Nuclear Magnetic Resonance (NMR) Spectroscopy
Part 1
Carbon 13 NMR
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.
• The latter (opposed) is slightly higher in energy than aligned with the field.
E is very small
Bo
Energy
Theory of NMR
• The small energy difference between the two alignments of magnetic spin corresponds to the energy of radio waves according to Einstein’s equation E=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.
h
Theory of NMR
• Our department’s NMR spectrometer (in Dobo 245) has a superconducting magnet with a field strength of 9.4 Tesla. On this instrument, 1H nuclei absorb (resonate) near a radiofrequency of 400 MHz; 13C 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).
Bo
e-
(9.4 T)
Theory of NMR
• 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).
• 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.
Bo
e-
Bi
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.
C
H
HH
H
C
H
ClH
H
C
H
ClH
Cl
C and H are deshielded C and H are more deshielded
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 (actually a ratio, in which the units cancel), but we assign ‘units’ of ppm or (Greek letter delta) units.
• 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
of C and only one type of H.Si
CH3
CH3
CH3
CH3
C13 Chemical Shift ( ) vs. Electronegativity
-10
0
10
20
30
40
50
60
70
80
90
1.5 2 2.5 3 3.5 4
Electronegativity
C1
3 C
he
mic
al
Sh
ift
Chemical Shifts
CH3 Si
CH3 C
CH3 N
CH3 O
CH3 F
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 (1º, 2º or 3º). These latter effects
are most important in 13C NMR, and in that context are usually called ‘steric’ effects.
• First we’ll focus on Carbon NMR spectra (they are simpler)
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 don’t have hydrogens attached.
• Carbon chemical shifts are usually reported as downfield from the carbon signal of tetramethylsilane (TMS).
13C Chemical Shifts
downfield upfield
20406080100120140160180200220 0
CH3
CH2
CH
C X (halogen)
C N
C O
C C
C N
C CC O
13C Chemical shift ()
TMSAromatic C
Predicting 13C Spectra
• Problem 13.6 Predict the number of carbon resonance lines in the 13C spectra of the following (= # unique Cs):
4 lines
plane of symmetry
CH3
C C
CC
C
CH3CH3
O
CH3
CH3
O
CH3
CH3
CC
cCH3
O
CH3 5 lines
5 lines CH3
C
CH3
CCH3
H
Predicting 13C Spectra
• Predicte the number of carbon resonance lines in the 13C spectra of the major product of the following reaction:
7 lines
5 lines
plane of symmetry
CH3
C
cc
C
CC
CH3 CH2
C
Cc
C
CC
CH2CH2
CH3 CH2ClCH3
orKOH
ethanol, heat ???
Predicting 13C Spectra
CH3
CH3
H3C CH3
C C
C
CC
C
H3C CH3
4 lines
C CCH3
CH3
CH3
CH3
2 lines
Symmetry Simplifies Spectra!!!
C CCH3
CH3
CH3
CH3
CH3
CDCl3 (solvent)
CH3CCH3
O
C
O
OCH3
CDCl3 (solvent)
CH3
CH3COCH3
O
C
O
CDCl3 (solvent)
CH3
CH3CH3COCH2CH3
O
C
O
OCH2
CH2
CH3CH3
CDCl3 (solvent)
CH3
CH3CH2COCH2CH3
O
C
O
OCH2
C6H12O2
C
O
CDCl3 (solvent)OCH2
CH3
CH3CH2CH2COCH2CH3
O
CH3CH2
CH2
ethyl butanoate
C
O
CH2CH2 CH3
CH3CCH2CH3
O
CH3
CDCl3 (solvent)
C
O
CH3
CDCl3 (solvent)
CH3C
OHH
H
HH
CC
C
CC
C
H
H
H
H
H
C C
C
C
and
expanded below
CH2 Br
CDCl3 (solvent)
CH3
CH3CH2CH2Br
CH2
CH2 OH
CH3
CDCl3 (solvent)
CH3CH2CH2OH CH2
CDCl3 (solvent)
CH2 OH
CH3
CH3CH2CH2CH2OH
CH2
CH2
CDCl3 (solvent)
CH2
CH3
CH3CH2CH2CH2CH2OHCH2
CH2
CH2 OH
CC
CH3
H
C
C
CDCl3 (solvent)
CDCl3 (solvent)
CH3
CH2
and
CH2
CCH3 CH2CH2CH2CH3
CH2
C
CH2
CH2 CH3
CDCl3 (solvent)
2-methyl-1-hexene.