Scribd
Upload
13 views36 pages

Lecture NMR 6

The document discusses various aspects of 2D NMR spectroscopy, including coupling constants and methods like COSY, HSQC, and HMBC. It explains the significance of geminal and vicinal coupling, the effects of NOE on decoupling, and the identification of nearest neighbors in molecular structures. Additionally, it highlights the use of difference spectra and the measurement of coupling constants in NMR analysis.

Uploaded by

Paula Andrea Charry Sanchez
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
13 views36 pages

Lecture NMR 6

The document discusses various aspects of 2D NMR spectroscopy, including coupling constants and methods like COSY, HSQC, and HMBC. It explains the significance of geminal and vicinal coupling, the effects of NOE on decoupling, and the identification of nearest neighbors in molecular structures. Additionally, it highlights the use of difference spectra and the measurement of coupling constants in NMR analysis.

Uploaded by

Paula Andrea Charry Sanchez
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
You are on page 1/ 36

2DNMR

Coupling Constants
Geminal Coupling are usually negative: CH2
Vicinal coupling usually positive:
CH-CH
Why?
Coupling is through bonding electrons;
consider the following model
2D NMR basically provides information about
connectivity and proximity

COSY spectroscopy (correlation spectroscopy)


(various pulse sequences are available
providing similar information)
HH COSY
H H COSY-90
Long range HH
COSY
H C COSY
HSQC method
gradient
select
HMQC
method

gradient
select
HMBC
method
2. Off-resonance decoupling
O

2
CH3

NOE enhancement observed


13
C NMR

Coupling is reduced, but multiplicity is retained; 1H irradiation 1 ppm upfield from TMS;
to observe multiplicity at C-3, 1H irradiation could be set to 10 ppm downfield from
signals can be integrated
Demonstration of the
effect of NOE on
decoupling
C-9 signal as a function of H
decoupling

C-9
3. Attached protons
4. Identification of nearest neighbors
HH

Identification of 1,1’-Me
Identification of 5-Me Identification of H4
Identification of 10-Me Identification of H3
Identification of H2

p=3

q=2
Selective Decoupling irradiate

triplet H4 doublet
little
interaction

normal spectrum
Results are often reported as difference spectra
10
Note: peak s 2
and 3 are
mislabeled
Measurement of CH coupling constants
Heteronuclear J resolved Spectrum
Identify the carbons by chemical shift

i h d f ab
e c
j g
Let test our assignments using ACD
An INADEQUATE
spectrum (incredible j i
natural abundance
double quantum
transfer experiment j h
spectroscopy)
measures 13C –13C
transfer of h
magnetization i f e
between two 13 C g d
i f
nuclei using natural d
abundance C g
f c
(detection of 1 in a,b
10000 molecules). e a,b
AX3

XAM2
where JAX= JAM
JXM = 0
Can we assign the peaks?

carbon count
2 =CC2
=CH 1 3 CH3

2 CH2
8,9,10

4,5

2,6
NOE Difference Spectra

Some NOE operates through space as well as through bonding


electrons. The through space interaction decreases as the inverse of
the sixth power of the through space distance of the nuclei. The
through space interaction occurs between nuclei that interact by a
dipolar interaction

The NOE difference spectrum is obtained by subtracting a normal


spectrum from one in which a specific proton is irradiated. An
measurable interaction can be expected up to about 4Å.
9
b

bb irradiated

a irradiated

2 6
10 9 8
b
c

irradiated c

Irradiated b
irradiated a

2 6
irradiated

irradiated
1
5 4
13
C NMR 1 4,5 9,10,8
10 3,7 2,6
1
CH2OH
4 3
2
5
6

8
7
8 9
4 9,10
5

OH

1
H NMR
1

6
2

You might also like