Selective Spin Decoupling (Double Resonance)

Intense irradiation of a proton at its resonance frequency in a

spin coupled system removes the protons coupling effect.
A powerful tool for
Determining connectivity
of protons through bonds
and assigning proton peaks.
Overlapping peaks can be
simplified by irradiating
one Or by irradiating the one. Or by irradiating the
coupling partner.
Strongly irradiate a proton
1
Strongly irradiate a proton
& detect the loss of coupling
in all the coupling protons
t, J = 6 Hz, 2H, H1
d, J = 3 Hz, 1H, H2
t, J = 6 Hz, 2H, H1
t, J = 3 Hz, 1H, H4
, , ,
td, J = 6.0, 3.0 Hz, 2H, H2
2
Nuclear Overhouser Enhancement (NOE)
It is a through space effect
Uses much weaker irradiation
A hi h i l i h i di d i ff d A proton which is closer in space to the irradiated one is affected
whether it is coupled to it or not. Effective distance is upto 4 .
If it is coupled it retains some coupling. p p g
NOE is usually less than 20%. So use NOE difference (subtract)
Polarization of nearby nuclei results in increase in population of higher
3
Polarization of nearby nuclei results in increase in population of higher
energy level in nearby non-irradiated protons and subsequent T1 relaxation
to lower energy state results in enhancement of intensity of nearby Hs
NOE difference spectra p
4
13
C NMR S t
13
C NMR Spectroscopy
Suvarn S. Kulkarni
Department of Chemistry
Indian Institute of Technology Bombay Indian Institute of Technology Bombay
CH 521 Lecture-6
NMR
In a magnetic field, a sample can
absorbs EM radiation in RF region at absorbs EM radiation in RF region at
frequencies governed by the
characteristics of the sample. characteristics of the sample.
Absorption is a function of certain
nuclei in the molecule nuclei in the molecule
A plot of frequencies Vs. peak
int nsiti s intensities
6
Differences between 1H and 13C
NMR NMR
In usual 13C the peaks are normally singlets In usual 13C the peaks are normally singlets
Large chemical shift range than 1H
13C peak intensities do not correlate with the 13C peak intensities do not correlate with the
no. of C atoms due to longer T
1
and NOE
Larger samples and longer times are required Larger samples and longer times are required
For a given D solvent the multiplicities of
solvent signal differ in 13C and 1H. nt gna ff r n an H.
E.g. CDCl
3
The progress in 1H NMR late 1950s while 13C The progress in 1H NMR late 1950s while 13C
started in 1970s. Why?
Carbon-13 NMR
Carbon-12 (
12
C) has no magnetic spin.
Carbon 13 (
13
C) has a magnetic spin (I Carbon-13 (
13
C) has a magnetic spin (I =
1/2), but is only 1.1% of the carbon in a
sample Its sensitivity is 1 6% that of sample. Its sensitivity is ~ 1.6% that of
1
H; the overall sensitivity is ~ 1/5700.
Ob i l CW h i i f l Obviously CW technique is not useful
Larger sample and longer time required g p g q
For carbon a technique called Fourier
transform spectroscopy is used.
8
transform sp ctroscopy s us .
Complements
1
H NMR.
Fourier Transform NMR F f m
Radio-frequency pulse given.
N l i b b d ( i ) Nuclei absorb energy and precess (spin)
like little tops.
A complex signal is produced, then decays A complex signal is produced, then decays
as the nuclei lose energy.
Free induction decay (FID) is converted to
spectrum spectrum.
9
Scale difference
You will notice at once that the scale is
much smaller in
1
H NMR, ranging over only much smaller in H NMR, ranging over only
about 10 p.p.m. instead of the 200 p.p.m.
needed for carbon. Why so? needed for carbon. Why so?
This is because the variation in the chemical
shift is a measure of the shielding of the shift is a measure of the shielding of the
nucleus by the electrons around it.
Th is in it bl l ss h n p ssibl in There is inevitably less change possible in
the distribution of two electrons around a
h dr n nucl us th n in th t f th i ht hydrogen nucleus than in that of the eight
valence electrons around a carbon nucleus.
Carbon
Home work
Chemical
Shifts Shifts
Table of approximate chemical shifts values for
13
C-
NMR. Most of these values for a carbon atom are
11
about 1520 times the chemical shift of a proton if
it were bonded to the carbon atom. Some deviations.
13
C chemical shift ranges
Standard
13
C chemical shift values
200 220 200 - 220
Spin-Spin Splitting p p p g
It is unlikely that a
13
C would be adjacent
to another
13
C (1 1% abundance) so to another C (1.1% abundance), so
splitting by carbon is negligible.
13
C will magnetically couple with attached
13
C will magnetically couple with attached
protons and adjacent protons.
L
1
J l f
13
C
1
H (110 320 H ) Large
1
J
CH
values for
13
C-
1
H (110-320 Hz),
&
2
J
CH
3
J
CH
values for
13
C-C-
1
H &
13
C-C-C-
CH CH
1
H (0-60 Hz) couplings (
1
H coupled spectra)
These complex splitting patterns with
16
h s comp sp tt ng patt rns w th
great overlaps are difficult to interpret.
Proton Spin
Decoupling Decoupling
To simplify the spectrum, a technique called as p y p
proton broadband decoupling is used.
Protons are continuously irradiated over a
b d f h idl broad frequency range, so they are rapidly
flipping and are not able to couple.
The carbon nuclei see an average of all the The carbon nuclei see an average of all the
possible proton spin states.
Thus each different kind of carbon gives a Thus, each different kind of carbon gives a
single, unsplit peak because carbon-hydrogen
splitting was eliminated.
18
p g
Cholesterol gives 27 singlets in 1H decoupled
13
C spectrum. Compare the simplicity.
Differences Between
1
H and
13
C Technique q
The gyromagnetic ratio of
13
C is one-fourth of that
of
1
H. So, resonance frequency is about one-fourth
that of hydrogen, 15.1 MHz instead of 60 MHz.
75.6 instead of 300.
P k t ti l t b f Peak areas are not proportional to number of
carbons.
Spin lattice relaxation time T varies for diff type Spin-lattice relaxation time T
1
varies for diff. type
of Carbon. If T
1
is short quat C are missed!
This is solved by inserting a delay interval Rd This is solved by inserting a delay interval Rd
Carbon atoms with more hydrogens absorb more
strongly. NOE accrues only for C with H. The
19
strongly. NOE accrues only for C with H. The
enhancement for quaternary C is practically zero!
Intensity increase is a nonlinear f
n
of no. of Hs
Gated proton Gated proton
decoupling
Considerable time saving than continuous broadband
decoupling (in which decoupler is always on)
It i l d t t i t l t t f NOE d till It is employed to retain at least part of NOE and still
maintain CH coupling
The broadband H decoupler is gated (switched) on The broadband H decoupler is gated (switched) on
during the relaxation delay process and gated off
during the brief acquisition period.
Th NOE ( l ) hi h h b ilt d i Thus NOE (slow process) which has built up during
the lengthy delay period, decays only partially during
the brief acquisition period. q p
Coupling (fast process) is immediately established and
remains throughout the acquisition.
C-H Coupling constants C H Coupling constants
Increase with Increase with
Increase in s character
S b tit ti ith ithd i Substitution with e- withdrawing group
With angular distortion
This may be observed in 1H decoupled spectra
Solvents
In
1
HNMR
CDCl
3
singlet at 7.26 arises
In
13
CNMR
There is no question of this CDCl
3
singletat7.26arises
duetoCHCl
3
impurity.
Thereisnoquestionofthis
peakin
13
Casallthe
protonsaresaturated
C Cl i i l 0
DMSOd6(CD
3
SOCD
3
)gives
aquintetat2.49dueto
impurity of HCD
2
SOCD
3
by
CDCl
3
givesatripletat77.0
(32Hz)in
13
C(2x1x1+1=3)
DMSO d6 gives a septet at impurityofHCD
2
SOCD
3
by
couplingwithD(2nI+1=5)
DMSOd6givesaseptetat
39.7(21Hz)by2x3x1+1=7
D analog of
Pascal triangle for H Pascal triangle for H
CDCl
3
In
13
C
3
D has spin = 1
A single D can adopt three different spins (I A single D can adopt three different spins (I
= 1, 2nI+1 = 3), where the spins have quantum
nos of -1,0,+1 , ,
In CDCl3 solution, the molecule can have D
with any one of the three spin states and all y p
are equally probable.
The triplet results from splitting of 13C peak
by D
Therefore we see three different chemical
hif f h C i CDCl3 ( i 1 1 1) shifts for the C atom in CDCl3 (ratio 1:1:1)
13C-D coupling constant is 32 Hz
Interpretation of
13
C
Diethyl phthalate
decoupled
coupled
2
J couplings
2
J and
3
J couplings
Quantitative analysis of 13C Quantitative analysis of 13C
It is not possible in broadband It is not possible in broadband
decoupled spectra because
1 13C nuclei with long T1 relaxation times 1. 13C nuclei with long T1 relaxation times
may not return to the eqm boltzmann
distribution between the pulses Thus distribution between the pulses. Thus
the signal do not achieve full amplitude
2 Th NOE i t 13C l i d 2. The NOE varies amongst 13C nuclei and
so signal intensities vary.
Inverse Gated
t d li proton decoupling
This technique is used for quantitative analysis of
13
C
H Decoupler is gated off at the beginning of the
l ti d l & t d t th t t f i iti relaxation delay & gated on at the start of acquisition
Thus, coupling (fast process) is not allowed in acquisition
NOE (slow process) builds up very slowly in a brief time NOE (slow process) builds up very slowly in a brief time
of acquisition & a low level of NOE is thus maintained
We get a
13
C spectrum consisting of singlets whose
intensity corresponds to the no. of
13
C it represents.
By using long relaxation delays R
d
> 5T
1
and by using
inverse gated H decoupling quantitative 13C is obtained inverse gated H decoupling quantitative 13C is obtained.
I
N
V
E
3
E
R
S
E
1
2
G
A
T
EE
D
H
D
E
CC
O
U
P
LL
I
N
G
Some
13
Cspectra
Look for correct number of C atoms
Combined
13
C and
1
H Spectra Combined
13
C and
1
H Spectra
33
Pyrolle-2-carboxaldehyde
1
H and
13
C-NMR of 1,2,2-
T i hl Trichloropropane
34
Problem Problem
A C
5
H
12
O
2
compound has strong infrared
5 12 2
p g
absorption at 3300 to 3400 cm
-1
The
1
H
NMR spectrum has three singlets at p g
0.9 , 3.45 and 3.2; relative areas
3:2:1. The
13
C NMR spectrum shows p
three signals all at higher field than 100
ppm. Suggest a structure for this pp gg
compound.
(CH
3
)
2
C(CH
2
OH)
2
Problem Problem
A C
4
H
8
O
2
compound has a strong
4 8 2
p g
infrared absorption at 1150 cm
-1
, but no
absorption at 3300 to 3400 cm
-1
. It's p
1
H NMR spectrum shows a singlet at
3.55 ppm. The
13
C NMR spectrum shows pp p
one signal at 66.5 ppm. Suggest a
structure for this compound. p
1 4 di 1,4-dioxane
Problem Problem
A C
5
H
11
N compound shows infrared
5 11
p
absorption at 3300 cm
-1
. It's
1
H NMR
spectrum has three signals: singlets at p g g
1.0 (6H), 1.4 (1H) and 2.7 (4H) ppm. The
13
C NMR spectrum has three signals, all p g
at fields higher than 100 ppm. Suggest a
structure for this compound. p
(CH
3
)
2
C(CH
2
)
2
NH 4 membered cyclic