Chapter 13 Nuclear Magnetic Resonance Spectroscopy

Intended learning outcomes:

1. To understand the principle for nuclear magnetic resonance (NMR)
-- Nuclear spins, resonance with radiofrequency
-- Shielding effects, chemical shifts ()
2. To interpret 13C NMR spectrum
-- Chemical shifts of peaks in broad-band decoupled spectrum
-- Additional structural information from DEPT-90 and 135 spectra
3. To interpret 1H NMR spectrum
-- Chemical shifts and integration of the absorption peaks
-- Additional structural information from splitting patterns
Nuclear Spin Orientation

Magnetic Nuclei
 Nuclear Magnetic Resonance Spectroscopy (NMR)
NMR: resonance between nuclear spins and radio frequencies under
an external magnetic field

1 2

B=0

1H and 13C nuclei

E1 = E2

1 2

B0  0

E1  E2
[Link]
 Resonance: spin-flip caused by radiofrequencies

Electromagnetic wave
h
Spin-flip

Resonance

Youtube:[Link]
 Magnetic Nuclei and Nonmagnetic Nuclei

1. All nuclei with odd number (2n+1) of

protons:
1H, 2H, 14N, 19F, 31P, etc

2. All nuclei with odd number (2n+1) of

neutrons:
13C

3. All nuclei with even (2n) number of

both protons and neutrons are not
spinning:
12C, 16O, 32S
 An NMR spectrometer

Youtube: [Link]
 An NMR spectrometer

700 MHz NMR 900 MHz NMR

16. 4 Tesla 21.2 tesla
Resonance affected by shielding of nuclei by electrons
One signal for all Hs?

don’t care about this orientation

spin
Response of e to B0:
e circulation always
generates a magnetic
B0 e Blocal field (Blocal) opposite
to B0

Beffective = B0 - Blocal
Lenz’s Law: [Link]

We call Blocal shielding effect of the electron.

The higher the electronic density around a nuclei,
the more pronounced is the shielding effect.
 Field Scan or Frequency Scan

Electromagnetic wave
h

Beffective = B0 - Blocal
Resonance affected by shielding of nuclei by electrons
Chemical shifts: relative indicator of the resonance frequency

Resonance frequency  B0, not a constant Si(CH3)4

Delta scale (δ): defined below, use tetramethylsilane (TMS) as reference

(ppm)
 Chemical shift: some simple facts

Range of chemical shift: TMS as standard (for 1H and 13C only)

1H, δ = 1 -10
13C, δ = 1-220

For two protons with δ = 1.0 and 1.5, difference in Hz of resonance ?

1. 100 MHz spectrometer,  = 0.5 (ppm),  = 0.5 x 100 = 50 Hz

2. 300 MHz spectrometer,  = 0.5 (ppm),  = 0.5 x 300 = 150 Hz

3. 500 MHz spectrometer,  = 0.5 (ppm),  = 0.5 x 500 = 250 Hz

4. 750 MHz spectrometer,  = 0.5 (ppm),  = 0.5 x 750 = 375 Hz

 13C NMR Spectroscopy
13CNMR spectra are hard to obtain, low abundance of 13C
12C% = 98.9, no NMR signal; 13C% = 1.1, give NMR signal

Fourier-transformed (TF)-NMR:
Seconds to obtain a spectrum, thousands of scans within hours
averaging of these scans enhances S/N by n1/2
 Interpretation of 13C-NMR spectrum

1. Count how many carbons are there in a molecule

2. Chemical shifts tell the likely chemical environment
3. How many hydrogens are connected to a particular carbon
Assigning resonance peaks to carbons: Example 1

C2 C3 C1 C4
Assigning resonance peaks to carbons: Example 2
Predict the 13C spectrum from a structure

CH2=CH COOCH2CH3
 DEPT 13C NMR Spectroscopy

DEPT: Distortionless enhancement by polarization transfer

Tell you whether a carbon is

CH3, CH2, CH, or quaternary carbon (C)

Ordinary 13C-NMR: broadband-decoupled spectrum, see all carbons

DEPT-90 13C-NMR: spectrum: CH carbons

CH only
DEPT-135 13C-NMR: CH, CH2, and CH3 carbons

Positive:
CH3, CH

Negative: CH2
Application of DEPT-technology
Application of 13C NMR: example

7 peaks 5 peaks
For each of the compounds below tell how many signals you would expect the
molecule to have in its normal, broadband decoupled 13C NMR spectra.
 Summary for 13C-NMR

1. Fourier transformation technology makes 13C NMR possible

2. 13CNMR spectrum reveals all carbons with information

on their environment

3. DEPT 13C NMR distinguishes C, CH, CH2, and CH3

4. 13C NMR can help answer many chemical problems

 Chapter 13

Nuclear Magnetic Resonance Spectroscopy

Part 2. 1H NMR
 1H- NMR Spectroscopy

1. Proton NMR is much more sensitive than 13C: 100% 1H

2. Integration of resonance peak is proportional to the proton number
3. Shielding effect: equivalent chemical environment = identical 
4. Spin-spin splitting: provide valuable bond connectivity information
5. The most important tool in structural determination

x / y = 1:3
y

x
 Homotopic and heterotopic protons
Compare two H’s: replace each H with X and compare the products
Homotopic protons: give the same products, identical 
Heterotopic protons: give constitutional isomers, different 

Homotopic

Heterotopic
 Enantiotopic and diastererotopic protons

Compare two H’s: replace each H with X and compare the products
Enantiotopic protons: give enantiomers, identical  in achiral environment
Diastereotopic protons: give diastereomers, different 

Enantiotopic

[Link]

Diastereotopic
Chemical equivalence of protons: Examples
 Chemical shifts (δ) in 1H NMR

1. Proton signals range from  0 to  10

2. Lower field (larger ppm) signals are H’s attached to sp2 C
3. Higher field (smaller ppm) signals are H’s attached to sp3 C
4. Electronegative atoms attached to adjacent C cause downfield shift
5. -system causes downfield shift
 Chemical shifts (δ) in 1H NMR
Electronegativity-induced deshielding is additive
 Strong deshielding effects of conjugated -systems

Benzene

Blocal

Applied
external field

B by aromatic ring current

Beffective = Bapplied + Blocal, strongly deshielded

 Deshielding effects of -systems

Double bonds Triple bonds

Proton  very sensitive to electronic environment
 Application of 1H and 13C NMR
H2C CH2 H2C CH3 H3C
H H
H2C H3C C C CH3 C CH2
CH
H2C CH2 H3C

1 2 3 4
Predict 1H and 13C NMR
 Spin-spin splitting in 1H NMR

Spin-spin splitting: split resonance signals into multiple peaks (multiplets)

1. caused by interaction between nearby nuclei, called coupling.
2. provide information about connectivity of sub-structures
 Spin-spin coupling between two protons
spin
Blocal

50% Bapplied H1 Bcouple H2 Bproton

e
C C
- Bcouple
spin
Blocal

Bapplied H1 Bcouple H2 Bproton

50% e
C C

+ Bcouple
 Spin-spin coupling in 1H-NMR

1. Coupling: distance = 3 bonds.

J = coupling constant
> 3 bonds, no coupling.
usually 0 - 18 Hz
Exceptions: all carbons in a -system
2. Coupling is reciprocal.
H1 splits H2 into two peaks with J12
H2 also splits H1 into two peaks with J21
J12 = J21 = J
3. Coupling is dependent on the spin state
of the neighboring nuclei

therefore, when there are > 1 equivalent neighboring nuclei, coupling

depends on the combination of the spin states of these nuclei
 Splitting by (>1) neighboring equivalent groups

CH3CH2Br

Degenercy = 3,
Degenercy = 3,
net spin = 
net spin = 

1:3:3:1 1:2:1
 Spin-spin coupling: n + 1 rule
CH3CH2Br: 3H in CH3 split CH2 into quartet (4 = 3 + 1)
2H in CH2 split CH3 into triplet (3 = 2 + 1)

n+1 rule: protons having n equivalent neighboring protons show (n + 1) peaks

Doublet, 2 = 1 +1
Septet, 7 = 6 +1
Spin-spin coupling: n + 1 rule and intensity ratio
 More complex spin-spin splitting patterns

Complex factor 1: overlapping of two or more multiple peaks.

Complex factor 2: a signal is split by > 2 groups of equivalent H’s
 Rules for spin-spin splitting in 1H NMR

1. Equivalent protons do not split each other

2. The signal of a proton with n equivalent neighboring H’s is split
into n + 1 peaks
3. Protons that are farther than two carbon atoms apart do not
split each other
 Structural determination with 1H NMR
2
C5H10O 1 4
3
 Sample Question

The mass spectrum of this compound shows a molecular ion at m/z

= 113, the IR spectrum has characteristic absorptions at 2270 and
1735 cm-1, and the 13C NMR spectrum has five signals.
Q 1: Based on the mass spectral data and the IR data, what
functional groups are present in this compound?

Q 2: How many types of nonequivalent protons are there in this

molecule?

Q 3: Describe the signal at 3.5 d in terms of its integration, splitting

pattern and chemical shift.

Q 4: Describe the signals at 4.35 d and 1.3 d in terms of their

integration, splitting and chemical shift.

Q 5: What is the significance of the 13C NMR data?

Q 6: What is the structure of this compound?

 Comparison of 1H with 13C NMR

A. Identification of sub-structure:
1H: CH , CH , CH, OH, NH, etc, can’t detect C
3 2
13C: all kinds of carbons

B. Intensity of resonance peaks:

1H: intensity proportional to number of hydrogens
13C: intensity is not indicative of carbon number

C. Connectivity of sub-structures:
1H: detailed info about interactions (spin-spin splitting)
13C: no such information

1H NMR provides far more structural information, most important.

 Summary for 1H-NMR

1. Equivalent or nonequivalent environment: proton equivalence

2. Chemical shifts indicate the electronic environment of protons
3. Intensity of resonance peak: proton number
4. Spin-spin coupling: provides bond connectivity information

MS: molecular weight;

IR: functional groups
NMR: detailed structures
Assignment (for your own practice):

Numbers based on 7th Ed:

13.25, 13.26, 13.27, 13.28, 13.30, 13.31, 13.32
13.36, 13.37, 13.38, 13.39, 13.40, 13.41
13.42, 13.45, 13.47, 13.50, 13.51, 13.52, 13.53
13.54, 13.55, 13.57, 13.58, 13.59, 13.60, 13.61
13.62, 13.63, 13.65, 13.66, 13.67, 13.68

Number based on 8th Ed:

13.24, 13.27, 13.28, 13.26, 13.29, 13.33, 13.34
13.32, 13.38, 13.35, 13.40, 13.36, 13.43
13.42, 13.39, 13.52, 13.54, 13.45, 13.55, 13.53
13.44, 13.57, 13.56, 13.58, 13.60, 13.59, 13.65
13.66, 13.64, 13.61, 13.63, 13.67, 13.68