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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

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2D2D--NMRNMR






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


Homonuclear Heteronuclear

Scalar Coupling (DQF-)COSY

TOCSY HMBCHETCOR

TOCSY HMBCHetero-TOCSY

HMQCINADEQUATE HMQCHSQC

Dipolar coupling NOESY

ROESYNOESY-HSQC

NOESY-HMQC

COSY (Correlated Spectroscopy)


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


Rectangular Pulseg

RF OnRF Off

ν = Very short frequency irradiation τ (μs)

time

ν1 = Very short frequency irradiation τp (μs)


2D NMR EXPERIMENT


2D NMR EXPERIMENT : ACETONE

Spin-Net Relaxation is disregarded !!


2D NMR EXPERIMENT : ACETONE


FT over t2 dimension

Interferogram

FT over t1 dimension



2D2D--NMRNMR






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

COPYRIGHT 1998


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


O

O

2. CORRELACIÓN: 1H-1H DQF-COSYTema 7: 2D NMR

Piperine


Piperine


Anethole


J 3 6Chamazulene

J = 3 6

J5,6 = 10.3J3,2 = 3.6

J6,5 = 10.3J2,3 = 3.6


Chamazulene



2D2D--NMRNMR





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


1D-TOCSYHOHAHA (Homonuclear Hartmann-Hann)



2D2D--NMRNMR






4. 13C-13C CORRELATION: INADEQUATE EXPERIMENT Unit 7: 2D NMR

INADEQUATE (Incredible Natural Abundance Double Quantum Transfer)

SCALARSCALAR13C-13C (1J)


OH1

2

3

4

5

6

13C-13C Coupling!!

100-500 mg sample

F2 axis in 13C δ

F1 axis Double Quantum Frequency


Caryophyllene Oxide (Sesquiterpene)Caryophyllene Oxide (Sesquiterpene)


12156, 14, 7 2113109145 211310914

Styrene Radical Polymerization HH*


H 1 2

344

Styrene Radical Polymerization


-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




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)




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)



2D2D--NMRNMR






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


26

7

O

Unit 7: 2D NMR


O

12

3 5

67

8 9 103

4 5

β-ionone

Unit 7: 2D NMR



1 7 6e 4e,3e 5OH

2

3a,6a8, 10

4a9

JH7-H2 = 2.6 Hz (70º)


NOESY


ROESY

Spin-LockNOE always positiveShorter experiment times than NOESYShorter experiment times than NOESY

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