C8953
NMR strukturní analýza
semináˇr
Introduction to 2D NMR & Homonuclear correlation - COSY
Ondˇrej Jurˇcek
ondrej.jurcek@ceitec.muni.cz
March 27, 2017
2D NMR
Second dimension f1
preparation period =⇒
coherence
evolution period t1
FT
−−→ f1
increments
evolution of coherence
mixing period
transfer of encoded
magnetisation
measurable signal
detection of signal t2
FT
−−→ f2
acq
t1
prep
evolution
mixing
detection
t2
5t1
4t1
3t1
2t1
t1
2D NMR
2D spektrum
FT in t1 - modulated 1D spectra
FT in t2 - 2D spectrum
COSY
easiest 2D experiment
correlates H nuclei based
on 2/3J coupling
through 2, 3, (4) bonds
antiphase off-diagonal
crosspeak between coupled
atoms
DQF-COSY - modiﬁcation of
basic sequence, diagonal
crosspeaks in absorption
phase
acq
t1 t2
))
90 9090
P E M D
f1
f2
f1
f2
Hints for beginners
Determination of individual spin systems - sharing off-diagonal crosspeaks
Isolated protons - only diagonal crosspeak
Already known rules: symmetry, diastereotopicity, most shielded/deshielded
atoms etc.
COSY : Betacyklodextrine
5.0
5.0
4.5
4.5
4.0
4.0
3.5
3.5
δ2 - 1H (ppm)
5.0 5.0
4.5 4.5
4.0 4.0
3.5 3.5
δ1-1H(ppm)
COSY : Betacyklodextrine
5.0
5.0
4.5
4.5
4.0
4.0
3.5
3.5
δ2 - 1H (ppm)
5.0 5.0
4.5 4.5
4.0 4.0
3.5 3.5
δ1-1H(ppm)
H1'-H1'
H1'-H2' H2'-H2'H3'-H2'
H3'-H4'
H3'-H3'
H4'-H4'
H5'-H4'
H6'-H5'
COSY : N-acetyllysine
8
8
6
6
4
4
2
2
0
0
δ2 - 1H (ppm)
8 8
6 6
4 4
2 2
δ1-1H(ppm)
COSY : N-acetyllysine
4
4
3
3
2
2
1
1
δ2 - 1H (ppm)
4.0 4.0
3.5 3.5
3.0 3.0
2.5 2.5
2.0 2.0
1.5 1.5
1.0 1.0
δ1-1H(ppm)
COSY : N-acetyllysine
4
4
3
3
2
2
1
1
δ2 - 1H (ppm)
4.0 4.0
3.5 3.5
3.0 3.0
2.5 2.5
2.0 2.0
1.5 1.5
1.0 1.0
δ1-1H(ppm)
H2-H3''
H2-H3'
H3''-H4
H3'-H4
H5-H4
H6-H5
H10-H10
H8-H2
COSY : Atropine
8
8
6
6
4
4
2
2
8 8
6 6
4 4
2 2
δ1-1H(ppm)
COSY : Atropine
5
5
4
4
3
3
2
2
1
1
5 5
4 4
3 3
2 2
δ1-1
H(ppm)
COSY : Atropine
5
5
4
4
3
3
2
2
1
1
5 5
4 4
3 3
2 2
δ1-1
H(ppm)
8OH-H8''
8OH-H8' H8''-H8'
H7'-H8'
H8''-H7'
H10-H11''/H16''
H10-H11'/H16'
H12-H11''
H12-H11'
H15-H16'
H15-H16''
H15-H14''
H12-H13
H13-H14''
H13-H14'
H14''-H14'
H17-H17
Chinin - 1D 1H
COSY - Chinin
10
10
8
8
6
6
4
4
2
2
δ2 - 1H (ppm)
8 8
6 6
4 4
2 2δ1-1H(ppm)
5
10
6
9
7
8
3
2
4
N
1
O
CH3
22
11
12
OH
17
16
N
13
15
14
18
19
20
21
COSY - Chinin
10 8 6 4 2
8 8
6 6
4 4
2 2
δ1-1H(ppm)
5
10
6
9
7
8
3
2
4
N
1
O
CH3
22
11
12
OH
17
16
N
13
15
14
18
19
20
21
COSY - Chinin
10
10
8
8
6
6
4
4
2
2
δ2 - 1H (ppm)
8 8
6 6
4 4
2 2δ1-1H(ppm)
5
10
6
9
7
8
3
2
4
N
1
O
CH3
22
11
12
OH
17
16
N
13
15
14
18
19
20
21
21
15,17
14,18
COSY - Chinin
10
10
8
8
6
6
4
4
2
2
δ2 - 1H (ppm)
8 8
6 6
4 4
2 2δ1-1H(ppm)
5
10
6
9
7
8
3
2
4
N
1
O
CH3
22
11
12
OH
17
16
N
13
15
14
18
19
20
21
21
15,17
14,18
H20-H21'/H21''
H20-H19
H19-H18'/18''
H14'/''-H15'/''
COSY - Chinin
10
10
8
8
6
6
4
4
2
2
δ2 - 1H (ppm)
8 8
6 6
4 4
2 2δ1-1H(ppm)
5
10
6
9
7
8
3
2
4
N
1
O
CH3
22
11
12
OH
17
16
N
13
15
14
18
19
20
21
15,17
H12-H17'/''
H11-H12
H3-H11
H2-H3
COSY - Chinin
10
10
8
8
6
6
4
4
2
2
δ2 - 1H (ppm)
8 8
6 6
4 4
2 2δ1-1H(ppm)
5
10
6
9
7
8
3
2
4
N
1
O
CH3
22
11
12
OH
17
16
N
13
15
14
18
19
20
21
H8-H6
H9-H8
NOESY-600ms
H6-H11
H8-H22 H6-H22
H3-H17
H2
H3
H9
H8
H6
H11
H11
H12
H17''
H17'
H21
H20
H19
H18'
H18''
H14''
H15''
H15'
H22
H16-H17'
H19-H16
Next seminar: 1H-1H NOESY