Proton NMR Spectroscopy

The NMR Phenomenon

Most nuclei possess an intrinsic angular momentum, P. Any spinning charged particle generates a magnetic field. P = [I(I+1)]1/2 h/2 where = spin quantum # I = 0, 1/2, 1, 3/2, 2,

Which nuclei have a spin?

If mass # and atomic # are both even, I = 0 and the nucleus has no spin. e.g. Carbon-12, Oxygen-16 For each nucleus with a spin, the # of allowed spin states can be quantized: For a nucleus with I, there are 2I + 1 allowed spin states.
1

H, 13C, 19F, 31P all have I = 1/2 E = (h/2)Bo

Spin states split in the presence of B0

-1/2 antiparallel

E +1/2 parallel no field applied field Bo

When a nucleus aligned with a magnetic field, B0, absorbs radiation frequency (Rf), it can change spin orientation to a higher energy spin state. By relaxing back to the parallel (+1/2) spin state, the nucleus is said to be in resonance. Hence,

NMR

Presence of Magnetic Field

NMR instruments typically have a constant Rf and a variable B0. A proton should absorb Rf of 60 MHz in a field of 14,093 Gauss (1.4093 T). Each unique probe nucleus (1H perhaps) will come into resonance at a slightly different and a very small percentage of - the Rf. All protons come into resonance between 0 and 12/1,000,000 (0 12 ppm) of the B0.

Energy Difference (E) Between Two Different Spin States of a Nucleus With I=1/2
-1/2 antiparallel

100 MHz

200 MHz

300 MHz

400 MHz

parallel +1/2

23,500

47,000

70,500

104,000

inc. magnetic field strength, Gauss

B0

What Does an NMR Spectrum Tell You?

# of chemically unique Hs in the molecule # of signals The types of Hs that are present e.g. aromatic, vinyl, aldehyde chemical shift The number of each chemically unique H integration The Hs proximity to eachother spin-spin splitting

How many signals in the Proton NMR Spectrum?

OCH3 CH3CH2CH2CH3 CH3 O CH3CH2OCCH2CH3 CH3

OCH3 CH3CH2CH2CH3 2 1 O CH3CH2OCCH2CH3 4 4 2 CH3 4 CH3

Chemical Equivalence
How many signals in 1H NMR spectrum?
CH3

O O O

Number of Equivalent Protons

CH3

5
O O

O 6 4

Vinyl Protons

Typical 1H NMR Scale is 0-10 ppm

The Scale

Tetramethylsilane (TMS)
Arbitrarily assigned a chemical shift of 0.00
CH3 CH3SiCH3 CH3 TMS

Chemical Shift Ranges, ppm

Diamagnetic Anisotropy Shielding and Deshielding

Deshielding in Alkenes

Shielding in Alkynes

Chemical Shift is Affected by Electron Density Around Nucleus

Increased electron density Shields nucleus upfield shift Decreased electron density Deshields nucleus downfield shift

from chemistry.msu.edu

Integration
Br CH3 H CH3 CH3 H

Methyl t-butyl ether (MTBE)

Toluene at Higher Field

Integral Trace
How many protons give rise to each signal?

Spin-Spin Splitting

The Doublet in 1H NMR

H a Hb C C

B0

Ha is coupled to H b Hb is parallel or anti-parallel to B 0 Ha splits into a 1:1 doublet peak

Hb in 1,1,2-Tribromoethane

The Triplet in 1H NMR

H a Hb C C Hb

Ha is coupled to Hb and Hb

B0

Hb can both be parallel, anti-parallel or one parallel and one anti-parallel Ha splits into a 1:2:1 triplet peak

Ha in 1,1,2-Tribromoethane

1,1,2-Tribromoethane

The Quartet in HMR

1
H C H C H H

B0
deshielded Chemical Shift

proton splits into n+1 quartet 1:3:3:1 n = # adjacent H's

shielded

Predict Splitting
ClCH2CH2Br ClCH2CH2Cl CH3 CHCl CH3 CH3CHCl2 CH3CH2NO2 CH3 CH3 C CH2Br CH3

1,1-Dichloroethane

Methyl Group appears as an Upfield Doublet

Methine H Appears as a Downfield Quartet

Ethyl benzene

Methyl Isopropyl Ketone

1-Nitropropane
O2N CH 2CH 2CH 3

2-Methyl-1-propanol

CH3 HOCH2CH CH3

Para Nitrotoluene

Why go to a higher field strength?

0.50 0.75
60 MHz 300 240 180 120 60 0 Hz

100 MHz 300 240 180 120 60 0 Hz

300 MHz 300 240 180 120 60 0 Hz

0.50 (t, 2H, J=10) 0.75 (t, 2H, J=10)

60 MHz 300 240 180 120 60 0 Hz

100 MHz 300 240 180 120 60 0 Hz

300 MHz 300 240 180 120 60 0 Hz

C-13 NMR Spectroscopy

C-13 chemical shifts

One signal for each chemically unique carbon

Coupling in C-13 NMR

the doublet in C-13 NMR
H C methine group

B0

C is coupled to H H is parallel or anti-parallel to B0 C splits into a 1:1 doublet peak

the triplet in C-13 NMR

B0

Ha C Hb

methylene group C is coupled to H a and H b Ha & H b can both be parallel, anti-parallel or one parallel and one anti-parallel C splits into a 1:2:1 triplet peak

the quartet in C-13 NMR

H C H H methyl group

B0
deshielded shielded

carbon splits into n+1 quartet 1:3:3:1 n = # attached H's

Butanone - Coupled and Decoupled

1,2,2-Trichloropropane 1 H and 13C NMR Spectra

Coupled C-13 NMR Spectrum

HC

CCH2CH2CH2CH3

CH2CO2H SPA

O CH3CH2OCCH2CCH3 coupled spectrum