Theory of NMR

The positively charged nuclei of certain elements (e.g., 13C and 1H) behave as tiny magnets. In the presence of a strong external magnetic field (Bo), these nuclear magnets align either with ( ) the applied field or opposed to ( ) the applied field.
Bo

The latter (opposed) is slightly higher in energy than aligned with the field. energy E is very small
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The small energy difference between the two alignments of magnetic spin corresponds to the energy of radio waves according to Einsteins equation E=h.
h

Application of just the right radiofrequency () causes the nucleus to flip to the higher energy spin state Not all nuclei require the same amount of energy for the quantized spin flip to take place. The exact amount of energy required depends on the chemical identity (H, C, or other element) and the chemical environment of the particular nucleus.

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 At a field strength of 9.4 Tesla. 1H nuclei absorb (resonate) near a radiofrequency of 400 MHz; 13 C nuclei absorb around 100 MHz. Nuclei are surrounded by electrons. The strong applied magnetic field (Bo) induces the electrons to circulate around the nucleus (left hand rule).

e-

Bo
(9.4 T)
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 The induced circulation of electrons sets up a secondary (induced) magnetic field (Bi) that opposes the applied field (Bo) at the nucleus (right hand rule).
Bi

e-

Bo
We say that nuclei are shielded from the full applied magnetic field by the surrounding electrons because the secondary field diminishes the field at the nuclei.
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Theory of NMR
The electron density surrounding a given nucleus depends on the electronegativity of the attached atoms. The more electronegative the attached atoms, the less the electron density around the nucleus in question. We say that that nucleus is less shielded, or is deshielded by the electronegative atoms. Deshielding effects are generally additive. That is, two highly electronegative atoms (2 Cl atoms, for example) would cause more deshielding than only 1 Cl atom.
H H C H H H H C Cl H
C and H are deshielded
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H H C Cl Cl
C and H are more deshielded
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Chemical Shift
We call the relative position of absorption in the NMR spectrum (which is related to the amount of deshielding) the chemical shift. It is a unitless number (a ratio in which the units cancel), but we assign units of ppm or (Greek letter delta). Different nuclei absorb EM radiation at different wavelength (energy required to cause resonance). Nuclei of a given type will resonate at different energies, depending on their chemical and electronic environment. The position (chemical shift, ) and pattern (splitting or multiplicity) of the NMR signals gives important information about the chemical environment of the nuclei.

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 For 1H, the usual scale of NMR spectra is 0 to 10 (or 12) ppm (or ). The usual 13C scale goes from 0 to about 220 ppm. The zero point is defined as the position of absorption of a standard, tetramethylsilane (TMS): This standard has only one type CH3 of C and only one type of H.

CH3 Si CH3 CH3

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Chemical Shifts
C13 Chemical Shift ( ) vs. Electronegativity
90 80

CH3 F CH3 O

C13 Chemical Shift

70 60 50 40 30 20 10 0 -10 1.5 2 2.5 3

CH3 N
CH3 C
CH3 Si

3.5

Electronegativity

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Chemical Shifts
Both 1H and 13C Chemical shifts are related to three major factors:
The hybridization (of carbon) Presence of electronegative atoms or electron attracting groups The degree of substitution (1, 2 or 3). These latter effects are most important in 13C NMR, and in that context are usually called steric effects.

First well focus on Carbon NMR spectra

(They are simpler.)

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CMR Spectra
Each unique C in a structure gives a single peak in the spectrum. There is rarely any overlap.
The carbon spectrum spans over 200 ppm; chemical shifts only 0.001 ppm apart can be distinguished; this allows for over 2x105 possible chemical shifts for carbon.

The intensity (size) of each peak is NOT directly related to the number of that type of carbon. Other factors contribute to the size of a peak:
Peaks from carbon atoms that have attached hydrogen atoms are bigger than those that dont have hydrogens attached.

Carbon chemical shifts are usually reported as downfield from the carbon signal of tetramethylsilane (TMS).
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13

C Chemical Shifts
CH3 CH2 CH C N Aromatic C C X (halogen) C N C O C C 80 60 40 20 0 TMS

C O 220 200 180 160 downfield

C C

140 120 100 13C Chemical shift ()

upfield

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Predicting 13C Spectra

Predict the number of carbon resonance lines in the 13C spectra of the following (= # unique Cs):
plane of symmetry CH CH
3 3

CH3 C C C

C C CH3 CH3
O

CH3 CH3 CH3 C C O c CH3

O CH3 CH3 C C H
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Predicting 13C Spectra

Predict the number of carbon resonance lines in the 13C spectra of the major product of the following reaction:
CH3 Cl KOH ethanol, heat CH3 or CH2 ???

CH3 C c

CH3 C c C C

CH2

CH2

CH2 C C C c C C

7 lines

5 lines

plane of symmetry

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Predicting C Spectra
13
CH3 CH3 C C C H3C CH3 H3C C C C CH3

4 lines

CH3 CH3

C C

CH3 CH3

CH3 CH3

C C

CH3 CH3

2 lines

Symmetry Simplifies Spectra!!!

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Acetone
O CH3 CCH3
CH3

O C

CDCl3(solvent)

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Methyl Acetate
O CH3 COCH3
O C CDCl3(solvent)

OCH3

CH3

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Ethyl Acetate
OCH3

CH3

O CH3 COCH3 3 CH
CH3

O C

CDCl3(solvent)

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Ethyl Propanoate
O CH3 3 CH COCH3 3 CH
CDCl3(solvent)

OCH3

CH3 CH3 CH3

O C

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2-Butanone
O CH3 CCH3 3 CH
CH3 CH3

CH3

O C

CDCl3(solvent)

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H C H O C C C C H C C H H CDCl3(solvent) CH3

expanded below

H O CH3 C
C

H H
C

C and C

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CH3 CH3

CH3 3 3 CH CH Br
CDCl3(solvent)

CH3 Br

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CH3CH2CH2OH
CH2 OH

CH2

CH3

CDCl3 (solvent)

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1-Butanol
CH3 OH

CH3

CH3 CH3

CH3 3 3 3 CH CH CH OH

CDCl3(solvent)

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1-methylcyclohexene
CH3 C C H

CDCl3(solvent)

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Equivalence
Ask yourself: If you interchange the two groups or atoms, will the compound be the same as the original (or the enantiomer), or is it different ? If its the same, then the two groups (or atoms) are equivalent.

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1. The chemical shift gives the environment of a proton. 2. The number of signals in a H NMR gives the number of sets of equivalent protons. 3. Integration gives the relative rations of protons in the sets. 4. SpinSpin splitting of NMR signals results from coupling of the proton that gives the signal to protons separated by: a.) two bonds (geminal)
1

H H

b.) three bonds (Vicinal) (most common)

C H

C H

5. The number of peaks in a split signal is equal to n+1 where n is the number of equivalent H.
1

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1,1-dichloroethane

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5.(continued) The Ethyl Group has a distinct pattern. (CH3CH2) Methyl protons of an ethyl group form a triplet with a 1:2:1 ratio. Methylene protons of an ethyl group form a quartet, 1:3:3:1 ratio Below: the NMR plot for Ethyl Bromide

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 Methyl protons of an isopropyl group form a doublet with a 1:1 ratio. CH Methine proton of an isopropyl group forms a heptet with a 1:6:15:26:15:6:1 ratio

CH CH3

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 A pair of nonequivalent protons spit each others signal into a pair of doublets.

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 Splitting from hydroxyl groups on alcohols is not observed because of rapid exchange of hydrogen with other alcohol molecules. 6. Many processes, such as conformational changes, occur faster than NMR can detect them. Cant detect difference between axial and equatorial protons in cyclohexane.

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