

15000

16000

17000

12000

13000

14000

15000

16000

17000

F1

F1

F2

F2

INADEQUATE 600 MHz

N

O

O

CH2CH3

ethyl nicotinate

1

2

3

4

5

6 78

1

7

6 2 4 5 3

8

INADEQUATE 150.9 MHz


Hz

2030405060708090100110120130140150160 ppm

-10000

-5000

10000

5000

0

-10000

-5000

10000

5000

0

Hz

1520253035404550556065 ppm

-4000

-5000

-6000

-7000

-8000

-9000

-4000

-5000

-6000

-7000

-8000

-9000

O

CH2

H

H CH3H3C

H3C 1

23

4

5

6

78

910

11

13

14

12

15

F1

F2

INADEQUATE 150.9 MHz

F1

8 13

C6-C7

1 7 6 2 4

5 3 14

9 11 12 10 15

5-4

5-6

4-3

4-12

1-9

1-2

1-11 9-10

10-11

3-2 11-14

11-15

8-13

8-7

8-9


The following correlations can be found in the INADEQUATE spectrum of caryophyllene oxide Carbon 1 correlates with carbons 2, 9, and 11 Carbon 2 correlates with carbons 1 and 3 Carbon 3 correlates with carbons 2 and 4 Carbon 4 correlates with carbons 3, 4, and 12 Carbon 5 correlates with carbons 4, and 6 Carbon 6 correlates with carbons 5, and 7 Carbon 7 correlates with carbons 6, and 8 Carbon 8 correlates with carbons 7, 9, and 13 Carbon 9 correlates with carbons 1, 8, and 10 Carbon 10 correlates with carbons 9 and 11 Carbon 11 correlates with carbons 1, 10, 14, and 15 Carbon 12 correlates with carbons 4 Carbon 13 correlates with carbons 8 Carbon 14 correlates with carbons 11 Carbon 15 correlates with carbons 11

O

CH2

H

H CH3H3C

H3C 1

23

4

5

6

78

910

11

13

14

12

15


1.52.02.53.03.54.04.55.05.5 ppm

2030405060708090100110120130140150 ppm

1H NMR 600 MHz

13C/DEPT 600 MHz

34503500 Hz

700750 Hz900950 Hz11501200 Hz

30003050 Hz 13501400 Hz


1 16 2 4

5

8

9

10

OH

1

6

2

4

5

1

8 9 10

OH

1

7

6 2

4 5

3

8

9

10

OH

3,7-dimethylocta-1,6-dien-3-ol

1

234

5 6

78

9

10

Answers for Student Exercises 5.8 431.52.02.53.03.54.04.55.05.56.0ppm ppm

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

ppm

1.52.02.53.03.54.04.55.05.56.0 ppm

20

40

60

80

100

120

140

20

40

60

80

100

120

140

F2

F2

F1

F1

HMQC 600 MHz

COSY 600 MHz

1 6 1

4

5

8

9

10

OH

1

7 6

2

4

5

3

8 9

10

1,6,1 2 4 5

8 9 10

2

OH


1

234

5 6

78

9

10


ppm

1.52.02.53.03.54.04.55.05.56.0 ppm

20

40

60

80

100

120

140

160

ppm

20

40

60

ppm

20

40

60

ppm

5.85.96.0 ppm

120

140

5.05.2 ppm

ppm

1.52.0 ppm

120

140

F1

F2

F1

F2

HMBC 600 MHz

1 6 2 4 5 1

8 9 10

1

7 6

2

4

5

3

8 9

10

OH

OH


1

234

5 6

78

9

10


Hz

20406080100120140 ppm

-15000

-10000

-5000

15000

10000

5000

0

-15000

-10000

-5000

15000

10000

5000

0

INADEQUATE 600 MHz

F1

F2

OH


1

234

5 6

78

9

10

INADEQUATE 150.9 MHz 1

7

6 2 4 5 3 8 9 10


46

3.43.63.84.04.24.44.64.85.05.2ppm

3.43.63.84.04.24.44.64.85.05.2 ppm

3.4

3.6

3.8

4.0

4.2

4.4

4.6

4.8

5.0

5.2

3.4

3.6

3.8

4.0

4.2

4.4

4.6

4.8

5.0

5.2

F1

HDO

1

1

G1

2

TOCSY 600 MHz

3 4

5 6

F1 Correlations from the three anomeric protons are drawn. These correlations show the ring protons for the three monosaccharide residues of lactose. Correlations among the ring protons are difficult to decipher due to overlap. Results from the 1D HOHAHA in Figure 5.26 agree with these findings.

2 5 3 4 6 6

G2 G3 G5 G6 G4


3.63.73.83.94.04.14.24.34.44.54.64.74.84.95.05.15.25.35.4 ppm

65707580859095100 ppm

1H NMR 600 MHz

13C/DEPT 600 MHz

OHO

H

H

H

HOH

HO

CH2OH

HOH

HO

H

H

HOH

HO

CH2

H

CH2OH

HCH2OH

HO H

H HO

OO

O

HDO

69.069.570.070.571.071.572.072.573.073.574.0 ppm

3.53.63.73.83.94.04.1 ppm


OHO

H

H

H

HOH

HO

CH2OH

HOH

HO

H

H

HOH

HO

CH2

H

CH2OH

HCH2OH

HO H

H HO

OO

O

-Glucose -Fructose

1

2

3 4

5

6

1

23

45

6

1

234

5

6

-GalactoseRing A Ring B

Ring C C1 C4

C5

C3

A1 A6

A2 A4 A5 A3

B1

B6

B2 B4 B5 B3

C1 C6 C2 C4

C5 C3

A1

A6

A2 A4 A5

A3

B1

B6 B2 B4 B5 B3

C1

C6 C6

C4

C3

B6

C3


3.503.553.603.653.703.753.803.853.903.954.004.05 ppm

3.503.553.603.653.703.753.803.853.903.954.004.05 ppm

1H NMR 600 MHz

Mixing time 20 ms

Mixing time 40 ms

Mixing time 80 ms

Mixing time 300 ms 5.40 ppm irradiated

Mixing time 300 ms 4.97 ppm irradiated

Mixing time 80 ms

Mixing time 40 ms

Mixing time 20 ms

1-d TOCSY 600 MHz

1-d TOCSY 600 MHz

A6

A2

A4

A5

A3

B6 B6

B2

B4 B5

B3


3.503.553.603.653.703.753.803.853.903.954.004.05 ppm

1H NMR 600 MHz

Mixing time 80 ms

Mixing time 40 ms

Mixing time 20 ms

1-d TOCSY 600 MHz

C4

C5

C6 C6

OHO

H

H

H

HOH

HO

CH2OH

HOH

HO

H

H

HOH

HO

CH2

H

CH2OH

HCH2OH

HO H

H HO

OO

O

-Glucose -Fructose

1

2

3 4

5

6

1

23

45

6

1

234

5

6

-GalactoseRing A Ring B

Ring C


3.63.84.04.24.44.64.85.05.25.4ppm ppm

3.6

3.8

4.0

4.2

4.4

4.6

4.8

5.0

5.2

5.4

3.6

3.8

4.0

4.2

4.4

4.6

4.8

5.0

5.2

5.4

ppm

3.53.63.73.83.94.04.14.2 ppm

3.5

3.6

3.7

3.8

3.9

4.0

4.1

4.2

F1

F1

F2

HDO

COSY 600 MHz

COSY 600 MHz

B6

C6

C3

A1

A6

A2

A4 A5

A3

B1

B6

B2 B4

B5

B3

C1

C6

C4

C5

C3

Answers for Student Exercises 5.10 513.63.84.04.24.44.64.85.05.25.4ppm ppm

3.6

3.8

4.0

4.2

4.4

4.6

4.8

5.0

5.2

5.4

3.6

3.8

4.0

4.2

4.4

4.6

4.8

5.0

5.2

5.4

ppm

3.53.63.73.83.94.04.14.2 ppm

3.5

3.6

3.7

3.8

3.9

4.0

4.1

4.2

F1

F1

F2

HDO

TOCSY 600 MHz

TOCSY 600 MHz

B6

C6

C3

A1

A6

A2

A4 A5

A3

B1

B6

B2 B4

B5

B3

C1

C6

C4

C5

C3


3.53.63.73.83.94.04.1 ppm

F2

F1

5.5ppm ppm

60

65

ppm

69

70

71

72

73

74

75

76

77

78

79

80

81

3.53.63.73.83.94.04.1 ppm

ppm

5.5 ppm

95

100

105

F1

F1

HMQC 600 MHz

A1

A6

A2

A4

A5

A3

B1

B6

B2

B4

B5

B3

C1 C6

C2

C4

C5

C3

A1 A6

A2 A4

A5 A3

B1

B6 B2 B4

B5

B3

C1

C6 C6 C4 C5 C3 B6


3.53.63.73.83.94.04.1 ppm

F2

F1

5.5ppm ppm

60

65

ppm

69

70

71

72

73

74

75

76

77

78

79

80

81

3.53.63.73.83.94.04.1 ppm

ppm

5.5 ppm

95

100

105

F1

F1

HMQC-TOCSY 600 MHz

A1

A6

A2

A4

A5

A3

B1

B6

B2

B4

B5

B3

C1 C6

C2

C4

C5

C3

A1 A6

A2 A4

A5 A3

B1

B6 B2 B4

B5

B3

C1

C6 C6 C4 C5 C3 B6


3.53.63.73.83.94.04.1 ppm

F2

F1

5.5ppm ppm

60

65

ppm

69

70

71

72

73

74

75

76

77

78

79

80

81

3.53.63.73.83.94.04.1 ppm

ppm

5.5 ppm

95

100

105

HMBC 600 MHz

F1

F1

A1

A6

A2

A4

A5

A3

B1

B6

B2

B4

B5

B3

C1 C6

C2

C4

C5

C3

A1 A6

A2 A4

A5 A3

B1

B6 B2 B4

B5

B3

C1

C6 C6 C4 C5 C3 B6


1.01.52.02.53.03.54.04.55.0 ppm

2030405060708090100110120130140 ppm

1H NMR 600 MHz

13C/DEPT 600 MHz

31003200 Hz

32.0 ppm

600700 Hz

10001100 Hz1300 Hz21002200 Hz

9001000 Hz

HO

CH3 CH3

H

HCH3

H

H

500600 Hz

21.5 ppm

HO

CH3 CH3

CH3

12

34

5

6 7

8

910

11 12

13

14

1516

17

181920

2122

2324

25

26

27

28

29

1

7 6

2 4

5

3

8

14

13

9

11 12

10

15 16

23

21

17 19

20

18

22

29

28 24

26

27 25

1 7

6 4

3

14

15

9

11

12 16 15

16

23

21

17 19

20

18

22

28

29

27 26

7,8,24,25


28 1

2

12


1.01.52.02.53.03.54.04.55.05.56.0ppm ppm

1

2

3

4

5

1

2

3

4

5

ppm

0.60.81.01.21.41.61.82.02.22.4 ppm

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

2.2

2.4

F1

F2

COSY 600 MHz

COSY 600 MHz

HO

CH3 CH3

CH3

12

34

5

6 7

8

910

11 12

13

14

1516

17

181920

2122

2324

25

26

27

28

29

1 7

2

4

3

14

12

15

16

22

19

20

18

23

29

28

26

1

7 8 24 25

6

4 2 2

4

9

2 11

12

15

16

21

17

19

18

28 17

27

4 7 7

20 24

7 7

1 7 21 7 2lr 7

2 1 8

7,11

15 16 17 15 7

27 26 to 25

29 to 28 29 to 28

15 to 14


0.60.81.01.21.41.61.82.02.2 ppm

F2

F1

5.5ppm ppm

15

20

25

30

35

40

45

50

55

60

65

70

0.60.81.01.21.41.61.82.02.2 ppm

ppm

5.5 ppm

130

140

3.6 ppm

3.6 ppm

HMQC 600 MHz

HO

CH3 CH3

CH3

12

34

5

6 7

8

910

11 12

13

14

1516

17

181920

2122

2324

25

26

27

28

29

1 7

6

2

4

5

3

8

17

13

9

11

12 12

15

16

23

21

14 19

20 18

22 29

28

24

26

27

25

1

7 6

2

4

3

8

17

9

11

12

10

15

16

23

21

14

19

20

18

22

29

28

24

26 27 25

1 2

7

28

16 15


0.60.81.01.21.41.61.82.02.2 ppm

F2

F1

5.5ppm ppm

15

20

25

30

35

40

45

50

55

60

65

70

0.60.81.01.21.41.61.82.02.2 ppm

ppm

5.5 ppm

130

140

3.6 ppm

3.6 ppm

HMBC 600 MHz

23-26 6-19 22,23-21 22,23-28

6-7 22,23-25 3-2 6-10 3-1 22,23-20 3-4 6-4 22,23-24 22,23-17

6-3 22-23 6-5 3-5

HO

CH3 CH3

CH3

12

34

5

6 7

8

910

11 12

13

14

1516

17

181920

2122

2324

25

26

27

28

29

1 7

2

8

9

11

12 12

15

23 14 19

20 18

22 29

28

24 7

6

4

3

17 16

21 26 27

25

1 2 28

16 15

6

4

5

3

17

13

16

21

26

27

25

1

2 8

9

11

12

10

15

23

14

19

20

18

22

29

28

24

7

12-18 17-18 14-18 24-29 28-29 28-29

24 25-26 27-26

1 19 28

12-11 24+25-27 9-11 26-27 16-15 14-15

24 25-28 29-28 17 15 14-16

4-2 7-8 1-2 24,28-25 28-25 15-8 14,9-(7,8)

. 15-8 12-8 27 26-25 4-10 1,2-10 8,7,-10 119 9-10 2-1 2-1 19 9-1 11-12 17-12 21-20 18-12 16-20 17-20

12-13 2-4 16-13 15,11-13 12,15,17-13 14-13 18-13

12-9, and 7-9 7,8,11 12 1-9 19-9

25-24 28-24 28-24 27,29,26-24

16-17 16 12 21 18-17

7-14 15 8-14 16 12 15-14 18-14

4-3 1,2 -3 2-3 1-3

4-6 7-6 1-6(4b) 7-6

20-23 24,25 28-23 28-23 27 26-23(4b)

20-22 24-22 17-22 21-22 4-5 7-5 1-5 7-5 19-5

13C Satellite peaks


2.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0 ppm

25303540455055606570 ppm

5100520053005400 Hz

1H NMR 600 MHz

13C/DEPT 600 MHz

170175 ppm

1 1 2 11 2 3 2 31 2 2# of protons

2400250026002700 Hz

80090010001100 Hz1800 Hz

Impurity

0o C in 5%/95% D2O/H2O

Threonine (Thr) (T) Serine (Ser) (S) Lysine (Lys) (K)

1H2N CH C

CH

HN

O

HO

CH3

CH C

CH2

HN

O

OH

CH C

CH2

OH

O

CH2

CH2

CH2

NH2

2

3

4

1

2

31

2

3

4

5

6

T4

KNH SNH

K6

T2

T4

T3

KNH

S2

SNH S3

K3

K6

K2

K4 K5

K3

T1 T2

T4

TNH

T3

S1

KNH

S2

SNH

S3

K1

K6

K2 K4

K5 K3


123456789ppm ppm

1

2

3

4

5

6

7

8

1

2

3

4

5

6

7

8

ppm

1.01.52.02.53.03.54.04.5 ppm

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

F1

F1

F2

COSY 600 MHz

COSY 600 MHz

T2

T4

TNH

T3

K3K3

S2

S3

K6

K2

K4 K5

K3

T2

T4

T3

KNH

S2

SNH

S3

K6

K2

K4 K5

K3


123456789ppm ppm

1

2

3

4

5

6

7

8

1

2

3

4

5

6

7

8

ppm

1.01.52.02.53.03.54.04.5 ppm

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

F1

F1

F2

TOCSY 600 MHz

TOCSY 600 MHz

T2

T4

TNH

T3

K3K3

S2

S3

K6

K2

K4 K5

K3

T2

T4

KNH2

T3

KNH

S2

SNH

S3

K6

K2

K4 K5

K3


ppm

7.58.08.59.0 ppm

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

7.07.58.08.5 ppm7.58.08.5 ppm

ppm

1.01.52.02.53.03.54.04.5 ppm

20

30

40

50

60

COSY 600 MHz ROESY 600 MHz TOCSY 600 MHz

HMQC 600 MHz

F1

F1

F2 F2

F2

F2


1H2N CH C

CH

HN

O

HO

CH3

CH C

CH2

HN

O

OH

CH C

CH2

OH

O

CH2

CH2

CH2

NH2

2

3

4

1

2

31

2

3

4

5

6

KNH SNH KNH

S2

SNH

T2

T4

T3

S2

S3

K6

K2

K4 K5

K3

T2 T4

T3

S2 S3 K6 K2

K4 K5

K3

T2

T4

KNH2

T3

KNH SNH

S3

K6

K2

K4 K5

K3


1H2N CH C

CH

HN

O

HO

CH3

CH C

CH2

HN

O

OH

CH C

CH2

OH

O

CH2

CH2

CH2

NH2

2

3

4

1

2

31

2

3

4

5

6

KNH2 KNH2


1.01.52.02.53.03.54.0 ppm

F2

F2

F1

F1

HMBC 600 MHz 8.08.59.0ppm ppm

20

30

40

50

60

ppm

8.08.59.0 ppm

168

170

172

174

176

178

1801.01.52.02.53.03.54.0 ppm

T2

T4

KNH2

T3

S1

S2

S3

K6

K2

K4

K5

K3

T1

T2

T4

T3

KNH

S2

SNH S3

K1

K6

K2 K4

K5

K3


1H2N CH C

CH

HN

O

HO

CH3

CH C

CH2

HN

O

OH

CH C

CH2

OH

O

CH2

CH2

CH2

NH2

2

3

4

1

2

31

2

3

4

5

6

S2-T1 T3-T1 T2-T1

S2-S1 K2-S1 T2,S3-S1 K2-K1 K3-K1

SNH-T1 KNH-S1 KNH-K1

T3 T2 K2 K6 K3 K5

K6 K3 K4

K2 K5 K4 K5 K4 K3 K3 K4 S3 T3 T4 S2 T2 T4

KNH-K3 KNH-K2

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