1) The document discusses nuclear magnetic resonance (NMR) spectroscopy and provides information on 1H NMR and 13C NMR. 2) Key points include which isotopes are NMR active, how NMR spectrometers work, the origins of chemical shifts and splitting patterns, and how to determine the number of expected signals in 1H NMR and 13C NMR spectra. 3) The document provides guidance on interpreting NMR spectra, including common chemical shift ranges and how molecular structure impacts splitting and signal integration.
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Nuclear Isotope Abundance Spin NMR?: .02% 1.1% Yes Yes No Yes No
1) The document discusses nuclear magnetic resonance (NMR) spectroscopy and provides information on 1H NMR and 13C NMR. 2) Key points include which isotopes are NMR active, how NMR spectrometers work, the origins of chemical shifts and splitting patterns, and how to determine the number of expected signals in 1H NMR and 13C NMR spectra. 3) The document provides guidance on interpreting NMR spectra, including common chemical shift ranges and how molecular structure impacts splitting and signal integration.
1) The document discusses nuclear magnetic resonance (NMR) spectroscopy and provides information on 1H NMR and 13C NMR. 2) Key points include which isotopes are NMR active, how NMR spectrometers work, the origins of chemical shifts and splitting patterns, and how to determine the number of expected signals in 1H NMR and 13C NMR spectra. 3) The document provides guidance on interpreting NMR spectra, including common chemical shift ranges and how molecular structure impacts splitting and signal integration.
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Nuclear Isotope Abundance Spin NMR?: .02% 1.1% Yes Yes No Yes No
1) The document discusses nuclear magnetic resonance (NMR) spectroscopy and provides information on 1H NMR and 13C NMR. 2) Key points include which isotopes are NMR active, how NMR spectrometers work, the origins of chemical shifts and splitting patterns, and how to determine the number of expected signals in 1H NMR and 13C NMR spectra. 3) The document provides guidance on interpreting NMR spectra, including common chemical shift ranges and how molecular structure impacts splitting and signal integration.
Copyright:
Attribution Non-Commercial (BY-NC)
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Chapter 14 - Nuclear Magnetic Resonance Spectroscopy
14.1 - Which elements have magnetic resonance properties?
! Isotopes with with nuclear spin are NMR active. A spinning nucleus is a tiny
magnet. ! A spinning nucleus is a tiny magnet.
isotope 1H 2H
nuclear spin abundance yes yes no yes no 99.98% 0.02% 98.9% 1.1% 99.8%
NMR?
12C 13C
16O
! Highly abundant isotopes are easier to detect.
14.1A The NMR Spectrometer - A Superconducting Magnet
! An NMR spectrometer employs a massive magnetic field generated by current in a superconducting copper coil. Every NMR has a slightly different magnetic field. magnetic eld
! No two NMR spectrometers have exactly the same magnetic field.
NMR spectrometer (cut open)
14.1A - Energetic Differences Between Two Nuclear Spin States
! The NMR magnetic field differentiates the two spin states of a nucleus: aligned with or aligned against. Those two spin states are not affected by the tumbling or rotation of molecules. ! It takes energy (E = h!) to ip nuclei out of alignment.
NMR magnetic field
NMR magnetic field
! The energy required to ip each nuclear spin is dependent on how much of the NMR magnetic eld the nucleus sees. Those differences are the chemical shift. Nearby magnetic nuclei add to or subtract from the NMR magnetic eld The electron cloud shields the nucleus from the NMR magnet
14.1 - Why we perform 1H NMR and 13C NMR separately
! 1H nuclei and 13C nuclei absorb in different regions of the radio frequency spectrum. You need to tune the NMR instrument for each region. ! 13C signals are tiny compared to 1H signals ! You can't fit 1H spectra and 13C spectra on the same plot.
1H
Cl Cl H C C O H C C H H
13C
14.1B - Strange Terms Because Every NMR Magnet is Different
! The absorption frequency varies with the magnetic field of every NMR machine.
We measure frequency relative to the additive tetramethylsilane (CH3)4Si (TMS).
! The frequency differences are proportional to the magnetic field.
We plot frequency differences in parts per million (ppm) and call it the chemical shift, with symbol ". 9.4 Tesla (940 kGauss) magnet in Irvine 10.3 Tesla (1030 kGauss) magnet in Hamburg 100,019,400 100,003,800 100,571,115
O C
Si C Cl 100,000,000 110,005,356
H H frequency (Hz)
any NMR magnet H
O C
Cl
H H
200
180
160
140
120
100
80
60
40
20
14.1A 13C NMR is simpler than 1H NMR so use it first
! 13C: The number of peaks = the number of (types of) carbon atoms ! 1H: The number of peaks ! the number of types of protons BrH C Br H C C H H H H
13C
NMR
! (ppm) 1H
NMR
! (ppm)
14.2 - How many signals should I expect in the 13C spectrum?
! Distinguishing the different types of carbons (or protons) will allow you to rapidly identify mis-matches between a spectrum and a proposed structure. ! Carbons that are chemically equivalent due to symmetry give one peak. ! Carbons that can switch positions due to tumbling or rapid bond rotation are equivalent.
O HO expected number of peaks
Cl OH
OH
Cl
Cl
HO
14.2 - How many signals should I expect in the 13C spectrum?
Cl HC CH3 Cl
or
Cl H2C CH2 Cl
14.2 - Use Symmetry to Predict the Number of 13C Signals
Cl
Cl 4 peaks
Cl
Cl 3 peaks
Cl 2 peaks
Cl
14.11,14.12 - 13C NMR Chemical Shift Ranges
! Know these chemical shift ranges. They are more useful than those in Table 14.5 ketones aldehydes 220-190 esters amides carboxylic acids 185-155 alkenes arenes 160-110
everything else 110 - 0
200
150
100
! (ppm)
! Watch out for peaks from the solvent CDCl3. CDCl3 shows up as three peaks at 77 ppm in the 13C spectrum. The minor contaminant CHCl 3 1 appears in the H NMR spectrum as a single peak at 7.24. 13C
CDCl3 3 peaks
CHCl3 contaminant
1H
7.6 7.4 7.2 7.0
14.11,14.12 - Practice Using 13C NMR Chemical Shift Ranges
220-190 O R C R(H) R 185-155 O C 160-110 C C 150 C C C C C C 100 C C 110 - 0
O,N
C X
C R,H
200
50
! Which product? OH H3PO4 CH3OH SN1 OCH3 or E1 or E1
14.2 - How many signals should I expect in the 1H spectrum?
! Chemically inequivalent protons give more than 1 peak.
H CH3CH2CH2Br H3C
C C
H CH3
H H3C
C C
H Cl
H H
Cl H H H
14.2 - Diastereotopic or Enantiotopic Protons? Use the Z-test.
! Enantiotopic protons are equivalent in 1H NMR. They have identical chemical shifts and dont split. ! The Z test. 1. Generate 2 structs by replacing the protons in question with the letter Z. Can assign R/S assuming Z has low priority. 2. If enantiomers, then the protons are enantiotopic Z test
H3C H H
H Cl H3C Cl H CH3
14.2 - Diastereotopic or Enantiotopic Protons? Use the Z-test.
! Diastereotopic protons are inequivalent in 1H NMR. They usually have different chemical shifts and usually split each other. ! The Z test. 1. Generate 2 structs by replacing the protons in question with the letter Z. Can assign R/S assuming Z has low priority. 2. If diastereomers, then the protons are diastereotopic. Z test
Cl H Br H H CH3
14.3B - 1H NMR Chemical Shift Ranges
! Table 14.1 and Figure 14.5 O C C H C H O C H C H O,N,X C H C C C H C C H
O C O H
12-9
8.0
6.5
4.5
2.5
1.5
0.5
" (ppm)
! The chemical shift of protons is determined by 3 effects
! The effects are additive (see aldehyde range above) ! N-H and O-H vary widely 1 - 6 ppm
14.3A,14.4 - Shielding and Deshielding Efects
! The NMR magnetic field causes # e- to create an opposing anisotropic magnetic field.
protons outside the pi system see a bigger field
7.34 1.43 ! (ppm)
14.3A,14.4 - Shielding and Deshielding Efects
! The effect of induced magnetic anisotropy depends on proximity to the pi system. ! Aromatic rings have biggest effect CH3CH2CH3 R R C C H CH2CH3 H
CH2CH3
! (ppm)
14.3A,14.4 - Shielding and Deshielding Efects
! Electronegative atoms deshield the electron cloud of protons so that they see more of the NMR magnetic field. The effects are additive.
eCl
H H
eCl 5.30 7.24 ! (ppm) 3.05
Cl Cl
deshielded: sees more of NMR field
14.5 - Integration of 1H NMR Peaks
! The area of peaks is proportional to the number of protons. Note that a short broad peak can have the same area as a tall narrow peak. ! If you know the molecular formula and number of hydrogens, you can convert peak area ratios into proton counts. I will simply give you the number of protons in each peak. from integration line from Mol. Form.
1.0 cm x + 1.5 cm x = 10H 2.5 cmx = 10H x = 4H per cm
C8H10O
1.5 cm 1980s style integration line ! Lab style 2.001 3.023
1.0 cm
14.6 Coupling between nuclei leads to splitting of peaks
! 1H neighbors couple. The bold proton will feel the magnetic eld from the NMR and the magnetic eld from neighboring protons.
Cl Br C C H H
Cl Br C C H H
! 13C nuclei don!t couple Since only one out of every 100 carbons is 13C, it is rare to have two 13C-13C neighbors.
NMR
NMR
14.6A,B - Analysis of Doublet and Triplet Splitting Patterns
origin of a doublet 1:1
origin of a triplet 1:2:1
! The coupling constant J is measured in Hz, not ppm. It is independent of the NMR magnet strength.
14.6C - Splitting Rules
! Protons separated by ! 3 bonds away WILL SPLIT.
! The coupling constant, J, is measured in Hz, not ppm. It is independent of the NMR magnet strength. ! Equivalent protons DONT SPLIT each other ! H-Bonded protons DONT SPLIT neighbors
Br H
Br H
Br H
Cl H
Ph
H H
14.6C - The n+1 Splitting Rule
! n equivalent neighboring protons give n+1 peaks H H H H H H
! The peak areas are predicted by Pascals triangle
