(a) 4 0folk.ntnu.no/audunfor/6. semester/Spektroskopi/Øvinger... · 2013-05-25 · Answers for...
Transcript of (a) 4 0folk.ntnu.no/audunfor/6. semester/Spektroskopi/Øvinger... · 2013-05-25 · Answers for...
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 # δH δC1 3.40 33.52 1.85 36.13 1.20 22.14 0.85 13.5
(a)
Answers for Student Exercises 5.1 2
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 # δH δC1 3.40 33.52 1.85 36.13 1.20 22.14 0.85 13.5
(a)
Answers for Student Exercises 5.1 3
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 O
1
23
4
5 6
7O
8 9
(b) (cyclohex-2-enyl)methyl acetate
Group # δH δC1 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)
Answers for Student Exercises 5.1 4
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 # δH δC1 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)
Answers for Student Exercises 5.1 5
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 # δH δC1 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)
Answers for Student Exercises 5.1 6
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 # δH δC10 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)
Answers for Student Exercises 5.1 7
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 # δH δC1 1.80 67.62 NA 84.63 2.20 25.04 1.50 21.25 0.85 12.5
H13 2
45
1
(d)
Answers for Student Exercises 5.1 8
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 # δH δC1 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)
Answers for Student Exercises 5.1 9
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 # δH δC1 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)
Answers for Student Exercises 5.1 10
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 # δH δC1 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)
Answers for Student Exercises 5.1 11
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 # δH δC1 3.20 55.82 6.14 143.53 4.63 102.04 2.05 23.15 1.00 13.6
(f)
Answers for Student Exercises 5.1 12
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 # δH δC1 3.20 55.82 6.14 143.53 4.63 102.04 2.05 23.15 1.00 13.6
(f)
Answers for Student Exercises 5.1 13
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 # δH δC1 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)
Answers for Student Exercises 5.1 14
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 # δH δC1 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)
Answers for Student Exercises 5.1 15
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 # δH δC1 1.20 11.62 3.40 61.03 4.95 113.3
(h)
Answers for Student Exercises 5.1 16
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 # δH δC1 1.20 11.62 3.40 61.03 4.95 113.3
(h)
Answers for Student Exercises 5.1 17
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 # δH δC1 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)
Answers for Student Exercises 5.1 18
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 # δH δC1 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)
Answers for Student Exercises 5.1 19
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 # δH δC1 2.10 17.52 2.60 33.53 1.60 29.6
2
(j)
Answers for Student Exercises 5.1 20
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 # δH δC1 2.10 17.52 2.60 33.53 1.60 29.6
2
1
3 to 3'
(j)
Answers for Student Exercises 5.1 21
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 # δH δC1 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)
Answers for Student Exercises 5.1 22
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 # δH δC1 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)
Answers for Student Exercises 5.1 23
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 # δH δC1 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)
Answers for Student Exercises 5.1 24
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 # δH δC1 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)
Answers for Student Exercises 5.1 25
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 # δH δC1 4.95 59.52 9.80 199.7
(m)
Answers for Student Exercises 5.1 26
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 # δH δC1 4.95 59.52 9.80 199.7
(m)
Answers for Student Exercises 5.1 27
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 # δH δC1cis 4.85 132.2
1trans 4.23 132.22 6.79 191.2
1cis
1trans
(n)
Answers for Student Exercises 5.1 28
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 # δH δC1cis 4.85 132.2
1trans 4.23 132.22 6.79 191.2
1cis 1trans
(n)
Answers for Student Exercises 5.1 29
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 # δH δC1 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)
Answers for Student Exercises 5.1 30
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 # δH δC1 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 5
4
3
2
1
8
76
Answers for Student Exercises 5.2
32
Carbon 13 Signals
1 2 3 4 5 6 7 8 CH3 CH2= 1H 1 Bonded α β β
2 α Bonded α β α S 3 β α Bonded α β β
I 4 β α Bonded α β
g 5 β α Bonded α β β n 6 l 7 β α Bonded α β a 8 β α Bonded l CH3 β α β Bonded
s CH2= β α β Bonded
H3C CH3
CH2
CH2HO
H 5
4
3
2
1
8
76
Answers for Student Exercises 5.4 33
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’
Answers for Student Exercises 5.4 34
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’
Answers for Student Exercises 5.5 35
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
Answers for Student Exercises 5.5 36
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
Answers for Student Exercises 5.6 37
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
CH2
CH3
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
Answers for Student Exercises 5.6 38
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
CH2
CH3
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
Answers for Student Exercises 5.6 39
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
CH2
CH3
ethyl nicotinate
1
2
3
4
5
6 78
1
7
6 2 4 5
3
8
INADEQUATE 150.9 MHz
Answers for Student Exercises 5.7 40
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
Answers for Student Exercises 5.7 41
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
Answers for Student Exercises 5.8 42
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
13C/DEPT NMR 150.9 MHz
1 1’6 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
3,7-dimethylocta-1,6-dien-3-ol
1
234
5 6
78
9
10
Answers for Student Exercises 5.8 44
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
3,7-dimethylocta-1,6-dien-3-ol
1
234
5 6
78
9
10
Answers for Student Exercises 5.8 45
Hz
20406080100120140 ppm
-15000
-10000
-5000
15000
10000
5000
0
-15000
-10000
-5000
15000
10000
5000
0
INADEQUATE 600 MHz
F1
F2
OH
3,7-dimethylocta-1,6-dien-3-ol
1
234
5 6
78
9
10
INADEQUATE 150.9 MHz 1
7
6 2 4 5 3 8 9
10
Answers for Student Exercises 5.9
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
α1
β1
G1
α2
TOCSY 600 MHz
α3
α4
α5 α6
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.
β2 β5 β3 β4
β6’ β6
G2 G3 G5 G6 G4
Answers for Student Exercises 5.10 47
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
13C/DEPT NMR 150.9 MHz
OHO
H
H
H
HOH
HO
CH2OH
HOH
HO
H
H
HOH
HO
CH2
H
CH2OH
HCH2OH
HO H
H HO
OO
O
α-Glucoseβ-Fructose
1
2
3 4
5
6
1
23
45
6
1
234
5
6
α-Galactose
Ring A Ring BRing 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
Answers for Student Exercises 5.10 48
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
Answers for Student Exercises 5.10 49
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
α-Glucoseβ-Fructose
1
2
3 4
5
6
1
23
45
6
1
234
5
6
α-Galactose
Ring A Ring BRing C
Answers for Student Exercises 5.10 50
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
Answers for Student Exercises 5.10 52
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’
Answers for Student Exercises 5.10 53
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’
Answers for Student Exercises 5.10 54
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’
Answers for Student Exercises 5.11 55
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
13C/DEPT NMR 150.9 MHz
28 1’
2’
12
Answers for Student Exercises 5.11 56
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
Answers for Student Exercises 5.11 57
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’
Answers for Student Exercises 5.11 58
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 1’9 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 1’19 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
Answers for Student Exercises 5.11 59
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
Answers for Student Exercises 5.11 60
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’
Answers for Student Exercises 5.11 61
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’
Answers for Student Exercises 5.11 62
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
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
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
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
KNH2 KNH2
Answers for Student Exercises 5.11 63
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
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
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