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2 D N M R
O R G A N I C
S P E C T R O S C O P Y
DR ANTHONY MELVIN CRASTO
PRESENTS
HELLO!
I AM DR ANTHONY
MELVIN CRASTO
WORLDDRUGTRACKER
HELPING MILLIONS
Agenda
1 2D NMR Basics.
2 2D COSY
3 HETCOR
4 TOCSY
5 DEPT
6 NOESY
7 ROESY
Two-dimensional nuclear magnetic resonance
spectroscopy (2D NMR)
• Two-dimensional nuclear magnetic resonance spectroscopy (2D NMR) is a set of
nuclear magnetic resonance spectroscopy (NMR) methods which give data plotted in a
space defined by two frequency axes rather than one. Types of 2D NMR include
correlation spectroscopy (COSY), J-spectroscopy, exchange spectroscopy
(EXSY), and nuclear Overhauser effect spectroscopy (NOESY). Two-dimensional
NMR spectra provide more information about a molecule than one-dimensional NMR
spectra and are especially useful in determining the structure of a molecule,
particularly for molecules that are too complicated to work with using one-dimensional
NMR.
• The first two-dimensional experiment, COSY, was proposed by Jean Jeener, a
professor at the Université Libre de Bruxelles, in 1971. This experiment was later
implemented by Walter P. Aue, Enrico Bartholdi and Richard R. Ernst, who published
their work in 1976
Structure Determination Procedures
1D 1H & 13C & DEPT (+MS 、 IR , basic chemical structure or
functional groups information)
Establish 13C-1H connections by thru bond JCH couplings
HMQC、HSQC、HSQC-TOCSY experiments
Establish 1H-1H connection (spin systems or partial pieces)
Decoupled 1H, 1D TOCSY, 2D 1H-1H COSY, TOCSY expts.
(usually starts with well-resolved 1H signals)
Long range connections ( connecting spin systems & assigning
quaternary carbon)
1D NOESY & 2D HMBC, NOESY, ROESY experiments
3D structure or conformation determination
1D NOESY & 2D NOESY, ROESY, (HSQC)-NOESY expts.
MY BLOGS
ORGANIC SPECTROSCOPY INTERNATIONAL
LINK….. http://orgspectroscopyint.blogspot.in/
ORGANIC SPECTROSCOPY INTERNATIONAL
Organic Chemists from Industry and academics to Interact on
Spectroscopy Techniques for Organic Compounds ie NMR, MASS,
IR, UV Etc. Starters, Learners, advanced, all alike, contains content
which is basic or advanced, by Dr Anthony Melvin Crasto,
Worlddrugtracker, email me ........... amcrasto@gmail.com, call +91
9323115463
LIONEL MY SON
He was only in first standard in school when I was hit by a
deadly one in a million spine stroke called acute transverse
mylitis, it made me 90% paralysed and bound to a wheel
chair,
Now I keep him as my source of inspiration and helping
millions, thanks to millions of my readers who keep me
going and help me to keep my son happy
2D NMR BASICS1
PROTON-PROTON CORRELATION THROUGH J-
COUPLING
2D NMR Basics.
• In actuality, the techniques we have already covered 1H, 13C, and DEPT are 2-D (frequency vs.
intensity) however, by tradition the intensity component is dropped when discussing
dimensionality
• In 2-D techniques, many FIDs (proto-NMR spectra) are taken one after another, with some
acquisition variable or pulse sequenced varied by small increments
• Since each FID is a collection of digitized data points in the first dimension (say 10 points to
make a spectrum) if 10 spectra are accumulated with an incremental change in variable, an FT
can be performed in the other dimension
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1-D FID
1-D spectra, each
with an incremental
variable change
FTs can be performed on
the vertical data sets
PROTON-PROTON CORRELATION THROUGH J-
COUPLING
2D NMR Basics.
• The first perturbation of the system (pulse) is called the preparation of the spin system.
• The effects of this pulse are allowed to coalesce; this is known as the evolution time, t1 (NOT T1
– the relaxation time)
• During this time, a mixing event, in which information from one part of the spin system is
relayed to other parts, occurs
• Finally, an acquisition period (t2) as with all 1-D experiments.
Preparation Evolution Acquisition
t1 t2
Mixing
NMR
spectrum
Structure
Chem. Shift
J Coupling
Peak Int.
NOE
Correlation
H-H,C-H
O
O
OH
O
CH3
O
H
OH
OH
OH
CH2OH
COOCH2
1
2
3
4
5
6
7
8
9
10
1''
2''3''
4''
5'' 6''
1'
2'3'
4'
5'
6'
7''
Applications:
• Sample quality control for Synthetic works.
• Elucidation of chemical structures.
• Getting functional group, bonding, dynamics, kinetics and chemical exchange information of molecules.
• 3D structures of the molecules.
NMR Applications in Chemistry
 Connections through space(dipolar coupling)
1D、2D NOESY,ROESY, HOESY(HSQC-NOESY)
usage: connecting spin systems 、structure determination
 Connections through bonds(spin-spin coupling)
Homonuclear: 1D、2D 1H-1H COSY, DQF-COSY, TOCSY
usage:spin system assignment
Heteronuclear:
Direct (detect 13C): APT, DEPT, HETCOR
Inverse (detect1H): HMQC, HSQC, HMBC, HSQC-COSY,
HSQC-TOCSY, HMQC-TOCSY
usage:assigning heteronuclei、connecting spin systems
Some common NMR experiments:
COSY spectrum is used for determining the connectivities
between protons on the basis of geminal and vicinal couplings.
Disadvantage: bulky dispersive diagonal peaks.
C C H
HH
Vicinal
Geminal
2D COSY — Homonuclear Shift COrrelation SpectroscopY
t1 AQ
The basic COSY (x=45° or 90°) pulse sequence
90° x°
t2
ppm
1.01.52.02.53.03.5 ppm
1.0
1.5
2.0
2.5
3.0
3.5
Current Data Parameters
NAME butcosy
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20001102
Time 8.04
INSTRUM DRX500
PROBHD 5 mm TBI 1H/
PULPROG cosygp
TD 1024
SOLVENT CDCl3
NS 1
DS 16
SWH 2185.315 Hz
FIDRES 2.134096 Hz
AQ 0.2345700 sec
RG 40.3
DW 228.800 usec
DE 6.00 usec
TE 288.0 K
D0 0.00000300 sec
D1 1.60000002 sec
D13 0.00000300 sec
D16 0.00010000 sec
IN0 0.00045765 sec
============ CHANNEL f1 =============
NUC1 1H
P0 3.00 usec
P1 6.00 usec
PL1 -4.00 dB
SFO1 500.1310815 MHz
============ GRADIENT CHANNEL ========
GPNAM1 sine.100
GPNAM2 sine.100
GPX1 0.00 %
GPX2 0.00 %
GPY1 0.00 %
GPY2 0.00 %
GPZ1 10.00 %
GPZ2 10.00 %
P16 1000.00 usec
F1 - Acquisition parameters
ND0 1
TD 256
SFO1 500.1311 MHz
FIDRES 8.535453 Hz
SW 4.369 ppm
FnMODE undefined
F2 - Processing parameters
SI 2048
SF 500.1300144 MHz
WDW QSINE
SSB 0
LB 0.00 Hz
GB 0
PC 0.20
F1 - Processing parameters
SI 1024
MC2 QF
SF 500.1300144 MHz
WDW QSINE
SSB 0
LB 0.00 Hz
GB 0
1 2 3 41
234
HO C
H1
H
C C C
H2
H
H3
H
H4
H
H
1-2
2-3
3-4
2D Gradient COSY-45
2D COSY NMR2
Correlated Spectroscopy
FT of the t1 domain, acetone
October 20, 2004 Joanna R. Long 15
2D Exchange NMR
A. S. Edison
University of Florida
t1 t2






FT of t2
FTint1willgive2Dfrequencyspectrum
PROTON-PROTON CORRELATION THROUGH J-
COUPLING
2D COSY.
• H-H COrrelation SpectroscopY (COSY):
• The pulse sequence for COSY is as follows:
• A 90o pulse in the x-direction is what we used for 1-D 1H NMR
• Here, after a variable “mixing” period, a second 90o pulse is performed, followed by
acquisition of a spectrum
19
90x90x
t1
t2
October 20, 2004 Joanna R. Long 16
15 l N•Ndimethylacetamide in 700 l d-chloroform at 29° C
A-B coupling in COSY Spectrum
CH3CH2CCH3
O
CH2CH3
Isobutyl Alcohol
OH
O
O
1H NMR Spectrum of Ipsenol
COSY Spectra of Ipsenol
Share a big idea or quote here.
HETCOR3
Heteronuclear through-bond correlation methods
• Heteronuclear correlation spectroscopy gives signal based upon coupling between
nuclei between two different types. Often the two nuclei are protons and another
nucleus (called a "heteronucleus"). For historical reasons, experiments which record
the proton rather than the heteronucleus spectrum during the detection period are
called "inverse" experiments.
• This is because the low natural abundance of most heteronuclei would result in the
proton spectrum being overwhelmed with signals from molecules with no active
heteronuclei, making it useless for observing the desired, coupled signals.
• With the advent of techniques for suppressing these undesired signals, inverse
correlation experiments such as HSQC, HMQC, and HMBC are actually much more
common today. "Normal" heteronuclear correlation spectroscopy, in which the
hetronucleus spectrum is recorded, is known as HETCOR
Heteronuclear multiple-bond correlation
spectroscopy (HMBC)
• HMBC detects heteronuclear correlations over longer ranges of about 2–4 bonds. The
difficulty of detecting multiple-bond correlations is that the HSQC and HMQC
sequences contain a specific delay time between pulses which allows detection only of
a range around a specific coupling constant. This is not a problem for the single-bond
methods since the coupling constants tend to lie in a narrow range, but multiple-bond
coupling constants cover a much wider range and cannot all be captured in a single
HSQC or HMQC experiment.
• In HMBC, this difficulty is overcome by omitting one of these delays from an HMQC
sequence. This increases the range of coupling constants that can be detected, and
also reduces signal loss from relaxation. The cost is that this eliminates the possibility
of decoupling the spectrum, and introduces phase distortions into the signal. There is a
modification of the HMBC method which suppresses one-bond signals, leaving only
the multiple-bond signals
Heteronuclear single-quantum correlation
spectroscopy (HSQC)
• HSQC detects correlations between nuclei of two different types which are separated
by one bond. This method gives one peak per pair of coupled nuclei, whose two
coordinates are the chemical shifts of the two coupled atoms.
• HSQC works by transferring magnetization from the I nucleus (usually the proton) to
the S nucleus (usually the heteroatom) using the INEPT pulse sequence; this first step
is done because the proton has a greater equilibrium magnetization and thus this step
creates a stronger signal. The magnetization then evolves and then is transferred back
to the I nucleus for observation. An extra spin echo step can then optionally be used to
decouple the signal, simplifying the spectrum by collapsing multiplets to a single peak.
The undesired uncoupled signals are removed by running the experiment twice with
the phase of one specific pulse reversed; this reverses the signs of the desired but not
the undesired peaks, so subtracting the two spectra will give only the desired
peaks.Heteronuclear multiple-quantum correlation spectroscopy (HMQC) gives an
identical spectrum as HSQC, but using a different method. The two methods give
similar quality results for small to medium-sized molecules, but HSQC is considered to
be superior for larger molecules
HETCOR (Heteronuclear chemical shift correlation, 1H - 13C COSY)
13C
1H t1 1 2
The standard pulse sequence for 13C-detected
1H-13C chemical shift correlation.
AQ
t2
1H decoupling
Removing JCH splittings
*But Inverse experiment has the following Advantages:
•increase sensitivity of detecting the less sensitive nuclei
•1H is in the direct detection dimension => larger np => better
resolution
HMBC (Heteronuclear Multiple-Bond Correlation Spectroscopy)
13C
1H t1 AQ
C2, C3 and C4: Quaternary or protonated carbons X: O, N
C1 C2 C3 C4
H1
C1 X C2 C3
H1
Pulse sequence for HMBC
Long range connections or connections between spin systems
HETCOR Spctrum of Ipsenol
N
COCH2CH3
O
H
H
H
H
Exercise 5.6, p. 291
N
COCH2CH3
O
H
H
H
H
Exercise 5.6, p. 292
O
CH3
ppm
1.01.52.02.53.03.5 ppm
10
15
20
25
30
35
40
45
50
55
60
65
Current Data Parameters
NAME buthsqc
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20001102
Time 10.31
INSTRUM DRX500
PROBHD 5 mm TBI 1H/
PULPROG invietgpsi
TD 1024
SOLVENT CDCl3
NS 1
DS 16
SWH 2185.315 Hz
FIDRES 2.134096 Hz
AQ 0.2345700 sec
RG 2298.8
DW 228.800 usec
DE 6.00 usec
TE 300.0 K
D0 0.00000300 sec
D1 2.00000000 sec
D4 0.00170000 sec
D11 0.03000000 sec
D13 0.00000300 sec
D16 0.00010000 sec
D24 0.00090000 sec
DELTA 0.00116720 sec
DELTA1 0.00110700 sec
IN0 0.00003600 sec
l3 256
============ CHANNEL f1 =============
NUC1 1H
P1 5.60 usec
P2 11.20 usec
P28 2500.00 usec
PL1 -4.00 dB
SFO1 500.1310815 MHz
============ CHANNEL f2 =============
CPDPRG2 garp
NUC2 13C
P3 17.70 usec
P4 35.40 usec
PCPD2 89.00 usec
PL2 -1.00 dB
PL12 13.00 dB
SFO2 125.7633722 MHz
============ GRADIENT CHANNEL ========
GPNAM1 sine.100
GPNAM2 sine.100
GPX1 0.00 %
GPX2 0.00 %
GPY1 0.00 %
GPY2 0.00 %
GPZ1 80.00 %
GPZ2 20.10 %
P16 1000.00 usec
F1 - Acquisition parameters
ND0 2
TD 512
SFO1 125.7634 MHz
FIDRES 27.126736 Hz
SW 110.437 ppm
FnMODE undefined
F2 - Processing parameters
SI 1024
SF 500.1300144 MHz
WDW SINE
SSB 2
LB 0.00 Hz
GB 0
PC 0.20
F1 - Processing parameters
SI 1024
MC2 echo-antiecho
SF 125.7577969 MHz
WDW SINE
SSB 2
LB 0.00 Hz
GB 0
HO C
H1
H
C C C
H2
H
H3
H
H4
H
H
1 2 3 4
1234
HSQC spectrum: H-C correlatedC-
dimensio
n
H-dimension
TOCSY4
Total correlation spectroscopy (TOCSY)
• The TOCSY experiment is similar to the COSY experiment, in that cross peaks of
coupled protons are observed. However, cross peaks are observed not only for nuclei
which are directly coupled, but also between nuclei which are connected by a chain of
couplings. This makes it useful for identifying the larger interconnected networks of
spin couplings. This ability is achieved by inserting a repetitive series of pulses which
cause isotropic mixing during the mixing period. Longer isotropic mixing times cause
the polarization to spread out through an increasing number of bonds.
• In the case of oligosaccharides, each sugar residue is an isolated spin system, so it is
possible to differentiate all the protons of a specific sugar residue. A 1D version of
TOCSY is also available and by irradiating a single proton the rest of the spin system
can be revealed. Recent advances in this technique include the 1D-CSSF-TOCSY
(Chemical Shift Selective Filter - TOCSY) experiment, which produces higher quality
spectra and allows coupling constants to be reliably extracted and used to help
determine stereochemistry.
• TOCSY is sometimes called "homonuclear Hartmann–Hahn spectroscopy" (HOHAHA)
2D NMR ORGANIC SPECTROSCOPY by DR ANTHONY CRASTO
A
TOCSY (TOtal Correlation SpectroscopY) or
HOHAHA(Homonuclear Hartman-Hahn Spectroscopy)
t1  MLEV17 AQ
Pulse sequence for a TOCSY spectrum.
Different mixing time gives different degree of relay of correlation.
At small mixing time, TOCSY spectrum is similar to COSY
spectrum. At long mixing time, gives total correlation.
HO C
H1
H
C C C
H2
H
H3
H
H4
H
H
HO C
H1
H
C C C
H2
H
H3
H
H4
H
H
HO C
H1
H
C C C
H2
H
H3
H
H4
H
HCOSY RL-COSY TOCSY
mixing time t2
DEPT5
DEPT-90, DEPT-135
Distortionless Enhancement by Polarization
Transfer
• Preferred procedure for determining #
protons attached to carbons
• Variable proton pulse angle q is set at 90o
and 135o
• In DEPT-90, only CH shows. In DEPT-135,
CH2’s are phased down, CH and CH3 are
phased up
DEPT: Distortionless Enhancement by Polarization Transfer
Heteronuclear expt.
Detection: 13C
Distinguish
CH, CH2, CH3
By suitable combination of
q=45, 90 & 135 spectra
All CH’s
Only CH
CH & CH3up
CH2 down
Adjustment of 1H pulse angle
Avoids overlapping multiplets
CH
CH2
CH3
2-Heptanone, CPD and DEPT-35
6-Methyl-5-hepten-2-ol
Standard CPD Spectrum
DEPT-90
DEPT-135
OH
O
CH3
DEPT-135
DEPT-90
2D NMR ORGANIC SPECTROSCOPY by DR ANTHONY CRASTO
<
>
Ipsenol
CPD, DEPT-135, DEPT 90
7
6
2
5 3
4 1
9
8,10
2D NOESY6
Nuclear Overhauser effect spectroscopy
(NOESY)In NOESY, the Nuclear Overhauser cross relaxation between nuclear spins during the mixing
period is used to establish the correlations. The spectrum obtained is similar to COSY, with
diagonal peaks and cross peaks, however the cross peaks connect resonances from nuclei that
are spatially close rather than those that are through-bond coupled to each other. NOESY
spectra also contain extra axial peaks which do not provide extra information and can be
eliminated through a different experiment by reversing the phase of the first pulse.
One application of NOESY is in the study of large biomolecules such as in protein NMR, which
can often be assigned using sequential walking.
The NOESY experiment can also be performed in a one-dimensional fashion by pre-selecting
individual resonances. The spectra are read with the pre-selected nuclei giving a large, negative
signal while neighboring nuclei are identified by weaker, positive signals. This only reveals which
peaks have measurable NOEs to the resonance of interest but takes much less time than the full
2D experiment. In addition, if a pre-selected nucleus changes environment within the time scale
of the experiment, multiple negative signals may be observed. This offers exchange information
similar to the EXSY (exchange spectroscopy) NMR method.
NOESY experiment is important tool to identify stereochemistry of a molecule in solvent whereas
single crystal XRD used to identify stereochemistry of a molecule in solid form.
2D NOESY (Nuclear Overhauser Enhancements SpectroscopY)
t1 m AQ
The NOESY pulse sequence.
—C — ~ —C —
Ha Hb VC*r -6, r0.5nm
r0.5nm
For resonance assignment, chemical structure elucidation &
3D structure determination
t2
ppm
3.54.04.55.05.56.06.57.07.5 ppm
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
Current Data Parameters
NAME cfynoesy
EXPNO 1
PROCNO 1
F2 - Acquisition Parameters
Date_ 20001103
Time 8.53
INSTRUM DRX500
PROBHD 5 mm TBI 1H/
PULPROG noesygptp
TD 1024
SOLVENT CDCl3
NS 8
DS 16
SWH 3443.526 Hz
FIDRES 3.362818 Hz
AQ 0.1488800 sec
RG 64
DW 145.200 usec
DE 6.00 usec
TE 288.0 K
D0 0.00000300 sec
D1 1.60000002 sec
D8 0.40000001 sec
D16 0.00010000 sec
d20 0.19890000 sec
IN0 0.00014520 sec
============ CHANNEL f1 =============
NUC1 1H
P1 6.00 usec
P2 12.00 usec
PL1 -4.00 dB
SFO1 500.1326379 MHz
============ GRADIENT CHANNEL ========
GPNAM1 sine.100
GPNAM2 sine.100
GPX1 0.00 %
GPX2 0.00 %
GPY1 0.00 %
GPY2 0.00 %
GPZ1 40.00 %
GPZ2 -40.00 %
P16 1000.00 usec
F1 - Acquisition parameters
ND0 2
TD 256
SFO1 500.1326 MHz
FIDRES 13.451274 Hz
SW 6.885 ppm
FnMODE undefined
F2 - Processing parameters
SI 1024
SF 500.1300144 MHz
WDW SINE
SSB 2
LB 0.00 Hz
GB 0
PC 0.20
F1 - Processing parameters
SI 1024
MC2 TPPI
SF 500.1300144 MHz
WDW SINE
SSB 2
LB 0.00 Hz
GB 0
N
N N
N
O
O
CH3
CH3
H3C
H
1
3
5
2
8
7
6
4
3-CH3, 5-H
Gradient NOESY
NOESY
gives sequential
assignment of peptides
21 2 3
CH2
CH2N C
H
N
O
H
C C
H
CH2O
N
H
C
CH2
C
H
OH
O
1 321
2D ROESY7
Rotating frame nuclear Overhauser effect
spectroscopy (ROESY)
• ROESY is similar to NOESY, except that the initial state is different. Instead of
observing cross relaxation from an initial state of z-magnetization, the equilibrium
magnetization is rotated onto the x axis and then spin-locked by an external magnetic
field so that it cannot precess. This method is useful for certain molecules whose
rotational correlation time falls in a range where the Nuclear Overhauser effect is too
weak to be detectable, usually molecules with a molecular weight around 1000 daltons,
because ROESY has a different dependence between the correlation time and the
cross-relaxation rate constant. In NOESY the cross-relaxation rate constant goes from
positive to negative as the correlation time increases, giving a range where it is near
zero, whereas in ROESY the cross-relaxation rate constant is always positive.
• ROESY is sometimes called "cross relaxation appropriate for minimolecules emulated
by locked spins" (CAMELSPIN)
Spin-lock
90°
t1 t2
2D ROESY pulse program
For small molecule NOE can be very small or zero,
ROESY can be used in place of NOESY experiment. ROE
intensity is also related to the H-H distances.
mixing time
2D ROESY spectrum of ethylbenzene
Structure of 12,14-
ditbutylbenzo[g]chrysene showing color
conding of rings
Aromatic region of the 2D ROESY spectrum of 12,14-
ditbutylbenzo[g]chrysene showing connectivity and separation into four
color-coded proton groups
CASE STUDY ..ASPIRIN1
1 H-NMR spectrum of acetylsalicylic acid
H, H-COSY spectrum of acetylsalicylic acid
THANK YOU!

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2D NMR ORGANIC SPECTROSCOPY by DR ANTHONY CRASTO

  • 1. 2 D N M R O R G A N I C S P E C T R O S C O P Y DR ANTHONY MELVIN CRASTO PRESENTS
  • 2. HELLO! I AM DR ANTHONY MELVIN CRASTO WORLDDRUGTRACKER HELPING MILLIONS
  • 3. Agenda 1 2D NMR Basics. 2 2D COSY 3 HETCOR 4 TOCSY 5 DEPT 6 NOESY 7 ROESY
  • 4. Two-dimensional nuclear magnetic resonance spectroscopy (2D NMR) • Two-dimensional nuclear magnetic resonance spectroscopy (2D NMR) is a set of nuclear magnetic resonance spectroscopy (NMR) methods which give data plotted in a space defined by two frequency axes rather than one. Types of 2D NMR include correlation spectroscopy (COSY), J-spectroscopy, exchange spectroscopy (EXSY), and nuclear Overhauser effect spectroscopy (NOESY). Two-dimensional NMR spectra provide more information about a molecule than one-dimensional NMR spectra and are especially useful in determining the structure of a molecule, particularly for molecules that are too complicated to work with using one-dimensional NMR. • The first two-dimensional experiment, COSY, was proposed by Jean Jeener, a professor at the Université Libre de Bruxelles, in 1971. This experiment was later implemented by Walter P. Aue, Enrico Bartholdi and Richard R. Ernst, who published their work in 1976
  • 5. Structure Determination Procedures 1D 1H & 13C & DEPT (+MS 、 IR , basic chemical structure or functional groups information) Establish 13C-1H connections by thru bond JCH couplings HMQC、HSQC、HSQC-TOCSY experiments Establish 1H-1H connection (spin systems or partial pieces) Decoupled 1H, 1D TOCSY, 2D 1H-1H COSY, TOCSY expts. (usually starts with well-resolved 1H signals) Long range connections ( connecting spin systems & assigning quaternary carbon) 1D NOESY & 2D HMBC, NOESY, ROESY experiments 3D structure or conformation determination 1D NOESY & 2D NOESY, ROESY, (HSQC)-NOESY expts.
  • 6. MY BLOGS ORGANIC SPECTROSCOPY INTERNATIONAL LINK….. http://orgspectroscopyint.blogspot.in/ ORGANIC SPECTROSCOPY INTERNATIONAL Organic Chemists from Industry and academics to Interact on Spectroscopy Techniques for Organic Compounds ie NMR, MASS, IR, UV Etc. Starters, Learners, advanced, all alike, contains content which is basic or advanced, by Dr Anthony Melvin Crasto, Worlddrugtracker, email me ........... amcrasto@gmail.com, call +91 9323115463
  • 7. LIONEL MY SON He was only in first standard in school when I was hit by a deadly one in a million spine stroke called acute transverse mylitis, it made me 90% paralysed and bound to a wheel chair, Now I keep him as my source of inspiration and helping millions, thanks to millions of my readers who keep me going and help me to keep my son happy
  • 9. PROTON-PROTON CORRELATION THROUGH J- COUPLING 2D NMR Basics. • In actuality, the techniques we have already covered 1H, 13C, and DEPT are 2-D (frequency vs. intensity) however, by tradition the intensity component is dropped when discussing dimensionality • In 2-D techniques, many FIDs (proto-NMR spectra) are taken one after another, with some acquisition variable or pulse sequenced varied by small increments • Since each FID is a collection of digitized data points in the first dimension (say 10 points to make a spectrum) if 10 spectra are accumulated with an incremental change in variable, an FT can be performed in the other dimension . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-D FID 1-D spectra, each with an incremental variable change FTs can be performed on the vertical data sets
  • 10. PROTON-PROTON CORRELATION THROUGH J- COUPLING 2D NMR Basics. • The first perturbation of the system (pulse) is called the preparation of the spin system. • The effects of this pulse are allowed to coalesce; this is known as the evolution time, t1 (NOT T1 – the relaxation time) • During this time, a mixing event, in which information from one part of the spin system is relayed to other parts, occurs • Finally, an acquisition period (t2) as with all 1-D experiments. Preparation Evolution Acquisition t1 t2 Mixing
  • 11. NMR spectrum Structure Chem. Shift J Coupling Peak Int. NOE Correlation H-H,C-H O O OH O CH3 O H OH OH OH CH2OH COOCH2 1 2 3 4 5 6 7 8 9 10 1'' 2''3'' 4'' 5'' 6'' 1' 2'3' 4' 5' 6' 7'' Applications: • Sample quality control for Synthetic works. • Elucidation of chemical structures. • Getting functional group, bonding, dynamics, kinetics and chemical exchange information of molecules. • 3D structures of the molecules. NMR Applications in Chemistry
  • 12.  Connections through space(dipolar coupling) 1D、2D NOESY,ROESY, HOESY(HSQC-NOESY) usage: connecting spin systems 、structure determination  Connections through bonds(spin-spin coupling) Homonuclear: 1D、2D 1H-1H COSY, DQF-COSY, TOCSY usage:spin system assignment Heteronuclear: Direct (detect 13C): APT, DEPT, HETCOR Inverse (detect1H): HMQC, HSQC, HMBC, HSQC-COSY, HSQC-TOCSY, HMQC-TOCSY usage:assigning heteronuclei、connecting spin systems Some common NMR experiments:
  • 13. COSY spectrum is used for determining the connectivities between protons on the basis of geminal and vicinal couplings. Disadvantage: bulky dispersive diagonal peaks. C C H HH Vicinal Geminal 2D COSY — Homonuclear Shift COrrelation SpectroscopY t1 AQ The basic COSY (x=45° or 90°) pulse sequence 90° x° t2
  • 14. ppm 1.01.52.02.53.03.5 ppm 1.0 1.5 2.0 2.5 3.0 3.5 Current Data Parameters NAME butcosy EXPNO 1 PROCNO 1 F2 - Acquisition Parameters Date_ 20001102 Time 8.04 INSTRUM DRX500 PROBHD 5 mm TBI 1H/ PULPROG cosygp TD 1024 SOLVENT CDCl3 NS 1 DS 16 SWH 2185.315 Hz FIDRES 2.134096 Hz AQ 0.2345700 sec RG 40.3 DW 228.800 usec DE 6.00 usec TE 288.0 K D0 0.00000300 sec D1 1.60000002 sec D13 0.00000300 sec D16 0.00010000 sec IN0 0.00045765 sec ============ CHANNEL f1 ============= NUC1 1H P0 3.00 usec P1 6.00 usec PL1 -4.00 dB SFO1 500.1310815 MHz ============ GRADIENT CHANNEL ======== GPNAM1 sine.100 GPNAM2 sine.100 GPX1 0.00 % GPX2 0.00 % GPY1 0.00 % GPY2 0.00 % GPZ1 10.00 % GPZ2 10.00 % P16 1000.00 usec F1 - Acquisition parameters ND0 1 TD 256 SFO1 500.1311 MHz FIDRES 8.535453 Hz SW 4.369 ppm FnMODE undefined F2 - Processing parameters SI 2048 SF 500.1300144 MHz WDW QSINE SSB 0 LB 0.00 Hz GB 0 PC 0.20 F1 - Processing parameters SI 1024 MC2 QF SF 500.1300144 MHz WDW QSINE SSB 0 LB 0.00 Hz GB 0 1 2 3 41 234 HO C H1 H C C C H2 H H3 H H4 H H 1-2 2-3 3-4 2D Gradient COSY-45
  • 17. FT of the t1 domain, acetone
  • 18. October 20, 2004 Joanna R. Long 15 2D Exchange NMR A. S. Edison University of Florida t1 t2       FT of t2 FTint1willgive2Dfrequencyspectrum
  • 19. PROTON-PROTON CORRELATION THROUGH J- COUPLING 2D COSY. • H-H COrrelation SpectroscopY (COSY): • The pulse sequence for COSY is as follows: • A 90o pulse in the x-direction is what we used for 1-D 1H NMR • Here, after a variable “mixing” period, a second 90o pulse is performed, followed by acquisition of a spectrum 19 90x90x t1 t2
  • 20. October 20, 2004 Joanna R. Long 16 15 l N•Ndimethylacetamide in 700 l d-chloroform at 29° C
  • 21. A-B coupling in COSY Spectrum
  • 25. O O
  • 26. 1H NMR Spectrum of Ipsenol
  • 27. COSY Spectra of Ipsenol
  • 28. Share a big idea or quote here.
  • 30. Heteronuclear through-bond correlation methods • Heteronuclear correlation spectroscopy gives signal based upon coupling between nuclei between two different types. Often the two nuclei are protons and another nucleus (called a "heteronucleus"). For historical reasons, experiments which record the proton rather than the heteronucleus spectrum during the detection period are called "inverse" experiments. • This is because the low natural abundance of most heteronuclei would result in the proton spectrum being overwhelmed with signals from molecules with no active heteronuclei, making it useless for observing the desired, coupled signals. • With the advent of techniques for suppressing these undesired signals, inverse correlation experiments such as HSQC, HMQC, and HMBC are actually much more common today. "Normal" heteronuclear correlation spectroscopy, in which the hetronucleus spectrum is recorded, is known as HETCOR
  • 31. Heteronuclear multiple-bond correlation spectroscopy (HMBC) • HMBC detects heteronuclear correlations over longer ranges of about 2–4 bonds. The difficulty of detecting multiple-bond correlations is that the HSQC and HMQC sequences contain a specific delay time between pulses which allows detection only of a range around a specific coupling constant. This is not a problem for the single-bond methods since the coupling constants tend to lie in a narrow range, but multiple-bond coupling constants cover a much wider range and cannot all be captured in a single HSQC or HMQC experiment. • In HMBC, this difficulty is overcome by omitting one of these delays from an HMQC sequence. This increases the range of coupling constants that can be detected, and also reduces signal loss from relaxation. The cost is that this eliminates the possibility of decoupling the spectrum, and introduces phase distortions into the signal. There is a modification of the HMBC method which suppresses one-bond signals, leaving only the multiple-bond signals
  • 32. Heteronuclear single-quantum correlation spectroscopy (HSQC) • HSQC detects correlations between nuclei of two different types which are separated by one bond. This method gives one peak per pair of coupled nuclei, whose two coordinates are the chemical shifts of the two coupled atoms. • HSQC works by transferring magnetization from the I nucleus (usually the proton) to the S nucleus (usually the heteroatom) using the INEPT pulse sequence; this first step is done because the proton has a greater equilibrium magnetization and thus this step creates a stronger signal. The magnetization then evolves and then is transferred back to the I nucleus for observation. An extra spin echo step can then optionally be used to decouple the signal, simplifying the spectrum by collapsing multiplets to a single peak. The undesired uncoupled signals are removed by running the experiment twice with the phase of one specific pulse reversed; this reverses the signs of the desired but not the undesired peaks, so subtracting the two spectra will give only the desired peaks.Heteronuclear multiple-quantum correlation spectroscopy (HMQC) gives an identical spectrum as HSQC, but using a different method. The two methods give similar quality results for small to medium-sized molecules, but HSQC is considered to be superior for larger molecules
  • 33. HETCOR (Heteronuclear chemical shift correlation, 1H - 13C COSY) 13C 1H t1 1 2 The standard pulse sequence for 13C-detected 1H-13C chemical shift correlation. AQ t2 1H decoupling Removing JCH splittings *But Inverse experiment has the following Advantages: •increase sensitivity of detecting the less sensitive nuclei •1H is in the direct detection dimension => larger np => better resolution
  • 34. HMBC (Heteronuclear Multiple-Bond Correlation Spectroscopy) 13C 1H t1 AQ C2, C3 and C4: Quaternary or protonated carbons X: O, N C1 C2 C3 C4 H1 C1 X C2 C3 H1 Pulse sequence for HMBC Long range connections or connections between spin systems
  • 35. HETCOR Spctrum of Ipsenol
  • 38. O CH3
  • 39. ppm 1.01.52.02.53.03.5 ppm 10 15 20 25 30 35 40 45 50 55 60 65 Current Data Parameters NAME buthsqc EXPNO 1 PROCNO 1 F2 - Acquisition Parameters Date_ 20001102 Time 10.31 INSTRUM DRX500 PROBHD 5 mm TBI 1H/ PULPROG invietgpsi TD 1024 SOLVENT CDCl3 NS 1 DS 16 SWH 2185.315 Hz FIDRES 2.134096 Hz AQ 0.2345700 sec RG 2298.8 DW 228.800 usec DE 6.00 usec TE 300.0 K D0 0.00000300 sec D1 2.00000000 sec D4 0.00170000 sec D11 0.03000000 sec D13 0.00000300 sec D16 0.00010000 sec D24 0.00090000 sec DELTA 0.00116720 sec DELTA1 0.00110700 sec IN0 0.00003600 sec l3 256 ============ CHANNEL f1 ============= NUC1 1H P1 5.60 usec P2 11.20 usec P28 2500.00 usec PL1 -4.00 dB SFO1 500.1310815 MHz ============ CHANNEL f2 ============= CPDPRG2 garp NUC2 13C P3 17.70 usec P4 35.40 usec PCPD2 89.00 usec PL2 -1.00 dB PL12 13.00 dB SFO2 125.7633722 MHz ============ GRADIENT CHANNEL ======== GPNAM1 sine.100 GPNAM2 sine.100 GPX1 0.00 % GPX2 0.00 % GPY1 0.00 % GPY2 0.00 % GPZ1 80.00 % GPZ2 20.10 % P16 1000.00 usec F1 - Acquisition parameters ND0 2 TD 512 SFO1 125.7634 MHz FIDRES 27.126736 Hz SW 110.437 ppm FnMODE undefined F2 - Processing parameters SI 1024 SF 500.1300144 MHz WDW SINE SSB 2 LB 0.00 Hz GB 0 PC 0.20 F1 - Processing parameters SI 1024 MC2 echo-antiecho SF 125.7577969 MHz WDW SINE SSB 2 LB 0.00 Hz GB 0 HO C H1 H C C C H2 H H3 H H4 H H 1 2 3 4 1234 HSQC spectrum: H-C correlatedC- dimensio n H-dimension
  • 41. Total correlation spectroscopy (TOCSY) • The TOCSY experiment is similar to the COSY experiment, in that cross peaks of coupled protons are observed. However, cross peaks are observed not only for nuclei which are directly coupled, but also between nuclei which are connected by a chain of couplings. This makes it useful for identifying the larger interconnected networks of spin couplings. This ability is achieved by inserting a repetitive series of pulses which cause isotropic mixing during the mixing period. Longer isotropic mixing times cause the polarization to spread out through an increasing number of bonds. • In the case of oligosaccharides, each sugar residue is an isolated spin system, so it is possible to differentiate all the protons of a specific sugar residue. A 1D version of TOCSY is also available and by irradiating a single proton the rest of the spin system can be revealed. Recent advances in this technique include the 1D-CSSF-TOCSY (Chemical Shift Selective Filter - TOCSY) experiment, which produces higher quality spectra and allows coupling constants to be reliably extracted and used to help determine stereochemistry. • TOCSY is sometimes called "homonuclear Hartmann–Hahn spectroscopy" (HOHAHA)
  • 43. A
  • 44. TOCSY (TOtal Correlation SpectroscopY) or HOHAHA(Homonuclear Hartman-Hahn Spectroscopy) t1  MLEV17 AQ Pulse sequence for a TOCSY spectrum. Different mixing time gives different degree of relay of correlation. At small mixing time, TOCSY spectrum is similar to COSY spectrum. At long mixing time, gives total correlation. HO C H1 H C C C H2 H H3 H H4 H H HO C H1 H C C C H2 H H3 H H4 H H HO C H1 H C C C H2 H H3 H H4 H HCOSY RL-COSY TOCSY mixing time t2
  • 45. DEPT5
  • 46. DEPT-90, DEPT-135 Distortionless Enhancement by Polarization Transfer • Preferred procedure for determining # protons attached to carbons • Variable proton pulse angle q is set at 90o and 135o • In DEPT-90, only CH shows. In DEPT-135, CH2’s are phased down, CH and CH3 are phased up
  • 47. DEPT: Distortionless Enhancement by Polarization Transfer Heteronuclear expt. Detection: 13C Distinguish CH, CH2, CH3 By suitable combination of q=45, 90 & 135 spectra All CH’s Only CH CH & CH3up CH2 down
  • 48. Adjustment of 1H pulse angle Avoids overlapping multiplets CH CH2 CH3
  • 54. < >
  • 55. Ipsenol CPD, DEPT-135, DEPT 90 7 6 2 5 3 4 1 9 8,10
  • 57. Nuclear Overhauser effect spectroscopy (NOESY)In NOESY, the Nuclear Overhauser cross relaxation between nuclear spins during the mixing period is used to establish the correlations. The spectrum obtained is similar to COSY, with diagonal peaks and cross peaks, however the cross peaks connect resonances from nuclei that are spatially close rather than those that are through-bond coupled to each other. NOESY spectra also contain extra axial peaks which do not provide extra information and can be eliminated through a different experiment by reversing the phase of the first pulse. One application of NOESY is in the study of large biomolecules such as in protein NMR, which can often be assigned using sequential walking. The NOESY experiment can also be performed in a one-dimensional fashion by pre-selecting individual resonances. The spectra are read with the pre-selected nuclei giving a large, negative signal while neighboring nuclei are identified by weaker, positive signals. This only reveals which peaks have measurable NOEs to the resonance of interest but takes much less time than the full 2D experiment. In addition, if a pre-selected nucleus changes environment within the time scale of the experiment, multiple negative signals may be observed. This offers exchange information similar to the EXSY (exchange spectroscopy) NMR method. NOESY experiment is important tool to identify stereochemistry of a molecule in solvent whereas single crystal XRD used to identify stereochemistry of a molecule in solid form.
  • 58. 2D NOESY (Nuclear Overhauser Enhancements SpectroscopY) t1 m AQ The NOESY pulse sequence. —C — ~ —C — Ha Hb VC*r -6, r0.5nm r0.5nm For resonance assignment, chemical structure elucidation & 3D structure determination t2
  • 59. ppm 3.54.04.55.05.56.06.57.07.5 ppm 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 Current Data Parameters NAME cfynoesy EXPNO 1 PROCNO 1 F2 - Acquisition Parameters Date_ 20001103 Time 8.53 INSTRUM DRX500 PROBHD 5 mm TBI 1H/ PULPROG noesygptp TD 1024 SOLVENT CDCl3 NS 8 DS 16 SWH 3443.526 Hz FIDRES 3.362818 Hz AQ 0.1488800 sec RG 64 DW 145.200 usec DE 6.00 usec TE 288.0 K D0 0.00000300 sec D1 1.60000002 sec D8 0.40000001 sec D16 0.00010000 sec d20 0.19890000 sec IN0 0.00014520 sec ============ CHANNEL f1 ============= NUC1 1H P1 6.00 usec P2 12.00 usec PL1 -4.00 dB SFO1 500.1326379 MHz ============ GRADIENT CHANNEL ======== GPNAM1 sine.100 GPNAM2 sine.100 GPX1 0.00 % GPX2 0.00 % GPY1 0.00 % GPY2 0.00 % GPZ1 40.00 % GPZ2 -40.00 % P16 1000.00 usec F1 - Acquisition parameters ND0 2 TD 256 SFO1 500.1326 MHz FIDRES 13.451274 Hz SW 6.885 ppm FnMODE undefined F2 - Processing parameters SI 1024 SF 500.1300144 MHz WDW SINE SSB 2 LB 0.00 Hz GB 0 PC 0.20 F1 - Processing parameters SI 1024 MC2 TPPI SF 500.1300144 MHz WDW SINE SSB 2 LB 0.00 Hz GB 0 N N N N O O CH3 CH3 H3C H 1 3 5 2 8 7 6 4 3-CH3, 5-H Gradient NOESY
  • 60. NOESY gives sequential assignment of peptides 21 2 3 CH2 CH2N C H N O H C C H CH2O N H C CH2 C H OH O 1 321
  • 62. Rotating frame nuclear Overhauser effect spectroscopy (ROESY) • ROESY is similar to NOESY, except that the initial state is different. Instead of observing cross relaxation from an initial state of z-magnetization, the equilibrium magnetization is rotated onto the x axis and then spin-locked by an external magnetic field so that it cannot precess. This method is useful for certain molecules whose rotational correlation time falls in a range where the Nuclear Overhauser effect is too weak to be detectable, usually molecules with a molecular weight around 1000 daltons, because ROESY has a different dependence between the correlation time and the cross-relaxation rate constant. In NOESY the cross-relaxation rate constant goes from positive to negative as the correlation time increases, giving a range where it is near zero, whereas in ROESY the cross-relaxation rate constant is always positive. • ROESY is sometimes called "cross relaxation appropriate for minimolecules emulated by locked spins" (CAMELSPIN)
  • 63. Spin-lock 90° t1 t2 2D ROESY pulse program For small molecule NOE can be very small or zero, ROESY can be used in place of NOESY experiment. ROE intensity is also related to the H-H distances. mixing time
  • 64. 2D ROESY spectrum of ethylbenzene
  • 65. Structure of 12,14- ditbutylbenzo[g]chrysene showing color conding of rings
  • 66. Aromatic region of the 2D ROESY spectrum of 12,14- ditbutylbenzo[g]chrysene showing connectivity and separation into four color-coded proton groups
  • 68. 1 H-NMR spectrum of acetylsalicylic acid
  • 69. H, H-COSY spectrum of acetylsalicylic acid