Chapter 14: Nuclear Magnetic Resonance Spectroscopy

I. Introduction of NMR Spectroscopy (14.1) II. 1H NMR: Number of Signals (14.2) III. 1H NMR: Position of Signals (14.3) IV. Chemical Shift of Protons on sp2 and sp Hybridized Carbons (14.4) V. 1H NMR: Intensity of Signals (14.5) VI. 1H NMR: Spin-Spin Splitting (14.6) VII. More Complex Examples of Splitting (14.7) VIII.Spin-Spin Splitting in Alkenes (14.8) IX. Other Facts About 1H NMR Spectroscopy (14.9) X. Using 1NMR to Identify an Unknown (14.10) XI. 13C NMR Spectroscopy (14.11)
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I. Introduction to NMR Spectroscopy

1H, 13C, 31P, 19F, 15N

Some nuclei have nuclear spin.

A. Basis of NMR Spectroscopy A spinning proton produces a magnetic field.

Bo
Absence of external magnetic field: spins oriented randomly Presence of external magnetic field Bo : more spins align with Bo
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RF Radiation h

E = h

Bo Two nuclear spin states separated by E Lower energy state nuclear spin magnetic moment aligned with Bo Higher energy state nuclear spin magnetic moment aligned against Bo Application of RF radiation pulse causes spin to flip from lower to higher energy state. Units of Bo are telsa (T); units of are hertz (Hz = s-1). is directly proportional to Bo: = Bo
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Fig. 14.1

How Fourier transform NMR works:

z z

Apply RF pulse

y x

along +x

y x

Spins precess about +z. Net magnetization (blue arrow) lies along +z.

After RF pulse, net magnetization relaxes into +z direction.

Signal is detected by looking along +y with an RF receiver:

Fourier transform

time domain

frequency domain

B. 1H NMR Spectroscopy
1H

NMR spectrum of CH3OC(CH3)3

upfield
(CH3)3C

Intensity

downfield
CH3O TMS

scale

10

6 4 Chemical Shift (ppm)

TMS is tetramethylsilane, (CH3)4Si, a chemical shift reference. t-Butyl methyl ether has sharp absorptions at 1.2 ppm and 3.2 ppm.
(ppm) = (Hz) downfield from TMS of NMR spectrometer (MHz)
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II. Number of Signals in 1H NMR Spectra

Protons in different chemical environments give different NMR signals. Equivalents protons have identical NMR signals. Examples:

Figure 14.2: Number of NMR Signals of Representative Organic Compounds

Substitution test for chemical shift nonequivalence: substitute each H with another atom (e.g. Cl). Example:
CH3

methylcyclobutane

Cl CH2Cl CH3

(chloromethyl)cyclobutane
CH3 Cl

1-chloro-1-methylcyclobutane
CH3 Cl

cis and trans-1-chloro-2-methylcyclobutanes

Cl CH3 Cl CH3

cis and trans-1-chloro-3-methylcyclobutanes

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A. Determining Equivalent Protons in Alkenes and Cycloalkanes

H H C N C N Ha Cl Hb C N

1,1-dicyanoethene Hs are equivalent 1 NMR signal

H H H

1-chloro-2-cyanoethene Ha and Hb nonequivalent 2 NMR signals

Hb Hc Hc Hb C N

H H

Ha

cyclopropane All Hs equivalent 1 NMR signal

cyanocyclopropane 3 types of Hs 3 NMR signals

How many NMR signals does methoxyethene give?

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B. Enantiotopic and Diastereotopic Protons Use substitution test to determine whether CH2 protons are equivalent. 1. Enantiotopic Protons
F H3C H Substitute each H with Cl H H3C F H F

Cl

H3C

Cl

fluoroethane

S-1-chloro-1fluoroethane

R-1-chloro-1fluoroethane

enantiomers CH2 protons of fluoroethane are enantiotopic. Enantiotopic protons are equivalent and give the same NMR signal.

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2. Diastereotopic Protons
H H H H H F H H H H Cl F H H F

Substitute each CH2 H with Cl

H Cl H

S-3-fluorocyclobutene

3S,4R-3-chloro- 3R,4R-3-chloro4-fluorocyclo4-fluorocyclocyclobutene cyclobutene

diastereomers CH2 protons of S-3-fluorocyclobutene are diastereotopic. Diastereotopic protons are always nonequivalent and give different NMR signals.

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III. Position of Signals in 1NMR Spectrum

A. Shielding and Deshielding Effects Orbital motion of the electron creates a magnetic field that opposes B0. Electron shields the nucleus from B0.

Figure 14.3: How Chemical Shift is Affected by Electron DensityAround a Nucleus

Shielding shifts absorptions upfield. Deshielding shifts absorptions downfield.

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B. Characteristic Chemical Shift Values

Type of Proton
sp3 C-H RCH3 R2CH2 R3CH Z = C, O, N
Z C C H

(ppm)
0.9 2 ~0.9 ~1.3 ~1.7 1.5 2.5 ~2.5

-CC-H Z = N, O, X
H C Z
H C C

2.5 4

4.5 6 6.5 8 9 10 10 12 15
13

H
O R C H R O C OH

RO-H or R2N-H

IV. Chemical Shift of Protons on sp2 and sp Hybridized Carbons

Circulating electrons affect the chemical shifts of Hs bound to multiply bonded carbons. A. Protons on Benzene Rings
Circulating electrons

H
B0

induced magnetic field

Circulating electrons create a ring current. Induced magnetic field reinforces B0 in vicinity of aromatic protons. Aromatic protons are deshielded and absorb downfield at 7.3 ppm.
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B. Protons on Carbon-Carbon Double Bonds

C
B0

H H

Induced magnetic field reinforces B0 in vicinity of vinyl protons.

Vinyl protons are deshielded and absorb downfield at 4.5 6 ppm. C. Protons on Carbon-Carbon Triple Bonds
H C

Induced magnetic field opposes B0 in vicinity of alkynyl proton. Alkynyl protons are shielded and absorb upfield at ~2.5 ppm.
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B0

V. Intensity of 1H NMR Signals

The area under an NMR signal is proportional to the number of protons that give rise to that signal.
1H

NMR spectrum of C5H12O

60

20

TMS

10

6 4 Chemical Shift (ppm)

Determining structure from integrals: 1. Add integrals: 60 + 20 = 80 2. Divide by number of Hs in formula: 80/12 = 6.7
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3. Divide each integral by 6.7: 20/6.7 = 3.0 (3 protons) 60/6.7 = 9.0 (9 protons) 4. Assign substructures: 3.2 ppm signal arises from 3 equivalent protons (1 CH3 group). This group must be attached to O, thereby giving OCH3. 1.2 ppm signal arises from 9 equivalent protons, consistent with 3 CH3 groups. Of the formula C5H12O, only C is left. 5. Draw the structure:
CH3 H3C O C CH3 CH3

t-butyl methyl ether

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VI. 1H NMR: Spin-Spin Splitting

Spin-spin splitting occurs between nonequivalent protons on the same carbon or adjacent carbons. Protons that split each others NMR signals are coupled. The splitting of the signal (in Hz) is called the coupling constant. Coupling with n adjacent protons splits a signal into n+1 peaks.

Chemical Shift (ppm)

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A. Why Spin-Spin Splitting Occurs

Number of Adjacent Protons 0 1 2 Adjacent Proton Spins none Splitting

singlet doublet triplet

quartet

Conclusion: n adjacent protons split NMR signal into n+1 peaks.

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B. More on Spin-Spin Splitting and the n + 1 Rule n 0 1 2 3 4 5 6 n+1 1 2 3 4 5 6 7 1 1 1 1 4 1 3 6 1 2 3 4 5 Peak Pattern 1 1 1 1 1 1 1 Name singlet doublet triplet quartet quintet sextet septet

5 10 10

6 15 20 15 6

The degree to which an NMR signal is split by spinspin coupling is measured by the coupling constant, J.

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C. More Features of Spin-spin Splitting 1. Equivalent protons do not spin couple.

Br-CH2-CH2-Br

One singlet only

2. Splitting is observed for nonequivalent protons on the same carbon or adjacent carbons.
Ha Hb CH3 C N Ha Cl Hb C N

Ha splits Hb into a doublet, and vice versa.

3. Splitting is usually not observed if the protons are separated by more than three bonds.
Ha and Hb are not coupled.
O H2C Ha C

2 proton quartet
CHCH3 Hb

3 proton triplet

3 proton singlet
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VII. More Complex Spin-Spin Splitting Patterns

More complex splitting occurs when the absorbing proton is coupled to nonequivalent protons on two (or more) adjacent carbons.

Figure 14.6: 1H NMR Spectrum of 2-Bromopropane

When adjacent nonequivalent protons form an equivalent set, the n+1 rule still holds.
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Figure 14.7: 1H NMR Spectrum of 1-Bromopropane

When n protons on one adjacent carbon and m protons on another adjacent carbon are not equivalent, the signal is split into (n+1)(m+1) peaks.

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Figure 14.8: Splitting Diagram for Hb Protons of 1-Bromopropane

Hb signal is split into 12 peaks, a triplet of quartets. If Jab >> Jbc, all 12 peaks are observed. If Jab ~ Jbc, peaks overlap and fewer peaks are observed.

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VIII. Spin-Spin Splitting in Alkenes

Characteristic coupling constants for disubstituted alkenes:
Ha C C Hb Ha C C Hb Ha C C Hb

geminal Hs Jgeminal 0-3 Hz

<

cis Hs Jcis 5-10 Hz

<

trans Hs Jtrans 11-18 Hz

Figure 14.9: 1H NMR Spectra for Alkenyl Protons of (E)- and (Z)-3-Chloropropenoic Acids

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Monosubstituted alkenes give more complex splitting patterns.

Figure 14.10: The 1H NMR Spectrum of Vinyl Acetate

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Hc C Hb C

Hd O O C CH3

Jbc = 1.2 Hz (geminal) Jcd = 6.5 Hz (cis) Jbd = 14 Hz (trans)

Figure 14.11: Splitting Diagram for Alkenyl Protons of Vinyl Acetate

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IX. More on 1NMR Spectroscopy

A. OH Protons

Figure 14.12: 1H NMR Spectrum of Ethanol OH proton of an alcohol usually does not split NMR signal of adjacent protons. Signal due to an OH proton not split by adjacent protons. OH protons exchange rapidly among ROH molecules.
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B. Cyclohexane Conformations
H H H H

Rapid conformational interconversion averages axial and equatorial proton chemical shifts. C. Protons on Benzene Rings

Figure 14.13: 1H NMR Spectra of Aromatic Protons

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X. Using 1H NMR to Identify an Unknown

Problem 14.24: Propose a structure for a compound of formula C7H14O2 with an IR absorption at 1740 cm-1 and the NMR data in the table. Absorption singlet triplet quartet (ppm) 1.2 1.3 4.1 Integral 26 10 6

Step 1: Identify functional group(s) and number of different types of protons. 1740 cm-1 IR absorption: C=O NMR data: 3 sets of nonequivalent protons

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Step 2: Determine number of protons that give rise to the three NMR absorptions. Integral total = 26 + 10 + 6 = 42 units Divide by number of protons: 42/14 = 3.0 integral units per H Divide integral for each absorption by this number and round to nearest digit: 26/3.0 = 8.7 10/3.0 = 3.3 6/3.0 = 2.0 9 Hs at 1.2 ppm 3 Hs at 1.3 ppm 2 Hs at 4.1 ppm

Step 3: Use splitting patterns to determine which Cs are bonded to each other. 9 proton singlet at 1.2 ppm arises from 3 CH3 groups bonded to C. 3 proton triplet at 1.3 ppm must be CH3 bonded to CH2. 2 proton quartet at 4.1 ppm must be CH2 bonded to CH3. 31

Step 4: Draw out the pieces and put them together to get the structure.

-OCH3 H3C C CH3

CH3CH2-

C O

CH3 O H3C C CH3 C OCH2CH3

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XI.

13C

NMR Spectroscopy

Physical basis same as 1H NMR spectroscopy.

13C

natural abundance is 1.1%.

1H - 13C spin splitting suppressed. All 13C peaks are singlets. Broader chemical shift range than 1H NMR. Peak intensity not proportional to number of absorbing carbons. A. Number of Signals in 13C NMR Spectra Number of signals equals number of different types of carbon in a molecule.
O

5 signals

7 signals

3 signals
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B. Position of Signals in 13C NMR Spectra Type of Carbon

sp3 C-H CC
H C Z
C C

(ppm)
5 45 65 100 30 - 80

Z = N, O, X

100 140

120 150

C O

160 210
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ppm

Figure 14.14: Representative 13C NMR Spectra

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