Proton Nuclear Magnetic Resonance (1H-NMR) Spectroscopy

Fundamental principle: The energy required to cause nuclear spin flip is a function of the magnetic environment experienced by the nucleus. Charged particle (nucleus or electron) in motion creates a magnetic field. In an external magnetic field, the magnetic moment (spin) of 1H nucleus (a proton) becomes aligned with the external field (lower energy) or against it (higher energy).

No external magnetic field Addition of energy results in nuclear spin flip:

With external magnetic field

Add energy E ~ 0.02 cal mol-1 = radio wave photons Relax (release energy)

Ground state Nuclear spin parallel to external magnetic field Lower energy

Excited state Nuclear spin antiparallel to external magnetic field Higher energy

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Lecture Supplement: Proton NMR Spectroscopy

External magnetic field

What does an NMR spectrum look like? NMR signal observed when radio waves supplied match E for nucleus under observation in the external magnetic field; proton is said to be in resonance.
NMR signal

Downfield (deshielded) low magnetic field strength

Intensity

Upfield (shielded) high magnetic field strength

Information From NMR Spectrum What information from the NMR spectrum is useful to deduce molecular structure? Number of signals Position of signals (chemical shift) Relative intensity of signals (integration) Splitting of signals (spin-spin coupling)

Number of Signals Protons in the same magnetic environment are equivalent: give same signal Nonequivalent protons give different signals Therefore number of signals = number of equivalent sets of protons in molecule Examples: HF versus HCl
H H C H Cl

H H C H

H C H Cl

H H C H

H C H OH

F H C F

Cl C Cl H

H F C H

Cl C Cl F

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CH3

Sample Spectra Verify what we have learned about equivalent protons.

CH3 CH3 C CH3 CH2OH

OH H H

H OH

Position of Signals: The Chemical Shift Magnetic field at nucleus influences E

Spin state energy
spin antiparallel to applied magnetic field E spin parallel to applied magnetic field

Magnetic field strength

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Lecture Supplement: Proton NMR Spectroscopy

What contributes to magnetic field felt by nucleus? Magnetic fields of earth and NMR spectrometer: same for all nuclei in molecule Magnetic fields provided by electrons and other nuclei in molecule: varies between nuclei in molecule

Chemical shift E scale that is independent of spectrometers magnetic field Chemical shift identical for a given proton regardless of spectrometer used Chemical shift unit = parts per million (ppm) Most proton chemical shifts 0-15 ppm range Represents E relative to reference proton: (CH3)4Si (tetramethylsilane; TMS) = 0.00 ppm by definition

How does chemical shift depend on molecular structure? Molecule (CH3)4Si CH4 CH3I CH3Br CH3Cl CH3F CH2Cl2 CHCl3 CCl4 How does electronegativity influence chemical shift? Electron cloud shields nucleus from applied magnetic field Electronegative atoms remove electron density from proton Less electron density = less shielding = higher chemical shift
1

H-NMR chemical shift 0.00 ppm

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Characteristic Proton NMR Chemical Shifts (ppm) RCH3 RCH2R acyclic RCH2R cyclic R3CH
R CH3

0.9 1.3 1.5

RCCH RNHCH3 RCH2X (X = Cl, Br, I) RCH2NR2

2.5 23 3.5

ArH RCHO, ArCHO RNH2 ArNH2

O

6.5 - 8 9.5 11 13

1.5 2.0

2.3 2.7

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1.8
R R

OCH3

3.8

N H

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O R
O

CH3

2.0 2.6

OCH2

3.3 4.1

ROH

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2.2 3.0
CH2R

R2C=CH2

5.0

ArOH

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ArCH3 ArCH2R

2.3 2.6

RCH=CR2

5.3

RCO2H

10 13

The exact chemical shift for each proton type does not need to be memorized. This table will be provided on an exam if needed. Similar functional group = similar chemical shift. Characteristic chemical shifts are averages for typical protons. Vary somewhat between molecules. Example:
O 2.01 ppm CH3O CH3
CH3 O 2.59 ppm

Other useful chemical shift observations Chemical shift RCH3 < RCH2R < R3CH, because EN of C > EN of H Electron-withdrawing or donating effects on chemical shift decrease with distance. Example:
CH4 CH3OH CH3CH2OH CH3CH2CH2OH 3.49 ppm 1.53 ppm

0.23 ppm

3.39 ppm

1.18 ppm

3.59 ppm

0.93 ppm

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Lecture Supplement: Proton NMR Spectroscopy

Unlike IR stretching frequencies, we cannot use characteristic chemical shifts table to assign proton types to NMR signals. Example: 3.8 ppm not always ROCH3 and 2.2 not always ArCH3. Exception: 6.5 8.0 ppm usually (not always) benzene ring protons.

3.7 ppm not necessarily OCH3 2.2 ppm not necessarily ArCH3

Probably benzene ring protons

TMS 0.00 ppm

Relative Intensity of Signals: Integration Beers Law: amount of energy absorbed or transmitted moles of stuff present For NMR, amount of radio energy proportional to area under peak in spectrum (area measurement = integration) Relative intensities of signals proportional to relative number of equivalent protons Integrals do not always correspond to exact number of protons

Sample NMR Spectra Verify what we have learned so far about equivalent protons, chemical shifts and integration.
H H C H OH

4.19 ppm: integral = 1.0 (1 H) 3.41 ppm: integral = 3.0 (3 H) Smallest integral often set = 1

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3.19 ppm: integral = 1.0 (6 H) 1.33 ppm: integral = 1.0 (6 H) Proton count = 6 : 6 Integration = 1 : 1 Integration gives ratio of protons, which is often not the exact number of protons.

Splitting of NMR Signals: Spin-Spin Coupling

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H-NMR spectrum of CH3CH2Br: more complex than we might have predicted!

CH3CH2Br

3.43 ppm: integral = 1.0 (2 H) 1.68 ppm: integral = 1.5 (3H)

Three lines a triplet

Four lines a quartet

What is the origin of this extra complexity?

Ha C C Hb

Ha, Hb parallel Ha, Hb antiparallel

Different spin flip energies (E) for Ha two chemical shifts for Ha Ha signal is split into two lines (a doublet)

Spin-spin coupling: spin of one nucleus influences the spin of another nucleus Splitting: effect on NMR spectrum caused by spin-spin coupling Coupling constant (J): spacing between lines in a splitting pattern
J

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What happens to splitting when there is more than one neighbor? Example: Ha has two neighbors (Hb and Hc)
Ha C C Hb Hc

Two neighbors parallel to Ha

equal energy

One parallel, one antiparallel to Ha Two neighbors antiparallel to Ha

Three possible neighbor spin states; Ha signal split into three lines (a triplet) in 1:2:1 ratio

a triplet

In general: the signal for a proton with n neighbors is split into n+1 lines. No neighbors singlet; one neighbor doublet; two neighbors triplet; three neighbors quartet; four neighbors pentet, etc.

Rules and Restrictions for Proton-Proton Spin-Spin Coupling What are the restrictions on spin-spin coupling? What constitutes a coupling neighbor? 1. Only nonequivalent protons couple.
X X
Ha Hb C H Hc C H Hd C H H C H H

Hb couples with Hc. Hb and Ha do not couple because they are equivalent. Hc and Hd do not couple because they are equivalent.

2. Protons separated by more than three single bonds usually do not couple.
Hb Ha C

X
C Hc

Hd C

Ha can couple with Hb Ha can couple with Hc Ha cannot couple with Hd

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Pi bonds do not count toward the bond limit, but the coupling constants may be too small to be resolved.
Hb C Ha Hd C C Hc

Ha can couple with Hb, Hc and Hd, but Jad may be small.

X
CH3

X
CH2CH3

The benzene ring coupling club: a benzene ring blocks some coupling that otherwise should be observed (i.e, J is too small).

All nonequivalent benzene ring protons may couple with each other, but the coupling constants may be too small to be resolved.
Ha Hb OCH3

Ha, Hb, Hc and Hd all couple with each other, but Jad may be small.

Hc Hd

CH3

Singlets

3. Signals for O-H and N-H protons are usually singlets. (Splitting of O-H or N-H protons is observed only in highly pure samples, and is very rare.)

H H2 N C H

H C H OH

Sample Spectra Verify what we have learned about equivalency, chemical shifts, integration and splitting.
1

H-NMR (ppm): 3.39 (triplet, integral = 1.0) 1.87 (sextet, integral = 1.0) 1.03 (triplet, integral = 1.5)

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H-NMR (ppm): 3.79 (septet, integral = 1.0) 1.31 (doublet, integral = 6.0)

H-NMR (ppm): 5.66 (multiplet, integral = 1.0) 1.98 (multiplet, integral = 2.0) 1.16 (multiplet, integral = 2.0) Multiplet: a splitting pattern that is too complex to decipher.

Non-First Order Splitting (such as a doublet of doublets) Normal splitting patterns occur when coupling constants of neighboring protons are equal. Example: The CH of CHCH2 is a triplet when Jab = Jac. When Jab Jac, more complex patterns arise, such as a doublet of doublets.
Ha C Hb C Hc

Jab = Jac normal triplet

Jab Jac doublet of doublets

For this course, we will assume that coupling constants are usually equal, and that normal splitting patterns will usually be observed. Exceptions are plentiful.

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H-NMR (ppm): 5.83 (doublet of doublets, integral = 1.0) Doublet of doublets = | | | |_ 4.93 - 4.82 (multiple, integral = 2.0) 1.00 (singlet, integral = 9.0)

H-NMR(ppm): 10.00 (singlet, integral = 1.0) 7.87 - 7.56 (multiplet, integral = 5.0)

H-NMR (ppm): 7.38 - 7.00 (multiplet, integral = 1.7) 2.34 (singlet, integral = 1.0) Splitting Jab seems to disappear as Ha Hb chemical shift difference becomes smaller.

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How do we decude molecular structure from NMR spectra? Formula: C9H12

H-NMR: 7.40 7.02 ppm (multiplet, integral = 5); 2.57 ppm (triplet, integral = 2); 1.64 ppm (sextet, integral = 2) and 0.94 ppm (triplet, integral = 3).

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