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ADVANCED NUCLEAR MAGNETIC RESONANCE (ANMR)ADVANCED NUCLEAR MAGNETIC RESONANCE (ANMR)
UNIT 7UNIT 7HOMONUCLEAR CORRELATION NMR SPECTROMETRY HOMONUCLEAR CORRELATION NMR SPECTROMETRY
2D2D--NMRNMR
1. INTRODUCTION AND THEORY
2. 1H-1H CORRELATION: COSY AND DQF-COSY EXPERIMENTS
3. 1H-1H CORRELATION: TOCSY EXPERIMENT
4. 13C-13C CORRELATION: INADEQUATE EXPERIMENT
1 15. 1H-1H CORRELATION THROUGH SPACE: NOESY AND ROESY
El autor/La autora se acoge al artículo 32 de la Ley de Propiedad Intelectual vigente respecto al uso parcial de obras ajenas, como imágenes, gráficos u otromaterial contenido en las diferentes diapositivas, dado el carácter y la finalidad exclusivamente docente y eminentemente ilustrativa de las explicaciones enclase de esta presentación. Facultad de Ciencias, Universidad de Alicante
Unit 7: 2D NMR
Bibliografía:
Spectrometric Identification of Organic Compounds, 7th Ed.Robert M. Silverstein, Francis X. Webster, David J. Kiemle
Chapter 5: Correlation NMR Spectrometry; 2-D NMRChapter 5: Correlation NMR Spectrometry; 2-D NMRpp. 245-285
Introduction to Spectroscopy, 4th Ed.Donald L. Pavia, Gary M. Lampman, George S. Kriz, James R. Vyvyan
Chapter 10: Nuclear Magnetic Resonance SpectroscopyChapter 10: Nuclear Magnetic Resonance SpectroscopyPart Five: Advanced NMR Techniques
pp. 587-657
200 and More NMR ExperimentsA Practical Course
Stefan Berger Siegmar BraunStefan Berger, Siegmar BraunChapter 10: The Second Dimension
pp. 362-448
MA2
Diapositiva 2
MA2 SpanishMaría Abad; 28/10/2014
ADVANCED NUCLEAR MAGNETIC RESONANCE (ANMR)ADVANCED NUCLEAR MAGNETIC RESONANCE (ANMR)
UNIT 7UNIT 7HOMONUCLEAR CORRELATION NMR SPECTROMETRY HOMONUCLEAR CORRELATION NMR SPECTROMETRY
2D2D--NMRNMR
1. INTRODUCTION AND THEORY
2. 1H-1H CORRELATION: COSY AND DQF-COSY EXPERIMENTS
3. 1H-1H CORRELATION: TOCSY EXPERIMENT
4. 13C-13C CORRELATION: INADEQUATE EXPERIMENT
1 15. 1H-1H CORRELATION THROUGH SPACE: NOESY AND ROESY
2D NMR
1. Introduction and theory Unit 7: 2D NMR
2D NMR
Helps to determine the structure of organic compounds when1D NMR spectra are not enough
Dimensions (xD) refer to the number of pulse sequences givenDimensions (xD) refer to the number of pulse sequences givento the sample (2-4)
Gives information about connectivity between nuclei
The key of xD experiments is in the scalar and dipolar couplings
1. Introduction and theory Unit 7: 2D NMR
Homonuclear Heteronuclear
Scalar Coupling (DQF-)COSY
TOCSY HMBCHETCOR
TOCSY HMBCHetero-TOCSY
HMQCINADEQUATE HMQCHSQC
Dipolar coupling NOESY
ROESYNOESY-HSQC
NOESY-HMQC
COSY (Correlated Spectroscopy)
1. Introduction and theory Unit 7: 2D NMR
COSY (Correlated Spectroscopy)
DQF-COSY (Double Quantum Filtered Correlated Spectroscopy) SCALAR1H-1H
TOCSY (Totally Correlated Spectroscopy)
INADEQUATE (Incredible Natural Abundance Double Quantum Transfer) SCALARINADEQUATE (Incredible Natural Abundance Double Quantum Transfer)
HETCOR (Heteronuclear Correlation)
13C-13C (1J)
SCALAR13C 1H (1J)
( )
HMQC (Heteronuclear Multiple Quantum Correlation)
13C-1H (1J)
SCALAR1H 13C (1J)
( )
HMBC (Heteronuclear Multiple Bond Coherence) SCALAR1H-13C (> 1J)
1H-13C (1J)
NOESY (Nuclear Overhauser Enhancement Spectroscopy)
H- C (> J)
DIPOLAR
ROESY (Rotating Frame Overhauser Enhancement Spectroscopy)
DIPOLAR1H-1H
1. Introduction and theory Unit 7: 2D NMR
Rectangular Pulseg
RF OnRF Off
ν = Very short frequency irradiation τ (μs)
time
ν1 = Very short frequency irradiation τp (μs)
1. Introduction and theory Unit 7: 2D NMR
2D NMR EXPERIMENT
1. Introduction and theory Unit 7: 2D NMR
2D NMR EXPERIMENT : ACETONE
Spin-Net Relaxation is disregarded !!
1. Introduction and theory Unit 7: 2D NMR
2D NMR EXPERIMENT : ACETONE
1. Introduction and theory Unit 7: 2D NMR
2D NMR EXPERIMENT : ACETONE
1. Introduction and theory Unit 7: 2D NMR
FT over t2 dimension
Interferogram
FT over t1 dimension
ADVANCED NUCLEAR MAGNETIC RESONANCE (ANMR)ADVANCED NUCLEAR MAGNETIC RESONANCE (ANMR)
UNIT 7UNIT 7HOMONUCLEAR CORRELATION NMR SPECTROMETRY HOMONUCLEAR CORRELATION NMR SPECTROMETRY
2D2D--NMRNMR
1. INTRODUCTION AND THEORY
2. 1H-1H CORRELATION: COSY AND DQF-COSY EXPERIMENTS
3. 1H-1H CORRELATION: TOCSY EXPERIMENT
4. 13C-13C CORRELATION: INADEQUATE EXPERIMENT
1 15. 1H-1H CORRELATION THROUGH SPACE: NOESY AND ROESY
2. 1H-1H CORRELATION: COSY AND DQF-COSYUnit 7: 2D NMR
2. 1H-1H CORRELATION: COSY AND DQF-COSYUnit 7: 2D NMR
COSY
DQF-COSY
θ = π/2; δ = miliseconds
Unit 7: 2D NMR2. 1H-1H CORRELATION: COSY AND DQF-COSY
COPYRIGHT 1998Sigma-Aldrich Co.
ALL RIGHTS RESERVED
7.5 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 0.0
Unit 7: 2D NMR2. 1H-1H CORRELATION: COSY AND DQF-COSY
COPYRIGHT 1998
Unit 7: 2D NMR2. 1H-1H CORRELATION: COSY AND DQF-COSY
COPYRIGHT 1998Sigma-Aldrich Co.
ALL RIGHTS RESERVED
O
O
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5
Unit 7: 2D NMR2. 1H-1H CORRELATION: COSY AND DQF-COSY
O
O
Unit 7: 2D NMR2. 1H-1H CORRELATION: COSY AND DQF-COSY
Unit 7: 2D NMR2. 1H-1H CORRELATION: COSY AND DQF-COSY
2. 1H-1H CORRELATION: COSY AND DQF-COSYUnit 7: 2D NMR
2. 1H-1H CORRELATION: COSY AND DQF-COSYUnit 7: 2D NMR
2. 1H-1H CORRELATION: COSY AND DQF-COSYUnit 7: 2D NMR
2. CORRELACIÓN: 1H-1H DQF-COSYTema 7: 2D NMR
Piperine
2. 1H-1H CORRELATION: COSY AND DQF-COSYUnit 7: 2D NMR
Piperine
2. 1H-1H CORRELATION: COSY AND DQF-COSYUnit 7: 2D NMR
Anethole
2. 1H-1H CORRELATION: COSY AND DQF-COSYUnit 7: 2D NMR
Anethole
2. 1H-1H CORRELATION: COSY AND DQF-COSYUnit 7: 2D NMR
J 3 6Chamazulene
J = 3 6
J5,6 = 10.3J3,2 = 3.6
J6,5 = 10.3J2,3 = 3.6
2. 1H-1H CORRELATION: COSY AND DQF-COSYUnit 7: 2D NMR
Chamazulene
2. 1H-1H CORRELATION: COSY AND DQF-COSYUnit 7: 2D NMR
Chamazulene
ADVANCED NUCLEAR MAGNETIC RESONANCE (ANMR)ADVANCED NUCLEAR MAGNETIC RESONANCE (ANMR)
UNIT 7UNIT 7HOMONUCLEAR CORRELATION NMR SPECTROMETRY HOMONUCLEAR CORRELATION NMR SPECTROMETRY
2D2D--NMRNMR
1. INTRODUCTION AND THEORY
2. 1H-1H CORRELATION: COSY AND DQF-COSY EXPERIMENTS
3. 1H-1H CORRELATION: TOCSY EXPERIMENT
4. 13C-13C CORRELATION: INADEQUATE EXPERIMENT
1 15. 1H-1H CORRELATION THROUGH SPACE: NOESY AND ROESYMA7
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3. 1H-1H CORRELATION: TOCSY EXPERIMENT Unit 7: 2D NMR
J A Ch S 1988 110 7870 7872
Study the behaviour of the spin system at lower magnetic fields than B0
J. Am. Chem. Soc., 1988, 110, 7870–7872
3. 1H-1H CORRELATION: TOCSY EXPERIMENT Unit 7: 2D NMR
3. 1H-1H CORRELATION: TOCSY EXPERIMENT Unit 7: 2D NMR
3. 1H-1H CORRELATION: TOCSY EXPERIMENT Unit 7: 2D NMR
3. 1H-1H CORRELATION: TOCSY EXPERIMENT Unit 7: 2D NMR
3. 1H-1H CORRELATION: TOCSY EXPERIMENT Unit 7: 2D NMR
1D-TOCSYHOHAHA (Homonuclear Hartmann-Hann)
ADVANCED NUCLEAR MAGNETIC RESONANCE (ANMR)ADVANCED NUCLEAR MAGNETIC RESONANCE (ANMR)
UNIT 7UNIT 7HOMONUCLEAR CORRELATION NMR SPECTROMETRY HOMONUCLEAR CORRELATION NMR SPECTROMETRY
2D2D--NMRNMR
1. INTRODUCTION AND THEORY
2. 1H-1H CORRELATION: COSY AND DQF-COSY EXPERIMENTS
3. 1H-1H CORRELATION: TOCSY EXPERIMENT
4. 13C-13C CORRELATION: INADEQUATE EXPERIMENT
1 15. 1H-1H CORRELATION THROUGH SPACE: NOESY AND ROESY
4. 13C-13C CORRELATION: INADEQUATE EXPERIMENT Unit 7: 2D NMR
INADEQUATE (Incredible Natural Abundance Double Quantum Transfer)
SCALARSCALAR13C-13C (1J)
4. 13C-13C CORRELATION: INADEQUATE EXPERIMENT Unit 7: 2D NMR
OH1
2
3
4
5
6
13C-13C Coupling!!
100-500 mg sample
F2 axis in 13C δ
F1 axis Double Quantum Frequency
4. 13C-13C CORRELATION: INADEQUATE EXPERIMENT Unit 7: 2D NMR
Caryophyllene Oxide (Sesquiterpene)Caryophyllene Oxide (Sesquiterpene)
4. 13C-13C CORRELATION: INADEQUATE EXPERIMENT Unit 7: 2D NMR
12156, 14, 7 2113109145 211310914
Styrene Radical Polymerization HH*
4. 13C-13C CORRELATION: INADEQUATE EXPERIMENT Unit 7: 2D NMR
H 1 2
344
Styrene Radical Polymerization
4. 13C-13C CORRELATION: INADEQUATE EXPERIMENT Unit 7: 2D NMR
-CH(Ph)CHPh-(Process A) Terminal CH2
Poly(styrene-α-13C) Mw: 7.6 × 103
( ) Terminal CH2(Process C)
y( y )
Poly(styrene-α-13C) Mw: 2.1× 104
Polystyreney y
Styrene Radical Polymerization
4. 13C-13C CORRELATION: INADEQUATE EXPERIMENT Unit 7: 2D NMR
Poly(styrene-α-13C) Mw: 7.6 × 103
1: 145.6-145.0 (s)2: 128.9-126.8 (d)3: 128.9-126.8 (d)4: 126.7-125.5 (d)6 5 5 (d)
: 40.4 (d): 47.4-42.5 (t)
: 48.5 (d): 32-33 (t)
CH2: 33.8, 33.6 (t)
Styrene Radical Polymerization
4. 13C-13C CORRELATION: INADEQUATE EXPERIMENT Unit 7: 2D NMR
Poly(styrene-α-13C) Mw: 7.6 × 103
Cα-CαCβ
Cα Cα(48.5, 49.5 ppm)
1: 145.6-145.0 (s)2: 128.9-126.8 (d)3: 128.9-126.8 (d)4: 126.7-125.5 (d)6 5 5 (d)
: 40.4 (d): 47.4-42.5 (t)
: 48.5 (d): 32-33 (t)
CH2: 33.8, 33.6 (t)
ADVANCED NUCLEAR MAGNETIC RESONANCE (ANMR)ADVANCED NUCLEAR MAGNETIC RESONANCE (ANMR)
UNIT 7UNIT 7HOMONUCLEAR CORRELATION NMR SPECTROMETRY HOMONUCLEAR CORRELATION NMR SPECTROMETRY
2D2D--NMRNMR
1. INTRODUCTION AND THEORY
2. 1H-1H CORRELATION: COSY AND DQF-COSY EXPERIMENTS
3. 1H-1H CORRELATION: TOCSY EXPERIMENT
4. 13C-13C CORRELATION: INADEQUATE EXPERIMENT
1 15. 1H-1H CORRELATION THROUGH SPACE: NOESY AND ROESY
5. 1H-1H CORRELATION THROUGH SPACE: NOE / NOESY / ROESYUnit 7: 2D NMR
nOeO2N Ha
Hb
Hd
Hc
O
Unit 7: 2D NMR5. 1H-1H CORRELATION THROUGH SPACE: NOE / NOESY / ROESY
O
O
HBHA
MenOe
Me'
Geraniol nOe experiments
Unit 7: 2D NMR
5. 1H-1H CORRELATION THROUGH SPACE: NOE / NOESY / ROESY
Geraniol nOe experiments
Unit 7: 2D NMR
5. 1H-1H CORRELATION THROUGH SPACE: NOE / NOESY / ROESY
26
7
O
Unit 7: 2D NMR
5. 1H-1H CORRELATION THROUGH SPACE: NOE / NOESY / ROESY
O
12
3 5
67
8 9 103
4 5
β-ionone
Unit 7: 2D NMR
5. 1H-1H CORRELATION THROUGH SPACE: NOE / NOESY / ROESY
Unit 7: 2D NMR5. 1H-1H CORRELATION THROUGH SPACE: NOE / NOESY / ROESY
Unit 7: 2D NMR
5. 1H-1H CORRELATION THROUGH SPACE: NOE / NOESY / ROESY
Unit 7: 2D NMR5. 1H-1H CORRELATION THROUGH SPACE: NOE / NOESY / ROESY
1 7 6e 4e,3e 5OH
2
3a,6a8, 10
4a9
JH7-H2 = 2.6 Hz (70º)
Unit 7: 2D NMR5. 1H-1H CORRELATION THROUGH SPACE: NOE / NOESY / ROESY
NOESY
Unit 7: 2D NMR5. 1H-1H CORRELATION THROUGH SPACE: NOE / NOESY / ROESY
ROESY
Spin-LockNOE always positiveShorter experiment times than NOESYShorter experiment times than NOESY
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