HYDROGEN-1 NUCLEAR MAGNETIC RESONANCE

Also known as Proton NMR Natural Hydrogen (H) is used in samples The spectrum is plot of the intensity of the peak against its chemical shift, measured in parts per million (ppm)

1HNMR SPECTRUM

Different features to provide information about a compounds structure a. Number of signals b. Position of signals c. Intensity of signals. d. Spin-spin splitting of signals

NUMBER OF SIGNALS
The number of NMR signals equals the number of different types of protons in a compound. Protons in different environment give different NMR signals.

1 NMR SIGNAL

2 Types of Hs 2 NMR SIGNALS

3Types of Hs 3 NMR SIGNALS

1 Type of H 1 NMR SIGNAL

2 Types of Hs 2 NMR SIGNALS

3Types of Hs 3 NMR SIGNALS

3Types of Hs 3 NMR SIGNALS

1 Type of H 1 NMR SIGNAL

2 Types of Hs 2 NMR SIGNALS

3Types of Hs 3 NMR SIGNALS

For cycloalkanes and alkanes, draw all bonds of hydrogen

All Hs are equivalent 1 NMR SIGNAL

3Types of Hs 3 NMR SIGNALS

POSITION OF SIGNALS
Shielded Nucleus Deshielded Nucleus

Nucleus feels a smaller resultant Nucleus feels a larger resultant field field

A larger magnetic field is induced

A smaller magnetic field is induced

Lower frequency is needed to achieve resonance

Higher frequency is needed to achieve resonance

Absorption shifts upfield

Absorption shifts downfield

POSITION OF SIGNALS

POSITION OF SIGNALS

The Hb protons are deshielded because they are closer to the electronegative Cl atom.

F is more electronegative than Br, thus Hb are more deshielded than the Ha protons

CHEMICAL SHIFTS
Protons in a given environment absorb in a predictable region in an NMR spectrum The Chemical Shift of a C-H bond increases with increasing alkyl substitution

CHEMICAL SHIFTS

CHEMICAL SHIFTS
Shielded protons absorb at lower chem shift (to the right) Deshielded protons absorb at higher chem shift (to the left)

INTENSITY OF SIGNALS
The area under an NMR signal is proportional to the number of absorbing protons An NMR spectrometer automatically integrates the area under the peaks, prints out a stepped curve Height of each step is proportional to the area under the peak, which is proportional to the number of absorbing protons

INTENSITY OF SIGNALS

SPIN-SPIN SPLITTING
Peaks are often split into multiple peaks due to magnetic interactions between nonequivalent protons on adjacent carbons N + 1 rule splitting is into one more peak than the number of Hs on the adjacent carbon(s).

SPIN-SPIN SPLITTING

There are three 2D spectra which are widely used for the structure determination of proteins with a mass of up to 10 kD

1. 2.

2D COSY,
2D NOESY

2-D NMR SPECTRA -HAVE TWO FREQUENCY AXES AND; -ONE INTENSITY AXIS.
COSE NOESY
1H-1Hshift-correlated

Structure elements can be determined

spectroscopy they identify protons that are coupled (i.e., that split each others signal)

COSY

NOESY

for determining which signals arise from neighboring protons (usually up to four bonds) COSY will tell you which protons are adjacent to one another help unambiguously assign which proton corresponds to which signal and all around connectivity

allows to correlate nuclei through space (distance smaller than 5). you could look at the NOESY data to determine which protons "see" one another to determine relative stereochemistry

2D COSY

2D NOESY

only signals of protons which are two or three bonds apart are visible in a COSY spectrum (red signals)

COSY

uses the dipolar interaction of spins (the nuclear Overhauser effect, NOE) for correlation of protons.

Condition:
a.

with spin-spin coupling between protonswith correlation

Cross peaks: pairs of protons

that are coupled -dots that are not on the diagonal

Dia peaks: coupling between

nuclei separated by 2-3 bond -diagonal of signals (A and B) divides the spectrum in two equal halves

Ha and Hb proton are coupled!

the two triangles in the figure have a common vertex, since the Hb protons are coupled to both the Ha and Hc protons

NOESY

Nuclear Overhauser Effect -the transfer of nuclear spin polarization from one nuclear spin population to another via crossrelaxation

Origin of the NOE Effect When a proton is close in space to another proton (or any other nuclei with spin > 0), their magnetic dipoles interact (Dipole-Dipole NOE signals are DD). for interaction, positive

small molecules in low-viscosity distinct from J coupling solvents and negative for very large molecules or very viscous solvents relative to a negative diagonal

NOESY
The correlation between H1' and H2' at 2.65 and 1.24 ppm is mostly COSY type. much weaker throughspace correlation appears between H1' and H2 at 2.65 and 7.20 ppm.

NOESY
Aromaric region of the 2D NOESY spectrum of 12,14ditbutylbenzo[g]chrysene

NOEs between
H-30, H-18 and H-19 equatorial H-18 and H-26 H-25, H-24 and H-26 H-27 and H-11 axial H-19 axial, H-12 equatorial, H-15 axial and H-8 H-28 and H-22
H-23 and H-24 H-10 and H-4